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  <front>
    <journal-meta><journal-id journal-id-type="publisher">ACP</journal-id><journal-title-group>
    <journal-title>Atmospheric Chemistry and Physics</journal-title>
    <abbrev-journal-title abbrev-type="publisher">ACP</abbrev-journal-title><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-18-1363-2018</article-id><title-group><article-title>Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland</article-title>
      </title-group><?xmltex \runningtitle{Soil COS, CO, and {$\chem{CO_{2}}$} fluxes at Hyyti{\"{a}}l{\"{a}}}?><?xmltex \runningauthor{W.~Sun et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Sun</surname><given-names>Wu</given-names></name>
          <email>wu.sun@ucla.edu</email>
        <ext-link>https://orcid.org/0000-0002-2333-6282</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Kooijmans</surname><given-names>Linda M. J.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-4758-3368</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Maseyk</surname><given-names>Kadmiel</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-3299-4380</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2 aff7">
          <name><surname>Chen</surname><given-names>Huilin</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-1573-6673</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Mammarella</surname><given-names>Ivan</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-8516-3356</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4 aff5">
          <name><surname>Vesala</surname><given-names>Timo</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4 aff5 aff6">
          <name><surname>Levula</surname><given-names>Janne</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4 aff5 aff6">
          <name><surname>Keskinen</surname><given-names>Helmi</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-3614-0542</ext-link></contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Seibt</surname><given-names>Ulli</given-names></name>
          <email>useibt@ucla.edu</email>
        <ext-link>https://orcid.org/0000-0001-6043-6269</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Department of Atmospheric and Oceanic Sciences, University of California, Los Angeles, CA 90095-1565, USA</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Centre for Isotope Research, University of Groningen, Nijenborgh 6, 9747 AG Groningen, the Netherlands</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>School of Environment, Earth and Ecosystem Sciences, Open University, Milton Keynes MK7 6AA, UK</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>Department of Physics, University of Helsinki, P.O. Box 68, 00014 Helsinki,
Finland</institution>
        </aff>
        <aff id="aff5"><label>5</label><institution>Department of Forest Sciences, University of Helsinki, P.O. Box 27, 00014 Helsinki, Finland</institution>
        </aff>
        <aff id="aff6"><label>6</label><institution>Hyytiälä Forestry Field Station, University of Helsinki, 35500 Korkeakoski, Finland</institution>
        </aff>
        <aff id="aff7"><label>7</label><institution>Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado, Boulder, CO, USA</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Wu Sun (wu.sun@ucla.edu) and Ulli Seibt (useibt@ucla.edu)</corresp></author-notes><pub-date><day>1</day><month>February</month><year>2018</year></pub-date>
      
      <volume>18</volume>
      <issue>2</issue>
      <fpage>1363</fpage><lpage>1378</lpage>
      <history>
        <date date-type="received"><day>27</day><month>February</month><year>2017</year></date>
           <date date-type="accepted"><day>3</day><month>January</month><year>2018</year></date>
           <date date-type="rev-recd"><day>18</day><month>September</month><year>2017</year></date>
           <date date-type="rev-request"><day>27</day><month>April</month><year>2017</year></date>
      </history>
      <permissions>
        
        
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/3.0/">https://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>
    <?pagebreak page1363?><p id="d1e195">Soil is a major contributor to the biosphere–atmosphere exchange of carbonyl
sulfide (COS) and carbon monoxide (CO). COS is a tracer with which to quantify
terrestrial photosynthesis based on the coupled leaf uptake of COS and
<inline-formula><mml:math id="M1" display="inline"><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:math></inline-formula>, but such use requires separating soil COS flux, which is
unrelated to photosynthesis, from ecosystem COS uptake. For CO, soil is
a significant natural sink that influences the tropospheric CO budget. In the
boreal forest, magnitudes and variabilities of soil COS and CO fluxes remain
poorly understood. We measured hourly soil fluxes of COS, CO, and <inline-formula><mml:math id="M2" display="inline"><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:math></inline-formula>
over the 2015 late growing season (July to November) in a Scots pine forest
in Hyytiälä, Finland. The soil acted as a net sink of COS and CO,
with average uptake rates around 3 <inline-formula><mml:math id="M3" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for COS and
1 <inline-formula><mml:math id="M4" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for CO. Soil respiration showed
seasonal dynamics controlled by soil temperature, peaking at around
4 <inline-formula><mml:math id="M5" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in late August and September and dropping
to 1–2 <inline-formula><mml:math id="M6" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in October. In contrast, seasonal
variations of COS and CO fluxes were weak and mainly driven by soil moisture
changes through diffusion limitation. COS and CO fluxes did not appear to
respond to temperature variation, although they both correlated well with
soil respiration in specific temperature bins. However,
<inline-formula><mml:math id="M7" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="normal">COS</mml:mi></mml:mrow><mml:mo>:</mml:mo><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:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M8" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mo>:</mml:mo><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:mrow></mml:math></inline-formula> flux ratios increased
with temperature, suggesting possible shifts in active COS- and CO-consuming
microbial groups. Our results show that soil COS and CO fluxes do not have
strong variations over the late growing season in this boreal forest and can
be represented with the fluxes during the photosynthetically most active
period. Well-characterized and relatively invariant soil COS fluxes
strengthen the case for using COS as a photosynthetic tracer in boreal
forests.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p id="d1e370">Soil is a significant sink of the trace gases carbonyl sulfide (COS) and
carbon monoxide (CO) <xref ref-type="bibr" rid="bib1.bibx13 bib1.bibx59" id="paren.1"/>, contributing
26–33 % of the global COS sink <xref ref-type="bibr" rid="bib1.bibx5 bib1.bibx40" id="paren.2"/> and
10–15 % of the global CO sink <xref ref-type="bibr" rid="bib1.bibx15 bib1.bibx29 bib1.bibx32" id="paren.3"/>. In the
atmosphere, COS is a major precursor to the stratospheric sulfate aerosols
that exert a negative radiative forcing <xref ref-type="bibr" rid="bib1.bibx7 bib1.bibx36" id="paren.4"/>, with the
cooling effect greater than the warming potential of anthropogenic COS, and
CO affects concentrations of methane and other important greenhouse gases by
regulating their sinks through reactions with the OH radical
<xref ref-type="bibr" rid="bib1.bibx17" id="paren.5"/>. Soil fluxes influence the mean concentrations and
distributions of COS and CO in the atmosphere, and consequently atmospheric
chemical processes and the Earth's radiative balance.</p>
      <p id="d1e388">COS participates in land carbon cycle processes due to its chemical
similarities to <inline-formula><mml:math id="M9" display="inline"><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:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx28 bib1.bibx43 bib1.bibx5" id="paren.6"/>. In leaf
chloroplasts and soil microbes, COS as a substrate of carbonic anhydrase is
hydrolyzed irreversibly to <inline-formula><mml:math id="M10" display="inline"><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:math></inline-formula> and <inline-formula><mml:math id="M11" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi mathvariant="normal">S</mml:mi></mml:mrow></mml:math></inline-formula>
<xref ref-type="bibr" rid="bib1.bibx51 bib1.bibx52 bib1.bibx63 bib1.bibx64 bib1.bibx27 bib1.bibx56 bib1.bibx26 bib1.bibx46" id="paren.7"/>.
The hydrolysis occurs in parallel to <inline-formula><mml:math id="M12" display="inline"><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:math></inline-formula> hydration, the main
physiological function of carbonic anhydrase <xref ref-type="bibr" rid="bib1.bibx2 bib1.bibx23" id="paren.8"/>.
Because of the irreversible COS hydrolysis in leaves, COS is taken up
concurrently with <inline-formula><mml:math id="M13" display="inline"><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:math></inline-formula> through stomata and is not emitted back from
leaves <xref ref-type="bibr" rid="bib1.bibx57 bib1.bibx63" id="paren.9"/>. This allows COS to serve as a tracer
with which to quantify terrestrial photosynthesis independently from respiration
<xref ref-type="bibr" rid="bib1.bibx43 bib1.bibx9 bib1.bibx60 bib1.bibx78 bib1.bibx1 bib1.bibx5 bib1.bibx6 bib1.bibx42" id="paren.10"/>.</p>
      <?pagebreak page1364?><p id="d1e464">Globally, the largest COS sink is leaf uptake, followed by soil uptake
<xref ref-type="bibr" rid="bib1.bibx5" id="paren.11"/>, whereas the major COS sources include ocean emissions from
biogenic and photochemical processes <xref ref-type="bibr" rid="bib1.bibx19 bib1.bibx39" id="paren.12"/>, and
anthropogenic emissions from industrial activities and biomass burning
<xref ref-type="bibr" rid="bib1.bibx10" id="paren.13"/>. Since ocean COS emissions are geographically separated
from the terrestrial COS sinks (leaf and soil), and anthropogenic emissions
are usually concentrated as point sources, the spatial separation of dominant
COS sources and sinks enables us to constrain land COS fluxes, and hence
photosynthetic carbon uptake, from atmospheric COS observations
<xref ref-type="bibr" rid="bib1.bibx9 bib1.bibx5 bib1.bibx24" id="paren.14"/>. However, for the use of COS as
a photosynthetic tracer, soil COS flux, which is unrelated to photosynthesis,
needs to be understood and separated from the ecosystem COS flux that is the
sum of leaf and soil fluxes <xref ref-type="bibr" rid="bib1.bibx42 bib1.bibx12 bib1.bibx72" id="paren.15"/>.</p>
      <p id="d1e482">Soils vary from COS sinks to sources depending on their physical and
biogeochemical conditions <xref ref-type="bibr" rid="bib1.bibx42 bib1.bibx74 bib1.bibx77 bib1.bibx18" id="paren.16"/>. Aerated
upland soils are primarily weak COS sinks, whereas anoxic wetland soils are
COS sources <xref ref-type="bibr" rid="bib1.bibx76" id="paren.17"/>. In unmanaged upland soils, the uptake rates
range from 0 to 12 <inline-formula><mml:math id="M14" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in field studies
<xref ref-type="bibr" rid="bib1.bibx62 bib1.bibx80 bib1.bibx4" id="paren.18"><named-content content-type="pre">e.g.,</named-content></xref>. Soil COS uptake depends
nonlinearly on soil temperature and moisture, with optimal conditions that
maximize the uptake <xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx69 bib1.bibx77" id="paren.19"/>. Soil COS
uptake also correlates positively with soil respiration
<xref ref-type="bibr" rid="bib1.bibx80 bib1.bibx4 bib1.bibx66" id="paren.20"/>, suggesting a link through microbial
activity between them.</p>
      <p id="d1e530">It has been assumed that soil COS flux is a minor component in the total COS
budget of non-wetland ecosystems when using COS for photosynthesis
measurements <xref ref-type="bibr" rid="bib1.bibx1" id="paren.21"><named-content content-type="pre">e.g.,</named-content></xref>. However, recent discoveries challenge
this assumption. Strong net emissions of COS have been observed from cropland
soils at high temperature <xref ref-type="bibr" rid="bib1.bibx42 bib1.bibx77" id="paren.22"/> and in an alpine
grassland under solar radiation <xref ref-type="bibr" rid="bib1.bibx33" id="paren.23"/>, highlighting the crucial role
of abiotic COS production in soil COS flux. In semi-arid ecosystems, the
rewetting of leaf litter after rainfall can stimulate pulses in COS uptake
that temporarily overwhelm leaf COS uptake <xref ref-type="bibr" rid="bib1.bibx66" id="paren.24"/>. Understanding the
factors that control soil COS flux variability is therefore essential to the
prediction of soil COS fluxes. In ecosystems where soil COS flux makes up
a potentially significant and variable fraction of the ecosystem COS budget,
failure to account for soil COS flux may lead to significant biases in the
photosynthesis estimates from the COS approach <xref ref-type="bibr" rid="bib1.bibx77" id="paren.25"/>. Ensuring
accurate photosynthesis measurements from the COS approach requires
understanding how soil COS flux is controlled by soil temperature, moisture,
and biotic factors.</p>
      <p id="d1e550">Soil CO flux is also the net balance between concurrent uptake and production
activities <xref ref-type="bibr" rid="bib1.bibx14 bib1.bibx15 bib1.bibx58 bib1.bibx30 bib1.bibx31 bib1.bibx8 bib1.bibx68 bib1.bibx49" id="paren.26"/>. Soil CO uptake is primarily due to microbial
activity <xref ref-type="bibr" rid="bib1.bibx25 bib1.bibx14 bib1.bibx73" id="paren.27"/> and involves more diverse
metabolic pathways compared with those in COS uptake
<xref ref-type="bibr" rid="bib1.bibx44 bib1.bibx32 bib1.bibx46" id="paren.28"/>. The key environmental factors controlling
CO uptake rates include soil moisture and temperature
<xref ref-type="bibr" rid="bib1.bibx15 bib1.bibx30 bib1.bibx81" id="paren.29"/>. Similar to COS uptake, there can exist an
optimal condition of soil moisture and temperature that maximizes the soil CO
uptake <xref ref-type="bibr" rid="bib1.bibx45 bib1.bibx30" id="paren.30"/>, but this feature has not been evaluated
extensively in different soil types. The moisture optimum can sometimes be
lower than the annual soil moisture range in natural conditions
<xref ref-type="bibr" rid="bib1.bibx30" id="paren.31"><named-content content-type="pre">e.g.,</named-content></xref> and thus may not be well defined in field
observations. Soil CO uptake has also been shown to correlate with soil
respiration in the laboratory (Hendrickson and Kubiseski, 1991), but this
correlation is yet to be investigated in field conditions.</p>
      <p id="d1e574">Soil can show net CO emissions. CO production in soils has been considered
largely abiotic <xref ref-type="bibr" rid="bib1.bibx15 bib1.bibx83" id="paren.32"/>, but microbes on fine roots have also
been reported to contribute significantly to CO production in the laboratory
<xref ref-type="bibr" rid="bib1.bibx31" id="paren.33"/>. Soil CO emissions generally increases with temperature and
solar radiation in field conditions
<xref ref-type="bibr" rid="bib1.bibx30 bib1.bibx81 bib1.bibx83 bib1.bibx68" id="paren.34"/>, indicating dominant
contributions from photochemical and thermal production. It remains poorly
understood how environmental factors control the variability of soil CO flux
in the field, because most studies on soil CO flux are laboratory incubations
of altered soil samples or short-term, sporadic field experiments.</p>
      <p id="d1e586">In general, soil fluxes of COS and CO are controlled by gas transport in the
soil column that responds to soil moisture <xref ref-type="bibr" rid="bib1.bibx65 bib1.bibx81" id="paren.35"><named-content content-type="pre">e.g.,</named-content></xref>
and by in situ reactions including uptake and production. Both COS and CO
uptake processes are mainly due to microbial activity
<xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx26 bib1.bibx3 bib1.bibx73" id="paren.36"/> and may correlate with
soil respiration through microbial activity
<xref ref-type="bibr" rid="bib1.bibx80 bib1.bibx4 bib1.bibx22" id="paren.37"/>, whereas their production processes
are predominantly abiotic and should respond to physical drivers. Similar to
other ecosystems, we hypothesize that soil temperature, moisture, and
microbial activity are the main drivers of soil COS flux in boreal forests,
and they have responses unique to this type of ecosystem. Despite limited
knowledge of soil CO processes, we expect similarities in the responses of
soil CO flux to soil physical variables and microbial activity compared to
the responses of COS flux, based on the reactive transport mechanism in the
soil column <xref ref-type="bibr" rid="bib1.bibx65 bib1.bibx47 bib1.bibx82" id="paren.38"/>. Here we report continuous
field measurements of soil COS, CO, and <inline-formula><mml:math id="M15" display="inline"><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:math></inline-formula> fluxes in a Scots pine
forest in southern Finland over the late growing season (July to November).
We explore diurnal and seasonal variabilities of the fluxes and identify the
major physical and biological drivers of the variabilities.</p>
</sec>
<sec id="Ch1.S2">
  <title>Materials and methods</title>
<sec id="Ch1.S2.SS1">
  <title>Site description</title>
      <?pagebreak page1365?><p id="d1e625">Field measurements were made at the SMEAR II site (Station for Measuring
Forest Ecosystem–Atmosphere Relations) at Hyytiälä Forestry Field
Station of the University of Helsinki (61.845<inline-formula><mml:math id="M16" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> N,
24.288<inline-formula><mml:math id="M17" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> E; 181 <inline-formula><mml:math id="M18" display="inline"><mml:mrow><mml:mi mathvariant="normal">m</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">a</mml:mi><mml:mo>.</mml:mo><mml:mi mathvariant="normal">s</mml:mi><mml:mo>.</mml:mo><mml:mi mathvariant="normal">l</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:math></inline-formula>). The station features a largely
homogeneous stand of Scots pine (<italic>Pinus sylvestris</italic>) planted in 1962
<xref ref-type="bibr" rid="bib1.bibx67 bib1.bibx70" id="paren.39"/>. The forest floor is covered by mosses
(<italic>Dicranum polysetum</italic>, <italic>Hylocomium splendens</italic>, and
<italic>Pleurozium schreberi</italic>) and understory herbs including bilberry
(<italic>Vaccinium myrtillus</italic>) and lingonberry (<italic>Vaccinium vitis-idaea</italic>) <xref ref-type="bibr" rid="bib1.bibx38" id="paren.40"/>. The climate is boreal, with 30-year-average
January and July temperatures of <inline-formula><mml:math id="M19" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>7.2 and
16.0 <inline-formula><mml:math id="M20" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>, respectively <xref ref-type="bibr" rid="bib1.bibx50" id="paren.41"/>. The average annual
precipitation is 711 <inline-formula><mml:math id="M21" display="inline"><mml:mi mathvariant="normal">mm</mml:mi></mml:math></inline-formula>, with summer and fall receiving somewhat more
than winter and spring <xref ref-type="bibr" rid="bib1.bibx50" id="paren.42"/>. Meteorological and ancillary data
such as surface pressure, air temperature, relative humidity, radiation,
precipitation, and soil temperature and moisture are continuously monitored
at the SMEAR II site (see <xref ref-type="bibr" rid="bib1.bibx21" id="altparen.43"/>, for description of the site
infrastructure). These data are available online at
<uri>http://avaa.tdata.fi/web/smart/smear/</uri>.<?xmltex \hack{\newpage}?></p>
      <p id="d1e733">Soils at the site are podzols of depths varying from 0.5 to 1.6 <inline-formula><mml:math id="M22" display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula>,
developed from glacial deposits. The O horizon is a porous mor-humus layer
laden with fine roots and mycorrhizae, distinct from the mineral soil
underneath. The thickness of the O horizon varies from 1 to 5 <inline-formula><mml:math id="M23" display="inline"><mml:mi mathvariant="normal">cm</mml:mi></mml:math></inline-formula>
<xref ref-type="bibr" rid="bib1.bibx48 bib1.bibx54" id="paren.44"/>, the bulk density is 0.10 <inline-formula><mml:math id="M24" display="inline"><mml:mrow><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>,
and the porosity is 0.67 <inline-formula><mml:math id="M25" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx53" id="paren.45"/>. The
O horizon is highly acidic (pH <inline-formula><mml:math id="M26" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 2.9 to 3.6) and rich in carbon content
(31–45 <inline-formula><mml:math id="M27" display="inline"><mml:mrow><mml:mi mathvariant="normal">wt</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>). The mineral soil underneath is of sandy loam
texture but also has a high fraction of gravels and stones
<xref ref-type="bibr" rid="bib1.bibx20" id="paren.46"/>. The A horizon is 4–8 <inline-formula><mml:math id="M28" display="inline"><mml:mi mathvariant="normal">cm</mml:mi></mml:math></inline-formula> thick, and it has a porosity
of 0.61 <inline-formula><mml:math id="M29" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> and a carbon content of 3–6 <inline-formula><mml:math id="M30" display="inline"><mml:mrow><mml:mi mathvariant="normal">wt</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>.
Beneath the A horizon, porosity and carbon content decrease with depth. The
mineral soil is less acidic than the humus layer, with pH around 4 to 5.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Experimental setup</title>
      <p id="d1e860">A quantum cascade laser spectrometer (QCLS, Aerodyne Research Inc.,
Billerica, MA, USA) was used to measure concentrations of COS, CO,
<inline-formula><mml:math id="M31" display="inline"><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:math></inline-formula>, and <inline-formula><mml:math id="M32" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> at 1 <inline-formula><mml:math id="M33" display="inline"><mml:mi mathvariant="normal">Hz</mml:mi></mml:math></inline-formula>. The instrument had overall
uncertainty (1 SD) of 7.5 <inline-formula><mml:math id="M34" display="inline"><mml:mi mathvariant="normal">ppt</mml:mi></mml:math></inline-formula> (parts per trillion) for COS,
3.3 <inline-formula><mml:math id="M35" display="inline"><mml:mi mathvariant="normal">ppb</mml:mi></mml:math></inline-formula> for CO, and 0.23 <inline-formula><mml:math id="M36" display="inline"><mml:mi mathvariant="normal">ppm</mml:mi></mml:math></inline-formula> for <inline-formula><mml:math id="M37" display="inline"><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:math></inline-formula>
<xref ref-type="bibr" rid="bib1.bibx34" id="paren.47"/>. An oil-free dry scroll pump (Varian TriScroll) was
connected to the QCLS to pull the sampling air through the analyzer. The QCLS
was housed inside a small cabin that was not air-conditioned. An automatic
background correction was performed every 6 h with an ultrahigh-purity
(<inline-formula><mml:math id="M38" display="inline"><mml:mo>&gt;</mml:mo></mml:math></inline-formula> 99.999 %) nitrogen cylinder to remove the curvature effect in the
baseline spectra. An air purifier (Gatekeeper CE-500K-I-4R) was used to scrub
trace amounts of CO from the cylinder air. The instrument was calibrated
against three working standards that had been calibrated to the NOAA or WMO
scale in the laboratory <xref ref-type="bibr" rid="bib1.bibx34" id="paren.48"/>.</p>
      <p id="d1e940">Soil fluxes were measured in two automated soil chambers (LI-8100A-104,
LI-COR Biosciences, Lincoln, NE, USA) modified to avoid COS emission
artifacts from chamber materials and operated in a flow-through configuration
<xref ref-type="bibr" rid="bib1.bibx42" id="paren.49"/>. These modifications included replacing the chamber bowl and
soil collar with stainless steel components, and removing or replacing other
small COS-producing parts. Dark chambers were selected to prevent
photochemical production of COS <xref ref-type="bibr" rid="bib1.bibx74" id="paren.50"><named-content content-type="pre">e.g.,</named-content></xref> or CO
<xref ref-type="bibr" rid="bib1.bibx68" id="paren.51"><named-content content-type="pre">e.g.,</named-content></xref> at the soil surface during chamber
measurements. The two chambers were placed in similar environments, about
10 <inline-formula><mml:math id="M39" display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula> apart. The moss layer or any other vegetation was removed to
expose the humus layer inside the chambers.</p>
      <p id="d1e963">The sampling system used a multi-position valve (Valco Instruments Co., Inc.)
to sample each soil chamber once per hour. Air was sampled from the open
chamber for 3 min; then the chamber was closed and the headspace air was
sampled for 9–10 min, followed by sampling from the open chamber for
2 min. Soil chamber 2 was added to the sampling system on 30 July 2015.
Prior to this date, soil chamber 1 was measured twice per hour.</p>
      <?pagebreak page1366?><p id="d1e966">To ensure that the chamber materials do not show apparent fluxes that bias
the measurements, we conducted blank-chamber tests with soil chamber 1 at the
start of the campaign. The chamber footprint was sealed off with a Teflon FEP
film to exclude soil fluxes and measure only the fluxes from chamber
materials. We found that the apparent fluxes of CO and <inline-formula><mml:math id="M40" display="inline"><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:math></inline-formula> from the
blank chamber were 0.00 <inline-formula><mml:math id="M41" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.10 and
<inline-formula><mml:math id="M42" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.05 <inline-formula><mml:math id="M43" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.15 <inline-formula><mml:math id="M44" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, respectively (Fig. S1
in the Supplement), and hence were not statistically different from zero.
However, we found a small positive COS flux
(0.66 <inline-formula><mml:math id="M45" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.48 <inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) that was statistically
different from zero in a one-sample <inline-formula><mml:math id="M47" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> test (<inline-formula><mml:math id="M48" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M49" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 3.40 and
<inline-formula><mml:math id="M50" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M51" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.02). We did not observe the blank-chamber COS emissions to depend
on temperature as in <xref ref-type="bibr" rid="bib1.bibx42" id="text.52"/>, since daily temperature changes were
small at the site. Because the same chamber was previously used at a site
with strong diurnal temperature variations but did not show
temperature-dependent COS emissions <xref ref-type="bibr" rid="bib1.bibx66" id="paren.53"/>, we assumed the
blank-chamber COS flux to be constant throughout the campaign period. We therefore
subtracted the mean blank-chamber COS flux from the measured COS fluxes in
both chambers and included the uncertainty term from the blank-chamber COS
flux into the calculation of the overall flux uncertainty. In doing so, we
also assumed soil chamber 2 to have the same blank-chamber COS flux as soil
chamber 1, since the chamber materials were the same.</p>
      <p id="d1e1106">The tubing connecting the chambers to the QCLS (Synflex <inline-formula><mml:math id="M52" display="inline"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> in.)
was flushed continuously to minimize wall effects for the sampled gases. The
segment of inlet tubing inside the chambers was perforated to enhance the
mixing of chamber air. The outlet tubing was pushed into the center of the
chamber bowl, with a filter attached to it. Airflow into the chambers was
provided by a diaphragm pump (KNF N811) with inlet at 0.5 <inline-formula><mml:math id="M53" display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula> height in
the vicinity of the chambers. The air flowing through the pump did not show
enhanced COS or CO concentrations. The flow rates into the chambers were set
to 1.5 <inline-formula><mml:math id="M54" display="inline"><mml:mi mathvariant="normal">slpm</mml:mi></mml:math></inline-formula> (standard liter per minute) before and 2.1 <inline-formula><mml:math id="M55" display="inline"><mml:mi mathvariant="normal">slpm</mml:mi></mml:math></inline-formula>
after 19 August 2015. Flow rates at the chambers, and pressure and flow rate
at the pump inlet were checked during regular site visits. To correct for
drifts, we interpolated the time series of chamber flow rate linearly from
a set of discrete field measurements, including the measured flow rate values
and the estimated values derived from linear correlations with pump flow
rates and inlet pressure. The residence time of the air in the chamber was
3–4 min, as calculated from the chamber effective volume (6.1 <inline-formula><mml:math id="M56" display="inline"><mml:mi mathvariant="normal">L</mml:mi></mml:math></inline-formula>)
and the flow rate.</p>
      <p id="d1e1149">In flow-through chambers, any imbalance between inlet and outlet flows
creates pressurization in the chamber headspace that drives vertical
advection in the soil column, leading to biases in measured fluxes
<xref ref-type="bibr" rid="bib1.bibx41" id="paren.54"/>. For soil fluxes, underpressure seems more problematic than
overpressure, because it would siphon up the soil pore air that is usually
enriched in <inline-formula><mml:math id="M57" display="inline"><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:math></inline-formula> by a few orders of magnitude. To prevent
pressure-related flux biases, we set the inlet flow slightly higher than the
outlet flow, with the small residual flow (approximately 0.1 <inline-formula><mml:math id="M58" display="inline"><mml:mi mathvariant="normal">slpm</mml:mi></mml:math></inline-formula>)
equilibrated through a vent at the top of the chamber <xref ref-type="bibr" rid="bib1.bibx79" id="paren.55"/>. The
residual flow that was dissipated would not affect the mass balance
calculation, because fluxes were always calculated using the flow rates
measured at the inlet.</p>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Flux calculation</title>
      <p id="d1e1182">Fluxes were calculated from the mass balance equation of chamber headspace
concentrations during chamber closure. Assuming the chamber air is well
mixed, the rate of change of headspace concentration of a gas species is the
balance of the inlet flux, the outlet flux, and the soil flux. The inlet
concentration is assumed to be the ambient concentration measured before
chamber closure, and the outlet concentration is what the analyzer measures
during chamber closure. We therefore obtain an equation of mass balance in
the chamber,

                <disp-formula id="Ch1.E1" content-type="numbered"><mml:math id="M59" display="block"><mml:mstyle class="stylechange" displaystyle="true"/><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mi>V</mml:mi><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>C</mml:mi></mml:mrow><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>=</mml:mo><mml:mi>q</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">a</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:mi>C</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mi>F</mml:mi><mml:mi>A</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

          where <inline-formula><mml:math id="M60" display="inline"><mml:mi>C</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M61" display="inline"><mml:mrow><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) is the chamber headspace concentration;
<inline-formula><mml:math id="M62" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">a</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M63" display="inline"><mml:mrow><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) is the ambient concentration;
<inline-formula><mml:math id="M64" display="inline"><mml:mi>q</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M65" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) is the inlet flow rate; <inline-formula><mml:math id="M66" display="inline"><mml:mi>V</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M67" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>) and
<inline-formula><mml:math id="M68" display="inline"><mml:mi>A</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M69" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>) are the chamber volume and footprint area, respectively;
and <inline-formula><mml:math id="M70" display="inline"><mml:mi>F</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M71" display="inline"><mml:mrow><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) is the flux rate to be determined. By
solving the differential equation of mass balance, the soil flux rate <inline-formula><mml:math id="M72" display="inline"><mml:mi>F</mml:mi></mml:math></inline-formula> is
then obtained from least square fit of the chamber headspace concentration
vs. time.</p>
      <p id="d1e1390">We implemented a baseline correction to account for changes in ambient
concentrations during chamber closure and instrument drift. The inlet
concentration was interpolated between the two opening periods before and
after chamber closure. This zero-flux baseline was subtracted from chamber
concentrations before calculating the flux from least square fitting. Some
measurement periods had wavelike noise in all measured gas concentrations,
likely due to instrument instability, which prevented the calculation of
reliable fluxes. Causes of the instrument instability were unclear, and we did
not find it to be related to condensation in the chamber. The affected flux
data points were filtered out by diagnosing the concentration vs. time plots,
and conspicuous outliers were also removed (Table S1 in the Supplement).</p>

      <?xmltex \floatpos{t}?><?pagebreak page1367?><fig id="Ch1.F1" specific-use="star"><caption><p id="d1e1395">Soil fluxes of <bold>(a)</bold> COS, <bold>(b)</bold> CO, and
<bold>(c)</bold> <inline-formula><mml:math id="M73" display="inline"><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:math></inline-formula> from two chambers in a pine forest in southern
Finland in summer and fall 2015. Also shown are <bold>(d)</bold> soil humus layer
(1–5 <inline-formula><mml:math id="M74" display="inline"><mml:mi mathvariant="normal">cm</mml:mi></mml:math></inline-formula>) and A horizon (2–5 <inline-formula><mml:math id="M75" display="inline"><mml:mi mathvariant="normal">cm</mml:mi></mml:math></inline-formula> below the humus layer)
temperatures (lines) and daily precipitation (bar plot), and
<bold>(e)</bold> gap-filled and smoothed soil moisture in the humus layer and
A horizon. Frequent gaps in raw soil moisture data (shown in transparent
colors) from September 2015 onwards were gap-filled (solid lines) based on the
correlation with soil moisture from a nearby location (see Sect. <xref ref-type="sec" rid="Ch1.S2.SS4"/>
for details).</p></caption>
          <?xmltex \igopts{width=483.69685pt}?><graphic xlink:href="https://acp.copernicus.org/articles/18/1363/2018/acp-18-1363-2018-f01.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S2.SS4">
  <title>Treatment of soil moisture data</title>
      <p id="d1e1453">Soil moisture data were measured with the Campbell TDR100 time-domain
reflector (Campbell Scientific, Logan, UT, USA) and provided by the SMEAR II
database. Sensors were in close proximity to the chambers
(<inline-formula><mml:math id="M76" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 5 <inline-formula><mml:math id="M77" display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula>). Since soil moisture measurements were associated with
high-frequency random noise, we ran a Savitzky–Golay filter with a 1-day
window to smooth the data while retaining the daily trends. After early
September 2015, soil moisture measurements had frequent gaps. A more complete
time series was available from soil profile measurements about 30 <inline-formula><mml:math id="M78" display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula>
north from the chamber site. Soil A horizon moisture at this site in August
was highly correlated with both the A horizon (<inline-formula><mml:math id="M79" display="inline"><mml:mrow><mml:msup><mml:mi>r</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.88</mml:mn></mml:mrow></mml:math></inline-formula>) and humus layer
(<inline-formula><mml:math id="M80" display="inline"><mml:mrow><mml:msup><mml:mi>r</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M81" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.93) moisture measurements near the chambers. We reconstructed
the missing measurements at our soil plots from the linear regressions using
August data. The gap-filled soil moisture data of both layers generally agreed
well with the intermittent measurements during that period
(root mean square error (RMSE) <inline-formula><mml:math id="M82" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.042 <inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for the humus layer and
0.015 <inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for the A horizon, respectively).</p>
</sec>
<sec id="Ch1.S2.SS5">
  <title>Statistical analysis</title>
      <p id="d1e1565">To extract smooth patterns of temperature and moisture dependence of soil
fluxes, we ran a 2-D local regression (LOESS) on COS, CO, and <inline-formula><mml:math id="M85" display="inline"><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:math></inline-formula>
fluxes against humus layer temperature and moisture (predictors). Unlike
linear regression, LOESS is a non-parametric method that does not require any
analytical expression of the underlying relationships. At each data point,
a low-degree polynomial is fitted to all its neighboring points, weighted by
distances, to give a smoothed estimate at the current point
<xref ref-type="bibr" rid="bib1.bibx11" id="paren.56"/>.<?xmltex \hack{\newpage}?></p>

<?xmltex \floatpos{t}?><?pagebreak page1369?><table-wrap id="Ch1.T1" specific-use="star"><caption><p id="d1e1586">A statistical summary of fluxes from the two soil chambers.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="10">
     <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:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Mean</oasis:entry>  
         <oasis:entry colname="col3">SD</oasis:entry>  
         <oasis:entry colname="col4">1st quartile</oasis:entry>  
         <oasis:entry colname="col5">Median</oasis:entry>  
         <oasis:entry colname="col6">3rd quartile</oasis:entry>  
         <oasis:entry colname="col7">Jun/Jul</oasis:entry>  
         <oasis:entry colname="col8">Aug</oasis:entry>  
         <oasis:entry colname="col9">Sep</oasis:entry>  
         <oasis:entry colname="col10">Oct/Nov</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">mean</oasis:entry>  
         <oasis:entry colname="col8">mean</oasis:entry>  
         <oasis:entry colname="col9">mean</oasis:entry>  
         <oasis:entry colname="col10">mean</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">SC1</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M87" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mrow class="chem"><mml:mi mathvariant="normal">COS</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M88" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M89" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.83</oasis:entry>  
         <oasis:entry colname="col3">1.01</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M90" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>3.38</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M91" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.75</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M92" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.17</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M93" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.55</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M94" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.74</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M95" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>3.25</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M96" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>3.76</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M97" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M98" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M99" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.00</oasis:entry>  
         <oasis:entry colname="col3">0.43</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M100" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.27</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M101" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.93</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M102" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.69</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M103" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.78</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M104" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.02</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M105" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.39</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M106" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.18</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M107" display="inline"><mml:mrow><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M108" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">3.18</oasis:entry>  
         <oasis:entry colname="col3">1.29</oasis:entry>  
         <oasis:entry colname="col4">2.29</oasis:entry>  
         <oasis:entry colname="col5">3.12</oasis:entry>  
         <oasis:entry colname="col6">4.02</oasis:entry>  
         <oasis:entry colname="col7">2.97</oasis:entry>  
         <oasis:entry colname="col8">4.13</oasis:entry>  
         <oasis:entry colname="col9">3.23</oasis:entry>  
         <oasis:entry colname="col10">1.10</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SC2</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M109" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mrow class="chem"><mml:mi mathvariant="normal">COS</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M110" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M111" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.47</oasis:entry>  
         <oasis:entry colname="col3">1.18</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M112" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>3.12</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M113" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.38</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M114" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.75</oasis:entry>  
         <oasis:entry colname="col7">NA<inline-formula><mml:math id="M115" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M116" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.15</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M117" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.80</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M118" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.79</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M120" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M121" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.76</oasis:entry>  
         <oasis:entry colname="col3">0.43</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M122" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.01</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M123" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.69</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M124" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.44</oasis:entry>  
         <oasis:entry colname="col7">NA</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M125" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.64</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M126" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.94</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M127" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.72</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M128" display="inline"><mml:mrow><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M129" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">3.84</oasis:entry>  
         <oasis:entry colname="col3">1.92</oasis:entry>  
         <oasis:entry colname="col4">2.42</oasis:entry>  
         <oasis:entry colname="col5">3.58</oasis:entry>  
         <oasis:entry colname="col6">5.23</oasis:entry>  
         <oasis:entry colname="col7">NA</oasis:entry>  
         <oasis:entry colname="col8">3.73</oasis:entry>  
         <oasis:entry colname="col9">5.12</oasis:entry>  
         <oasis:entry colname="col10">1.94</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e1589">
<inline-formula><mml:math id="M86" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula> “NA” means “not available”.</p></table-wrap-foot></table-wrap>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><caption><p id="d1e2372">Monthly-mean diurnal trends of soil chamber fluxes of
COS <bold>(a–d)</bold>, CO <bold>(e–h)</bold>, and <inline-formula><mml:math id="M130" display="inline"><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:math></inline-formula> <bold>(i–l)</bold>, and
temperature in the humus layer and in the A horizon <bold>(m–p)</bold>, averaged
in 1 h bins. The <inline-formula><mml:math id="M131" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axes are local time during winter (UTC <inline-formula><mml:math id="M132" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 2). Red and
blue curves are mean diurnal trends of SC1 and SC2,
respectively <bold>(a–l)</bold>. Brown and orange represent temperature in the
humus layer and in the A horizon, respectively <?xmltex \hack{\mbox\bgroup}?><bold>(m–p)</bold><?xmltex \hack{\egroup}?>. All shaded
areas indicate <inline-formula><mml:math id="M133" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1 SD. Note that for soil temperature the
<inline-formula><mml:math id="M134" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axis ranges change by month. The July 2015 subset includes 2 days of
data from June, and the October 2015 subset includes 2 days from November.</p></caption>
          <?xmltex \igopts{width=483.69685pt}?><graphic xlink:href="https://acp.copernicus.org/articles/18/1363/2018/acp-18-1363-2018-f02.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><?pagebreak page1370?><fig id="Ch1.F3" specific-use="star"><caption><p id="d1e2445">Monthly-mean diurnal trends of apparent deposition velocities of COS
and CO (<inline-formula><mml:math id="M135" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub><mml:mo>/</mml:mo><mml:mo>[</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">COS</mml:mi></mml:mrow><mml:msub><mml:mo>]</mml:mo><mml:mrow><mml:mn mathvariant="normal">0.5</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">m</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and
<inline-formula><mml:math id="M136" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:msub><mml:mi>F</mml:mi><mml:mtext>CO</mml:mtext></mml:msub><mml:mo>/</mml:mo><mml:mo>[</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:msub><mml:mo>]</mml:mo><mml:mrow><mml:mn mathvariant="normal">0.5</mml:mn><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">m</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>) in the two chambers, averaged
in 1 h bins. Different monthly periods are color-coded.</p></caption>
          <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://acp.copernicus.org/articles/18/1363/2018/acp-18-1363-2018-f03.pdf"/>

        </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><caption><p id="d1e2515">Pearson correlations between fluxes and environmental variables for
the two soil chambers. <inline-formula><mml:math id="M137" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mtext>soil,O</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M138" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mtext>soil,A</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> are soil
temperatures in the humus layer and in the A horizon, respectively.
Similarly, <inline-formula><mml:math id="M139" display="inline"><mml:mrow><mml:msub><mml:mi>w</mml:mi><mml:mtext>soil,O</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M140" display="inline"><mml:mrow><mml:msub><mml:mi>w</mml:mi><mml:mtext>soil,A</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> are soil moisture
(<inline-formula><mml:math id="M141" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) in the humus layer and in the A horizon.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="8">
     <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:colspec colnum="8" colname="col8" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">COS</oasis:entry>  
         <oasis:entry colname="col3">CO</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M143" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mtext>soil,O</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mtext>soil,A</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M145" display="inline"><mml:mrow><mml:msub><mml:mi>w</mml:mi><mml:mtext>soil,O</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M146" display="inline"><mml:mrow><mml:msub><mml:mi>w</mml:mi><mml:mtext>soil,A</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M147" display="inline"><mml:mrow><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">(<inline-formula><mml:math id="M148" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">mol</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col3">(<inline-formula><mml:math id="M149" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">mol</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col4">(<inline-formula><mml:math id="M150" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C)</oasis:entry>  
         <oasis:entry colname="col5">(<inline-formula><mml:math id="M151" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C)</oasis:entry>  
         <oasis:entry colname="col6">(<inline-formula><mml:math id="M152" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col7">(<inline-formula><mml:math id="M153" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col8">(<inline-formula><mml:math id="M154" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">SC1</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M155" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M156" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">0.022</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M157" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.096<inline-formula><mml:math id="M158" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">0.327</oasis:entry>  
         <oasis:entry colname="col5">0.307</oasis:entry>  
         <oasis:entry colname="col6">0.308</oasis:entry>  
         <oasis:entry colname="col7">0.293</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M159" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.212</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M160" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>CO</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M161" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">0.592<inline-formula><mml:math id="M162" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M163" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.590</oasis:entry>  
         <oasis:entry colname="col4">0.254</oasis:entry>  
         <oasis:entry colname="col5">0.180</oasis:entry>  
         <oasis:entry colname="col6">0.560</oasis:entry>  
         <oasis:entry colname="col7">0.555</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M164" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.205</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M165" display="inline"><mml:mrow><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M166" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M167" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.204<inline-formula><mml:math id="M168" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.249<inline-formula><mml:math id="M169" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">0.462</oasis:entry>  
         <oasis:entry colname="col5">0.524</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M170" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.007</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M171" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.033</oasis:entry>  
         <oasis:entry colname="col8">1</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SC2</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M172" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M173" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">0.019</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M174" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.060<inline-formula><mml:math id="M175" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">0.163</oasis:entry>  
         <oasis:entry colname="col5">0.161</oasis:entry>  
         <oasis:entry colname="col6">0.184</oasis:entry>  
         <oasis:entry colname="col7">0.178</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M176" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.491</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M177" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>CO</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2">0.531<inline-formula><mml:math id="M179" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M180" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.317</oasis:entry>  
         <oasis:entry colname="col4">0.075</oasis:entry>  
         <oasis:entry colname="col5">0.041</oasis:entry>  
         <oasis:entry colname="col6">0.231</oasis:entry>  
         <oasis:entry colname="col7">0.226</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M181" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.474</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M182" display="inline"><mml:mrow><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M183" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M184" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.223<inline-formula><mml:math id="M185" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.373<inline-formula><mml:math id="M186" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">0.388</oasis:entry>  
         <oasis:entry colname="col5">0.399</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M187" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.041</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M188" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.038</oasis:entry>  
         <oasis:entry colname="col8">1</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e2582">
<inline-formula><mml:math id="M142" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula>For pairs for which we do not expect an underlying mechanistic
reason for their correlations, for example, CO flux and COS concentration.</p></table-wrap-foot></table-wrap>

</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results</title>
<sec id="Ch1.S3.SS1">
  <title>COS flux</title>
      <?pagebreak page1368?><p id="d1e3444">Soils in both chambers behaved as COS sinks, with average fluxes of
<inline-formula><mml:math id="M189" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.8 (<inline-formula><mml:math id="M190" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1.0) and <inline-formula><mml:math id="M191" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.5 (<inline-formula><mml:math id="M192" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1.2) <inline-formula><mml:math id="M193" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for
SC1 and SC2, respectively (Fig. <xref ref-type="fig" rid="Ch1.F1"/>a; Table <xref ref-type="table" rid="Ch1.T1"/>). The two
chambers exhibited broadly similar patterns of COS fluxes (Figs. <xref ref-type="fig" rid="Ch1.F1"/>a
and <xref ref-type="fig" rid="Ch1.F2"/>a–d). COS emissions were rare, accounting for only 0.1 %
cases of SC1 and 1.5 % cases of SC2. Most emission cases
were not statistically different from zero, and the few large emissions
appeared to be transient and isolated cases unrelated to temperature or
moisture change. Overall, soil COS fluxes at this site were comparable to
reported values in similar ecosystems, for example,
<inline-formula><mml:math id="M194" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.5 <inline-formula><mml:math id="M195" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> from a Swedish boreal forest soil in
<xref ref-type="bibr" rid="bib1.bibx61" id="text.57"/>.</p>
      <p id="d1e3547">There was a weak increasing trend in soil COS uptake (or decreasing net COS
flux) throughout the campaign (Table <xref ref-type="table" rid="Ch1.T1"/>). This increasing trend was
not significant during the peak growing months (July and August) but became
stronger towards the end of the growing season (September and October). This
trend in COS uptake appeared to coincide with the decreasing trends in soil
temperature and moisture (Fig. <xref ref-type="fig" rid="Ch1.F1"/>d and e).</p>
      <p id="d1e3554">No significant diurnal trend was observed in COS fluxes
(Fig. <xref ref-type="fig" rid="Ch1.F2"/>a–d), although surface (0.5 <inline-formula><mml:math id="M196" display="inline"><mml:mi mathvariant="normal">m</mml:mi></mml:math></inline-formula>) COS concentration
often changed from around 300 <inline-formula><mml:math id="M197" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">mol</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> at night to
400 <inline-formula><mml:math id="M198" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">mol</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> at midday. Surprisingly, we found no correlation
between COS fluxes and ambient COS concentrations (<inline-formula><mml:math id="M199" display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M200" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.005; Fig. S2
in the Supplement), indicating that COS uptake was not concentration-limited
at the daily timescale. The deposition velocity of COS (uptake normalized by
concentration) showed a weak diurnal variability (Fig. <xref ref-type="fig" rid="Ch1.F3"/>a and b);
however, this seemed to be an apparent effect of the lower ambient COS
concentration at night <xref ref-type="bibr" rid="bib1.bibx35" id="paren.58"/>.</p>

      <?xmltex \floatpos{t}?><?pagebreak page1371?><fig id="Ch1.F4"><caption><p id="d1e3622">Smoothed patterns of soil COS <bold>(a)</bold>, CO <bold>(b)</bold>, and
<inline-formula><mml:math id="M201" display="inline"><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:math></inline-formula> <bold>(c)</bold> fluxes as functions of soil humus layer temperature
and moisture, constructed using 2-D local regression. Darker colors indicate
stronger COS or CO uptake, or stronger <inline-formula><mml:math id="M202" display="inline"><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:math></inline-formula> emission.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://acp.copernicus.org/articles/18/1363/2018/acp-18-1363-2018-f04.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><?pagebreak page1372?><fig id="Ch1.F5" specific-use="star"><caption><p id="d1e3665">Relationships between COS and <inline-formula><mml:math id="M203" display="inline"><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:math></inline-formula> fluxes <bold>(a)</bold> and
between CO and <inline-formula><mml:math id="M204" display="inline"><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:math></inline-formula> fluxes <bold>(b)</bold>. The slopes are modulated
by soil humus layer temperatures (colored).</p></caption>
          <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://acp.copernicus.org/articles/18/1363/2018/acp-18-1363-2018-f05.pdf"/>

        </fig>

      <p id="d1e3702">Smoothed 2-D patterns of soil COS uptake as a function of soil temperature
and moisture were constructed with the LOESS method (Sect. <xref ref-type="sec" rid="Ch1.S2.SS5"/>). Soil
moisture rather than temperature was the dominant physical driver of soil COS
uptake, with uptake rates decreasing with increasing moisture
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>a). There was only a weak tendency of increasing COS uptake
with decreasing temperature. Soil COS uptake was positively correlated with
soil respiration (Fig. <xref ref-type="fig" rid="Ch1.F5"/>), consistent with previous observations
<xref ref-type="bibr" rid="bib1.bibx80 bib1.bibx4 bib1.bibx66" id="paren.59"/>. However, the relationship between soil
COS uptake and respiration seemed to divide into different branches delimited
by soil temperature bins (Fig. <xref ref-type="fig" rid="Ch1.F5"/>).</p>
</sec>
<sec id="Ch1.S3.SS2">
  <title>CO flux</title>
      <p id="d1e3722">CO was also taken up by soils in both chambers, with average fluxes of
<inline-formula><mml:math id="M205" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.00 (<inline-formula><mml:math id="M206" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.43) and <inline-formula><mml:math id="M207" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.76 (<inline-formula><mml:math id="M208" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.43) <inline-formula><mml:math id="M209" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in
SC1 and SC2, respectively (Table <xref ref-type="table" rid="Ch1.T1"/>). Although the two chambers were
placed in similar conditions, SC1 always had slightly stronger uptake than
SC2, indicating small-scale heterogeneity. Both chambers had only a few and
very weak CO emission cases (0.1 % of SC1 and 0.5 % of SC2).</p>
      <p id="d1e3782">In contrast to soil COS flux, there was clear diurnal variability in CO flux,
consistent across all months (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). CO uptake was significantly
lower during the daytime than at night, with up to
0.5 <inline-formula><mml:math id="M210" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> difference (30–50 % of nighttime CO
uptake). We found weak correlations between soil CO flux and ambient CO
concentration (<inline-formula><mml:math id="M211" display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M212" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M213" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.590 and <inline-formula><mml:math id="M214" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.317 for SC1 and SC2, respectively,
Table <xref ref-type="table" rid="Ch1.T2"/>; Fig. S2). However, the relative diurnal amplitudes of CO
concentration were too small (less than 10 % in monthly-mean diurnal
trends; not shown) to explain the diurnal variability in CO uptake.
Significant diurnal variability was also present in CO deposition velocity
(Fig. <xref ref-type="fig" rid="Ch1.F3"/>c and d), with the midday values about 40 % smaller than
those around midnight. The diurnal variability in CO uptake was also
unrelated to soil temperature, since it was out of phase with soil
temperature variations (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). Instead, CO uptake was weakly
correlated with the below-canopy radiation (rank correlation <inline-formula><mml:math id="M215" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.51 and
0.35 for SC1 and SC2, respectively; Fig. S6 in the Supplement), which varied
diurnally, suggesting that the midday reduction in CO uptake might be
partially due to photochemical CO production at the soil surface.</p>
      <p id="d1e3855">During the campaign period, the month with the highest soil CO uptake
was September (Table <xref ref-type="table" rid="Ch1.T1"/>; Fig. <xref ref-type="fig" rid="Ch1.F2"/>). The increase
of CO uptake in September appeared to result from the decrease of soil
moisture rather than changes in soil temperature (Fig. <xref ref-type="fig" rid="Ch1.F4"/>). CO uptake
was also weakly correlated with <inline-formula><mml:math id="M216" display="inline"><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:math></inline-formula> flux (Fig. <xref ref-type="fig" rid="Ch1.F5"/>;
Table <xref ref-type="table" rid="Ch1.T2"/>), branching into different clusters depending on temperature
bins. This pattern resembled the relationship between COS and <inline-formula><mml:math id="M217" display="inline"><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:math></inline-formula>
fluxes (Fig. <xref ref-type="fig" rid="Ch1.F5"/>).</p>
</sec>
<sec id="Ch1.S3.SS3">
  <?xmltex \opttitle{{$\chem{CO_{2}}$} flux}?><title><inline-formula><mml:math id="M218" display="inline"><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:math></inline-formula> flux</title>
      <p id="d1e3910">The average <inline-formula><mml:math id="M219" display="inline"><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:math></inline-formula> fluxes during the campaign period were
3.2 (<inline-formula><mml:math id="M220" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1.3) and 3.8 (<inline-formula><mml:math id="M221" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1.9) <inline-formula><mml:math id="M222" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for SC1
and SC2, respectively. Soil respiration showed strong seasonal variations
that correlated with soil temperature changes (Table <xref ref-type="table" rid="Ch1.T2"/> and
Fig. <xref ref-type="fig" rid="Ch1.F4"/>; Figs. S3 and S4 in the Supplement). Monthly mean soil
respiration in SC1 increased from 3.0 <inline-formula><mml:math id="M223" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in
July to 4.1 <inline-formula><mml:math id="M224" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in August, the warmest month. As
soil temperature began to decrease in September, soil respiration dropped to
3.2 <inline-formula><mml:math id="M225" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in SC1 but increased in SC2, indicating
possible small-scale differences between the two chamber locations. There was
no well-defined relationship between soil moisture and respiration
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>).</p>
      <p id="d1e4057">We did not see strong temperature-driven diurnal trends in soil respiration
(Fig. <xref ref-type="fig" rid="Ch1.F2"/>), mainly because daily temperature variations were small
(2–3 <inline-formula><mml:math id="M226" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> diurnal amplitude in the humus layer). Temperature
dependence of soil respiration at the daily timescale was generally weak
since most of the days had low correlations between <inline-formula><mml:math id="M227" display="inline"><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:math></inline-formula> flux and
temperature (see Fig. S8 in the Supplement for a histogram of the
corresponding daily <inline-formula><mml:math id="M228" display="inline"><mml:mrow><mml:msup><mml:mi>r</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> values), despite the overall higher correlation
between soil respiration and temperature over the campaign period
(Table <xref ref-type="table" rid="Ch1.T2"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>). Interestingly, a small decrease in
respiration at midday was found in the July diurnal trend of <inline-formula><mml:math id="M229" display="inline"><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:math></inline-formula> flux
in SC1 (Fig. <xref ref-type="fig" rid="Ch1.F2"/>i). Daytime <inline-formula><mml:math id="M230" display="inline"><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:math></inline-formula> flux in July was on average
0.44 <inline-formula><mml:math id="M231" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> lower than nighttime <inline-formula><mml:math id="M232" display="inline"><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:math></inline-formula> flux,
and this difference was statistically significant
(<inline-formula><mml:math id="M233" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> <inline-formula><mml:math id="M234" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 1 <inline-formula><mml:math id="M235" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M236" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">8</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in a two-sample <inline-formula><mml:math id="M237" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> test). The slightly
higher nighttime respiration in July might be related to A horizon
temperature that peaked at midnight. Other months did not show such a pattern.</p>
</sec>
</sec>
<sec id="Ch1.S4">
  <title>Discussion</title>
<sec id="Ch1.S4.SS1">
  <title>Physical and biological factors controlling COS and CO fluxes</title>
      <p id="d1e4217">The net soil flux of COS or CO is generally the balance of concurrent sink
and source activities. Here we explore how physical and biological factors
drive the variability in the net fluxes of COS and CO, and infer their
effects on the gross uptake (i.e., actual microbial uptake without accounting
for the concurrent production) of COS and CO.</p>
      <p id="d1e4220">Soil moisture is the key determinant of the net soil COS flux
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>a), reflecting the variability of the gross COS uptake, since
COS production is controlled mainly by temperature <xref ref-type="bibr" rid="bib1.bibx77" id="paren.60"/>. Due to
the fact that net uptake dominates soil COS flux, and that soil temperature
does not show a strong variability (Fig. <xref ref-type="fig" rid="Ch1.F2"/>a–d), COS production, if
present at all, is likely a minor and constant component. The moisture
dependence of COS uptake activity typically manifests as a bell-shaped curve
with a moisture optimum <xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx69 bib1.bibx77" id="paren.61"/>. Below
the moisture optimum, microbial uptake of COS is limited by water
availability, whereas above it, COS uptake is limited by the diffusional
supply of COS from the atmosphere because soil gas diffusivity decreases with
moisture content <xref ref-type="bibr" rid="bib1.bibx65 bib1.bibx47" id="paren.62"/>. In this study, the decrease of COS
uptake with increasing soil moisture (Fig. <xref ref-type="fig" rid="Ch1.F4"/>a) is characteristic of
the diffusion-limited regime in COS uptake. The diffusion-limited regime
indicates that the moisture optimum for COS uptake was likely below the
observed soil moisture range and that most COS uptake happened beneath the
surface humus layer.</p>
      <p id="d1e4239">There is only a weak tendency of decreasing net COS uptake with increasing
temperature (Fig. <xref ref-type="fig" rid="Ch1.F4"/>a). The lack of strong temperature dependence is
not surprising given that 90 % of the data were measured in the narrow
temperature range of 8.3–16.4 <inline-formula><mml:math id="M238" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> (humus layer).
A temperature optimum for COS uptake cannot be identified within the observed
temperature range but likely exists below this range since COS uptake here
tends to increase slightly with decreasing temperature (Fig. <xref ref-type="fig" rid="Ch1.F4"/>a).
The low temperature optimum would differ from previous laboratory studies
that report temperature optimum values of around 20<inline-formula><mml:math id="M239" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>
<xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx69" id="paren.63"/>, suggesting a need to constrain this
parameter under field conditions.</p>
      <p id="d1e4270">Soil CO flux variability is also dominated by moisture dependence and did not
show any significant temperature dependence (Fig. <xref ref-type="fig" rid="Ch1.F4"/>b). Previous
studies show that the moisture dependence of CO uptake also follows
a bell-shaped curve with a moisture optimum, which qualitatively resembles
that of soil COS uptake <xref ref-type="bibr" rid="bib1.bibx45 bib1.bibx30" id="paren.64"/>. Because CO uptake in the
soil is subject to the same reactive transport mechanism as in COS uptake,
the decrease of CO uptake with increasing soil moisture indicates that CO
uptake is also diffusion-limited and the majority of uptake activity should
happen below the surface humus layer. The absence of temperature-driven
variability in net CO uptake suggests the lack of significant abiotic thermal
production of CO, yet other production activity may still exist.</p>
      <p id="d1e4279">A unique feature of soil CO flux is the diurnal cycle showing reduced daytime
net uptake (Fig. <xref ref-type="fig" rid="Ch1.F2"/>e–h), contrasting with soil COS flux that shows
no significant diurnal variability. The correlation between CO uptake and
below-canopy radiation (Sect. <xref ref-type="sec" rid="Ch1.S3.SS2"/>; Fig. S2) implies that there might
be photochemical production at the surface humus layer during the campaign.
Although opaque chambers were used to prevent photochemical production of CO
during measurements (Sect. <xref ref-type="sec" rid="Ch1.S2.SS2"/>), when the chamber was open and not
being measured, the soil surface was exposed in the sun and photochemical
production might have happened. CO production at the surface, if present, may alter
the vertical CO profile and consequently affects surface flux measurements,
because gas transport in the soil column is a slow process. Strong diurnal
variability in soil CO flux due to photochemical production has previously
been reported in a boreal forest <xref ref-type="bibr" rid="bib1.bibx83" id="paren.65"/>, a temperate mixed-wood plain
<xref ref-type="bibr" rid="bib1.bibx16" id="paren.66"/>, and a reed canary grass cropland <xref ref-type="bibr" rid="bib1.bibx49" id="paren.67"/>.
Hence, photochemical production is a possible daytime source of CO that can
be responsible for the diurnal cycle of net CO flux. Future studies on soil
CO flux will need to operate the chamber in constant darkness to confirm or
falsify the existence of photochemical CO production.</p>

      <?xmltex \floatpos{t}?><?pagebreak page1373?><fig id="Ch1.F6"><caption><p id="d1e4300">Ratios of COS vs. <inline-formula><mml:math id="M240" display="inline"><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:math></inline-formula> and CO vs. <inline-formula><mml:math id="M241" display="inline"><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:math></inline-formula> fluxes
determined from zero-intercept linear regressions across soil temperature
bins. Error bars are showing <inline-formula><mml:math id="M242" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>2 standard errors (or 95.5 % confidence
interval). Flux ratios are generally smaller in SC2 because of higher
<inline-formula><mml:math id="M243" display="inline"><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:math></inline-formula> fluxes.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://acp.copernicus.org/articles/18/1363/2018/acp-18-1363-2018-f06.pdf"/>

        </fig>

      <p id="d1e4349">Both COS and CO fluxes appear to correlate well with soil respiration when
divided into specific temperature bins (Fig. <xref ref-type="fig" rid="Ch1.F5"/>). To characterize the
sensitivities of COS and CO fluxes to respiration, mean flux ratios
(<inline-formula><mml:math id="M244" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M245" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>CO</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula>) are
calculated in each temperature bin, approximated by the slope of the
zero-intercept linear regression (Fig. <xref ref-type="fig" rid="Ch1.F6"/>). The sensitivity of COS or
CO uptake to respiration is stronger at lower temperature, as indicated by
the more negative <inline-formula><mml:math id="M246" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> or
<inline-formula><mml:math id="M247" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>CO</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> ratio (Fig. <xref ref-type="fig" rid="Ch1.F6"/>). The temperature
dependence of the <inline-formula><mml:math id="M248" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> ratio shows an asymptotic
feature at higher temperature, which corresponds well with the temperature
dependence of the concentration-normalized COS-to-<inline-formula><mml:math id="M249" display="inline"><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:math></inline-formula> flux ratio
(also known as soil relative uptake, SRU) reported from temperate forest
soils <xref ref-type="bibr" rid="bib1.bibx4" id="paren.68"/>. Note that the normalization by ambient
concentrations usually shrinks SRU by a factor of 1 to 1.15 with respect to
the flux ratio but does not change its temperature dependence feature. The
range of SRU values (<inline-formula><mml:math id="M250" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.8 to <inline-formula><mml:math id="M251" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.5) in <xref ref-type="bibr" rid="bib1.bibx4" id="text.69"/> is therefore
comparable to the range of <inline-formula><mml:math id="M252" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> ratio in SC2 but
significantly smaller than that in SC1 (Fig. <xref ref-type="fig" rid="Ch1.F6"/>). The qualitative
similarity in the temperature dependence of the
<inline-formula><mml:math id="M253" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> ratio from different sites suggests that
this relationship can be a generalizable feature for soils. Interestingly,
the transition from linear increase to constant ratio occurs around
10 <inline-formula><mml:math id="M254" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> at our site (Fig. <xref ref-type="fig" rid="Ch1.F6"/>), compared to
30 <inline-formula><mml:math id="M255" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> in the temperate sites <xref ref-type="bibr" rid="bib1.bibx4" id="paren.70"/>,
indicating a soil- or site-specific feature. In addition, the newly discovered
relationship between the <inline-formula><mml:math id="M256" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>CO</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> ratio and
temperature can be used to simulate soil CO uptake empirically.</p>
      <p id="d1e4599">There remains the question of why the relationship between COS or CO uptake and
respiration divides into different branches defined by soil temperature
(Fig. <xref ref-type="fig" rid="Ch1.F5"/>), despite the observation that COS or CO uptake does not
show strong temperature dependence (Fig. <xref ref-type="fig" rid="Ch1.F4"/>). Since microbial
activity underpins COS or CO uptake, each branch in the uptake–respiration
pattern may represent the behavior of a distinct microbial group. The
temperature dependence of flux ratios hence may indicate shifts in active
COS- and CO-consuming microbial groups caused by temperature. For example,
microbial groups that have optimal uptake at a lower temperature may have
a stronger sensitivity of COS (or CO) uptake to respiration than groups
active at higher temperature. The asymptote values of
<inline-formula><mml:math id="M257" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>COS</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M258" display="inline"><mml:mrow><mml:msub><mml:mi>F</mml:mi><mml:mtext>CO</mml:mtext></mml:msub><mml:mo>:</mml:mo><mml:msub><mml:mi>F</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:mrow></mml:math></inline-formula>
(Fig. <xref ref-type="fig" rid="Ch1.F6"/>) hence would reflect the uptake to respiration sensitivity
behavior of microbial groups active at higher temperature. Collectively, the
sum of COS uptake (or CO uptake) contributions from the ensemble of microbial
groups may not show a well-defined temperature response like that in
respiration. Although we cannot rule out the possibility that the flux ratio
vs. temperature pattern is influenced by divergent temperature responses of
microbial uptake and abiotic production
<xref ref-type="bibr" rid="bib1.bibx77 bib1.bibx30 bib1.bibx68" id="paren.71"><named-content content-type="pre">e.g.,</named-content></xref>, abiotic production is unlikely
to correlate with respiration. A mechanistic explanation for the temperature
dependence of flux ratios requires a clear-cut separation of uptake and
production processes and further understanding of the microbial communities
involved in COS uptake or CO uptake.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <title>Variations of soil fluxes over the late growing season</title>
      <p id="d1e4664">Neither COS flux nor CO flux exhibits strong seasonality, mainly because soil
temperature variation was not strong and soil moisture was not low enough to
severely limit microbial activity. For example, <xref ref-type="bibr" rid="bib1.bibx77" id="text.72"/> have shown
that COS uptake is inhibited when soil moisture is below around
0.10 <inline-formula><mml:math id="M259" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in incubation experiments, yet in this campaign
soil moisture was above this threshold most of the time. From August to
October, monthly mean net soil uptake of COS increased slightly from 2.7 to
3.8 <inline-formula><mml:math id="M260" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, and that of CO increased from 1.0 to
1.2 <inline-formula><mml:math id="M261" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, despite a significant drop in humus layer
temperature from 13.5 to 5.5 <inline-formula><mml:math id="M262" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>. As discussed previously, the
increase was due to increased gas diffusivity caused by declining soil
moisture. Soil microbial activities for COS and CO uptake at this site
appeared tolerant of low temperature at the end of the growing season
(October/November). Given the lack of temperature-related seasonality in COS
or CO uptake, it is possible that a shift in active microbial groups might
have acted to stabilize the overall uptake against changes in soil physical
variables.</p>
      <p id="d1e4754">Soil respiration in SC1 increased significantly from July to August (3.0 to
4.1 <inline-formula><mml:math id="M263" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>), concurrent with a slight increase in
the mean soil temperature (12.8 to 13.5 <inline-formula><mml:math id="M264" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>). As shown in
<xref ref-type="bibr" rid="bib1.bibx54" id="text.73"/>, soil respiration at the site is controlled not only by
temperature but also by gas diffusivity and photosynthate input from the
vegetation. Since soil moisture dropped greatly after July (Fig. <xref ref-type="fig" rid="Ch1.F1"/>),
the increase in respiration was more likely driven by the aeration of soil
than by just a slight increase in soil temperature. In early October, soil
respiration was suppressed by the abrupt decrease in soil temperature and
gradually dropped to below 1 <inline-formula><mml:math id="M265" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>
(Fig. <xref ref-type="fig" rid="Ch1.F1"/>). In addition, the declining ecosystem photosynthetic
activity after August <xref ref-type="bibr" rid="bib1.bibx71" id="paren.74"/> would reduce photosynthate input to
the soil and therefore might also contribute to the decrease in respiration.
However, since the soil plots in both chambers were cleared of understory
vegetation before the campaign, autotrophic respiration would rely on
photosynthate supply from trees at a distance and should therefore make up
a much smaller fraction in the total soil respiration than at a vegetated
soil plot. The smaller contribution of autotrophic respiration is also
supported by the lower August soil respiration of around
4 <inline-formula><mml:math id="M266" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in our campaign compared with the August
soil respiration of around 6 <inline-formula><mml:math id="M267" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">mol</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in
<xref ref-type="bibr" rid="bib1.bibx55" id="text.75"/> from a vegetated area at the same site. Overall, the
seasonal pattern of <inline-formula><mml:math id="M268" display="inline"><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:math></inline-formula> flux is mainly driven by soil temperature and
moisture, and to a lesser extent by photosynthate input.</p>
</sec>
<sec id="Ch1.S4.SS3">
  <title>Implications of using COS as a photosynthetic tracer</title>
      <p id="d1e4912">The soil at this boreal forest site (podzol) was consistently a weak sink of
COS during the late growing season. Soil uptake of COS was around
10–20 % of the daytime mean ecosystem uptake of
20.8 <inline-formula><mml:math id="M269" display="inline"><mml:mrow><mml:mi mathvariant="normal">pmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx35" id="paren.76"><named-content content-type="post">with daytime defined as the period
with solar elevation angle <inline-formula><mml:math id="M270" display="inline"><mml:mo>&gt;</mml:mo></mml:math></inline-formula> 20<inline-formula><mml:math id="M271" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> therein</named-content></xref>. Soil COS
uptake did not show strong diurnal and seasonal variations, nor did it show
any abrupt increase induced by rain events
<xref ref-type="bibr" rid="bib1.bibx66 bib1.bibx75" id="paren.77"><named-content content-type="pre">cf.</named-content></xref>. Moreover, soil COS uptake
variability was well explained by changes in soil moisture and respiration,
and it would be possible to construct an empirical model for soil COS flux
based on its relationship with soil moisture, temperature, and <inline-formula><mml:math id="M272" display="inline"><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:math></inline-formula>
flux (Figs. <xref ref-type="fig" rid="Ch1.F4"/> and <xref ref-type="fig" rid="Ch1.F5"/>). Hence, we expect that soil COS uptake
can be reliably accounted for when using COS as a photosynthetic tracer at
this site.</p>
      <?pagebreak page1374?><p id="d1e4983">Since soil COS uptake did not show a well-defined response to soil
temperature or moisture but correlates well with respiration when divided
into specific temperature bins (Figs. <xref ref-type="fig" rid="Ch1.F4"/> and <xref ref-type="fig" rid="Ch1.F5"/>), simulating
soil COS uptake in this boreal forest will rely on using soil respiration as
an important statistical predictor. In this case, the parameterization scheme
used in <xref ref-type="bibr" rid="bib1.bibx5" id="text.78"/> and the empirical relationship based on the soil relative
uptake ratio (COS uptake to <inline-formula><mml:math id="M273" display="inline"><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:math></inline-formula> emission ratio normalized by their
concentrations) as in <xref ref-type="bibr" rid="bib1.bibx4" id="text.79"/> will be useful in predicting COS
uptake, provided that diffusion in the soil column is properly resolved
<xref ref-type="bibr" rid="bib1.bibx65 bib1.bibx47" id="paren.80"><named-content content-type="pre">e.g.,</named-content></xref>.</p>
</sec>
<sec id="Ch1.S4.SS4">
  <title>Implications on soil–atmosphere CO exchange</title>
      <p id="d1e5019">The global soil CO budget remains uncertain due to limited field observations
and the lack of modeling studies. Our results from a boreal forest site help
bridge the gap in the understanding of soil CO exchange in this important
biome. CO uptake by soil is usually characterized by the deposition velocity
of CO, because ambient CO concentration varies spatially. At this site, CO
deposition velocity lies in the range of 0.1–0.35 <inline-formula><mml:math id="M274" display="inline"><mml:mrow><mml:mi mathvariant="normal">mm</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>
(Fig. <xref ref-type="fig" rid="Ch1.F3"/>), similar to previous studies in boreal forests
<xref ref-type="bibr" rid="bib1.bibx83 bib1.bibx37" id="paren.81"/> and slightly less than those in temperate forests
<xref ref-type="bibr" rid="bib1.bibx58 bib1.bibx81" id="paren.82"/>. CO deposition velocity shows a weak
decreasing trend with increasing soil moisture (Fig. S7 in the Supplement),
which is broadly similar to the negative correlation found in
<xref ref-type="bibr" rid="bib1.bibx81" id="text.83"/>, indicating a prominent diffusional control on CO uptake.</p>
      <p id="d1e5050">Globally, soils contribute to a significant but poorly constrained CO sink.
The current estimate of global soil CO uptake
(<inline-formula><mml:math id="M275" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 300 <inline-formula><mml:math id="M276" display="inline"><mml:mrow><mml:mi mathvariant="normal">Tg</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in <xref ref-type="bibr" rid="bib1.bibx32" id="altparen.84"/>) is equivalent to
a global mean uptake of 2.3 <inline-formula><mml:math id="M277" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, averaged over the
total land area (1.49 <inline-formula><mml:math id="M278" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M279" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">8</mml:mn></mml:msup></mml:math></inline-formula> <inline-formula><mml:math id="M280" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">km</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>). This global mean
value is significantly higher than the mean CO uptake
(<inline-formula><mml:math id="M281" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 1 <inline-formula><mml:math id="M282" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) observed at this boreal forest in
the late growing season. Recent field observations of soil CO uptake in
temperate ecosystems are also smaller than this global mean, for example,
less than 1 <inline-formula><mml:math id="M283" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in a grassland in Italy
<xref ref-type="bibr" rid="bib1.bibx68" id="paren.85"/> and 0.78 <inline-formula><mml:math id="M284" display="inline"><mml:mrow><mml:mi mathvariant="normal">nmol</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">s</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> in a grassland in
Denmark <xref ref-type="bibr" rid="bib1.bibx8" id="paren.86"/>. If we assume the soil from this site is
representative of boreal forest soils, it follows that temperate and tropical
soils must have higher CO uptake capacity to compensate for the relatively
low soil CO uptake in the boreal forest compared with the global mean, or the
current estimate of global soil CO uptake needs to be revisited.
<?xmltex \hack{\newpage}?></p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <title>Conclusions</title>
      <p id="d1e5235">The boreal forest soil studied here behaves consistently as a sink of COS and
CO during the late growing season. Soil COS and CO uptake appear to be
largely insensitive to temperature, at least within the narrow temperature
(3–16 <inline-formula><mml:math id="M285" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>) and moisture range
(0.10–0.38 <inline-formula><mml:math id="M286" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) at this site. In contrast to laboratory
experiments, controls on fluxes can be difficult to identify in field
conditions due to concurrent changes in temperature, moisture, and microbial
community. We find that soil moisture is the dominant physical driver for
soil COS and CO uptake, and the uptake rate generally decreases with soil
moisture, suggesting that microbial uptake is limited by the diffusional
supply of COS and CO into the soil column. The relationship between COS
uptake and respiration and that between CO uptake and respiration are
regulated by soil temperature, leading to the temperature dependence of
<inline-formula><mml:math id="M287" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="normal">COS</mml:mi></mml:mrow><mml:mo>:</mml:mo><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:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M288" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mo>:</mml:mo><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:mrow></mml:math></inline-formula> flux ratios. In future
studies, measuring soil vertical profiles of COS and CO will help resolve the
interplay between physical transport and biological uptake. Furthermore,
studies on microbial dynamics are needed to shed light on the mechanisms
relating COS and CO uptake with respiration.</p>
      <p id="d1e5304">Compared with total ecosystem uptake of COS, soil COS uptake is a small
fraction (10–20 %). Soil COS uptake does not show significant diurnal or
long-term variability in the peak growing season (July and August) and thus
will not be a dominant source of uncertainty when inferring photosynthesis
from COS measurements.</p>
      <p id="d1e5307">Soil CO uptake shows a reduced midday uptake rate and deposition velocity,
possibly related to the photochemical production of CO at the surface organic
layer. A comparison of soil CO uptake in this boreal forest with the
estimated global mean shows that boreal forest soils have relatively low CO
uptake activity. Similar studies on soil CO fluxes are needed in other biomes
to better constrain the magnitude and distribution of global
biosphere–atmosphere CO exchange.</p>
</sec>

      
      </body>
    <back><notes notes-type="dataavailability">

      <p id="d1e5314">Data presented here can be found in the University of
California Curation Center (UC3) Merritt data
repository at <uri>http://n2t.net/ark:/c5146/r39p4r</uri> (Sun et al., 2017) with <ext-link xlink:href="https://doi.org/10.15146/R39P4R" ext-link-type="DOI">10.15146/R39P4R</ext-link> or in Zenodo with
<ext-link xlink:href="https://doi.org/10.5281/zenodo.322936" ext-link-type="DOI">10.5281/zenodo.322936</ext-link>.</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e5326"><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="https://doi.org/10.5194/acp-18-1363-2018-supplement" xlink:title="pdf">https://doi.org/10.5194/acp-18-1363-2018-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><notes notes-type="authorcontribution">

      <p id="d1e5332">US, KM, HC, and TV designed the research. LMJK, KM, IM, JL, and HK conducted field experiments. WS and
LMJK performed data analysis. WS and US wrote the paper with contributions
from all co-authors.</p>
  </notes><?xmltex \hack{\newpage}?><notes notes-type="competinginterests">

      <?pagebreak page1375?><p id="d1e5339">The authors declare that they have no conflict of interest.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e5345">This study was supported by the European Commission's Seventh Framework
Programme (FP7/2007–2013) in the InGOS project (284274); the Academy of
Finland projects Centre of Excellence (118780), Academy Professor (284701 and
282842), and CARB-ARC (286190); ICOS-Finland (281255); and the NOAA contract
NA13OAR4310082. We acknowledge support at the SMEAR II (Station for Measuring
Forest Ecosystem–Atmosphere Relations) Hyytiälä field station,
Finland. Wu Sun was supported by the University of California Institute for
the Study of Ecological and Evolutionary Climate Impacts (ISEECI) GSR
fellowship.<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> Edited by: Min Shao<?xmltex \hack{\newline}?>
Reviewed by: two anonymous referees</p></ack><ref-list>
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    <!--<article-title-html>Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland</article-title-html>
<abstract-html><p class="p">Soil is a major contributor to the biosphere–atmosphere exchange of carbonyl
sulfide (COS) and carbon monoxide (CO). COS is a tracer with which to quantify
terrestrial photosynthesis based on the coupled leaf uptake of COS and
CO<sub>2</sub>, but such use requires separating soil COS flux, which is
unrelated to photosynthesis, from ecosystem COS uptake. For CO, soil is
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boreal forest, magnitudes and variabilities of soil COS and CO fluxes remain
poorly understood. We measured hourly soil fluxes of COS, CO, and CO<sub>2</sub>
over the 2015 late growing season (July to November) in a Scots pine forest
in Hyytiälä, Finland. The soil acted as a net sink of COS and CO,
with average uptake rates around 3 pmol m<sup>−2</sup> s<sup>−1</sup> for COS and
1 nmol m<sup>−2</sup> s<sup>−1</sup> for CO. Soil respiration showed
seasonal dynamics controlled by soil temperature, peaking at around
4 µmol m<sup>−2</sup> s<sup>−1</sup> in late August and September and dropping
to 1–2 µmol m<sup>−2</sup> s<sup>−1</sup> in October. In contrast, seasonal
variations of COS and CO fluxes were weak and mainly driven by soil moisture
changes through diffusion limitation. COS and CO fluxes did not appear to
respond to temperature variation, although they both correlated well with
soil respiration in specific temperature bins. However,
COS : CO<sub>2</sub> and CO : CO<sub>2</sub> flux ratios increased
with temperature, suggesting possible shifts in active COS- and CO-consuming
microbial groups. Our results show that soil COS and CO fluxes do not have
strong variations over the late growing season in this boreal forest and can
be represented with the fluxes during the photosynthetically most active
period. Well-characterized and relatively invariant soil COS fluxes
strengthen the case for using COS as a photosynthetic tracer in boreal
forests.</p></abstract-html>
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