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  <front>
    <journal-meta><journal-id journal-id-type="publisher">AMT</journal-id><journal-title-group>
    <journal-title>Atmospheric Measurement Techniques</journal-title>
    <abbrev-journal-title abbrev-type="publisher">AMT</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Atmos. Meas. Tech.</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1867-8548</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/amt-11-1833-2018</article-id><title-group><article-title>COCAP: a carbon dioxide analyser for small unmanned<?xmltex \hack{\newline}?> aircraft systems</article-title><alt-title>COCAP: a carbon dioxide analyser for small unmanned aircraft systems</alt-title>
      </title-group><?xmltex \runningauthor{M. Kunz et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Kunz</surname><given-names>Martin</given-names></name>
          <email>mkunz@bgc-jena.mpg.de</email>
        <ext-link>https://orcid.org/0000-0002-6226-4744</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Lavric</surname><given-names>Jost V.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-3610-9078</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Gerbig</surname><given-names>Christoph</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-1112-8603</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Tans</surname><given-names>Pieter</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Neff</surname><given-names>Don</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Hummelgård</surname><given-names>Christine</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Martin</surname><given-names>Hans</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-5019-7153</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Rödjegård</surname><given-names>Henrik</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Wrenger</surname><given-names>Burkhard</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff5">
          <name><surname>Heimann</surname><given-names>Martin</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-6296-5113</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Max Planck Institute for Biogeochemistry, Jena, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>NOAA Earth System Research Laboratory, Global Monitoring Division,
Boulder, Colorado, USA</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>SenseAir AB, Delsbo, Sweden</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>Ostwestfalen-Lippe University of Applied Sciences, Höxter, Germany</institution>
        </aff>
        <aff id="aff5"><label>5</label><institution>Division of Atmospheric Sciences, Department of Physics, University
of Helsinki, Helsinki, Finland</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Martin Kunz (mkunz@bgc-jena.mpg.de)</corresp></author-notes><pub-date><day>29</day><month>March</month><year>2018</year></pub-date>
      
      <volume>11</volume>
      <issue>3</issue>
      <fpage>1833</fpage><lpage>1849</lpage>
      <history>
        <date date-type="received"><day>21</day><month>June</month><year>2017</year></date>
           <date date-type="rev-request"><day>7</day><month>November</month><year>2017</year></date>
           <date date-type="rev-recd"><day>30</day><month>January</month><year>2018</year></date>
           <date date-type="accepted"><day>22</day><month>February</month><year>2018</year></date>
      </history>
      <permissions>
        
        
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018.html">This article is available from https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018.html</self-uri><self-uri xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018.pdf">The full text article is available as a PDF file from https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018.pdf</self-uri>
      <abstract>
    <p id="d1e191">Unmanned aircraft systems (UASs) could provide a cost-effective way to close
gaps in the observation of the carbon cycle, provided that small yet accurate
analysers are available. We have developed a COmpact Carbon dioxide analyser
for Airborne Platforms (COCAP). The accuracy of COCAP's carbon dioxide
(CO<inline-formula><mml:math id="M1" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) measurements is ensured by calibration in an environmental
chamber, regular calibration in the field and by chemical drying of sampled
air. In addition, the package contains a lightweight thermal stabilisation
system that reduces the influence of ambient temperature changes on the
CO<inline-formula><mml:math id="M2" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor by 2 orders of magnitude. During validation of COCAP's
CO<inline-formula><mml:math id="M3" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> measurements in simulated and real flights we found a measurement
error of 1.2 <inline-formula><mml:math id="M4" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M5" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> or better with
no indication of bias. COCAP is a self-contained package that has proven well
suited for the operation on board small UASs. Besides carbon dioxide dry air
mole fraction it also measures air temperature, humidity and pressure. We
describe the measurement system and our calibration strategy in detail to
support others in tapping the potential of UASs for atmospheric trace gas
measurements.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p id="d1e247">Atmospheric measurements of carbon dioxide (CO<inline-formula><mml:math id="M6" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) are essential for our
understanding of the carbon cycle and how it changes in a warming climate.
Such measurements are made on a regular basis by global networks of surface
stations, by specially instrumented aircraft and by research ships
<xref ref-type="bibr" rid="bib1.bibx16" id="paren.1"/>. When local influences are filtered out, the
data from these measurements allow the identification of global trends and
the characterisation of major greenhouse gas sources and sinks, generally on
the scale of continents <xref ref-type="bibr" rid="bib1.bibx9 bib1.bibx5" id="paren.2"/>. This
top-down approach to the quantification of the carbon cycle is well
established.</p>
      <p id="d1e265">In contrast, for observations on smaller scales conventional strategies often
suffer from severe limitations. Specifically, the transition region between
micro- and mesoscale in the sense of <xref ref-type="bibr" rid="bib1.bibx19" id="text.3"/> poses a
challenge. It comprises horizontal extents of 200 m to 20 km and periods
from minutes to hours. Manned research aircraft do not fully cover this
region due to minimum flight altitude requirements and their in most cases
high airspeed. Missed approaches allow the collection of air samples close to
the ground, but this manoeuvre may only be performed at sites where the
aircraft could actually land. Furthermore, because the operation of manned
aircraft is costly, they are typically deployed for short periods of time
only. On the other hand, stationary observations on instrumented masts or
towers can deliver continuous data streams for long periods of time. However,
they are fixed to a single location and take measurements from few vertical
levels up to a maximum altitude limited by the height of the structure.</p>
      <p id="d1e271">Unmanned aircraft systems (UASs), also called remotely piloted aircraft
systems (RPASs), unmanned aerial<?pagebreak page1834?> vehicles (UAVs) or “drones”, have the
potential to fill this observational gap. Their use for research purposes has
increased substantially over the past years. UASs that are capable of fully
autonomous flight are now available for a few thousand euros, which has become
possible by the development of small and cheap electronics for satellite
navigation and inertial measurements as well as a growing consumer market.
Especially smaller UASs with a mass of few kilograms are becoming more and
more attractive for research. They have low system costs and can be operated
by one or two persons. Obtaining operating permission is easier for
lightweight platforms, and custom modifications do not require certification.</p>
      <p id="d1e274">A fundamental limitation of small UASs is their payload capacity, both in
space and mass. One reason why small UASs have been used in the field of
meteorology for many years (e.g.
<xref ref-type="bibr" rid="bib1.bibx8 bib1.bibx25 bib1.bibx22" id="altparen.4"/>) is the
availability of compact and lightweight instrumentation for the measurement
of air temperature, humidity and pressure. Airborne studies of the carbon
cycle, however, require accurate gas sensors, which are hard to miniaturise.
Atmospheric signals on the micro- and mesoscale in CO<inline-formula><mml:math id="M7" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> for example are
typically in the range 1–100 <inline-formula><mml:math id="M8" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M9" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, while the
background CO<inline-formula><mml:math id="M10" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction<fn id="Ch1.Footn1"><p id="d1e318">Throughout this
paper, <inline-formula><mml:math id="M11" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> denotes the CO<inline-formula><mml:math id="M12" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction
at a point, i.e. the result of an in situ measurement.</p></fn> <inline-formula><mml:math id="M13" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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>
is about 400 <inline-formula><mml:math id="M14" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M15" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. If the sensitivity of a CO<inline-formula><mml:math id="M16" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
sensor drifts by only 1 % during flight, e.g. due to the changes in
ambient temperature, the resulting change by 4 <inline-formula><mml:math id="M17" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M18" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>
will obscure small signals.</p>
      <p id="d1e410">Solutions for the measurement of greenhouse gases on board unmanned platforms
have been found, but are not yet widely used, likely for practical or
financial reasons. <xref ref-type="bibr" rid="bib1.bibx3" id="text.5"/> deployed a custom-built
laser-based water vapour, carbon dioxide and methane analyser on the NASA
SIERRA UAS, but the dimensions of 30 cm <inline-formula><mml:math id="M19" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 30 cm <inline-formula><mml:math id="M20" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 28 cm
and the mass of 20 kg prevent the use of this analyser on smaller systems.
<xref ref-type="bibr" rid="bib1.bibx13" id="text.6"/> developed a smaller laser-based analysers for carbon
dioxide or methane dry air mole fraction with a mass of 2 kg and a size of
20 cm <inline-formula><mml:math id="M21" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 5 cm <inline-formula><mml:math id="M22" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 5 cm. The estimated drift in
<inline-formula><mml:math id="M23" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> during 5–10 min flights with a small helicopter was
1 %, which limits the system's suitability for environmental studies.
<xref ref-type="bibr" rid="bib1.bibx27" id="text.7"/> deployed a 3.5 kg measurement package
containing a nondispersive infrared CO<inline-formula><mml:math id="M24" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor on a UAS. They reported a
comparably low bias of 0.21 <inline-formula><mml:math id="M25" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M26" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> during tests with
temperature changes similar to the conditions during flight. However, their
setup requires 1 min of in-flight calibrations every 6 min and comprises
two gas cylinders, a pump and a drying cartridge in addition to a
20 cm <inline-formula><mml:math id="M27" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 14 cm <inline-formula><mml:math id="M28" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 8 cm main module.</p>
      <p id="d1e509">Recently, attempts have been made to equip UASs with commercial, off-the-shelf
CO<inline-formula><mml:math id="M29" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensors designed for indoor air quality measurements. Their
advantages are low cost, compact size and small mass of the measurement
system. <xref ref-type="bibr" rid="bib1.bibx4" id="text.8"/> flew a 500 g payload containing
such a CO<inline-formula><mml:math id="M30" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor on a small multicopter, but due to its high
uncertainty (30 ppm plus 3 % of reading according to manufacturer's
specifications) the resulting data are hard to interpret. Numerous other
groups have improved the accuracy of compact sensors by custom calibrations
<xref ref-type="bibr" rid="bib1.bibx31 bib1.bibx21 bib1.bibx24 bib1.bibx15" id="paren.9"><named-content content-type="pre">e.g.</named-content></xref>.
In some of these studies, measurement uncertainties below
5 <inline-formula><mml:math id="M31" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M32" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> have been achieved
<xref ref-type="bibr" rid="bib1.bibx24 bib1.bibx15" id="paren.10"/>. However, none of
these efforts aimed at the deployment of the sensors on UASs, which requires
immunity to rapid changes in pressure and temperature as well as a high time
resolution.</p>
      <p id="d1e561">Aiming for a measurement package that is compact <italic>and</italic> accurate, we
have developed COCAP, the COmpact Carbon dioxide analyser for Airborne
Platforms. In Sect. <xref ref-type="sec" rid="Ch1.S2"/> we provide a detailed
description of our measurement system, consisting of (1) COCAP, (2) a device
that enables calibrations in the field and (3) an unmanned aircraft that
carries COCAP. Section <xref ref-type="sec" rid="Ch1.S3"/> focuses on our strategy to
ensure accurate measurements through calibration of COCAP's sensors. In
Sect. <xref ref-type="sec" rid="Ch1.S4"/> we present the results from different tests
that we carried out to assess COCAP's performance.</p>
</sec>
<sec id="Ch1.S2">
  <title>The measurement system</title>
<sec id="Ch1.S2.SS1">
  <title>COCAP</title>
      <p id="d1e584">COCAP measures CO<inline-formula><mml:math id="M33" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction, temperature, relative humidity
and pressure of ambient air. Furthermore, flow rate, pressure and temperature
at different locations inside the analyser are recorded. We designed COCAP as
an independent package containing not only sensors but also control and data
logging capabilities as well as a GPS receiver that provides position data
and acts as a time source. The mass of COCAP is 1 kg, excluding battery.</p>

      <fig id="Ch1.F1" specific-use="star"><caption><p id="d1e597">Flow of air, electrical power and data
inside COCAP. FC – mass flow controller; TT – temperature transmitter
(sensor); PT – pressure transmitter; FT – mass flow transmitter. The NDIR
(nondispersive infrared) CO<inline-formula><mml:math id="M34" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor contains additional temperature
sensors which are not included in this schematic view.</p></caption>
          <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f01.png"/>

        </fig>

      <p id="d1e615">A schematic view of COCAP is provided in Fig. <xref ref-type="fig" rid="Ch1.F1"/>.
The different components are described in the following subsections.</p>
<sec id="Ch1.S2.SS1.SSS1">
  <title>Carbon dioxide sensor</title>
      <p id="d1e625">COCAP measures carbon dioxide using a sensor from SenseAir AB based on their
HPP (High Performance Platform) family of gas sensors
<xref ref-type="bibr" rid="bib1.bibx10" id="paren.11"/>. It is a nondispersive infrared sensor
operating at a wavelength of 4.26 <inline-formula><mml:math id="M35" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>m. The optical path has a length
of 128 cm, which is obtained by 16 passes in an 8 cm long White cell
<xref ref-type="bibr" rid="bib1.bibx28" id="paren.12"/>. The total internal volume of the cell is
48 cm<inline-formula><mml:math id="M36" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula>. The mirrors are fabricated using plastic moulding which lowers
the production cost. Heating elements and temperature sensors that enable
temperature stabilisation of the optics are moulded into the mirrors. The
sensor's mass is 80 g, including electronics.</p>
</sec>
<?pagebreak page1835?><sec id="Ch1.S2.SS1.SSS2">
  <title>Other components in the gas sampling line</title>
      <p id="d1e657">Air that is drawn into COCAP's sample line is chemically dried as a first
step. We use magnesium perchlorate (105873, Merck KGaA, Germany) in
cartridges built in-house from aluminium (Fig. S4 in the Supplement). For
improved drying performance we sieve the magnesium perchlorate and use only
particles smaller than 2 mm. A single drying cartridge holds 1.5 g of
magnesium perchlorate, which is sufficient to dry nearly saturated air at a
temperature of 24 <inline-formula><mml:math id="M37" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and a flow rate of 300 mL min<inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> to a
water mole fraction of less than 200 <inline-formula><mml:math id="M39" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M40" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for 1 h.</p>
      <p id="d1e700">Downstream of the drying cartridge a 0.2 <inline-formula><mml:math id="M41" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>m filter (CM-0118,
<uri>CO2Meter.com</uri>, USA) protects the pump, flow regulator and CO<inline-formula><mml:math id="M42" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor
from particles. The air flow through the gas line is driven by a diaphragm
pump (NMS 020 B, KNF Neuberger GmbH, Germany) and throttled to a flow rate of
300 mL min<inline-formula><mml:math id="M43" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> by the mechanical flow controller (PCFCDH-1N1-V, Beswick
Engineering Inc., USA). At this flow rate the pump reaches a differential
pressure of 350 hPa, whereas the flow controller is preset at the factory to
a higher pressure difference of 700 hPa. We lowered the setting of the flow
controller, but tests indicate that in the current configuration the flow
rate is directly proportional to ambient pressure, i.e. the flow controller
behaves like a needle valve. In future designs we recommend to better tune
the flow controller for performance at low pressure differences or to reduce
mass by replacing it with a needle valve.</p>
      <p id="d1e734">The temperature of sample air is measured inside the inlet and the outlet of
the CO<inline-formula><mml:math id="M44" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor with miniature thermistors (NCP15XH103F03RC, Murata Ltd.,
Japan) that are suspended from 0.2 mm diameter wire (Figs. S2 and S3 in the
Supplement). Pressure is measured with a compact piezoresistive pressure
sensor (LPS331AP, STMicroelectronics, Switzerland). This model was chosen for
its small physical size, high resolution and digital interface. As it lacks a
connection port, we glued a 3-D-printed cap with a turned stainless steel
port connector to the PCB so that it forms an airtight enclosure around the
pressure sensor (Fig. S5 in the Supplement). The sample pressure is measured
downstream of the CO<inline-formula><mml:math id="M45" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor close to its outlet. As the flow between
the measurement cell and this point is virtually unrestricted, we assume
equal pressure; i.e. we treat the reading of the pressure sensor as the
pressure of the air inside the CO<inline-formula><mml:math id="M46" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor's measurement cell.</p>
      <p id="d1e764">Finally, the mass flow rate of the sample air is measured with an analogue
sensor (AWM3300V, Honeywell, USA). Downstream of the mass flow sensor the
sample air is released from the gas line into COCAP's housing.</p>
</sec>
<sec id="Ch1.S2.SS1.SSS3">
  <title>Ambient sensors</title>
      <p id="d1e773">The measurement of features in temperature and humidity on the scale of tens
of metres with UASs that can move several metres per second requires fast
measurements with time constants on the order of 1 s. This calls for
unrestricted or even forced ventilation of the sensing elements. To this end
we designed a small (60 mm <inline-formula><mml:math id="M47" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 35 mm) printed circuit board (PCB)
that can be mounted in the most suitable location for any UAS (Fig. S6 in the Supplement).
Temperature is measured with a platinum resistance thermometer (Platinum
600 <inline-formula><mml:math id="M48" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C MiniSens Pt1000, IST AG, Switzerland), humidity is measured
with a capacitive humidity sensor (P14 rapid in wired configuration, IST AG,
Switzerland). Both sensors protrude over the edge of the PCB, which minimises
thermal mass and improves ventilation. They are protected from mechanical
damage and contamination by an aluminium tube (length 30 mm, inner diameter
12 mm). The tube is polished on the outside to prevent heating by the sun
and anodised matte black on the inside which avoids reflection and focussing
of sunlight onto the sensors. On fixed-wing UASs we mount the PCB
facing forward, while on rotary-wing UASs we mount it facing upward in the downwash of the
rotors.</p><?xmltex \hack{\newpage}?>
</sec>
<?pagebreak page1836?><sec id="Ch1.S2.SS1.SSS4">
  <title>Data logger</title>
      <p id="d1e799">The data from all sensors are recorded to a memory card by a data logger. For
this purpose we modified an electronics board designed for the operation with
SenseAir's HPP gas sensors (Hök Instruments AB, Sweden) by adding
connectors that provide an interface for the GPS receiver and different
digital sensors. The board runs firmware written for COCAP at the MPI for
Biogeochemistry <xref ref-type="bibr" rid="bib1.bibx12" id="paren.13"/>. Sensor data are recorded at
1 Hz. If a sensor samples at a higher rate, the measurements are averaged
over 1 s. Data are continuously output via a serial interface and can
be transmitted to a computer by means of an adaptor cable or a pair of radio
modules (XBee 868, Digi International Inc., USA), allowing for real-time data
visualisation and analysis. In addition, the data logger controls the
built-in heaters of the CO<inline-formula><mml:math id="M49" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor to a user-adjustable temperature.</p>
</sec>
<sec id="Ch1.S2.SS1.SSS5">
  <title>Temperature stabilisation</title>
      <p id="d1e820">The temperature inside and outside COCAP influences the measurement of carbon
dioxide in different ways. First, the density of the sample air and therefore
the number of absorbing molecules in the measurement cell is inversely
proportional to absolute temperature (ideal gas law;
<xref ref-type="bibr" rid="bib1.bibx6" id="altparen.14"/>). Secondly, electronic components and the
optical bandpass filter in the CO<inline-formula><mml:math id="M50" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor exhibit drift with temperature
<xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx23" id="paren.15"/>. Thirdly, the intensity
of the absorption lines of any gas depends on temperature, which makes the
optical depth of the sample air temperature dependent
<xref ref-type="bibr" rid="bib1.bibx17" id="paren.16"/>. Fourthly, changes in temperature influence the
emission strength of the IR source. Fifthly, thermal expansion may cause
mechanical deformations of the optical assembly. We correct the
<inline-formula><mml:math id="M51" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> readings for drift with temperature (see
Sect. <xref ref-type="sec" rid="Ch1.S3.SS1"/>), but experience with earlier setups
shows that for best possible precision an active stabilisation of temperature
is needed.</p>
      <p id="d1e859">The HPP CO<inline-formula><mml:math id="M52" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor has built-in heaters and temperature sensors that are
thermally coupled to the optical surfaces, the IR source and the optical
detector. In an earlier version of COCAP we covered the CO<inline-formula><mml:math id="M53" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor with
isolating material and preheated the air stream with a heated tube that was
connected to the sensor inlet. In this setup, the temperature at three points
could be precisely controlled to 50 <inline-formula><mml:math id="M54" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, but the distribution of
temperature was inhomogeneous and varying with ambient conditions. Although a
total of nine temperature sensors were present at different locations in COCAP,
the uneven temperature distribution made it impossible to fully determine the
system's thermal state and a satisfactory temperature correction could not be
established.</p>
      <p id="d1e889">Consequently, we redesigned the stabilisation system to minimise temperature
differences around the CO<inline-formula><mml:math id="M55" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. This goal requires a setup where the
heat exchange between different parts of the sensor happens much faster than
dissipation of heat from the sensor to the changing environment. In many
instruments this is achieved by means of massive bodies of copper or
aluminium, which are characterised by high thermal diffusivity. However, as
the mass of large metal parts is unacceptable for our application, we use air
to transport heat inside COCAP. The lower thermal diffusivity of air is
compensated for by forced convection driven by a fan. A heater, a temperature
sensor and a custom PCB are connected and programmed as a control loop that
stabilises the air temperature at 50 <inline-formula><mml:math id="M56" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. The warm air stream
circulates throughout COCAP's housing (Fig. S1 in the Supplement) so that the CO<inline-formula><mml:math id="M57" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor is not
only decoupled from changes in ambient temperature
but all electronics boards benefit from the stabilisation as well.</p>
      <p id="d1e919">While being flown on a UAS the temperature around COCAP can change by several
degrees within seconds. Compensation for these changes requires a fast control
loop, which calls for a heating element and a temperature sensor with low
thermal mass. We built the heating element (Fig. <xref ref-type="fig" rid="Ch1.F2"/>)
from 38 surface-mount technology resistors (nominal resistance 360 <inline-formula><mml:math id="M58" display="inline"><mml:mi mathvariant="normal">Ω</mml:mi></mml:math></inline-formula>,
length <inline-formula><mml:math id="M59" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> width 2 mm <inline-formula><mml:math id="M60" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 1.25 mm, rated power 0.5 W)
which are connected in parallel and provide a maximum heating power of 15 W
at 12 V.</p>

      <fig id="Ch1.F2"><caption><p id="d1e947">Fan and heating element used to stabilise
temperature inside COCAP. The heating element is made of surface-mount
technology resistors soldered to two concentric rings of wire. It is located
just above the air inlet of the radial fan.</p></caption>
            <?xmltex \igopts{width=184.942913pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f02.png"/>

          </fig>

      <p id="d1e956">We installed the heating element just above the air inlet of the fan
(RLF 35-8/12 N, ebm-papst Mulfingen GmbH &amp; Co. KG, Germany). Placing the
heating element at the outlet of the fan would reduce the response time, but
would likely result in a less homogeneous temperature distribution across the air
stream.</p>
      <p id="d1e959">The temperature sensor (“air stream sensor”,
Fig. <xref ref-type="fig" rid="Ch1.F3"/>) in the control loop is a miniature
thermistor (NCP15XH103F03RC, Murata Ltd., Japan). It is placed close to the
detector of the CO<inline-formula><mml:math id="M61" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor and oriented perpendicular to the flow of
circulating air to minimise flow resistance.</p>

      <fig id="Ch1.F3"><caption><p id="d1e974">Sensor used for the measurement of the
temperature of the air circulating inside COCAP. The sensing element (located
in the centre of the blue 3-D-printed frame) is a miniature thermistor
(1 mm <inline-formula><mml:math id="M62" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 0.5 mm <inline-formula><mml:math id="M63" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 0.5 mm). Two 23 mm long pieces of
0.5 mm wire are soldered to both sides of the thermistor. They conduct heat,
facilitating the measurement of a temperature that is averaged across the air
stream.</p></caption>
            <?xmltex \igopts{width=184.942913pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f03.png"/>

          </fig>

      <p id="d1e997">Fan, heating element and air stream sensor are connected to an in-house-built
control board (Figs. S7 and S8 in the Supplement) that runs a<?pagebreak page1837?> PID
(proportional–integral–derivative) controller implemented in software. The
temperature-dependent resistance of the air stream sensor is measured in a
Wheatstone bridge configuration with a resolution of 1 mK at 50 <inline-formula><mml:math id="M64" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C.
A trimmer potentiometer allows calibration of the temperature measurement.
The control board detects whether the thermistor is shorted or disconnected and
disables heating in such cases.</p>
      <p id="d1e1009">The power dissipation of the heating element is controlled by pulse-width
modulation with 16 bit resolution. The control board monitors the current
drawn by the fan and powers the heating element only if the fan is operating
normally. This protection prevents damage to the heating element, which would
overheat if the fan is disconnected or broken.</p>
      <p id="d1e1013">The performance of the temperature stabilisation under flight conditions is
discussed in Sects. <xref ref-type="sec" rid="Ch1.S4.SS1.SSS2"/> and
<xref ref-type="sec" rid="Ch1.S4.SS2.SSS2"/>.</p>
</sec>
<sec id="Ch1.S2.SS1.SSS6">
  <title>Battery</title>
      <p id="d1e1026">COCAP requires a source of electrical power with a voltage in the range
10.2–14.0 V. We use a single lithium polymer battery with a nominal voltage
of 11.1 V. The battery life time depends on the ambient temperature, but
generally we can operate COCAP for more than 1 h from a 2200 mAh
battery weighing 200 g. By choosing a different battery size the package can
be optimised for lower mass or longer run time.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Field calibration device</title>
      <p id="d1e1036">In order to make the handling of gas standards in the field easier and safer
we developed a field calibration device (Fig. S9 in the Supplement). It
consists of a gas cylinder dolly, accommodating two 10 L aluminium
cylinders, and a valve box. The cylinders are securely tied to the dolly so
that they can stay in place at all times, which simplifies transportation.
Inside the valve box a three way valve allows switching between the two gas
standards or shutting off the gas stream. The flow rate is controlled to
400 mL min<inline-formula><mml:math id="M65" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> with a mechanical flow controller (PCFCDH-1N1-V, Beswick
Engineering Inc., USA). The connection to COCAP has an open-split
configuration so that there is always an 100 mL min<inline-formula><mml:math id="M66" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> overflow and the
gas standard is delivered at ambient pressure. At a field site three steps
are necessary to make the system ready for use: (1) removing the protective
caps from the cylinders, (2) mounting (including leak checking and flushing)
of the pressure regulators (model 14, Air Liquide USA LLC) and (3) connecting
them to the valve box. For details of the field calibration sequence and gas
standards see Sect. <xref ref-type="sec" rid="Ch1.S3.SS3"/></p>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Unmanned aircraft system</title>
      <p id="d1e1070">COCAP has no dependence on any external system and can therefore be deployed
on a variety of UASs. The only requirements are a payload capacity of
typically 1.2 kg (depending on the choice of battery; see
Sect. <xref ref-type="sec" rid="Ch1.S2.SS1.SSS6"/>) and space for the
14 cm <inline-formula><mml:math id="M67" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 14 cm <inline-formula><mml:math id="M68" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 42 cm package, either inside the fuselage
or attached to the outside of the vehicle. Sufficient ventilation must be
ensured to prevent overheating. In Germany, UASs can be operated without a
permit at low heights up to 100 m above ground level if their take-off mass
is lower than 5 kg. COCAP's size and mass generally allow for this
limit to be met. We have operated COCAP on multicopters and carried out successful
tests on a fixed-wing aircraft.</p>
<sec id="Ch1.S2.SS3.SSS1">
  <title>Multicopters</title>
      <p id="d1e1094">Multicopters are rotorcraft with more than two rotors. They are generally
easier to handle than fixed-wing aircraft due to their hovering ability and
their built-in electronic control systems. Multicopters feature vertical
take-off and landing as well as arbitrarily low vertical and horizontal
flight speed. However, for aerodynamic reasons they typically have a lower
endurance than fixed-wing aircraft of similar mass. Moreover, the strong
mixing around and below the rotors gives rise to an uncertainty of the origin
of a measured air sample. We alleviate this problem by sampling air through a
carbon fibre tube with the inlet placed sideways or above the rotors.</p>
      <p id="d1e1097">So far we have flown COCAP on two different multicopters. One is an
octocopter (S1000, DJI Ltd., China) with a total take-off mass of 9.2 kg.
The other one is a quadcopter (custom-built, Sensomotion UG, Germany, and
Ostwestfalen-Lippe University of Applied Sciences, Germany, Fig. S10 in the Supplement)
weighing 4.8 kg with COCAP mounted. Both multicopters are electrically
powered and provide at least 10 min of flight time.</p>
</sec>
<sec id="Ch1.S2.SS3.SSS2">
  <title>Fixed-wing aircraft</title>
      <p id="d1e1106">Fixed-wing aircraft require a minimum air speed to fly and generally depend
on an airstrip or additional equipment like<?pagebreak page1838?> bungees and nets for take-off and
landing. However, they tend to have higher endurance and longer reach than
multicopters. We carried out successful flight tests with an electrically
powered fixed-wing aircraft (X8, Skywalker Technology Ltd., China) using a
dummy that has the same mass and size as COCAP. The complete system weighed
approximately 3.6 kg.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS4">
  <title>Cost estimation</title>
      <p id="d1e1116">The cost estimate provided here includes materials and components in the
state in which we procured them but excludes any labour associated with their
modification and assembly. We estimate the material costs for COCAP at
EUR 4500 and for the field calibration device (including two cylinders, but
not the gas standards inside) at EUR 3300. The recurring costs for gas
standards and drying agent are a few euros per flight and thus negligible.</p>
      <p id="d1e1119">Commercial off-the-shelf multicopters with a payload capacity of at least
1.2 kg are available for EUR 3000, including essential equipment such as
battery, charger and remote control.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <title>Calibration</title>
<sec id="Ch1.S3.SS1">
  <?xmltex \opttitle{Calibration curve of the CO${}_{{2}}$
sensor}?><title>Calibration curve of the CO<inline-formula><mml:math id="M69" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
sensor</title>
      <p id="d1e1144">A nondispersive infrared gas sensor measures the fraction of one component in
a mixture of gases utilising the characteristic absorption bands that many
substances exhibit in the infrared. The HPP sensor inside COCAP outputs a
signal that is approximately proportional to the intensity of infrared
radiation that has passed through the gas mixture. Absorption by one
constituent of the gas reduces the intensity, but the relation between the
mole fraction of this component and the intensity is non-linear and depends
on temperature and pressure of the gas. Furthermore, sensor elements like the
infrared source and detector can have a temperature dependence that
influences the measurement. Generally, the carbon dioxide mole fraction
<inline-formula><mml:math id="M70" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> of the gas mixture can be calculated as
            <disp-formula id="Ch1.E1" content-type="numbered"><mml:math id="M71" display="block"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>,</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">G</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:msub><mml:mi>p</mml:mi><mml:mi mathvariant="normal">G</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:mi mathvariant="normal">…</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where <inline-formula><mml:math id="M72" display="inline"><mml:mi>s</mml:mi></mml:math></inline-formula> is the infrared signal, <inline-formula><mml:math id="M73" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">G</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M74" display="inline"><mml:mrow><mml:msub><mml:mi>p</mml:mi><mml:mi mathvariant="normal">G</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are
temperature and pressure of the gas mixture, respectively, and the ellipsis
indicates that other quantities may be included in the calculation. The
function <inline-formula><mml:math id="M75" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula> will henceforth be called the “calibration curve” of the
carbon dioxide sensor.</p>
      <p id="d1e1245">Although an ab initio calculation of the calibration curve is in principle
possible, we did not follow this approach due to lack of information (e.g.
the precise transmission characteristics of the optical bandpass filter).
Instead, we made a series of measurements with known CO<inline-formula><mml:math id="M76" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole
fraction under changing ambient conditions and used regression analysis to
approximate the calibration curve. To this end we placed COCAP in an
environmental chamber where ambient temperature and pressure could be varied
over the range expected in field deployments
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>b, c).</p>

      <fig id="Ch1.F4"><caption><p id="d1e1260">Conditions during one of
the experiments carried out to define a calibration curve for the CO<inline-formula><mml:math id="M77" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
sensor: <bold>(a)</bold> CO<inline-formula><mml:math id="M78" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction <inline-formula><mml:math id="M79" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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>
measured with a reference analyser, <bold>(b)</bold> ambient temperature <inline-formula><mml:math id="M80" display="inline"><mml:mi>T</mml:mi></mml:math></inline-formula>, and
<bold>(c)</bold> ambient pressure <inline-formula><mml:math id="M81" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula>. <bold>(d)</bold> Normalised infrared signal
<inline-formula><mml:math id="M82" display="inline"><mml:mi>s</mml:mi></mml:math></inline-formula> from the optical detector of COCAP's CO<inline-formula><mml:math id="M83" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. The variations in
pressure influence the observed signal more strongly than the changes in
<inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> by 200 <inline-formula><mml:math id="M85" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M86" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, which illustrates
the need for a precise pressure correction.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f04.png"/>

        </fig>

      <p id="d1e1380">Temperature was changed in a step pattern from 28 to 0 <inline-formula><mml:math id="M87" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C while
pressure was smoothly adjusted from 1100 to 700 hPa and back during each
temperature step. These disparate patterns were chosen to ease the
attribution of sensitivities to one of the independent variables. Sample air
with gradually changing CO<inline-formula><mml:math id="M88" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction was provided to COCAP
from a spherical, stainless steel, 8 L buffer volume that was continuously
flushed with air from one of two gas cylinders
(Fig. <xref ref-type="fig" rid="Ch1.F5"/>).</p>

      <fig id="Ch1.F5"><caption><p id="d1e1405">Setup used to determine a
calibration curve for the CO<inline-formula><mml:math id="M89" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. FC is a mass flow controller. The
8 L buffer volume was flushed with either of two gas standards differing in
CO<inline-formula><mml:math id="M90" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> content, providing a slowly changing CO<inline-formula><mml:math id="M91" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction.
The second three-way valve is used to deliver nitrogen with zero CO<inline-formula><mml:math id="M92" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> at
the beginning and the end of each experiment.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f05.png"/>

        </fig>

      <p id="d1e1450">One cylinder contained a lower-than-ambient CO<inline-formula><mml:math id="M93" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction
(349.9 <inline-formula><mml:math id="M94" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M95" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), while the other one was enriched with CO<inline-formula><mml:math id="M96" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
(648.6 <inline-formula><mml:math id="M97" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M98" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>). At a flow rate of 400 mL min<inline-formula><mml:math id="M99" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> the
buffer volume acted as a low-pass filter with a time constant of 20 min
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>a). Air leaving COCAP was
directed to a Picarro G2401 cavity ring-down spectroscopy (CRDS) analyser
<xref ref-type="bibr" rid="bib1.bibx18" id="paren.17"/> that had been calibrated to the WMO
CO<inline-formula><mml:math id="M100" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> X2007 scale and served as a reference. Open splits upstream and
downstream<?pagebreak page1839?> of COCAP ensured that sample air was delivered to both analysers
at chamber pressure despite different flow rates (COCAP 300 mL min<inline-formula><mml:math id="M101" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>,
Picarro G2401 200 mL min<inline-formula><mml:math id="M102" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>).</p>
      <p id="d1e1561">The dominant features in the infrared signal
(Fig. <xref ref-type="fig" rid="Ch1.F4"/>d) are the step changes in
<inline-formula><mml:math id="M103" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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 the influence of pressure changes. Note that in a
nondispersive infrared sensor the signal is inversely related to the amount
of absorbing molecules in the measurement cell. Hence, both low
<inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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 low pressure lead to a high signal. The gradual
changes in <inline-formula><mml:math id="M105" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> by 200 <inline-formula><mml:math id="M106" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M107" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> between
00:40 and 06:30 h have a smaller
influence on the infrared signal than the changes in pressure do. This shows
the importance of a precise correction for ambient influences.</p>
      <p id="d1e1631">In total we carried out three experiments similar to the one depicted in
Fig. <xref ref-type="fig" rid="Ch1.F4"/> on consecutive days. The
variation in temperature and pressure were the same for all experiments, but
the initial CO<inline-formula><mml:math id="M108" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction in the buffer volume differed and
the switching between low-CO<inline-formula><mml:math id="M109" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and high-CO<inline-formula><mml:math id="M110" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> cylinders took place at
different times.</p>
      <p id="d1e1663">Regression analysis of the experimental data was carried out in GNU
Octave using the <italic>leasqr</italic> function from the <italic>optim</italic>
package. It is an implementation of the Levenberg–Marquardt algorithm
for non-linear least-squares regression that allows the variation
of some parameters of a model while others are fixed. This capability
enabled a stepwise approach in which we fitted one part of a model
at a time until finally all parameters could be set free In contrast,
straightforward fitting of a complete model at once did not converge.
We attribute this to the high number of parameters (10 or more) and
to the lack of initial values sufficiently close to the optimum.</p>
      <p id="d1e1672"><?xmltex \hack{\newpage}?>The models that we fitted to the experimental data are of the form

                <disp-formula specific-use="align" content-type="numbered"><mml:math id="M111" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E2"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:msub><mml:mi>x</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>,</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>p</mml:mi><mml:mo>,</mml:mo><mml:mi mathvariant="normal">…</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E3"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">Outlet</mml:mi></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>(</mml:mo><mml:mi>p</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>⋅</mml:mo><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>,</mml:mo><mml:mi mathvariant="normal">…</mml:mi><mml:mo>)</mml:mo><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mi>c</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

            The function <inline-formula><mml:math id="M112" display="inline"><mml:mrow><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> represents the inlet temperature and <inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> the pressure
inside the measurement cell of the CO<inline-formula><mml:math id="M114" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. The fraction
<inline-formula><mml:math id="M115" display="inline"><mml:mrow><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>/</mml:mo><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> originates from the ideal gas law, but in many of our models it
has a more general form, including constant and quadratic terms to account
for other effects like temperature or pressure broadening of absorption
lines. The function <inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is a polynomial of second or third order that
approximates the non-linear relation between amount of absorbing molecules in
the measurement cell and light intensity at the detector. Finally, the
purpose of <inline-formula><mml:math id="M117" display="inline"><mml:mrow><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is to correct the detector signal for disturbances, e.g.
gain drift with temperature.</p>
      <p id="d1e1874">In our regression analysis we repeatedly performed three steps:
(1) formulation of a model, (2) fitting of the model to the experimental data
by minimising the sum of squared residuals and (3) evaluation of the model
performance. Given the large number of parameters in the models, the second
step was susceptible to “overfitting”, i.e. fitting to a point at which the
model represents not only an underlying process but also random variations
in the experimental data. We countered overfitting in two ways. On the one
hand, we rejected models in which an additional parameter reduced the sum of
squared residuals only insignificantly. On the other hand, we validated the
fitted models against independent data measured on a different day, which
allowed us to assess the stability of the parameters over time. Based on
these considerations we chose the following calibration curve:

                <disp-formula specific-use="align" content-type="numbered"><mml:math id="M118" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E4"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:msub><mml:mi>x</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">Outlet</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow><mml:mrow><mml:mi>p</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>(</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:msubsup><mml:mi>g</mml:mi><mml:mn mathvariant="normal">4</mml:mn><mml:mn mathvariant="normal">3</mml:mn></mml:msubsup><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">5</mml:mn></mml:msub><mml:msubsup><mml:mi>g</mml:mi><mml:mn mathvariant="normal">4</mml:mn><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>+</mml:mo><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">6</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">7</mml:mn></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E5"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi>g</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>,</mml:mo><mml:mi>p</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mi>s</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">8</mml:mn></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">9</mml:mn></mml:msub><mml:mi>p</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">10</mml:mn></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

            <inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> through <inline-formula><mml:math id="M120" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">10</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> are the parameters fitted in the regression. The
capability of this calibration curve to compensate for ambient influences is
illustrated in Fig. <xref ref-type="fig" rid="Ch1.F6"/>.</p>

      <fig id="Ch1.F6"><caption><p id="d1e2063"><bold>(a)</bold> Normalised infrared signal of
COCAP's CO<inline-formula><mml:math id="M121" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor under changing ambient conditions. This is a subset
of the data shown in Fig. <xref ref-type="fig" rid="Ch1.F4"/>d.
<bold>(b)</bold> <inline-formula><mml:math id="M122" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> calculated using the calibration curve
(Eqs. <xref ref-type="disp-formula" rid="Ch1.E4"/> and <xref ref-type="disp-formula" rid="Ch1.E5"/>) compared to the
measurements of a reference analyser (Picarro G2401). The
<inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> signal is recovered despite strong influences from
changing pressure.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f06.png"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS2">
  <title>Calibration of ambient sensors</title>

<table-wrap id="Ch1.T1" specific-use="star"><caption><p id="d1e2131">Summary of the calibration of
COCAP's ambient sensors: conditions during calibration, correction model and
root mean square error (RMSE) of the corrected indications with respect to
the reference. <inline-formula><mml:math id="M124" display="inline"><mml:mi>T</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math id="M125" display="inline"><mml:mi>U</mml:mi></mml:math></inline-formula> and <inline-formula><mml:math id="M126" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> are uncorrected temperature, relative
humidity and pressure, respectively. <inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is the corrected air
temperature. n/a – not applicable.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="6">
     <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:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Sensor</oasis:entry>  
         <oasis:entry colname="col2">Temperature</oasis:entry>  
         <oasis:entry colname="col3">Relative humidity</oasis:entry>  
         <oasis:entry colname="col4">Pressure</oasis:entry>  
         <oasis:entry colname="col5">Model</oasis:entry>  
         <oasis:entry colname="col6">RMSE</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">in <inline-formula><mml:math id="M128" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C</oasis:entry>  
         <oasis:entry colname="col3">in %</oasis:entry>  
         <oasis:entry colname="col4">in hPa</oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Temperature</oasis:entry>  
         <oasis:entry colname="col2">5–40</oasis:entry>  
         <oasis:entry colname="col3">50</oasis:entry>  
         <oasis:entry colname="col4">1000</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M129" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:msup><mml:mi>T</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi>T</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">0.04 <inline-formula><mml:math id="M130" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Humidity</oasis:entry>  
         <oasis:entry colname="col2">10–30</oasis:entry>  
         <oasis:entry colname="col3">15–100</oasis:entry>  
         <oasis:entry colname="col4">1000</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M131" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:msup><mml:mi>U</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi>U</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mi>U</mml:mi><mml:mo>⋅</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">5</mml:mn></mml:msub><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">1.4 %</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Pressure</oasis:entry>  
         <oasis:entry colname="col2">0–40</oasis:entry>  
         <oasis:entry colname="col3">n/a</oasis:entry>  
         <oasis:entry colname="col4">400–1000</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M132" display="inline"><mml:mrow><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:msup><mml:mi>p</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi>p</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">1.1 hPa</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e2434">We calibrated COCAP's temperature, humidity and pressure sensors prior to
measurements in the field. The general calibration approach was the same for
all three sensor types: As a first step, we placed them together with a
reference instrument in an environmental chamber, varied the relevant ambient
conditions and recorded the indications of both the sensor under test and the
reference. As a second step, we fitted a model that relates the indications
of the sensor under test to the reference measurements. This model can later
be used to correct sensor indications during field measurements.</p>
      <p id="d1e2437">Calibration of the temperature and humidity sensors was carried out in a
PSL-2KPH chamber (ESPEC Corp., Japan).<?pagebreak page1840?> A chilled-mirror dew point hygrometer
(Michell Dewmet TDH) with a measurement uncertainty of 0.1 <inline-formula><mml:math id="M133" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for
temperature and 0.2 <inline-formula><mml:math id="M134" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for dew point served as the reference.
The reference and the sensor under test were placed close to each other and actively
ventilated during the measurements.</p>
      <p id="d1e2458">The pressure sensors were calibrated in a CH3030 chamber (SIEMENS AG,
Germany). The reference instrument (Druck DPI 740, General Electric Company,
USA) has a measurement uncertainty of 0.26 hPa.</p>
      <p id="d1e2462">Details of the calibrations are listed in
Table <xref ref-type="table" rid="Ch1.T1"/>. The correction model for the
humidity sensor depends not only on the raw humidity signal but also on air
temperature. It therefore relies on the corrected indication of the
temperature sensor.</p>
      <p id="d1e2467">A potential source of error in the humidity calibrations are the different
response times of the chilled-mirror dew point hygrometer and the slower
reacting capacitive humidity sensor. We avoid the introduction of a bias by
calibrating with slowly varying symmetric humidity patterns, i.e. by using
the same rate of change during humidity increase and decrease.</p>
</sec>
<sec id="Ch1.S3.SS3">
  <title>Field calibration</title>
      <p id="d1e2476">The CO<inline-formula><mml:math id="M135" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction reported by COCAP drifts over time (see
Sect. <xref ref-type="sec" rid="Ch1.S4.SS1.SSS1"/>), necessitating periodic calibration. We
decided against in-flight calibrations to reduce the system mass, to save
space and to have the full flight time available for the measurement of
ambient air. Instead we sample two gas standards before and after each flight
using the field calibration device described in
Sect. <xref ref-type="sec" rid="Ch1.S2.SS2"/>. One of the standards has a
CO<inline-formula><mml:math id="M136" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction close to clean ambient air
(397.57 <inline-formula><mml:math id="M137" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M138" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>); the other one is enriched with CO<inline-formula><mml:math id="M139" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
(447.44 <inline-formula><mml:math id="M140" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M141" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>). Both standards consist of natural air
collected at the Max Planck Institute for Biogeochemistry in Jena, Germany;
i.e. the standards are similar in isotopic composition to the air that we
typically measure in the field. This way we avoid isotope-related errors that
can occur with synthetic air standards <xref ref-type="bibr" rid="bib1.bibx26" id="paren.18"/>. The
standards are sampled for 5 min each. We discard the first 3 min to
ensure that the measurement system is well flushed, leaving 2 min for
averaging. This time span is a compromise between noise reduction (the
minimum standard error of the mean would be achieved by averaging over
4 min; see Sect. <xref ref-type="sec" rid="Ch1.S4.SS1.SSS1"/>) on the one hand and
consumption of gas standards and time spent for the field calibration (and
lost for ambient measurements) on the other.</p>
      <p id="d1e2554">During data analysis, the calibration curve (see
Sect. <xref ref-type="sec" rid="Ch1.S3.SS1"/>) is applied to all measurements of COCAP,
resulting in a time series of CO<inline-formula><mml:math id="M142" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction. Averaging is
carried out for each gas standard and each sampling period by calculating the
arithmetic mean of the CO<inline-formula><mml:math id="M143" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction. Next, “virtual”
standard measurements are created by interpolating between the calculated
averages linearly in time. Using these virtual standard measurements two
correction parameters <inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:mi>a</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (slope) and <inline-formula><mml:math id="M145" display="inline"><mml:mrow><mml:mi>b</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (offset) are calculated for
each point in time between the first and last standard measurement such that
the difference between corrected measurement and assigned value vanishes. The
corrected CO<inline-formula><mml:math id="M146" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction is thus calculated as
            <disp-formula id="Ch1.E6" content-type="numbered"><mml:math id="M147" display="block"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mi>a</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>s</mml:mi><mml:mo>,</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>p</mml:mi><mml:mo>,</mml:mo><mml:mi mathvariant="normal">…</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mi>b</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p><?xmltex \hack{\newpage}?>
</sec>
</sec>
<?pagebreak page1841?><sec id="Ch1.S4">
  <title>Performance tests</title>
<sec id="Ch1.S4.SS1">
  <title>In the lab</title>
<sec id="Ch1.S4.SS1.SSS1">
  <?xmltex \opttitle{Allan deviation of CO${}_{{2}}$
dry air mole fraction}?><title>Allan deviation of CO<inline-formula><mml:math id="M148" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
dry air mole fraction</title>
      <p id="d1e2703">The influence of white noise on a measurement can be reduced by averaging
over several samples. However, the precision achievable by averaging
is limited by drift of the instrument over time; i.e. over long averaging
periods the imprecision caused by drift becomes larger than the imprecision
caused by noise. Allan or two-sample variance <inline-formula><mml:math id="M149" display="inline"><mml:mrow><mml:msubsup><mml:mi mathvariant="italic">σ</mml:mi><mml:mi>y</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>(</mml:mo><mml:mi mathvariant="italic">τ</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>
is a measure commonly used to analyse these two sources of error.
It is defined as <xref ref-type="bibr" rid="bib1.bibx1" id="paren.19"/>

                  <disp-formula id="Ch1.E7" content-type="numbered"><mml:math id="M150" display="block"><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msubsup><mml:mi mathvariant="italic">σ</mml:mi><mml:mi>y</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msubsup><mml:mo>(</mml:mo><mml:mi mathvariant="italic">τ</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">1</mml:mn><mml:mn mathvariant="normal">2</mml:mn></mml:mfrac></mml:mstyle><mml:mfenced open="〈" close="〉"><mml:mo>(</mml:mo><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>y</mml:mi><mml:msup><mml:mo>)</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mfenced><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

            where <inline-formula><mml:math id="M151" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>y</mml:mi></mml:mrow></mml:math></inline-formula> is the difference between two consecutive averages over a
period of <inline-formula><mml:math id="M152" display="inline"><mml:mi mathvariant="italic">τ</mml:mi></mml:math></inline-formula> and the angle brackets denote the expected value. The square
root of the Allan variance is called Allan deviation <inline-formula><mml:math id="M153" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">σ</mml:mi><mml:mi>y</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>.</p>
      <p id="d1e2799">To characterise noise and drift of COCAP we connected the analyser in an open-split configuration to a cylinder containing natural air with a CO<inline-formula><mml:math id="M154" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry
air mole fraction of 384.3 <inline-formula><mml:math id="M155" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M156" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. This air sample was
measured in a lab environment over a period of 24 h. The Allan deviation of
this dataset (Fig. <xref ref-type="fig" rid="Ch1.F7"/>) reaches a minimum of
approximately 0.2 <inline-formula><mml:math id="M157" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M158" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> at an averaging period of
230 s.</p>

      <fig id="Ch1.F7"><caption><p id="d1e2853">Allan deviation of unfiltered CO<inline-formula><mml:math id="M159" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry
air mole fraction <inline-formula><mml:math id="M160" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">σ</mml:mi><mml:mrow><mml:mi>x</mml:mi><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> versus averaging period <inline-formula><mml:math id="M161" display="inline"><mml:mi mathvariant="italic">τ</mml:mi></mml:math></inline-formula>.
Air from a cylinder was measured under laboratory conditions and during the
simulated flights described in Sect <xref ref-type="sec" rid="Ch1.S4.SS1.SSS2"/>. The
latter is depicted until <inline-formula><mml:math id="M162" display="inline"><mml:mrow><mml:mi mathvariant="italic">τ</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1000</mml:mn></mml:mrow></mml:math></inline-formula> s, i.e. one-sixth of the length of the
time series. The characteristic <inline-formula><mml:math id="M163" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula> slope of white noise is indicated by
the black line.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f07.png"/>

          </fig>

      <p id="d1e2924">For averaging periods shorter than 100 s the curve has a slope of
<inline-formula><mml:math id="M164" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mn mathvariant="normal">1</mml:mn><mml:mn mathvariant="normal">2</mml:mn></mml:mfrac></mml:mstyle></mml:mrow></mml:math></inline-formula> in the log–log plot, which is characteristic of white noise.
At <inline-formula><mml:math id="M165" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">τ</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1800</mml:mn></mml:mrow></mml:math></inline-formula> s, the typical time between field calibrations,
the Allan deviation is approximately 0.7 <inline-formula><mml:math id="M166" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M167" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> and
dominated by drift. Our correction scheme (see
Sect. <xref ref-type="sec" rid="Ch1.S3.SS3"/>) removes offset and gain errors at the
point in time when the field calibrations were carried out and uses linear
interpolation between the calibrations. Therefore, the largest uncorrected
drift is expected to be lower than 0.4 <inline-formula><mml:math id="M168" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M169" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, the Allan
deviation for <inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mn mathvariant="normal">1</mml:mn><mml:mn mathvariant="normal">2</mml:mn></mml:mfrac></mml:mstyle><mml:msub><mml:mi mathvariant="italic">τ</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">900</mml:mn></mml:mrow></mml:math></inline-formula> s.
Figure <xref ref-type="fig" rid="Ch1.F7"/> also shows the Allan deviation of COCAP's
<inline-formula><mml:math id="M171" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measurements during the simulated flights described in
Sect. <xref ref-type="sec" rid="Ch1.S4.SS1.SSS2"/>. Forced ventilation and substantial
changes in ambient pressure and temperature during the simulated flights lead
to an increased Allan deviation compared to the measurements in a lab
environment. Estimation of the expected drift for
<inline-formula><mml:math id="M172" display="inline"><mml:mrow><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mn mathvariant="normal">1</mml:mn><mml:mn mathvariant="normal">2</mml:mn></mml:mfrac></mml:mstyle><mml:msub><mml:mi mathvariant="italic">τ</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">900</mml:mn></mml:mrow></mml:math></inline-formula> s is not feasible due to artefacts that
become visible at averaging periods beyond 400 s.</p>
</sec>
<sec id="Ch1.S4.SS1.SSS2">
  <title>Simulated flights</title>
      <p id="d1e3065">An instrument that is flown on a small UAS can be exposed to rapid changes in
temperature and pressure, especially if the flight pattern covers a large
range in altitude. To assess the measurement error caused by such changes, we
simulated three consecutive flights between 0 and 1000 m above sea level
(Fig. <xref ref-type="fig" rid="Ch1.F8"/>a, b) in an environmental chamber (CH3030,
SIEMENS AG, Germany).</p>

      <fig id="Ch1.F8"><caption><p id="d1e3071">Stability test in an environmental
chamber. The variations in ambient pressure <inline-formula><mml:math id="M173" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> and temperature <inline-formula><mml:math id="M174" display="inline"><mml:mi>T</mml:mi></mml:math></inline-formula>
approximately represent three flights between 0 and 1000 m above sea level
in the International Standard Atmosphere. Air with constant dry air mole
fraction of CO<inline-formula><mml:math id="M175" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> was supplied to COCAP from a cylinder. Calibrations were
carried out before and after the flights (not shown) using two gas standards
(397.5 and 447.4 <inline-formula><mml:math id="M176" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M177" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>). The dry air mole fraction
<inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measured with COCAP has been smoothed by convolution
with a Gauss window of 200 s full width at half maximum in order to reduce
the high-frequency noise. The sharp features in pressure were caused by
turning the environmental chamber's pressure regulation off after and back on
before each flight.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f08.png"/>

          </fig>

      <p id="d1e3138">Temperature and pressures were controlled to approximately resemble the
International Civil Aviation Organization Standard Atmosphere
<xref ref-type="bibr" rid="bib1.bibx11" id="paren.20"/>. Each simulated flight had a duration of 20 min
with 5 min ascent and 15 min descent. After a 20 min break without changes
in<?pagebreak page1842?> temperature and pressure this pattern was repeated. Only dry air samples
from cylinders were supplied to COCAP; hence no drying cartridge was
necessary. Otherwise, the analyser was operated in standard configuration,
including pump and flow control. An open split with overflow upstream of the
analyser's inlet ensured that air was sampled at the pressure of the
environmental chamber at all times. First we measured two gas standards with
CO<inline-formula><mml:math id="M179" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fractions of 397.5 and 447.4 <inline-formula><mml:math id="M180" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M181" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>
for 5 min each at 15 <inline-formula><mml:math id="M182" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and 100 kPa. Afterwards, air with
418.6 <inline-formula><mml:math id="M183" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M184" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> CO<inline-formula><mml:math id="M185" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> was supplied over a period of 2 h while the environmental chamber was simulating three flights as
detailed above. Finally, we sampled the two gas standards again for 5 min
each at 15 <inline-formula><mml:math id="M186" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and 100 kPa. The <inline-formula><mml:math id="M187" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measurement by
COCAP is affected by different sources of error: random noise, drift over
time, calibration errors and drift with temperature and pressure. We reduced
the noise by convoluting the time series with a Gauss window of 200 s full
width at half maximum (Fig. <xref ref-type="fig" rid="Ch1.F8"/>c). A two-point
calibration was derived from the standard measurements at the beginning and
end of the test and applied to the full time series using linear
interpolation in time. This cancelled out linear drift over time, but due to
the influence of noise on the measurement of the gas standards and
non-linearity in the instrument response, a calibration error remains. Drift
with temperature and pressure is corrected for with the calibration curve
described in Sect. <xref ref-type="sec" rid="Ch1.S3.SS1"/>, but this correction does
not completely eliminate the effect of these parameters on the measurement
result. The <inline-formula><mml:math id="M188" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> time series in
Fig. <xref ref-type="fig" rid="Ch1.F8"/>c exhibits a local minimum whenever pressure
and temperature are minimal, with a maximum deviation from the assigned value
of the cylinder (418.6 <inline-formula><mml:math id="M189" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M190" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>) of
<inline-formula><mml:math id="M191" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.2 <inline-formula><mml:math id="M192" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M193" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> at 02:10 h. The bias of the mean over the whole test, representing the combined
effect of the calibration error and drift with temperature and pressure, was
<inline-formula><mml:math id="M194" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.03</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M195" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M196" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. The standard deviation of the 1 Hz time
series before convolution with a Gauss window was
2.7 <inline-formula><mml:math id="M197" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M198" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>; the standard deviation after convolution was
0.41 <inline-formula><mml:math id="M199" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M200" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>.</p>
      <p id="d1e3370">Figure <xref ref-type="fig" rid="Ch1.F9"/> shows time series of
temperatures measured at different points inside COCAP during the
simulated flights.</p>

      <fig id="Ch1.F9"><caption><p id="d1e3377">Temperatures inside and
outside COCAP under simulated flight conditions (depicted in
Fig. <xref ref-type="fig" rid="Ch1.F8"/>a and b). The temperature sensors in
the detector, inlet and outlet of the CO<inline-formula><mml:math id="M201" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor are uncalibrated; hence
they have an unknown offset of up to 1.1 <inline-formula><mml:math id="M202" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. The detector is about
5 K warmer than the other parts (note the broken temperature axis) due to
heat transfer from the component block which is heated to 55 <inline-formula><mml:math id="M203" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C.
Ambient temperature is plotted at a different scale as it varies 2 orders
of magnitude more than the stabilised internal temperatures. The spikes in
air stream temperature are related to fast pressure changes in the
environmental chamber (see Fig. <xref ref-type="fig" rid="Ch1.F8"/>a).</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f09.png"/>

          </fig>

      <p id="d1e3417">Statistics of these time series are given in
Table <xref ref-type="table" rid="Ch1.T2"/>.</p>

<table-wrap id="Ch1.T2"><caption><p id="d1e3424">Mean <inline-formula><mml:math id="M204" display="inline"><mml:mover accent="true"><mml:mi>T</mml:mi><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:math></inline-formula>, standard
deviation <inline-formula><mml:math id="M205" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula> and range <inline-formula><mml:math id="M206" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">max</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">min</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
of temperatures under simulated flight conditions.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <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:thead>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M207" display="inline"><mml:mover accent="true"><mml:mi>T</mml:mi><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:math></inline-formula> in <inline-formula><mml:math id="M208" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M209" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula> in mK</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M210" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">max</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">min</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4">in mK</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Ambient</oasis:entry>  
         <oasis:entry colname="col2">12.83</oasis:entry>  
         <oasis:entry colname="col3">2366</oasis:entry>  
         <oasis:entry colname="col4">8786</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Air stream</oasis:entry>  
         <oasis:entry colname="col2">50.00</oasis:entry>  
         <oasis:entry colname="col3">4</oasis:entry>  
         <oasis:entry colname="col4">79</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Inlet</oasis:entry>  
         <oasis:entry colname="col2">50.25</oasis:entry>  
         <oasis:entry colname="col3">10</oasis:entry>  
         <oasis:entry colname="col4">50</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Outlet</oasis:entry>  
         <oasis:entry colname="col2">50.12</oasis:entry>  
         <oasis:entry colname="col3">32</oasis:entry>  
         <oasis:entry colname="col4">110</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Detector</oasis:entry>  
         <oasis:entry colname="col2">54.86</oasis:entry>  
         <oasis:entry colname="col3">10</oasis:entry>  
         <oasis:entry colname="col4">50</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e3623">The differences in the observed patterns result from the air circulation
inside COCAP's housing: first, heated air from the fan streams along the
inlet tube of the CO<inline-formula><mml:math id="M211" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. Next, it passes the air stream sensor (see
Sect <xref ref-type="sec" rid="Ch1.S2.SS1.SSS5"/>). Finally, it reaches the outlet
tube and the detector of the CO<inline-formula><mml:math id="M212" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor.</p>
      <p id="d1e3646">The air stream sensor is part of the control loop and therefore its
temperature stays close to the set point of 50 <inline-formula><mml:math id="M213" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. The inlet and
outlet temperature sensors measure the temperature of the sample gas, which
indirectly reflects the temperature of the air circulation because heat is
exchanged through the walls of the inlet and outlet tubes. The temperatures
of the outlet exhibit minima whenever the ambient temperature is reduced.
This is caused by increased heat transfer from the circulating air to outside
COCAP's housing. The inlet shows the inverse behaviour, i.e. increasing
temperature under reduced ambient temperature, because it is located between
fan and air stream sensor. In a colder environment the air has to be heated
more to keep the temperature at the air stream sensor constant, so the
temperature at the inlet rises.</p>
      <p id="d1e3658">The temperature of the detector varied qualitatively similarly to that of the
outlet because detector and outlet are located close to each other. However,
the temperature of the detector is approximately 5 K higher and the
amplitude of the temperature variations is roughly 3 times lower than at
the outlet. This is due to the detector's thermal coupling to the component
block, which is temperature-controlled to 55 <inline-formula><mml:math id="M214" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. Overall, the
temperature stabilisation reduces the variability in the internal
temperatures by 2 orders of magnitude compared to the changes in ambient
temperature (see Table <xref ref-type="table" rid="Ch1.T2"/>).</p>
</sec>
</sec>
<?pagebreak page1843?><sec id="Ch1.S4.SS2">
  <title>Field deployment</title>
<sec id="Ch1.S4.SS2.SSS1">
  <title>Measurements with an instrumented
van</title>
      <p id="d1e3684">Testing COCAP under realistic conditions requires the measurement of
<inline-formula><mml:math id="M215" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> in ambient air with varying composition. Specifically,
changes in humidity are desirable to reveal potential problems with the
drying of the sample gas and changes in CO<italic/><sub>2</sub> content
allow validation of COCAP's calibration curve. To this end, a reference
instrument must simultaneously sample the same air as COCAP. Laser-based
instruments are widely used for high-accuracy measurements of greenhouse
gases (e.g. <xref ref-type="bibr" rid="bib1.bibx14" id="altparen.21"/>) and therefore suitable to be used as
a reference, but at a mass of more than 10 kg they are too large to fly on
any UAS available for this work. As an intermediate step between stationary
indoor testing and UAS flights we integrated COCAP into the “Mobile Lab”
<xref ref-type="bibr" rid="bib1.bibx20" id="paren.22"/>, an instrumented van equipped with a CRDS
analyser for carbon dioxide, carbon monoxide, methane and water (G2401-m,
Picarro Inc., USA). Air was sampled at 3.5 m above street level. Field
calibrations (see Sect. <xref ref-type="sec" rid="Ch1.S3.SS3"/>) were carried out by
injecting air from cylinders with slightly higher-than-ambient pressure into
the sampling line at regular intervals.</p>
      <p id="d1e3714">As COCAP and the CRDS analyser were connected to the same sampling
line, delay and mixing caused by tubing and inlet filter affected
them equally. However, the flushing time for the analyser's measurement
cells is different, which makes direct comparison of their readings
inappropriate. In the following we explain how we handled this issue
mathematically.</p>
      <p id="d1e3717">The flushing process can be described as a convolution of the CO<inline-formula><mml:math id="M216" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry
air mole fraction at the inlet of the sampling line, <inline-formula><mml:math id="M217" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>,
with an analyser-specific instrument function <inline-formula><mml:math id="M218" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>:

                  <disp-formula specific-use="align" content-type="numbered"><mml:math id="M219" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E8"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi>x</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>∗</mml:mo><mml:mi>f</mml:mi><mml:mo>)</mml:mo><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E9"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>=</mml:mo><mml:munderover><mml:mo movablelimits="false">∫</mml:mo><mml:mrow><mml:mo>-</mml:mo><mml:mi mathvariant="normal">∞</mml:mi></mml:mrow><mml:mi mathvariant="normal">∞</mml:mi></mml:munderover><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mi mathvariant="normal">d</mml:mi><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

              The response <inline-formula><mml:math id="M220" display="inline"><mml:mrow><mml:mi>x</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> of the analyser is the reported CO<inline-formula><mml:math id="M221" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole
fraction. Due to causality, <inline-formula><mml:math id="M222" display="inline"><mml:mrow><mml:mi>x</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> cannot depend on future CO<inline-formula><mml:math id="M223" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air
mole fractions at the inlet. Hence, the lower limit of the integration can be
set to zero:

                  <disp-formula id="Ch1.E10" content-type="numbered"><mml:math id="M224" display="block"><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mi>x</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:munderover><mml:mo movablelimits="false">∫</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mi mathvariant="normal">∞</mml:mi></mml:munderover><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mi mathvariant="normal">d</mml:mi><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>

            The instrument function <inline-formula><mml:math id="M225" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is not known a priori, but it can be estimated
from the response to a step change in <inline-formula><mml:math id="M226" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. Such step
changes occurred at the end of calibration measurements when the supply of
gas standard into the sampling line was shut off. From the data we found that
for both analysers the response <inline-formula><mml:math id="M227" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">SC</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> to a step change can be
modelled by an exponential decay of the form

                  <disp-formula id="Ch1.E11" content-type="numbered"><mml:math id="M228" display="block"><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">SC</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mi>t</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:msup><mml:mo>+</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

            where <inline-formula><mml:math id="M229" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M230" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are the CO<inline-formula><mml:math id="M231" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fractions before
and after the step change, respectively, and <inline-formula><mml:math id="M232" display="inline"><mml:mi mathvariant="italic">τ</mml:mi></mml:math></inline-formula> is the characteristic
time constant of the flushing process. We determined time constants of 13 s
for COCAP and 25 s for the CRDS analyser. To find the function <inline-formula><mml:math id="M233" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> we
differentiate Eq. <xref ref-type="disp-formula" rid="Ch1.E10"/>:

                  <disp-formula specific-use="align" content-type="numbered"><mml:math id="M234" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E12"><mml:mtd/><mml:mtd><mml:mrow><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mi mathvariant="normal">d</mml:mi><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mi>x</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mo>=</mml:mo></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mi mathvariant="normal">d</mml:mi><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:munderover><mml:mo movablelimits="false">∫</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mi mathvariant="normal">∞</mml:mi></mml:munderover><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mi mathvariant="normal">d</mml:mi><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E13"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mo>=</mml:mo></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:munderover><mml:mo movablelimits="false">∫</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mi mathvariant="normal">∞</mml:mi></mml:munderover><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mi mathvariant="normal">d</mml:mi><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mi mathvariant="normal">d</mml:mi><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

              In the case of a step change at the inlet, the differentiation yields the Dirac
delta function <inline-formula><mml:math id="M235" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>, scaled by the height of the step
<inline-formula><mml:math id="M236" display="inline"><mml:mrow><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>:

                  <disp-formula specific-use="align" content-type="numbered"><mml:math id="M237" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E14"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mi mathvariant="normal">d</mml:mi><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">SC</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:munderover><mml:mo movablelimits="false">∫</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mi mathvariant="normal">∞</mml:mi></mml:munderover><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi mathvariant="italic">δ</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>-</mml:mo><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>)</mml:mo><mml:mi mathvariant="normal">d</mml:mi><mml:msup><mml:mi>t</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E15"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

              Rearranging and applying Eq. <xref ref-type="disp-formula" rid="Ch1.E11"/>,

                  <disp-formula specific-use="align" content-type="numbered"><mml:math id="M238" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E16"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mi mathvariant="normal">d</mml:mi><mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">SC</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E17"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mi>t</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:msup></mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">∞</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E18"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mi>t</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:msup></mml:mrow><mml:mi mathvariant="italic">τ</mml:mi></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

              This means that the instrument function of either analyser can be described
with an exponential decay which has the same time constant as the analyser's
step response. For practical reasons, we treat <inline-formula><mml:math id="M239" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> as equal to zero
outside <inline-formula><mml:math id="M240" display="inline"><mml:mrow><mml:mn mathvariant="normal">0</mml:mn><mml:mo>≤</mml:mo><mml:mi>t</mml:mi><mml:mo>≤</mml:mo><mml:mn mathvariant="normal">5</mml:mn><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:math></inline-formula>. Because no carbon dioxide is created or removed
inside the analysers, the time integral over <inline-formula><mml:math id="M241" display="inline"><mml:mrow><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> must be equal to one,
necessitating normalisation of the truncated response function:
              <disp-formula id="Ch1.E19" content-type="numbered"><mml:math id="M242" display="block"><mml:mrow><mml:msup><mml:mi>f</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mfenced open="{" close=""><mml:mtable class="array" columnalign="left left"><mml:mtr><mml:mtd><mml:mn mathvariant="normal">0</mml:mn></mml:mtd><mml:mtd><mml:mrow><mml:mi mathvariant="normal">if</mml:mi><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mi>t</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msup><mml:mi>e</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:mfrac></mml:mstyle></mml:mtd><mml:mtd><mml:mrow><mml:mi mathvariant="normal">if</mml:mi><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mn mathvariant="normal">0</mml:mn><mml:mo>≤</mml:mo><mml:mi>t</mml:mi><mml:mo>≤</mml:mo><mml:mn mathvariant="normal">5</mml:mn><mml:mi mathvariant="italic">τ</mml:mi></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd><mml:mn mathvariant="normal">0</mml:mn></mml:mtd><mml:mtd><mml:mrow><mml:mi mathvariant="normal">if</mml:mi><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mi>t</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">5</mml:mn><mml:mi mathvariant="italic">τ</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:mfenced></mml:mrow></mml:math></disp-formula>
            Through the measurement process both analysers effectively convolute the
<inline-formula><mml:math id="M243" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> signal present at the inlet of the sampling line with
their respective instrument function. To make the results comparable, we
convolute the measurements of each analyser with the instrument function of
<italic>the other</italic> analyser. If both measurements were perfect, this would
yield identical results because convolution is commutative:

                  <disp-formula specific-use="align" content-type="numbered"><mml:math id="M244" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E20"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">COCAP</mml:mi></mml:msub><mml:mo>⋅</mml:mo><mml:msub><mml:mi>f</mml:mi><mml:mi mathvariant="normal">CRDS</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>⋅</mml:mo><mml:msub><mml:mi>f</mml:mi><mml:mi mathvariant="normal">COCAP</mml:mi></mml:msub><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:msub><mml:mi>f</mml:mi><mml:mi mathvariant="normal">CRDS</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E21"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">Inlet</mml:mi></mml:msub><mml:mo>⋅</mml:mo><mml:msub><mml:mi>f</mml:mi><mml:mi mathvariant="normal">CRDS</mml:mi></mml:msub><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:msub><mml:mi>f</mml:mi><mml:mi mathvariant="normal">COCAP</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E22"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mo>=</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">CRDS</mml:mi></mml:msub><mml:mo>⋅</mml:mo><mml:msub><mml:mi>f</mml:mi><mml:mi mathvariant="normal">COCAP</mml:mi></mml:msub><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

              Here <inline-formula><mml:math id="M245" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">COCAP</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M246" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">CRDS</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are the CO<inline-formula><mml:math id="M247" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air
mole fractions<?pagebreak page1844?> measured by COCAP and the CRDS analysers, respectively.
Convoluting each analyser's measurement with the instrument function of the
other analyser can therefore be viewed as an equalisation of the flushing
times of both analysers.</p>
      <p id="d1e4925">We carried out the experiment with the Mobile Lab in Boulder, Colorado, USA,
on 15 October 2015. We drove up and down a road that covers 700 m in
elevation (1650–2360 m above sea level), exposing COCAP to the same
pressure changes that would occur during a flight at these altitudes. The
temperature inside the van increased from 14 <inline-formula><mml:math id="M248" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C to 20 <inline-formula><mml:math id="M249" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C
during the drive. Despite the substantial changes in ambient conditions, the
measurements from both analysers agree to within 2 <inline-formula><mml:math id="M250" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M251" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>
during most of the experiments (Fig. <xref ref-type="fig" rid="Ch1.F10"/>).</p>

      <fig id="Ch1.F10"><caption><p id="d1e4969"><bold>(a)</bold> CO<inline-formula><mml:math id="M252" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole
fraction <inline-formula><mml:math id="M253" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> of ambient air measured by COCAP and a CRDS
analyser during a car drive. The three step-like patterns originate from the
field calibration during which two gas standards are sampled. The peak at
09:16 occurred while waiting at a traffic light on a busy street.
<bold>(b)</bold> Difference and smoothed difference of <inline-formula><mml:math id="M254" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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>
measured by COCAP minus <inline-formula><mml:math id="M255" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measured by the CRDS analyser.
The smoothing is implemented by convolution with a Gauss window of 200 s
full width at half maximum. The measurements of both analysers have been
corrected using the field calibrations and the flushing times have been
equalised as explained in the text.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f10.png"/>

          </fig>

      <p id="d1e5037">Differences are mainly caused by limitations of the simple model for the
instrument functions, which become apparent during fast changes in
<inline-formula><mml:math id="M256" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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 by sensor noise. They are reduced to less than
1 <inline-formula><mml:math id="M257" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M258" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> when high-frequency variations are filtered out.
The negative bias of about <inline-formula><mml:math id="M259" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.8 <inline-formula><mml:math id="M260" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M261" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> observed between
09:55 and 10:15 LT might be the effect of
sunlight exposure. At the time of the experiment, the temperature
stabilisation described in Sect. <xref ref-type="sec" rid="Ch1.S2.SS1.SSS5"/> had
not yet been implemented, which is why COCAP was sensitive to changes in
ambient conditions.</p>
</sec>
<sec id="Ch1.S4.SS2.SSS2">
  <title>Lannemezan flights</title>
      <p id="d1e5109">The so far highest flight of COCAP on a UAS was carried out in Lannemezan,
France, on 20 May 2016 at 15:30 UTC (17:30 local time). COCAP was mounted
under a custom-built multicopter (Sensomotion UG, Germany, and
Ostwestfalen-Lippe University of Applied Sciences, Germany, Fig. S10 in the
Supplement). Starting from an elevation of 600 m above sea level a maximum
height of 430 m above ground level was reached. The flight took place under
clear sky in a light breeze (2 m s<inline-formula><mml:math id="M262" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> wind speed). It served as a
real-world test of COCAP's temperature stabilisation
(Fig. <xref ref-type="fig" rid="Ch1.F11"/>).</p>

      <fig id="Ch1.F11"><caption><p id="d1e5127">Stability of COCAP's internal
temperatures during a flight to a maximum height of <inline-formula><mml:math id="M263" display="inline"><mml:mrow><mml:mi>h</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">430</mml:mn></mml:mrow></mml:math></inline-formula> m above ground
level. <inline-formula><mml:math id="M264" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> is ambient pressure, <inline-formula><mml:math id="M265" display="inline"><mml:mi>T</mml:mi></mml:math></inline-formula> is temperature. Note the broken
temperature axis and the different scaling used for ambient, outlet and
detector temperature.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f11.png"/>

          </fig>

      <p id="d1e5162">While ambient pressure <inline-formula><mml:math id="M266" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> changed by 5 kPa and ambient temperature
<inline-formula><mml:math id="M267" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">Ambient</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> by 4.5 <inline-formula><mml:math id="M268" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C during the flight, the temperature
of the air stream at the CO<inline-formula><mml:math id="M269" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor's outlet <inline-formula><mml:math id="M270" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">Outlet</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
varied by only 0.13 <inline-formula><mml:math id="M271" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and the temperature of the optical detector
<inline-formula><mml:math id="M272" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">Detector</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> by only 0.02 <inline-formula><mml:math id="M273" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C.</p>
</sec>
<sec id="Ch1.S4.SS2.SSS3">
  <title>Comparison to the atmospheric observatory Lindenberg</title>
      <p id="d1e5248">In order to verify COCAP's in-flight measurements of ambient CO<inline-formula><mml:math id="M274" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air
mole fraction, we made a comparison to the atmospheric observatory
Lindenberg. The Lindenberg observatory is part of the Integrated Carbon
Observation System (ICOS, <uri>http://www.icos-ri.eu</uri>) and meets the World
Meteorological Organization (WMO) Global Atmosphere Watch (GAW)
recommendations for high-accuracy atmospheric trace gas measurements
<xref ref-type="bibr" rid="bib1.bibx30" id="paren.23"/>. The Lindenberg observatory (ICOS short name: LIN) is
located in the eastern part of Germany (52<inline-formula><mml:math id="M275" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>10<inline-formula><mml:math id="M276" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> N,
14<inline-formula><mml:math id="M277" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>07<inline-formula><mml:math id="M278" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> E) in a flat, rural<?pagebreak page1845?> area. At LIN a 99 m mast is
equipped with inlets at 2.5, 10, 40 and 98 m above ground level. Air is
drawn from all inlets continuously, but only one sampling line is analysed at
a time. The gas analyser is switched to a different sampling line every 5 min (“quasi-continuous sampling”). It measures carbon dioxide and
methane dry air mole fraction.</p>
      <p id="d1e5303">We mounted COCAP on the same multicopter that was used in Lannemezan (see
Sect. <xref ref-type="sec" rid="Ch1.S4.SS2.SSS2"/>) and carried out a total of 21 flights
close to the mast (distance less than 150 m) on 18 and 27 October 2016,
using the same setup on both days. During each flight, the multicopter
ascended vertically to 100 m above ground level at a climb rate of
0.5 m s<inline-formula><mml:math id="M279" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, followed by a descent at a rate of 2 m s<inline-formula><mml:math id="M280" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. The same
pattern was then repeated at approximately 70 m distance from the first
ascent. Each flight lasted 9 min and the two ascents were separated in time
by 4 min. The only exception was flight 7, which we had to abort after the
first ascent due to a technical problem with the multicopter.</p>
      <p id="d1e5332">In flight, the multicopter mixes the air around it. To avoid artefacts
in our measurements caused by this mixing, we sampled air from 70 cm
above the rotors. Furthermore, for the analysis detailed below we
used only the data collected during the ascents, i.e. when the UAS
was flying into and sampling undisturbed air. In each flight, we carried
out the second ascent upwind of the first ascent, which ensured that
the mixing caused by the first ascent did not degrade the measurements
during the second ascent.</p>
      <p id="d1e5335">On the evening of 18 October, the sky was cloudy with occasional drizzle, the
wind speed was low (1.5 m s<inline-formula><mml:math id="M281" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), and the lowest 100 m of the
atmosphere was weakly stable. On the early evening of 27 October, conditions
were similar, but without precipitation. After 21:00 LT on 27 October, the
sky cleared up, followed by the formation of radiation fog.</p>
      <p id="d1e5351">At the mast's 2.5 and 10 m inlets, the variability of the CO<inline-formula><mml:math id="M282" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air
mole fraction was larger than above due to respiration fluxes from soil and
vegetation that were intermittently mixed upwards by turbulence. This high
variability makes these levels less suitable for comparison to COCAP, as our
flights were not synchronised with the sampling at the mast. We were not
allowed to fly higher than 100 m; hence the 98 m inlet was not well covered
by the flight pattern. We therefore focus our comparison on the 40 m inlet
of the mast.</p>

      <?xmltex \floatpos{p}?><fig id="Ch1.F12"><caption><p id="d1e5365">Large dots represent calibrated
measurements taken by COCAP during the ascents at a height of
(40 <inline-formula><mml:math id="M283" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 10) m above ground, small dots are measurements from the LIN
mast's 40 m inlet. Times are in local time (UTC+2). The sun set at 18:02 LT
on 18 October and at 17:43 LT on 27 October. The gaps in the station data
are due to the measurement of other inlets and working tanks at those times.</p></caption>
            <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f12.png"/>

          </fig>

      <?xmltex \floatpos{p}?><fig id="Ch1.F13"><caption><p id="d1e5383"> <bold>(a)</bold> Data from COCAP are same as
in Fig <xref ref-type="fig" rid="Ch1.F12"/>. Measurements from the mast's
40 m inlet have been averaged over a period that starts 20 min before and
ends 20 min after the respective flight. No measurements from the mast are
available for flight 10 because calibration cylinders have been measured at
this time. <bold>(b)</bold> <inline-formula><mml:math id="M284" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measured by COCAP minus
<inline-formula><mml:math id="M285" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measured by LIN. Error bars indicate the noise level of
COCAP's CO<inline-formula><mml:math id="M286" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor after deconvolution (see text). Flights 1 through 9
were carried out on 18 October, flights 10 through 21 on 27 October
(indicated by dashed vertical line).</p></caption>
            <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://amt.copernicus.org/articles/11/1833/2018/amt-11-1833-2018-f13.png"/>

          </fig>

      <?pagebreak page1846?><p id="d1e5440">After applying the calibration curve to the measurements of COCAP's CO<inline-formula><mml:math id="M287" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>
sensor, we corrected for its temporal response by deconvolution. For each
ascent, we then calculated the arithmetic mean of the measurements taken
between a height of 30 and 50 m. Figure <xref ref-type="fig" rid="Ch1.F12"/>
shows these means together with the LIN measurements at 40 m plotted against
time. Overall, there is good agreement between COCAP and LIN. The variability
in COCAP's data is higher, likely caused by a low-pass effect of the mast's
sampling system. Further differences are due to the measurements being taken
100–150 m apart and at different times. Finally, instrument noise leads to
discrepancies. All these factors should have a zero mean effect, whereas a
consistent bias between COCAP and the Lindenberg observatory would indicate a
problem with the calibration. A change in bias over time would suggest
instrument drift.</p>
      <p id="d1e5454">To better assess the presence of bias, we averaged the measurements
from the mast's 40 m inlet over a period starting 20 min before
and ending 20 min after the respective flight (Fig. <xref ref-type="fig" rid="Ch1.F13"/>a).</p>
      <p id="d1e5460">We then calculated the difference between the measurements by COCAP and LIN
(Fig. <xref ref-type="fig" rid="Ch1.F13"/>b). Additionally, we estimated the noise level
of COCAP's CO<inline-formula><mml:math id="M288" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. The correction for COCAP's finite time response
by deconvolution has the side effect of amplifying high-frequency electronic
noise. Therefore, we did not use the Allan deviation of the data described in
Sect <xref ref-type="sec" rid="Ch1.S4.SS1.SSS1"/> but calculated the Allan deviation of the
deconvoluted time series. During each ascent, the multicopter climbed from 30
to 50 m height in approximately 40 s. In analysing a period during which a
standard gas was measured, we found an Allan deviation of
1 <inline-formula><mml:math id="M289" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M290" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for <inline-formula><mml:math id="M291" display="inline"><mml:mrow><mml:mi mathvariant="italic">τ</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">40</mml:mn></mml:mrow></mml:math></inline-formula> s. This number is represented as
error bars in Fig. <xref ref-type="fig" rid="Ch1.F13"/>b.</p>
      <p id="d1e5510">Table <xref ref-type="table" rid="Ch1.T3"/> contains the mean difference between the
measurements by COCAP and LIN. A bias of zero lies within 1 standard error
of the mean difference. This is also true for both nights considered
individually and for both ascents of all flights considered individually.
Table <xref ref-type="table" rid="Ch1.T4"/> lists the results of statistical tests of
three hypotheses: (1) no bias between COCAP and LIN, (2) no change in the
mean difference between COCAP and LIN from 18 October to 27 October and
(3) no change in the mean difference between COCAP and LIN from the first to
the second ascends. None of the hypotheses was rejected (<inline-formula><mml:math id="M292" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">0.7</mml:mn></mml:mrow></mml:math></inline-formula> in all
cases).</p>

<table-wrap id="Ch1.T3"><caption><p id="d1e5531">Mean of the difference between COCAP's
CO<inline-formula><mml:math id="M293" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction measurements <inline-formula><mml:math id="M294" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">COCAP</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and the
corresponding measurements by LIN <inline-formula><mml:math id="M295" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">LIN</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M296" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>1 standard error).
Subsets of COCAP's measurements are also analysed. </p></caption><oasis:table frame="topbot"><oasis:tgroup cols="2">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">COCAP measurements</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M297" display="inline"><mml:mover accent="true"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">COCAP</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">LIN</mml:mi></mml:msub></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">in <inline-formula><mml:math id="M298" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M299" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">All</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M300" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.23</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.45</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">18 October</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M301" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.16</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.85</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">27 October</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M302" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.28</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.49</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">All first ascents</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M303" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.39</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.66</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">All second ascents</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M304" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.06</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.52</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<table-wrap id="Ch1.T4"><caption><p id="d1e5738">Statistical tests for bias. Here <inline-formula><mml:math id="M305" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula>
denotes measurements by COCAP and the index defines a subset: “A”
for all measurements, “18” and “27” for 18 and 27 October, respectively,
and “A1” and “A2” for first and second ascent, respectively. <inline-formula><mml:math id="M306" display="inline"><mml:mrow><mml:mi>D</mml:mi><mml:mo>(</mml:mo><mml:mi>x</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>
represents the difference between <inline-formula><mml:math id="M307" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> and the corresponding measurements
by LIN. An overline denotes the arithmetic mean.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="3">
     <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:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Null hypothesis</oasis:entry>  
         <oasis:entry colname="col2">Statistical test</oasis:entry>  
         <oasis:entry colname="col3">Test result <inline-formula><mml:math id="M308" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M309" display="inline"><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mi>D</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">C</mml:mi></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">Welch's <inline-formula><mml:math id="M310" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> test</oasis:entry>  
         <oasis:entry colname="col3">0.75</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M311" display="inline"><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mi>D</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover><mml:mo>=</mml:mo><mml:mover accent="true"><mml:mrow><mml:mi>D</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mn mathvariant="normal">27</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">Welch's <inline-formula><mml:math id="M312" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> test</oasis:entry>  
         <oasis:entry colname="col3">0.72</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M313" display="inline"><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mi>D</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mrow><mml:mi mathvariant="normal">A</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover><mml:mo>=</mml:mo><mml:mover accent="true"><mml:mrow><mml:mi>D</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mrow><mml:mi mathvariant="normal">A</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">Student's <inline-formula><mml:math id="M314" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> test</oasis:entry>  
         <oasis:entry colname="col3">0.75</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e5962">The physical connection between COCAP and the multicopter did not include a
dedicated shock absorber (see Fig. S10 in the Supplement). Although COCAP's
plastic foam housing and the flexibility of the mounting straps provided
limited mechanical isolation, sudden movements and vibrations of the
multicopter due to turbulence, rotor unbalance and flight manoeuvres have
been partially transmitted to the measurement system. In theory, these
mechanical disturbances could deteriorate the accuracy of the
<inline-formula><mml:math id="M315" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measurements, e.g. by causing misalignment of the
optical bench of the CO<inline-formula><mml:math id="M316" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. The data collected during the flights
at LIN, however, do not exhibit increased noise levels or instrument drift
compared to data collected on the ground, suggesting that the movements and
vibrations did not degrade COCAP's performance.</p>
      <p id="d1e5989">We conclude that the measurements gave no indication of (1) calibration
problems, (2) uncorrected drift of COCAP between 18 and 27 October, (3) drift
of COCAP during flight or (4) degradation of COCAP's accuracy due to
vibrations and sudden movements of the multicopter.</p>
</sec>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <title>Summary and conclusions</title>
      <p id="d1e6001">With COCAP we have designed and built a self-contained analyser for the
measurement of CO<inline-formula><mml:math id="M317" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air mole fraction, temperature, humidity and
pressure of ambient air on board UASs. COCAP is typically operated under
ambient conditions that change quickly and over wide ranges. These
challenging conditions can compromise the accuracy of CO<inline-formula><mml:math id="M318" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensors. We
ensure COCAP's accuracy by (1) temperature stabilisation, (2) drying of
sample air, (3) a calibration curve that includes correction terms for
temperature and pressure and (4) regular field calibrations. When
high-frequency noise is filtered out, COCAP's measurements of CO<inline-formula><mml:math id="M319" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry
air mole fraction were found to deviate from a reference by not more than
1.2 <inline-formula><mml:math id="M320" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M321" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> during simulated flights and by not more than
1 <inline-formula><mml:math id="M322" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>mol mol<inline-formula><mml:math id="M323" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> during deployment in an instrumented van. In a
comparison to the ICOS observatory Lindenberg no indication of bias or
uncorrected drift was observed.</p>
      <p id="d1e6070">Since the design of COCAP, newer versions of SenseAir's HPP sensor family
have become available. They exhibit lower drift and lower noise at a slightly
smaller form factor <xref ref-type="bibr" rid="bib1.bibx2" id="paren.24"/>. The integration of
the newer sensors into COCAP would be straightforward and is expected to
further improve the accuracy of the <inline-formula><mml:math id="M324" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> measurements.</p>
      <p id="d1e6091">With a volume of 14 cm <inline-formula><mml:math id="M325" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 14 cm <inline-formula><mml:math id="M326" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 42 cm and a mass of 1 kg
COCAP fits onto small UASs with a take-off mass below 5 kg. It is therefore a
cost-effective tool to study carbon dioxide in the lowest 100–1000 m of
Earth's atmosphere. On<?pagebreak page1847?> a multicopter or fixed-wing aircraft, COCAP enables
measurements at a finer scale than manned aircraft and without restrictions
of minimum flight altitude. On a tethered balloon, COCAP can take
measurements for longer time spans without being bound to fixed altitudes
like an instrumented mast or tower.</p>
      <p id="d1e6108">The techniques presented in this article are applicable to other measurement
systems as well. Many sensors benefit from a stable temperature, and we have
shown how an effective temperature stabilisation can be achieved within the
mass, size and power restrictions of a small UAS. Likewise, the presented
method for obtaining a calibration curve can be applied to other gas sensors.
Regular calibrations are important to ensure the accuracy of trace gas
measurements and we have given an example how to implement them in a
practicable way.</p>
      <p id="d1e6112">Flying a CO<inline-formula><mml:math id="M327" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> analyser on small UASs opens up new possibilities in
studying the carbon cycle. As a first application we have constrained
nocturnal carbon dioxide fluxes of vegetation using series of
<inline-formula><mml:math id="M328" display="inline"><mml:mrow><mml:msub><mml:mi>x</mml:mi><mml:mrow><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> profiles in a budget method (Kunz et al., 2018). A
similar approach could be used to estimate CO<inline-formula><mml:math id="M329" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> emissions of cities,
ideally by simultaneously deploying several UASs at different downwind
locations. Furthermore, the strength of point sources like power plants or
factories could be estimated by applying a mass balance technique as is
commonly used in aircraft-based studies (<xref ref-type="bibr" rid="bib1.bibx7" id="altparen.25"/>
and references therein). The main advantages of small UASs over manned
aircraft in these applications is their full vertical coverage from the
ground to several hundred metres height and their much lower acquisition and
operating cost. As small unmanned aircraft are typically limited to a range
between 1 and 50 km in a single flight, they are best suited for studying
smaller areas. Their low air speed and high manoeuvrability enables them to
sample the atmosphere with high spatial resolution. Equipped with an analyser
for carbon dioxide, UASs could also become a powerful validation tool for
efforts to model dispersion of tracers on fine scales, e.g. inside street
canyons.</p>
      <p id="d1e6151">Due to their unique capabilities and low cost, we foresee that the use of
unmanned aircraft in the Earth sciences will significantly increase in the
near future. We have shown how accurate measurements of the CO<inline-formula><mml:math id="M330" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> dry air
mole fraction can be taken on board small UASs and we anticipate these
platforms to play an important role in closing gaps in the observation of the
carbon cycle.</p>
</sec>

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

      <p id="d1e6167">The analyses presented here are based on many different
experiments and use a combination of two or three different data sources in
most cases. Compiling the data into a uniform, self-describing collection
suitable for upload to a repository would be a great effort. Given the fact
that our experiments were aimed at characterising COCAP, reuse of the data by
other groups seems unlikely. Hence, we did not upload our measurement data to
a repository. However, data from individual experiments are available from the
corresponding author upon request.</p>

      <p id="d1e6170">Data from the ICOS station Lindenberg can be requested from ICOS-D
(<uri>http://www.icos-infrastruktur.de/en/mitarbeiter/atmosphaerenprogramm/</uri>).</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e6176"><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="https://doi.org/10.5194/amt-11-1833-2018-supplement" xlink:title="pdf">https://doi.org/10.5194/amt-11-1833-2018-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><notes notes-type="competinginterests">

      <p id="d1e6182">Christine Hummelgård, Hans Martin and Henrik
Rödjegård work for SenseAir AB, the manufacturer of the HPP sensor
family. The other authors declare that they have no conflict of interest.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e6188">We thank Maksym Bryzgalov (SenseAir AB, Sweden) for helping with the
configuration and integration of the CO<inline-formula><mml:math id="M331" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> sensor. Hök Instruments AB
(Sweden) kindly provided software for COCAP's data logger. We thank Wieland
Jeschag and Till Fastnacht for adapting this software to our needs. We
acknowledge Jürgen Kaulfuß, who designed and built the field calibration
device. Calibration standards were prepared by the gas lab of the MPI for
Biogeochemistry Jena and we are grateful for their support. We thank Frank
Beyrich, Matthias Lindauer, Udo Rummel and Marcus Schumacher (Deutscher
Wetterdienst, Germany) for access to the Lindenberg station, technical
support and data sharing. We gratefully acknowledge the authors of various
open-source software packages that were used in the project and for the
preparation of the manuscript, in particular GNU Octave (including the
<italic>optim</italic> package), KiCad, gnuplot, GIMP, Inkscape, LyX and LaTeX. We
thank the Max Planck Society for generous financial support. Martin Kunz thanks COST
(European Cooperation in Science and Technology) and the German Academic
Exchange Service (DAAD) for funding.<?xmltex \hack{\\\\}?> The article processing charges
for this open-access <?xmltex \hack{\newline}?> publication were covered by the Max
Planck Society.<?xmltex \hack{\\\\}?> Edited by: Russell Dickerson<?xmltex \hack{\\}?> Reviewed by:
two anonymous referees</p></ack><ref-list>
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