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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Discussion papers
https://doi.org/10.5194/amt-2019-130
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-2019-130
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 05 Apr 2019

Research article | 05 Apr 2019

Review status
This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Measurement Techniques (AMT).

Caution with Spectroscopic NO2 Reference Cells (Cuvettes)

Ulrich Platt1,2 and Jonas Kuhn1,2 Ulrich Platt and Jonas Kuhn
  • 1Institute of Environmental Physics (IUP), Heidelberg University, INF 229, D-69120 Heidelberg, Germany
  • 2Max Planck Institute for Chemistry, Mainz, Germany

Abstract. Spectroscopic measurements of atmospheric trace gases, e.g. by Differential Optical Absorption Spectroscopy (DOAS) are frequently supported by recording the trace gas column density (CD) in absorption cells (cuvettes), which are temporarily inserted into the light-path. The idea is to verify the proper working of the instruments, to check the spectral registration (wavelength calibration and spectral resolution), and to perform some kind of calibration (absolute determination of trace gas CDs). In principle DOAS applications do not require absorption cell calibration, however in practice measurements with absorption cells in the spectrometer’s light path are frequently performed. In addition, trace gas absorption cells are used as a central component in gas correlation spectroscopy instruments.

Here we show at the example of NO2 absorption cells that the effective CD seen by the instrument can deviate greatly from expected values (by orders of magnitude). Analytical calculations and kinetic model studies show the dominating influence of photolysis and dimerisation of NO2. In particular, this means that the partial pressure of NO2 in the cell matters. However, problems can be particular severe at high NO2 pressures (around 105 Pa) as well as low NO2 partial pressures (of the order of a few 100 Pa). Also, it can be of importance whether the cell contains pure NO2 or is topped up with air or oxygen (O2). Some suggestions to improve the situation are discussed.

Ulrich Platt and Jonas Kuhn
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Ulrich Platt and Jonas Kuhn
Ulrich Platt and Jonas Kuhn
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Latest update: 20 Apr 2019
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Short summary
Measurements of atmospheric trace gases by absorption spectroscopy, are frequently supported by recording the amount of trace gas in absorption cells. These are typically small glass (or quartz) cylinders containing the gas to be studied. Here we show at the example of NO2 absorption cells that the effective amount of gas seen by the instrument can deviate greatly from expected values (by orders of magnitude in severe cases). Some suggestions to improve the situation are discussed.
Measurements of atmospheric trace gases by absorption spectroscopy, are frequently supported by...
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