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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 03 Jun 2019

Research article | 03 Jun 2019

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

Investigation of adsorption/desorption behavior of small volume cylinders and its relevance for atmospheric trace gas analysis

Ece Satar1,2, Peter Nyfeler1,2, Bernhard Bereiter1,2,3, Céline Pascale4, Bernhard Niederhauser4, and Markus Leuenberger1,2 Ece Satar et al.
  • 1Climate and Environmental Physics, Physics Institute, University of Bern, Bern, Switzerland
  • 2Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
  • 3Empa, Laboratory for Air Pollution / Environmental Technology, Dübendorf, Switzerland
  • 4Federal Institute of Metrology METAS, Bern, Switzerland

Abstract. Atmospheric trace gas measurements of greenhouse gases are critical in their precision and accuracy. In the past 5 years, atmospheric measurement and gas metrology communities have turned their attention to possible surface effects due to pressure and temperature variations during a standard cylinder’s lifetime. This study concentrates on this issue by introducing newly built small volume aluminum and steel cylinders which enable the investigation of trace gases and their affinity for adsorption/desorption on various surfaces over a set of temperature and pressure ranges. The presented experiments are designed to test the filling pressure dependencies up to 30 bar, and temperature dependencies from −10 °C up to 180 °C for these prototype cylinders. We present measurements of CO2, CH4, CO and H2O using a cavity ring down spectroscopy analyzer under these conditions. Moreover, we investigated CO2 amount fractions using a novel quantum cascade laser spectrometer system enabling measurements at pressures as a low as 5 mbar. This extensive dataset revealed that until pressures as low as 150 mbar the enhancement in the amount fraction of CO2 relative to its initial value (at 1200 mbar) is limited to 0.12 μmol mol−1 for the prototype aluminum cylinder. Up to 80 °C, the aluminum cylinder showed superior results and less response to varying temperature compared to the steel cylinder. For CO2, these changes were insignificant at 80 °C for the aluminum cylinder, whereas a 0.11 μmol mol−1 enhancement for the steel cylinder was observed. High temperature experiments showed that for both cylinders irreversible temperature effects occur especially above 130 °C.

Ece Satar et al.
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Short summary
Good quality measurements of atmospheric trace gases are only possible with regular calibrations and stable measurements from the standard cylinders. This study investigates instabilities due to surface effects on newly built aluminum and steel cylinders. We present measurements over a set of temperature and pressure ranges for the amount fractions of CO2, CO, CH4, and H2O using a commercial and a novel laser spectroscopic analyzer.
Good quality measurements of atmospheric trace gases are only possible with regular calibrations...