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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-2019-259
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-2019-259
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 17 Jul 2019

Submitted as: research article | 17 Jul 2019

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

Stability of Halocarbons in Whole Air Samples from the Upper Troposphere and Lowermost Stratosphere

Tanja J. Schuck1, Ann-Katrin Blank1, Elisa Rittmeier1, Jonathan Williams2, Carl A. M. Brenninkmeijer2, Andreas Engel1, and Andreas Zahn3 Tanja J. Schuck et al.
  • 1Goethe University Frankfurt, Germany
  • 2Max Planck Institute for Chemistry Mainz, Germany
  • 3Karlsruhe Institute of Technology, Germany

Abstract. Measurements of halogenated hydrocarbons in ambient air frequently rely on canister sampling followed by offline laboratory analysis. This allows for a large number of compounds to be analysed under stable conditions, maximising measurement precision. However, individual compounds might be affected during sampling and storage of canister samples. In order to assess halocarbon stability in whole air samples from the upper troposphere and lowermost stratosphere, we performed stability tests using the air sampling unit High REsolution Sampler (HIRES) which is part of the CARIBIC (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) instrument package. HIRES holds 88 light-weight stainless steel cylinders that are pressurized in flight to 4.5 bar using metal bellows pumps. The HIRES sampling unit was first deployed in 2010, but has up to now not been used for regular halocarbon analysis with exception of chloromethane. The sample collection unit was tested for sampling and storage effects of 28 halogenated compounds. The focus was on compound stability in the stainless steel canisters during storage of up to five weeks and on the influence of ozone, since flights take place in the upper troposphere and lowermost stratosphere with ozone mixing ratios of up to several hundred ppbV. Most of the investigated (hydro)chlorofluorocarbons and long-lived hydrofluorocarbons were found to be stable over a storage time of up to five weeks and were unaltered by ozone being present during pressurization. Some compounds such as for example dichloromethane, trichloromethane and tetrachloroethene started to decrease in the canisters after a storage time of more than two weeks or exhibited lowered mixing ratios in samples pressurized with ozone present. Few compounds such as for example tetrachloromethane and tribromomethane were found to be not stable in the HIRES stainless-steel canisters independent of ozone levels. Also growth was observed during storage for some species, namely for HFC-152a, HFC-23, and Halon-1301.

Tanja J. Schuck et al.
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Tanja J. Schuck et al.
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Short summary
Air sample collection aboard aircraft is a tool to measure atmospheric trace gas mixing ratios at altitude. We present results on the stability of 28 halocarbons during storage of air samples collected in stainless steel flasks inside an automated air sampling unit which is part of the CARIBIC instrument package. Selected fluorinated compounds grew during the experiments while short-lived compounds got depleted. Selected substances were additionally influenced by high mixing ratios of ozone.
Air sample collection aboard aircraft is a tool to measure atmospheric trace gas mixing ratios...
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