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Discussion papers | Copyright
https://doi.org/10.5194/acp-2018-441
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 05 Jun 2018

Research article | 05 Jun 2018

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

ROOOH: the Missing Piece of the Puzzle for OH measurements in low NO Environments

Christa Fittschen1, Mohamad Al Ajami1, Sebastien Batut1, Valerio Ferracci2,3, Scott Archer-Nicholls2, Alexander T. Archibald2,4, and Coralie Schoemaecker1 Christa Fittschen et al.
  • 1Université Lille, CNRS, UMR 8522, PhysicoChimie des Processus de Combustion et de l’Atmosphère – PC2A, Lille, 59000, France
  • 2University of Cambridge, Centre for Atmospheric Science, Department of Chemistry, Lensfield Road, Cambridge, CB2 1EW, UK
  • 3Cranfield University, Centre for Environmental and Agricultural Informatics, College Road, Cranfield MK43 0AL, UK
  • 4National Centre for Atmospheric Science, Cambridge, UK

Abstract. Field campaigns have been carried out with the FAGE technique in remote biogenic environments in the last decade to quantify the in situ concentrations of OH, the main oxidant in the atmosphere. These data have revealed concentrations of OH radicals up to a factor of 10 higher than predicted by models, whereby the disagreement increases with decreasing NO concentration. This was interpreted as a major lack in our understanding of the chemistry of biogenic VOCs, particularly isoprene, which are dominant in remote pristine conditions. But interferences in these measurements of unknown origin have also been discovered for some FAGE instruments. We present in this paper convincing experimental and modeling evidence that the disagreement between model and measurement is due to interference by the unexpected decomposition of a new class of molecule, ROOOH, in the FAGE instruments. Including ROOOH reflects the missing piece of the puzzle in our understanding of OH in the atmosphere.

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Short summary
Concentrations of OH, the main oxidant in the atmosphere, were measured in biogenic environments up to a factor of 10 higher than predicted by models. This was interpreted as a major lack in our understanding of the chemistry of biogenic VOCs. But interferences of unknown origin have also been discovered and here we present experimental and modeling evidence that the interference is due to the unexpected decomposition of a new class of molecule, ROOOH, in the FAGE instruments.
Concentrations of OH, the main oxidant in the atmosphere, were measured in biogenic environments...
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