ROOOH: a missing piece of the puzzle for ...
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DOI :
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Title :
ROOOH: a missing piece of the puzzle for OH measurements in low-NO environments?
Author(s) :
Fittschen, Christa [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Al Ajami, Mohamad [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
BATUT, Sebastien [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Ferracci, Valerio [Auteur]
University of Cambridge [UK] [CAM]
Archer-Nicholls, Scott [Auteur]
University of Cambridge [UK] [CAM]
Archibald, Alexander T. [Auteur]
National Centre for Atmospheric Science [Leeds] [NCAS]
Schoemaecker, Coralie [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]

Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Al Ajami, Mohamad [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
BATUT, Sebastien [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Ferracci, Valerio [Auteur]
University of Cambridge [UK] [CAM]
Archer-Nicholls, Scott [Auteur]
University of Cambridge [UK] [CAM]
Archibald, Alexander T. [Auteur]
National Centre for Atmospheric Science [Leeds] [NCAS]
Schoemaecker, Coralie [Auteur]

Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Journal title :
Atmospheric Chemistry and Physics
Abbreviated title :
Atmos. Chem. Phys.
Volume number :
19
Pages :
349-362
Publisher :
Copernicus GmbH
Publication date :
2019-01-10
ISSN :
1680-7324
HAL domain(s) :
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Chimie/Chimie théorique et/ou physique
Chimie/Chimie théorique et/ou physique
English abstract : [en]
Field campaigns have been carried out with the FAGE (fluorescence assay by
gas expansion) technique in remote biogenic environments in the last decade
to quantify the in situ concentrations of OH, the main oxidant in ...
Show more >Field campaigns have been carried out with the FAGE (fluorescence assay by gas expansion) 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 (volatile organic compounds), 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: using a pre-injector, all ambient OH is removed by fast reaction before entering the FAGE cell, and any remaining OH signal can be attributed to an interference. This technique is now systematically used for FAGE measurements, allowing the reliable quantification of ambient OH concentrations along with the signal due to interference OH. However, the disagreement between modelled and measured high OH concentrations of earlier field campaigns as well as the origin of the now-quantifiable background OH is still not understood. We present in this paper the compelling idea that this interference, and thus the disagreement between model and measurement in earlier field campaigns, might be at least partially due to the unexpected decomposition of a new class of molecule, ROOOH, within the FAGE instruments. This idea is based on experiments, obtained with the FAGE set-up of the University of Lille, and supported by a modelling study. Even though the occurrence of this interference will be highly dependent on the design and measurement conditions of different FAGE instruments, including ROOOH in atmospheric chemistry models might reflect a missing piece of the puzzle in our understanding of OH in clean atmospheres.Show less >
Show more >Field campaigns have been carried out with the FAGE (fluorescence assay by gas expansion) 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 (volatile organic compounds), 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: using a pre-injector, all ambient OH is removed by fast reaction before entering the FAGE cell, and any remaining OH signal can be attributed to an interference. This technique is now systematically used for FAGE measurements, allowing the reliable quantification of ambient OH concentrations along with the signal due to interference OH. However, the disagreement between modelled and measured high OH concentrations of earlier field campaigns as well as the origin of the now-quantifiable background OH is still not understood. We present in this paper the compelling idea that this interference, and thus the disagreement between model and measurement in earlier field campaigns, might be at least partially due to the unexpected decomposition of a new class of molecule, ROOOH, within the FAGE instruments. This idea is based on experiments, obtained with the FAGE set-up of the University of Lille, and supported by a modelling study. Even though the occurrence of this interference will be highly dependent on the design and measurement conditions of different FAGE instruments, including ROOOH in atmospheric chemistry models might reflect a missing piece of the puzzle in our understanding of OH in clean atmospheres.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Non spécifiée
Administrative institution(s) :
Université de Lille
CNRS
CNRS
Research team(s) :
PhysicoChimie de l'Atmosphère (PCA)
Submission date :
2020-10-07T12:40:13Z
2020-10-08T07:59:52Z
2020-10-08T07:59:52Z
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