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Discussion papers
https://doi.org/10.5194/acp-2019-801
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2019-801
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 20 Sep 2019

Submitted as: research article | 20 Sep 2019

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

Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone

Bénédicte Picquet-Varrault1, Ricardo Suarez-Bertoa2, Marius Duncianu3, Mathieu Cazaunau1, Edouard Pangui1, Marc David1, and Jean-François Doussin1 Bénédicte Picquet-Varrault et al.
  • 1LISA, UMR CNRS 7583, Université Paris-Est Créteil, Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil, France
  • 2European Commission Joint Research Centre (JRC), Ispra, Italy
  • 3System Analyst Interscience BV, Brussels, Belgium

Abstract. Multifunctional organic nitrates, including carbonyl nitrates, are important species formed in NOx rich atmospheres by the degradation of VOCs. These compounds have been shown to play a key role in the transport of reactive nitrogen and consequently in the ozone budget, but also to be important components of the total organic aerosol. However, very little is known about their reactivity in both gas and condensed phases. Following a previous study we published on the gas-phase reactivity of β-nitrooxy ketones, the photolysis and the reaction with OH radicals of 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, respectively a β-nitrooxy ketone and a γ-nitrooxy ketone, were investigated for the first time in simulation chambers. Ambient photolysis frequencies calculated for 40° latitude North were found to be (4.2 ± 0.6) × 10−5 s−1 and (2.2 ± 0.7) × 10−5 s−1 for 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, respectively. These results demonstrate that photolysis is a very efficient sink for these compounds with atmospheric lifetimes of few hours. It was also concluded that, similarly to α-nitrooxy ketones, β-nitrooxy ketones have enhanced UV absorption cross sections and quantum yields equal or close to unity. γ-nitrooxy ketones have been shown to have lower enhancement of cross sections which can easily be explained by the increasing distance between the two chromophore groups. Thanks to a products study, branching ratio between the two possible photodissociation pathways are also proposed. Rate constants for the reaction with OH radicals were found to be (2.9 ± 1.0) × 10−12 cm3 molecule−1 s−1 and (3.3 ± 0.9) × 10−12 cm3 molecule−1 s−1, respectively. These experimental data are in good agreement with rate constants estimated by the SAR of Kwok and Atkinson (1995) when using the parametrization proposed by Suarez-Bertoa et al. (2012) for carbonyl nitrates. Comparison with photolysis rates suggests that OH-initiated oxidation of carbonyl nitrates is a less efficient sink that photodissociation but is not negligible in polluted area.

Bénédicte Picquet-Varrault et al.
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Short summary
Multifunctional organic nitrates are important atmospheric species which are known to play a key role in the transport of reactive nitrogen and in the aerosol composition. However, very little is known about their atmospheric reactivity. Here we provide an experimental study to investigate the photolysis and the reaction with OH radicals of two carbonyl nitrates. Atmospheric implications and influence of the chemical structure on the reactivity are discussed.
Multifunctional organic nitrates are important atmospheric species which are known to play a key...
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