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Preprints
https://doi.org/10.5194/acp-2020-504
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2020-504
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

  08 Jun 2020

08 Jun 2020

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A revised version of this preprint was accepted for the journal ACP and is expected to appear here in due course.

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinene

Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault Axel Fouqueau et al.
  • Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), UMR 7583, CNRS, Université Paris-Est-Créteil et Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil, France

Abstract. Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. During the night, they react very rapidly with the nitrate radical (NO3), leading to the formation of a variety of functionalized products including organic nitrates and to large amounts of secondary organic aerosols (SOA). Organic nitrates (ONs) 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 while SOA are known to play a direct and indirect role on the climate. However, the reactivity of BVOCs with NO3 remains poorly studied. The aim of this work is to provide new kinetic and mechanistic data for two monoterpenes (C10H16), α- and γ-terpinene, through experiments in simulation chambers. These two compounds, which have very similar chemical structures, have been chosen in order to fill the lack of experimental data but also to highlight the influence of the chemical structure on the reactivity.

Rate constants have been measured using both relative and absolute methods. They were found to be (1.2 ± 0.5) x 10-10 and (2.9 ± 1.1) x 10-11 cm3 molecule-1 s-1 for α- and γ-terpinene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrate and SOA yields have been determined. While organic nitrate formation yields appear to be similar, SOA yields exhibit large differences with γ-terpinene being a much more efficient precursor of aerosols. In order to provide explanations for this difference, chemical analysis of the gas phase products were performed at the molecular scale. Detected products allowed proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

Axel Fouqueau et al.

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Axel Fouqueau et al.

Axel Fouqueau et al.

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