An experimental study of the reactivity of terpinolene and <i>β</i>-caryophyllene with the nitrate radical
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Published:2022-05-18
Issue:10
Volume:22
Page:6411-6434
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ISSN:1680-7324
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Container-title:Atmospheric Chemistry and Physics
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language:en
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Short-container-title:Atmos. Chem. Phys.
Author:
Fouqueau Axel, Cirtog Manuela, Cazaunau Mathieu, Pangui Edouard, Doussin Jean-François, Picquet-Varrault BénédicteORCID
Abstract
Abstract. Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. They can
rapidly react with the nitrate radical (NO3) during the nighttime to form a
number of functionalized products. Among them, organic nitrates (ONs) have
been shown to behave as reservoirs of reactive nitrogen and consequently
influence the ozone budget and secondary organic aerosols (SOAs), which are
known to have a direct and indirect effect on the radiative balance and
thus on climate. Nevertheless, BVOC + NO3 reactions remain poorly understood. Thus,
the primary purpose of this study is to furnish new kinetic and mechanistic
data for one monoterpene (C10H16), terpinolene, and one
sesquiterpene (C15H24), β-caryophyllene, using simulation
chamber experiments. These two compounds have been chosen in order to
complete the few experimental data existing in the literature. Rate
constants have been measured using both relative and absolute methods. They
have been measured to be (6.0 ± 3.8) ×10-11 and (1.8 ± 1.4) ×10-11 cm3 molec.−1 s−1 for
terpinolene and β-caryophyllene respectively. Mechanistic studies
have also been conducted in order to identify and quantify the main reaction
products. Total organic nitrates and SOA yields have been determined. Both
terpenes appear to be major ON precursors in both gas and particle phases
with formation yields of 69 % for terpinolene and 79 % for β-caryophyllene respectively. They are also major SOA precursors, with
maximum SOA yields of around 60 % for terpinolene and 90 % for β-caryophyllene. In order to support these observations, chemical analyses
of the gas-phase products were performed at the molecular scale using
a proton transfer reaction–time-of-flight–mass spectrometer (PTR-ToF-MS) and FTIR. Detected products allowed proposing chemical mechanisms
and providing explanations through peroxy and alkoxy reaction pathways.
Publisher
Copernicus GmbH
Subject
Atmospheric Science
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