Formation of Highly Oxygenated Organic Molecules from alpha-Pinene Ozonolysis : Chemical Characteristics, Mechanism, and Kinetic Model Development

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Molteni , U , Simon , M , Heinritzi , M , Hoyle , C R , Bernhammer , A-K , Bianchi , F , Breitenlechner , M , Brilke , S , Dias , A , Duplissy , J , Frege , C , Gordon , H , Heyn , C , Jokinen , T , Kürten , A , Lehtipalo , K , Makhmutov , V , Petäjä , T , Pieber , S M , Praplan , A P , Schobesberger , S , Steiner , G , Stozhkov , Y , Tomé , A , Tröstl , J , Wagner , A C , Wagner , R , Williamson , C , Yan , C , Baltensperger , U , Curtius , J , Donahue , N M , Hansel , A , Kirkby , J , Kulmala , M , Worsnop , D R & Dommen , J 2019 , ' Formation of Highly Oxygenated Organic Molecules from alpha-Pinene Ozonolysis : Chemical Characteristics, Mechanism, and Kinetic Model Development ' , ACS Earth and Space Chemistry , vol. 3 , no. 5 , pp. 873-883 . https://doi.org/10.1021/acsearthspacechem.9b00035

Title: Formation of Highly Oxygenated Organic Molecules from alpha-Pinene Ozonolysis : Chemical Characteristics, Mechanism, and Kinetic Model Development
Author: Molteni, Ugo; Simon, Mario; Heinritzi, Martin; Hoyle, Christopher R.; Bernhammer, Anne-Kathrin; Bianchi, Federico; Breitenlechner, Martin; Brilke, Sophia; Dias, António; Duplissy, Jonathan; Frege, Carla; Gordon, Hamish; Heyn, Claudia; Jokinen, Tuija; Kürten, Andreas; Lehtipalo, Katrianne; Makhmutov, Vladimir; Petäjä, Tuukka; Pieber, Simone M.; Praplan, Arnaud P.; Schobesberger, Siegfried; Steiner, Gerhard; Stozhkov, Yuri; Tomé, António; Tröstl, Jasmin; Wagner, Andrea C.; Wagner, Robert; Williamson, Christina; Yan, Chao; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Hansel, Armin; Kirkby, Jasper; Kulmala, Markku; Worsnop, Douglas R.; Dommen, Josef
Other contributor: University of Helsinki, Institute for Atmospheric and Earth System Research (INAR)
University of Helsinki, Helsinki Institute of Physics
University of Helsinki, INAR Physics
University of Helsinki, Institute for Atmospheric and Earth System Research (INAR)
University of Helsinki, Institute for Atmospheric and Earth System Research (INAR)
University of Helsinki, Finnish Meteorological Institute (FMI)
University of Helsinki, INAR Physics
University of Helsinki, INAR Physics
University of Helsinki, INAR Physics
University of Helsinki, Institute for Atmospheric and Earth System Research (INAR)
University of Helsinki, INAR Physics



Date: 2019-05
Language: eng
Number of pages: 11
Belongs to series: ACS Earth and Space Chemistry
ISSN: 2472-3452
DOI: https://doi.org/10.1021/acsearthspacechem.9b00035
URI: http://hdl.handle.net/10138/302522
Abstract: Terpenes are emitted by vegetation, and their oxidation in the atmosphere is an important source of secondary organic aerosol (SOA). A part of this oxidation can proceed through an autoxidation process, yielding highly oxygenated organic molecules (HOMs) with low saturation vapor pressure. They can therefore contribute, even in the absence of sulfuric acid, to new particle formation (NPF). The understanding of the autoxidation mechanism and its kinetics is still far from complete. Here, we present a mechanistic and kinetic analysis of mass spectrometry data from α-pinene (AP) ozonolysis experiments performed during the CLOUD 8 campaign at CERN. We grouped HOMs in classes according to their identified chemical composition and investigated the relative changes of these groups and their components as a function of the reagent concentration. We determined reaction rate constants for the different HOM peroxy radical reaction pathways. The accretion reaction between HOM peroxy radicals was found to be extremely fast. We developed a pseudo-mechanism for HOM formation and added it to the AP oxidation scheme of the Master Chemical Mechanism (MCM). With this extended model, the observed concentrations and trends in HOM formation were successfully simulated.
Subject: 116 Chemical sciences
HOM
terpene oxidation
autoxidation
dimers
peroxy radicals
chamber study
CLOUD
atmospheric oxidation mechanism
OXIDIZED RO2 RADICALS
GAS-PHASE OZONOLYSIS
MULTIFUNCTIONAL PRODUCTS
TROPOSPHERIC DEGRADATION
SULFURIC-ACID
AUTOXIDATION
PROTOCOL
FIELD
NO2
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