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

Journal Article · Wed Apr 03 00:00:00 EDT 2019 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.9b00035· OSTI ID:1513034

Molteni, Ugo  ^[1]; Simon, Mario ^[2]; Heinritzi, Martin ^[2]; Hoyle, Christopher R. ^[1]; Bernhammer, Anne-Kathrin ^[3]; Bianchi, Federico  ^[4]; Breitenlechner, Martin ^[5]; Brilke, Sophia ^[2]; Dias, António ^[6]; Duplissy, Jonathan  ^[7]; Frege, Carla ^[1]; Gordon, Hamish ^[8]; Heyn, Claudia ^[1]; Jokinen, Tuija ^[4]; Kürten, Andreas ^[2]; Lehtipalo, Katrianne ^[9]; Makhmutov, Vladimir ^[10]; Petäjä, Tuukka ^[4]; Pieber, Simone M.  ^[11]; Praplan, Arnaud P. ^[12] ; Schobesberger, Siegfried ^[13]; Steiner, Gerhard ^[5]; Stozhkov, Yuri ^[10]; Tomé, António ^[14]; Tröstl, Jasmin ^[1]; Wagner, Andrea C. ^[2]; Wagner, Robert ^[4]; Williamson, Christina ^[2]; Yan, Chao ^[4]; Baltensperger, Urs ^[1]; Curtius, Joachim ^[2]; Donahue, Neil M. ^[15]; Hansel, Armin  ^[16]; Kirkby, Jasper ^[17]; Kulmala, Markku ^[18]; Worsnop, Douglas R. ^[19]; Dommen, Josef  ^[1]

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1. Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerland
2. Institute for Atmospheric and Environmental Sciences, Goethe University Frankfurt, 60438 Frankfurt am Main, Germany
3. Ionicon GesmbH, 6020 Innsbruck, Austria
4. Institute for Atmospheric and Earth System Research (INAR)/Physics, Faculty of Science, University of Helsinki, Post Office Box 64, FI-00014 Helsinki, Finland
5. Institute for Ion and Applied Physics, University of Innsbruck, 6020 Innsbruck, Austria
6. Faculty of Sciences, University of Lisbon, Campo Grande 016, 1749-016 Lisboa, Portugal
7. Institute for Atmospheric and Earth System Research (INAR)/Physics, Faculty of Science, University of Helsinki, Post Office Box 64, FI-00014 Helsinki, Finland, Helsinki Institute of Physics, FI-00014 Helsinki, Finland
8. University of Leeds, Leeds LS2 9JT, United Kingdom
9. Institute for Atmospheric and Earth System Research (INAR)/Physics, Faculty of Science, University of Helsinki, Post Office Box 64, FI-00014 Helsinki, Finland, Finnish Meteorological Institute, Erik Palménin Aukio 1, 00560 Helsinki, Finland
10. Lebedev Physical Institute of the Russian Academy of Sciences, Leninsky Prospekt 53, 119991 Moscow, Russia
11. Department of Environmental Systems Science, ETH Zurich, 8092 Zürich, Switzerland
12. Finnish Meteorological Institute, Erik Palménin Aukio 1, 00560 Helsinki, Finland
13. Institute for Atmospheric and Earth System Research (INAR)/Physics, Faculty of Science, University of Helsinki, Post Office Box 64, FI-00014 Helsinki, Finland, Department of Applied Physics, University of Eastern Finland, Post Office Box 1627, 70211 Kuopio, Finland
14. Instituto Dom Luiz (IDL), Universidade da Beira Interior, 6201-001 Covilhã, Portugal
15. Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
16. Ionicon GesmbH, 6020 Innsbruck, Austria, Institute for Ion and Applied Physics, University of Innsbruck, 6020 Innsbruck, Austria
17. Institute for Atmospheric and Environmental Sciences, Goethe University Frankfurt, 60438 Frankfurt am Main, Germany, CERN, CH-1211 Geneva, Switzerland
18. Institute for Atmospheric and Earth System Research (INAR)/Physics, Faculty of Science, University of Helsinki, Post Office Box 64, FI-00014 Helsinki, Finland, Helsinki Institute of Physics, FI-00014 Helsinki, Finland, Aerosol and Haze Laboratory, Beijing University of Chemical Technology, Beijing 100029, China
19. Institute for Atmospheric and Earth System Research (INAR)/Physics, Faculty of Science, University of Helsinki, Post Office Box 64, FI-00014 Helsinki, Finland, Aerodyne Research, Incorporated, 45 Manning Road, Billerica, Massachusetts 01821, United States

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.

• Research Organization: Carnegie Mellon Univ., Pittsburgh, PA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: SC00014469; SC0014469
• OSTI ID: 1513034
• Alternate ID(s): OSTI ID: 1508847; OSTI ID: 1513250
• Journal Information: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Vol. 3 Journal Issue: 5; ISSN 2472-3452
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
atmospheric oxidation mechanism
autoxidation
chamber study
CLOUD
dimers
HOM
peroxy radicals
terpene oxidation
HOM
terpene oxidation
autoxidation
dimers
peroxy radicals
chamber study
CLOUD
atmospheric oxidation mechanism