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

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.

Authors:
ORCiD logo [1];  [2];  [2];  [1];  [3]; ORCiD logo [4];  [5];  [2];  [6]; ORCiD logo [7];  [1];  [8];  [1];  [4];  [2];  [9];  [10];  [4]; ORCiD logo [11];  [12] more »;  [13];  [5];  [10];  [14];  [1];  [2];  [4];  [2];  [4];  [1];  [2];  [15]; ORCiD logo [16];  [17];  [18];  [19]; ORCiD logo [1] « less
+ Show Author Affiliations
  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
Publication Date:
Research Org.:
Carnegie Mellon Univ., Pittsburgh, PA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1513034
Alternate Identifier(s):
OSTI ID: 1508847; OSTI ID: 1513250
Grant/Contract Number:  
SC00014469; SC0014469
Resource Type:
Published Article
Journal Name:
ACS Earth and Space Chemistry
Additional Journal Information:
Journal Name: ACS Earth and Space Chemistry Journal Volume: 3 Journal Issue: 5; Journal ID: ISSN 2472-3452
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

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., and Dommen, Josef. Formation of Highly Oxygenated Organic Molecules from α-Pinene Ozonolysis: Chemical Characteristics, Mechanism, and Kinetic Model Development. United States: N. p., 2019. Web. doi:10.1021/acsearthspacechem.9b00035.
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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. Formation of Highly Oxygenated Organic Molecules from α-Pinene Ozonolysis: Chemical Characteristics, Mechanism, and Kinetic Model Development. United States. https://doi.org/10.1021/acsearthspacechem.9b00035
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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., and Dommen, Josef. Wed . "Formation of Highly Oxygenated Organic Molecules from α-Pinene Ozonolysis: Chemical Characteristics, Mechanism, and Kinetic Model Development". United States. https://doi.org/10.1021/acsearthspacechem.9b00035.
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@article{osti_1513034,
title = {Formation of Highly Oxygenated Organic Molecules from α-Pinene Ozonolysis: Chemical Characteristics, Mechanism, and Kinetic Model Development},
author = {Molteni, Ugo and Simon, Mario and Heinritzi, Martin and Hoyle, Christopher R. and Bernhammer, Anne-Kathrin and Bianchi, Federico and Breitenlechner, Martin and Brilke, Sophia and Dias, António and Duplissy, Jonathan and Frege, Carla and Gordon, Hamish and Heyn, Claudia and Jokinen, Tuija and Kürten, Andreas and Lehtipalo, Katrianne and Makhmutov, Vladimir and Petäjä, Tuukka and Pieber, Simone M. and Praplan, Arnaud P. and Schobesberger, Siegfried and Steiner, Gerhard and Stozhkov, Yuri and Tomé, António and Tröstl, Jasmin and Wagner, Andrea C. and Wagner, Robert and Williamson, Christina and Yan, Chao and Baltensperger, Urs and Curtius, Joachim and Donahue, Neil M. and Hansel, Armin and Kirkby, Jasper and Kulmala, Markku and Worsnop, Douglas R. and Dommen, Josef},
abstractNote = {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.},
doi = {10.1021/acsearthspacechem.9b00035},
journal = {ACS Earth and Space Chemistry},
number = 5,
volume = 3,
place = {United States},
year = {Wed Apr 03 00:00:00 EDT 2019},
month = {Wed Apr 03 00:00:00 EDT 2019}
}
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https://doi.org/10.1021/acsearthspacechem.9b00035
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