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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
  1. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  2. Goethe Univ., Frankfurt (Germany)
  3. Ionicon GesmbH, Innsbruck (Austria)
  4. Univ. of Helsinki (Finland)
  5. Univ. of Innsbruck (Austria)
  6. Univ. of Lisbon (Portugal)
  7. Univ. of Helsinki (Finland); Helsinki Inst. of Physics (Finland)
  8. Univ. of Leeds (United Kingdom)
  9. Univ. of Helsinki (Finland); Finnish Meteorological Inst. (FMI), Helsinki (Finland)
  10. Russian Academy of Sciences (RAS), Moscow (Russian Federation)
  11. ETH Zurich (Switzerland)
  12. Finnish Meteorological Inst. (FMI), Helsinki (Finland)
  13. Univ. of Helsinki (Finland); Univ. of Eastern Finland, Kuopio (Finland)
  14. Univ. da Beira Interior, Covilhã (Portugal). Instituto Dom Luiz (IDL)
  15. Carnegie Mellon Univ., Pittsburgh, PA (United States)
  16. Ionicon GesmbH, Innsbruck (Austria); Univ. of Innsbruck (Austria)
  17. Goethe Univ., Frankfurt (Germany); European Organization for Nuclear Research (CERN), Geneva (Switzerland)
  18. Univ. of Helsinki (Finland); Helsinki Inst. of Physics (Finland); Beijing Univ. of Chemical Technology (China)
  19. Univ. of Helsinki (Finland); Aerodyne Research, Inc., Billerica, MA (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) (SC-22)
OSTI Identifier:
1513034
Alternate Identifier(s):
OSTI ID: 1508847; OSTI ID: 1513250
Grant/Contract Number:  
SC0014469; SC00014469
Resource Type:
Published Article
Journal Name:
ACS Earth and Space Chemistry
Additional Journal Information:
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.
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. doi:10.1021/acsearthspacechem.9b00035.
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. doi:10.1021/acsearthspacechem.9b00035.
@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 = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acsearthspacechem.9b00035

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