Formation of Highly Oxygenated Organic Molecules from alpha-Pinene Ozonolysis

Chemical Characteristics, Mechanism, and Kinetic Model Development

Ugo Molteni, Mario Simon, Martin Heinritzi, Christopher R. Hoyle, Anne-Kathrin Bernhammer, Federico Bianchi, Martin Breitenlechner, Sophia Brilke, António Dias, Jonathan Duplissy, Carla Frege, Hamish Gordon, Claudia Heyn, Tuija Jokinen, Andreas Kürten, Katrianne Lehtipalo, Vladimir Makhmutov, Tuukka Petäjä, Simone M. Pieber, Arnaud P. Praplan & 17 others Siegfried Schobesberger, Gerhard Steiner, Yuri Stozhkov, António Tomé, Jasmin Tröstl, Andrea C. Wagner, Robert Wagner, Christina Williamson, Chao Yan, Urs Baltensperger, Joachim Curtius, Neil M. Donahue, Armin Hansel, Jasper Kirkby, Markku Kulmala, Douglas R. Worsnop, Josef Dommen

Research output: Contribution to journalArticleScientificpeer-review

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.
Original languageEnglish
JournalACS Earth and Space Chemistry
Volume3
Issue number5
Pages (from-to)873-883
Number of pages11
ISSN2472-3452
DOIs
Publication statusPublished - May 2019
MoE publication typeA1 Journal article-refereed

Fields of Science

  • 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

Cite this

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 alpha-Pinene Ozonolysis : Chemical Characteristics, Mechanism, and Kinetic Model Development. In: ACS Earth and Space Chemistry. 2019 ; Vol. 3, No. 5. pp. 873-883.
@article{410d05b9d00642c997c930d31710d5cf,
title = "Formation of Highly Oxygenated Organic Molecules from alpha-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.",
keywords = "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",
author = "Ugo Molteni and Mario Simon and Martin Heinritzi and Hoyle, {Christopher R.} and Anne-Kathrin Bernhammer and Federico Bianchi and Martin Breitenlechner and Sophia Brilke and Ant{\'o}nio Dias and Jonathan Duplissy and Carla Frege and Hamish Gordon and Claudia Heyn and Tuija Jokinen and Andreas K{\"u}rten and Katrianne Lehtipalo and Vladimir Makhmutov and Tuukka Pet{\"a}j{\"a} and Pieber, {Simone M.} and Praplan, {Arnaud P.} and Siegfried Schobesberger and Gerhard Steiner and Yuri Stozhkov and Ant{\'o}nio Tom{\'e} and Jasmin Tr{\"o}stl and Wagner, {Andrea C.} and Robert Wagner and Christina Williamson and Chao Yan and Urs Baltensperger and Joachim Curtius and Donahue, {Neil M.} and Armin Hansel and Jasper Kirkby and Markku Kulmala and Worsnop, {Douglas R.} and Josef Dommen",
year = "2019",
month = "5",
doi = "10.1021/acsearthspacechem.9b00035",
language = "English",
volume = "3",
pages = "873--883",
journal = "ACS Earth and Space Chemistry",
issn = "2472-3452",
publisher = "American Chemical Society Journals",
number = "5",

}

Molteni, U, Simon, M, Heinritzi, M, Hoyle, CR, 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, SM, Praplan, AP, Schobesberger, S, Steiner, G, Stozhkov, Y, Tomé, A, Tröstl, J, Wagner, AC, Wagner, R, Williamson, C, Yan, C, Baltensperger, U, Curtius, J, Donahue, NM, Hansel, A, Kirkby, J, Kulmala, M, Worsnop, DR & 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

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

In: ACS Earth and Space Chemistry, Vol. 3, No. 5, 05.2019, p. 873-883.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Formation of Highly Oxygenated Organic Molecules from alpha-Pinene Ozonolysis

T2 - Chemical Characteristics, Mechanism, and Kinetic Model Development

AU - Molteni, Ugo

AU - Simon, Mario

AU - Heinritzi, Martin

AU - Hoyle, Christopher R.

AU - Bernhammer, Anne-Kathrin

AU - Bianchi, Federico

AU - Breitenlechner, Martin

AU - Brilke, Sophia

AU - Dias, António

AU - Duplissy, Jonathan

AU - Frege, Carla

AU - Gordon, Hamish

AU - Heyn, Claudia

AU - Jokinen, Tuija

AU - Kürten, Andreas

AU - Lehtipalo, Katrianne

AU - Makhmutov, Vladimir

AU - Petäjä, Tuukka

AU - Pieber, Simone M.

AU - Praplan, Arnaud P.

AU - Schobesberger, Siegfried

AU - Steiner, Gerhard

AU - Stozhkov, Yuri

AU - Tomé, António

AU - Tröstl, Jasmin

AU - Wagner, Andrea C.

AU - Wagner, Robert

AU - Williamson, Christina

AU - Yan, Chao

AU - Baltensperger, Urs

AU - Curtius, Joachim

AU - Donahue, Neil M.

AU - Hansel, Armin

AU - Kirkby, Jasper

AU - Kulmala, Markku

AU - Worsnop, Douglas R.

AU - Dommen, Josef

PY - 2019/5

Y1 - 2019/5

N2 - 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.

AB - 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.

KW - 116 Chemical sciences

KW - HOM

KW - terpene oxidation

KW - autoxidation

KW - dimers

KW - peroxy radicals

KW - chamber study

KW - CLOUD

KW - atmospheric oxidation mechanism

KW - OXIDIZED RO2 RADICALS

KW - GAS-PHASE OZONOLYSIS

KW - MULTIFUNCTIONAL PRODUCTS

KW - TROPOSPHERIC DEGRADATION

KW - SULFURIC-ACID

KW - AUTOXIDATION

KW - PROTOCOL

KW - FIELD

KW - NO2

U2 - 10.1021/acsearthspacechem.9b00035

DO - 10.1021/acsearthspacechem.9b00035

M3 - Article

VL - 3

SP - 873

EP - 883

JO - ACS Earth and Space Chemistry

JF - ACS Earth and Space Chemistry

SN - 2472-3452

IS - 5

ER -