Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber

Nina Sarnela, Tuija Jokinen, Jonathan Duplissy, Chao Yan, Tuomo Nieminen, Mikael Ehn, Siegfried Schobesberger, Martin Heinritzi, Sebastian Ehrhart, Katrianne Lehtipalo, Jasmin Tröstl, Mario Simon, Andreas Kürten, Markus Leiminger, Michael J. Lawler, Matti P. Rissanen, Federico Bianchi, Arnaud P. Praplan, Jani Hakala, Antonio Amorim & 11 others Marc Gonin, Armin Hansel, Jasper Kirkby, Josef Dommen, Joachim Curtius, James N. Smith, Tuukka Petäjä, Douglas R. Worsnop, Markku Kulmala, Neil M. Donahue, Mikko Sipilä

Research output: Contribution to journalArticleScientificpeer-review

Abstract

Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate alpha-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H-2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5-6.5% for HOM formation and 22-32% for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20-50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

Original languageEnglish
JournalAtmospheric Chemistry and Physics
Volume18
Issue number4
Pages (from-to)2363-2380
Number of pages18
ISSN1680-7316
DOIs
Publication statusPublished - 19 Feb 2018
MoE publication typeA1 Journal article-refereed

Fields of Science

  • 114 Physical sciences
  • VOLATILE ORGANIC-COMPOUNDS
  • IONIZATION MASS-SPECTROMETRY
  • ATMOSPHERIC SULFURIC-ACID
  • GAS-PHASE OZONOLYSIS
  • PARTICLE FORMATION
  • AEROSOL FORMATION
  • CHEMICAL-IONIZATION
  • OXIDATION-PRODUCTS
  • GROWTH-RATES
  • WATER-VAPOR

Cite this

Sarnela, Nina ; Jokinen, Tuija ; Duplissy, Jonathan ; Yan, Chao ; Nieminen, Tuomo ; Ehn, Mikael ; Schobesberger, Siegfried ; Heinritzi, Martin ; Ehrhart, Sebastian ; Lehtipalo, Katrianne ; Tröstl, Jasmin ; Simon, Mario ; Kürten, Andreas ; Leiminger, Markus ; Lawler, Michael J. ; Rissanen, Matti P. ; Bianchi, Federico ; Praplan, Arnaud P. ; Hakala, Jani ; Amorim, Antonio ; Gonin, Marc ; Hansel, Armin ; Kirkby, Jasper ; Dommen, Josef ; Curtius, Joachim ; Smith, James N. ; Petäjä, Tuukka ; Worsnop, Douglas R. ; Kulmala, Markku ; Donahue, Neil M. ; Sipilä, Mikko. / Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber. In: Atmospheric Chemistry and Physics. 2018 ; Vol. 18, No. 4. pp. 2363-2380.
@article{2bbad543d5964f798a1088fe193fe987,
title = "Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber",
abstract = "Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate alpha-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H-2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5-6.5{\%} for HOM formation and 22-32{\%} for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20-50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.",
keywords = "114 Physical sciences, VOLATILE ORGANIC-COMPOUNDS, IONIZATION MASS-SPECTROMETRY, ATMOSPHERIC SULFURIC-ACID, GAS-PHASE OZONOLYSIS, PARTICLE FORMATION, AEROSOL FORMATION, CHEMICAL-IONIZATION, OXIDATION-PRODUCTS, GROWTH-RATES, WATER-VAPOR",
author = "Nina Sarnela and Tuija Jokinen and Jonathan Duplissy and Chao Yan and Tuomo Nieminen and Mikael Ehn and Siegfried Schobesberger and Martin Heinritzi and Sebastian Ehrhart and Katrianne Lehtipalo and Jasmin Tr{\"o}stl and Mario Simon and Andreas K{\"u}rten and Markus Leiminger and Lawler, {Michael J.} and Rissanen, {Matti P.} and Federico Bianchi and Praplan, {Arnaud P.} and Jani Hakala and Antonio Amorim and Marc Gonin and Armin Hansel and Jasper Kirkby and Josef Dommen and Joachim Curtius and Smith, {James N.} and Tuukka Pet{\"a}j{\"a} and Worsnop, {Douglas R.} and Markku Kulmala and Donahue, {Neil M.} and Mikko Sipil{\"a}",
year = "2018",
month = "2",
day = "19",
doi = "10.5194/acp-18-2363-2018",
language = "English",
volume = "18",
pages = "2363--2380",
journal = "Atmospheric Chemistry and Physics",
issn = "1680-7316",
publisher = "COPERNICUS GESELLSCHAFT MBH",
number = "4",

}

Sarnela, N, Jokinen, T, Duplissy, J, Yan, C, Nieminen, T, Ehn, M, Schobesberger, S, Heinritzi, M, Ehrhart, S, Lehtipalo, K, Tröstl, J, Simon, M, Kürten, A, Leiminger, M, Lawler, MJ, Rissanen, MP, Bianchi, F, Praplan, AP, Hakala, J, Amorim, A, Gonin, M, Hansel, A, Kirkby, J, Dommen, J, Curtius, J, Smith, JN, Petäjä, T, Worsnop, DR, Kulmala, M, Donahue, NM & Sipilä, M 2018, 'Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber', Atmospheric Chemistry and Physics, vol. 18, no. 4, pp. 2363-2380. https://doi.org/10.5194/acp-18-2363-2018

Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber. / Sarnela, Nina; Jokinen, Tuija; Duplissy, Jonathan; Yan, Chao; Nieminen, Tuomo; Ehn, Mikael; Schobesberger, Siegfried; Heinritzi, Martin; Ehrhart, Sebastian; Lehtipalo, Katrianne; Tröstl, Jasmin; Simon, Mario; Kürten, Andreas; Leiminger, Markus; Lawler, Michael J.; Rissanen, Matti P.; Bianchi, Federico; Praplan, Arnaud P.; Hakala, Jani; Amorim, Antonio; Gonin, Marc; Hansel, Armin; Kirkby, Jasper; Dommen, Josef; Curtius, Joachim; Smith, James N.; Petäjä, Tuukka; Worsnop, Douglas R.; Kulmala, Markku; Donahue, Neil M.; Sipilä, Mikko.

In: Atmospheric Chemistry and Physics, Vol. 18, No. 4, 19.02.2018, p. 2363-2380.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber

AU - Sarnela, Nina

AU - Jokinen, Tuija

AU - Duplissy, Jonathan

AU - Yan, Chao

AU - Nieminen, Tuomo

AU - Ehn, Mikael

AU - Schobesberger, Siegfried

AU - Heinritzi, Martin

AU - Ehrhart, Sebastian

AU - Lehtipalo, Katrianne

AU - Tröstl, Jasmin

AU - Simon, Mario

AU - Kürten, Andreas

AU - Leiminger, Markus

AU - Lawler, Michael J.

AU - Rissanen, Matti P.

AU - Bianchi, Federico

AU - Praplan, Arnaud P.

AU - Hakala, Jani

AU - Amorim, Antonio

AU - Gonin, Marc

AU - Hansel, Armin

AU - Kirkby, Jasper

AU - Dommen, Josef

AU - Curtius, Joachim

AU - Smith, James N.

AU - Petäjä, Tuukka

AU - Worsnop, Douglas R.

AU - Kulmala, Markku

AU - Donahue, Neil M.

AU - Sipilä, Mikko

PY - 2018/2/19

Y1 - 2018/2/19

N2 - Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate alpha-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H-2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5-6.5% for HOM formation and 22-32% for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20-50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

AB - Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate alpha-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H-2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5-6.5% for HOM formation and 22-32% for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20-50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

KW - 114 Physical sciences

KW - VOLATILE ORGANIC-COMPOUNDS

KW - IONIZATION MASS-SPECTROMETRY

KW - ATMOSPHERIC SULFURIC-ACID

KW - GAS-PHASE OZONOLYSIS

KW - PARTICLE FORMATION

KW - AEROSOL FORMATION

KW - CHEMICAL-IONIZATION

KW - OXIDATION-PRODUCTS

KW - GROWTH-RATES

KW - WATER-VAPOR

U2 - 10.5194/acp-18-2363-2018

DO - 10.5194/acp-18-2363-2018

M3 - Article

VL - 18

SP - 2363

EP - 2380

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

SN - 1680-7316

IS - 4

ER -