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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 α-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 (SO 2) 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 somemore » 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 20–50min 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 there action parameters more comprehensive for broader use.« less
Authors:
 [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1] ; ORCiD logo [3] ;  [4] ;  [5] ; ORCiD logo [6] ;  [7] ;  [4] ;  [4] ;  [8] ;  [9] ; ORCiD logo [1] ; ORCiD logo [1] ;  [10] ;  [1] ;  [11] more »;  [12] ; ORCiD logo [8] ; ORCiD logo [13] ; ORCiD logo [7] ; ORCiD logo [4] ; ORCiD logo [9] ; ORCiD logo [1] ;  [14] ; ORCiD logo [1] ; ORCiD logo [15] ;  [1] « less
  1. Univ. of Helsinki, Helsinki (Finland)
  2. Univ. of Eastern Finland, Kuopio (Finland)
  3. Univ. of Helsinki, Helsinki (Finland); Univ. of Eastern Finland, Kuopio (Finland); Univ. of Washington, Seattle, WA (United States)
  4. Goethe Univ. Frankfurt, Frankfurt am Main (Germany)
  5. Goethe Univ. Frankfurt, Frankfurt am Main (Germany); Max-Planck Institute of Chemistry, Mainz (Germany)
  6. Univ. of Helsinki, Helsinki (Finland); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  7. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  8. Univ. of Innsbruck, Innsbruck (Austria)
  9. Univ. of California, Irvine, CA (United States)
  10. Finnish Meteorological Institute, Helsinki (Finland)
  11. CENTRA, Lisbon (Portugal)
  12. Tofwerk AG, Thun (Switzerland)
  13. Goethe Univ. Frankfurt, Frankfurt am Main (Germany); European Organization for Nuclear Research (CERN), Geneva (Switzerland)
  14. Univ. of Helsinki, Helsinki (Finland); Aerodyne Research Inc., Billerica, MA (United States)
  15. Univ. of Helsinki, Helsinki (Finland); Carnegie Mellon Univ., Pittsburgh, PA (United States)
Publication Date:
Grant/Contract Number:
SC0014469
Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 18; Journal Issue: 4; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Research Org:
Univ. of California, Irvine, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES
OSTI Identifier:
1505587

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., and Sipilä, Mikko. Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber. United States: N. p., Web. doi:10.5194/acp-18-2363-2018.
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. United States. doi:10.5194/acp-18-2363-2018.
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., and Sipilä, Mikko. 2018. "Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber". United States. doi:10.5194/acp-18-2363-2018. https://www.osti.gov/servlets/purl/1505587.
@article{osti_1505587,
title = {Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber},
author = {Sarnela, Nina and Jokinen, Tuija and Duplissy, Jonathan and Yan, Chao and Nieminen, Tuomo and Ehn, Mikael and Schobesberger, Siegfried and Heinritzi, Martin and Ehrhart, Sebastian and Lehtipalo, Katrianne and Tröstl, Jasmin and Simon, Mario and Kürten, Andreas and Leiminger, Markus and Lawler, Michael J. and Rissanen, Matti P. and Bianchi, Federico and Praplan, Arnaud P. and Hakala, Jani and Amorim, Antonio and Gonin, Marc and Hansel, Armin and Kirkby, Jasper and Dommen, Josef and Curtius, Joachim and Smith, James N. and Petäjä, Tuukka and Worsnop, Douglas R. and Kulmala, Markku and Donahue, Neil M. and Sipilä, Mikko},
abstractNote = {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 α-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 (H2), 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 20–50min 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 there action parameters more comprehensive for broader use.},
doi = {10.5194/acp-18-2363-2018},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 4,
volume = 18,
place = {United States},
year = {2018},
month = {2}
}