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
N1 - Funding Information:
Acknowledgements. We would like to thank CERN for supporting CLOUD with technical and financial resources. We also thank Theo Kurtén for valuable input on ion molecule collision frequencies. This research has received funding from the EC Seventh Framework Programme (Marie Curie Initial Training Network CLOUD-ITN no. 215072, MC-ITN CLOUD-TRAIN no. 316662, ERC-StG-ATMOGAIN no. 278277, ERC-Advanced ATMNUCLE grant no. 227463, ERC-StG-GASPARCON no. 714621 and ERC-StG-COALA no. 638703), the German Federal Ministry of Education and Research (project nos. 01LK0902A and 01LK1222A), the Swiss National Science Foundation (project nos. 200020_135307, 200020_152907, 20FI20_149002, 200021_140663 and and grant P2EZP2_168787), the Academy of Finland Center of Excellence programme (grant no. 307331), the Academy of Finland (CoE project no. 1118615, LASTU project no. 135054; 296628 and 299574), the Nessling Foundation, the Austrian Science Fund (FWF; project no. J3198-N21), the EU’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie (no. 656994), the Swedish Research Council, Vetenskapsrådet (grant no. 2011-5120), the Portuguese Foundation for Science and Technology (project no. CERN/FP/116387/2010), the Presidium of the Russian Academy of Sciences and the Russian Foundation for Basic Research (grants 08-02-91006-CERN and 12-02-91522-CERN), Dreyfus Award EP-11-117, the Davidow Foundation, the US National Science Foundation (grants AGS1136479, AGS1447056, AGS1439551 and CHE1012293), the US Department of Energy (grant DE-SC00014469) and the FP7 project BACCHUS (grant agreement 603445).
Funding Information:
We would like to thank CERN for supporting CLOUD with technical and financial resources. We also thank Theo Kurtén for valuable input on ion molecule collision frequencies. This research has received funding from the EC Seventh Framework Programme (Marie Curie Initial Training Network CLOUD-ITN no. 215072, MC-ITN CLOUD-TRAIN no. 316662, ERC-StG-ATMOGAIN no. 278277, ERC-Advanced ATMNUCLE grant no. 227463, ERC-StG-GASPARCON no. 714621 and ERC-StG-COALA no. 638703), the German Federal Ministry of Education and Research (project nos. 01LK0902A and 01LK1222A), the Swiss National Science Foundation (project nos. 200020-135307, 200020-152907, 20FI20-149002, 200021-140663 and and grant P2EZP2-168787), the Academy of Finland Center of Excellence programme (grant no. 307331), the Academy of Finland (CoE project no. 1118615, LASTU project no. 135054; 296628 and 299574), the Nessling Foundation, the Austrian Science Fund (FWF; project no. J3198-N21), the EU's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie (no. 656994), the Swedish Research Council, Vetenskapsrådet (grant no. 2011-5120), the Portuguese Foundation for Science and Technology (project no. CERN/FP/116387/2010), the Presidium of the Russian Academy of Sciences and the Russian Foundation for Basic Research (grants 08-02-91006-CERN and 12-02-91522-CERN), Dreyfus Award EP-11-117, the Davidow Foundation, the US National Science Foundation (grants AGS1136479, AGS1447056, AGS1439551 and CHE1012293), the US Department of Energy (grant DE-SC00014469) and the FP7 project BACCHUS (grant agreement 603445).
Publisher Copyright:
© Author(s) 2018.
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 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 20-50 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 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 20-50 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.
UR - http://www.scopus.com/inward/record.url?scp=85042451097&partnerID=8YFLogxK
U2 - 10.5194/acp-18-2363-2018
DO - 10.5194/acp-18-2363-2018
M3 - Article
AN - SCOPUS:85042451097
SN - 1680-7316
VL - 18
SP - 2363
EP - 2380
JO - Atmospheric Chemistry and Physics
JF - Atmospheric Chemistry and Physics
IS - 4
ER -