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Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation

Frege, Carla and Flagan, Richard C. (2018) Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation. Atmospheric Chemistry and Physics, 18 (1). pp. 65-79. ISSN 1680-7316. https://resolver.caltech.edu/CaltechAUTHORS:20180119-152905326

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Abstract

It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1–2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α-pinene at 5 °C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and −25 °C). Most negative HOM clusters include a nitrate (NO_3−) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH_4+) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ∼ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (−25 °C), the presence of C30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.5194/acp-18-65-2018DOIArticle
https://www.atmos-chem-phys.net/18/65/2018/PublisherArticle
https://doi.org/10.5281/zenodo.1133985DOIData
ORCID:
AuthorORCID
Flagan, Richard C.0000-0001-5690-770X
Additional Information:© 2018 Author(s). This work is distributed under the Creative Commons Attribution 3.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 05 May 2017 – Discussion started: 29 May 2017. Revised: 31 Oct 2017 – Accepted: 10 Nov 2017 – Published: 04 Jan 2018. Data availability: Data related to this article are available online at https://doi.org/10.5281/zenodo.1133985. We would like to thank CERN for supporting CLOUD with important technical and financial resources, and for providing a particle beam from the CERN Proton Synchrotron. We also thank P. Carrie, L.-P. De Menezes, J. Dumollard, K. Ivanova, F. Josa, I. Krasin, R. Kristic, A. Laassiri, O. S. Maksumov, B. Marichy, H. Martinati, S. V. Mizin, R. Sitals, A. Wasem and M. Wilhelmsson for their important contributions to the experiment. 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, the ERC-Starting grant MOCAPAF no. 57360, the ERC-Consolidator grant NANODYNAMITE no. 616075 and ERC-Advanced grant ATMNUCLE no. 227463), European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 656994, the PEGASOS project funded by the European Commission under the Framework Programme 7 (FP7-ENV-2010-265148), the German Federal Ministry of Education and Research (project nos. 01LK0902A and 01LK1222A), the Swiss National Science Foundation (project nos. 200020_152907, 206021_144947 and 20FI20_159851), the Academy of Finland (Center of Excellence project no. 1118615), the Academy of Finland (135054, 133872, 251427, 139656, 139995, 137749, 141217, 141451, 299574), the Finnish Funding Agency for Technology and Innovation, the Väisälä Foundation, the Nessling Foundation, the University of Innsbruck research grant for young scientists (Cluster Calibration Unit), the Portuguese Foundation for Science and Technology (project no. CERN/FP/116387/2010), the Swedish Research Council, Vetenskapsrådet (grant 2011-5120), the Presidium of the Russian Academy of Sciences and Russian Foundation for Basic Research (grants 08-02-91006-CERN and 12-02-91522-CERN), the US National Science Foundation (grants AGS1447056, and AGS1439551), and the Davidow Foundation. We thank the tofTools team for providing tools for mass spectrometry analysis. The authors declare that they have no conflict of interest.
Funders:
Funding AgencyGrant Number
CERNUNSPECIFIED
Marie Curie Fellowship215072
Marie Curie Fellowship316662
European Research Council (ERC)57360
European Research Council (ERC)616075
European Research Council (ERC)227463
Marie Curie Fellowship656994
European Research Council (ERC)265148 PEGASOS
Bundesministerium für Bildung und Forschung (BMBF)01LK0902A
Bundesministerium für Bildung und Forschung (BMBF)01LK1222A
Swiss National Science Foundation (SNSF)200020_152907
Swiss National Science Foundation (SNSF)206021_144947
Swiss National Science Foundation (SNSF)20FI20_159851
Academy of Finland1118615
Academy of Finland135054
Academy of Finland133872
Academy of Finland251427
Academy of Finland139656
Academy of Finland139995
Academy of Finland137749
Academy of Finland141217
Academy of Finland141451
Academy of Finland299574
Finnish Funding Agency for Technology and InnovationUNSPECIFIED
Väisälä FoundationUNSPECIFIED
Nessling FoundationUNSPECIFIED
University of InnsbruckUNSPECIFIED
Fundação para a Ciência e a Tecnologia (FCT)CERN/FP/116387/2010
Swedish Research CouncilUNSPECIFIED
Vetenskapsrådet2011-5120
Presidium of the Russian Academy of SciencesUNSPECIFIED
Russian Foundation for Basic Research08-02-91006-CERN
Russian Foundation for Basic Research12-02-91522-CERN
NSFAGS-1447056
NSFAGS-1439551
Davidow FoundationUNSPECIFIED
Issue or Number:1
Record Number:CaltechAUTHORS:20180119-152905326
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180119-152905326
Official Citation:Frege, C., Ortega, I. K., Rissanen, M. P., Praplan, A. P., Steiner, G., Heinritzi, M., Ahonen, L., Amorim, A., Bernhammer, A.-K., Bianchi, F., Brilke, S., Breitenlechner, M., Dada, L., Dias, A., Duplissy, J., Ehrhart, S., El-Haddad, I., Fischer, L., Fuchs, C., Garmash, O., Gonin, M., Hansel, A., Hoyle, C. R., Jokinen, T., Junninen, H., Kirkby, J., Kürten, A., Lehtipalo, K., Leiminger, M., Mauldin, R. L., Molteni, U., Nichman, L., Petäjä, T., Sarnela, N., Schobesberger, S., Simon, M., Sipilä, M., Stolzenburg, D., Tomé, A., Vogel, A. L., Wagner, A. C., Wagner, R., Xiao, M., Yan, C., Ye, P., Curtius, J., Donahue, N. M., Flagan, R. C., Kulmala, M., Worsnop, D. R., Winkler, P. M., Dommen, J., and Baltensperger, U.: Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation, Atmos. Chem. Phys., 18, 65-79, https://doi.org/10.5194/acp-18-65-2018, 2018.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:84431
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:20 Jan 2018 00:27
Last Modified:03 Oct 2019 19:18

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