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Hydrotrioxide (ROOOH) formation in the atmosphere

Berndt, Torsten and Chen, Jing and Kjærgaard, Eva R. and Møller, Kristian H. and Tilgner, Andreas and Hoffmann, Erik H. and Herrmann, Hartmut and Crounse, John D. and Wennberg, Paul O. and Kjaergaard, Henrik G. (2022) Hydrotrioxide (ROOOH) formation in the atmosphere. Science, 376 (6596). pp. 979-982. ISSN 0036-8075. doi:10.1126/science.abn6012. https://resolver.caltech.edu/CaltechAUTHORS:20220531-369780600

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Abstract

Organic hydrotrioxides (ROOOH) are known to be strong oxidants used in organic synthesis. Previously, it has been speculated that they are formed in the atmosphere through the gas-phase reaction of organic peroxy radicals (RO₂) with hydroxyl radicals (OH). Here, we report direct observation of ROOOH formation from several atmospherically relevant RO₂ radicals. Kinetic analysis confirmed rapid RO₂ + OH reactions forming ROOOH, with rate coefficients close to the collision limit. For the OH-initiated degradation of isoprene, global modeling predicts molar hydrotrioxide formation yields of up to 1%, which represents an annual ROOOH formation of about 10 million metric tons. The atmospheric lifetime of ROOOH is estimated to be minutes to hours. Hydrotrioxides represent a previously omitted substance class in the atmosphere, the impact of which needs to be examined.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1126/science.abn6012DOIArticle
https://doi.org/10.17894/UCPH.99BF9F39-EC48-4AFE-B426-CF6EF0D3EA70DOIROOOH-archive
https://doi.org/10.5281/zenodo.6373045DOIECHAM-HAMMOZ model output files
ORCID:
AuthorORCID
Berndt, Torsten0000-0003-2014-6018
Chen, Jing0000-0001-6545-6197
Kjærgaard, Eva R.0000-0001-8838-0084
Møller, Kristian H.0000-0001-8070-8516
Tilgner, Andreas0000-0003-4021-4874
Hoffmann, Erik H.0000-0003-4560-0125
Herrmann, Hartmut0000-0001-7044-2101
Crounse, John D.0000-0001-5443-729X
Wennberg, Paul O.0000-0002-6126-3854
Kjaergaard, Henrik G.0000-0002-7275-8297
Additional Information:© 2022 the authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original US government works. https://www.science.org/about/science-licenses-journal-article-reuse. Submitted 8 December 2021; accepted 20 April 2022. The authors thank A. Rohmer and K. Pielok for technical assistance and the tofTools team for providing the data analysis tools. This work used resources of the Deutsches Klimarechenzentrum (DKRZ) granted by its Scientific Steering Committee (WLA) under project ID bb1128. H.G.K. acknowledges funding from the Independent Research Fund Denmark (9040-00142B) and the High Performance Computing Center at the University of Copenhagen. E.H.H. and H.H. acknowledge funding from the German Research Foundation (project ORIGAMY, no. 447349939). P.O.W. and J.D.C. received financial support from the US National Science Fund (CHE-1905340). P.O.W. and H.G.K. received funding from the Alfred P. Sloan Foundation under award no. G-2019-12281. Author contributions: Conceptualization: T.B. and H.G.K. Methodology: All authors. Experiments: T.B. and J.D.C. Calculations: J.C., E.R.K., K.H.M., and H.G.K. Global modeling: A.T., E.H.H., H.H., and P.O.W. Writing – original draft: T.B. and H.G.K. Writing – review and editing: All authors. The authors declare that they have no competing interests. Data and materials availability: All theoretical calculation output files are available online through the public research data archive of the University of Copenhagen (25). All ECHAM-HAMMOZ model output files are available online through the public research data archive Zenodo (26). All other data are available in the main text or the supplementary materials.
Funders:
Funding AgencyGrant Number
Independent Research Fund Denmark9040-00142B
University of CopenhagenUNSPECIFIED
Deutsche Forschungsgemeinschaft (DFG)447349939
NSFCHE-1905340
Alfred P. Sloan FoundationG-2019-12281
Issue or Number:6596
DOI:10.1126/science.abn6012
Record Number:CaltechAUTHORS:20220531-369780600
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220531-369780600
Official Citation:Hydrotrioxide (ROOOH) formation in the atmosphere. Torsten Berndt, Jing Chen, Eva R. Kjærgaard, Kristian H. Møller, Andreas Tilgner, Erik H. Hoffmann, Hartmut Herrmann, John D. Crounse, Paul O. Wennberg, Henrik G. Kjaergaard. Science, 376 (6596); DOI: 10.1126/science.abn6012
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114957
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:31 May 2022 16:06
Last Modified:31 May 2022 16:06

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