Hydrotrioxide (ROOOH) formation in the atmosphere

Creators: Berndt, Torsten; Chen, Jing; Kjærgaard, Eva R.; Møller, Kristian H.; Tilgner, Andreas; Hoffmann, Erik H.; Herrmann, Hartmut; Crounse, John D.; Wennberg, Paul O.; Kjaergaard, Henrik G.

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.

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.

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