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Observational evidence for Criegee intermediate oligomerization reactions relevant to aerosol formation in the troposphere

Caravan, R. L. [Argonne National Laboratory (ANL), Argonne, IL (United States); California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Laboratory (JPL); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000229367952)·Bannan, T. J. [Univ. of Manchester (United Kingdom)] (ORCID:0000000217606522)·Winiberg, F. A. F. [California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Laboratory (JPL)]·Khan, M. A. H. [Univ. of Bristol (United Kingdom)] (ORCID:0000000178363344)·Rousso, A. C. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Princeton Univ., NJ (United States)] (ORCID:0000000257103233)·Jasper, A. W. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000302169347)·Worrall, S. D. [Aston Univ., Birmingham (United Kingdom); Univ. of Manchester (United Kingdom)] (ORCID:0000000319693671)·Bacak, A. [Ankara Univ. (Turkey); Univ. of Manchester (United Kingdom)]·Artaxo, P. [Univ. of Sao Paulo (Brazil)] (ORCID:0000000177543036)·Brito, J. [Univ. Lille (France)] (ORCID:0000000244209442)·Priestley, M. [IVL Swedish Environmental Research Inst., Gothenburg (Sweden); Univ. of Manchester (United Kingdom)]·Allan, J. D. [Univ. of Manchester (United Kingdom)] (ORCID:0000000164924876)·Coe, H. [Univ. of Manchester (United Kingdom)] (ORCID:0000000232641713)·Ju, Y. [Princeton Univ., NJ (United States); Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)] (ORCID:0000000256562075)·Osborn, D. L. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Univ. of California, Davis, CA (United States)]·Hansen, N. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000213750797)·Klippenstein, S. J. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000162979187)·Shallcross, D. E. [Univ. of Bristol (United Kingdom)] (ORCID:0000000176149221)·Taatjes, C. A. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000292710282)·Percival, C. J. [Univ. of Manchester (United Kingdom); California Institute of Technology (CalTech), Pasadena, CA (United States)] (ORCID:000000032525160X)
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Abstract

Criegee intermediates are reactive intermediates that are implicated in transforming the composition of Earth’s troposphere and in the formation of secondary organic aerosol, impacting Earth’s radiation balance, air quality and human health. Yet, direct identification of their signatures in the field remains elusive. Here, from particulate and gas-phase mass-spectrometric measurements in the Amazon rainforest, we identify sequences of masses consistent with the expected signatures of oligomerization of the CH 2 OO Criegee intermediate, a process implicated in ozonolysis-driven aerosol formation. In this study, we assess the potential contributions of oligomerization through laboratory ozonolysis experiments, direct kinetic studies of Criegee intermediate reactions, and high-level theoretical calculations. Global atmospheric models built on these kinetics results indicate that Criegee intermediate chemistry may play a larger role in altering the composition of Earth’s troposphere than is captured in current atmospheric models, especially in areas of high humidity. However, the models still capture only a relatively small fraction of the observed signatures, suggesting considerable underestimates of Criegee intermediate concentrations and reactivity and/or the dominance of other, presently uncharacterized, oxidation mechanisms. Resolving the remaining uncertainties in emission inventories and the effects of atmospheric water vapour on key chemical reactions will be required to definitively assess the role of Criegee intermediate oligomerization reactions.

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Caravan, R. L. [Argonne National Laboratory (ANL), Argonne, IL (United States); California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Laboratory (JPL); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000229367952), Bannan, T. J. [Univ. of Manchester (United Kingdom)] (ORCID:0000000217606522), Winiberg, F. A. F. [California Institute of Technology (CalTech), Pasadena, CA (United States). Jet Propulsion Laboratory (JPL)], Khan, M. A. H. [Univ. of Bristol (United Kingdom)] (ORCID:0000000178363344), Rousso, A. C. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Princeton Univ., NJ (United States)] (ORCID:0000000257103233), Jasper, A. W. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000302169347), Worrall, S. D. [Aston Univ., Birmingham (United Kingdom); Univ. of Manchester (United Kingdom)] (ORCID:0000000319693671), Bacak, A. [Ankara Univ. (Turkey); Univ. of Manchester (United Kingdom)], Artaxo, P. [Univ. of Sao Paulo (Brazil)] (ORCID:0000000177543036), Brito, J. [Univ. Lille (France)] (ORCID:0000000244209442), Priestley, M. [IVL Swedish Environmental Research Inst., Gothenburg (Sweden); Univ. of Manchester (United Kingdom)], Allan, J. D. [Univ. of Manchester (United Kingdom)] (ORCID:0000000164924876), Coe, H. [Univ. of Manchester (United Kingdom)] (ORCID:0000000232641713), Ju, Y. [Princeton Univ., NJ (United States); Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)] (ORCID:0000000256562075), Osborn, D. L. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Univ. of California, Davis, CA (United States)], Hansen, N. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000213750797), Klippenstein, S. J. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000162979187), Shallcross, D. E. [Univ. of Bristol (United Kingdom)] (ORCID:0000000176149221), Taatjes, C. A. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000292710282), Percival, C. J. [Univ. of Manchester (United Kingdom); California Institute of Technology (CalTech), Pasadena, CA (United States)] (ORCID:000000032525160X). 2024-03-05. Observational evidence for Criegee intermediate oligomerization reactions relevant to aerosol formation in the troposphere. https://doi.org/10.1038/s41561-023-01361-6

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