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 CH2OO Criegee intermediate, a process implicated in ozonolysis-driven aerosol formation. 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.
| Original language | English |
|---|---|
| Pages (from-to) | 219-226 |
| Number of pages | 8 |
| Journal | Nature Geoscience |
| Volume | 17 |
| Issue number | 3 |
| Early online date | 5 Mar 2024 |
| DOIs | |
| Publication status | Published - 5 Mar 2024 |
Bibliographical note
Copyright © UChicago Argonne, LLC Operator of Argonne National Laboratory and NASA Jet Propulsion Laboratory, under exclusive licence to Springer Nature Limited, 2024. This version of the article has been accepted for publication, after peer review and is subject to Springer Nature’s AM terms of use [https://www.springernature.com/gp/open-research/policies/accepted-manuscript-terms], but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: https://doi.org/10.1038/s41561-023-01361-6Data Access Statement
The data supporting the findings of this study are shown as figures or tables available in the main text or Supplementary Information, and are available alongside the master equation input and output files at https://doi.org/10.5281/zenodo.10267863.The codes used for the theoretical kinetics work are available at https://tcg.cse.anl.gov/papr/, https://github.com/auto-mech, https://comp.chem.umn.edu/dint/ and https://github.com/Auto-Mech/PIPPy, or are commercially available. The codes used for the atmospheric modelling work are available at https://github.com/chmahk/stochem.
Funding
This material is based on work supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences (BES), US Department of Energy (USDOE; R.L.C., A.C.R., A.W.J., D.L.O., N.H., S.J.K. and C.A.T.). Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for USDOE’s National Nuclear Security Administration under contract DE-NA0003525. Argonne National Laboratory is supported by the USDOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences under contract no. DE-AC02-06CH11357. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. The contributions of R.L.C. were in part supported by an appointment to the National Aeronautics and Space Administration (NASA) Postdoctoral Program at the NASA Jet Propulsion Laboratory, administered by the Universities Space Research Association under contract with NASA. This research was carried out in part by the Jet Propulsion Laboratory, California Institute of Technology, under contract with the NASA, supported by the Upper Atmosphere Research and Tropospheric Chemistry program (F.A.F.W. and C.J.P). D.E.S. and M.A.H.K. were supported by NERC (NE/K004905/1), the Primary Science Teaching Trust and Bristol ChemLabS. The fieldwork was supported by the FAPESP-University of Manchester SPRINT initiative (T.J.B., S.D.W., A.B., M.P., J.D.A., H.C. and C.J.P.). P.A. acknowledges funding from FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo, 2017/17047-0 and 2023/04358-9). Y.J. was partly supported by grants from the DOE Plasma Science Center (DE-SC0020233), DOE BES (DE-AC0209CH11466), and the National Science Foundation (NSF-EFRI CBET-2029425). IMT Nord Europe (J.B.) acknowledges financial support from the Labex CaPPA project, funded by the French National Research Agency (ANR, contract ANR-11-LABX-0005-01) and the CPER ECRIN, financed by the Regional Council ‘Hauts-de-France’ and the European Regional Development Fund (ERDF). This Article describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the Article do not necessarily represent the views of the USDOE or the United States Government. The Sandia authors own all right, title, and interests in and to the article and are solely responsible for its contents. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this article or allow others to do so, for United States Government purposes. The DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan https://www.energy.gov/downloads/doe-public-access-plan
| Funders | Funder number |
|---|---|
| Bristol ChemLabS | |
| FAPESP-University of Manchester | |
| NSF-EFRI | CBET-2029425 |
| Regional Council ‘Hauts-de-France | |
| Upper Atmosphere Research and Tropospheric Chemistry program | |
| National Science Foundation (NSF) | |
| U.S. Department of Energy | |
| National Aeronautics and Space Administration | |
| Office of Science | DE-AC02-05CH11231 |
| Basic Energy Sciences | DE-AC0209CH11466 |
| National Nuclear Security Administration | DE-NA0003525 |
| California Institute of Technology | |
| California Institute of Technology | |
| Chemical Sciences, Geosciences, and Biosciences Division | DE-AC02-06CH11357 |
| Universities Space Research Association | |
| Department of Energy Plasma Science Center, University of Michigan | DE-SC0020233 |
| Natural Environment Research Council | NE/K004905/1 |
| Agence Nationale de la Recherche | ANR-11-LABX-0005-01 |
| Fundação de Amparo à Pesquisa do Estado de São Paulo | 2017/17047-0, 2023/04358-9 |
| European Regional Development Fund | |
| Primary Science Teaching Trust |