A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface.
- Artiglia L Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Edebeli J Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Orlando F Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Chen S Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Lee MT Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Corral Arroyo P Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Gilgen A Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Bartels-Rausch T Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Kleibert A Swiss Light Source, Paul Scherrer Institut, 5232, Villigen, Switzerland.
- Vazdar M Division of Organic Chemistry and Biochemistry, Rudjer Bošković Institute, Bijenička 54, 10000, Zagreb, Croatia.
- Andres Carignano M Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 34110, Doha, Qatar.
- Francisco JS Department of Chemistry, University of Nebraska-Lincoln, 433 Hamilton Hall, Lincoln, NE, 68588-0304, USA.
- Shepson PB Department of Chemistry, and Department of Earth, Atmospheric and Planetary Sciences, Purdue University, West Lafayette, IN, 46097, USA.
- Gladich I Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 34110, Doha, Qatar. igladich@hbku.edu.qa.
- Ammann M Laboratory of Environmental Chemistry, Paul Scherrer Institut, 5232, Villigen, Switzerland. markus.ammann@psi.ch.
- 2017-09-28
Published in:
- Nature communications. - 2017
English
Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO-] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapour interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapour interface compared with the bulk aqueous phase.Heterogeneous oxidation of bromide in atmospheric aqueous environments has long been suspected to be accelerated at the interface between aqueous solution and air. Here, the authors provide spectroscopic, kinetic and theoretical evidence for a rate limiting, surface active ozonide formed at the interface.
- Language
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- English
- Open access status
- gold
- Identifiers
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- DOI 10.1038/s41467-017-00823-x
- PMID 28951540
- Persistent URL
- https://folia.unifr.ch/global/documents/186734
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