University of Oulu

Shuzhen Chen, Luca Artiglia, Fabrizio Orlando, Jacinta Edebeli, Xiangrui Kong, Huanyu Yang, Anthony Boucly, Pablo Corral Arroyo, Nønne Prisle, and Markus Ammann. Impact of Tetrabutylammonium on the Oxidation of Bromide by Ozone. ACS Earth and Space Chemistry 2021 5 (11), 3008-3021, DOI:10.1021/acsearthspacechem.1c00233.

Impact of tetrabutylammonium on the oxidation of bromide by ozone

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Author: Chen, Shuzhen1,2; Artiglia, Luca1; Orlando, Fabrizio1;
Organizations: 1Laboratory of Environmental Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland
2Institute of Atmospheric and Climate Sciences, ETH Zürich, 8006 Zürich, Switzerland
3Center for Atmospheric Research, University of Oulu, 90014 Oulu, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 2.9 MB)
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Language: English
Published: American Chemical Society, 2021
Publish Date: 2022-01-28


The reaction of ozone with sea-salt derived bromide is relevant for marine boundary layer atmospheric chemistry. The oxidation of bromide by ozone is enhanced at aqueous interfaces. Ocean surface water and sea spray aerosol are enriched in organic compounds, which may also have a significant effect on this reaction at the interface. Here, we assess the surface propensity of cationic tetrabutylammonium at the aqueous liquid−vapor interface by liquid microjet X-ray photoelectron spectroscopy (XPS) and the effect of this surfactant on ozone uptake to aqueous bromide solutions. The results clearly indicate that the positively charged nitrogen group in tetrabutylammonium (TBA), along with its surface activity, leads to an enhanced interfacial concentration of both bromide and the bromide ozonide reaction intermediate. In parallel, off-line kinetic experiments for the same system demonstrate a strongly enhanced ozone loss rate in the presence of TBA, which is attributed to an enhanced surface reaction rate. We used liquid jet XPS to obtain detailed chemical composition information from the aqueous-solution−vapor interface of mixed aqueous solutions containing bromide or bromide and chloride with and without TBA surfactant. Core level spectra of Br 3d, C 1s, Cl 2p, N 1s, and O 1s were used for this comparison. A model was developed to account for the attenuation of photoelectrons by the carbon-rich layer established by the TBA surfactant. We observed that the interfacial density of bromide is increased by an order of magnitude in solutions with TBA. The salting-out of TBA in the presence of 0.55 M sodium chloride is apparent. The increased interfacial bromide density can be rationalized by the association constants for bromide and chloride to form ion-pairs with TBA. Still, the interfacial reactivity is not increasing simply proportionally with the increasing interfacial bromide concentration in response to the presence of TBA. The steady state concentration of the bromide ozonide intermediate increases by a smaller degree, and the lifetime of the intermediate is 1 order of magnitude longer in the presence of TBA. Thus, the influence of cationic surfactants on the reactivity of bromide depends on the details of the complex environment at the interface.

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Series: ACS earth and space chemistry
ISSN: 2472-3452
ISSN-E: 2472-3452
ISSN-L: 2472-3452
Volume: 5
Issue: 11
Pages: 3008 - 3021
DOI: 10.1021/acsearthspacechem.1c00233
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
1172 Environmental sciences
116 Chemical sciences
Funding: This project was supported by the Swiss National Science Foundation (grant no 169176). This project received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program, Project SURFACE (grant agreement no. 717022). N.P. also gratefully acknowledges the financial contribution from the Academy of Finland, including grant nos. 308238, 314175, and 335649.
EU Grant Number: (717022) SURFACE - The unexplored world of aerosol surfaces and their impacts.
Academy of Finland Grant Number: 308238
Detailed Information: 308238 (Academy of Finland Funding decision)
314175 (Academy of Finland Funding decision)
335649 (Academy of Finland Funding decision)
Copyright information: © 2021 The Authors. Published by American Chemical Society