Articles | Volume 2, issue 1
https://doi.org/10.5194/ar-2-31-2024
https://doi.org/10.5194/ar-2-31-2024
Research article
 | 
19 Mar 2024
Research article |  | 19 Mar 2024

Photocatalytic chloride-to-chlorine conversion by ionic iron in aqueous aerosols: a combined experimental, quantum chemical, and chemical equilibrium model study

Marie K. Mikkelsen, Jesper B. Liisberg, Maarten M. J. W. van Herpen, Kurt V. Mikkelsen, and Matthew S. Johnson

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Cited articles

Abou-Ghanem, M., Oliynyk, A. O., Chen, Z., Matchett, L. C., McGrath, D. T., Katz, M. J., Locock, A. J., and Styler, S. A.: Significant variability in the photocatalytic activity of natural titanium-containing minerals: implications for understanding and predicting atmospheric mineral dust photochemistry, Environ. Sci. Technol., 54, 13509–13516, 2020. a
Achterberg, E. P., Holland, T. W., Bowie, A. R., Mantoura, R. F. C., and Worsfold, P. J.: Determination of iron in seawater, Anal. Chim. Acta, 442, 1–14, 2001. a, b
Allan, W., Struthers, H., and Lowe, D.: Methane carbon isotope effects caused by atomic chlorine in the marine boundary layer: Global model results compared with Southern Hemisphere measurements, J. Geophys. Res.-Atmos., 112, D04306, https://doi.org/10.1029/2006JD007369, 2007. a
Angle, K. J., Crocker, D. R., Simpson, R. M., Mayer, K. J., Garofalo, L. A., Moore, A. N., Mora Garcia, S. L., Or, V. W., Srinivasan, S., Farhan, M., and Sauer, J. S.: Acidity across the interface from the ocean surface to sea spray aerosol, P. Natl. Acad. Sci. USA, 118, e2018397118, https://doi.org/10.1073/pnas.2018397118, 2021. a
Badia, A., Reeves, C. E., Baker, A. R., Saiz-Lopez, A., Volkamer, R., Koenig, T. K., Apel, E. C., Hornbrook, R. S., Carpenter, L. J., Andrews, S. J., Sherwen, T., and von Glasow, R.: Importance of reactive halogens in the tropical marine atmosphere: a regional modelling study using WRF-Chem, Atmos. Chem. Phys., 19, 3161–3189, https://doi.org/10.5194/acp-19-3161-2019, 2019. a
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Short summary
We analyze the mechanism whereby sunlight and iron catalyze the production of chlorine from chloride in sea spray aerosol. This process occurs naturally over the North Atlantic and is the single most important source of chlorine. We investigate the mechanism using quantum chemistry, laboratory experiments, and aqueous chemistry modelling. The process will change depending on competing ions, light distribution, acidity, and chloride concentration.
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