| 1. |
- Artiglia, Luca, et al.
(author)
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A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
- 2017
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In: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 8
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Journal article (peer-reviewed)abstract
- 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 center dot 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.
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| 3. |
- Kong, Xiangrui, et al.
(author)
-
Surface solvation of Martian salt analogues at low relative humidities
- 2022
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In: Environmental Science: Atmospheres. - : Royal Society of Chemistry (RSC). - 2634-3606. ; 2:2, s. 137-145
-
Journal article (peer-reviewed)abstract
- Salt aerosols play important roles in many processes related to atmospheric chemistry and the climate systems on both Earth and Mars. Complicated and still poorly understood processes occur on the salt surfaces when interacting with water vapor. In this study, ambient pressure X-ray photoelectron spectroscopy (APXPS) is used to characterize the surface chemical environment of Martian salt analogues originating from saline lakes and playas, as well as their responses to varying relative humidities. Generally, APXPS shows similar ionic compositions to those observed by ion chromatography (IC). However, XPS is a surface-sensitive method while IC is bulk-sensitive and differences are observed for species that preferentially partition to the surface or the bulk. Element-selective surface enhancement of Cl− is observed, likely caused by the presence of SO42−. In addition, Mg2+ is concentrated on the surface while Na+ is relatively depleted in the surface layer. Hence, the cations (Na+ and Mg2+) and the anions (Cl− and SO42−) show competitive correlations. At elevated relative humidity (RH), no major spectral changes were observed in the XPS results, except for the growth of an oxygen component originating from condensed H2O. Near-edge X-ray absorption fine structure (NEXAFS) measurements show that the magnesium and sodium spectra are sensitive to the presence of water, and the results imply that the surface is fully solvated already at RH = 5%. The surface solvation is also fully reversible as the RH is reduced. No major differences are observed between sample types and sample locations, indicating that the salts originated from saline lakes commonly have solvated surfaces under the environmental conditions on Earth.
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