Liquid jet X-ray photoelectron spectroscopy is used under near ambient pressure conditions to characterize Fe aqueous solutions. Counter ions, such as Cl and Br ions, added to the solution lead to changes in the first solvation sphere of the Fe-aqua complex in solution. Binding energy shifts of 0.4 eV to lower binding energy are observed in the Cl 2p spectra, 2 eV to higher binding energy in the Fe 2p spectra and no shifts are observed in the Br 3d spectra. Depletion of the Cl species is observed at the interface, caused by coordination with Fe. Depletion of Cl at the liquid/vapor interface may have significant impacts on oxidative chemistry at the interface of atmospheric aerosols that contain both chloride and iron. The Cl complexation with the Fe ions will also affect the Fenton chemistry that is dependent on this metal ion.
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