Abstract. Episodes of ozone depletion attributed to chemistry of gas phase bromine compounds in marine regions of the Arctic boundary layer have been reported at polar sunrise. Models tbr the source of brominated compounds in the marine Arctic troposphere have focussed on surface chemistry of sea salt ice and aerosols even though the molar ratio of CI-to Br-in sea salt is expected to be -•660 to 1. X-ray photoelectron spectroscopy (XPS) studies described here show, for the first time, substantial segregation of Br-to the surface of NaC1 samples with low level Br-dopant. Water vapor exposure plays an important role as it provides enhanced ionic mobility in such systems allowing the surface segregation as the system approaches thermodynamic equilibrium. Our XPS results are confirmed by scanning electron microscopy (SEM) imaging of the salt sample surface after water vapor exposure, which shows NaBr crystallites that form at the surface. Our experiments provide the first experimental evidence for surface segregation in mixed alkali halide solids. The segregation phenomenon displayed here is likely to play an important role in a wide range of atmospheric phenomena that involve surface reactions of sea salt particles and aerosols.