Sodium chloride solutions have been used extensively as a model of seawater in both theoretical and experimental studies of the chemistry of sea salt aerosol. Many groups have found that chloride anions are present at the air-solution interface. This observation has been important for the development of a mechanism for the heterogeneous production of molecular chlorine from chloride in sea salt aerosol. However, while sodium chloride is a major constituent of seawater, it is by no means the only salt present. Seawater contains one Mg2+ for every eight Na+. Mg2+ is naturally occurring in ocean waters from mineral deposits in the Earth's crust and biological sources. Mg2+ forms a hexahydrate structure, rather than contact ion pairs with chloride anion, and this impacts the ordering of water in solution. In this study, we use molecular dynamics simulations, ab initio calculations, and vibrational sum frequency generation (SFG) spectroscopy to explore the effect of the Mg2+ cation and its tightly bound solvation shell on the surface propensity of chloride, ion-ion interactions, and water structure of the air-solution interface of concentrated chloride salt solutions. In addition, we provide molecular level details that may be relevant to the heterogeneous reactions of chloride in deliquesced sea salt aerosols. In particular, we show that the presence of the divalent Mg2+ cation does not modify the surface propensity of chloride compared to Na+ and hence, its availability to interfacial reaction, although some differences in the behavior of chloride may occur due to specific ion interactions. In this work, we also discuss the SFG free OH band at the surface of salt solutions and conclude that it is often not straightforward to interpret.