This work examines the interactions of cations with two mineral surfaces, quartz (SiO₂) and corundum (Al₂O₃) to gain mechanistic insights into those interactions through the use of flow microcalorimetry, quartz crystal microbalance measurements, and density functional theory. The adsorption and exchange of alkali and alkaline earth cations onto the quartz mineral surface was conducted at pH 4.0 and 8.0. The heats of adsorption and exchange were found to increase along the lyotropic series, Li⁺ < Na⁺ < K⁺ < Rb⁺ < Cs⁺ and Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺, and were strongly correlated with the cation bulk hydration enthalpy. The adsorption of Al³⁺, Cr³⁺, and Mn²⁺ was investigated on the quartz and corundum mineral surfaces at pH 3.8. Adsorption behavior was seen for all cations on both surfaces, with the exception of Mn²⁺ on quartz. The adsorption of these cations was a function of both cation hydration and hydrolysis.