The interaction of Al(III), Sc(III), and La(III) with muscovitewater interfaces was studied at pH 4 and 10 mM NaCl using second harmonic generation (SHG) and X-ray photoelectron spectroscopy (XPS). SHG data for Sc(III) and La(III) suggest complete and/or partial irreversible adsorption that is attributed by XPS to the growth of Sc(III) and La(III) hydroxides/oxides on the muscovite surface. Al(III) adsorption appears to coincide with the growth of gibbsite (Al(OH)3) deposits on the muscovite surface, as indicated by the magnitude of the interfacial potential computed from the SHG data. This interpretation of the data is consistent with previous studies reporting the epitaxial growth of gibbsite on the muscovite surface under similar conditions. The implication of our findings is that the surface charge density of mica may change (and in the case of Al(III), even flip sign from negative (mica) to positive (gibbsite)) when Al(III), Sc(III), or La(III) is present in aqueous phases in contact with heterogeneous geochemical media rich in mica-class minerals, even at subsaturation conditions.