Infra-red examination of a weathered biotite and of biotites that have been converted to vermiculites and subsequently oxidized, indicates that oxidation of octahedral ferrous ions to ferric ions is associated with a reversible conversion of hydroxyl ions to oxide ions. Subsequently, in high-iron biotites, there is an irreversible loss of ferric ions from the octahedral layer, resulting in an increased number of dioctahedral sites. Electron microscopy and X-ray diffraction indicate that ejected ferric ions form either amorphous interlayer oxides or, when bromine is used as an oxidant, a crystalline external phase of β-FeOOH. The high refractive index of some oxidized vermiculites is shown to be due largely to submicroscopic iron oxides.