Potassium coordination in trioctahedral micas investigated by K-edge XANES spectroscopy

Fine-grained homogeneous powder samples of thirteen trioctahedral micas, mostly intermediate members of the phlogopite - annite solid solution series, and samples close to the phlogopite, fluor-phlogopite and tetra-ferriphlogopite end members have been examined at the potassium K-edge by X-ray absorption fine structure spectroscopy. The interlayer K+ cation is in a coordination that is certainly lower than 12, in contrast to what is expected from the ideal hexagonal symmetry model of the mica structure, and approaches - but it does not reach - coordination 6, as it should be when the effective ligands are the three nearest outer bridging oxygens of two facing upper and lower tetrahedral sheets. The observed range of coordinations implies that only some of the three inner bridging oxygen atoms in each sheet are involved, thus leading to 6 +/-(1...6) effective configurations depending on the composition of the individual mica terms. The effective coordination number was found to vary continuously with composition from 11 to 7 and to be related to the tetrahedral rotation angle (alpha) according to two different linear relationships for the phlogopite - annite series (Fe2+Mg-1 exchange vector, involving the octahedral sheet only) and the phlogopite - tetra-ferriphlogopite series (Fe3+Al-1 vector, involving the tetrahedral sheet), respectively. Substitutions affecting either the A cation in the interlayer or the X anion in the octahedral sheet also affect the observed trends. In particular, the latter substitution effect is best seen in two near end member phlogopites, where the fluorine to hydroxyl substitution (F- (OH)(-)(-1) exchange vector), which greatly changes the alpha tetrahedral rotation angle is, reflected in the experimental K XANES spectra by modifying not only the energy but also the intensities of most multiple scattering features.