Characterization of alunite supergroup minerals by Raman spectroscopy

Raman spectroscopy has been used to study the molecular structure of different natural minerals of the alunite supergroup (AB(3)(XO(4))(2)(OH)(6)), with A=K(+), Na(+), Ca(2+), Sr(2+), Ba(2+), B=Al(3+), Fe(3+) and X=S(6+), P(5+). The influence of the ions, in A-, B- and X-sites, is highlighted in the Raman spectra by variations in the position of certain vibrations and is discussed in association with published crystallographic data in order to describe the observed differences. It was found that A-site substitutions are characterized by wavenumber shifts of the vibrations involving hydroxyl groups. The positions of these vibrational bands vary linearly with the ionic radius of the ions in this site. B-site substitutions induce shifts of all bands due to structural modifications that lead to differences in the chemical environment around the hydroxyl and XO(4) groups and changes in B-O bond lengths. A correlation showed that these shifts correlate well with the ionic radii of the B-ions. The spectra of compounds containing both sulfate and phosphate groups are described by numerous vibration bands caused by a complex elemental composition and a symmetry change of the XO(4) groups. This study has also made it possible to generalize substitution effects on the wavenumbers of several vibrations and show that Raman spectroscopy could be a powerful tool for identifying and distinguishing minerals of the alunite supergroup.