Spectroscopic characterisation and crystal field calculations of varicoloured kyanites from Loliondo, Tanzania

Orange, ochre-coloured, light green and dark blue varieties of kyanite, ideally Al₂SiO₅, from Loliondo, Tanzania, have been characterised by electron microprobe analysis and polarised infrared and optical absorption spectroscopy. All colour varieties show elevated Fe contents of 0.39 to 1.31 wt.% FeO, but Ti contents only in the range of the EMP detection limit. Orange and ochre-coloured crystals have Mn contents of 0.23 and 0.06 wt.% MnO, respectively, the dark blue kyanite contains 0.28 wt.% Cr₂O₃, while the light green sample is nearly free from transition metal cations other than Fe. Polarised infrared spectra reveal OH defect concentrations of 3 to 17 wt.ppm H₂O with structural OH defects partially replacing the O_B (O2) oxygen atoms. Polarised optical absorption spectra show that the colour of all four varieties is governed by crystal field d-d transitions of trivalent cations, i.e. Fe³⁺ (all samples), Mn³⁺ (orange and ochre) and Cr³⁺ (blue kyanite), replacing Al in sixfold coordinated triclinic sites of the kyanite structure. Intervalence charge transfer, the prevalent colour-inducing mechanism in ‘usual’ (Cr-poor) blue kyanites, seems to play a very minor, if any, role in the present samples. Crystal field calculations in both a ‘classic’ tetragonal and in the semiempirical Superposition Model approach, accompanied by distance- and angle-least-squares refinements, indicate that Fe³⁺ preferably occupies the Al4 site, Cr³⁺ prefers the Al1 and Al2 sites, and Mn³⁺ predominantly enters the Al1 site. In each case specific local relaxation effects were observed according to the crystal chemical preferences of these transition metal cations. Furthermore, the high values obtained in the calculations for the interelectronic repulsion parameter Racah B correspond to a high ionic contribution to Me³⁺–O bonding in the kyanite structure. In the particular case of the blue sample, band positions specifically related to the high Racah B value enable this ‘unusual’ type of blue colouration of kyanite solely due to Cr³⁺ cations.