V3+-bearing, Mg-rich, strongly disordered olenite from a graphite deposit near Amstall, Lower Austria: A structural, chemical and spectroscopic investigation

An optical absorption spectrum, structural and chemical data of green Vand Cr-bearing tourmaline from the graphite deposit at Weinberg Mountain, west of the village of Amstall, Lower Austria, were obtained. To address the role of V and Cr in the spectrum of tourmaline, examination of additional samples of Vand Cr-containing tourmalines was conducted. This study confi rmed that V and Cr produce similar spectra in tourmalines. However, the wavelengths of the 600 nm region band (E\\c), and the 440 nm region band (E⊥c) varied in relation to the proportion of Cr in the sample. Likewise, the intensity of the 680 nm region spin-forbidden bands varies in proportion to the absolute amount of Cr in the sample. Molar absorption coeffi cients for both V and Cr in tourmaline were determined for the 600 nm region. For the E⊥c band, ε(V) = 12.3 ± 0.7; ε(Cr) = 39.7 ± 1.4; and for the E\\c band, ε(V) = 11.9 ± 2.0; ε(Cr) =15.9 ± 2.8. In each case the Cr bands are more intense than the corresponding V band. These features can be used to confi rm that the spectroscopic features of the Amstall tourmaline come dominantly from V. The optimized formula, calculated using structural and chemical data for the core of a 4 mm wide crystal, is (Na0.69Ca0.16K0.01 0.14) (Al1.46Mg1.34V0.11Ti0.05Cr0.02Fe0.02) (Al4.77Mg1.23) (BO3)3 (Si5.70Al0.30) O18 [(OH)3.87O0.13], with a = 15.984(2), c = 7.222(2) Å, R = 0.017. The optimized formula, calculated using structural and chemical data for the rim, is (Na0.67Ca0.24K0.01 0.08) (Al1.57Mg1.24V0.11 Ti0.05Cr0.02Fe0.01) (Al4.84Mg1.16) (BO3)3 (Si5.90Al0.10) O18 [(OH)3.35O0.65], with a = 15.9175(5), c = 7.1914(4) Å, R = 0.014. Whereas the V and Cr contents stay constant, Mg decreases from the core to the rim. This is refl ected by decreasing (from 2.013 to 2.003 Å) and distances (from 1.938 to 1.930 Å). The relative short distances and the enlarged distances show that Al and Mg are strongly disordered between the Y and Z sites in this tourmaline. We assume that the strong Mg-Al disorder between the Y and the Z sites in this tourmaline derived from a high-T overprint (~750 °C, ~6–9 kbar) during crystallization, which is supported by a relatively high amount of Al and low vacancies at the X site.