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1 Institut für Mineralogie und Kristallographie, Geozentrum, Universität Wien, Althanstrasse 14, 1090 Vienna, Austria
2 Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125-2500, U.S.A.
3 Department of Geology, Miami University, Oxford, Ohio 45056, U.S.A.
4 Mineralogisches Institut, Universität Heidelberg, Im Neuenheimer Feld 236, 69120 Heidelberg, Germany
Correspondence: * E-mail: andreas.ertl{at}a1.net
Pink, Mn-bearing "oxy-rossmanite" from a pegmatite in a quarry near Eibenstein an der Thaya, Lower Austria, has been characterized by crystal structure determination, chemical analyses (EMPA, SIMS), and optical absorption and infrared spectroscopy. Crystal structure refinements in combination with the chemical analyses give the optimized formulae X(
0.53Na0.46Ca0.01)Y(Al2.37Li0.33Mn2+0.25Fe2+0.04Ti4+0.01) ZAl6 T(Si5.47Al0.28B0.25)O18 (BO3)3 V[(OH)2.85O0.15] W[O0.86(OH)0.10F0.04], with a = 15.8031(3), c = 7.0877(3) Å, and R = 0.017 for the sample with 2.05 wt% MnO, and X(0.53Na0.46Ca0.01)Y (Al2.35Li0.32Mn2+0.28 Fe2+0.04Ti4+0.01) ZAl6 T(Si5.51Al0.25B0.24)O18 (BO3)3 V[(OH)2.80O0.20] W[O0.86(OH)0.10F0.04] for a sample with a = 15.8171(3), c = 7.0935(2) Å, R = 0.017, and 2.19 wt% MnO. Although the structure refinements show significant amounts of [4]B, the <T-O> bond-lengths (~1.620 Å) mask the incorporation of [4]B because of the incorporation of [4]Al. The <T-O> distances, calculated using the optimized T site occupancies, are consistent with the measured distances. This "oxy-rossmanite" shows that it is possible to have significant amounts of [4]B and [4]Al in an Al-rich tourmaline. The "oxy-rossmanite" from Eibenstein has the highest known Al content of all natural tourmalines (~47 wt% Al2O3; ~8.6 apfu Al). The near-infrared spectrum confirms both that hydroxyl groups are present in the Eibenstein tourmaline and that they are present at a lower concentration than commonly found in other lithian tourmalines. The integrated intensity (850 cm–2) of the OH bands in the single-crystal spectrum of "oxy-rossmanite" from Eibenstein is distinctly lower than for other Li-bearing tourmaline samples (970–1260 cm–2) with OH contents >3.0 pfu. These samples fall on the V site = 3 (OH) line in the figure defining covariance of the relationship between the bond-angle distortion (
oct2) of the ZO6 octahedron and the <Y-O> distance. On a bond-angle distortion-<Y-O> distance diagram "oxy-rossmanite" from Eibenstein lies between the tourmalines that contain 3 (OH) at the V site, and natural buergerite, which contains 0.3 (OH) and 2.7 O at the V site. No H could be found at the O1 site by refinement, and the spherical electron density in the difference-Fourier map around the O1 site supports the conclusion that this site is mainly occupied by O. The pink color comes from the band at 555 nm that is associated with Mn3+ produced by natural irradiation of Mn2+. This is the first time a tourmaline is described that has a composition that falls in the field of the previously proposed hypothetical species "oxy-rossmanite".
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