Abstract
Olenitic tourmaline with high amounts of tetrahedral B (up to 2.53 [4]B pfu) has been synthesized in a piston-cylinder press at 4.0 GPa, 700 °C, and a run duration of 9 days. Crystals are large enough (up to 30 × 150 μm) to allow for reliable and spatially resolved quantification of B by electron microprobe analysis (EMPA), single-crystal X-ray diffraction, and polarized single-crystal Raman spectroscopy. Tourmalines with radial acicular habit are zoned in [4]B-concentration [core: 2.53(25) [4]B pfu; rim: 1.43(15) [4]B pfu], whereas columnar crystals are chemically homogeneous [1.18(15) [4]B pfu]. An amount of 1.4(1) [4]B pfu was found in the columnar tourmaline by single-crystal structure refinement (SREF) (R = 1.94%). The EMPA identify [T]Si−1[V,W]O−1[T]B1[V,W](OH)1 as the main and [X]⃞-1[T]Si–1[X]Na1[T]B1 as minor exchange vectors for [4]B-incorporation, which is supported by the SREF. Due to the restricted and well-defined variations in chemistry, Raman bands in the OH-stretching region (3000–3800 cm−1) are unambiguously assigned to a specific cation arrangement. We found the sum of the relative integrated intensity (Irel) of two low-frequency bands at 3284–3301 cm−1 (ν1) and 3367–3390 cm−1 (ν2) to positively correlate with the [4]B concentrations: [4]B [pfu] = 0.03(1) × [Irel (ν1) + Irel (ν2)]. Hence, those bands correspond to configurations with mixed Si/B occupancy at the T site. Our semi-quantitative correlation also holds for well-characterized natural [4]B-bearing tourmaline from the Koralpe, Austria. This work shows the potential for Raman spectroscopy as a non-destructive method for the chemical classification of (precious) natural tourmaline, and as a tool to rapidly characterize chemical zonation of tourmalines in thin section.
Special collection information can be found at http://www.minsocam.org/MSA/AmMin/special-collections.html.
Acknowledgments
We thank H.-P. Nabein for generating the XRD patterns and U. Dittmann for EMP sample preparation. E. Berryman is acknowledged for native speaker proofreading. This study was supported by funding from the Deutsche Forschungsgemeinschaft granted to G.F. and W.H. (FR 557/31-1; HE 2015/16-1) and to A.E. by the Austrian Science Fund (FWF) project no. P-26903-N19. We thank the associate editor Hans-Peter Schertl, Andrey Korsakov, and an anonymous reviewer for their constructive comments.
References cited
Armstrong, J.T. (1995) CITZAF: A package of correlation programs for the quantitative electron microbeam X-ray analysis of thick polished materials, thin films, and particles. Microbeam Analysis, 4, 177–200.Search in Google Scholar
Bast, R., Scherer, E.E., Mezger, K., Austrheim, H., Ludwig, T., Marschall, H.R., Putnis, A., and Löwen, K. (2014) Boron isotopes in tourmaline as a tracer of metasomatic processes in the Bamble sector of Southern Norway. Contributions to Mineralogy and Petrology, 168, 1069.10.1007/s00410-014-1069-4Search in Google Scholar
Bastin, G.F., and Heijligers, H.J.M. (1990) Quantitative electron-probe microanalysis of ultralight elements (boron-oxygen). Scanning, 12, 225–236.10.1002/sca.4950120408Search in Google Scholar
Berryman, E.J., Wunder, B., and Rhede, D. (2014) Synthesis of K-dominant tourmaline. American Mineralogist, 99, 539–542.10.2138/am.2014.4775Search in Google Scholar
Berryman, E.J., Wunder, B., Wirth, R., Rhede, D., Schettler, G., Franz, G., and Heinrich, W. (2015a) An experimental study on K and Na incorporation in dravitic tourmaline and insight into the origin of diamondiferous tourmaline from the Kokchetav Massif, Kazakhstan. Contributions to Mineralogy and Petrology, 129, 28.10.1007/s00410-015-1116-9Search in Google Scholar
Berryman, E.J., Wunder, B., Ertl, A., Koch-Müller, M., Rhede, D., Scheidl, K., Giester, G., and Heinrich, W. (2015b) Investigation of synthetic K-dravite, dravite, oxy-uvite, and magnesio foitite using SREF and Raman spectroscopy. Physics and Chemistry of Minerals, in press, http://dx.doi.org/10.1007/ s00269-015-0776-3.Search in Google Scholar
Cempírek, J., Novák, M., Ertl, A., Hughes, J.M., Rossman, G.R., and Dyar, M.D. (2006) Fe-bearing olenite with tetrahedrally coordinated Al from an abyssal pegmatite at Kutná Horza, Czech Republic: Structure, crystal chemistry, optical and XANES spectra. Canadian Mineralogist, 44, 23–30.10.2113/gscanmin.44.1.23Search in Google Scholar
Clark, C.M., Wadoski, E.R., and Freeman, E.D. (2008) Tourmaline chemistry and the IIIB site. American Mineralogist, 93, 409–413.10.2138/am.2008.2599Search in Google Scholar
Ertl, A., and Brandstätter, F. (1998) Olenit mit Borüberschuß in einem Metapegmatit östlich der Stoffhütte, Koralpe, Steiermark, Österreich. Mitteilung der Abteilung für Mineralogie am Landesmuseum Joanneum, 62/63, 3–21.Search in Google Scholar
Ertl, A., Pertlik, F., and Bernhardt, H.-J. (1997) Investigations on olenite with excess boron from the Koralpe, Styria, Austria. Österreichische Akadamie der Wissenschaften, Mathematisch-naturwissenschaftliche Klasse, Abteilung 1, Anzeiger, 134, 3–10, Wien.Search in Google Scholar
Ertl, A., Rossman, G.R., Hughes, J.M., Prowatke, S., and Ludwig, T. (2005) Mnbearing “oxy-rossmanite” with tetrahedrally coordinated Al and B from Austria: Structure, chemistry, and infrared and optical spectroscopic study. American Mineralogist, 90, 481–487.10.2138/am.2005.1683Search in Google Scholar
Ertl, A., Hughes, J.M., Prowatke, S., Ludwig, T., Prasad, P.S.R., Brandstätter, F., Körner, W., Schuster, R., Pertlik, F., and Marschall, H. (2006) Tetrahedrally coordinated boron in tourmaline from the liddicoatite-elbaite series from Madagascar: Structure, chemistry, and infrared spectroscopic studies. American Mineralogist, 91, 1847–1856.10.2138/am.2006.2245Search in Google Scholar
Ertl, A., Hughes, J.M., Prowatke, S., Ludwig, T., Brandstätter, F., Körner, W., and Dyar, M.D. (2007) Tetrahedrally coordinated boron in Li-bearing olenite from “mushroom” tourmaline from Momeik, Myanmar. Canadian Mineralogist, 45, 891–899.10.2113/gscanmin.45.4.891Search in Google Scholar
Ertl, A., Tillmanns, E., Ntaflos, T., Francis, C., Giester, G., Körner, W., Hughes, J.M., Lengauer, C., and Prem, M. (2008) Tetrahedrally coordinated boron in Al-rich tourmaline and its relationship to the pressure-temperature conditions of formation. European Journal of Mineralogy, 20, 881–888.10.1127/0935-1221/2008/0020-1869Search in Google Scholar
Ertl, A., Giester, G., Ludwig, T., Meyer, H.P., and Rossman, G.R. (2012) Synthetic B-rich olenite: Correlations of single-crystal structural data. American Mineralogist, 97, 1591–1597.10.2138/am.2012.4060Search in Google Scholar
Fantini, C., Tavares, M.C., Krambrock, K., Moreira, R.L., and Righi, A. (2014) Raman and infrared study of hydroxyl sites in natural uvite, fluor-uvite, magnesio-foitite, dravite and elbaite tourmalines. Physics and Chemistry of Minerals, 41, 247–254.10.1007/s00269-013-0642-0Search in Google Scholar
Fischer, R.X., and Tillmanns, E. (1988) The equivalent isotropic displacement factor. Acta Crystallographica, C44, 775–776.10.1107/S0108270187012745Search in Google Scholar
Gatta, G.D., Bosi, F., McIntyre, G.J., and Skogby, H. (2014) First accurate location of two proton sites in tourmaline: A single-crystal neutron diffraction study of oxy-dravite. Mineralogical Magazine, 78, 681–692.10.1180/minmag.2014.078.3.15Search in Google Scholar
Gonzalez-Carreño, T., Fernandez, M., and Sanz, J. (1988) Infrared and electron microprobe analysis of tourmalines. Physics and Chemistry of Minerals, 15, 452–460.10.1007/BF00311124Search in Google Scholar
Gourdant, J.P., Robert, J.-L., and Sanz, J. (1997) Tetrahedrally coordinated aluminium in synthetic tourmalines. In Tourmaline 1997 Symposium, Abstract volume, Nové Mesto na Morave, Czech Republic, 29.Search in Google Scholar
Hawthorne, F.C. (1996) Structural mechanisms for light-element variations in tourmaline. Canadian Mineralogist, 34, 123–132.Search in Google Scholar
Hawthorne, F.C. (2002) Bond-valence constraints on the chemical composition of tourmaline. Canadian Mineralogist, 40, 789–797.10.2113/gscanmin.40.3.789Search in Google Scholar
Henry, D.J., and Dutrow, B.L. (1996) Metamorphic tourmaline and its petrological application. Reviews in Mineralogy, 33, 503–557.Search in Google Scholar
Henry, D.J., Kirkland, B.L., and Kirkland, D.W. (1999) Sector-zoned tourmaline from the cap rock of a salt dome. European Journal of Mineralogy, 11, 263–280.10.1127/ejm/11/2/0263Search in Google Scholar
Henry, D.J., Novak, M., Hawthorne, F.C., Ertl, A., Dutrow, B.L., Uher, P., and Pezzotta, F. (2011) Nomenclature of the tourmaline-supergroup minerals. American Mineralogist, 96, 895–913.10.2138/am.2011.3636Search in Google Scholar
Hughes, J.M., Ertl, A., Dyar, M.D., Grew, E., Shearer, C.K., Yates, M.G., and Guidotti, C.V. (2000) Tetrahedrally coordinated boron in a tourmaline: Boron-rich olenite from Stoffhütte, Koralpe, Austria. Canadian Mineralogist, 38, 861–868.10.2113/gscanmin.38.4.861Search in Google Scholar
Hughes, K.-A., Hughes, J.M., and Dyar, M.D. (2001) Chemical and structural evidence for [4]B ↔ [4]Si substitution in natural tourmalines. European Journal of Mineralogy, 13, 743–747.10.1127/0935-1221/2001/0013-0743Search in Google Scholar
Hughes, J.M., Ertl, A., Dyar, M.D., Grew, E., Wiedenbeck, M., and Brandstätter, F. (2004) Structural and chemical response to varying [4]B content in zoned Fe-bearing olenite from Koralpe, Austria. Canadian Mineralogist, 38, 447–454.10.2138/am-2004-2-326Search in Google Scholar
Kalt, A., Schreyer, W., Ludwig, T., Prowatke, S., Bernhardt, H.-J., and Ertl, A. (2001) Complete solid solution between magnesian schorl and lithian excess-boron olenite in a pegmatite from the Koralpe (eastern Alps, Austria). European Journal of Mineralogy, 13, 1191–1205.10.1127/0935-1221/2001/0013-1191Search in Google Scholar
Kowalski, P.M., Wunder, B., and Jahn, S. (2013) Ab initio prediction of equilibrium boron isotope fractionation between minerals and aqueous fluids at high P and T. Geochimica et Cosmochimica Acta, 101, 285–301.10.1016/j.gca.2012.10.007Search in Google Scholar
Krosse, S. (1995) Hochdrucksynthese, Stabilität und Eigenschaften der Borosilikate Dravit und Kornerupin sowie Darstellung und Stabilitätsverhalten eines neuen Mg-Al-Borates. Dissertation, Ruhr-Universität Bochum, Germany, 135 pp.Search in Google Scholar
Larson, A.C., and Von Dreele, R.B. (1987) Generalized structure analysis system. Los Alamos National Laboratory Report LAUR 86-748.Search in Google Scholar
Lussier, A.J., Aguiar, P.M., Michaelis, V.K., Kroeker, S., and Hawthorne, F.C. (2009) The occurrence of tetrahedrally coordinated Al and B in tourmaline: An 11B and 27Al MAS NMR study. American Mineralogist, 94, 785–792.10.2138/am.2009.3000Search in Google Scholar
MacMillan, P.F., and Hofmeister, A.M. (1988) Infrared and Raman spectroscopy. Reviews in Mineralogy, 18, 99–159.Search in Google Scholar
Marler, B., and Ertl, A. (2002) Nuclear magnetic resonance and infrared spectroscopy study of excess-boron olenite from Koralpe, Styria, Austria. American Mineralogist, 87, 364–367.10.2138/am-2002-2-321Search in Google Scholar
Marler, B., Borowski, M., Wodara, U., and Schreyer, W. (2002) Synthetic tourmaline (olenite) with excess boron replacing silicon in the tetrahedral site: II. Structural analysis. European Journal of Mineralogy, 14, 763–771.10.1127/0935-1221/2002/0014-0763Search in Google Scholar
Marschall, H.R., Ertl, A., Hughes, J.M., and McCommon, C. (2004) Metamorphic Naand OH-rich disordered dravite with tetrahedral boron associated with omphacite, from Syros, Greece: Chemistry and structure. European Journal of Mineralogy, 16, 817–823.10.1127/0935-1221/2004/0016-0817Search in Google Scholar
Marschall, H.R., Ludwig, T., Altherr, R., Kalt, A., and Tonarini, S. (2006) Syros metasomatic tourmaline: Evidence for high-δ11B fluids in subduction zones. Journal of Petrology, 47, 1915–1942.10.1093/petrology/egl031Search in Google Scholar
Meyer, C., Wunder, B., Meixner, A., Romer, R.L., and Heinrich, W. (2008) Boron-isotopic fractionation between tourmaline and fluid: An experimental re-investigation. Contributions to Mineralogy and Petrology, 156, 259–267.10.1007/s00410-008-0285-1Search in Google Scholar
Miller, C. (1990) Petrology of the type locality eclogites from the Koralpe and Saualpe (Eastern Alps, Austria). Schweizerische Mineralogische und Petrographische Mitteilungen, 70, 287–300.Search in Google Scholar
Miller, C., and Thöni, M. (1997) Eo-Alpine eclogitization of Permian MORBtype gabbros in the Koralpe (Eastern Alps, Austria): New geochronological, geochemical and petrological data. Chemical Geology, 137, 283–310.10.1016/S0009-2541(96)00165-9Search in Google Scholar
Mirwald, P.W., and Massonne, H.-J. (1980) Quartz-coesite transition and the comparative friction measurements in piston-cylinder apparatus using talc-alsimag-glass (TAG) and NaCl high pressure cells: A discussion. Neues Jahrbuch für Mineralogische Monatshefte, 1980, 469–477.Search in Google Scholar
Moore, J.N., Christenson, B.W., Allis, R.G., Browne, P.R.L., and Lutz, S.J. (2004) The mineralogical consequences and behaviour of descending acid-sulfate waters: An example from the Karaha-Telaga Bodas geothermal system, Indonesia. Canadian Mineralogist, 42, 1483–1499.10.2113/gscanmin.42.5.1483Search in Google Scholar
Schreyer, W., Wodara, U., Marler, B., van Aken, P., Seifert, F., and Robert, J.-L. (2000) Synthetic tourmaline (olenite) with excess boron replacing silicon on the tetrahedral site: I. Synthesis conditions, chemical and spectroscopic evidence. European Journal of Mineralogy, 12, 529–541.10.1127/0935-1221/2000/0012-0529Search in Google Scholar
Schreyer, W., Hughes, J.M., Bernhardt, H-J., Kalt, A., Prowatke, S., and Ertl, A. (2002) Reexamination of olenite from the type locality: Detection of boron in tetrahedral coordination. European Journal of Mineralogy, 14, 935–942.10.1127/0935-1221/2002/0014-0935Search in Google Scholar
Sheldrick, G.M. (1997) SHELXL-97, a program for crystal structure refinement. University of Göttingen, Germany.Search in Google Scholar
Skogby, H., Bosi, F., and Lazor, P. (2012) Short-range order in tourmaline: A vibrational spectroscopic approach to elbaite. Physics and Chemistry of Minerals, 39, 811–816.10.1007/s00269-012-0536-6Search in Google Scholar
Strüwe, K., and Powell, R. (1995) PT paths from modal proportions: application to the Koralm Complex, Eastern Alps. Contributions to Mineralogy and Petrology, 119, 83–93.10.1007/BF00310719Search in Google Scholar
Tagg, S.L., Cho, H., Dyar, M.D., and Grew, E.S. (1999) Tetrahedral boron in naturally occurring tourmaline. American Mineralogist, 84, 1451–1455.10.2138/am-1999-0925Search in Google Scholar
Trumbull, R.B., Krienitz, M.-S., Grundmann, G., and Wiedenbeck, M. (2009) Tourmaline geochemistry and δ11B variation as a guide to fluid-rock interaction in the Habachtal emerald deposit, Tauern Window, Austria. Contributions to Mineralogy and Petrology, 157, 411–427.10.1007/s00410-008-0342-9Search in Google Scholar
van Hinsberg, V.J., and Schumacher, J.C. (2007) Intersector element partitioning in tourmaline: A potentially powerful single crystal thermometer. Contributions to Mineralogy and Petrology, 153, 289–301.10.1007/s00410-006-0147-7Search in Google Scholar
van Hinsberg, V.J., Henry, D.J., and Marschall, H.R. (2011) Tourmaline: An ideal indicator of its host environment. Canadian Mineralogist, 29, 1–16.10.3749/canmin.49.1.1Search in Google Scholar
Veličkov, B. (2002) Kristallchemie von Fe, Mg-Turmalinen: Synthese und spektroskopische Untersuchungen. Dissertation, TU Berlin, Germany, 175 pp.Search in Google Scholar
von Goerne, G., Franz, G., and Heinrich, W. (2001) Synthesis of tourmaline solid solutions in the system Na2O-MgO-Al2O3-SiO2-B2O3-H2O-HCl and distribution of Na between tourmaline and fluid at 300 to 700 °C and 200 MPa. Contributions to Mineralogy and Petrology, 141, 160–173.10.1007/s004100100243Search in Google Scholar
Wodara, U. (1996) Synthese und Eigenschaften von Turmalinen im System Na2O-Al2O3-SiO2-B2O3-H2O. Diploma thesis, Ruhr-University Bochum, Germany, 99 pp.Search in Google Scholar
Wodara, U., and Schreyer, W. (2001) X-site vacant Al-tourmaline: A new synthetic end-member. European Journal of Mineralogy, 13, 521–532.10.1127/0935-1221/2001/0013-0521Search in Google Scholar
Wunder, B., Berryman, E., Plessen, B., Rhede, D., Koch-Müller, M., and Heinrich, W. (2015) Synthetic and natural ammonium-bearing tourmaline. American Mineralogist, 100, 250–256.10.2138/am-2015-5055Search in Google Scholar
Manuscript handled by Hans-Peter Schertl.
© 2016 by Walter de Gruyter Berlin/Boston