TY - JOUR A1 - Kutzschbach, Martin A1 - Wunder, Bernd A1 - Krstulovic, Marija A1 - Ertl, Andreas A1 - Trumbull, Robert B. A1 - Rocholl, Alexander A1 - Giester, Gerald T1 - First high-pressure synthesis of rossmanitic tourmaline and evidence for the incorporation of Li at the X site JF - Physics and chemistry of minerals / in cooperation with the International Mineralogical Association (IMA) N2 - Lithium is an important component of some tourmalines, especially in chemically evolved granites and pegmatites. All attempts at synthesizing Li-rich tourmaline have so far been unsuccessful. Here we describe the first synthesis of rossmanitic tourmaline at 4 GPa and 700 degrees C in the system Li2OAl2O3SiO2B2O3H2O (LASBH) from seed-free solid starting materials consisting of a homogenous mixture of Li2O, gamma-Al2O3, quartz and H3BO3. The solid run products after 12-day run duration comprise rossmanitic tourmaline (68 wt%), dumortierite (28 wt%) and traces of spodumene (3 wt%) and coesite (1 wt%). Tourmaline forms idiomorphic, large prismatic crystals (30 X 100 mu m), which are inclusion free and chemically unzoned. The refined cell dimensions of the tourmaline are: a = 15.7396(9) angstrom, c = 7.0575(5) angstrom, V = 1514.1(2) angstrom 3. Conventionally, the Li+ ion is assumed to exclusively occupy the octahedral Y site in the tourmaline structure to a maximum of 2 Li per formula unit (pfu). However, the chemical composition of our synthetic tourmaline determined by electron microprobe and secondary ion mass spectroscopy results in the formula: (X)(square Li-0.67(11)(0.33(11)))(Y)(Al2.53(10)Li0.47(10))(Z)(Al-6)T(Si5.42(15)B0.58(15))O-18(B)(BO3)(3)(V+W)[(OH)(2.40(3))O-1.60(3)], wherein a significant amount of Li occupies the X site for charge balance requirements. Reliable assignment of the OH-stretching vibrations in a polarized single-crystal Raman spectrum such as a single-crystal XRD structure refinement, confirms the incorporation of Li at the X site [0.24(9) and 0.15(5) Li-X pfu, respectively]. The SREF data show that the LiO1 distances are shortened significantly in order to compensate for the smaller ionic radius of Li+ compared to Na+, K+ or Ca2+ at the X site, i.e., Li is closer to the Si6O18 ring and to a sevenfold coordination with oxygen. KW - High-pressure synthesis KW - Tourmaline KW - Rossmanite KW - Crystal chemistry KW - X site occupancy KW - SIMS KW - SREF KW - Li isotope fractionation Y1 - 2016 U6 - https://doi.org/10.1007/s00269-016-0863-0 SN - 0342-1791 SN - 1432-2021 VL - 44 SP - 353 EP - 363 PB - Springer CY - New York ER - TY - JOUR A1 - Kutzschbach, Martin A1 - Wunder, Bernd A1 - Wannhoff, Iris A1 - Wilke, Franziska Daniela Helena A1 - Couffignal, Frédéric A1 - Rocholl, Alexander T1 - Raman spectroscopic quantification of tetrahedral boron in synthetic aluminum-rich tourmaline JF - American mineralogist : an international journal of earth and planetary materials N2 - The Raman spectra of five B-[4]-bearing tourmalines of different composition synthesized at 700 degrees C/4.0 GPa (including first-time synthesis of Na-Li-B-[4]-tourmaline, Ca-Li-B-[4]-tourmaline, and Ca-bearing square-B-[4]-tourmaline) reveal a strong correlation between the tetrahedral boron content and the summed relative intensity of all OH-stretching bands between 3300-3430 cm(-1). The band shift to low wavenumbers is explained by strong O3-H center dot center dot center dot O5 hydrogen bridge bonding. Applying the regression equation to natural B-[4]-bearing tourmaline from the Koralpe (Austria) reproduces the EMPA-derived value perfectly [EMPA: 0.67(12) B-[4] pfu vs. Raman: 0.66(13) B-[4] pfu]. This demonstrates that Raman spectroscopy provides a fast and easy-to-use tool for the quantification of tetrahedral boron in tourmaline. The knowledge of the amount of tetrahedral boron in tourmaline has important implications for the better understanding and modeling of B-isotope fractionation between tourmaline and fluid/melt, widely used as a tracer of mass transfer processes. KW - Tourmaline KW - high pressure KW - synthesis KW - tetrahedral boron KW - Raman KW - SIMS KW - Lithium KW - Beryllium and Boron: Quintessentially Crustal Y1 - 2021 U6 - https://doi.org/10.2138/am-2021-7758 SN - 0003-004X SN - 1945-3027 VL - 106 IS - 6 SP - 872 EP - 882 PB - Mineralogical Society of America CY - Washington, DC [u.a.] ER -