@article{KutzschbachWunderKrstulovicetal.2016,
  author    = {Kutzschbach, Martin and Wunder, Bernd and Krstulovic, Marija and Ertl, Andreas and Trumbull, Robert B. and Rocholl, Alexander and Giester, Gerald},
  title     = {First high-pressure synthesis of rossmanitic tourmaline and evidence for the incorporation of Li at the X site},
  series = {Physics and chemistry of minerals / in cooperation with the International Mineralogical Association (IMA)},
  volume    = {44},
  journal   = {Physics and chemistry of minerals / in cooperation with the International Mineralogical Association (IMA)},
  publisher = {Springer},
  address   = {New York},
  issn      = {0342-1791},
  doi       = {10.1007/s00269-016-0863-0},
  pages     = {353 -- 363},
  year      = {2016},
  abstract  = {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.},
  language  = {en}
}