Natrotitanite, ideally (Na0.5Y0.5)Ti(SiO4)O, a new mineral from the Verkhnee Espe deposit, Akjailyautas mountains, Eastern Kazakhstan district, Kazakhstan: description and crystal structure

Abstract Natrotitanite, ideally (Na0.5Y0.5)Ti(SiO4)O, is a new mineral from the Verkhnee Espe rare-element deposit at the northern exo-contact of the Akjailyautas granite massif in the northern part of the Tarbagatai mountain range, Eastern Kazakhstan. Both the mineral and the name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2010-033). Star-shaped aggregates of small short prisms of yellow or yellowish white (Na,Y,REE)-bearing titanite rimmed by thin (~2 μm) rims of natrotitanite are embedded in yttrium-bearing fluorite and replace narsarsukite. Associated minerals are microcline, albite, quartz, riebeckite, aegirine, biotite, astrophyllite, rutile, zircon and elpidite. Natrotitanite is milky white to yellowish grey, transparent to translucent, and has a white streak and a vitreous lustre. It shows pale orange cathodoluminescence but does not fluoresce under ultraviolet light. It shows no cleavage or parting, and is brittle; the calculated density is 3.833 g cm-3. The indices of refraction, measured with the Bloss spindle stage for the wavelength 590 nm using a gel filter, are α = 1.904, γ = 2.030, and these values are in accord with the mean refractive index, 1.988, calculated from the Gladstone-Dale relation. Natrotitanite is monoclinic, C2/c, a = 6.5691(2), b = 8.6869(3), c = 7.0924(2) Å, P = 114.1269(4)°, V = 369.4(2) Å3, Z= 4, a:b:c = 0.7562:1: 0.8164. The seven strongest lines in the X-ray powder diffraction pattern [in the order d (Å), I, (hkl)] are as follows: 2.597, 10, (130); 3.248, 8, (112̅); 2.994, 6, (200); 1.641, 4, (330); 4.941, 3, (HO); 1.498, 3, (400); 2.273, 3, (113̅). Chemical analysis by electron microprobe gave Nb2O5 1.28, SiO2 27.83, TiO2 35.00, SnO2 0.57, V2O3 0.36, Fe2O3 0.23, Y2O3 7.87, Ce2O3 0.83, Sm2O3 0.26, Gd2O3 0.46, Tb2O3 0.17, Dy2O3 2.45, Ho2O3 0.16, Er2O3 2.24, Tm2O3 0.50, Yb2O3 2.53, Nd2O3 0.35, Lu2O3 0.28, MnO 0.33, CaO 8.16, Na2O 5.55, F 1.52 O ≡ F -0.64, sum 98.71 wt.%. The resulting empirical formula is (Na0.39Ca0.32Y0.15Dy0.03Yb0.03 Er0.03Ce0.01Ho0.01Tm0.01Gd0.01Nd0.01)∑1.00(Ti0.95Nb0.02Sn0.01Fe3+0.01Mn0.01 V0.01)∑1.01Si1.01O4.00(O0.83F0.17), calculated on the basis of 3 cations per formula unit. The general formula is written as (Na,Ca,Y,REE)TiSiO4(O,F), and the endmember formula is (Na0.5Y0.5)Ti(SiO4)O. The crystal structure of a composite optically continuous crystal of natrotitanite and (Na, Y)-bearing titanite was mounted on a Bruker D8 three-circle diffractometer equipped with a rotating anode generator (MoKα radiation), a multi-layer optics incident-beam path and an APEX-II CCD detector. The crystal structure was refined in space group C2/c to a final R1 index of 1.8%. Natrotitanite is isostructural with titanite, (Na + Y + REE) replacing Ca at the Ca site in the titanite structure.

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