Trebiskyite, the First Titanium-Decavanadate Mineral

Abstract

Abstract Trebiskyite, Na3Mg2[TiV9O28]·22H2O, from the Pickett Corral mine, Bull Canyon, Montrose County, Colorado, USA, is the first mineral containing essential Ti as a component of a decavanadate polyanion. Crystals are thin prisms or needles up to ∼0.3 mm in length, occurring as individuals and in divergent sprays. Trebiskyite crystals are translucent yellow with vitreous luster and pale-yellow streak and are non-fluorescent under both longwave and shortwave ultraviolet illumination. The crystals exhibit elongation on [001] and are modified by several 0kl prism forms, possibly corresponding to {010}, {011}, and {012}. The Mohs hardness is ca. 2 based on scratch tests. Crystals have brittle tenacity with irregular fracture. No apparent cleavage, nor twinning, was evident, and the mineral is readily soluble in H2O. The density measured by flotation in methylene iodide-toluene mixture is 2.38(2) g/cm3. The calculated density is 2.352 g/cm3 for the empirical formula and 2.343 g/cm3 for the ideal formula. Electron microprobe analyses provided the empirical formula Na3.39Mg1.87V8.75Ti1.25O50H44.00, based on Ti + V = 10 apfu, O = 50 apfu, with the Na content having been determined from the refined crystal structure. Trebiskyite is monoclinic, space group P21/c, a = 9.478(4), b = 21.426(11), c = 11.267(5) Å, β = 114.572(7)°, V = 2080.8(13) Å3, Z = 2. The structure was refined from 6642 reflections to a final R1 = 0.0517 for reflections I > 2σ(I). The structural unit of trebiskyite, (TiV9O28)7−, is built from a Ti-substituted decavanadate polyanion, (V10O28)6−, found in other members of the pascoite family. Chemically, trebiskyite is closely related to lasalite, Na2Mg2[V10O28]·20H2O, and huemulite, Na4Mg[V10O28]·24H2O; however, trebiskyite contains a novel structural arrangement that is unique among the decavanadate minerals. The interstitial complex in trebiskyite has the ideal formula {[Na3Mg2(H2O)19](H2O)3} and consists of chains of distorted octahedrally coordinated Na+ and regular Mg[O(H2O)5] octahedra. The observed low incident bond valence to the V1 site (4.45 vu) and marked deviation in vanadyl and V–Oeq bond lengths indicate that this site is host to the essential Ti4+ identified during chemical analyses.