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Predictive crystal-chemical relations in Ti-silicates based on the TS block

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Abstract

In a group of minerals of reasonable complexity in which the structure topology is related but not identical, the general relation between structure topology and chemical composition is not known. This problem is of major significance. The structural hierarchy and stereochemistry are described for 27 titanium disilicate minerals that contain the TS (titanium-silicate) block, a central trioctahedral (O) sheet and two adjacent (H) sheets of [5]- and [6]-coordinated polyhedra and (Si2O7) groups and related delindeite. The TS block is characterized by a planar cell based on translation vectors, t 1 and t 2 , with t 1 ∼ 5.5 and t 2 ∼ 7 Å and t 1 ∧ t 2 close to 90°. The general formula of the TS block is A P2 B P2 M H 2 M O 4 (Si 2 O 7 ) 2 X 4 + n, where M H2 and M O4 = cations of the H and O sheets; MH = Ti (= Ti + Nb), Zr, Mn2+, Ca; MO = Ti, Zr, Mn2+, Ca, Na; AP and BP are cations at the peripheral (P) sites = Na, Ca, Ba; X = anions = O, OH, F; n = 0, 2, 4; the core part of the TS block is shown in bold and is invariant. Cations in each sheet of the TS block form a close-packed layer and the three layers are cubic close packed.

There are three topologically distinct TS blocks, depending on the type of linkage of two H sheets and the central O sheet. The H sheets of one TS block attach to the O sheet in the same manner. All structures consist of a TS block and an I (intermediate) block that comprises atoms between two TS blocks. Usually, the I block consists of alkali and alkaline-earth cations, (H2O) groups and oxyanions (PO4)3−, (SO4)2− and (CO3)2−. These structures naturally fall into four groups, based on differences in topology and stereochemistry of the TS block. In Group I, Ti = 1 apfu Ti occurs in the O sheet, and (Si2O7) groups link to a Na polyhedron of the O sheet (linkage 1). In Group II, Ti = 2 apfu, Ti occurs in the H sheet, and (Si2O7) groups link to two M 2+ octahedra of the O sheet adjacent along t 2 (linkage 2). In Group III, Ti = 3 apfu, Ti occurs in the O and H sheets, and (Si2O7) groups link to the Ti octahedron of the O sheet (linkage 1). In Group IV, Ti = 4 apfu (the maximum possible content of Ti in the TS block), Ti occurs in the O and H sheets, and (Si2O7) groups link to two Ti octahedra of the O sheet adjacent along t 1 (linkage 3). The stability of the TS block is due to the ability of Ti (Nb) to have an extremely wide range in Ti (Nb)-anion bond lengths, 1.68–2.30 Å, which allows the chemical composition of the TS block to vary widely. In crystal structures so far known, only one type of TS block occurs in a structure. The TS block propagates close-packing of cations onto the I block. The general structural principles and the relation between structure topology and chemical composition are described for the TS-block minerals. These principles allow prediction of structural arrangements and possible chemical compositions, and testing whether or not all aspects of the structure and chemical formula of a mineral are correct. Here, I show how these principles work, and review recent results that show the effectiveness of these principles as a predictive technique.

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Authors and Affiliations

  1. Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of Sciences, Staromonetnyi per. 35, Moscow, 119017, Russia

    E. V. Sokolova

  2. Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada

    E. V. Sokolova

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Original Russian Text © E.V. Sokolova, 2010, published in Geologiya Rudnykh Mestorozhdenii, 2010, Vol. 52, No. 5, pp. 457–474.

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Sokolova, E.V. Predictive crystal-chemical relations in Ti-silicates based on the TS block. Geol. Ore Deposits 52, 410–427 (2010). https://doi.org/10.1134/S1075701510050065

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