The Cape Cross–Uis pegmatite belt, Damara Orogen, north-central Namibia hosts multiple Ta–Nb- and Sn-oxide-bearing pegmatites. Columbite-group minerals, tapiolite, cassiterite and minor ixiolite and wodginite occur in abundance within pegmatites and display various compositional and internal structural mineralogical variations. Ta–Nb oxides display various zonation patterns indicative of multiple crystallisation phases, whereas cassiterite is dominantly homogeneous with minor euhedral columbite-group mineral inclusions. Ta–Nb oxides are mostly rich in Fe, with fractionation patterns in the columbite quadrilateral being sub parallel to the Ta/(Ta + Nb) axis; increasing Ta/(Ta + Nb) with little change in Mn/(Mn + Fe), which is consistent with classical trends in beryl-to-spodumene rare-element pegmatites. In addition, these trends suggest that co-crystallising minerals compete with Ta–Nb oxides for elements such as Mn, preventing Ta–Nb oxides from attaining Mn-rich compositions during the fractionation process. Cassiterite shows similar fractionation patterns with Fe > Mn and notable increases in the Ta content. Minor-element substitution in Ta–Nb oxides shows sharp decreases with increasing fractionation supporting the hypothesis that newly stabilised co-occurring minerals compete with columbite-group minerals for certain elements. Tapiolite shows the same minor-element trend, however, only for Sn and Ti suggesting cassiterite was a dominant competing mineral. Although crystallisation of Ta–Nb oxides from an aqueous fluid at the late-stages of pegmatite genesis is highly debated, significantly elevated Ta contents in metasomatised country rock, compared to unaltered country rock, may give new insight, suggesting that Ta may indeed partition into, and be transported by, an exsolved aqueous fluid. However, further studies of the country rock metasomatic contacts are required as currently the dataset is limited. The degree of fractionation as depicted by Ta–Nb and Sn oxides within pegmatites, indicate that a zonation from primitive to evolved pegmatites surrounding granites is not present and that pegmatites are probably not related to granites in the typical parent–daughter relationship.

Structural modifications as a function of the degree of order (Q) in FeTa2O6 ferrotapiolite have been characterized by means of single-crystal X-ray diffraction (SC-XRD). A total of 26 datasets covering the range of Q between 0.154 and 1 have been obtained by thermal treatments followed by quenching of natural tapiolite crystals. Ordering of Fe2+ at the A sites and of Ta5+ at the B sites causes a linear increase in the a/c lattice constants ratio, as a consequence of a linear decrease of the c dimension and only slight modifications of the a parameter. Calibration of a/c vs. Q represents a very useful tool for a rapid determination of the degree of order of tapiolite samples. Polyhedral volumes of the two octahedral sites vary linearly with Q as a consequence of the different ionic radii of the two species. Both the sites remain almost regular at all Q values but the B site shows an increasing off-centre displacement of the cation with increasing Q. Observed structure factors of supercell reflections, characterized by l ≠ 3n, increase linearly as a function of Q, thus representing a further tool for a quick evaluation of the degree of order.

The Koktokay No. 3 granitic pegmatite, Altai, northwestern China, is a strongly zoned rare-element granitic pegmatite, where the petrographic zones were distinguished into two groups: outer zones (I to IV) and inner zones (V to IX). Nb-Ta oxides and zircon are investigated in this paper by using quantitative electron-microprobe analyses (EMPA) and backscattered-electron (BSE) imaging. Columbite-tantalite and zircon occur in most textural zones, whereas tapiolite and uranmicrolite are mainly restricted to zone VII. Manganocolumbite and zircon from the outer zones (zones II and IV) are homogeneous except for a few exceptions, whereas manganotantalite and hafnian zircon from the inner zones (V–VII) are obviously heterogeneous and strongly zoned. Chemically, Ta/(Nb+Ta) in columbite-tantalite and Hf/(Zr+Hf) in zircon increase from the outer to the inner zones on one hand, and from core to rim in single zoned crystals on the other hand. Observations of intra-zonal variations of the chemical composition of Nb-Ta oxides and zircon in the Koktokay No. 3 granitic pegmatite may suggest that the outer zones crystallize under magmatic conditions, whereas the inner zones crystallize under fluid-rich magmatic conditions, and locally under hydrothermal conditions. The extreme enrichments of columbite-tantalite in Ta, and of zircon in Hf, as well as the occurrence of uranmicrolite and tapiolite, indicate an elevated evolution of the Koktokay No. 3 granitic pegmatite.

The crystal chemistry of tapiolite is more complicated than previously recognized. Perusal and synthesis of relatively recent publications reveals a ‘hidden’ story about tapiolite, one that: (1) permits quantification of the effects of Mn, Fe3+, Ti (and Sn) upon the unit-cell parameters of maximally ordered tapiolite; (2) shows that the effect of Nb = Ta substitution upon unit-cell parameters is insignificant; (3) casts doubt on the usefulness of heating experiments for accurately evaluating cation order in tapiolite; (4) suggests that rutile exsolves from tapiolite upon heating in air at lower temperatures than previously established; (5) shows that the maximum solubility of TiO2 in FeTa2O6 tapiolite during the later stages of crystallization of granitic pegmatites is ∼1 mol.%; (6) shows that the heating paths for at least some natural tapiolite samples are not necessarily linear, consisting of two sequential steps; (7) sheds doubt on the usefulness of unit-cell parameters as quantitative measures of long-range cation order, Q, in tapiolite; but (8) does show that the intensity ratio I011/I110 can provide an accurate and reasonably precise measure of cation order in tapiolite.