The intracrystalline cation distributions in fourteen natural Zn-aluminate spinels were determined by means of X-ray single-crystal structural refinement, supported for some samples by Mössbauer spectroscopy.

Zinc substitutes for Mg and subordinately Fe2+ and its relevant changes in content, from 0.10 to 0.96 atoms per formula unit (apfu), are not related to variations of cell parameter. The latter is determined mainly by the substitution Fe3+ ⇌ Al. In agreement with data from synthetic samples, a small but definite amount of Zn (up to 0.06 apfu) is located in the octahedral M site. Fe2+, when present, shows a preference for tetrahedral coordination.

An improved value of the tetrahedral Zn(T)-O distance (1.960 Å) was obtained, integrating the set of interatomic distances used for the determination of cation distribution in spinels.

The crystal chemistry of a natural, gem-quality, blue-grey Zn-rich spinel crystal from Jemaa, Kaduna State, Nigeria, was studied using electron microprobe, single-crystal X-ray diffraction, optical absorption and Raman spectroscopies. The composition of the crystal approaches the gahnite endmember (ZnAl2O4), ∼94 mol.%, with the remainder being dominated by a hercynite component (FeAl2O4). The unit-cell dimension is 8.0850(3) Å and the tetrahedral and octahedral bond distances are determined as T–O 1.9485(6) Å and M–O 1.9137(3) Å. Crystal chemical analysis resulted in the empirical structural formula T(Zn0.94Fe2+0.03Al0.03)M (Al1.96Fe2+0.03Fe3+0.01)O4, which shows Zn and Al almost fully ordered in the tetrahedrally and octahedrally coordinated T and M sites, respectively. Raman spectra obtained using the excitation of the blue 473.1 nm line of a Nd:YAG laser display three of the five Raman-active modes predicted for the general oxide spinel group of minerals. These are the Eg mode at 420.6 cm–1 and the T2g modes at 510 cm–1 and 661 cm–1, due to vibrations in the AlO6 octahedra. Optical absorption spectra recorded in the UV/VIS-NIR-MIR range 2000 29000 cm–1 show a dominant absorption band at ∼5000 cm–1 which is caused by spin-allowed electronic d–d transitions in Fe2+ located at the T sites. The blue-grey hue exhibited by the sample is mainly due to spin-forbidden electronic transitions in TFe2+ and to MFe2+ ↔MFe3+ intervalence charge transfer, and the poor saturation of the colour is due to the small concentration of Fe2+ and Fe3+.

Quartz-gahnite-sillimanite asssemblages are described from a supracrustal enclave at Kraaifontein, 45 km south-west of Springbok in the Namaqualand Metamorphic Complex, South Africa. The assemblage formed by prograde reaction in the granulite facies zone during the 1100 Ma Namaqua event, possibly as the result of desulphidation of sphalerite. Subsequent lower-amphibolite-facies retrogression occurred in close proximity to shear zones during an early Pan-African metamorphic event at 700 Ma. Zincian staurolite formed as overgrowths on gahnite in a hydration reaction involving the consumption of gahnite, quartz, and sillimanite. Compositional zoning to more zinc-rich rims in gahnite at Kraaifontein is unrelated to the retrograde reaction, but is interpreted as a result of changing conditions during the prograde Namaqua event.

We report an unusual occurrence of margarite, corundum, gahnite and zincohögbomite from the Raleigh terrane in the Piedmont Province of Virginia. The assemblage occurs in a chlorite-rich blackwall associated with a small metamorphosed ultramafic rock body. The blackwall is dominated by chlorite, but also contains distinctive clusters (1–4 mm across) that typically consist of ragged Zn-rich spinel grains surrounded by masses of randomly oriented margarite. Also spatially associated with spinel are smaller grains of corundum and högbomite. In most cases, spinel and högbomite are sufficiently enriched in Zn to be called gahnite and zincohögbomite, respectively. Some högbomite grains are distinctly banded in back-scattered electron images, primarily reflecting variations in Zn-content. Textures suggest that högbomite formed at the expense of spinel (although locally the reverse relationship holds), and högbomite compositions mimic those of spinel. Margarite appears to be a later phase, and textures imply formation via reactions with spinel, corundum and, possibly, chlorite. This occurrence of Zn-rich spinel and högbomite is clearly related to the bulk composition of the blackwall rock, which contains >2500 ppm Zn. The origin of this Zn-rich composition is unclear, but could be due to a small amount of sphalerite or zincian-staurolite in the protolith.

The Zn-spinel gahnite has been discovered in the ∼3.75 Ga Isua Greenstone Belt, West Greenland. It is light blue-green to colourless in hand specimen and colourless in thin section as opposed to most other gahnites which are dark green to brown. The gahnites from Isua have very low Fe and Mg contents, and their compositions are thus close to the endmember gahnite. The gahnite was formed, during metamorphism, from sphalerite, in the absence of Fe-rich sulphides.