The systematics of cation ordering in binary spinel solid solutions have been investigated using an interatomic potential model combined with Monte Carlo simulations. The formalism to describe a system containing three cation species ordering over two non-equivalent sub-lattices is developed and the method applied to the MgAl2O4-FeAl2O4 binary solid solution. Our results compare favourably with experimental measurements of site-occupancy data, although the experiments display a slightly larger degree of non-ideality than the simulations. A possible kinetic origin of the non-ideal behaviour was examined by performing simulations in which only exchange of Mg and Fe2+ between tetrahedral and octahedral sites was permitted below the Al-blocking temperature of 1160 K. This approach improves the agreement with the experimental site occupancies, and suggests that the blocking temperature for moving Mg and Fe2+ between tetrahedral and octahedral sites is significantly lower than for moving Al

Experimental breakdown of staurolite + inclusions of albite and muscovite (representing an aluminous Fe-rich metapelitic composition) occurs within the KNFMASH system at 800°C and 0.1 GPa under fluid-present conditions over periods of 2 days to 8 weeks. The overall melt-producing reaction is staurolite + muscovite + plagioclase + vapour = hercynite + corundum + mullite + quartz + liquid, and involves three reactions; staurolite + vapour = hercynite + corundum + quartz + liquid, albite + vapour = mullite + liquid, and muscovite + vapour = mullite + liquid. Melt (glass) compositions are siliceous (77.2–64.5 wt.% SiO2), peraluminous (A/CNK = 1.5–5.5), and have granite-trondjhemite compositions in terms of normative Ab-Ab-Or contents. Textures indicate that quartz formed later than corundum. The corundum + quartz + hercynite assemblage after staurolite is considered to be metastable and only likely to be found in nature where staurolite-bearing rocks have undergone rapid heating and melting followed by quenching.

In this work a single crystal of synthetic hercynite, FeAl2O4, was investigated by X-ray diffraction up to 7.5 GPa and at room temperature, in order to determine its pressure–volume equation of state. The unit-cell volume decreases non-linearly with a reduction of 3.4% (i.e. 18.43 Å3). The pressure–volume data were fitted to a third-order Birch-Murnaghan equation of state providing the following coefficients: V0 = 542.58(3)Å3, KT0 = 193.9(1.7) GPa, K' = 6.0(5). These results are consistent with previous investigations of Cr and Al spinels measured with the same experimental approach but the KT0 differs significantly from the experimental determination carried out more than 40 years ago by Wang and Simmons (1972) by the pulse echo overlap method. Our new results were used to redetermine the FeAl2O4(hercynite) = FeO(wüstite) + Al2O3(corundum) equilibrium in P–T space and obtain geobarometric information for Cr-Al spinels found as inclusions in diamond.

Manganese incorporation in synthetic hercynite, and partitioning between hercynite and silicate melt synthesized at 1.0 GPa, 1250°C, and at an fO2 buffered by Fe–FeO, has been studied by X-ray absorption spectroscopy and single-crystal X-ray structure refinement. Spectra indicate the presence of both Mn2+ and Mn3+ (and possibly also Mn4+) in synthetic hercynite and partitioning of Mn2+ into the melt phase, and Mn3+ into hercynite, respectively, under run conditions. X-ray refinement is consistent with partial disorder of Fe and Al across tetrahedral and octahedral sites. A higher than expected degree of Fe-Al disorder in the Mn-bearing hercynite can be explained by preferential incorporation of Mn2+ onto the tetrahedral site, and indicates that Fe-Al disorder in pure, stoichiometric hercynite cannot necessarily be used to determine closure temperatures in natural spinel. However, partitioning of Mn2+ and Mn3+ between melt and hercynite suggests that Mn incorporation in hercynite could be used as a measure of fO2 conditions in magmas during spinel crystallization.