Intermediate compositions along the bornite–digenite join exsolve during quenching from above-solvus temperatures. This involves vacancy clustering and cation ordering processes, and is facilitated by fast cation diffusion rates in the presence of a large (10–25%) metal vacancy population. Samples of six different compositions across the bornite–Cu9S5 join, synthesised from component elements in sealed quartz capsules, were water-quenched from 600°C and analysed using high-resolution neutron powder diffraction (HRPD). Time-of-flight spectra measured at room temperature showed all intermediate compositions had exsolved into mixtures of bornite and low digenite with a 5.0a superstructure. No evidence for the presence of any other phase was found. Variations in the lattice parameters of the exsolved bornite phase were observed for different bulk compositions across the join, and ascribed to variations in the degree of order. Bornite exsolved from digenite-rich compositions may not be fully ordered due to the much lower solvus temperatures at the Cu-rich end of the solid solution. As only slight differences were observed between the diffraction patterns of a visibly exsolved and a rapidly quenched sample of the same bulk composition, the formation of optically-visible exsolution lamellae on {100} is ascribed to a process of coalescence of sub-microscopic domains initially formed during the quenching process. The rapid kinetics of exsolution at geologically low temperatures, explains the lack of authenticated natural occurrences of intermediate compositions in the solid solution in nature, and the limited degree of stoichiometric variation observed in end-members.

Alkali feldspar phenocrysts (bulk composition Or75.0Ab24.6An0.4) in the subsolvus Shap granite comprise a fine-scale mixture of subregular pristine crypto- and micro-perthites with altered, micropore-rich feldspar with irregular microstructures. The regular perthites are strain-controlled intergrowths of Albite and/or Periclinetwinned albite exsolution lamellae within tweed orthoclase. The microperthites formed at ⩽ 590°C by heterogeneous nucleation of thin albite films which coarsened to > 1 µm length. Cryptoperthites developed at < 400°C by homogeneous nucleation of sub-µm long platelets between films. Platelets are coherent, but the coarser microperthite lamellae are semi-coherent, with pairs of misfit dislocations sub-regularly spaced along the albite-orthoclase interface. As much as 30% of any one feldspar crystal is turbid, a result of the formation of numerous µm to sub-µm sized micropores during deuteric alteration. In some areas, deuteric fluids gained access to the interior of feldspar crystals by exploiting semi-coherent film lamellae. Albite was selectively dissolved and micropore-rich irregular microcline was reprecipitated in its place. In other parts of the feldspars deuteric recrystallization completely cross-cuts the pristine microtextures and patch perthites have formed. These are coarse, incoherent to semi-coherent intergrowths of irregular microcline (replacing tweed orthoclase) and Albite-twinned albite. The deuteric reactions occurred at < 400°C; the main driving force for dissolution and reprecipitation was decrease in the elastic strain energy at the coherent interfaces of crypto-and micro-perthite lamellae, and the recrystallization of tweed orthoclase to irregular microcline.

The study discusses the mineralogical, geochemical and thermometric properties of rock-forming blue quartz from eight worldwide occurrences. Compared to non-blue quartz, blue quartz contains significant amounts of submicron-sized (1 μm—100 nm) and nanometre-sized (<100 nm) inclusions. Mica, ilmenite and rutile constitute the most abundant submicron-sized inclusions, and are formed probably by syngenetic precipitation in the boundary layer between quartz and melt (entrapment model). Nanometre-sized rutile possibly originated by epigenetic exsolution of Ti from the quartz structure (exsolution model). Rayleigh scattering of light by nano-particulate inclusions best explains the origin of the blue colour. Blue quartz is generally Ti-rich (∼100—300 ppm) and formed at high temperatures (∼700°C—900°C). The large number, and high spatial density, of tiny xenocrystic inclusions of Ti-bearing minerals make calculations of crystallization temperatures using the Ti-in-quartz thermometer unreliable. The geological significance of blue quartz remains obscure.

Three almandine-rich metamorphic garnets have been studied by analytical electron microscopy and electron microprobe analysis. Electron microprobe analyses with total Fe calculated as Fe2+ show that there are no significant departures from stoichiometry due to the presence of Fe3+ in any of the garnets studied. However, in the transmission electron microscope (TEM) all the garnets were found to contain myriad spherical, iron-rich particles up to 400 Å in diameter. Microdiffraction techniques have revealed that the particles are a cubic spinel phase, consistent with magnetite. There is no crystallographic relationship between the host garnet and the particles, a rare situation for exsolution processes. The presence of such particles is interpreted in terms of the exsolution of magnetite from almandine garnet during cooling. This can apparently occur at temperatures below 55°C. The size of the particles is a qualitative indicator of the cooling rate of the rock, but is also dependent on the original Fe3+ content of the host garnet.

Trace mineral assemblages in the bornite- and chalcopyrite-rich Cu-Fe zone of the Ocna de Fier-Dognecea skarn deposits, Banat, SW Romania provide additional constraints on the genesis of this classic zoned skarn system. Observed assemblages substantiate a model, in which the Cu-Fe zone forms the proximal fluid-plume root of the system. Observed trace mineral assemblages in the magnesian forsterite-bearing skarns crystallized at ~650°C in a volatile-rich environment, evidenced by widespread phlogopite, ludwigite, valleriite and apatite. The entire assemblage thus belongs to the initial stage of skarn formation. Prolonged cooling led to sequential exsolution of trace mineral phases from bornite and chalcopyrite during the retrograde stage, although still at temperatures in excess of 500°C. Bornite is typified by the abundance of exsolved phases along cleavage planes and along crystal margins, notably chalcopyrite and pyrrhotite, but also cobalt pentlandite, carrollite, wittichenite, galena, mawsonite, silver and electrum. Chalcopyrite hosts cobalt pentlandite, carrollite, wittichenite, galena and a sequence of Se- and Te-bearing minerals (kawazulite, bohdanowiczite, hessite, volynskite), along, although not restricted to, grain margins. The assemblage bornite-chalcopyrite-magnetite, with the trace phases, cobalt pentlandite, carrollite, wittichenite and various Se- and Te-bearing minerals represents a characteristic assemblage common to a disparate range of deposits formed at temperatures in excess of 500°C in the presence of volatiles and typified by relatively low fS2 fluids.

Pyrrhotites in polished sections from more than twenty stratabound massive sulphide and magmatic nickel-copper deposits in Norway were studied under the microscope using the magnetic colloid method. In both types of deposits, two distinct styles of intergrowths between monoclinic and hexagonal pyrrhotites were found: crystallographically-controlled lamellar intergrowths and fissure-controlled irregular intergrowths.

Lamellar intergrowths consist of crystallographically oriented monoclinic lamellae occurring in a hexagonal matrix and were produced originally by exsolution from hexagonal pyrrhotite on cooling. Irregular intergrowths comprise blades and patches of monoclinic pyrrhotite occurring along fissures and grain boundaries of hexagonal pyrrhotite, and were formed by interactions between hexagonal grains and sulphur-rich hydrothermal solutions.

Increase in lamella thickness and spacing, development of lamella zonations, wedge-shaped composite ends, boxworks and composite lamellae were caused by progressive lamellae coarsening and maturation during natural annealing, which could have been promoted by anisotropic stress. Metamorphic recrystallization and annealing tend to homogenize pyrrhotite and erase preexisting exsolution lamellae.

In the large serpentinite body at Zöblitz, which is part of the Gneiss-Eclogite Unit of the Saxonian Erzgebirge, ilmenite rods have been detected in olivine. Although these rods are ≤1 μm wide, they can be unequivocally identified as ilmenite using electron backscatter diffraction. We also applied this method to prove that ilmenite is topotactically intergrown with the olivine host ([100]ol ‖ [001]ilm). This relation was found previously, e.g. for ilmenite exsolved from olivine of garnet peridotite from Alpe Arami, Swiss Alps. The degree of this exsolution phenomenon in the Alpe Arami rocks was taken as an indication of the original formation of a Ti-bearing mineral at depths of ∽300 km. As in the olivines of the serpentinite from Zöblitz, the density of the ilmenite rods is significantly less than in the rock from Alpe Arami. We think that our observation is compatible with previous P-T estimates of close to 4 GPa and 1000–1100°C for the ultramafic bodies in the central Saxonian Erzgebirge.

Ortho- and clinopyroxenes within partially-hydrated harzburgites from Elba and Val di Cecina (Italy) show lamellar exsolution textures and variable replacement by biopyriboles, talc-chlorite-serpentine mixed layers and serpentine. Chemical and geothermometric data suggest that the pyroxenes crystallized at 1240–1051°C, followed by subsolidus exsolution at slightly lower T (1145–1025°C for clinopyroxene lamellae + orthopyroxene matrix pairs and a 1033–982°C range for orthopyroxene lamellae + clinopyroxene matrix pairs).

Investigation by transmission electron microscopy of exsolved enstatite and augite reveals a multistage hydration process. The first stage (highest T, probably in the amphibole stability field) leads to the formation of biopyribole lamellae within exsolved augite, leaving the enstatite matrix unaffected. The second stage (~500–300°C) corresponds to the topotactic replacement of enstatite by layer silicates (talc + chlorite + serpentine, with (001)layer silicates parallel to (100)enstatite). Enstatite is also replaced by randomly oriented, poorly crystalline serpentine. The last hydration stage (<300°C) corresponds to the disappearence of augite and recrystallization of serpentine, leading to completely hydrated bastites with random lizardite lamellae, polygonal serpentine and minor chrysotile.

A carbonatite dyke from the Sarnu-Dandali alkaline complex, Rajasthan, India, contains a remarkable suite of rare earth, strontium-rich minerals with spectacular primary textures.

Sr, Mn-rich calcite in the outer 5 mm of the dyke contains exsolved lamellae of carbocernaite, (Ca,Na)(Sr,Ce,Ba)(CO3)2, orientated parallel to its twin and cleavage planes. The amount of exsolved carbocernaite increases away from the dyke margin as the Sr content of the calcite increases to a maximum 13 wt.%. Sr levels as high as this in calcite have previously been recorded only in experimental work. The carbocernaite exsolution suggests that Sr-rich calcium carbonate can be a host for major amounts of REE in carbonatite magma.

Separated by a sharp internal boundary, is a complex possibly cotectic intergrowth of carbocernaite and Sr-rich calcite with late Ca-rich strontianite (19 wt.% CaO). Other minerals in the dyke include baryte, pyrrhotite, alabandite, sphalerite and occasional bastnäsite-(La) and thorite. Bands of late britholite-(Ce) traverse the dyke.

The host rock for the dyke is fenitized melanephelinite which is itself traversed by narrow, <1 mm, carbonatite veins beleived to predate the carbonatite dyke. Allanite, britholite-(Ce) and rare monazite-(Ce), developed at the boundary between the carbonatite dyke and the fenite, may have been produced by a reaction between the dyke and the wall rock, or may be related to the later britholite mineralisation.

The textures and mineral compositions indicate primary crystallisation. They are unique amongst rare earth-rich carbonatites which are usually late-stage phenomena with signs of secondary alteration.

Comparison with experimental data available for the calcite-strontianite system suggests conditions of 500°C and 2 kbar for coexisting Sr-rich calcite and Ca-rich strontianite. A smaller scale intergrowth of calcite containing only 2.9 wt.% SrO and coexisting Ca-strontianite may correspond to a further unmixing at 350°C and 2 kbar. Since no experimental data are available for a calcite-carbocernaitestrontianite system, mineral chemistries and the interpreted sequence of crystallisation have been used to construct a hypothetical phase diagram.

Phase relations along the join bornite (Cu5FeS4)-digenite (Cu8.52Fe0.12S4.88) have been redefined using a combination of in situ high-resolution neutron diffraction and differential scanning calorimetry (DSC). Time-of-flight neutron diffraction patterns were collected on a synthetic sample of bn90 at 16 temperatures between 35 and 350°C. This data is compared with data from a natural end-member bornite sample obtained in an earlier study under identical conditions. Phase relations along the bornite-digenite join are inferred from the temperature evolution of the lattice parameters and the intensity of subcell and supercell reflections of coexisting phases.

The DSC scans over the temperature range 50–300°C were performed on a natural digenite sample and samples synthesized at 5 mol.% intervals along the join Cu5FeS4-Cu9S5. The thermal anomalies are correlated with structural phase transitions in componen phases and the solvus temperature for each bulk composition. A phase diagram topology is defined, which was consistent with both diffraction and calorimetric data, but in marked contrast to previous diagrams, shows a consolute point at X = Cu5FeS4 and T = 265°C. This temperature corresponds to that of the tricritical intermediate-high transition in bornite. Isothermal annealing experiments carried out on synthetic starting materials for up to 7 months showed coarsening behaviour consistent with the revised phase diagram topology.

The occurrence of MnO exsolution in periclase host crystals from Långban, Sweden, is described. The composition of the periclase is Mg0.942 Mn0.046Zn0.012O, and it coexists with exsolved manganosite crystals with a composition of Mn0.909Mg0.082Zn0.008O. Crystals of hausmannite are also present, indicating fO2 conditions approaching the MnO–Mn3O4 equilibrium.

Activity-composition data for the system MgO–MnO is critically reviewed. The data obtained from solid electrolyte measurements are rejected because of the unrealistic calculated equilibration temperatures and the large deviations from the gas equilibration Mn-Pt activity measurements. The large errors associated with the gas equilibration measurements, especially at large XMnO, also introduces uncertainties associated with the asymmetric interaction parameters. The non-parametric ‘jack-knife’ method was used to determine the asymmetric interaction parameters and their standard deviations from the data of Wood et al. (1994) and Tsai and Muan (1992). These were calculated as WMnO = 21.2 kJ/mol, σWMnO = 2.5 kJ/mol and WMgO = 8.2 kJ/mol, σWMgO = 3.3 kJ/mol.

Using the asymmetric interaction parameters, WMnO = 19.9 kJ/mol and WMgO = 13.7 kJ/mol for the system MgO–MnO as determined by Wood et al. (1994) and the equations for two-phase equilibrium as formulated by Thompson (1967), equilibration temperatures of 334°C and 466°C were calculated. The difference between the calculated temperatures is ascribed to inaccuracies in the experimentally determined interaction parameters.

Macro- and micro-perthitic microclines from pegmatites from Perth, Ontario (Wards catalogue 46 E 0510) and Keystone, South Dakota (Wards 46 E 5125) have been studied using light and electron microscopy. A sample of the type perthite from Perth, Ontario (Hunterian Museum, Glasgow, M2361)was compared using light microscopy. It differs in bulk composition and microtexture from the Wards sample. The Perth sample from Wards is a mesoperthite, with sub-periodic ∼mm-thick albite veins near (100), with irregular surfaces. The microcline has regular tartan twins and formed fromorthoclase by a continuous process. The Keystone sample is a microperthite, with non-periodic albite veins mainly in {110}. Irregular tartan twins, volumes of irregular microcline and subgrains suggest that the microcline formed by dissolution–reprecipitation. Microcline in both samplescontains semicoherent cryptoperthitic albite films that formed after the development of tartan twins. The bulk compositions of these intergrowths imply exsolution below ∼400°C. Diffusion parameters imply sustained heating for between 0.11 My at 400°C, 1.5 GPa and 8.4 My at 300°C,1 GPa. Unrealistic times are required at 200°C. Subsequently, the crystals reacted with a fluid leading to replacive growth of the vein perthites. Unusually, Albite twin composition planes in replacive subgrains have sub-periodic dislocations, formed by coalescence of advancing growthtwins. Processes that might lead to periodic, replacive intergrowths are discussed. The Perth and Keystone feldspars have been used for experimental work on dissolution during weathering and on anomalous thermoluminescence fading. Their microtextures make them unsuitable for obtaining propertiesthat can be extrapolated to feldspars in general.

Ilmenite–pyrophanite crystals from a garnet pegmatite dyke from the Upper Codera Valley (Sondrio, Italian Alps) showing exsolutions of titanohematite and columbite-tantalite were investigated by scanning and transmission electron microscopy. The titanohematite precipitates share the same crystallographic orientation of the ilmenite-pyrophanite host, are bean-shaped when observed on sections inclined to the pinacoidal section, and are elongated when observed on sections closer to the prism section, possibly because of their discoidal shape parallel to (001). The columbite-tantalite precipitates form a hexagonal network of needles elongated along ⟨110⟩ of the ilmenite–pyrophanite and titanohematite host. The following crystallographic relationship was established: [100]Col//[001]Ilm; [001]Col//[110]Ilm; , which can be explained in terms of preservation of the oxygen close packing between the ilmenite and columbite structures. The interfaces between any two of the three different phases are coherent but show lattice strain contrast and sometimes dislocations because of their different unit-cell dimensions. On the basis of textural observations, titanohematite is supposed to exsolve first, followed by columbite-tantalite at temperatures below 500°C. The addition of MnO to the Fe2O3–FeTiO3 system is supposed to considerably influence the topology of the related T-X phase diagram and the solubility of Nb2O5 and Ta2O5 in this system.