At high temperature, MgAl2O4 spinel is stabilized by disorder of Mg and Al between octahedral and tetrahedral sites. This behaviour has been measured up to 1700 K in recent neutron experiments, but the extrapolation of subsequently fitted thermodynamic models is not reliable. First principles simulation of the electronic structure of such minerals can in principle accurately predict disorder, but would require unfeasibly large computing resources. We have instead parameterized on-site and short-ranged cluster potentials using a small number of electronic structure simulations at zero temperature. These potentials were then used in large-scale statistical simulations at finite temperatures to predict disordering thermodynamics beyond the range of experimental measurements. Within the temperature range of the experiment, good agreement is obtained for the degree of order. The entropy and free energy are calculated and compared to those from macroscopic models.

Small, euhedral Mn-rich garnets (32–52 mol. % spessartine) from the Cairngorm granite, Eastern Grampian Highlands, Scotland, are considered to be of magmatic origin and have not been derived from the assimilation of metasedimentary material, despite their occurrence largely at the margins of the pluton. Similar garnets also occur in a late cross-cutting aplite sheet. The garnets in the granite crystallized early in the sequence and are thought to have formed in response to the ponding of Mn-rich fluids against the wall of the pluton. This Mn enrichment of the fluid phase continued throughout the evolution of the pluton, resulting in Mn-rich biotites and opaque oxides and the localized crystallization of Mn-rich garnets in aplite. Garnet contains up to 1.67 wt. % Y, but has not played a major role in the geochemical evolution of the Cairngorm granite, which has high SiO2 (72–77%) and is enriched in Y and HREE. Chemical analyses of garnets, biotites and rocks are given.

Titanite occurs in the groundmass of a holocrystalline volcanic ejectum collected in the pyroclastic rocks of the Vico Volcanic complex at Tre Croci, near Viterbo, Italy. The host rock is composed of abundant K-feldspar and minor plagioclase, biotite, clinopyroxene and a feldspathoid (sodalite). Titanite is typically associated with zirconolite, biotite and Fe-oxides. It has a medium Al content (Al2O3 + Fe2O3 = 4–6 wt.%) and contains significant amounts of Zr and LREE, with a chondrite- normalised REE pattern similar to those of titanites from other alkaline rocks. Titanite has been corroded by fluids probably rich in dissolved F and P during a late alteration stage, with evidence for some remobilization and redistribution of the REE and actinide elements.

Calc-alkaline dacites from the Setouchi volcanic belt contain garnet crystals that are classified petrographically and chemically into two types: type I and type M. Type-M garnets are characterized by acicular sillimanite inclusions or dissolution textures, and may be accompanied by xenolith fragments. They exhibit extensive compositional zoning with an increase in MgO/FeO and decrease in MnO content towards the margin. These petrographical and compositional features are identical to those of garnets from metamorphic xenoliths entrained in the Setouchi volcanic rocks, suggesting a xenocrystic origin for the type-M garnets. In contrast, type-I garnets lack sillimanite inclusions and have different rim compositions from the type-M garnets. Transmission electron microscope analysis has revealed the presence of minute glass inclusions in the type-I garnets, which indicate conclusively that these garnets grew in the presence of a melt. Type-I garnets have oscillatory zoning characterized by an antipathetic variation between FeO and MgO. This zoning was probably caused by magma heterogeneity within magma batch. Differences in rim compositions between the two types of garnets, and the presence of reaction rims indicate that the xenocrystic type-M garnets were incorporated into the magma after phenocrystic type-I garnet became unstable due to decompression during magma ascent.

Pure dry chlorine at 250 to 350° C is shown to have no action on the principal silicate and phosphate phases of meteorites, but reacts quantitatively with the sulphide and phosphide phases and with kamacite; taenite does not react if it contains more than about 20 to 25 % Ni; some rare meteoritic minerals have not yet been tested. Volatile chlorides (including SiCl4) distil, and non-volatile chlorides can be leached out with water. Based on these observations, a method has been devised and applied to the analysis of a number of chondrites and to the purification of olivine and pyroxene separated by physical methods. The amount of Si present in the metal of enstatite chondrites, and the distribution of P, Ga, Ge, Ti, Cr, Mn, Ca, and Mg between oxidized and non-oxidized phases can readily be determined, and some results are presented. From the limited data so far available, Co appears to be concentrated in kamacite; gallium in the metallic phase is mainly in the taenite; germanium is strongly siderophile in the common chondrites but some is present in the silicate of the enstatite chondrites; titanium is markedly chalcophile in the enstatite chondrites, less so in the common chondrites, and the same applies to chromium; phosphorus is present as phosphide in the enstatite chondrites, but as phosphate in the hypersthene chondrites.

We have performed experiments to determine the extents to which Fe and H2O are lost from hydrous basaltic melts contained in Au80Pd20 and graphite-lined Pt capsules at 0.7 –1 GPa and 1300–1350°C. All experiments were performed in the piston-cylinder apparatus. In order to minimize the possibility of rupture of the AuPd capsule and to control H2O loss we used a double-capsule method. The inner welded 2 mm diameter Au80Pd20 capsule was placed inside a welded 3 mm diameter Pt capsule, the intervening space being packed with hydrous sample. Loss of FeO* from the sample was found to be ≤4% relative in both the Au80Pd20 and graphite-lined Pt capsules in experiments of up to 24 h duration. Loss of H2O is greater and it depends on the oxidation state of the starting materials and the nature of the capsule. For starting mixes fired at 1 log fO2 unit above the quartz-fayalite-magnetite (QFM) buffer at 1 atm, H2O loss from Au80Pd20 capsules averaged 9% relative. Starting mixes fired at 1 log fO2 unit below the QFM buffer at 1atm lost, on average, 32% of their H2O when run in Au80Pd20 capsules at high pressure. All samples run in graphite-lined Pt capsules experienced dramatic H2O loss, averaging 52% relative, irrespective of initial oxidation state. We conclude that Au80Pd20 capsules are suitable for high-pressure hydrous melting experiments and that the sample loses very little Fe. In order to minimize H2O-loss, however, it is important that the starting materials be relatively oxidized.

In calcites and dolomites in seven African carbonatites, SrO, FeO and MnO occur in concentrations from 1 to 2 wt.%, whereas Ce, Y, Cu and Zn occur only at the ppm level. Sr, Ce and Y partition preferentially into calcite relative to co-existing dolomite, whereas Fe and Mn favour dolomite. Sr partitions preferentially into calcite relative to co-exisiting apatite, but the light rare-earth elements partition into apatite. Magnetite from Kerimasi contains up to 13 wt.% MgO and 6 wt.% MnO, extending the known ranges in composition of magnetites from carbonatites.

Olivines containing up to 6.1 wt.% P2O5 occur in association with apatite and an unnamed NaCaMg phosphate phase. Phosphoran olivine has been recorded only in pallasite meteorites and from one other terrestrial occurrence. The rarity of palpable phosphorus substitution for silicon may be related to the fact that in most terrestrial rocks, phosphorus is incorporated initially, and remains as, apatite; thus phosphorus excess in an undersilicated environment must be uncommon. However the highly capricious distribution of phosphorus in individual olivines from this and the meteoritic occurences suggests disequilibrium, and questions whether phosphoran olivine is ever stable relative to combinations of P-free olivine and phosphate/phosphide minerals.

Spodumene pegmatites, aplites and schists from the Aclare Li prospect of SE Ireland host sporadically developed, small, red, euhedral garnets. Chemical data indicate that the pegmatite- and aplite-hosted garnets are rich in spessartine and are similar to garnets in many African Li-rich pegmatites. Partial melting as a source of the garnets is unlikely due to the large spessartine component, the abundance of inclusions within the garnets and the general P-T-X evolution of the pegmatite body. It is suggested that an aqueous fluid was exsolved during pegmatite crystallisation and complexed available Mn. Movement of this fluid to the intermediate zone of the pegmatite body produced areas of high Mn concentrations which permitted the crystallisation of spessartine-rich garnets at low pressures (<3 kbar).

A chemical and petrographic study of charnockites and pyroxene/hornblende-bearing granulites has been undertaken, and the data used in an interpretation of the petrogenesis of these rocks. Major- and trace-element analyses of fourteen rocks are presented, together with majorelement analyses of seven orthopyroxenes, seven clinopyroxenes, two garnets, and three hornblendes. The compositions of the coexisting ferromagnesian minerals are used to obtain estimates of the likely pressure/temperature conditions of equilibration (5-7 kbar and 700±50°C of the various mineral assemblages.

Ice-hosted sediments in glaciers and icebergs from Antarctica and Svalbard contain authigenic nanoparticulates of schwertmannite, ferrihydrite and goethite that formed during sulphide oxidation. These phases indicate the existence of subglacial biogeochemical hotspots containing fluids of low pH (2—4), rich in dissolved Fe(III) and sulphate. Nanophase Fe is partially bioavailable and potentially important to global biogeochemical cycles, since the flux delivered by icebergs to the Southern Ocean is comparable to the flux of soluble, bioavailable Fe from aeolian dust.

There is an association between the development of cleavage domes, a texture reflecting the displacement of insoluble matrix grains by porphyroblasts growing under a bulk hydrostatic stress, and textural sector-zoning. This has been found in garnet, staurolite, chiastolite, pyrite and possibly emerald porphyroblasts. Sector-zoned porphyroblasts form by lineage growth normal to the crystal faces. This causes several distinctive textures (type 1 inclusions and type 2 intergrowths, inclusion bands, growth prongs), all of which are directly or indirectly related to displacement growth. Graphite or other carbonaceous material is ubiquitous in samples showing textural sector-zoning.

Fluids, together with alteration and ore mineral assemblages, were studied in representative hydrothermal gold-bearing quartz veins from the western part of the Variscan belt in France (La Bellière, Montagne Noire district, Villeranges-Le Châtelet district, and Limousin province). Petrographic studies of the relationships between ores, fluid inclusions, microfracturing and quartz textures show that chronological and genetic relationships between gold deposition and fluid trapping may be very complex and difficult to establish for veins which show multi-stage fracturing and shearing. Systematic studies of secondary fluid inclusions in microcracks and recrystallized zones of the early quartz veins indicate two contrasting physical-chemical conditions: 1 relatively high temperature (250–400°C) and pressure (>1 kbar) event with CO2-CH4-H2S-N2 (±H2O-NaCl)-rich fluids related to the early sulphide deposition; 2 lower temperature (150–250°C) and pressure with aqueous fluids related to the late native-gold-sulphide (or sulphosalt) assemblage, which constitutes the economic ores in some deposits.

In deposits where gold occurs predominantly in a combined state within arsenopyrite and pyrite (Châtelet and Villeranges), primary fluid inclusions in authigenic quartz combs cogenetic with arsenopyrite are almost purely aqueous (H2O-NaCl) and have a low salinity (1–4 wt. % NaCl). P-T conditions (150–250°C), nearly hydrostatic pressures) are similar to those of the second stage in the multi-stage quartz veins.

Consideration of chemical equilibria in the C-O-H-N-S system using microthermometric and Raman spectrometric analysis for the fluids, together with data obtained from mineralogical studies, show that during gold deposition, fO2 was below hematite-magnetite buffer at Villeranges and around the Ni-NiO buffer at La Bellière and Montagne Noire. fS2 calculations based on H2S analyses are in good agreement with mineral assemblage estimates and close to that fixed by the pyrite-pyrrhotite boundary at high temperature. Ore fluid pH was significantly lower than in the host rocks as shown by the complete alteration of the host rocks into a quartz-K-mica assemblage. The data illustrate that during the late Hercynian, fluid circulation evolved from high P-T conditions, in some cases linked to late magma intrusions, towards conditions typical of later hydrothermal systems of the geothermal type.

The chemical, mineralogical, and textural changes involved in the weathering of basalt have been traced through various stages from fresh rock (which has a cation exchange capacity of 10 meq/100 g due to the presence of a swelling chlorite mineral) to reddened basaltic rubble consisting of interstratified montmorillonite-illite, hematite, and anatase. The cation exchange capacities of the rocks increase progressively with the formation of secondary clay from labradorite as Al, Fe, and Ti accumulate and Si, Mg, Ca, and Na are depleted—much of the K is retained in the secondary clay mineral. The weathering is considered to be contemporaneous with the formation of the Antrim bauxites but not so intense.

Carbonates of the magnesite-siderite series have been found and analysed in carbonatites from the Lueshe, Newania, Kangankunde, and Chipman Lake complexes. This series has been represented until now only by a few X-ray identifications of magnesite and three published analyses of siderite and breunnerite (magnesian siderite). Most of the siderite identified in carbonatites in the past has proved to be ankerite, but the new data define the complete solid-solution series from magnesite to siderite. They occur together with dolomite and ankerite and in one rock with calcite. The magnesites, ferroan magnesites and some magnesian siderites may be metasomatic/hydrothermal in origin but magnesian siderite from Chipman Lake appears to have crystallized in the two-phase calcite + siderite field in the subsolidus CaCO3-MgCO3-FeCO3 system. Textural evidence in Newania carbonatites indicates that ferroan magnesite, which co-exists with ankerite, is a primary liquidus phase and it is proposed that the Newania carbonatite evolved directly from a Ca-poor, Mg-rich carbonatitic liquid generated by partial melting of phlogopite-carbonate peridotite in the mantle at pressures >32 kbar.

A study of the composition and unit cell data of a suite of lead-rich minerals of the alunite-jarosite group from the oxidized zone of the ore body at Broken Hill, New South Wales, Australia, has revealed almost complete XO4 (X = As, P, S) solid solution in these minerals at this deposit. The species in the group noted are hidalgoite, hinsdalite, beudantite, segnitite and plumbogummite. These minerals at Broken Hill exhibit a number of growth textures, including oscillatory zoning, colloform banding and replacements. Zoning in these minerals is due to the segregation of Al- and Fe-rich members, and compositions indicate a strong coupling of Fe3+ with and Al with

The compositions of apatite crystals from seven Skaergaard rocks were obtained by electron-probe microanalysis. These span the range of occurrence from the base to the top of the exposed zones of the layered series. Apatite occurs as an intercumulus phase in the lower zones, but becomes a cumulus phase at a structural height of 1850 m (c. 98 % crystallized), defining the base of Upper Zone b. All apatite analyses show a high F:Cl ratio. There is a slight but significant increase in F and decrease in Cl when the apatite becomes a cumulus phase, the F/Cl values changing from < 10 to > 30. Variations in F:Cl:OH are attributed to differential volatile migration from trapped intercumulus liquid sites. The apatite data provide new support for ferrodiorite-granophyre liquid immiscibility.

Syntheses for the three members of the copper hydroxyl nitrate family – the polymorphs rouaite and gerhardtite, and likasite – are presented along with powder diffraction data and unit-cell parameters. The solubilities, determined in 0.05 M KNO3 solution after equilibration at 25°C for 10 days were used to calculate activity-based solubility product constants. The Gibbs energies of formation, obtained from the solubility products, are –653.2±0.7 kJ/mol, –655.1±1.2 kJ/mol and –1506.4±1.1 kJ/mol, for rouaite, gerhardtite, and likasite (Cu3NO3(OH)5·2H2O), respectively. The values for the polymorphs rouaite and gerhardtite validate the observations of Oswald that gerhardtite is the most stable polymorph at room temperature and that the preparation of predominantly rouaite in syntheses carried out at room temperature must be due to the metastability and low rate of conversion to the more stable gerhardtite.

A previously suggested simple relationship in a diagram of(Al2O3vs. MgO + FeO + Fe2O3)opx for the distinction between igneous and metamorphic orthopyroxenes is shown to be inadequate. A revised diagram is presented and its limitations are discussed. A diagram showing Fe2+/(Fe2+ + Mg) vs. 100Ca/(Fe2+ + Mg + Ca) for orthopyroxenes coexisting with Ca-rich clinopyroxenes proves to be useful for the discrimination of igneous and metamorphic orthopyroxenes and for evaluation of the extent and physical conditions of regional orthopyroxene re-equilibration.

The geochemistry of late Caledonian minettes from across the orogenic belt is compared in order to constrain the composition of the Caledonian sub-continental lithospheric mantle (SCLM). All the minettes are similar petrographically and chemically and several samples have characteristics typical of near primary mantle melts. Samples from the Northern Highlands and the Caledonian foreland show enrichment in many trace elements (notably LILE and LREE) relative to those from the Grampians, the Southern Uplands and northern England, coupled with distinct Nd and Sr isotope characteristics. Processes such as fractional crystallization, crustal assimilation, and partial melting played a negligible role in creating the differences between the two groups which reflect long-term, time-integrated differences in the compositions of their SCLM sources. The Great Glen Fault appears to represent the boundary between these two lithospheric mantle domains. Other currently exposed Caledonian tectonic dislocations cannot be correlated directly with compositional changes within the SCLM. The chemical provinciality displayed by the minettes shows some resemblance to that within other late Caledonian igneous suites, including the newer granites, suggesting that the minettes may represent the lithospheric mantle contributions to these rocks.