The effect of cation vacancies upon the thermal expansion and crystal structure of a synthetic defect spinel with composition Mg0.4Al2.4☐0.2O4 was investigated by X-ray diffraction, in situ, at temperatures up to 1273 K. No evidence of symmetry violations from the Fd3m evenat the highest temperature were noted. The volume thermal expansion is markedly less than that of stoichiometric MgAl2O4 spinel, regardless of the degree of inversion. The u oxygen atomic coordinate remains constant throughout the temperature range investigated, with the M–O an dT–O bond lengths showing identical rates of expansivities. An analysis of the evolution of polyhedral volumes with temperature indicates that at 1273 K the octahedron inflates by 0.099 Å3 and the tetrahedron by 0.056 Å3. The expansion of the octahedron is significantly greater than in stoichiometric MgAl2O4 spinel, whereas the expansion of the tetrahedron is similar. The results demonstrate that an excess of Al in the spinel structure accompanied by the formation of cation vacancies strongly affect an important thermodynamic property, in this case, thermal expansion. Such an effect must be considered for those phases stable inthe Earth’s mantle where 4–5 wt.% Al2O3 is thought to be present.

Agates from the Bighorn district in Montana (USA), the so-called Dryhead area, and their adjacent host rocks have been examined in the present study. Analyses by XRD, polarizing microscopy, LA-ICP-MS, cathodoluminescence (CL), SEM and of oxygen isotopes were performed to obtain information surrounding the genesis of this agate type.

Investigations of the agate microstructure by polarizing microscopy and CL showed that chalcedony layers and macrocrystalline quartz crystals may have formed by crystallization from the same silica source by a process of self-organization. High defect densities and internal structures (e.g. sector zoning) of quartz indicate that crystallization went rapidly under non-equilibrium conditions. Most trace-element contents in macrocrystalline quartz are less than in chalcedony due to a process of ‘selfpurification’, which also caused the formation of Fe oxide inclusions and spherules.

Although the agates formed in sedimentary host rocks, analytical data indicate participation of hydrothermal fluids during agate formation. Trace elements (REE distribution patterns, U contents up to 70 ppm) and CL features of agate (transient blue CL), as well as associated minerals (fluorite, REE carbonates) point to the influence of hydrothermal processes on the genesis of the Dryhead agates. However, formation temperatures <120°C were calculated from O-isotope compositions between 28.9‰ (quartz) and 32.2‰ (chalcedony).

Plimerite, ideally Zn (PO4)3(OH)5, is a new mineral from the Block 14 Opencut, Broken Hill, New SouthWales. It occurs as pale-green to dark-olive-green, almost black, acicular to prismatic and bladed crystals up to 0.5 mm long and as hemispherical aggregates of radiating acicular crystals up to 3 mm across. Crystals are elongated along [001] and the principal form observed is {100} with minor {010} and {001}. The mineral is associated with hinsdalite-plumbogummite, pyromorphite, libethenite, brochantite, malachite, tsumebite and strengite. Plimerite is translucent with a pale-greyish-green streak and a vitreous lustre. It shows an excellent cleavage parallel to {100} and {010} and distinct cleavage parallel to {001}. It is brittle, has an uneven fracture, a Mohs’ hardness of 3.5–4, D(meas.) = 3.67(5) g/cm3 and D(calc.) = 3.62 g/cm3 (for the empirical formula). Optically, it is biaxial negative with α = 1.756(5), β = 1.764(4), γ = 1.767(4) and 2V(calc.) of –63º; pleochroism is X pale-greenish-brown, Y pale-brown, Z pale-bluish-green; absorption Z > X > Y; optical orientation XYZ = cab. Plimerite is orthorhombic, space group Bbmm, unit-cell parameters: a = 13.865(3) Å, b = 16.798(3) Å, c = 5.151(10) Å, V = 1187.0(4) Å3 (single-crystal data) and Z = 4. Strongest lines in the X-ray powder diffraction pattern are [d (A˚ ), I, hkl]: 4.638, (50), (111); 3.388, (50), (041); 3.369, (55), (131); 3.168, (100), (132); 2.753, (60), (115); 2.575, (90), (200); 2.414, (75), (220); 2.400, (50), (221); 1.957, (40), (225). Electron microprobe analysis yielded (wt.%): PbO 0.36, CaO 0.17, ZnO 20.17, MnO 0.02, Fe2O3 29.82, FeO 2.98, Al2O3 4.48, P2O5 32.37, As2O5 0.09, H2O (calc) 6.84, total 97.30 (Fe3+/Fe2+ ratio determined by Mössbauer spectroscopy). The empirical formula calculated on the basis of 17 oxygens is Ca0.02Pb0.01Zn1.68Al0.60P3.09As0.01O17.00H5.15. The crystal structure was solved by direct methods and refined to an R1 index of 6.41% for 1332 observed reflections from single-crystal X-ray diffraction data (Mo-Kα radiation, CCD area detector). The structure of plimerite is isotypic with that of rockbridgeite and is based on face-sharing trimers of (Mϕ6) octahedra which link by sharing edges to form chains, that extend in the b-direction. Chains link to clusters comprising pairs of corner-sharing (Mϕ6) octahedra that link to PO4 tetrahedra forming sheets parallel to (001). The sheets link via octahedra and tetrahedra corners into a heteropolyhedral framework structure. The mineral name honours Professor Ian Plimer for his contributions to the study of the geology of ore deposits.

Uraniferous particles from contaminated environmental samples were analysed by scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDXA) and microfocus extended X-ray absorption fine structure (mEXAFS) spectroscopy. The particles of interest are uranium oxides, which were released into the environment by the combustion of scrap depleted uranium (DU) metal at a factory in Colonie, New York, USA. Most of the identified particles appear to have primary, ‘as emitted’ morphologies; some have evidence of minor dissolution, including corrosion pitting. Polycrystalline and often hollow microscopic spheres were identified, which are similar to particles produced by DU munitions impacting armoured targets. They are attributed to the autothermic oxidation of melt droplets. The compositions of the analysed spheres are dominated by UO2+x with variable amounts of U3O8, two of the least soluble and least bioaccessible phases of U. These particles, collected from dusts and soils, have survived more than 25 y in the terrestrial environment. This study further supports the case for using Colonie as an analogue for battlefield DU contamination.

Cámaraite — ideally Ba3NaTi4Fe82+(Si2O7)4O4(OH)4F3 — is triclinic, space group C, a = 10.6965(7) Å, b = 13.7861(9) Å, c = 21.478(2) Å, α = 99.345(1)°, β = 92.315(2)°, γ = 89.993(2)°, V = 3122.6(4) Å3, Z = 4, Dcalc. = 4.018 g cm–3, from the Verkhnee Espe alkaline deposit, Akjailyautas Mountains, Kazakhstan, has been solved and refined to R1 5.87% on the basis of 6682 unique reflections (Fo >4σF). The crystal structure of cámaraite can be described as a combination of a TS block and an intermediate (I) block. The TS (titanium silicate) block consists of HOH sheets (H-heteropolyhedral, O-octahedral), and is characterized by a minimal cell based on translation vectors t1 and t2, with t1 ~5.5 and t2 ~7 Å and t1 ^ t2 close to 90°. We describe the crystal structure of cámaraite using a double minimal cell, with 2t1 and 2t2 translations. In the O sheet, there are eight [6]-coordinated MO sites occupied mainly by Fe2+ and Mn, with minor Fe3+, Mg, Zr, Ca and Zn with <MO–ϕ> = 2.185 Å. Eight MO sites give, ideally Fe82+ p.f.u. In the H sheet, there are four [6]-coordinated MH sites occupied almost solely by Ti (Ti = 4 a.p.f.u.), with <MH–ϕ= = 1.963 Å, and eight [4]-coordinated Si sites occupied solely by Si, with <Si—0> = 1.621 Å. The topology of the TS block is as in Group II of the Ti-disilicates (Ti = 2 a.p.f.u. per minimal cell) in the structure hierarchy of Sokolova (2006). There are six peripheral (P) sites, four [8–12]-coordinated Ba-dominant AP sites, giving ideally 3 Ba p.f.u., and two [10]-coordinated Na-dominant BP sites, giving ideally 1 Na p.f.u. There are two I blocks: the I1 block is a layer of Ba atoms (two AP sites); the I2 block is a layer of Ba (two AP sites) and Na atoms (two BP sites). Along c, there are two types of linkage of TS blocks: (1) TS blocks link via AP cations which constitute the I1 block, and (2) TS blocks link via common vertices of MH octahedra (as in astrophyllite-group minerals) and AP and BP cations which constitute the I2 block. Cámaraite is the only mineral of Group II with two types of linkage of TS blocks and two types of I blocks in its structure. The relation of cámaraite to the Group-II minerals is discussed.

Marbles and interlayered coesite-bearing eclogites near the village ofSanqingge in the Sulu ultrahighpressure (UHP) terrane ofeastern China were studied to estimate their P-T evolution. Using garnet, omphacite and phengite as geothermobarometers, the coesite eclogites are calculated to have experienced P-T conditions of3.4 –3.7 GPa and ~600ºC (stage I), followed by decompression and a slight temperature decrease to 2.7–3.2 GPa and 520–560ºC respectively (stage II) and later to 2.6–2.8 GPa and ~500ºC (stage III). No water influx affected the eclogites until reaching amphibolite facies conditions of 0.5–1.3 Gpa and 595–685ºC (stage IV). As we interpret the occasional appearance ofcalcite with magnesite relics in the core as a reaction ofUHP dolomite and magnesite with Ca-rich fluids at stage IV to form CaCO3, the calculated pressure for stage I could be the maximum pressure experienced by these rocks. Thus, the crustal material ofthe Sanqingge quarry, originally sedimentary carbonates (now marbles) and interstratified basic tuffs (now eclogites), has been buried to a depth of ≥ 120 km at ~600ºC. This burial occurred in a subduction setting along a very low geotherm of 5–6ºC/km. The exhumation possibly occurred in the environment ofa subduction channel.

Electron microprobe data are presented for chevkinite-group minerals from granulite-facies rocks and associated pegmatites of the Napier Complex and Mawson Station charnockite in East Antarctica and from the Eastern Ghats, South India. Their compositions conform to the general formula for this group, viz. A4BC2D2Si4O22 where, in the analysed specimens A = (rare-earth elements (REE), Ca, Y, Th), B = Fe2+, Mg, C = (Al, Mg, Ti, Fe2+, Fe3+, Zr) and D = Ti and plot within the perrierite field of the total Fe (as FeO) (wt.%) vs. CaO (wt.%) discriminator diagram of Macdonald and Belkin (2002). In contrast to most chevkinite-group minerals, the A site shows unusual enrichment in the MREE and HREE relative to the LREE and Ca. In one sample from the Napier Complex, Y is the dominant cation among the total REE + Y in the A site, the first reported case of Y-dominance in the chevkinite group. The minerals include the most Al-rich yet reported in the chevkinite group (≤9.15 wt.% Al2O3), sufficient to fill the C site in two samples. Conversely, the amount of Ti in these samples does not fill the D site, and, thus, some of the Al could be making up the deficiency at D, a situation not previously reported in the chevkinite group. Fe abundances are low, requiring Mg to occupy up to 45% of the B site. The chevkinite-group minerals analysed originated from three distinct parageneses: (1) pegmatites containing hornblende and orthopyroxene or garnet; (2) orthopyroxene-bearing gneiss and granulite; (3) highly aluminous paragneisses in which the associated minerals are relatively magnesian or aluminous. Chevkinite-group minerals from the first two parageneses have relatively high FeO content and low MgO and Al2O3 contents; their compositions plot in the field for mafic and intermediate igneous rocks. In contrast, chevkinite-group minerals from the third paragenesis are notably more aluminous and have greater Mg/Fe ratios.

This study documents the textures and chemical evolution of igneous quartz (Qz) in granite from the Oslo Rift (Norway) during the magmatic-hydrothermal transition. Contrary to the other major igneous phases, primary quartz is well preserved. SEM-CL imaging documents four types of quartz (Qz1— Qz4). Qz1: bright primary magmatic quartz that grew under H2O-undersaturated conditions and developed a conspicuous sector zoning. Qz2: light grey luminescent secondary quartz that surrounds Qz1 and altered Qz1 in a ‘non-destructive’ process. Qz3: is usually darker than Qz2 and intersects Qz1 and Qz2. It is formed by dissolution/recrystallization processes involving saline deuteric fluids. Qz4: found in narrow cracks and patches of black quartz intersecting all the other types. EPMA in situ analyses of the different quartz generations confirm that the intensity of luminescence of quartz is positively correlated with the Ti content of the quartz. Aluminium and K are mostly incorporated in quartz in the form of [AlO4/K+]0 centre defects. In the Drammen granite, the Ti and Al contents of Qz1 averages 200 ppm and 80 ppm respectively. Titanium in Qz1 varies from 50 to 95 ppm in the peralkaline granite known as ekerite, whereas Al is irregular and ranges between 100 ppm and values below the limit of detection (LODAl at 2σ = 14 ppm). In all samples, Qz2 and Qz3 are strongly depleted in Ti and Al compared to Qz1. Either the Ti content in Qz2 is falling gradually towards Qz1 or more abruptly, whereas it is sharp from Qz3 towards Qz1 and Qz2. Potassium is variable in all four quartz types and samples, and ranges from values below the detection limit (LODk, at 2σ = 8 ppm) to 120 ppm. Grains in Qz4, being only 1–2µm wide, could not be resolved with the EPMA beam. In all granites, quartz crystallized from haplogranitic melts at P ~1.5 kbar and T = 700—750°C. SEM-CL and EPMA studies of igneous Oslo Rift quartz illustrate vividly the complex chemical and physical processes that characterize the magmatic-hydrothermal transition in shallow granitic systems and show that the chemistry of primary aqueous fluids is strongly modified from its primary igneous composition before eventually being expelled from the granitic system and perhaps incorporated in ore-forming hydrothermal convection systems.

Daliranite, ideally PbHgAs2S6, a new sulphosalt from the Zarshouran Au-As deposit, Takab region, Iran, occurs as a rare sulphosalt species at the Carlin-type Zarshouran Au-As deposit North of the town of Takab in the Province of West Azarbaijan, Iran. The new species is associated with orpiment, rarely with galkhaite, hutchinsonite and cinnabar. The strongly silicified matrix of the specimens has veinlets of sphalerite, with rare inclusions of galena and various (Cu)-Pb-As(Sb) sulphosalts. Daliranite occurs as matted nests of acicular and flexible fibres up to 200 μm in length and a width less than a few μm. The colour is orange-red with a pale orange-red streak and the lustre is adamantine. The mineral is transparent and does not fluoresce. The Mohs hardness is <2. Electron microprobe analyses give the empirical formula Pb0.95Tl0.01Hg1.04As2.10S5.91, ideally PbHgAs2S6, a new sulphosalt from the Zarshouran Au-As deposit, Takab region, Iran; the calculated density is 5.93 g cm–3. Unit-cell parameters were determined by an electron-diffraction study and refined from X-ray powder data. Daliranite is monoclinic primitive with a = 19.113(5) Å, b = 4.233(2) Å, c = 22.958(8) Å, β = 114.78(5)°, V = 1686.4 Å3 and Z = 8, a:b:c = 4.515:1:5.424, space group P2, Pm or P2/m. The strongest X-ray powder-diffraction lines [d in Å, (I), (hkl)] are: 8.676, (80), (200); 4.654, (50), (401); 3.870, (40), (211); 3.394, (50), (113); 3.148, (40b), (602); 2.892, (50), (600); 2.724, (100), (703); 2.185, (50), (319). The formula shows a sulphur excess which may correspond to S—S bonding (persulphide). The new sulphosalt is a late phase in the crystallization sequence, and was formed after orpiment, contemporaneously with quartz II, at a temperature between 157 and 193°C. The name honours Dr Farahnaz Daliran (University of Karlsruhe, Germany) in recognition of her outstanding contributions to research on ore deposits, especially Au, Zn and Fe, in Iran.

Two Ca-Zr-Ti oxides, zirconolite CaZrTi2O7 and calzirtite Ca2Zr5Ti2O16, occur as minute interstitial crystals in skarn (forsterite-spinel-calcite, with rhythmic banding) ejecta from the 1631 eruption of Vesuvius. The substitutions in zirconolite observed here mainly include Nb-for-Ti (typical for zirconolites in alkaline magmatic surroundings) and (Th,U)-for-Ca, and produce a crystal-chemical formula Ca0.9–1Th0.04–0.12U0.04–0.10ZrTi1.36–1.61Nb0.09–0.22(Fe,Mg,Al)0.29–0.47O7. The skarn, which occurs in contact with a pyroxenite of magmatic origin, displays a mineralogical zoning with Zr-, Ti-, Nb- and (U,Th)-rich oxides (e.g. Nb-perovskite and zirconolite) close to the pyroxenite (<2 mm), whereas those oxides observed further from the pyroxenite (>1 cm) are richer still in Zr but (Ti, Nb, U, Th)-poor or free (e.g. calzirtite and baddeleyite ZrO2). Textural relationships between minerals provide evidence for a metasomatic development of the skarn at the expense of the pyroxenite, through drastic leaching of Na, K, Si, Fe. The same process is responsible for the zoning in the skarn (leaching of Fe, Si, Ti, Nb, U and Th), in which Zr was less mobilized than other HFSE. This process, related to the circulation of fluids equilibrated with carbonates, is responsible for those forsterite-spinel (± calcite) skarns which can be observed as remnants in a large part of the 1631 ejecta. Such endoskarns probably formed repeatedly during at least the last millennia of Vesuvius’ history, and existed prior to the emplacement at shallow depth of the 1631 magma whose chamber walls were different from the limestone/dolostone classically assumed to host the Vesuvius magmas (Fulignati et al., 2005).

The crystal structure of charoite was investigated mainly by using selected-area electron diffraction (SAED), X-ray diffraction (XRD) and high-resolution electron microscopy (HREM). SAED and XRD patterns indicate that the structure has a monoclinic cell: a = 32.296, b = 19.651, c = 7.16 Å, β = 96.3° and V = 4517 Å3. The space group inferred from systematic absences and HREM images is P21/m. A model of the charoite structure is proposed that is based on the features of related Ca-alkaline silicate structures and HREM images. The structure of charoite consists of three different silicon-oxygen radicals (polymerized SiO4 tetrahedra) which are located between Ca polyhedra. Two of these radicals form continuous tubular structures comprising pectolite-like tetrahedral chains. Calcium polyhedra are joined to form blocks, each of which consists of four columns sharing edges and apices. Potassium and H2O molecules are probably located inside the tubular silicate radicals. From these results, a general formula is derived: K6-7(Ca,Na)18[(Si6O17)(Si12O30)(Si18O45)](OH,F)2.nH2O with two formula units in the unit cell (Z = 2).