In situ laser ablation high resolution ICP-MS analyses of scheelite from hydrothermal veins at the Archaean Mt. Charlotte gold deposit (Western Australia) show inhomogeneous REE distribution at small scale (<100 μm). In a limited number of samples, variations of the cathodoluminescence (CL) colours from blue to yellow are linked to the REE content of scheelite, and reveal oscillatory zoning of the REE with zone widths between 1 μm and 100 μm. However, CL failed to reveal the zoning in most inhomogeneous scheelite samples. A nuclear microprobe has been used to characterize the distribution of REE in these samples. No reasonable map for the distribution of REE could be obtained by particle induced X-ray emission, because of interferences with W-L lines. However, monochromatic ionoluminescence (IL) maps collected at the wavelength of the main REE3+ luminescence peaks revealed oscillatory zoning. Therefore, IL is a powerful tool for mapping the distribution of REE in natural scheelite. Monochromatic IL maps allow us to determine the nature of the inhomogeneous distribution of REE in scheelite, fundamental information for using the REE in this mineral as a marker for the chemistry of ore-forming fluids, and for interpreting Sm-Nd isotopic data.

The phase transitions in tridymite and the nature of the high-temperature phase are investigated using a combination of Rigid Unit Mode theory, neutron total scattering measurements analysed using the Reverse Monte Carlo method, and molecular dynamics simulations. The unusually large number of phase transitions in tridymite can be explained within the Rigid Unit Mode theory. The Rigid Unit Mode theory also gives an interpretation of the disordered high-temperature phase as revealed by the neutron scattering data and the molecular dynamics simulations. There is a close correspondence between the structure of the disordered high-temperature phase of tridymite and that of β-cristobalite.

Physical and chemical properties of lustrous black mica from greisen veins at the Bom Futuro tin mine indicate that it is a relatively Fe-F-rich, Li-poor zinnwaldite with a composition near the midpoint of the polylithionite-siderophyllite join. On the basis of 22 oxygens, the mica contains 1.28–1.73 atoms of Li with an average octahedral occupancy of 5.61 and a filled interlayer site. Compositional variation reflects the net effects of alteration, coupled tetrahedral-octahedral substitutions, and petrogenetic factors related to vein fluid chemistry. Geological constraints and compositional data suggest the Bom Futuro zinnwaldite crystallized at T ≈ 500°, P ≈ 1–500 bar, and fO2 ≈ 10−23. High Mn-Zn concentrations in the Bom Futuro mica appear to be a feature of Fe-Li micas from evolved anorogenic granitic systems not shared by orogenic counterparts.

The crystal structures of synthetic Pb3O2(CO3) and NaPb2(OH)(CO3)2, have been solved by direct methods and refined to R = 0.062 and 0.024, respectively. Pb3O2(CO3) is orthorhombic, Pnma, a = 22.194(3), b = 9.108(1), c = 5.7405(8) Å, V = 1160.4(3) Å3, Z = 8. There are four symmetrically distinct Pb2+ cations in irregular coordination polyhedra due to the effect of stereoactive s2 lone electron pairs. The structure is based upon double [O2Pb3] chains of [O(1)Pb4] and [O(2)Pb4] oxocentred tetrahedra and CO3 groups. The [O2Pb3] chains are parallel to the c axis, whereas the CO3 groups are parallel to the (010) plane. NaPb2(OH)(CO3)2 is hexagonal, P63mc, a = 5.276(1), c = 13.474(4)Å, V = 324.8(1) Å3, Z = 2 and has been solved by direct methods. There are two symmetrically distinct Pb2+ cations in asymmetric coordination polyhedra due to the effect of stereoactive s2 lone-electron pairs. The single symmetrically unique Na+ cation is in trigonal prismatic coordination. The structure is based on hexagonal sheets of Pb atoms. Within these sheets, Pb atoms are located at vertices of a 36 net, such that each Pb atom has six adjacent Pb atoms that are ~5.3 Å away. Two sheets are stacked in a close-packing arrangement, forming layers that contain the (CO3) groups. The layers are linked by OH groups that are linearly coordinated by two Pb2+ cations. Na+ cations are located between the layers. The structure is closely related to the structures of other lead hydroxide carbonates (leadhillite, macphersonite, susannite, hydrocerussite, ‘plumbonacrite’).

In the 1944 Vesuvius eruption, the shallow magma chamber was disrupted during the highly energetic explosive phases. Abundant cognate xenoliths such as subvolcanic fergusites and cumulates, hornfels, skarns and rare marbles occur in tephra deposits.

Mineral chemistry, melt inclusions in minerals and glassy matrix compositions show that fergusites (highly crystalline rocks made of leucite, clinopyroxene, plagioclase, olivine, apatite, oxides and glass) do not correspond to melt compositions but result from combined sidewall accumulation of crystals, formed from K-tephriphonolitic magma resident in the chamber, and in situ crystallization of the intercumulus melt. Very low H2O contents in the intercumulus glass are revealed by FTIR and apatite composition. Whole rock compositions are essentially determined by the bulk mineral assemblages.

Glass–bearing fergusites constitute the outer shell of the magma chamber consisting of a highly viscous crystal mush with a melt content in the range 20–50 wt.%. The leucite/(clinopyroxene+olivine) modal ratio, varies with the extraction order of magmas from the chamber, decreasing upwards in the stratigraphic sequence. This reflects a vertical mineralogical zonation of the crystal mush. These data contribute to the interpretation of the subvolcanic low–pressure crystallization processes at the magma chamber sidewalls affecting alkaline potassic magmas.

We report on the occurrence, petrology and geochemistry of recently recognized leucocratic plagioclase-rich microgranular inclusions hosted by two granite facies in the late-Caledonian Galway Granite, Connemara, Ireland. They have been recorded at 66 localities along an ESE trending, 4 km wide corridor which incorporates the contact zone between their host granites (i.e. The Megacrystic Granite and the Mingling and Mixing Zone Granodiorite). The inclusions are discoidal in shape and oriented parallel to the general ESE trending foliation in the granites with the most elongate (6.0 × 0.6 cm) occurring in zones of strongest fabric intensity. Contacts between the inclusions and the host granite are sharp with no chilled margin visible. They display a fine-grained (<1 mm) interlocking texture with occasional crystals of plagioclase ranging up to 2 mm in length. Microprobe analysis shows that the plagioclase is essentially oligoclase (An22–32) in composition and is similar to that (i.e. An21–30) occurring in the host granites. Furthermore, the oligoclase accounts for between 61 and 78% of the mode which is reflected in the major element chemistry of the inclusions. Other minerals (in decending order of abundance) include K-feldspar, quartz, biotite and magnetite. The origin of the inclusions is unclear. However, the results of the microprobe analysis provide evidence of a link between them and their host granites.

The crystal structure of faustite, ZnAl6(PO4)4(OH)8.4H2O, was determined using single-crystal data (Mo-Kα X-radiation, CCD area detector, 1624 unique reflections, R1 = 4.91%, wR2 = 9.23%), and compared with results of a reinvestigation of the structure of its copper analogue turquoise, CuAl6(PO4)4(OH)8.4H2O (2737 unique reflections, R1 = 2.81%, wR2 = 6.90%). Both are isostructural and crystallize in space group P, with a = 7.419(2) [turquoise: 7.410(1)], b = 7.629(3) [7.633(1)], c = 9.905(3) [9.904(1)] Å, α = 69.17(2) [68.42(1)], β = 69.88(2) [69.65(1)], γ = 64.98(2) [65.05(1)]°, V = 462.2(3) [460.27(10)] Å3, and Z = 1. The structure consists of distorted MO6 polyhedra (M = Zn, Cu), AlO6 octahedra and PO4 tetrahedra. By edge- and corner-sharing of these polyhedra a fairly dense three-dimensional framework is formed which is further strengthened by a system of hydrogen bonds. The metal atoms in the unique MO6 (M = Zn or Cu) polyhedron show a distorted [2+2+2]-coordination, the distortion being more pronounced in turquoise. About 10% of the M site is vacant in both minerals. In turquoise, a previously undetected structural site with a very low occupancy of (possibly) Cu is present at the position (Ý,0,Ý).

Feldspar of composition Ca0.2Pb0.8Al2Si2O8 (PbF80An20) was synthesized from melt and subsequently isothermally annealed at T = 960°C for 4 days. In situ HT X-ray powder spectra of PbF80An20 feldspar, triclinic I1̄ at room temperature, were collected in the temperature range 20–800°C, and a displacive continuous ferroelastic transition to a I2/c monoclinic phase was observed. An analysis of the symmetry-required components of the spontaneous strain tensor reveals the second order character (β = 0.46 ± 0.02) of the transition with TC = 680 ± 15°C. A linear coupling was observed between the e4 and e6 components of the spontaneous strain. The transition is analogous to those observed, with increasing temperature, along the join An–SrF and in disordered Na-rich alkali feldspars. A comparison with Ca0.2Sr0.8Al2Si2O8 feldspar (TC = 680°C, McGuinn and Redfern, 1997) shows that PbF80An20 has a higher spontaneous strain (εs = 0.028 in PbF80An20vs 0.020 in Ca0.2Sr0.8Al2Si2O8) and a higher e4 component, possibly related to the higher distortion of the non-tetrahedral polyhedron in lead feldspar.

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.

Thermal reduction in wolframite (composition: Fe1-xMnxWO4 (0.08<x<0.87)) from different deposits in Argentina, was analysed using a temperature-programmed reduction (TPR) technique. X-ray powder diffraction analysis (XRPD), vibrational spectroscopy (IR and Raman), scanning electron microscopy (SEM) and electron microprobe analysis (EDAX) were used to assess the relationship between reactivity degree in a reducing atmosphere (H2 10% – N2 90%) and chemical composition of wolframite.Similar studies were carried out with other related minerals, especially the ones found in natural deposits as alteration or association products. Stability of the solid solution serial members is correlated with redox properties of divalent cations.

Cordierite+orthoamphibole (Crd+Oam)-bearing gneisses in the Cormacks Lake complex are regionally associated with metapelites containing prismatic sillimanite and K-feldspar, metabasites that locally contain metamorphic orthopyroxene, and other high-grade rocks in the Central Gneiss (Dashwoods) subzone, in the southwestern Newfoundland Appalachians. Retrograde features formed at the expense of the granulite-facies assemblages are ubiquitous. For example, in some migmatitic rocks, garnet is resorbed by Crd+Oam, and in metapelites, cordierite separates corroded garnet and sillimanite. Mineral thermobarometry suggests that, following granulite-facies metamorphism (T<785°C, P<7.5 kbar), retrogression occurred as the Cormacks Lake gneisses cooled through Mg-Fe diffusional blocking temperatures as they decompressed to a pressure of ∼3–4 kbar. Given the absence of Barrovian (or higher pressure) mineral assemblages in the metapelites, regional tectonic reconstructions involving the thrusting of a neighbouring terrane (Notre Dame subzone) over the Central Gneiss subzone appear to be supported only by the moderate pressure determined for the granulite facies event. Although scarcely discernible given re-equilibration effects and the imprecision of thermobarometers, subsequent decompression nonetheless had a marked impact on the mineralogy of the gneisses.

Near infrared absorption (NIR) spectra of natural morphologically cubic polycrystalline diamonds (cuboid) were obtained at room temperature, and the stretching plus bending combination band of molecular water was observed. The spectrum consisted of the main band at 5180 cm-1 due to liquid water and a shoulder at 5000 cm-1. The 5000 cm-1 band suggests the presence of a phase with stronger hydrogen bonding in inclusions in the diamond. This shoulder absorption decreased on heating to 120°C. The combination band of H2O at high pressure and temperature was measured using a resistively heated diamond cell and the pressure dependence of the peak position was obtained. Comparison with the present experimental results indicates that the spectral changes induced by heating of the cuboid corresponded to melting of a high-pressure form of ice, and the shoulder absorption at 5000 cm-1 arises from ice VI at 1.9 GPa. On the other hand, the liquid water, a main component of the fluid inclusions in the cuboid, was not under high pressure judging from the frequency of the combination band. This contrast might relate to the texture of the cuboid diamond. The spectral observation enables us to estimate the residual pressure of mantle fluid encapsulated in these diamonds. The diamond-cell data also provide high-P-T NIR fingerprint spectra that could be useful for identifying H2O phases and confining pressures in other samples.

The crystal structure of Na4[Cu4O2(SO4)4] MeCl (Me: Na,Cu,☐) has been solved by direct methods and refined to R1 = 0.028 using 2466 independent reflections. The compound is tetragonal with space group P4/n, a = 18.451(1)Å, c = 4.9520(2)Å, Z = 4. The two main building units running parallel to the c-axis comprise: (1) slabs containing SO4 and OCu4 tetrahedra; and (2) chains of corner sharing Me(Cl,O)6 octahedra. The displacement ellipsoids of the atoms occupying the Me sites and of the Cl ions indicate a short-range static disorder. Copper in the slabs exhibits a (4+1) coordination. Both elements form a tunnel structure in which additional Na atoms are incorporated for charge compensation. The structure is closely related to the mineral piypite (K4Cu4O2(SO4)4 MeCl (Me: Na,Cu,☐)): . Furthermore, the structure has a pronounced pseudo-translational symmetry: apart from some of the oxygen sites, all of the nineteen crystallographically distinct positions are related by a pseudo F centring.

The crystal structure of mattheddleite (Pb5(Si1.5S1.5)O12(Cl0.57OH0.43), P63/m, a = 10.0056(6), c = 7.4960(9) Å) from Leadhills, Scotland has been determined to R = 0.065. The structure is that of apatite where Pb replaces Ca, equal amounts of S and Si replace P and the X anion is OH + Cl. The composition deduced from the structural refinement differs from that of microprobe analyses by giving full occupancy of the tetrahedral site and equal Si and S to preserve charge balance. We conclude that the microprobe analysis is incorrect possibly due to large and inaccurate absorption corrections. For the crystal analysed, the X anion position is zoned from an OH-rich interior to a Cl-rich exterior. The Pb(2) atom is disordered which may be analogous to the disordering of the Ca(2) site in Cl-rich, Ca apatites.

Detailed chemical analyses of different portions of laboratory-grown sector-zoned clinopyroxene been provided by Skulski et al. (1994). These data have been plotted here in PC-IR diagrams results indicate equilibrium crystallization and protosite control of element selection.

High-resolution, neutron time-of-flight, powder diffraction data have been collected on natural crocoite between 873 and 1073 K. Thermal analysis carried out in the 1920s had suggested that chemically pure PbCrO4 exhibited two structural phase transitions, at 964 K, to the β phase, and at 1056 K, to the γ phase. In this study, no evidence was found for the α-β structural phase transition, however a high-temperature phase transition was found at ∼1068 K from the ambient-temperature monazite structure type to the baryte structure type. The phase transition, close to the temperatures reported for the β to γ phase modifications, is first order and is accompanied by a change in volume of −1.6%. The crystal structure of this phase has been refined using the Rietveld method to agreement factors of Rp = 0.018, Rwp = 0.019, Rp = 0.011. No evidence for premonitory behaviour was found in the temperature dependence of the monoclinic lattice constants rom 873 K to 1063 K and these have been used to determine the thermal expansion tensor of crocoite just below the phase transition. At 1000 K the magnitudes of the tensor coefficients are α11, 2.66(1) × 10−5 K−1; α22, 2.04(1) × 10−5 K−1; α33, 4.67(4) × 10−5 K−1; and α13, −1.80(2) × 10−5 K−1 using the IRE convention for the orientation of the tensor basis. The orientation of the principal axes of the thermal expansion tensor are very close to those reported previously for the temperature range 50–300 K.

In the Yichun granite complex (SE China), columbite group minerals, microlite and cassiterite are the main Nb, Ta, Sn-bearing minerals. They are mainly concentrated in the uppermost albite-lepidolite granite. Rutile is the only Nb, Ta-bearing phase in the geochemically primitive muscovite-zinnwaldite granite. The chemical evolution of the columbite group minerals (the most abundant and commonly zoned Nb, Ta-bearing minerals) indicates a complex crystallization history of the host granites with: (1) fractional crystallization at depth, reflected by a strong increase of Mn/(Mn+Fe) ratios with a moderate increase of Ta/(Ta+Nb) ratios from the muscovite-zinnwaldite granite to the Li-mica granite and then the most fractionated topaz-lepidolite granite; and (2) emplacement of successive magma batches corresponding to the different units of the granite complex with progressive crystallization of each unit, mainly reflected by a strong increase of Ta/(Ta+Nb) ratios with moderate variation of Mn/(Mn+Fe) ratios during the growth of the zoned crystals. The data are compared with those from the RMG of Ezzirari (Morocco), Montebras, Beauvoir and Chèdeville (France).

Ruatapu cave has developed beneath a block of hydrothermally altered Quaternary vitric tuff in the active Orakei Korako geothermal field. The cave extends ∼45 m, with a vertical drop of 23 m, to a shallow pool of clear, sulfate-rich (∼.450 µg/g), warm (T = 43–48°C), acid (pH = 3.0) water. Steam, accompanied by H2S, rises from the pool surface, from a second pool nearby, and from fumaroles and joints in the ignimbrite, to condense on surfaces within the cave. Oxidation of the H2S to H2SO4 produces acid sulfate fluids which react with the surficial rocks to generate three principal and distinct assemblages of secondary minerals. Kaolinite ± opal-A ± cristobalite ± alunite ± alunogen dominate the assemblage at the cave mouth; the essential Al, K and Si are derived from the tuffs and Na, Ca, Fe and Mg removed. In the main body of the cave the highly limited throughflow of water results in the more soluble of the leached constituents, notably Na and K, being retained in surface moisture and becoming available to form tamarugite and potash alum as efflorescences, in part at the expense of kaolin, along with lesser amounts of alunogen, meta-alunogen, mirabilite, halotrichite, kalinite, gypsum and, possibly, tschermigite; the particular species being determined by the prevailing physico-chemical conditions. Heat and moisture assist in moving Fe out of the rock to the air-water interface but, unlike typical surficial acid alteration systems elsewhere in the TVZ, there is an insufficient flow of water, of appropriate Eh-pH, to continue to move Fe out of the cave system. Much becomes locally immobilized as Fe oxides and oxyhydroxides that mottle the sides and roof of the cave. Jarosite crusts have developed where acid sulfate pool waters have had protracted contact with ignimbrite wallrock coated with once-living microbial mats. Subsequent lowering of the waters has caused the porous jarositic crusts to alter to potash alum ± akaganéite or schwertmannite. Meteoric water, with chloride concentrations of up to 10,000 µg/g, seeping through the roof produces a white, semi-thixotropic slurry which when dried yields 5.7 wt.% chloride and consisted of tamarugite plus halite. Some of this chloride (and sulfate) eventually enters the pool waters which have Cl− concentrations of 200 µg/g. This implies that the pools are not necessarily fed by a neutral pH alkali chloride fluid ascending from the geothermal reservoir, but are perched waters heated by ascending steam and fed largely by steam condensate.

The high-pressure behaviour (up to 30 kbar) of dehydrated analcime, Na[AlSi2O6), has been studied in detail using polarized microscopy and Raman micro-spectroscopy. Samples were compressed using a diamond anvil cell in a quasi-hydrostatic medium (glycerol or water-ice). Two transitions at 3.7 and 11 kbar were observed.

At the first transition, phase II is observed under cross polarized light as a contrasting black zone, moving from the edge to the centre of the sample. At this transition the strong Raman doublet at ∼480 and 500 cm−1 transforms discontinuously to a singlet, which is similar to that of quasi-cubic natural analcime. This transition, with an increase of effective symmetry, seems unusual on increasing pressure.

The analcime framework may be thought of as an array of four-, six-, or eight-membered interconnected rings. Phase transitions in the analcime group are considered in the literature in terms of deformations of the six-membered rings. However, the present work shows that these phase transitions should be associated with deformations of the four-membered rings (as the minimum size secondary building units) by rotation of rigid TO4 units. The strongest Raman band frequency is correlated with the mean T-O-T angle inside the four-membered ring: a rate of 4.5 cm−1/degree was found for analcimes and leucites. Using this correlation, one can estimate from Raman data the possible deformation of four-membered rings at the phase transitions.

We have developed a cluster variation method (CVM) model based on cuboctahedral and octahedral basis clusters containing 13 and 6 atoms, respectively, and applied it to the analysis of the thermodynamic mixing properties of (Zn,Fe)S solid solutions. The model, in which the internal energy of the lattice is approximated by next to nearest neighbour (nnn) pair interactions and many-body interactions associated with nearest neighbour (nn) equilateral triangles, describes the FeS contents of sphalerites equilibrated with pyrrhotite and pyrite, and with pyrrhotite and iron metal within experimental uncertainties. The model predicts moderate deviations from ideality; the mean values of the Lewis and Randall activity coefficient of FeS and ZnS are, 1.48 and 1.03, respectively. Predictions of the model are in qualitative agreement with cell-edge data. The model also predicts that sphalerites undergo long-range ordering to lower-symmetry structures at temperatures only slightly below those investigated experimentally, a result in agreement with inferences from an existing Mössbauer investigation of synthetic sphalerites.

More realistic models in which interactions are ascribed to larger species (nn triangular and centred square species) predict that such long-range ordering occurs at even higher temperatures and underscore the need for better characterization of the structures of (Zn,Fe)S minerals.