The thermodynamics and kinetics of CO2 speciation in silicate melts have been studied by measuring the concentration of CO2mol and carbonate in jadeite glass annealed at 575, 450 and 400°C. Assuming that the reaction is

1

where CO2mol..Obr represents a CO2 molecule weakly bonded to a bridging oxygen in the network and CO3 represents a bridging carbonate group with no net negative charge, ΔH for the reaction is –17 (+4/–8) kJ mol−1 and ΔS is –24 (+6/–9) J K−1 mol−1. The rate of equilibration of the species was measured at each temperature and the rate constants were deduced. The temperature dependence of the rate constants was used to determine the activation energy of the forward and reverse reactions which are 68 (+3/–31) kJ mol−1 and 86 (+1/–69) kJ mol−1 respectively. The data suggest that CO2mol may be much more abundant in silicate melts than previously assumed on the basis of studies of CO2-bearing glasses. Models of solubility, diffusion, and isotope fractionation should take this into account.

Lattice parameters of synthetic titanite powder, CaTiOSiO4, have been determined between room temperature and 1023 K. Only the e11 and e13 components contribute significantly to the strain tensor associated with the antiferroelectric-paraelectric phase transition at Tc = 487 K. A finite strain component e13 is observed in the paraelectric phase for 487 K < T < 825 K. The disappearance of this shear strain marks the isosymmetric transition near 825 K. The temperature evolution of the volume strain and of e11 is proportional to the squared order parameter observed in single-crystal diffraction experiments. The magnitude of the volume strain is sufficiently large to relate the observed near tricritical behaviour of the antiferroelectric-paraelectric phase transition to strain coupling.

The crystal structure of ulrichite, CaCu2+(UO2)(PO4)2·4H2O (space group P21/c, a = 12.784(3), b = 6.996(1), c = 13.007(3)Å, β = 91.92(1)°, V = 1162.7(4)Å3, Z = 4) was redetermined using X-ray diffraction data measured from a twinned crystal with Mo-Kα radiation and a CCD area detector (2510 unique reflections with Fo > 4σ(Fo), R1 = 8.8%). Ulrichite crystallizes in space group P21/c rather than C2/m reported previously. The newly determined atomic positions give reasonable coordination polyhedra. One unique Ca atom is irregularly coordinated by eight O atoms (<Ca–O> = 2.46 Å). One unique U atom shows a {2+5} coordination with characteristic bond angles and lengths (1.806(11)Å, 1.842(12)Å and five bonds between 2.252(15) and 2.441(11)Å). Furthermore, the structure contains groups in which strongly elongated CuO6 ‘octahedra’ (also describable as CuO4 squares) are corner-linked to two PO4 tetrahedra via two opposite, equatorial O atoms. Edge- and corner-sharing UO7, CaO8 and PO4 polyhedra form heteropolyhedral sheets parallel to (001) that are linked to adjacent sheets via the CuO6 ‘octahedra’ and hydrogen bonds.

The Denchai gem sapphire deposits in Phrae Province, northern Thailand are closely associated with late Cenozoic alkaline basaltic rocks. The sapphires occur in alluvial placer deposits in palaeo-channels at shallow depths. Electron microprobe analysis of minor and trace element contents (Fe, Ti, Cr, Ga and V) of the sapphires indicate the following oxide abundances: Fe2O3 (0.32–1.98 wt.%), TiO2 (0.01–0.23 wt.%), Cr2O3 (<0.01 wt.%), Ga2O3 (0.01–0.03 wt.%) and V2O5 (<0.03 wt.%). Optical studies of sapphires revealed three types of primary fluid/melt inclusions. CO2-rich inclusions (Type I) contain three phases (LH2O + LCO2 + V) with the vapour phase comprising <10–15 vol.%. The presence of CO2 was confirmed by microthermometry and laser Raman analysis. Polyphase inclusions (Type II) (vapour + liquid + solid) contain a fluid bubble (20–30 vol.%), an aqueous phase (10–15 vol.%) and several solid phases. Silicate-melt inclusions (Type III) comprise vapour bubbles, silicate glass and solid phases. Proton-induced X-ray emission (PIXE) analysis revealed high concentrations of K (~;4 wt.%) as well as Ca (~;0.5 wt.%), Ti (~;1 wt.%), Fe (~;2 wt.%), Mn (~;0.1 wt.%), V (<0.03 wt.%), Rb (~;70 ppm) and Zr (~;200 ppm) in the silicate glass. The Ga2O3 abundances and Cr2O3/Ga2O3 values (<1) of the sapphires favour their formation by magmatic processes. The presence of CO2-rich fluids and high K concentrations in the silicate melt inclusions link the origin of the Denchai gem sapphires to CO2-rich alkaline magmatism.

The commissioning and operation of apparatus for neutron diffraction at simultaneous high temperatures and pressures is reported. The basic design is based on the Paris-Edinburgh cell using opposed anvils, with internal heating. Temperature is measured using neutron radiography. The apparatus has been shown in both on-line and off-line tests to operate to a pressure of 7 GPa and temperature of 1700°C. The apparatus has been used in a neutron diffraction study of the crystal structure of deuterated brucite, and results for 520°C and 5.15 GPa are presented. The diffraction data that can be obtained from the apparatus are of comparable quality to previous high-pressure studies at ambient temperatures, and are clearly good enough for Rietveld refinement analysis to give structural data of reasonable quality.

The construction of zirconium (Zr) budgets for metamorphic reactions in high-grade rocks provides new insight into zircon growth during metamorphism. In this study we target reactions involving garnet, as they enable zircon growth to be related to known pressure and temperature conditions. Two reactions involving the breakdown of Zr-bearing garnet from Rogaland, SW Norway have been investigated in detail, showing contrasting behaviour of Zr, with zircon formation being subject to the solubility of Zr in product phases. In the decompression reaction garnet + sillimanite + quartz → cordierite, Zr released during garnet breakdown cannot be incorporated into the cordierite structure, resulting in zircon nucleation and growth. In contrast, for the reaction garnet + biotite + sillimanite + quartz → osumilite + orthopyroxene + spinel + magnetite, no new zircon growth takes place, despite the garnet involved containing more than double the Zr concentration of the former reaction. In the latter case, all the Zr released by garnet breakdown can be detected in the product phases osumilite and orthopyroxene, thereby preventing growth of new metamorphic zircon. This study highlights the potential for high resolution geochronology in metamorphic rocks by relating zircon growth to specific metamorphic reactions.

North Motzfeldt is an intrusive igneous centre within the Igaliku (formerly spelt Igaliko) complex, Gardar Province, South Greenland. A detailed field description of the centre is given, with preliminary geochemical and isotopic data. The North Motzfeldt centre is intruded into Ketilidian granitoid basement rocks, and current exposure retains parts of the original roof against earlier Gardar eruptives and clastic sediments of the Eriksfjord formation. The unconformity between the Ketilidian and the overlying Eriksfjord is believed to have been crucial in the siting of the centre. The centre is subdivided into two major units, NM1 and NM2. This was followed by significant peralkaline nepheline microsyenite in sheets, characterized by rare element-rich accessory minerals including rinkite-mł sandrite, pyrochlore and låvenite. A significant microsyenite body is called NM3. A preliminary Rb-Sr isochron of 1226±27 Ma indicates a far younger age for the centre than previously thought (~;1350 Ma). Cross-cutting relationships between North Motzfeldt and rocks of the adjacent Motzfeldt centre require a reappraisal of the chronology of Motzfeldt magmatism. We suggest that rocks previously believed to comprise the Motzfeldt centre represent the products of multiple phases of magmatism from Early- to Mid-Gardar times.

The Raman spectrum of holmquistite, a Li-containing orthorhombic amphibole from Bessemer City, USA has been measured. The OH-stretching region is characterized by bands at 3661, 3646, 3634 and 3614 cm−1 assigned to 3 Mg–OH, 2 Mg + Fe2+–OH, Mg + 2Fe2+–OH and 3 Fe2+–OH, respectively. These Mg and Fe2+ cations are located at the M1 and M3 sites and have a Fe2+/(Fe2+ + Mg) ratio of 0.35. The 960–1110 cm−1 region represents the antisymmetric Si–O–Si and O–Si–O stretching vibrations. For holmquistite, strong bands are observed around 1022 and 1085 cm−1 with a shoulder at 1127 cm−1 and minor bands at 1045 and 1102 cm−1. In the region 650–800 cm−1 bands are observed at 679, 753 and 791 cm−1 with a minor band around 694 cm−1 attributed to the symmetrical Si–O–Si and Si–O vibrations. The region below 625 cm−1 is characterized by 14 vibrations related to the deformation modes of the silicate double chain and vibrations involving Mg, Fe, Al and Li in the various M sites. The 502 cm−1 band is a Li–O deformation mode while the 456, 551 and 565 cm−1 bands are Al–O deformation modes.

A magmatic calcic amphibole (M4Ca≥1.50) characterized by large Sr and F contents (SrO>1 wt.%, F>2.5 wt.%) is described. According to the crystal-chemical formula, the amphibole can be classified as a strontian fluoro-magnesiohastingsite and the presence of Sr cations in the A sites is suggested. The amphibole occurs in the groundmass of ultrapotassic lavas from the Alban Hills Volcanic District (Central Italy). This peculiar chemical composition is due to the lavas' groundmass compositional trend occurring under low silica-activity conditions. We suggest that the occurrence of F amphiboles allows us to consider the Alban Hills Volcanic District magmas to be as rich in F as other ultrapotassic magmas.

The ultrastructures of parisite-(Ce) from a rare-earth mineral deposit of Sichuan Province, southwest China, have been observed and investigated by selected area electron diffraction (SAED) and high resolution electron microscopy (HREM). Six new polytypes 4H, 10H, 16H, 18R, 24R and 30R were determined in parisite-(Ce), as were their crystal structure types, subcell (a′c‴, a′c″, a′c′) and supercell (ac) parameters, reflection conditions, polytype features and probable space groups. The HREM studies revealed the complex polytypism in parisite-(Ce) whereby the six new polytypes, formed by long-period ordered stacking, always coexist with the common polytype parisite-(Ce)-6R by syntaxy and thus constitute the complex microstructural ‘syntactic polycrystals’, the host of which is the polytype parisite-(Ce)-6R.

Pararsenolamprite, the third polymorph of native As, is found at the Mukuno mine, Oita Prefecture, Japan. It is orthorhombic, Pmn21 or P21nm, a = 3.633(2), b = 10.196(2), c= 10.314(2)Å, Z = 18. The seven strongest lines in the X-ray powder diffraction pattern are: 5.17 (100) (002), 4.60 (24) (012), 3.259 (58) (013), 2.840 (27) (032), 2.580 (22) (004), 2.299 (23) (024), and 1.794 (26) (105). Electron microprobe analysis gives As 91.89, Sb 7.25, S 0.48, total 99.62 wt.% (mean of 8), and lead to the empirical formula, As0.96Sb0.03S0.01. It is lead grey in colour and opaque with metallic lustre and black streak. It is sectile and brittle with perfect cleavage on [001]. The VHN25 is 66–91 kg/mm2, corresponding to 2–2.5 in Mohs' hardness scale. The measured and calculated densities are 5.88(5) g/cm3 and 6.01 g/cm3, respectively. In reflected plane-polarized light in air, it is white with a slightly greenish blue tint. Anisotoropy is strong, dark brown to dark greenish grey. Bireflectance is distinct; parallel to elongation it is creamy; perpendicular to elongation it is brown, grey and green. Internal reflections are absent. The reflectance spectra are tabulated in the text.

Pararsenolamprite occurs as euhedral crystals in close association with arsenic, stibnite and quartz in a Sb-As-Ag-Au-bearing quartz vein cutting altered Neogene andesite from the Mukuno mine. It forms radial or parallel aggregates of bladed cystals up to 0.8 mm in length.