EXAFS spectroscopy has been used to monitor changes in divalent cation site geometries across the P2/c-P1̄ phase transition in the sanmartinite (ZnWO4)-cuproscheelite (CuWO4) solid solution at ambient and liquid nitrogen temperatures. In the ZnWO4 end member, Zn occupies axially-compressed ZnO6 octahedra with two axial Zn-O bonds at approximately 1.95 Å and four square planar Zn-O bonds at approximately 2.11 Å. The substitution of Zn by Cu generates a second Zn environment with four short square planar Zn-O bonds and two longer axial Zn-O bonds. The proportion of the latter site increases progressively as the Cu content increases. Cu EXAFS reveals that the CuO6 octahedra maintain their Jahn-Teller axially-elongate geometry throughout the majority of the solid solution and only occur as axially-compressed octahedra well within the stability field of the Zn-rich phase with monoclinic long-range order.

The triple-chain pyriboles jimthompsonite, clinojimthompsonite, and probably chesterite and its monoclinic polytype occur in Lewisian amphibolite-facies ultramafic rocks near Achmelvich, N.W. Scotland. These minerals are intergrown with one another and with amphiboles in prismatic porphyroblasts up to 3 cm long, which are associated with chlorite, carbonate, magnetite and, in some cases, talc. Rocks containing triple-chain silicates have been found at three localities, in each case outcropping in a layer < 1.5 m thick. Clinojimthompsonite is the most abundant triple-chain silicate and generally forms euhedral wedge-shaped overgrowths, measuring up to 1 mm in the b-axis direction, on the {010} faces of actinolite cores. The mineral assemblages are probably of Inverian age.

The identification of the triple-chain phases is based mainly on cleavage angle, extinction angle, backscattered electron intensity and, in the case of clinojimthompsonite, on X-ray diffraction data. Microprobe analyses support the identifications. The triple-chain silicates have compositions lying in the system MgO-FeO-SiO2-H2O, with only trace amounts of other components.

The cell dimensions of the coarsest clinojimthompsonite are: a = 9.862 ± 0.002 Å, b = 27.184 ± 0.020 Å, c = 5.298 ± 0.004 Å, β = 109.61° ± 0.14° V = 1337.9 ± 1.8 Å3, and its optical properties are as follows: α = 1.600 β = 1.619 γ = 1.628 (all ± 0.001) and optic axial plane = (010). The 2Vα of clinojimthompsonite = 67 ±2°.

Back-scattered electron microscopy reveals that although substantial volumes of single-phase clinojimthompsonite are common, (010) intergrowths of Mg,Fe-amphiboles, jimthompsonite polytypes and chesterite polytypes occur locally on scales down to 0.1 µm and probably smaller, indicating considerable chain-width disorder.

The triple-chain pyriboles are not pseudomorphous after amphibole and probably grew during prograde Inverian metamorphism. Chemographic constraints suggest that they could have formed from forsterite-bearing assemblages, possibly as the result of infiltration of CO2-rich fluid. Thermodynamic calculations for associated high-variance ultramafic rocks place an upper limit of c. 600–700°C on the temperature of metamorphism.

The large number of chemically similar pyriboles and their disposition within compound prisms suggests that crystallization was kinetically controlled. A simple ‘template’ model is propesed to explain the observed patterns, in which the identity of the Mg,Fe-pyribole nucleating at any point on a preexisting actinolite or Mg,Fe-pyribole substrate is controlled by silicate-chain width and/or symmetry (ortho vs. clino), depending on the orientation of the substrate crystal face.

Mineral chemistry and whole-rock compositional data are reported for two lavas of picritic basalt from the Palaeocene lava field of west-central Skye, Scotland. Whole-rock compositions for both flows plot on Thompson's (1982) 9 kbar cotectic for olivine + plagioclase + clinopyroxene + liquid. Both flows contain highly forsteritic olivine phenocrysts (c. Fo89), which enclose early-precipitated crystals of chrome-spinel (Al2O3: c. 25 wt.%; Cr2O3: c. 36 wt.%; FeO + Fe2O3: c. 20 wt.%; MgO: c. 15 wt.%). The olivine compositions indicate equilibrium with picritic basalt magma compositions, as represented by the whole-rock compositions of both lavas. A high-pressure origin for the chrome-spinels is suspected on the basis of their textural association and aluminous composition. Compositional comparisons between the whole-rock and mineral chemistry characteristics of both flows and a picritic basalt chill facies of the temporally- and spatially-associated Rum Igneous Complex suggests that similar parental magmas were involved.

Low-temperature experiments in the ‘dry’ ternary Cu-Bi-S system, conducted by using sulphidation methods down to 120°C produced a new metastable solid solution series Cu10Bi2S13-Cu5Bi2S8 at 178°C coexisting with CuS. This transformed slowly at 190–200°C to an assemblage of either CuS-(Cu,Bi)8S9 or CuS-Bi2S3 or both, depending on available sulphur. Sulphidation experiments on Cu3BiS3 similarly revealed a solid solution range for the phase (Cu,Bi)8S9 of up to Cu/Bi = 3/2 at 178–190°C, and a lower stability limit of 138°C Isothermal sections of the system were constructed at 200 and 300°C, based on the new information collected but excluding the metastable series.

Cretaceous, strongly alkaline mafic igneous provinces occur around the margins of the Ordovician to Cretaceous Paraná sedimentary basin of southern Brazil. The Serra do Bueno diatreme is situated in the southern portion of the largest of these alkaline provinces, the Alto Paranaíba Igneous Province in Minas Gerais. The well-exposed diatreme crops out close to the south-west surface limit of the São Francisco craton and is adjacent to several other poorly exposed ultramafic alkaline pipes, previously described variously as kimberlites (Barbosa, 1991) and lamproites (Ramsay and Tompkins, in press). The diatreme has two distinct facies: (1) a crater facies dominated by lapilli tuffs; and (2) a magmatic hypabyssal facies formed by a relatively fresh ultramafic (MgO = 15 wt.%) potassic (K2O/Na2O = ∼ 1.5) intrusion that contains xenoliths of meta-sediments, feldspathic gneiss and dunite. It is massive and porphyritic, with large olivine phenocrysts (Fo87) and smaller crystals of diopside (Ca50Mg44Fe6), phlogopite, perovskite, ilmenite and zeolites in a fine-grained groundmass that contains altered leucite and up to 20% devitrified glass. The Serra do Bueno intrusion shows a strong enrichment in light relative to heavy rare earth elements, with La/Yb of ∼85. Its initial 87Sr/86Sr (0.705176) and 143Nd/144Nd (0.512312) isotopic ratios are similar to those of other intrusions (e.g. Limeira 2) and lavas (e.g. Presidente Olegário) in the Alto Paranaíba Igneous Province. This suggests that these Late Cretaceous alkaline magmas were all derived from a similar source, predominantly within the subcontinental lithospheric mantle.

Laser 40Ar/39Ar analyses have yielded an isochron of 90 ± 4 Ma for the Serra do Bueno intrusion. This age is higher than the corresponding K/Ar bulk-rock age for the same sample but similar to K/Ar ages determined on mica separates from both intrusive and extrusive rocks in the Alto Paranaíba Igneous Province.

Relative concentrations of elements in the minerals of fine-grained sediments can be inferred from element-mineral correlation coefficients. The technique is applied to the distribution of REE in Middle Ordovician shales from South Wales analysed by ICPAES, Leco C/S125 and XRD. Phosphate and chlorite show mid-REE enrichment; muscovite + biotite shows mid-REE depletion. The complementarity of the chlorite and muscovite + biotite patterns may be due to fractionation during diagenetic recrystallisation. Partial correlation analysis is used to infer the presence of zircon.

Synthetic end-member strontium feldspar (SrAl2Si2O8) has been studied in a diamond-anvil cell at elevated pressures up to 10.3 GPa using energy-dispersive X-ray powder diffraction. Cell parameters have been refined between ambient pressure and 6 GPa. SrAl2Si2O8 undergoes a ferroelastic phase transition from the ambient pressure monoclinic space group I2/c to the high-pressure triclinic space group I at 3.2 ± 0.4 GPa. The transition appears to be first-order and the ferroelastic and co-elastic components of the spontaneous strain tensor have been calculated.

Metasomatic interaction on a cm scale between calc-silicate pods and the enclosing sillimanite + biotite + tourmaline gneiss at Partridge Breast Lake, northern Manitoba, Canada, led to the development of an inner (by calc-silicate rock), hornblende-rich reaction zone and an outer, biotite-rich zone. The boundary between the reaction zones is interpreted as the original calc-silicate/metapelite interface. Compared with its metapelitic protolith, the biotite zone shows a two- to twenty-fold depletion in the concentrations of incompatible trace elements (notably the light rare earths, U, Th, Nb, Ta, Zr and Hf). In contrast, the relative concentrations of trace elements remained nearly constant during the mineralogical transformation of the calc-silicate rock to the hornblende zone. The depletion of trace elements in the biotite zone is attributed to the dissolution of accessory phases (e.g. monazite). Although stable at the metamorphic conditions (∼600–650°C at ∼ 4.5 kbar) prevalent during metasomatism, Mg-rich tourmaline is absent in the biotite zone, suggesting that either the pH or composition (e.g. the (Al + Si)/(Ca + Mg + Fe) ratio) of the aqueous fluid phase was inappropriate for the preservation of this mineral.

Nearly boron-free kornerupine is locally abundant in pods or lenses of coarse-grained, non-foliated, Mg- and Al-rich rocks that occur at high metamorphic grades in early Proterozoic metapelitic rocks from the Reynolds Range, Northern Territory, Australia. This is the third reported occurrence of boron-free kornerupine worldwide. The samples consist almost entirely of coarse-grained kornerupine and its breakdown products sapphirine, cordierite, and gedrite or orthopyroxene. The kornerupine contains only 0.45 wt.% B2O3, corresponding to 0.098 B atoms per 22 (O, OH), and closely approximates 11:10:11 in terms of molar ratios of (MgO + FeOtotal):Al2O3:SiO2, with XMg = Mg/(Mg + Fetotal) = 0.874. The unusual textures and bulk compositions of the rocks in the pods are interpreted to have resulted from metasomatism and high-grade metamorphism (750 to 800° and ∼ 4.5 kbar) of precursors that may have included sedimentary Mg-rich clays. Rocks containing boron-poor, and relatively boronrich kornerupine (2.18 wt.% B2O3; XMg = 0.892) are separated in outcrop by as little as 10 m of the foliated cordierite-quartzite country rock and other rock types, suggesting that the compositions or amounts of the metasomatic fluids varied on a local scale.

Coexisting scapolite, biotite and hornblende in scapolite-biotite rocks from the Tongmugou Pb-Zn deposit, Qinling, northwestern China are characterized by high levels of chlorine. Scapolite composition varies from EqAn27 to EqAn47 with 47–80 wt.% Cl. The scapolite composition is a sensitive indicator of the NaCl activity in coexisting hydrothermal fluid. Biotite contains 0.3–1.2 wt. % Cl and also has high F contents (0.2–0.7 wt.%). The hornblende is a Cl-rich hastingsite with Cl>3.5 wt.% and high (Na2O + K2O) contents (3.2–3.9 wt. %), high Xk [= K/(K + Na)] values (0.45–0.55) and high XFc [= Fe/(Fe + Mg)] values (0.76–0.79). The chlorine within these minerals is thought to be derived from evolved seawater. The scapolite-biotite rocks are products of Cl-rich alteration of volcanoclastic sedimentary rocks during submarine hydrothermal processes. Multiple-stage hydrothermal activity culminated with the circulation of a high-NaCl fluid that was also responsible for the formation of the massive sulphide deposits.

Based on petrographic, mineralogical and geochemical data, two groups of rodingites have been documented from the polymetamorphic Vumba Schist Belt of Botswana. Group I rodingites contain relict chromite grains with zoned uvarovite-grossular + clinopyroxene + epidote/zoisite ± quartz, whereas group II rodingites contain no chromite and uvarovite. Although the presence of chromite with Cr/(Cr + Al + Fe3+) ratio > 90, similar to chromites found in komatiites, suggests a possible komatiitic origin of group I rodingites, the major and trace element chemical data of most analysed basic rocks from this belt indicate that the protoliths of both groups of rodingites are related to basalt/gabbro of komatiitic affinity. The rodingites formed during the M3 phase of metamorphism.

The Loch Shin monzogranite is host to quartz veins bearing the sulphosalts aikinite, hammarite, lindströmite, krupkaite, gladite and pekoite, which belong to the aikinite-bismuthinite series, and represents the first significant occurrence of this series in the United Kingdom. Inclusions of the sulphotelluride tetradymite occur in krupkaite-gladite. Berryite is present as inclusions in chalcopyrite. Electron microprobe analyses reveal a range of compositions in individual crystal masses from hammarite to krupkaite in one sample, and from krupkaite to gladite in a second. Compositions between friedrichite and hammarite and gladite and pekoite are notably absent.

The recent discovery of hyalophane [(K,Ba)Al1−2Si3−2O8] on the North range segment of the Early Proterozoic Cuyuna Iron Range of east-central Minnesota has shed new light on the depositional environment of these rocks. This Ba-feldspar occurs in a 10 m thick interval within the main iron-formation and typically contains between 8 and 26 mol.% celsian (BaAl2Si2O8). Its occurrence in several textural settings suggests that barium was being deposited at various stages in the paragenetic history of the iron-formation. Some of the hyalophane grains occur as the cores of micronodules, which are structurally similar to oolites or oncolites, but mineralogically are very complex. The hyalophane also occurs as rims on core grains of diverse mineral composition and as discrete phases in late crosscutting veins.

Hyalophane, like other Ba-silicates, has a very restricted paragenesis. They are associated typically either with sedimentary manganese and ferromanganese deposits, or with Cu-Pb-Zn-Ba deposits. The presence of hyalophane in the Early Proterozoic manganiferous iron ores of east-central Minnesota casts doubt on the historic interpretation of these deposits as typical Superior-type sedimentary iron-formations and instead supports the view that these deposits, at least in part, consist of chemical sediments from a hydrothermal fumarolic system. The suggested involvement of a hydrothermal system is also supported by the occurrence of aegirine within the hyalophane-rich layer, and the occurrence of tourmalinites and Sr-rich baryte veins elsewhere in the Cuyuna North range.

A 65 × 107 µm grain of euhedral tetrataenite (ordered FeNi) attached to a similarly sized grain of troilite occurs within an impact-melt rock clast in the Jelica LL6 chondrite breccia. After impact melting, immiscible metallic Fe-Ni and troilite droplets formed within the silicate melt progenitor of the clast. At ⩾1200°C while the surrounding silicate was still partly molten, euhedral taenite with ∼ 50 wt.% Ni began crystallizing in one of the metal-troilite droplets. Troilite nucleated at one edge of the euhedral taenite grain and began to crystallize at ∼870°C. At 320°C the metal phase underwent an ordering reaction and formed tetrataenite. The unrecrystallized clast-host boundary and the differences in olivine composition and degree of polycrystallinity of troilite between the clast and Jelica host indicate that the clast was incorporated into Jelica during a late-stage brecciation event.

Major, trace element composition and Sr isotopic data were collected for gabbroic rocks, plagiogranites and albitites in the ophiolite assemblage from Swat Valley (NW Frontier Province, Pakistan). Petrographic study revealed that these rocks were subjected to important structural and mineralogical modifications due to greenschist-epidote-amphibolite facies sub-sea-floor metamorphism and to brecciation. On the other hand, the examination of whole rock chemical composition and of chemical trends showed that these rocks were affected by some chemical modifications, concerning especially Na2O, K2O and Rb. The very low contents of HFS (high field strength) and RE elements found in gabbroic rocks and plagiogranites were considered to be a primary magmatic feature pointing in part to their cumulitic nature and in part to an origin from a refractory parental magma. The Sr isotopic data indicate that gabbroic rocks and plagiogranites were subjected to exchange with sea water. The particular chemical features shared by gabbroic rocks and plagiogranites suggested that fractional crystallization was a possible evolution process. In contrast, albitites are characterized by anomalously high contents in HFSE and LREE and by values of the 87Sr/86Sr ratio very close to sea water. These features suggest a more complex origin with respect to gabbroic rocks and plagiogranites.

Within a suite of felsic-free, mica-rich alkaline ultramafic rocks of the Schryburt Lake carbonatite complex of northwestern Ontario, loparite and Ba-Fe hollandite occur in intimate association with perovskite. The host rocks have variable modal proportions of Mg-olivine, phlogopite, magnetite, ilmenite, apatite and carbonate (generally calcite) with minor Mg-salite. Thus, they correspond to ultramafic lamprophyres (i.e. aillikites), in the sense of Rock (1990) or the lamprophyric facies of the melilitite clan, in the sense of Mitchell (1993).

Perovskite is the principal titanate phase, forming both euhedral and anhedral grains, the latter showing evidence of marginal resorption. It exhibits complex zonal patterns due principally to variations in the light rare earth elements, Na and Nb. In the nomenclature suggested, they may be termed perovskite and cerian perovskite. Loparite forms as small euhedral overgrowths on corroded perovskite cores. Chemically they are essentially solid solutions of loparite, lueshite and perovskite. Consequently, they may be termed calcian-loparite, calcian niobian loparite, niobian calcian loparite, loparite and niobian loparite. Titanates of the hollandite group are rare accessory minerals whose composition closely approach that of the septatitanate BaFe2+Ti7O16.

The complex zoning of the perovskite grains has been attributed to the periodic introduction of carbonatite-derived fluids enriched in REE, Na and Nb into the silicate system during perovskite crystallization. Subsequent reaction of the early perovskite with F-bearing fluids leads to a localized environment enriched in Ti, Na, Nb and REE derived from both the fluid phase and the unstable perovskite. Loparite subsequently crystallizes from these micro-chemical environments.

Phase relations in the system PbS-PbSe-PbTe were investigated in the temperature range between 1150 and 300°C. There is a complete solid solution series along the join PbS-PbSe, whereas miscibility gaps exist below ∼ 350°C and 805°C along joins PbSe-PbTe and PbS-PbTe, respectively. Both gaps extend into the ternary system, and the range of the gap between PbS and PbTe reduces in size with temperature as well as Se-content.

By using the subregular model of mixing (Ganguly and Saxena, 1987), mixing energetics and activity composition relations of PbX were derived. The temperature-dependence of the interaction parameters was calculated to be 5057.6 − 1.7T, 9605.2 − 4.4T, 3933.2 − 3.1T (T < 500°C), 6410.3 − 6.35T (T < 500°C) 1649 − 0.26T, 1594.6 − 0.2T, and 12906.3 − 17.3T for WWSte, WTeS, WSeTe, WTeSe, WSSe, WSeS, and WSSeTe, respectively. A critical temperature along the join PbS-PbSe at ∼ 100°C was obtained from interaction parameter calculation, which suggests the separation of the PbS-PbSe series.

Correlation of solid-solution ranges established in this study with natural occurrences was made.

The compositions of coexisting and individual cooperite (ideally PtS) and braggite (ideally (Pt,Pd)S) grains from the Merensky Reef of the Bushveld Complex, as well as cooperite, braggite and vysotskite (ideally PdS) grains from the UG-2 of the Bushveld Complex were investigated. There is a clearly defined miscibility gap between cooperite and braggite, but no evident gap between braggite and vysotskite. Partition coefficients between cooperite and braggite are determined on coexisting phases. The KDbraggite/cooperite in atomic ratios are estimated to be 0.54 for Pt, 15.81 for Pd and 5.93 for Ni. For Rh and Co the KDbraggite/cooperite are estimated to be > 1.40 and > 1.46 respectively. No systematic behaviour is detected for Fe and Cu. Coupled substitutions of Pd + Ni for Pt in cooperite and braggite/vysotskite are indicated. Within the cooperite of the Merensky Reef, the Pd:Ni ratio is approximately 9:11. The substitution trend in braggite, which extends to vysotskite in the UG-2, is dependent on the base-metal sulphide (BMS) association. If pentlandite is the dominant Ni-bearing BMS, the Pd:Ni ratio is about 7:3 in the Merensky Reef and in the UG-2. Millerite as the dominant Ni-bearing BMS in the UG-2 changes this ratio to 3:1. It is concluded that the Ni-content in braggite/vysotskite from BMS assemblages does not depend on the NiS activity, but rather on temperature of formation.

Vaterite, a CaCO3 polymorph, is a rare mineral that is said to be metastable under all known conditions. According to the literature, vaterite precipitated from carbonate solution recrystallizes spontaneously to calcite or aragonite. Yet vaterite has been identified in hard tissues of organisms, in gallstones, in contact metamorphic aureoles, in zones of thermal metamorphism, in a meteorite, and in cone-in-cone concretions. Newly precipitated vaterite has formed at the expense of carbonate rock in drilling fluids in wells of New York, Michigan, Nevada, Texas, and New Zealand. Petrographic examination reveals a light brown core of Ca3SiO5 surrounded by a colourless rim of vaterite. The δ18OPDB of New York vaterite is −12.4‰ and that of the Michigan vaterite is −17.6‰, which reflect the oxygen isotopic composition of meteoric freshwater used in drilling. The δ13CPDB value of −19.2‰ for New York vaterite and that of −17.6‰ for Michigan vaterite suggest that natural gas dissolved original carbonate in the subsurface. Drilling records from both wells indicate that natural gas was released into the drilling muds from the formations exposed at the time vaterite was encountered. Crossplots of the oxygen and carbon isotopic ratios overlap those of spurrite rocks in thermal metamorphic zones in Israel. A C-14 radiocarbon analysis of the Michigan vaterite gave an age of 953±39 yr. BP. 88.8±0.6% is modern carbon and 11.2% is dead carbon. Hence this carbon, and therefore the vaterite, is essentially modern. A sample of the New York vaterite yielded a modern age.