Four grains of zirconolite and baddeleyite have been found in two plagioclase-rich adcumulates from the Laouni layered intrusion (Southern Hoggar, Algeria). Zirconolite is poor in REE; baddeleyite is chemically close to ZrO2 and contains minor amounts of Hf. They are considered to be crystallization products of pockets of intercumulus liquid. The preferential distribution of zirconolite in anorthosite is explained in terms of expulsion of the intercumulus liquid by sintering or annealing of plagioclase. The crystallization of baddeleyite reflects the sharp increase of Zr in the trapped intercumulus liquid.

This study reports on experimental results concerning methyl-tert-butyl-ether (MTBE, C5H12O) adsorption from water into the pores of siliceous zeolite ferrierite (FER) by combining powder X-ray diffraction analyses and chromatography techniques. Rietveld structure refinement (Immm space group) highlighted the presence of two crystallographically independent MTBE sites located in the 10-ring channel parallel to the [001] direction (MTBE1) and in the ferrierite cage (MTBE2), respectively. On the whole, Rietveld refinement revealed clearly the incorporation of ~1.8 MTBE molecules per unit cell, in very good agreement with the weight loss given by thermogravimetric analyses, and saturation capacity as determined by adsorption isotherms. Rapid kinetics combined with good adsorption suggests that FER can be used beneficially as an adsorbent medium in removing this emerging organic contaminant from water.

Oxidation zones and mine wastes are metal-rich, near-surface environments, natural and man-made critical zones of ore deposits, respectively. They contain a number of minerals which, despite their metastability, occur consistently and in abundance. Field studies, presented as examples in this work, show that metastable minerals form not only directly from aqueous solutions, but also from more complex precursors, such as nanoparticles, gels, X-ray amorphous solids, or clusters. Initial precipitation of metastable phases and their conversion to stable phases is described by the Ostwald's step rule. Thermodynamic data show that there is a tendency, but no rule, that structurally more complex phases are also thermodynamically more stable. The Ostwald's step rule could then state that the initial metastable phases are structurally simple and easily assembled from aqueous solutions, nanoparticles, gels, disordered solids, or clusters. The structural similarity of the precursor and the forming phase is a kinetic factor favouring the crystallisation of the new phase. Calculation of saturation indices for mine drainage solutions show that they are mostly supersaturated with respect to the stable phases and the aqueous concentrations are sufficient to precipitate metastable minerals. In our fieldwork, we often encounter gelatinous substances with copper, manganese or tungsten that slowly convert to metastable oxysalt minerals. Another possibility is the crystallisation of various metastable minerals from solid, homogeneous ‘resins’ that are X-ray amorphous. Minerals typical for near-surface environments may be stabilised by their surface energy at high specific surface areas. For example, ferrihydrite is often described as a metastable phase but can be shown to be stable with respect to nanosised hematite.

Thomsonite was first recognized by H. J. Brooke (1820) in a JL study of the mesotypes or 'needlestones'. The 'needlestone' of Lochwinnoch and Old Kilpatrick, Dumbartonshire, was found to be an independent species, in addition to the natrolite, mesolite, and scolecite into which k. F. Gehlen and J. N. Fachs, and J. N. Fuchs, had divided the mesotype of R. J. Haüy. The new species was named thomsonite, in honour of Dr. T. Thomson, who analysed the material a few months later.

During an analysis by X-ray diffraction techniques of some fine-grained leucite-lamproites from the west Kimberley area of Western Australia the author became interested in the rntile in these rocks. Although rutile had been repeatedly observed under the microscope (1, 2), its presence could not be confirmed using X-ray diffraction methods. At the author's request, Professor R. T. Prider supplied a small amount of the mineral which had been identified as rutile. A study of this mineral showed it to be a new mineral similar to rutile in its optical properties.

Garnets undergo readjustment of ion-assemblages under external mechanical and thermal stresses; this adjustment favours those paths that annul the very cause to which it is due. Metal ions in garnets being replaceable, with rising metamorphism garnets become reluctant to accommodate ions of larger ionic radii.

Data from recent literature on chemical analyses of garnets from rocks belonging to different grades of regional metamorphism reveal that the (FeO + MgO) content of garnet varies linearly with (CaO + MnO) content. As the Fe/Mg ratio does not vary appreciably, a fair estimate of metamorphic grade can be made from a knowledge of (CaO + MnO) or of (FeO +MgO) individually or even, with less confidence, of FeO or MgO alone. From the study of the available data it is found that (CaO + MnO) and (FeO + MgO)/(CaO + MnO) provide the best indicators of progressive metamorphism. Cell edges of garnets decrease progressively with increasing metamorphism and this may also be used as a fairly good index of metamorphism. When cell edges are plotted against (FeO + MgO)/(CaO + MnO), a hyperbolic curve is obtained.

This saponite, which is closely associated with zeolites such as stillbirth, heulandite, thomsonite, and gonnardite, occurs in vesicles in basalt. It has the composition: 1·02M+ (Mg5·84Mn0·01Al0·03Fe0·08) (Si6·99Al1·01)O20(OH)4, according to a new method for calculating the ionic formulae of smectites: this method also enables determination of the temperature at which all sorbed moisture is removed—in this instance about 800°C. The exchangeable cations are largely Ca2+. The chemical, thermal, and X-ray data are discussed with reference to other saponite samples. Electron-microscope examination showed a tendency to elongation in the direction of the α-axis. It is concluded that the saponite is of excellent purity and free from interstratification.

Aluminous Ca-rich clinopyroxenes (5.95-7.63 wt % Al2O3) are next in abundance to leucite in the basic alkaline potassic lavas from Monte Somma and Vesuvius, Italy, and occur as phenocrysts (1 to 7 mm), micropbenocrysts (< 1 mm), and groundmass granules. Zoning of various types is a conspicuous feature in these pyroxenes. Optical and chemical data are presented and a comparison is made between these pyroxenes and similar ones from alkali basalts. It is known from published data that Al2O3 fluctuates strongly in the oscillatory zones of Vesuvian pyroxenes. This can be explained as due to temperature variation in the magma, to magma variation in silica content due to contamination, to oscillations in leucite precipitation, or to a combination of these factors. Of these three factors, oscillations in leucite precipitation, as it appears, would be more effective than the others since it would have a greater control over Si/A1 availability in the magma.

The Tyndrum Pb-Zn mineralization occurs as veins and vein breccias in NE-SW trending fractures associated with the Tyndrum-Glen-Fyne fault. The major minerals are quartz, galena, and sphalerite with minor chalcopyrite and baryte. Tetrahedrite (sometimes silver-and cadmium-rich), pyrargyrite, marcasite, and pyrite occur as small inclusions (< 100 µm) in the galena-rich veins. Sphalerite formed early in the depositional sequence, mainly in breccias, with increasing amounts of galena and chalcopyrite deposited in the later vein stages of mineralization. Uraniferous veins post-date the main Pb-Zn mineralization and contain uraninite, calcite, baryte, galena, sphalerite, chalcopyrite, argentite, chalcocite, tetrahedrite, and safflorite.

Fluid inclusion studies reveal that the mineralizing solutions contained c.20 wt. % equivalent NaCl + KCl, had an Na/K ratio of 3 : 1 and were boiling during mineral precipitation.

The Tyndrum fault controlled the upward flow of the hydrothermal solutions and its intersection with fractures in quartzites favoured the siting of the veins. The depositional sequence is explained by an increase in temperature during the mineralizing episode. The uraniferous veins may be a late oxidized stage of the main Pb-Zn mineralization.

Zoning texture in sphalerite has been described in many studies, although its genesis and ore formation process are poorly constrained. In this investigation, we compare the in situ trace element and isotopic composition of colour-zoned sphalerites from Nayongzhi, South China, to explain the zoning growth process. Petrographic observations identified two broad types of zoned sphalerite, core–rim (CR) and core–mantle–rim (CMR) textures. Each zoned sphalerite displays two or three colour zones, including brown core, light colour bands and/or pale-yellow zones. In situ laser ablation inductively coupled plasma mass spectrometry trace-element analyses show that the three colour zones display variable trace-element compositions. Brown cores exhibit distinctly high Mn, Fe, Co, Ge, Tl and Pb concentrations, whereas pale-yellow and light colour zones have elevated Ga, Cd, Sn, In and Sb concentrations. Copper, Sb, In and Sn show slight variations between pale-yellow and light zones, the latter having higher In and Sn, but lower Cu and Sb abundances. Given the low concentration range of Pb, Ge, Tl, Mn Sb, Cd, etc., the colour of sphalerite is attributed mainly to Fe compositional variation. The δ34S values of sphalerite from Nayongzhi range from +22.3 to +27.9‰, suggesting reduced sulfur was generated by thermochemical sulfate reduction of marine sulfate in ore-hosted strata. Single-crystal colour-zoned sphalerite exhibits intracrystalline δ34S variation (up to 4.3‰), which is attributed to the δ34S composition of H2S in the original fluid. The lack of correlation between trace elements and δ34S values indicates episodic ore solution influxes and mixes with the reduced sulfur-rich fluid derived from the aquifers of the ore-hosted strata, which play a key role in the formation of the zoned Nayongzhi sphalerite. In conclusion, in situ trace element and S isotope studies of zoned sphalerite crystals might provide insight into the ore-forming process of MVT deposits.

A number of geothermometers and geobarometers involving coexisting garnet, biotite, and cordierite have been used to calculate the pressures and temperatures of metamorphism of the Cashel thermal aureole in Connemara. Temperatures from the garnetbiotite thermometer show a wide variation between calibrations, and are markedly different from those obtained from the garnet-ordierite thermometer. These variations, together with the possibility of extensive reequilibration between garnet and cordierite rims and biotite, indicate that the use of exchange reaction thermometry, for these rocks at least, may be invalid. The various calibrations of the garnet-cordierite-sillimanitequartz geobarometer give reasonably consistent pressure estimates which, after allowance for partial pressures of water, indicate pressures of metamorphism of about 5±1 kb.

The partitioning of Sr, Ba and Rb between alkali feldspar and melt has been determined at 0.1 GPa water vapour pressure, mainly on one Na-rich series and one K-rich series within the system nepheline-kalsilite-quartz. Experiments were also carried out with small amounts of the anorthite molecule or peralkaline components (Na, K metasilicates). The compositions of the alkali feldspars and coexisting quenched glasses were determined by electron microprobe analysis. Except for some peralkaline compositions, the crystal/liquid partition coefficients for Sr and Ba are always >1; the crystal/liquid partition coefficient for Rb is always <1. For sodic alkali feldspars DSr > DBa and for potassic feldspars DSr < DBa. Partition coefficients for Sr and Ba increase: (1) with decreasing temperature; (2) with increasing Or content of feldspar; (3) with increasing silica-undersaturation of the melt; (4) with decreasing peralkalinity. The variation in the value of DRb is less clear, but it is higher for K-rich feldspars. Multiple linear regression equations are fitted to correlate ln(D) with independent compositional and physical variables. Where rock/groundmass major-element data are available for felsic natural rocks, equations are recommended for obtaining reliable alkali feldspar partition coefficients for modelling fractional crystallization processes. The structural properties of silicate melts and crystal chemical relations are used to rationalize trends in partition coefficients.

Z-phase was obtained hydrothermally at 120 °C by decomposition of Al-substituted tobermorite and by reaction of lime and colloidal silica. X-ray and electron diffraction show that the structural element is hexagonal, with a 9·65, c 15·3 Å, and good {0001} cleavage. Reversible water loss and lattice shrinkage occur on heating, the layer thickness (c) decreasing to 12.1 Å at 400 °C. For material in equilibrium with air of normal humidity, the composition is probably between CaO. 2SiO2. 1·7H2O and CaO. 2SiO2. 2H2O; Z = 8 for the structural element. New t.g. and infrared absorption data are presented; the infra-red spectrum closely resembles that of gyrolite, but OH ions attached only to Ca appear to be absent. Conditions of formation are discussed; if Z-phase has any stability field, it is below 120 °C. Crystal structures for Z-phase, gyrolite, and truscottite are suggested, based on the known structure of reyerite.

Crystals of the compound Na4(UO2)(CO3)3 have been synthesized and the structure has been solved. It is trigonal with a= 9.3417(6), c = 12.824(1) Å, V = 969.2(1) Å3, space group Pc1 and Z = 4. The structure was refined on the basis of F2 (wR2 = 4.2%) for all unique data collected using Mo-Kα X-radiation and a CCD-based detector. The final R1 was 2.0%, calculated for 534 unique observed (Fo ≥ 4σF) reflections, and the goodness-of-fit (S) was 0.91. The structure contains a uranyl tricarbonate cluster composed of a uranyl hexagonal bipyramid that shares three equatorial edges with CO3 triangles. The uranyl tricarbonate clusters are connected through NaO6 and NaO5 polyhedra, forming a heteropolyhedral framework structure. This compound may be related to a uranyl carbonate phase with the same composition which has been reported as an alteration phase on the surface of Chernobyl ‘lava’, and as a mineral in the Jachymov ore district, Czech Republic.

Three voluminous Quaternary phonolitic pumice fall deposits erupted from the compositionally-zoned Tenerife magma chamber exhibit variability in Sr and Pb isotope ratios. It has been previously argued that the Sr isotope variations are due to syn-eruptive interaction between magma and hydrothermal fluids (Palacz and Wolff, 1989). Pb compositions are not correlated with Sr, and are believed to reflect magmatic values. Pb isotope ratios exhibit regular variation with degree of fractionation, and one zoned deposit is heterogeneous in Pb. The highest values seem to characterize the most fractionated upper parts of the zoned system. This is unlikely to be a consequence of magmatic recharge. Isotopic and trace element behaviour is instead consistent with combined assimilation and fractional crystalliza- tion, involving the recycling of material containing relatively radiogenic Pb, from within the volcanic edifice. Assimilation of sediment intercalated within the submarine portion of the pile is ruled out by the isotopic data. The most probable contaminant is a felsic igneous rock. Early trachytes reported by Sun (1980) have the required Pb isotope compositions and may approximately represent the assimilant.

The crystal-chemical relationships occurring within a single grain of monazite-(Ce) from Vetralla, Vico Volcanic Complex, north of Rome, are outlined. The sample is from a miarolitic cavity in a holocrystalline ejectum consisting of K-feldspar plus minor plagioclase, mica and Fe-oxides, collected from a pyroclastic explosive level. The Gandolfi film (Cu-Kα radiation) can be indexed in space group P21/n with a = 6.816(4); b = 6.976(4); c = 6.471(3) Å; β = 103.63(3)°; V = 299.0(6) Å3. Electron-probe microanalyses plot within the field of monazite along the huttonite-monazite edge of the huttonite-monazite-brabantite triangle. Despite patchy and irregular zoning, the grain shows a clear enrichment towards pure monazite at the outer rim. A constant Th:Si ratio of 1:1 indicates the existence of a simple solid-solution between huttonite and monazite. The substitution can be written as Th4+ + Si4+ → REE3+ + P5+ without requiring any electrostatic compensation by divalent cations, or by anionic groups. The REE distribution pattern is compatible with that of monazites from syenitic rocks.

This review details a selection of occupational lung diseases, particularly fibrosis (scarring) and tumours that can arise following exposure to mineral dusts. Also described are the sequential repair processes of the lung including oedema, inflammation, epithelial changes and finally scarring. The features by which a dust can be considered bioreactive including shape, size, surface area, durability and surface chemistry is discussed together with the importance of the mass deposited in the lung and particle clearance, particularly through lymphatic drainage. Emphasis is given to the importance of surface chemistry in that crystalline minerals, especially silicas, are often highly bioreactive whereas amorphous silicas or crystalline forms that have aged in the laboratory have lesser activity. Nevertheless, all forms of crystalline silica are particularly hazardous with the long-term ability to produce irreversible disease (fibrosis) when administered to experimental animals.

Agates from a 430 Ma host at Stockdale Beck, Cumbria, England have been characterized. The crystallite size of the Stockdale Beck agates was found to be ~60% greater than any other agates from five regions aged 400–1100 Ma. Raman spectroscopy identified moganite in all agates tested except those from Stockdale Beck. Infrared spectroscopy showed that the silanol content of the Stockdale Beck agates was near zero. The properties of agates from Stockdale Beck and the 1.84–3.48 Ga metamorphosed hosts found in Western Australia were similar but different from agates found in other hosts aged 400–1100 Ma. Cathodoluminescence demonstrates further differences between agates from hosts aged 13–1100 Ma and those from Stockdale Beck and Western Australia. Agates from the latter areas have a lower proportion of defects causing a red emission band (~660 nm) but an increased proportion of defects causing blue (~470 nm) and orange (~640 nm) emission bands. Agates found in hosts aged 13–1100 Ma are also differentiated from the Stockdale Beck and Western Australian agates in a ternary plot of the relative intensities of violet to blue to orange emission bands. Single scans producing this combination of colours are only found in the Stockdale Beck and Western Australian agates. The properties shown by the Stockdale Beck and Western Australian agates demonstrate that an agate or chalcedony infill can be used to identify post-deposition palaeoheating within a host rock.

The mineral in bones and teeth is an impure form of hydroxylapatite (HAP), the principal impurity being 2—5 wt.% carbonate. This mineral dissolves during remodelling of bone and also in dental caries as a result of the action of acids produced by osteoclasts and by bacteria, respectively. In enamel, demineralization proceeds with preferential loss of carbonate relative to phosphate. Surprisingly, in the early stages, the demineralization is subsurface. In order to facilitate the understanding of physical chemical aspects of these processes, we have undertaken studies of demineralization in model systems. We give three examples here. The first two used scanning microradiography in which the specimen is stepped across a 10—30 μm diameter X-ray beam. Intensity measurements allow calculation of the mineral mass per unit area in the X-ray path through the specimen. In the first experiment, porous HAP sections were separated from a reservoir of acidic buffer by a column initially filled with water (the diffusion length) and scanned with the X-ray beam perpendicular to the axis of the diffusion length. The rate of total loss of mineral along each profile was calculated from the scans. The rate of demineralization fell as the diffusion length increased. We believe the explanation is that the rate-controlling step is the diffusion of dissolved HAP away from the solid to the buffer reservoir. In the second experiment, demineralizing solution and water were pumped alternately, for equal lengths of time, past blocks of porous HAP or enamel. The X-ray beam was perpendicular to the exposed surface. As the rate of switching between solutions decreased, the mean rate of demineralization also fell. We propose that this effect is due to retention of acid in the pores of the HAP during the time when water flows, allowing further demineralization to take place during this time. The third study used X-ray microtomography, a form of 3D microscopy, to study the loss of mineral in compacted carbonate apatite powders. The powders were packed in six 10 mm internal diameter acrylic cylinders to a depth of 4 mm (after pressing). One end was covered with a porous polyethylene disc and each tube placed in acidic buffer for 70 days. Periodic examination by microtomography showed the development of subsurface demineralization. Infrared spectroscopy of the dissected-out surface layers showed preferential loss of carbonate over phosphate by comparison with deeper layers. Rietveld analysis of X-ray powder diffraction data showed changes in the crystallographic structures of the apatites between the initial and dissected-out apatite.

Cathodoluminescence (CL) petrography of nepheline syenites of the Igaliko complex, Gardar province, South Greenland shows that sodalites possess embayed contacts against nepheline, and have formed by a process of metasomatic replacement. This texture is demonstrated clearly by CL, since sodalite luminesces bright orange and nepheline is poorly luminescent. The transformation from nepheline to sodalite results in a volume change which leads to a network of fractures in which deep-blue luminescent fluorite is precipitated. Fluorite is formed since the chlorination process involved in the transformation causes localised reductions of the salinity of the fluid and therefore a decrease in the solubility of fluorite. Sodalite-fluorite textures observed using CL allow sodalites of secondary origin in alkaline igneous rocks to be identified.

Nephelines and sodalites, when observed using scanning electron microscopy, possess small micropores. By analogy with recent work on alkali feldspars, pervasive alteration of nephelines may occur by fluid flow assisted by a permeable micropore network.