Two contrasting types of Hercynian U-rich granites can be distinguished by their accessory minerals: (1) subalkaline potassic granites (amphibole-biotite±pyroxene) characterized by apatite-zircon-thorite-sphene-allanite and rare ThO2-rich uraninite, in order of appearance in the magma, and (2) leucocratic granites (biotite and muscovite) which contain monazite-zircon-apatite-xenotime-ThO2-poor uraninite and Ti oxides. Intermediate accessory mineral associations may also exist.

The mineralogy, crystallization history, and geochemistry of two high K-U-Th granites from the Vosges, France, is described. Their assemblage of U- and Th-bearing accessory minerals is listed, in order of appearance in the magma, in Group 1 (above). Trace elements (U, Th, Zr, Hf) and preliminary data on REE are discussed. In a layered sequence of the Crêtes granite, thorite, with up to 15% UO2, is shown to be important during differentiation. There is a decrease of the Th/U ratio corresponding to a slight decrease of the Th content whereas there is an increase of the U content at the end of differentiation. The Crêtes and Ballons granites have REE patterns characterized by LREE enrichment with a La/Yb ratio of about 28 (Crêtes granite) and a slight negative Eu anomaly. These relationships are typical of subalkaline potassic granites of the Hercynian. The trace element associations are similar to those of the shoshonite association with high U, Th, LREE and Ba, Rb, and Sr contents. A hypothetical model for uranium mineralization associated with such granites is discussed in the light of these data.

A. De Schulten published a crystallographic and optical investigation of the bismuth oxyhalides in 1900. He succeeded in preparing minute square plates capped with pyramidal planes, but evidently the difficulties of manipulation prevented the measurement of interfacial angles. He did, however, record a negative uniaxial figure observed in a direction perpendicular to the plane of the square plates of all three salts BiOCl, BiOBr, and BiOI. The present work was undertaken to extend A. de Schulten's observations, to measure the axial ratios, and to determine the crystal-structure.

Eudialyte-group minerals (EGM) represent the most important index minerals of persodic agpaitic systems. Results are presented here of a combined EPMA, Mössbauer spectroscopy and LA-ICP-MS study and EGM which crystallized in various fractionation stages from different parental melts and mineral assemblages in silica over- and undersaturated systems are compared. Compositional variability is closely related to texture, allowing for reconstruction of locally acting magmatic to hydrothermal processes. Early-magmatic EGM are invariably dominated by Fe whereas hydrothermal EGM can be virtually Fe-free and form pure Mn end-members. Hence the Mn/Fe ratio is the most suitable fractionation indicator, although crystal chemistry effects and co-crystallizing phases play a secondary role in the incorporation of Fe and Mn into EGM. Mössbauer spectroscopy of EGM from three selected occurrences indicates the Fe3+/ΣFe ratio to be governed by the hydration state of EGM rather than by the oxygen fugacity of the coexisting melt. Negative Eu anomalies are restricted to EGM that crystallized from alkali basaltic parental melts while EGM from nephelinitic parental melts invariably lack negative Eu anomalies. Even after extensive differentiation intervals, EGM reflect properties of their respective parental melts and the fractionation of plagioclase and other minerals such as Fe-Ti oxides, amphibole and sulphides.

Petrographic features and compositions of titanites in eclogites within the ultra-high pressure metamorphic terrane in central Dabieshan are documented and phase equilibria and thermobarometric implications discussed. Carbonate-bearing eclogite pods in marble at Shuanghe contain primary metamorphic aluminous titanites, with up to 39 mol.% Ca(Al,Fe3+)FSiO4 component. These titanites formed as part of a coesite-bearing eclogite assemblage and thus provide the first direct petrographic evidence that AlFTi−1O−1 substitution extends the stability of titanite, relative to rutile plus carbonate, to pressures within the coesite stability field. However, it is emphasised that A1 and F contents of such titanites do not provide a simple thermobarometric index of P—T conditions but are constrained by the activity of fluorine, relative to CO2, in metamorphic fluids — as signalled by observations of zoning features in these titanites.

These ultra-high pressure titanites show unusual breakdown features developed under more H2O-rich amphibolite-facies conditions during exhumation of these rocks. In some samples aluminous titanites have been replaced by ilmenite plus amphibole symplectites, in others by symplectitic intergrowths of secondary, lower Al and F, titanite plus plagioclase. Most other coesite-bearing eclogite samples in the central Dabieshan terrane contain peak assemblage rutile often partly replaced by grain clusters of secondary titanites with customary low Al and F contents.

To understand the fate and impact of gas produced within a repository for radioactive waste, a series of laboratory and field scale experiments have been performed on the Callovo-Oxfordian claystone (COx), the proposed host rock for the French repository. Results show the movement of gas is through a localized network of pathways, whose properties vary temporarily and spatially within the claystone. Significant evidence exists from detailed laboratory studies for the movement of gas along highly unstable pathways, whose aperture and geometry vary as a function of local stress, gas and porewater pressures. The coupling of these parameters results in the development of significant time-dependent effects, impacting on all aspects of COx behaviour, from gas breakthrough time, to the control of deformation processes. Variations in gas entry, breakthrough and steady-state pressures are indicative of microstructural heterogeneity which exerts an important control on the movement of gas. The localization of gas flow is also evident in preliminary results from the large scale gas injection test (PGZ) where gas flow is initially focussed within the excavation damaged zone (EDZ), which acts as a preferential pathway for gas. Numerical models based on conventional two-phase flow theory are unable to adequately describe the detailed observations from laboratory tests.

Combustion experiments up to 1400°C were carried out with subbituminous coals from the Teruel power station, the Teruel Mining District, the Santa Eulalia coal deposit and with lignite from the As Pontes power station in Spain. The characterisations of the occurrence and distribution of inorganic matter and its transformation during combustion of these coals were carried out by means of X-ray diffraction and optical and electron microscopy. The combustion experiments show that the incorgainc transformations during the combustion of all the coals studied vary depending on the sulphur and calcium contents. The sulphur, iron and calcium contents govern the quality of anhydrite crystallisation (which takes place between 600 and 900°C Furthermore, the high calcium oxide content produces the fouling of the combustion wastes at relatively low temperatures (1200°C), prevents the occurrence of mullite and magnetite in the ashes and leads to the crystallistation of anorthite and esseneite during the colling. The comparison of the inorganic phases of fly ashes and slags from the Teruel power station with those of the experimental wastes shows that the inorganic transformations during coal combustion in the power station can be predicted by means of laboratory furnace experiments provided that the residence time in the flame and the effect of the cooling and evacuation controls of gases and particles from the power station are taken in consideration.

Corrosion, water radiolysis and microbial degradation will result in the generation of gas within repositories designed for the geological disposal of high-level radioactive waste. It is therefore crucial in the design of such facilities that the relevant mechanisms allowing gas migration through repository materials, both engineered barriers and clay-based candidate host rocks, are correctly identified. In Belgium, the Boom Clay represents a candidate host material for which the advective gas breakthrough characteristics and transport properties have been extensively tested and are well defined by numerous studies. The Boom Clay displays a significant capacity for self-sealing and both laboratory and field tests indicate that advective gas transport occurs not by visco-capillary flow, but instead through the formation of pressure-induced dilatant pathways. In this study, we present results from a gas injection test designed to demonstrate the presence of these features by injecting nanoparticulate tracers with helium gas into a sample of Boom Clay. The results provide conclusive evidence for the formation of transient, dilatant gas pathways within a candidate clay-based host rock. This technique provides a novel diagnostic tool for the identification of processes governing multi-phase flow, supporting robust long-term assessments of repository performance.

The effects of ion irradiation in the ABO4-type compounds were compared by performing experiments on four materials that include the most common crystal structures (monazite vs. zircon) and chemical compositions (phosphates vs. silicates) for these phases. Pure synthetic single crystals of ZrSiO4, monoclinic ThSiO4, LaPO4 and ScPO4 were irradiated using 800 keV Kr+ ions. Radiation damage accumulation was monitored as a function of temperature in situ in a transmission electron microscope. The activation energies for recrystallization during irradiation were calculated to be 3.1–3.3 eV for the orthosilicates but only 1.0–1.5 eV for the isostructural orthophosphates. For the ion-beam-irradiated samples, the critical temperature, above which the recrystallization processes are faster than damage accumulation and amorphization cannot be induced, is >700°C for ZrSiO4 but it is only 35°C for LaPO4. At temperatures above 600°C, zircon decomposed during irradiation into its component oxides (i.e. crystalline ZrO2 plus amorphous SiO2). The data are evaluated with respect to the proposed use of the orthophosphates and orthosilicates as host materials for the stabilization and disposal of high-level nuclear waste. The results show that zircon with 10 wt.% Pu would have to be maintained at temperatures in excess of 300°C in order to prevent it from becoming completely amorphous. In contrast, a similar analysis for the orthophosphates implies that monazite-based waste forms would not become amorphous or undergo a phase decomposition.

The speciation of antimony is strongly influenced by its oxidation state (V, III, 0, —III). Redox processes under anaerobic groundwater conditions may therefore greatly alter the environmental behaviour of Sb. Employing X-ray absorption and photoelectron spectroscopy, we show here that Sb(V) is reduced to Sb(III) by magnetite and mackinawite, two ubiquitous Fe(II)-containing minerals, while Sb(III) is not reduced further. At the surface of magnetite, Sb(III) forms a highly symmetrical sorption complex at the position otherwise occupied by tetrahedral Fe(III). The Sb(V) reduction increases with pH, and at pH values >6.5 Sb(V) is completely reduced to Sb(III) within 30 days. In contrast, at the mackinawite surface, Sb(V) is completely reduced across a wide pH range and within 1 h. The Sb(V) reduction proceeds solely by oxidation of surface Fe(II), while the oxidation state of sulphide is conserved. Independent of whether Sb(V) or Sb(III) was added, an amorphous or nano-particulate SbS3-like solid formed.

The late Cretaceous Kızıldağ ophiolite forms one of the best exposures of oceanic lithospheric remnants of southern Neotethys to the north of the Arabian promontory in Turkey. The ultramafic to mafic cumulate rocks, displaying variable thickness (ranging from 165 to 700 m), are ductiley deformed, possibly in response to syn-magmatic extension during sea-floor spreading and characterized by wehrlite, olivine gabbro, olivine gabbronorite and gabbro. The gabbroic cumulates have an intrusive contact with the wehrlitic cumulates in some places. The crystallization order of the cumulus and intercumulus phases is olivine (Fo86–77)± chromian spinel, clinopyroxene (Mg#92–76), plagio-clase(An95–83), orthopyroxene(Mg#87–79). The olivine, clinopyroxene, orthopyroxene and plagioclase in ultramafic and mafic cumulate rocks seem to have similar compositional range. This suggests that these rocks cannot represent a simple crystal line of descent. Instead the overlapping ranges in mineral compositions in different rock types suggest multiple magma generation during crustal accretion for the Kızıldağ ophiolite. The presence of high Mg# of olivine, clinopyroxene, orthopyroxene, and the absence of Ca-rich plagioclase as an early fractionating phase co-precipitating with forsteritic olivine, suggest that the Kızıldağ plutonic suite is not likely to have originated in a mid-ocean ridge environment. Instead the whole-rock and mineral chemistry of the cumulates indicates their derivation from an island arc tholeiitic (IAT) magma. All the evidence indicates that the Kızıldağ ophiolite formed along a slow-spreading centre in a fore-arc region of a suprasubduction zone tectonic setting.

At the abandoned pyrite mine at Genna Luas (Sardinia, Italy), melanterite is the most environmentally important secondary phase associated with pyrite oxidation. A complete cycle, including formation on pyrite surface, dissolution in water, precipitation from water and subsequent alteration, can be observed. The oxidation of pyrite to melanterite is related mainly to the ‘intrinsic’ features of the Genna Luas pyrite, such as its cryptocrystalline pseudo-colloidal texture. During melanterite formation on pyrite there is transient storage of Fe2+, SO42- and acidity. This is controlled mainly by wetting-drying seasonal cycles. Laboratory experiments have shown that the simple dissolution of melanterite is an acidity-generating process which affects the geochemistry of water and, indirectly, contributes to the supply of the Fe3+ required for the aqueous oxidation of pyrite. According to this geochemical model, the interaction between rainwaters and ground pyritic materials accumulated in heaps generates hyperacidic saline waters (pH = 0.6; TDS = 300 g/l) with very high SO42+ contents (203 g/l), Fe2+ contents (73 g/l), Zn contents (11 g/l), and numerous potentially toxic elements. Melanterite precipitates from these waters (SIMelanterite = 0.15, calculated using PHRQPITZ software), giving rise to attractive emerald green crystal aggregates which, when exposed to air, alter to a fine white powder composed mainly of melanterite, and minor amounts of rozenite and szomolnokite.

The technique of investigating 3-dimensional interconnections and the shapes of crystals in a rock by X-ray computerized tomography (CT) and image analysis was developed using a graphic granite specimen as an example. Fifty 2-dimensional tomographic images (slices) of the graphic granite were obtained ‘non-destructively’ using a medical X-ray CT scanner. Since a CT value of the specimen was decreased with increasing cross-sectional sample area by the effect of beam-hardening, the CT value was corrected using the area of each slice. Binary images of the slices were made comparing one of them with a thin-section of the slice. Using the binary images, connection analysis of quartz rods in the graphic granite specimen was performed on the basis of percolation theory (cluster labelling). This analysis showed that at least 89.9% of the quartz rods were connected in three dimensions. Furthermore, the 3-dimensional shape of the quartz rods was analysed using the 2-point correlation function calculated from the binary images. The average shape of the quartz rods was obtained by fitting an ellipsoid to the high-value region of the 2-point correlation function. The elongation axis of the ellipsoid agreed well with the crystallographic c-axes of the quartz rods.

Slag dumps occur at several historical smelting sites in north Queensland, Australia. The microcrystalline slags contain primary slag phases, relict flux, ore and furnace materials and secondary weathering related minerals. Common primary slag phases are glass, Zn-rich fayalite (± Zn-rich kirschsteinite) and Zn-rich hedenbergite. Other minor minerals include wollastonite, Zn-rich melilite, Zn-rich iscorite (Fe7SiO10), magnetite as well as a number of sulphides (pyrrhotite, galena, bornite, sphalerite, wurtzite), metallic phases (Ag, Cu, Pb, Sb), alloys (Cu3Sn), and unknown metal compounds. The slag materials contain wt.% concentrations of Zn and elevated levels of Ag, As, Cd, Cu, Ni, Pb, Sb and W. Glass, hedenbergite and fayalite/kirschsteinite are the main repositories of Zn, whereas much of the Cu and Pb is hosted by glass, sulphides, Cu3Sn alloys, metallic Cu and Pb, and unknown CuSb, AsSnPb and FeAsCu compounds. The slags are undergoing contemporaneous reaction with air and rainwater. The weathering results in the release of metals and metalloids from primary slag phases, particularly from glass, and the partial immobilization of these metals in secondary soluble and insoluble minerals in the slag heaps. Zinc exhibits pronounced chemical mobility and reports together with elevated Ca and sulphate into surface seepages (up to 10.2 mg l−1 Zn at pH 6.97). The slag dumps represent long-term sources of metal pollutants, particularly of Zn, to local ground and surface waters.

In this study, direct evidence for the formation of magnetite via a green rust intermediate is reported. The Fe(II) induced transformation of ferrihydrite, was quantified in situ and under O2-free conditions using synchrotron-based time-resolved energy dispersive X-ray diffraction. At pH 9 and Fe(II)/Fe(III) ratios of 0.5 and 1, rapid growth (6 min) of sulphate green rust and its subsequent transformation to magnetite was observed. Electron microscopy confirmed these results, showing the initial rapid formation of hexagonal sulphate green rust particles, followed by the corrosion of the green rust as magnetite growth occurred, indicating that the reaction proceeds via a dissolution-reprecipitation mechanism. At pH 7 and Fe(II)/Fe(III) ratio of 0.5, sulphate green rust was the stable phase, with no transformation to magnetite.

The geology of the 2.7 Ga Stillwater Complex in South-Central Montana is reviewed with a focus on the role of volatiles in locally modifying both the crystallization sequence of the evolving parent magma and the initially precipitated solid assemblages to favour olivine ± chromite. A secondary origin for these two minerals is particularly probable for the olivine-bearing rocks of the Banded series and, at a minimum, also increasing their modal abundance in the Peridotite zone of the Ultramafic series. Direct evidence for volatiles includes the presence of high-temperature fluid inclusions in pegmatoids and hydrous melt inclusions (now crystallized) in chromite and olivine from both the Ultramafic and the Banded series rocks. Indirect evidence includes the boninitic character of the parent magma, the presence of volatile-bearing minerals including high-temperature carbonates, rock textures, and Cl / F variations in apatite. Mechanisms which favour the formation of olivine (± chromite) over pyroxene include volatile phase boundary shifts induced by added H2O, incongruent melting of pyroxene by hydration of a partly-molten mush, and the near- to sub-solidus replacement of pyroxene by olivine and chromite by silica-undersaturated fluids. These mechanisms cast doubt that magmas with different liquid lines of descent were involved in the crystallization of the Stillwater Complex. A dry Stillwater magma would have been mineralogically and modally much less varied and lacking in high-grade platinum-group element and chromium deposits.

Zircon- and reidite-type ZrSiO4 produced by shock recovery experiments at different pressures have been studied using infrared (IR) and Raman spectroscopy. The v3 vibration of the SiO4 group in shocked natural zircon shows a spectral change similar to that seen in radiation-damaged zircon: a decrease in frequency and increase in linewidth. The observation could imply a possible similar defective crystal structure between the damaged and shocked zircon. The shock-pressure-induced structural phase transition from zircon (I41/amd) to reidite (I41/a) is proven by the occurrence of additional IR and Raman bands. Although the SiO4 groups in both zircon- and reidite-ZrSiO4 are isolated, the more condensed scheelite gives rise to Si–O stretching bands at lower frequencies, suggesting a weakening of the bond strength. Low-temperature IR data of the reidite-type ZrSiO4 show an insignificant effect of cooling on the phonon modes, suggesting that the structural response of reidite to cooling-induced compression is weak and its thermal expansion is very small.

Clinopyroxenes are dominant in highly potassic, silica undersaturated mafic volcanics occurring on the western rim of the uplifted, rifted East African craton. A kimbcrlite style of eruption provides nodules of alkali clinopyroxenite (clinopyroxene + titaniferous phlogopite+titanomagnetite, apatite, sphene, and rare corroded olivine) which have similar bulk chemistry to the feldspathoid-bearing lavas. Many nodules display metasomatic textures supporting a formation from the alteration of pre-existing material; clinopyroxene growth is characterized by complex, non-oscillatory colour zoning. Comparison of natural clinopyroxene chemistry with published data for elinopyroxenes crystallized from synthetic potassium-rich mafic material, suggests that a significant proportion of the nodules crystallized at upper-mantle pressures. Neither garnet- nor orthopyroxene-bearing nodules have ever been recorded from south-west Uganda, suggesting that metasomatism of the local mantle has proceeded far enough to obliterate all recognizable remnants of four-phase lherzolite.

The nomenclature of CaZrTi2O7 minerals has become very confused, such that zirconolite, zirkelite and polymignite each have acquired multiple meanings and represent five different crystal structures. To resolve these inconsistencies, the IMA approved resolutions as follows. Zirconolite is the non- crystalline (metamict) mineral or mineral with undetermined polytypoid of CaZrTi2O7. Zirconolite-3O is the three-layered orthorhombic polytypoid of CaZrTi2O7. Zirconolite-3T is the three-layered trigonal polytypoid of CaZrTi2O7. Zirconolite-2M is the two-layered monoclinic polytypoid of CaZrTi2O7. Polymignite (metamict) is discarded as equivalent to zirconolite. Zirkelite is the cubic mineral with formula (Ti,Ca,Zr)O2−x.

Ultramafic to marie plutons in the Olyutor Range, North Kamchatka, represent the magmatic roots of a late Eocene arc, related to the westward subduction of the Komandorsky Basin beneath the Asian continental margin. Olyutor Range plutons are concentrically zoned with cumulate dunite cores mantled by a wehrlite-pyroxenite transitional zone and, in turn, by a narrow gabbroic rim.

Spinel is a common accessory mineral in these arc plutonics, and we present analyses of spinels from a range of lithologies. A continuous compositional trend is observed from Cr-spinel in the ultramafics to Cr-rich magnetite in marginal gabbros. Complex chemical zoning patterns within individual spinel grains suggest an interplay between fO2, fractionation, volatile content and subsequent sub-solidus reequilibration of spinel with co-existing silicates (mainly olivine).

In general, the spinels from magmatic arc environments are characterised by high total Fe and high Fe3+ contents compared to MORB and boninitic spinels and higher Cr-values relative to oceanic basin spinels. These differences imply a high oxygen fugacity during arc petrogenesis. Differences are also observed between plutonic spinels from arcs and low-Ti supra-subduction zone ophiolites. Low-Ti ophiolitic spinels are generally poorer in iron and richer in Cr, and hence are similar in composition and perhaps tectonic setting to fore-arc boninitic spinels.

In a recent paper Taylor has shown that three distinct hydration levels exist within the ‘calcium silicate hydrate (l)’ group of artificial preparations (Taylor, 1953a, p. 168). The individual hydrates may be distinguished from the position of the 002 reflection in X-ray powder photographs. The d spacings corresponding to the three hydrates of this group examined during the present investigation are 14.6, 11.3, and 9.6 Å. These hydrates have H2O : SiO2 molar ratios of approximately 2.0, 1.0, and 0.5 respectively.

A recent examination of the minerals crestmoreite and riversideite (Taylor, 1953b) has shown that both these minerals are intimate inter-growths of members of the above hydrate series with the mineral wilkeite. Both the artificial preparations and the crestmoreite-riversideite intergrowths have failed to provide material suitable for detailed optical study.