The evolution of the trace-element patterns of quartz during crystallization of pegmatite melt was investigated using laser ablation inductively coupled plasma mass spectrometry. The contents of Al, B, Ba, Be, Cr, Fe, Ge, Li, Mn, P, Rb, Sn, Sr and Ti were analysed in quartz from the border, intermediate and core zones of four granitic pegmatites differing in degree of fractionation and origin. The material investigated originates from the pegmatite district of the Strážek Unit, Moldanubian Zone, Bohemian Massif, Czech Republic and includes: lepidolite LCT (Li-Cs-Ta) pegmatite from Rožná; berylcolumbite LCT pegmatite from Věžná; anatectic pegmatite from Znětínek; and intragranitic NYF (Nb-Y-F) pegmatite Vladislav from the Třebíč Pluton. The abundances of the elements analysed varied over wide intervals: <1 to 32 ppm Li, 0.5 to 6 ppm B, <1 to 10 ppm Ge, 1 to 10 ppm P, 10 to 450 ppm Al, 1 to 45 ppm Ti and <1 to 40 ppm Fe (average sample contents). Concentrations of Be, Rb, Sr, Sn, Ba, Cr and Mn are usually <1 ppm. Quartz from LCT pegmatites exhibits a distinct evolutionary trend with a decrease in Ti and an increase in Al, Li and Ge from the pegmatite border to the core. In comparison with the most fractionated rare-metal granites, pegmatitic quartz is relatively depleted in Al and Li, but strongly enriched in Ge. Quartz from simple anatectic and NYF pegmatites is poor in all trace elements with their evolution marked by a decrease in Ti and a small increase in Ge. There is little Al or Li and neither shows any systematic change with pegmatite evolution. Using the Ti-in-quartz thermobarometer, the outer zones of the Znětínek and Vladislav pegmatites crystallized at ∼670°C, whereas the border zone in the Rožná pegmatite yields a temperature near 610°C.

Intrusive calcite-carbonatite ejecta (sovite) in the lowermost tephra layers of the Mt. Vulture alkaline mafic-ultramafic volcano (Upper Pleistocene), is the first intrusive carbonatite sample from southern Europe. The sovite is of coarse granularity and shows some textural and mineralogical layering. It is mainly formed of calcite (up to 3.5 wt.% MgO, and 0.53 wt.% SrO), less dolomite (average 18.2 wt.% MgO, and up to 2.1 wt.% SrO), spinel (60 wt.% Al2O3, 26.5 wt.% MgO, 10.7 wt.% FeO) and olivine (Fo99). Perovskite and apatite have been found only as microlites. Intergranular vugs are scattered throughout the rocks and small composite inclusions occur in calcite.

The mineral chemistry, high temperature melt inclusions, overall isotopic compositions, and the REE distribution are consistent with a primary igneous origin. Compared with world average sovite compositions, the Vulture sovite has lower LILE and HFSE but Rb, Sr, Th and U are high. The REE abundance is typical of carbonatites, having an LREE/HREE value of ∼100. The δ13C (−4.8% SMOW) is in the range for mantle-derived carbonatites. The 143Nd/144Nd (0.512648±15) and 87Sr/86Sr (0.705978±10) ratios show close similarity between the sovite and the Vulture alkaline mafic rocks. The sovite ejecta are interpreted as a crystallization product of carbonate ultramafic liquid. In common with many shallow-level carbonatites from other localities, the recrystallization of rather pure Mg-calcite, the presence of dissolution vugs and the depletion of some HFSE and the relatively high δ18O values, suggest that a secondary process, such as hydrothermal leaching, affected the rock.

Three natural spinels of different places of occurrence and compositions were investigated by means of microprobe chemical analysis, single crystal X-ray diffraction and Mössbauer spectroscopy. All cation distributions between T and M sites were calculated from microprobe and XRD experimental data, by means of a mathematical model with appropriate assumptions. Fe2+ and Fe3+ assignments calculated in this way were compared with those observed in Mössbauer spectra. The satisfactory agreement found proves, at least in the samples studied, the reliability of the model and the assumptions used. In the spinels examined, such results show Fe2+ and Fe3+ virtually ordered in T and M sites respectively. Mössbauer data also revealed Fe2+ in different tetrahedral sites due to the next-nearest neighbour effect, probably as a consequence of spinel genetic conditions.

Nevil Story-Maskelyne described in 1870 the mineral constituents of the Bustee meteorite, which was observed to fall in 1852 near Bustee about 45 miles west of Goruckpur, India. The stone, weighing 1429 grams, now preserved in the British Museum collections, was found to consist chiefly of enstatite and diopside, and two constituents proved to be new minerals. Pale, chestnut-brown spherules of calcium sulphide, CaS, Story-Maskelyne named oldhamite and golden-yellow octahedra found embedded chiefly in the oldhamite he named osbornite. One side of the meteorite has been ground to reveal the nodules of oldhamite and a coloured lithograph in W. Flight's book ‘A chapter in the history of meteorites’ reproduces the appearance of the chief mineral constituents very well. The minute octahedra of osbornite are easily visible with a lens in the meteorite itself.

The application of Raman spectroscopy to the study of the mixed cationic Pb-Cu and Pb-Cu-Ag minerals: boleite, cumengeite and diaboleite has enabled their molecular structures to be compared. Each of these three minerals shows different hydroxyl-stretching vibrational patterns, but some similarity exists in the Raman spectra of the hydroxyl-deformation modes. The low-wavenumber region is characterized by the bands assigned to the cation-chloride stretching and bending modes. Phosgenite is also a mixed chloride-carbonate mineral and a comparison is made with the molecular structure of the aforementioned minerals. Raman spectroscopy lends itself to the study of these types of minerals in complex mineral systems of secondary mineral formation.

During chemical weathering and natural hydrothermal reactions, apatite can form by replacing calcium carbonates. In hydrothermal experiments in which aragonite and calcite single crystals have been reacted with phosphate solutions, the carbonates are replaced by polycrystalline hydroxylapatite (HAP). In both cases the crystals have retained their overall morphology while their compositions have changed significantly. The HAP appears to have a crystallographic relationship to the parent carbonate crystals. The textural relationships are consistent with an interface-coupled dissolution-precipitation mechanism. Structural relationships and relative molar volumes and solubilities appear to be factors that greatly affect replacement reactions.

New stability constant data are presented for the minerals blixite, mendipite and the compound Pb7O6Cl2.2H2O at 298.2 K and P = 105 Pa. Mendipite is in fact a metastable phase at this temperature, being thermodynamically stable under the appropriate conditions at temperatures above about 29°C Kinetic influences are of some significance with respect to the sequence of formation of solid phases in the PbO-HCl-HH2O system, and these have been elucidated for some important reactions. Penfieldite and fiedlerite appear to be metastable phases at all temperatures at 105 Pa. The results have been used to reassess the conditions of formation of the lead(II) oxy- and hydroxychloride phases that are known to form as minerals and as corrosion products of lead-containing artefacts. The effect of CO2 on the system is also described.

At Niquelândia, Cr extracted from the soil (5,000–9,300 mg.kg-1) is likely the result of the Cr-bearing Fe-oxides compared to the Cr-spinels, showing that low Cr-containing minerals present in the dunite (enstatite, olivine and clay minerals) have been completely dissolved. The chromites, accumulated inside soil profiles, have undergone chemical weathering, leading to a Cr enrichment during soil genesis. Traces of dissolution inside the soil chromites suggest that they can be slowly weathered. In this case chromites could represent a diffuse source of available Cr(III) within the soil profiles.

Structural transformations between the different hydration states of three vermiculite samples from Sta. Olalla (Huelva, Spain), Paulistana (Piaui, Brasil) and West China, have been observed by X-ray diffraction at atmospheric pressure, P = 1.4 x 10–2 mbar and P = 2.4 x 10–4 mbar. The samples were studied in flake and powder forms. The effect of vacuum has been proven to be the same as that of temperature, i.e. it causes dehydration of vermiculite, but with a different evolution through the different hydration states. In fact, under vacuum, the process seems to be inhibited at a one-water layer hydration state (1-WLHS), without a further dehydration of samples to a zero-water layer hydration state (0-WLHS).

Furthermore, the dehydration process has been shown to occur through different interstratified states in each vermiculite. This result has been related to the interlayer Mg-cation content, due to its affinity to water molecules. The interstratified states have been analysed by the direct Fourier-transform method. The vermiculite from Sta. Olalla exhibits the most complex process, with formation of three different interstratified phases: two phases characterized by an interstratification of interplanar distances, d = 11.5 –13.8 Å and d = 9.6 –11.5 Å , respectively, and a practically segregated phase characterized by d = 13.8 Å . For the vermiculite from China, an interstratified phase not previously reported has been found, with an interplanar distance of 12.10 Å.

The inhibition of dehydration at 1-WLHS, as observed, could be used in applications such as adsorption and separation technology of gases and liquids, or in heterogeneous catalysis processes.

Basalts dredged from the floor of the deep ocean show general tholeiitic affinities. Some samples are rich in aluminium and of very similar composition to the Warner high-alumina basalt from California. Both olivine tholeiite and high-alumina basalt have been found in the form of glass in dredgings from the Mid-Atlantic Ridge, indicating that liquid magmas of both compositions have been erupted on to the sea bed in this area. In explanation of this association a tentative hypothesis of fractional melting of hydrated upper mantle material is proposed. It is suggested that under the mid-ocean ridges the ‘basaltic fraction’ of the mantle is locally in the form of an amphibole. Fractional incongruent melting of this amphibole appears to be a possible explanation of the range of composition encountered in dredged glass samples.

Aspects of the (bio)geochemical cycling of metals (including Fe, Cu, Pb, Zn, Hg, As, Sb, U, Tc, Np) at or near the Earth's surface are discussed with reference to the recent work of the authors. Key stages of the breakdown of metalliferous minerals, transport of metals as solution complexes or colloidal precipitates, and interaction of metals in solution with the surfaces of minerals are considered. Emphasis is on molecular-scale observations using techniques such as scanning probe microscopy, photoelectron and (synchrotron) X-ray spectroscopies. The importance of the biological/mineralogical interface is also emphasized with reference to the bacterial colonization of mineral surfaces and formation of biofilms, and their influence on mineral surface reactivity and flow of fluids through rocks and sediments. Also noted is the importance of relating molecular and micro-scale observations to macroscopic phenomena. Molecular-scale understanding is central to attempts to model many processes of relevance in mineral exploration and exploitation, and in the containment of hazardous wastes and remediation of polluted areas. Mineralogists have a central role to play in the relevant environmental sciences and technologies.

Concretionary siderite horizons are quite common in massive clay sequences. One such horizon, from the Westphalian of Yorkshire, has been studied in detail. Two iron-rich carbonate minerals occur together although they cannot be distinguished in thin section on account of very fine grain size. One is much richer in magnesium (pistomesite) than the other (siderite). The latter is rela-tively rich in manganese and the heavier stable carbon isotope 13C whereas the former carbonate is richer in calcium and 12C. The most important iron source is thought to have been hydrated iron oxides originating in soils. Much of the carbonate carbon started as organic molecules. The siderite appears to have formed earlier than the pistomesite. The stratiform character of these deposits appears to reflect siltier horizons in the mudstones, which presumably channelled pore water migration during compaction. This is probably why such carbonate horizons were formerly believed to be of simple sedimentary rather than diagenetic origin.

Supersaturation-Nucleation-Time (S-N-T) diagrams are shown to be a useful tool to predict nucleation during reactive-transport processes in porous media. Such diagrams can be determined experimentally or estimated from theoretical calculations based on classical nucleation theory. With this aim, a ‘pragmatic’ understanding of the nucleation rate equation is adopted here and the meaning and magnitude of the interfacial tension and induction time discussed. Theoretical diagrams and experimental data are shown to match fairly well as long as there is an appropriate choice of the ‘relevant’ volume for induction-time calculations.

Compositional data—that is data where concentrations are expressed as proportions of a whole, such as percentages or parts per million—have a number of peculiar mathematical properties which make standard statistical tests unworkable. In particular correlation analysis can produce geologically meaningless results. Aitchison (1986) proposed a log-ratio transformation of compositional data which allows inter-element relationships to be investigated. This method was applied to two sets of geochemical data—basalts from Kilauea Iki lava lake and grantic gneisses from the Limpopo Belt—and geologically 'sensible' results were obtained. Geochemists are encouraged to adopt the Aitchison method of data analysis in preference to the traditional but invalid approach which uses compositional data.

Fluids can play a direct role in exhumation by influencing exhumation mechanisms and the driving processes for these mechanisms. In addition, the process of exhumation leads to the development of fluid-related features that in themselves may not drive exhumation. Fluids involved in exhumation are generally derived from dehydration reactions occurring during decompression, but at shallower crustal levels may also involve the introduction of exotic fluids. The composition of fluids attending exhumation are generally saline – CO2 mixtures, but N2, CH4, H2O mixtures have also been recorded. Studies of fluid features related to exhumation have found that fluids may contribute to density changes and the initiation of partial melting during decompression, as well as the development of extensive vein systems. However, the preservation of geochemical signatures related to fluid processes occurring prior to high-P and ultrahigh-P metamorphism indicates that large-scale pervasive fluid flow systems, in general, do not operate at any stage during the exhumation history. Large-scale channelled fluid flow may have operated in detachment faults and shear zones related to exhumation, and this requires further study. The most significant role of fluids during exhumation appears to be their controlling influence on the preservation of high-P or ultrahigh-P rocks.

Corundum xenocrysts from alkaline basalt fields differ in characteristics and hence lithospheric origins. Trace element, fluid/melt inclusion and oxygen isotope studies on two eastern Australian corundum deposits are compared to consider their origins. Sapphires from Weldborough, NE Tasmania, are magmatic (high-Ga, av. 200 ppm) and dominated by Fe (av. 3300 ppm) and variable Ti (av. 400 ppm) as chromophores. They contain Cl, Fe, Ga, Ti and CO2-rich fluid inclusions and give δ18O values (5.1–6.2‰) of mantle range. Geochronology on companion zircons suggests several sources (from 290 Ma to 47 Ma) were disrupted by basaltic melts (47 ± 0.6 Ma). Gem corundums from Barrington, New South Wales, also include magmatic sapphires (Ga av. 170 ppm; δ18O (4.6–5.8‰), but with more Fe (av. 9000 ppm) and less Ti (av. 300 ppm) as chromophores. Zircon dating suggests that gem formation preceded and was overlapped by Cenozoic basaltic melt generation (59–4 Ma). In contrast, a metamorphic sapphire-ruby suite (low-Ga, av. 30 ppm) here incorporates greater Cr into the chromophores (up to 2250 ppm). Fluid inclusions are CO2-poor, but melt inclusions suggest some alkaline melt interaction. The δ18O values (5.1–6.2‰) overlap magmatic sapphire values. Interactions at contact zones (T = 780–940°C) between earlier Permian ultramafic bodies and later alkaline fluid activity may explain the formation of rubies.

The Olympic Dam iron-oxide copper-gold-silver-uranium deposit, South Australia, contains three dominant U minerals: uraninite; coffinite; and brannerite. Microanalytical and petrographic observations provide evidence for an interpretation in which brannerite and coffinite essentially represent the products of U mineralizing events after initial deposit formation at 1.6 Ga. Marked compositional and textural differences between the various types of brannerite and coffinite highlight the role of multiple stages of U dissolution and reprecipitation.

On the basis of petrography (size, habit, textures and mineral associations) and compositional variation, brannerites are divided into four distinct groups (brannerite-A, -B, -C and -D), and coffinite into three groups (coffinite-A, -B and -C). Brannerite-A ranges in composition from what is effectively uraniferous rutile to stoichiometric brannerite, and has elevated (Mg +Mn + Na + K) and (Fe + Al) compared to other brannerite types. It displays the most diverse range of morphologies, including complex irregular-shaped aggregates, replacement bands, and discrete elongate seams. The internal structure of brannerite-A consists of randomly-oriented hair-like needles and blades. Brannerite-B (>5 μm in size) is generally prismatic and typically associated with baryte and REY minerals (REE+Y= REY). Brannerite-C and -D are both associated with Cu-(Fe)-sulfides and are typically composed of irregular masses and blebs (10–50 μm in size) with a more uniform or massive internal structure. Brannerite-D is distinct from -C and always contains inclusions of galena. Brannerite-B to -D all contain elevated ΣREY, with brannerite-B and -C having elevated As, and brannerite-D having elevated Nb.

All coffinite is typically globular (each globule is 2–10 μm in size) to collomorphic in appearance. Coffinite-A ranges from discrete globules to collomorphic bands completely encompassing quartz. Coffinite-B is always found with uraninite, and includes collomorph coffinite enveloped by massive uraninite, as well as aureoles of coffinite on the margins of uraninite crystals. Coffinite-C is associated with brannerite and REY minerals. The majority of coffinite is heterogeneous.

Brannerite and coffinite have probably precipitated as part of a late-stage hydrothermal U-event, which might have involved the dissolution and/or reprecipitation of earlier precipitated uraninite, or could represent the products of a later U mineralizing event. Evidence which supports formation of late-stage coffinite and brannerite includes: (1) low-Pb contents of both minerals; (2) coffinite is commonly found on the edges of uraninite, implying later deposition; and (3) coffinite is often found on the edge of brannerite aggregates, suggestive of brannerite precipitation occurred before coffinite. Moreover, there are many features (e.g. banding, scalloped edges, alteration rinds, variable compositions etc.) indicative of hydrothermal alteration processes.

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.

Ion probe data are documented for zircons from tuffs within the early Llandovery, the mid-Caradoc and the Ludlow. 206Pb/238U ages for tuff magmatism have been interpreted using mixture-modelling to distinguish inheritance and Pb loss. Comparisons with the reference zircon SL13 have been improved through a direct determination of the component of secondary ion discrimination caused by changes in target potential.

Interpretation of the SHRIMP data for the Birkhill ash (Scotland, Llandovery) is ambiguous. The more conservative possibility is that most zircons are 439 Ma, in close agreement with the previous isotope dilution ages for the same zircon concentrate. The other is that the 439 Ma group should be split into an inherited population at ˜447 Ma, with a minority at ˜434 Ma that corresponds with the ash volcanism. Although imprecise, the latter is detectably younger than the multi-grain MSID age, which itself might be a composite of the same two ages.

Most zircon analyses from the mid Caradoc Pont-y-ceunant Ash, Wales, fit an age-group at 452.5 Ma, similar to its published 206Pb/238U age by MSID, with a definite older age group at ˜476 Ma but none showing Pb loss. By contrast, those from the Millbrig bentonite (Virginia) of the same age mainly fall in a well-defined post-eruption age group at 435 Ma, while the remainder give 456 Ma. Most zircon analyses from the Kinnekulle bentonite, Sweden, fall into an apparent 464 Ma group which exceeds other estimates for the mid-Caradoc magmatism. It is interpreted to be a composite age, caused by an inability to resolve it into a younger magmatic and older inherited group owing to the larger analytical errors of the Kinnekulle data. The best SHRIMP estimate for the mid-Caradoc volcanism is 452.6±1.7 Ma found by combining the ages for the three volcanic units. During unmixing of the combined ages, the Kinnekulle ages are redistributed and the 464 Ma ‘group’ vanishes. Precambrian grains are present in all the above volcanics.

The original and new zircon analyses from the Laidlaw Volcanics (Canberra, Australia) of Ludlow age, are dominated by three groups of inherited zircons at ˜436 Ma, ˜450 Ma and ˜476 Ma, which makes it unfavourable for time-scale definition using zircons. The youngest zircon age group is 417.5 Ma (˜30%), but this is not associated with overgrowths on older grains or with wholly younger grains. Instead, it is composed of sporadic low ages within older grains suggestive of Pb loss rather than magmatic zircon growth. Nevertheless, the age for volcanism is 420.7±1.1 Ma based on published Rb-Sr and K-Ar dating, so that the youngest zircon group does appear to be associated with volcanism.

One zircon U-Pb age for the Frasnian by MSID is much older than a precise age by other decay schemes, and another for the Lochkovian is significantly older than a recent SHRIMP age for the same Stage. By small changes in the common Pb composition, both MSID ages can be changed from single volcanic ages affected by Pb loss to an inherited and younger volcanic age, which removes the conflict with the other determinations.

A zircon-based geological time-scale is constructed from the Ordovician to the Carboniferous using the time-points presented and discussed in Parts I and II of this paper.

New major and trace element chemical analyses of trioctahedral micas of the Cornubian batholith emphasize their enrichment in a ‘trace-alkali element’ association (Li, Rb, Cs, F, Nb, Mn) and their deficiency in a ‘femic element’ association (Zr, Ce, Th as well as Mg and Ti) compared with micas from many other granite suites, although there are similarities with some Hercynian granites and with rare metal pegmatites. The new data demonstrate a continuous series from siderophyllite through zinnwaldite to lepidolite, principally as a result of Li-R2+ substitution as indicated by Foster (1960), although a more complete replacement is (Li, Al) = (Fe2+, Fe3+, Ti). It is suggested that the ranges of these micas are based upon the Li content in the unit cell formula and the ratio of Li to R2+, in effect, a compromise between the ranges proposed by Foster (1960) and Rieder (1970). Microprobe analyses lack Li2O, but can be plotted on FeO-SiO2 and FeO-Al2O3-SiO2 diagrams (wt. or atom %) in order to locate compositions within the trioctahedral LiFe micas and to distinguish between lepidolite and muscovite.

An examination of 55 new mica analyses shows that hornfels biotites are richer in Mg and that the Cornubian Type A granite (as classifed by Exley and Stone, 1982) micas are richer in Ti and Fe compared with those of Type B granites. Micas from microgranite dykes appear to be poorer in femic elements and richer in trace alkalis and F compared with their Type B granite hosts, consistent with their differentiation from the latter. Mica chemistry is consistent with the magmatic evolution of the A-B-microgranite sequence in the biotite granites, the transformation of Types B to D upon emplacement of E, the derivation of Types E from B by extreme differentiation or metasomatic transformation and mobilization, and the in situ differentiation of Types G from E.