A suite of ultramafic-mafic alkaline igneous rocks in the Damodar Valley, eastern India, contains carbonate, phosphate and titanate minerals that are not characteristic or common in minettes or lamproites, but are typical of orangeites (Group II kimberlite) from southern Africa. Phlogopite grains from the Damodar alkaline rocks yield mean 40Ar/39Ar ages of 116.6±0.8 Ma, 113.5±0.5 Ma and 109.1±0.7 Ma (1σ errors) using laser dating techniques. These ages are similar to the Rb-Sr ages of African orangeites, which lie mostly in the range 121 to 114 Ma. Prior to this study, only one possible occurrence of orangeite (the ∼820 m.y.-old Aries pipe, Western Australia) was known outside the Kaapvaal craton and its environs. If the Damodar alkaline rocks are bona fide orangeites, it is likely that they were generated at depths of >150 km, within the stability field of diamond.

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.

Zircon commonly occurs as one of important accessory HFSE-bearing minerals in A-type granite. A detailed electron microprobe study was carried out on zircon from the Laoshan complex, Eastern China, which is composed of I- and A-type granites. Zircon from the I-type rocks is relatively poor in trace elements (HfO2<2 wt.%, UO2, ThO2 and Y2O3 <1 wt.%), but that from the A-type rocks is richer in Hf, U, Th and Y. Hafnian zircon with a HfO2 content of up to 12.37 wt.% was found in the arfvedsonite granite, which is considered the most evolved facies in the A-type suite. Enrichment in Hf is generally observed at the rims of zircon crystals relative to the cores. The Hf enrichment in zircon, and the association of exotic REE- and HFSE-bearing minerals are linked to hydrothermal activity, suggesting that during the last stage of crystallization of the A-type magma, fluids enriched in REE, HFSE, F−, CO32− and PO43− were released.

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.

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.

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.

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.

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.

A structure hierarchy is developed for chain-, ribbon- and tube-silicate based on the connectedness of one-dimensional polymerisations of (TO4)n− tetrahedra, where T = Si4+ plus P5+, V5+, As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+. Such polymerisations are described by a geometrical repeat unit (with ng tetrahedra) and a topological repeat unit (or graph) (with nt vertices). The connectivity of the tetrahedra (vertices) in the geometrical (topological) repeat units is denoted by the expression cTr (cVr) where c is the connectivity (degree) of the tetrahedron (vertex) and r is the number of tetrahedra (vertices) of connectivity (degree) c in the repeat unit. Thus cTr = 1Tr12Tr23Tr34Tr4 (cVr = 1Vr12Vr23Vr34Vr4) represents all possible connectivities (degrees) of tetrahedra (vertices) in the geometrical (topological) repeat units of such one-dimensional polymerisations. We may generate all possible cTr (cVr) expressions for chains (graphs) with tetrahedron (vertex) connectivities (degrees) c = 1 to 4 where r = 1 to n by sequentially increasing the values of c and r, and by ranking them accordingly. The silicate (sensu lato) units of chain-, ribbon- and tube-silicate minerals are identified and associated with the relevant cTr (cVr) symbols. Following description and association with the relevant cTr (cVr) symbols of the silicate units in all chain-, ribbon- and tube-silicate minerals, the minerals are arranged into decreasing O:T ratio from 3.0 to 2.5, an arrangement that reflects their increasing structural connectivity. Considering only the silicate component, the compositional range of the chain-, ribbon- and tube-silicate minerals strongly overlaps that of the sheet-silicate minerals. Of the chain-, ribbon- and tube-silicates and sheet silicates with the same O:T ratio, some have the same cVr symbols (vertex connectivities) but the tetrahedra link to each other in different ways and are topologically different. The abundance of chain-, ribbon- and tube-silicate minerals decreases as O:T decreases from 3.0 to 2.5 whereas the abundance of sheet-silicate minerals increases from O:T = 3.0 to 2.5 and decreases again to O:T = 2.0. Some of the chain-, ribbon- and tube-silicate minerals have more than one distinct silicate unit: (1) vinogradovite, revdite, lintisite (punkaruaivite) and charoite have mixed chains, ribbons and/or tubes; (2) veblenite, yuksporite, miserite and okenite have clusters or sheets in addition to chains, ribbons and tubes. It is apparent that some chain-ribbon-tube topologies are favoured over others as of the ~450 inosilicate minerals, ~375 correspond to only four topologically unique graphs, the other ~75 minerals correspond to ~46 topologically unique graphs.

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.

The cathodoluminescence (CL) of cassiterite (SnO2) from the paragenetic sequence in the lodes at South Crofty Mines has been used in the interpretation of the processes which govern mineral deposition. Luminescence is controlled by the substitution of Ti, Fe and W for Sn in the cassiterite lattice. Ti and W behave as luminescence activators whereas Fe quenches luminescence. The observed colours and intensity of the luminescence are believed to result from the interplay between these effects. Successive generations of cassiterite formed during the separate stages of paragenetic evolution show different luminescence colours. These are believed to reflect changes in bulk composition of the fluid, which is indicated by the systematic variation in the composition of tourmaline in the associated gangue.

CL also reveals details of growth and deformation in individual crystals. Growth textures observed in CL are broad concentric growth banding, oscillatory zoning and sector zoning. Sector boundaries often show a zig-zag form which is indicative of competitive growth of adjacent crystal faces. Interpretation of CL textures is used to support the hypothesis that cassiterite growth took place under two main regimes. These are, firstly, conditions in which fluid pressure decreased abruptly when tectonic reactivation caused dilation of parts of the lode fracture system and secondly, conditions of sustained hydraulic pressure within fractured vein fill. In tectonically induced fractures the crystals are stubby, have non-equivalent growth faces and are commonly tetragonal bipyramidal forms in which sector zoning is invariably present. In hydraulic fractures crystals take a predominantly tetragonal prismatic form. Thus, it is believed that growth under these contrasting conditions leads to distinctive morphology and zoning in cassiterite, providing a basis for typomorphic characterisation.

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.

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 Virulundo carbonatite in Angola is one of the largest in the world and contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias and trachytoids). The primary magmatic pyrochlore is fluorine dominant and typically contains about equal molar quantities of Ca and Na at the A site. High-temperature hydrothermal processes have resulted in the pseudomorphic replacement of the primary pyrochlore by a second generation of pyrochlore with less F and Na. Low-temperature hydrothermal replacement of the first and second generation pyrochlore, associated with quartz-carbonate-fluorite vein formation in the carbonatite, has produced a third generation of pyrochlore, with a high Sr content. The Sr appears to have been released by low-temperature hydrothermal replacement of the primary magmatic carbonates. Finally, supergene alteration processes have produced late-stage carbonates, goethite, hollandite and rare earth element (REE) minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Cerium separated from the other REE s in oxidizing conditions and Ce4+ was incorporated into a late generation of supergene pyrochlore, which is strongly enriched in Ba and strongly depleted in Ca and Na.

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.

The southern part of the Cretaceous Kohistan island arc is occupied by an extensive belt dominantly comprised of amphibolites. These include banded amphibolites of partly meta-volcanic parentage, and non-banded amphibolites derived from intrusive rock. In addition to being relict, banding has also been produced by shear deformation, metamorphic/metasomatic segregation and, possibly, by lit-par-lit injection of plagiogranitic material. Non-banded amphibolites also occur as retrograde products of noritic granulites forming the lopolithic Chilas complex. The chemistry of 37 rocks has been compared with those of known tectonic environments. The amphibolites have chemical characteristics similar to volcanic rocks found in island arcs and most of the analyses apparently support affinity with the calc-alkaline series. The amphibolites consist essentially of hornblende, plagioclase and/or epidote. Garnet and clinopyroxene have developed locally in rocks of appropriate bulk composition. Metamorphism may have taken place during the mid-Cretaceous under conditions of 550 to 680°C and 4.5 to 6.5 kbar PH2O. The metamorphic grade appears to increase from the centre of the southern belt toward the Chilas complex to the north and Indus-Zangbo suture (IZS) to the south. In the vicinity of the IZS, garnet-clinopyroxene ± amphibole assemblage developed locally in response to high P-T.

For complex rocks in which the structure of minerals, rather than their chemical composition, changes with progressive evolution of the system, it makes sense to try and monitor such an evolving system through the progressive change in the crystal structures of the constituent phases. In effect, the paragenetic sequences of minerals in such complex environments should be related to the crystal structures of the constituent minerals. In order to consider variations in structure topology, we need to organize crystal structures into hierarchical schemes, using the hypothesis that structures may be hierarchically ordered according to the polymerization of the coordination polyhedra with higher bondstrengths. Structural units are organized according to the mode of polymerization: unconnected polyhedra, clusters, chains, sheets and frameworks.

The bond-valence structure of (OH) and (H2O) shows that on one side, (OH) and H2O are strong Lewis bases; on the other side, they are weak Lewis acids. As a result, a very important role of both (OH) and (H2O) is to prevent polymerization of the structural unit in specific directions. Thus, the dimensionality of the structural unit is controlled primarily by the amount and role of hydrogen in the structure. The way in which we have formulated these ideas also allows development of a predictive framework within which specific aspects of the chemistry and structure of phosphates can be considered.

This approach to mineral structure, applied via the idea of a structural unit, can play a major role in developing structural hierarchies in order to bring about some sort of order to the plethora of hydroxyhydrated-phosphate structures. Furthermore, by combining the idea of binary structural representation with bond-valence theory, we see the eventual possibility of predicting stoichiometry and structural characteristics of these minerals, particularly those in complex low-temperature hydrothermal environments