Concentrations of organic acids ranging up to several thousand parts per million have previously been found in oil-field waters. These acids are of interest because of their potential to enhance porosity by the dissolution of carbonates and aluminosilicates. They are believed to be generated from organic geopolymers (kerogen) in the late-diagenetic-early-catagenetic stage of thermal maturation.

During the course of artificial maturation experiments in which kerogens of varying type were heated in the presence of water (so-called ‘hydrous pyrolysis’) and different minerals, the distribution and abundance of low molecular weight water-soluble acids were determined by gas chromatography and gas chromatography-mass spectrometry. Preliminary results suggest that significant quantities of mono- and di-carboxylic acids are produced during hydrous pyrolysis. The amounts and types of acid appear to vary as a function of kerogen type, maturity and mineralogy. Implications of these findings regarding the development of secondary porosity are discussed.

We review recent advances on the physical principles of crystallization in multicomponent systems, and use them to provide a framework for interpreting petrological and geochemical observations from igneous intrusions. The thermal structure of crystallizing boundary layers imposes strong constraints on the chemical and mineralogical compositions of the solid that can form from a given melt. The thermal problem is largely independent of the chemical composition of the melt, and sets the course of crystallization. A key problem to understand is the temperature of the solidification front (which we take to mean that point at which the last drop of liquid solidifies) particularly in the geologically relevant case in which the temperature at the cold boundary is below the eutectic temperature. Focussing on the solidification front rather than on the liquidus is a valuable perspective. Adcumulus growth requires specific conditions and much can be learned from trying to understand how these can develop from given starting conditions. We discuss the physical reasons and field evidence for the existence of mushy layers, where solid fraction and temperature vary by large amounts. In such regions of the magma chamber, thermodynamic equilibrium is nearly achieved locally and, for a given temperature, this specifies the composition of the interstitial melt. Thus, in a magma chamber, the whole liquid line of descent is present simultaneously. Compositional convection is likely to set in, and this exchange between the interior of the mushy layer and the main reservoir leads to a chemically stratified solid, and to adcumulus growth. The contribution of crystal settling to the floor cumulates is evaluated as a function of the magnitude of convective heat flux through the roof. It is shown that crystal settling is unlikely to overwhelm in-situ nucleation and growth at the floor.

The system of intrusive sheets in the Lower Carboniferous formations of the north of England, familiar to geologists throughout the world as the Great Whin Sill, has a voluminous early literature which it is unnecessary to summarize here. It will be sufficient to refer to the classical papers by Topley and Lebour on the field relationships (1) and by Teall on the detailed petrography (4), each of which contains an ample bibliography of the earlier literature. The most recent general account is by Prof. E. J. Garwood (9), who contributed a careful discussion of the evidence bearing on the period of intrusion.

Teall's great paper closely followed on one devoted to some of the dikes of the north of England (3), and in it he drew attention to the remarkable petrographical Similarity between the rocks of the Heft and High Green dikes and that of the Whin Sill (4, p. 656).

Geochemical anomalies can be used in mineral resource exploration. We demonstrate a technique for mapping anomalies. The Gangdese mineral district in Tibet, west China was chosen as a study area for identifying geochemical anomalies and predicting Cu mineral resources using sediment geochemical data. The results show that the anomalies are associated both with known deposits in the middle of the study area, but also with E—W and N——E oriented faults in the north of area. These areas should be explored for undiscovered Cu mineral deposits.

Detailed electron-microprobe line profiles and small-area compositional maps of zoned garnets in a sample of high-pressure-high-temperature granulite show features inconsistent with commonly applied diffusion models. Larger grains of an early garnet generation have their highest Ca contents in domains away from the rim or inclusions but show a sharp fall in Ca balanced by increased Mg and Fe (and slightly higher XMg) towards inclusions and the rim. In domains with secondary biotite, the sharp decrease in Ca is accompanied by variations in XMg dependent upon proximity to biotite, thus producing one-sided, asymmetric profiles with XMg lower against biotite. As a consequence, rim compositions of the same grain are different on the sides adjacent and away from biotite and there is no relationship between grain size and rim XMg. Such a zoning pattern requires that grain-boundary diffusion is as slow as volume diffusion and implies the absence of a diffusion-enhancing grain-boundary fluid phase during the majority of the rock's high-temperature exhumation history. Diffusion models ignoring this probability could yield either cooling rates that were too fast, or extrapolated ages based on closure temperature models that were too old.

A second garnet generation in the same rock, grown in a Ca-rich domain resulting from kyanite breakdown, has irregularly distributed patches, identified by compositional mapping, containing higher Ca than the first-formed garnet but at lower XMg. Use of such garnet compositions for geothermobarometrical determination of the high-pressure granulite stage would clearly lead to erroneous results. The presence of such contrasting garnet compositions in a granulite-facies rock is clearly evidence of disequilibrium, and further supports the proposition that there was a lack of an effective transport medium even at the mm scale.

The study of the materials from these two recently discovered occurrences has added much to the knowledge of meteorite craters. The two present many points in common and they supplement one another. At Henbury there is a much better development of the meteoric iron, while at Wabar the silica-glass predominates.

The surfaces of quartz crystals that were partially dissolved in superheated, H2O-saturated rhyolite melt are covered with hemispherical embayments; each embayment is judged to have formed where a gas bubble in the melt approached the crystal. ‘Flux-line attack’ and ‘upward-drilling’ of the refractory lining of glass tanks are analogous processes. As a bubble nears a dissolving solid it enters a compositional boundary layer in the melt, resulting in melt of variable surface tension surrounding the bubble. This unstable situation results in small-scale convection of the melt about the bubble (Marangoni convection) which can cause locally enhanced dissolution rate of the solid. It is suggested that this mechanism could cause round embayments to form in quartz phenocrysts in acid volcanic and sub-volcanic rocks. Criteria by which embayed phenocrysts formed by dissolution can be distinguished from those formed by unstable growth are reviewed briefly.

The self diffusion of oxygen has been studied in prepared natural crystals of albite, grossular garnet, quartz, and ruffle by isotope exchange with hydrothermal water enriched in 18O, and subsequent analysis by ion microprobe. Measured oxygen diffusion coefficients (D) in quartz (‖c) may be described by D = 1.08 × 10−11 exp(−31.5 kcal/RT) cm2s−1 at 600−750°C and 1 kbar water pressure. For grossular, D = 2.5 × 10−16 cm2s−1 at 1050°C and 8 kbar, and D = 4.8 × 10−17 cm2s−1 at 850 °C and 2 kbar. All ruffle crystals exhibited variable amounts of corrosion, and an approximate diffusion coefficient of D(‖c) = 3.16 × 10−15 cm2s−1 cm2s−1 was obtained at 1050 °C and 1 kbar. Oxygen diffusion coefficients in albite, perpendicular to (001) faces, have been determined as a function of pressure at 600 °C Between 0.5 and 8.0 kbar pressure no systematic variation in the results was observed and most of the data may be described by D = 4.1 (±0.5) × 10−15 cm2s−1. Slow oxygen diffusion rates in quartz and garnet suggest that these minerals should have high ‘closure temperatures’ for oxygen exchange, and may provide reliable oxygen isotope exchange geothermometers.

A FORTRAN program has been written which inputs amphibole analyses, and outputs complete IMA-approved names, along with tabulated analyses, formula units, and IMA classification parameters. Several important corrections, additions, and amendments to the IMA scheme were found to be necessary. Two newly approved names have been incorporated—sadanagaite (ferro-pargasitic amphibole with Si < 5.5), and nyboite (alkali amphibole with (Na+K)A ⩾ 0.5, Fe3 ⩽ AlVI, Si < 7.5). The name anophorite (alkali amphibole with (Na+K)A ⩾ 0.5, Fe3 > AlVI, Si < 7.5) has been reinstated to complement nyboite, with the approval of the Amphibole Subcommittee of the IMA. Results of computer processing of several hundred analyses, which together cover the range of IMA-approved names, are summarized. These indicate substantial differences between IMA and previous nomenclature. The IMA-favoured procedure for reallocating total Fe in microprobe data is quite effective, except in kaersutites. Over half the analyses processed have anomalously high cations (e.g. Ca > 2), or cation totals (e.g. T + C + B > 15), commonly reflecting low H2O determinations. These prevent strict obeyance of the IMA site occupancy calculation rules. This problem can often be overcome by recalculation free of H2O, but other cases require modifications to the IMA rules. In particular, ‘misclassification’ of certain sodic-calcic amphiboles as edenite follows from transferring large excesses of C cations to the B site.

In a diffusion-controlled process of nucleation and growth, adjacent porphyroblasts compete with one another for nutrients. When the effects of this competition are evaluated quantitatively for garnet porphyroblasts in pelitic rocks from the Picuris Range of New Mexico (U.S.A.), significant correlations arise between crystal sizes and the volumes of the domains from which the crystals drew their nutrients. These correlations strengthen the conclusion drawn from earlier work on spatial dispositions, zoning patterns, and crystal size distributions that the kinetics of intergranular diffusion governed the crystallisation of these porphyroblasts.

Computer simulations indicate that competition for nutrients during diffusion-controlled growth may have small but detectable effects on crystal size frequency distributions. Diffusional competition therefore introduces relatively minor inaccuracies into attempts to extract quantitative information on crystallisation processes from size distributions using models for the growth of isolated porphyroblasts. In contrast, the effects of diffusional competition on patterns of compositional zoning may be substantial, especially for porphyroblasts in rocks for which chemical inhomogeneity of the precursor leads to strongly clustered spatial dispositions. In such rocks, clustering may alter the patterns of compositional zoning in ways that obscure evidence for diffusion-controlled growth.

We use an approach based upon the atomistic or Born model of solids, in which potential functions represent the interactions between atoms in a structure, to calculate the infrared and Raman vibrational frequencies of forsterite. We investigate a variety of interatomic potentials, and find that although all the potentials used reproduce the structural and elastic behaviour of forsterite, only one potential (THB1) accurately predicts its lattice dynamics. This potential includes ‘bond-bending’ terms, that model the directionality of the Si-O bond, which we suggest plays a major role in determining the structural and physical properties of silicates. The potential was derived empirically from the structural and physical data of simple oxides, and its ability to model the lattice dynamics of forsterite is a significant advance over previous, force-constant models, which have been simply derived by fitting to the spectroscopic data that they aim to model. The success that we have had in predicting the lattice dynamics of forsterite indicates that the potential provides the previously elusive yet fundamental, quantitative link between the microscopic or atomistic behaviour of a mineral and its macroscopic or bulk thermodynamic properties.

Brachiopods are a phylum of shell-forming sessile marine invertebrates which have existed since the early Cambrian. Two very different biomaterial design strategies for their shells evolved early in their history. Both strategies use hybrid fibre composites, however, one is based on mineral fibres embedded in ~2 wt.% of organic biopolymer sheaths and the inorganic fibres are calcite single crystals. In the second strategy the fibres are biopolymers and are reinforced with Ca-phosphate nanoparticles to form a fibrous nanocomposite. Here the organic component (chitin) dominates. The Ca-phosphate nanoparticle-reinforcement strategy is not unlike that in vertebrate bone, however, the microscale structure is laminated with alternating laminae which have a different degree of mineralization.

The calcitic shells feature an outer compact layer of calcite micro- and nanoparticles protecting the inner fibrous layer from the outside. Transmission electron microscopy of the fibrous layer reveals intercrystalline and intracrystalline biopolymers. The calcitic shell material is stiff with nano-indentation E-moduli of 63±8 GPa and relatively hard (Vickers microhardness up to 400 HV 0.0005/10 and nanohardness 4±0.5 GPa). Compared to inorganic calcite the microhardness is doubled and the nanohardness increases by 60%. We attribute this increased hardness to intracrystalline biopolymers. The nano-indentation E-moduli of the chitinophosphatic shells range from 3 to 55 GPa as a result of the varying degree of mineralization between their laminae, and similarly their nanohardness varies between 0.1 and 3 GPa. For brachiopods burrowing inside the sediment, the alternation of non-mineralized laminae with thin, more strongly mineralized laminae provides abrasion-resistance, hardness and longitudinal stiffness while it preserves the flexibility provided by the organic component for bending movements.

The Pan-African orogenic shield rocks of eastern Egypt were intruded by several anorogenic within- plate granitic complexes, including Mounts Abu-Kharif and El-Dob. These two massifs were emplaced at the intersection of a fault system and a shear zone. The two massifs are made up of hypersolvus peralkaline granites, consisting essentially of perthitic alkali feldspar (55–65 vol.%), quartz (30–35%), and alkali amphibole (ferrorichterite to arfvedsonite; 5–12%), with accessory zircon, apatite and ilmenite. The rocks are evolved in composition, are relatively enriched in Nb (53–75 ppm), Y (34–72 ppm), Zr (421–693 ppm), Ga (26–29 ppm), and the REE (294–562 ppm), and depleted in Al, Mg, Ca, Sr, Ba and Eu. The REE patterns are sub-parallel, LREE -enriched over HREE , and show prominent negative Eu anomalies. The rocks exhibit mineralogical and chemical traits typical of within-plate A-type granites. Rb-Sr radiometric age dating produced a Cambrian age of 522±21 Ma, and an initial 87Sr/86Sr ratio of 0.7080±0.0042. Thus, the investigated peralkaline granitic rocks were emplaced following the termination of the Pan-African orogeny. The rocks are interpreted to have formed in an extensional tectonic environment during a phase of cooling, relaxation, crustal attenuation, and fracturing of the newly-formed shield.

Results of geochemical modelling indicate that the magma may have formed by a large degree of batch partial melting (F = 0.57) of Pan-African calc-alkaline shield rocks, which had been metasomatized possibly by a Na-rich fluid. The volatile flux may have caused fenitization-type reactions along fissures and re-activated Pan-African fractures prior to anatexis, and is considered to have played a role as an important agent of heat transfer. Shear heating, caused possibly by a rapid change in the direction of plate motions beneath eastern Egypt during the Early Palaeozoic, is likely to have produced temperatures necessary for crustal anatexis. The confining pressure must have been released by fissuring of the crust. Magma ascent may have been facilitated by reactivation of pre-existing Pan-African fractures.

Uranium-lead isotope dating of two zircon inclusions in sapphires from the Central Province, NSW. gives ages of 35.9 ± 1.9 and 33.7 ± 2.1 million years (Ma). These ages fall within the range of basalt potassium-argon ages of 19 to 38Ma and zircon fission track ages of 2 to 49Ma for the timing of volcanism of the Central Province, NSW. These data, combined with the observation that corundum is found associated with many alkali basaltic provinces, indicate a genetic link between the growth of large corundum crystals and the processes involved in alkali basaltic magma generation. The reported failure of experimental attempts to grow corundum from a corundum-bearing basaltic composition, and more significantly, the abundance of incompatible elements such as U, Th, Zr, Nb and Ta in inclusion minerals indicate that the crystallization process is not simple. Corundum and the other minerals found as its inclusions (zircon, columbite, thorite, uranium pyrochlore, alkali feldspar etc.) could not have crystallized from most basaltic compositions. A more complex process must occur in which crystallization takes place when there are high proportions of incompatible elements and volatiles in the melt. These crystallization products are then carried to the surface by upward movement of later magmas. The extent of this process presumably determines whether a particular basaltic province carries sufficient corundum to be worked into economic concentrations of sapphire.

Microbial metabolism has the potential to control the biogeochemistry of redox-active radionuclides in a range of geodisposal scenarios. In this study, sediments from a high pH lime workings site were incubated under carefully controlled anaerobic conditions, at a range of alkali pH values with added electron donors and electron acceptors, to explore the limits and rates of bioreduction in a sediment system analogous to intermediate-level nuclear waste. There was a clear succession in the utilization of electron acceptors (in the order nitrate > Fe(III)-citrate > Fe(III) oxyhydroxide > sulfate), in accordance with calculated free energy yields and Eh values over the pH range 10–12. The rate and extent of bioreduction decreased at higher pH, with an upper limit for the processes studied at pH 12. The biochemical limits for such processes are discussed, alongside the potential impact of such forms of microbial metabolism on the solubility of a range of redox active radionuclides that will feature heavily in the safety case for the geological disposal of intermediate-level nuclear waste.

The composition of chevkinite and perrierite, the most common members of the chevkinite group, is closely expressed by the formula A4BC2D2Si4O22, where A = (La,Ce,Ca,Sr,Th), B = Fe2+, C = (Fe2+,Fe3+,Ti,Al,Zr,Nb) and D = Ti. The A site is dominated by a strong negative correlation between (Ca+Sr) and the REE. Chondrite-normalized REE patterns are very variable, e.g. in LREE/HREE and Eu/Eu*. The C site is dominated by Ti, Al and Fe2+, in very variable proportions. Most chevkinites and perrierites are close to stoichiometric, with cation sums between 12.9 and 13.5, compared to the theoretical 13. There is no single, generally applicable charge balancing substitution scheme in the group; however, the general relationship

defines a linear array with r2 = 0.91. Chevkinite and perrierite are shown to be compositionally distinct on the basis of CaO, FeO*, Al2O3 and Ce2O3 abundances. Chevkinite forms mainly in chemically evolved parageneses, such as syenites, rhyolites and fenites associated with carbonatite complexes. Perrierite is more commonly recorded from igneous rocks of mafic to intermediate composition. The compositional characteristics and possible structural formulae of other members of the chevkinite group are reviewed briefly.

The limits and effect on cell size of silver substitution into synthetic tetrahedrite, Cu10(Zn,Fe,Cd2) Sb4S13, are investigated for comparison with natural tetrahedrite. The limit of Ag substitution into natural zincian tetrahedrite is ∼ 4 atoms per half unit cell and into iron tetrahedrite ∼ 6.5 atoms (with rare exceptions). The cell size of natural tetrahedrite increases with increasing Ag content up to 4 atoms but decreases with further Ag substitution. The highest Ag substitution achieved in synthetic tetrahedrites was 4.7 atoms in Zn2-tetrahedrite, 7.02 atoms in Cd2-tetrahedrite and 6.80 atoms in Fe2-tetrahedrite. The cell size of synthetic tetrahedrites shows a continuous increase with increasing Ag content, the largest cell size of a = 10.927 Å being in the Cd2-tetrahedrite with 7.02 atoms Ag. The iron content of tetrahedrite systematically increased from 1.1 to 2.0 atoms per half unit cell tetrahedrite with increase from 0 to ∼ 4 atoms Ag. The different limit of Ag substitution between Zn2 and Cd2 tetrahedrite can be explained by size constraints on the expanding structure. An explanation is given for a limit of 7 atoms Ag substitution in tetrahedrite using a combined electron band/molecular orbital approach.

Previous studies of low-grade metamorphism in the Southern Uplands accretionary terrain indicated prehnite-pumpellyite facies/anchizone conditions developed throughout the area, except for local preservation of trench-slope sediments and an accreted seamount at zeolite facies/advanced diagenetic grade. New graptolite reflectance data are presented that show a general northward increase in temperature in the Southern Uplands. The results from two cross-strike traverses in the southern and central belts in contemporaneous sequences, using illite crystallinity, illite lateral spacing (bo) , and graptolite reflectance, indicate the development of systematic accretion-related low-grade metamorphism. Well-developed and constant anchizone conditions occur throughout the NE (Langholm) traverse, associated with common, F1 accretion-related folding and a regionally penetrative S1 cleavage. In the SW (Kirkcudbright) traverse, however, the youngest, last accreted packets are preserved at a transitional diagenetic stage and lack a penetrative S1 cleavage. Illite crystallinity, graptolite reflectance, and bo increase systematically northward through earlier accreted packets, reaching values of the NE traverse only at the northern end. The concomitant increase of bo with illite crystallinity suggests the relatively high P-low T trajectory characteristic of subduction zones. Integration of metamorphic and structural data relates increasing intensity of aceretion-related F1 folding, developmertt of S1 fabric, and onset of later fold phases to grade of metamorphism and structural level within the accretionary pile.

A cementitious backfill has been proposed in many geological disposal concepts for intermediate-level waste and low-level waste in the UK and elsewhere. In this paper, the main features of the chemical evolution of backfill and the associated changes in the near-field pH are illustratedwith results from recent work. For example, interaction of the groundwater with calcium silicate hydrate (C-S-H) phases in a backfill is expected to play an important role in the long-term pH-buffering behaviour. Existing experimental data for the dissolution of C-S-H gels are compared withrecent experimental results from leach tests on gels of a lower calcium to silicon ratio (C/S) to provide a consistent set of data across the full C/S range. The results confirm that a congruent dissolution point around C/S = 0.8 is approached by leaching from below (i.e. for gels with 0.29< C/S < 0.8), as well as from above, as reported elsewhere. In addition, a spreadsheet model has been developed to calculate the volume of backfill required at the vault scale to meet specified pH performance criteria. This model includes the major reactions of the backfill with thegroundwater, waste encapsulants and waste components. It can also consider the effects of specific waste packages on local pH performance to allow comparison with the vault-scale calculations.

Cathodoluminescence (CL) imaging and spectroscopy, as well as backscattered electron imaging, were used to assign the occurrence of several mineral phases and rock structures in altered nordmarkites and calcite-bearing granites from the Nb-Zr-REE deposits from Khaldzan Buregte and Tsakhir (Mongolian Altai) to three events: (1) intrusion of barren nordmarkites; (2) intrusion of small bodies of calcite-bearing granites with metasomatic alteration of the wall-rocks; and (3) alteration by F-rich fluids.

Unusual red and yellow CL caused by Fe3+ and Mn2+ emission centres were detected in microcline and albite. Fe3+ centres were also established (along with others) in quartz, zircon, and possibly in fluorite.

Magmatic and metasomatic rock structures and internal structures of the minerals coexist in the samples. The primary magmatic features were in part preserved during alteration. In contrast, the internal and the centre structures may be changed during alteration even in non-replaced mineral phases. Euhedral minerals may be formed by secondary processes as shown for lath-shaped albite. The occurrence of pseudomorphs, the inheritance of elements during replacement, and the mechanical effects of secondary minerals on earlier mineral phases during metasomatic growth are proposed as criteria for the reconstruction of the mineral succession in altered rocks. Snowball structures may be formed as a result of metasomatic alteration rather than as a magmatic intergrowth.