A possible structure for kaolinite was first put forward by Pauling (1930) in a paper dealing generally with the structures of layer-type minerals, chlorites, micas, &c. He suggested that the structure consisted of a sheet of Si–O tetrahedra arranged in a hexagonal network with a superposed sheet of Al–(O,OH) octahedra, the two together forming a layer of composition Al2Si2O5(OH)4 (fig. 2). Ross and Kerr (1931), from a detailed microscopic study of the kaolin minerals, concluded that the symmetry of kaolinite is ‘probably monoclinic’. The first attempt at a detailed structure analysis was made by Gruner (1932a) from X-ray powder photographs. The reflections, some 40 altogether, were indexed on the basis of a monoclinic cell with a 5·14, b 8·90, c 14·51Å., β 100° 12′.

In a previous paper attention was drawn to the close similarity in mineral and chemical composition of chondritic meteoric stones. In the case of about forty chondrites it was shown that, apart from variations in the amount of nickel-iron, not only are the constituent minerals present in very similar amounts, but their chemical compositions vary to no very great extent. In that paper sufficient importance was not attached to the variations in the amount of nickel-iron.

The distribution of the minor impurities, aluminium and silicon, between co-existing phases in altered ilmenite grains from three Western Australian localities has been investigated using SEM and electronmicroprobe analyses. A striking dependence of the impurity levels on the Ti/(Ti + Fe) fraction is observed. For compositions with Ti/(Ti + Fe) between 0.45 and 0.60, i.e. between ferrian-ilmenite and pseudorutile, the impurity content is virtually independent of Ti/(Ti + Fe), and is very low (0.2 wt. % Al2O3. 0.05 wt. % SiO2). For compositions between those of rutile and pseudorutile, there is a direct correlation between the impurity contents and the Ti content of the alteration phase. The impurity levels increase with increasing Ti/(Ti+Fe) to about 3 wt. % Al2O3 and 1 wt. % SiO2 for compositions close to TiO2. Thus during the latter stages of ilmenite alteration, alumina and silica are extracted from the ambient environment and are coprecipitated with, or adsorbed on to, the alteration products. The observed dependence of the alumina and silica contents on extent of alteration is consistent with a two-stage alteration mechanism earlier proposed (Grey and Reid, 1975).

Dissolved water has significant effects on the physical and chemical properties of silicate melts. Some of the different approaches towards understanding these effects are reviewed here. Spectroscopic measurements on hydrous glasses quenched from melts provide good models for the structure of the melts at the glass transition temperature (Tg). Such measurements suggest that the mechanism of dissolution of water in silicate melts varies strongly with the bulk composition. In particular framework aluminosilicate compositions seem to have very different dissolution mechanisms from Al-free compositions. The water speciation reactions are temperature dependent, with some of the molecular water which is present in glasses at room temperature being converted to hydroxyl at high temperatures. This conversion probably occurs only above Tg. Data on the kinetics of the speciation reaction and the dynamics of microscopic processes in hydrous silicate melts are also discussed. Finally some important aims of future work on hydrous silicate melts are suggested

Secondary ion mass spectrometry (SIMS) techniques have been used to study the variation of C isotope ratio and N abundance within selected diamonds in relation to their crystal growth zones. The growth zones are seen in cathodoluminescence (CL), and include both octahedral and cuboid zones within typical diamonds of external octahedral morphology. Compositions were determined by use of a primary 133Cs+ ion beam and measurement of 12C−, 13C, and 12C14N− secondary ions at high mass resolution on a Cameca ims-4f ion microprobe at Edinburgh University.

In each of the diamonds, different growth zones have marked differences in N abundance, which are as great as 0–1400 ppm within one diamond. Changes of several hundred ppm N are common across both octahedral and cuboid growth zones, and appear sharp and abrupt at the boundaries of the growth zones. In general for the common blue CL, luminescence increases with N abundance. The changes in N abundance across fine scale (∼100 µm) growth zones show that the total N contents determined by IR spectroscopy may show great variations of abundance. In contrast, within detection limits, δ13C appears constant across many growth zone boundaries. Thus the factors controlling uptake of N from the fluid/melt reservoir in which natural diamonds grow often do not influence δ13C. No evidence of progressive variation or fractionation of C isotopes during growth was found.

Some original variation in C isotope composition may have been eliminated by diffusion of C atoms subsequent to growth, because of the storage of natural diamonds over millions of years in the Earth's mantle at temperatures of 950–1250°C. Such atomic mobility does not homogenize N distribution because of the proven tendency of N to form aggregates of atoms. A survey of experimental estimates of single atom (C) diffusion parameters, suggests that diffusion distances of ∼100 µm are likely at high temperatures (∼1100°C) over long time periods (∼1.0 Ga). Therefore, with refinement of the diffusion parameters and measurements, the extent of C isotope homogenization in natural diamonds, as well as N aggregation state, might provide quantitative evidence of their time-temperature history under mantle conditions.

Biological weathering is a function of biotic energy expenditure. Growth and metabolism of organisms generates acids and chelators, selectively absorbs nutrient ions, and applies turgor pressure and other physical forces which, in concert, chemically and physically alter minerals. In unsaturated soil environments, plant roots normally form symbiotic mycorrhizal associations with fungi. The plants provide photosynthate-carbohydrate-energy to the fungi in return for nutrients absorbed from the soil and released from minerals. In ectomycorrhiza, one of the two major types of mycorrhiza of trees, roots are sheathed in fungus, and 15—30% of the net photosynthate of the plants passes through these fungi into the soil and virtually all of the water and nutrients taken up by the plants are supplied through the fungi. Here we show that ectomycorrhizal fungi actively forage for minerals and act as biosensors that discriminate between different grain sizes (53—90 μm, 500—1000 μm) and different minerals (apatite, biotite, quartz) to favour grains with a high surface-area to volume ratio and minerals with the highest P content. Growth and carbon allocation of the fungi is preferentially directed to intensively interact with these selected minerals to maximize resource foraging.

The kinetics and mechanisms of dissolution of the major base metal sulphide minerals, pyrite, chalcopyrite, galena and sphalerite in acidic (chloride) media have been investigated. Minerals were ground in air, then dissolved in air-equilibrated solutions at pH 2.5, while monitoring the redox potential. Solution samples were analysed by ICP-AES and HPLC, and surfaces of residual sulphides analysed using XPS. Dissolution of aerial oxidation products on pyrite particles in the first 15 min apparently led to a sulphur-rich surface, and was followed by slower dissolution of pyrite itself, driven by oxygen reduction, and resulting in net production of protons. Chalcopyrite dissolution resulted in a Cu, S-rich (near) surface layer, accompanied by net consumption of protons. Apparently incongruent dissolution of galena and sphalerite may reflect the formation of elemental S at the surface. The rates of dissolution of chalcopyrite, galena and sphalerite in the presence of pyrite were determined, respectively, as 18, 31 and 1.5 times more rapid than in single-mineral experiments. These data were consistent with galvanically-promoted mineral oxidation of the other sulphides in the presence of pyrite. In the case of galena, the experimental data suggested extensive release of Pb ions and development of a sulphur-rich surface during galvanically-promoted dissolution.

This report embodies recommendations on zeolite nomenclature approved by the International Mineralogical Association Commission on New Minerals and Mineral Names. In a working definition of a zeolite mineral used for this review, interrupted tetrahedral framework structures are accepted where other zeolitic properties prevail, and complete substitution by elements other than Si and Al is allowed. Separate species are recognized in topologically distinctive compositional series in which different extra-framework cations are the most abundant in atomic proportions. To name these, the appropriate chemical symbol is attached by a hyphen to the series name as a suffix except for the names harmotome, pollucite and wairakite in the phillipsite and analcime series. Differences in spacegroup symmetry and in order—disorder relationships in zeolites having the same topologically distinctive framework do not in general provide adequate grounds for recognition of separate species. Zeolite species are not to be distinguished solely on Si : Al ratio except for heulandite (Si : Al < 4.0) and clinoptilolite (Si : Al ⩾ 4.0). Dehydration, partial hydration, and over-hydration are not sufficient grounds for the recognition of separate species of zeolites. Use of the term ‘ideal formula’ should be avoided in referring to a simplified or averaged formula of a zeolite.

Newly recognized species in compositional series are as follows: brewsterite-Sr, -Ba; chabazite-Ca, - Na, -K; clinoptilolite-K, -Na, -Ca; dachiardite-Ca, -Na; erionite-Na, -K, -Ca; faujasite-Na, -Ca, -Mg; ferrierite-Mg, -K, -Na; gmelinite-Na, -Ca, -K; heulandite-Ca, -Na, -K, -Sr; levyne-Ca, -Na; paulingite-K, -Ca; phillipsite-Na, -Ca, -K; stilbite-Ca, -Na.

Key references, type locality, origin of name, chemical data, IZA structure-type symbols, space-group symmetry, unit-cell dimensions, and comments on structure are listed for 13 compositional series, 82 accepted zeolite mineral species, and three of doubtful status. Herschelite, leonhardite, svetlozarite, and wellsite are discredited as mineral species names. Obsolete and discredited names are listed.

In situ flow-cell ATR-FTIR using a hematite-coated germanium crystal was used to investigate the chemical interactions between Pseudomonas putida and hematite in real time, when compared with cells not attached to the mineral surface. ATR-FTIR spectra of bacteria growing on hematite showed a shift in the carboxylate signal when compared to the samples obtained from free cells, indicating a chemical interaction between the carboxylate groups and the Fe metal ions of the hematite surface. Small differences in the polysaccharide and phosphoryl regions of the IR spectra of bacteria attached to hematite were also observed. This work shows how the use of in-situ flow-cell experiments with a mineral-coated germanium crystal allows a better description of the bacterial interactions with minerals in real time, as an initial step to understand the fundamental mechanisms involved in the relationship between bacteria and mineral surfaces.

The dissolution rates of spheres of two magnesian olivines, two plagioclases, and quartz in tholeiitic basalt have been determined at three super-liquidus temperatures and one-atmosphere pressure. There are considerable differences in the rates among the minerals, e.g. at 1210°, 12° above the liquidus temperature of the basalt, labradorite dissolves at 86 µm/h. and the magnesian olivines at 9 and 14 µm/h. The rates are not time dependent and this, coupled with the existence of concentration gradients in the composition of quenched melt adjacent to partially dissolved crystals, indicates that the dissolution rates are dictated by a combination of diffusion and convection of components to and from the crystal-liquid interface. Values for the activation enthalpy of dissolution are small for quartz and plagioclase (40–50 kcal mol−1) but large for olivine 73–118 kcal mol−1). Dissolution of plagioclase in rock melts seems to be a much more rapid process than crystal growth, whereas olivines apparently dissolve and grow at similar rates. Crystal dissolution is sufficiently slow that ascending, crystal-bearing magma may become superheated and yet fail to dissolve the crystal fraction before quenching; this may be the reason that olivine phenocrysts are often rounded.

Soils are the dominant terrestrial sink for carbon, containing three times as much C as above-ground plant biomass, and acting as a host for both organic and inorganic C, as soil organic matter and pedogenic carbonates, respectively. This article reviews evidence for the generation within the soil solution of dissolved C derived from plants and recognition of its precipitation as carbonates. It then considers the potential value of this process for artificially-mediated CO2 sequestration within soils. The ability of crops such as wheat to produce organic acid anions as root exudates is substantial, generating 70 mol/(y kg) of exuded C, equivalent to the plant's own ‘body weight’. This is still an order of magnitude less than measured C production from Icelandic woodlands (Moulton et al., 2000), which have no other possible source of C. Thus, there is apparently no shortage of available dissolved C, as bicarbonate in solution, and so the formation of pedogenic carbonates will be controlled by the availability of Ca. This is derived from mineral weathering, primarily of silicate minerals (natural plagioclase feldspars and pyroxenes; artificial cement and slag minerals). Within the UK, existing industrial arisings of calcium silicate minerals from quarrying, demolition and steel manufacture that are fine-grained and suitable for incorporation into soils are sufficient to account for 3 MT CO2 per year, compensating for half of the emissions from UK cement manufacture. Pursuing these arguments, it is shown that soils have a role to play as passive agents in the removal of atmospheric CO2, analogous to the use of reed beds to clean contaminated waters.

In the central granulite belt of Sri Lanka, garnet-pyroxene granulites of granitic and gabbro-noritic composition are the most abundant rock types. The micro-structures and mineral chemistry data prove complete attainment of textural and large-scale chemical equilibrium during and following a phase of extreme penetrative deformation at conditions of the granulite facies (800–850 °C, 5 to 9 kbar). On a local scale, especially along the intergranular system, continued cation exchange decoupling from the early ceasing net-transfer reactions destroyed the near-peak metamorphic equilibrium. The extreme compositional variation of the coexisting ferro-magnesian phases (Fe/(Fe + Mg): gar 0.98−0.65, opx 0.92−0.40, cpx 0.88−0.28) and the near-isothermal conditions of equilibration throughout the studied area enabled examination of the effects of non-ideal mixing in garnet and pyroxenes on the equilibrium constants of reactions used in geothermobarometry, and tests on the quality of commonly applied thermometers/barometers and the validity of activity models adopted in the calibrations. The Sri Lankan data set reveals more or less pronounced compositional dependences for all of the tested gar-opx/gar-cpx Fe-Mg exchange thermometers and the opx + plg ⇌ gar + qtz barometers. Evidently the recommended solution models do not adequately describe the mixing properties of the involved ferro-magnesium mineral phases (garnet, orthopyroxene and clinopyroxene).

In order to better understand the formation and evolution processes of ultrahigh pressure (UHP) felsic rocks, we determined the ages of various domains of zircon and monazite crystals from the diamondiferous quartzofeldspathic rocks of the Saxonian Erzgebirge. According to cathodoluminescence imagery and Th/U ratios, three zircon zones were distinguished. Each was dated using several spot analyses from a sensitive high-resolution ion microprobe analysing Pb, U and Th isotopes. The results were: (1) core zone – 21 analyses: Th/U ≤ 40.023 and 337.0±2.7 Ma (2σ, combined 206Pb/238U-207Pb/235U age); (2) diamond-bearing intermediate zone – 23 analyses: Th/U ≥ 50.037 and 336.8±2.8 Ma; and (3) rim zone – 12 analyses: Th/U = 0.015–0.038 (plus one analysis of 0.164) and 330.2±5.8 Ma. The U-Pb obtained ages are virtually concordant. Furthermore, two oscillatory zoned zircon cores (Th/U ≥ 50.8) yielded (~concordant) ages of ~400 Ma. Six SHRIMP analyses of monazites gave an age of 332.4±2.1 Ma. In addition, Pb, Th and U contents in monazite were analysed with an electron microprobe (EMP). A mean age of 324.7±8.0 (2σ) Ma was acquired from 113 analyses.

By combining the defined ages with previously published P-T conditions, minimum velocities for burial and exhumation were estimated. In addition, we present a likely geodynamic scenario involving age data from the literature as well as this study: beginning 340 million years ago, gneisses at the base of a thickened continentalcrust (~1.8 GPa, 650ºC) were transported to depths of at least 130 km, possibly as deep as 250 km. Here they were heated (>1050ºC) and partially melted and as a result began to rise rapidly. The burial and subsequent ascent back to a depth of 50 km, where zircon rims and monazite formed, took only a few million years and perhaps significantly less.

The solubility of arsenic in anoxic soil and sediment pore waters is strongly influenced by complexation with dissolved sulphide. Despite their importance in arsenic chemistry, thioarsenite complexes have not been well characterized, and considerable questions remain regarding their structure, protonation state, and relative stabilities. Here we use X-ray absorption spectroscopy to examine the type and structure of aqueous arsenic-sulphur complexes in sulphidic solutions under neutral to alkaline pH. Arsenic formed a variety of thioarsenites, including AsS(SH)(OH)—, As(SH)S22—, AsS33—and As(SH)4— complexes. The relative fraction of each species varied strongly with the S:As ratio — with the fraction of AsS(SH)(OH)— greatest at low S:As and trithioarsenites dominating As speciation when S:As ratios exceeded 3 in solution. As much as 40% of the total As also was present as AsS3S3+x(SH)3—x—x in solutions at S:As ratios of 3 or greater. Sulphide complexation was somewhat dependent on pH, with sulphide complexation generally increasing with pH. The speciation observed in these experiments is similar to, though distinct from, speciation predicted based on As2S3 solubility (inferred to contain AsS2— and AsS3S3+x(SH)—x3—x) and chromatographic separation of arsenic species (which does not identify polymeric species). Thus, these data indicate that stability constants for arsenic sulphide complexes must be reappraised.

Piston-cylinder cell assemblies experience inhomogeneous pressure distribution upon pressurization due to the variable compressibilities of the cell components. This results in the sample experiencing a pressure lower than expected, given the applied force of the piston. Although the effect is generally compensated for by applying a ‘friction’ correction, there have been wide variations in the corrections applied for some of the harder cell materials. We have determined friction correction factors for a range of cell assemblies commonly used in our laboratory relative to select well-characterized phase equilibria. Single-sleeve NaCl cells require, using the piston-in technique, very small corrections of the order −0.05 GPa for 12.7 mm diameter, and less for larger diameter assemblies. Four separate calibrations of the single sleeve 12.7 mm BaCO3 cell show that it requires a correction of −9%. This factor is entirely independent of temperature and pressure within the range 1000 to 1600°C and 1.5 to 3.2 GPa. This result is in contrast to the results of Fram and Longhi (1992) who claim that the correction for BaCO3 cells is highly dependent on pressure. For the assemblies included in this study there is an increase in the pressure correction required in the order of 12.7 mm diameter NaCl-pyrex −3%; 19 mm talc-pyrex −3.6%; 12.7 mm BaCO3 −9% and 12.7 mm BaCO3-silica glass −13%.

At the Ashanti concession, Ghana, gold-bearing quartz veins and disseminated sulphide lodes occur in narrow (1-3 m) shear zones with altered argillites and metatholeiite host rocks. The mineralisation is concealed by up to 10 m of kaolinite-mica forest ochrosol soils, beneath which is a saprolitic zone of leached rock extending down 60-70 m to the hypogene ore zone. In the unweathered hypogene orebody, gold occurs as free grains in quartz, as sub-microscopic inclusions in the disseminated arsenopyrite, as gold tellurides and as aurostibite. The gold is released from the hypogene orebody by physical dissaggregation and chemical dissolution, the latter involving hydroxyl, thiosulphate, cyanide, and fulvate complexing. Dissolution and reprecipitation of the gold appears to have taken place largely in situ with little evidence of supergene enrichment. Consequently, the gold mineralogy of the soils is complex with residual and secondary gold grains exhibiting widely different textural and compositional characteristics. Residually enriched grains display pitted, rounded surfaces and have silver-depleted rims, while supergene gold grains are compositionally homogenous and have unpitted surfaces. The supergene grains display platelet, dendritic, irregular and octahedral habit. A fine grained spongy form of gold has also been observed from weathered telluride-bearing quartz veins. Much of the secondary gold is intergrown with iron oxides and hydroxides. The gold mineralogy of the Ashanti soils appears to be controlled by physico-chemical processes active during the lateritic pedogenesis producing residual and supergene enrichment of gold.

Studies of the stability of the oxides schafarzikite, FeSb2O4, and tripuhyite, FeSbO4, have been undertaken to clarify the roles these secondary minerals may have in determining the dispersion of antimony in oxidizing environments. Solubilities were determined at 298.15 K in aqueous HNO3, and these data were used to calculate values of ΔGfϴ at the same temperature. The derived Δ Gfϴ (s, 298.15 K) values for FeSb2O4 and FeSbO4 are – 959.4±4.3 and – 836.8±2.2 kJ mol–1, respectively. These results have been compared with electrochemically derived data, extrapolated from 771–981 K. The present study shows conclusively that although the mobility of Sb above the water table is limited by simple Sb(III) and Sb(V) oxides and stibiconite-group minerals, depending upon the prevailing redox potential and pH, tripuhyite is an important ultimate sink for Sb in the supergene environment. It is highly insoluble even in strongly acidic conditions and its anomalous stability at ambient temperatures causes the common mineral goethite, FeOOH, to react to form tripuhyite at activities of Sb(OH)5(aq) as low as 10–11. The comparatively limited numbers of reported occurrences of tripuhyite in the supergene zone are almost certainly due to the fact that its physical properties, especially colour and habit, are remarkably similar to those of goethite. In contrast, the small number of reported occurrences of schafarzikite can be related to its decomposition to tripuhyite as redox potentials rise at the top of the supergene zone and the fact that it decomposes to sénarmontite, Sb2O3, in acidic conditions, releasing Fe2+ ions into solution. In general, the findings confirm the immobility of Sb in near-surface conditions. Geochemical settings favouring the formation of the above minerals have been assessed using the results of the present study and data from the literature.

Textural and chemical data are reviewed for amphiboles occurring in Cr-diopside series and Al-augite series xenoliths; as megacrysts in a variety of igneous environments; and also as minor phases in tectonic slices of upper-mantle peridotite. New data are given for pargasite and associated phases in a lherzolite from Tanzania and in kelyphite replacing garnet in a S. African kimberlite xenolith. It is concluded that only pargasites and titaniferous pargasites occurring in Cr-diopside series blocks have formed under upper-mantle conditions. Although amphibole is present in the upper mantle, as suggested by Oxburgh (1964), its relative paucity suggests it is not a major alkali and water storage site; phlogopite is a more likely candidate, particularly in the deeper parts of the upper mantle.

Taking advantage of the bent uranyl-peroxide-uranyl interaction found in studtite, 26 nanoscale clusters have been synthesized using uranyl hexagonal bipyramids. Sixteen of these clusters are built from uranyl hexagonal bipyramids only. Eight contain pyrophosphate groups that bridge between uranyl polyhedra, and two contain oxalate groups that adopt a similar structural role. These clusters contain from 20 to 60 uranyl polyhedra and have diameters in the range ∼1.5 to 3 nm. All spontaneously selfassemble in aqueous solution under ambient conditions.

A reproducible and simple protocol to synthesize and stabilize the metastable CaCO3·nH2O phase termed amorphous calcium carbonate (ACC) was developed in order to allow the characterization of its structure at the nanoscale using high-resolution microscopy combined with Raman spectroscopy and X-ray diffraction. ‘Stable’ ACC consists of relatively smooth spherical particles, 50—200 nm in size, that have XRD and Raman patterns with no intense peaks or sharp bands, as expected from amorphous material. Furthermore, high-resolution imaging also supports this finding but in addition, beam-damage induced crystallization and the concomitant formation of locally ordered domains in the ACC spheres are discussed.