The affinity between certain organic compounds and clays has been known for many years. Lloyd reported the adsorptive capacity of fuller's earth for alkaloids in 1916 without theorizing extensively about the mechanism. Smith reacted organic bases and their salts with bentonite and presented evidence that the reaction was one of base-exchange or metathesis, while Hauser has discovered that certain organic compounds of bentonite have the property of swelling and dispersing in organic liquids. This paper reports observations on the rather striking conversion of bentonite from the hydrophilic to the organophilic condition and proposes a mechanism to explain the observed phenomena.

Understanding the biogeochemical behaviour of arsenic in the weathering and shallow subsurface environment depends critically upon determining the nature and distribution of the chemical species present in natural waters. To this end, coupled ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS) is widely used, though species fractionation during ultrasonic nebulization, and matrix-dependent ionization in the plasma are analytical issues that need to be addressed. Hexapole collision cell technology is shown to be effective in suppressing chloride-based polyatomic interferences. Irrespective of the analytical technique used, As(III)/As(V) ratios of natural waters may change substantially during storage due to (1) differential adsorption of arsenic species on hydrated ferric oxides (HFOs); and (2) microbial activity. A wide range of apparently contradictory speciation changes observed by various workers can be rationalized in terms of the differences of microbial consortia present in different water samples. Arsenic speciation in certain water types can be stabilized for days or even weeks by combined filtration, acidification and refrigeration whilst the addition of EDTA and the use of 0.1 mm filters is indicated for iron-rich waters and waters with high activities of redox-active bacteria, respectively. Although the use of hydrochloric acid has been reported elsewhere as resulting in the apparent oxidation of As(III), we show that for certain water types it acts as an extremely effective preservative of arsenic speciation.

Mineral compositions of small peridotite bodies in an Ordovician collision zone of the Vermont Appalachians provide important clues to their tectonic environment of origin. The bodies have been deformed and partially serpentinized under greenschist- to lower amphibolite-facies conditions during the Ordovician and Devonian. Before serpentinization, the peridotite bodies were dunite as shown by their mineral assemblage and by their high MgO, and low Ti and Al whole-rock contents. Despite deformation and metamorphism, remnant olivine and spinel grains occur; their compositions are taken to represent conditions prior to regional metamorphic events. High Mg/(Mg+Fe) in olivine and very high Cr/(Cr+Al) in spinel indicate that the peridotites formed as highly-depleted mantle residues. The compositions are similar to those in harzburgite and dunite from some ophiolites and from fore-arc regions of subduction zones. Accordingly, the southern Vermont peridotites probably formed in a forearc, supra-subduction zone during the Early Palaeozoic. They were subsequently emplaced by obduction of the upper plate of an east-facing subduction complex.

Over 200 sediment samples taken from ten holes drilled in the Galapagos Hydrothermal Mounds Field during D.S.D.P. Leg 70 have been analysed for twenty-one elements. The three main sediment lithologies recognized are siliceous carbonate ooze, Mn-oxide crust, and an Fe-rich silicate (nontronite), the latter two being of hydrothermal origin. The major element composition of the hydrothermal deposits is similar in each mound hole, suggesting that formation conditions and hydrothermal solution composition have been constant both geographically and with time. The large variations which occur in the concentration of some trace elements in the Mn-oxide crusts and in transition metal ratios in the nontronite compared with the pelagic ooze suggests a hydrothermal supply to the mounds of Li, Mo, Pb, and Ba in addition to Mn, Fe, and silica.

The data are compatible with suggestions that the nontronite formed at depth in the pelagic sediment blanket by replacement of biogenic ooze, whilst the Mn crusts formed at or near the sediment-water interface. Pelagic sediments in the mounds which have not been replaced are similar in composition to pelagic sediments from non-mounds holes.

Electron-microscope observations of the oxidation products of olivine suggest that oxidation results in the formation ofplatelets of an ‘oxidized olivine’ phase, which has a superstructure of the olivine structure. Subsequently this intermediate phase breaks down by a cellular decomposition process to a eutectoidal intergrowth of magnetite and pyroxene. This intergrowth is responsible for the dendritic magnetite inclusions commonly observed in some olivines from Rhum.

Millimetric, ellipsoidal monazite nodules found within Lower Palaeozoic sedimentary rocks in Wales, south-west England and Brittany are characterised by a pronounced zonation of light and heavy REE, an inclusion fabric of low-grade metamorphic minerals indistinguishable from the host rock and a low Th content. They are interpreted as the product of in situ recrystallization of detrital monazites derived from pegmatitic or granitic source rocks and are potentially useful as indicators of Lower Palaeozoic sedimentary rock provenance.

In the Swedish KBS-3 repository concept, there is potential for gas to be generated from corrosion of ferrous materials under anoxic conditions, combined with the radioactive decay of the waste and radiolysis of water. A full understanding of the probable behaviour of this gas phase within the engineered barrier system (EBS) is therefore required for performance assessment. We demonstrate key features from gas transport experiments on pre-compacted Mx80 bentonite, under laboratory and field conditions, and discuss their implications in terms of a conceptual model for gas migration behaviour. On both scales, major gas entry is seen to occur close to the sum of the porewater and swelling pressures of the bentonite. In addition, gas pressure at breakthrough is profoundly sensitive to the number and location of available sinks for gas escape. Observations of breakthrough can be explained by the creation of dilatational pathways, resulting in localized changes in the monitored porewater pressures and total stresses. These pathways are highly unstable, evolving spatially and temporally, and must consequently influence the gas permeability as their distribution/geometry develops.

Such observations are poorly embodied by conventional concepts of two-phase flow, which do not fully represent the key processes involved. Although dilatancy based models provide a better description of these processes, the paucity of data limits further development and validation of these models at present.

Paragenetic, textural, and chemical characteristics of columbite-tantalite minerals are examined as steps towards identifying the metallogenetic processes of their host granitoids. Columbite-tantalite-bearing granitoids of the Eastern Desert province of Egypt can be categorized into: (i) metaluminous alkali granites; (ii) peraluminous Li-albite granites; and (iii) metasomatized biotite and/or muscovite granite (i.e. apogranites).

Columbite of the alkali granite is of FeNb2O6 composition and associated with annite. The low F and Li contents of the associated mica precludes the important role of these volatile elements during the late stage of evolution of the alkali granites, thus delaying fractionation of Mn over Fe and Ta over Nb.

Compositionally, columbite-tantalite of the Li-albite granites is constrained between MnNb2O6 and MnTa2O6 (the Ta/(Nb+Ta)atom. ratio ranges between 0.10 and 0.80). This low to high ratio and the association of columbite-tantalite with topaz, fluorite and lithian micas (in the series zinnwaldite-white mica) indicate a higher solubility for Ta-fluoride complex compounds and their more stabilized state at lower temperatures in Li- and F-rich sodic melts. The columbite-tantalite commonly exhibits a mottled or patchy zoned texture with the rims consistently higher in Ta than the cores, reflecting the later effect of a corrosive supercritical vapour phase.

The columbites of metasomatized granites range in composition between FeNb2O6 and MnNb2O6. They are characterized by high Ti and U, and low Ta contents (the Ta/(Nb+Ta)atom. ranges between 0.01 and 0.15), indicating deposition from alkaline (K+ Na+ -rich), and relatively high-temperature interacting fluids. However, the Mn-enriched columbites are commonly encountered in the apical parts of the apogranites and formed in response to high μKF and μLiF required for stabilizing the associated Li-siderophyllite or zinnwaldite. Columbites of the apogranites commonly exhibit progressive (either normal or reverse) zoning which can be attributed to the disequilibrium conditions (e.g. sudden change in the pH) between the growing crystal and the solutions.

The commissioning and operation of apparatus for neutron diffraction at simultaneous high temperatures and pressures is reported. The basic design is based on the Paris-Edinburgh cell using opposed anvils, with internal heating. Temperature is measured using neutron radiography. The apparatus has been shown in both on-line and off-line tests to operate to a pressure of 7 GPa and temperature of 1700°C. The apparatus has been used in a neutron diffraction study of the crystal structure of deuterated brucite, and results for 520°C and 5.15 GPa are presented. The diffraction data that can be obtained from the apparatus are of comparable quality to previous high-pressure studies at ambient temperatures, and are clearly good enough for Rietveld refinement analysis to give structural data of reasonable quality.

Jeffbenite, ideally Mg3Al2Si3O8, previously known as tetragonal-almandine-pyrope-phase ('TAPP’), has been characterized as a new mineral from an inclusion in an alluvial diamond from São Luiz river, Juina district of Mato Grosso, Brazil. Its density is 3.576 g/cm3 and its microhardness is ∼7. Jeffbenite is uniaxial (-) with refractive indexes ω = 1.733(5) and ε = 1.721 (5). The crystals are in general transparent emerald green.

Its approximate chemical formula is (Mg262Fe2+0.27)(Al186Cr016)(Si2 g2Al018)O12 with very minor amounts of Mn, Na and Ca. Laser ablation ICP-MS showed that jeffbenite has a very low concentration of trace elements. Jeffbenite is tetragonal with space group I42d, cell edges being a = 6.5231(1) and c = 18.1756(3) Å. The main diffraction lines of the powder diagram are [d (in Å), intensity, hkl]: 2.647, 100, 2 0 4; 1.625, 44, 3 2 5; 2.881, 24, 2 1 1; 2.220, 19, 2 0 6; 1.390, 13, 4 2 4; 3.069, 11,2 0 2; 2.056, 11,2 2 4; 1.372, 11,2 0 12.

The structural formula of jeffbenite can be written as (M1)(M2)2(M3)2(T1)(T2)2O12 with M1 dominated by Mg, M2 dominated by Al, M3 dominated again by Mg and both T1 and T2 almost fully occupied by Si. The two tetrahedra do not share any oxygen with each other (i.e. jeffbenite is classified as an orthosilicate).

Jeffbenite was approved as a new mineral by the IMA Commission on New Minerals and Mineral Names with the code IMA 2014-097. Its name is after Jeffrey W. Harris and Ben Harte, two world-leading scientists in diamond research. The petrological importance of jeffbenite is related to its very deep origin, which may allow its use as a pressure marker for detecting super-deep diamonds. Previous experimental work carried out on a Ti-rich jeffbenite establishes that it can be formed at 13 GPa and 1700 K as maximum P-T conditions.

Synthetic pentlandite surfaces were subjected to oxidation by a range of inorganic oxidants, and the resultant alteration of the surface studied by a range of surface-sensitive spectroscopic techniques. The oxidants used were air during heating to relatively low temperatures (150°C), steam, ammonium hydroxide, hydrogen peroxide, and sulphuric acid. Electrochemical oxidation was also undertaken. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), conversion electron Mössbauer spectroscopy (CEMS), and spectral reflectance measurements were used to characterize the surface compositions. New data for the binding energies of core electrons in pentlandite and violarite, based on the fitted XPS spectra, are proposed. For pentlandite and violarite respectively, values of 707.3 eV and 708.4 eV for the Fe 2p3/2, 853.0 eV and 853.2 eV for the Ni 2p3/2, and 161.2 eV for the S 2p in both sulphides, were obtained. After oxidation the pentlandite surfaces indicated nickel enrichment in the subsurface, with the formation of violarite. The immediate oxidized surface, of approximately 10Å thickness, indicated a range of iron oxides and hydroxides (Fe3O4, Fe2O3 and FeOOH, with possible Fe1−xO and Fe(OH)3), nickel oxide (NiO), and iron sulphates (FeSO4, Fe2(SO4)3). The proportions of the phases present in the surface layer are inferred to be a consequence of both the strength of the oxidant employed, and the thermodynamic stability of the phases, as can be illustrated using partial pressure and Eh/pH diagrams. A sequence of oxidation is proposed, accounting for the sub-surface enrichment in violarite, and the development of the oxidized surface, which is inferred to have a major affect on the rates of oxidation.

Cathodoluminescence (CL) imaging and spectroscopy are outstanding methods in several fields of geosciences. Cathodoluminescence can be examined using a wide variety of electron-beam equipment. Of special interest to geologists are optical microscopes (OMs) equipped with an electron gun. scanning electron microscopes (SEMs) and electron microprobes. Despite the similar kind of excitation, the results obtained may show marked differences. These are related to the use of focused or defocused as well as a scanned or stationary electron beam and the kind of signal acquisition. Images obtained by OM-CL (hot or cold acceleration) and SEM-CL differ due to different spatial resolution, true colour, grey-scale, or monochromatic detection, contrast inversion, phosphorescence effects, etc.

Instrumentation used for spectroscopic studies may differ in sequential or parallel signal acquisition, wavelength range, spectral resolution, and the kind of analytical spot limitation. This is particularly important when investigating transient CL, rare earth element (REE) emissions, or luminescence in the near UV and IR regions as well as samples with small grain sizes and contrasting CL behaviour of adjacent mineral phases.

In the present study, the influence of analytical parameters is demonstrated for certain mineral examples including zircon, fluorite, apatite, feldspar, quartz, corundum, kaolinite, and dickite.

Tertiary alkali basaltic rocks from the Southern Highlands, New South Wales, contain two types of clinopyroxene crystals, which exhibit excellent morphological development of hour-glass zoning. These are small, quench clinopyroxene crystals and large, abundant, euhedral phenocrysts. Electron microprobe analyses show that the different zone sectors derive from compositional differences, with variation in TiO2 and Al2O3 contents inversely with SiO2 content being most significant. Increased depth of colour of titanaugites depends on increased coupled substitution of Al for Si in tetrahedral sites and of Ti3− in an M1 site, while pleochroism is enhanced by increasing Fe content. It is suggested that the formation of hour-glass zoning is determined by an environment of crystallization where initial crystal growth is rapid relative to ionic diffusion in the melt, resulting in different chemistry for different growth directions within the crystal. This implies that, under certain conditions, kinetic factors, as well as the chemical composition of the host magma, may be significant in determining the chemical composition of phases precipitated, particularly where more than one crystallographic direction of growth is possible.

The accessory minerals rutile and apatite have been studied in 77 known porphyry copper deposits. Their value as indicators has been well established on the basis of specific chemical and paragenetic variations which they show.

Rutile occurs as the only Ti-mineral in the quartz-sericite zone, is dominant in the biotite-orthoclase zone, and is generally found in the inner fringes of the chlorite-epidote zone. It forms in these zones mainly as a result of the destruction of sphene, but also from biotite and hornblende.

The length: width ratio of rutile crystals is 1·5:1 in the centre of a porphyry system, increasing gradually outward to 2:1. A characteristic red colour displayed in thin section is attributed to a high copper content ranging from 100 to 500 ppm. The ratio of Cr+V:Nb+Ta is also unusually high.

Apatite shows evidence of a complicated history of corrosion and redeposition accompanied by outward migration during the life of the porphyry system. The migration parallels that of copper and typically extends far into the host rocks. The apatite is enriched in chlorine. A plot of a versus c shows a clear separation of apatites of various genetic types, including tin and molybdenum porphyries.

Electron probe microanalysis of tourmaline from late-stage aplites and mineralized (Sn-W) pegmatites from the Hub Kapong batholith of peninsular Thailand has revealed considerable chemical variation, and has shown that skeletal tourmaline crystals predominate within the pegmatites. The tourmalines show substitution towards the schorl end-member of the schorl-dravite series, as well as substitution towards alkali-free or proton deficient tourmaline. The extent of both substitutions increases (a) from aplites to pegmatites and (b) from core to rim within a single grain and so is believed to become greater with increasing degrees of differentiation of the aplite-pegmatite system. The development of skeletal crystals within the pegmatites and non-skeletal crystals within the aplites is believed to be due to the different kinetics of crystal growth obtaining within a hydrous, pegmatitic, fluid (viz. heterogeneous nucleation and comparatively rapid crystal growth rates) which in turn arise from differences in the structure of the aplitic magma and pegmatitic fluid. The observed chemical and morphological variation shown by the tourmalines is used to discuss the petrogenesis of the aplites and pegmatites, and associated ore deposits. During differentiation, the volatile content of the aplite magmas increased, leading to water saturation and the separation of a hydrous pegmatitic fluid. After a period of coexistence, possibly in chemical equilibrium, the crystallization of the pegmatites continued once the aplite magma had completely consolidated.

The importance of impact cratering on terrestrial planets is obvious from the abundance of craters on their surfaces. On Earth, active geological processes rapidly obliterate the cratering record. To date only about 170 impact structures have been recognized on the Earth's surface. Mineralogical, petrographic, and geochemical criteria are used to identify the impact origin of such structures or related ejecta layers. The two most important criteria are the presence of shock metamorphic effects in mineral and rock inclusions in breccias and melt rocks, as well as the demonstration, by geochemical techniques, that these rocks contain a minor extraterrestrial component. There is a variety of macroscopic and microscopic shock metamorphic effects. The most important ones include the presence of planar deformation features in rock-forming minerals, high-pressure polymorphs (e.g. of coesite and stishovite from quartz, or diamond from graphite), diaplectic glass, and rock and mineral melts. These features have been studied by traditional methods involving the petrographic microscope, and more recently with a variety of instrumental techniques, including transmission electron microscopy, Raman spectroscopy, cathodoluminescence imaging and spectroscopy, and high-resolution X-ray computed tomography. Geochemical methods to detect an extraterrestrial component include measurements of the concentrations of siderophile elements, mainly of the platinum-group elements (PGEs), and, more recently, chromium and osmium isotopic studies. The latter two methods can provide confirmation that these elements are actually of meteoritic origin. The Cr isotopic method is also capable of providing information on the meteorite type. In impact studies there is now a trend towards the use of interdisciplinary and multi-technique approaches to solve open questions.

Some 200 ultramafic xenoliths and their basaltic hosts from five French localities were studied. New analyses are presented, which show the five host-rocks to be nepheline- and olivine-normative. Seven bulk analyses of xenoliths from four localities, together with analyses of their constituent diopsides and, for six, of their orthopyroxenes, are also presented. Xenoliths from four occurrences appear to have equilibrated at pressures between about 8 to 18 kb at sub-basaltic solidus temperatures. Suites of xenoliths are chemically different. Histograms were used to determine compositions of depleted and ‘undepleted’ upper mantle. A suite of peridotite xenoliths from the Bult-fontein kimberlite pipe is no less depleted in fusible oxides than xenoliths from two French localities. ‘Undepleted’ upper mantle is very similar to ‘pyrolite’ in composition, except that the latter has much higher TiO2, Na2O, and K2O contents. No xenolith encountered in this work has a bulk composition that could yield more than 12% oceanic tholeiite on partial melting.

The Permian magmatic province of the Oslo rift, south-east Norway, includes large volumes of felsic and silicic rocks. Based on their geochemical character, these rocks may be divided into two main groups. The Larvik larvikites (monzonites) are highly enriched in large ion lithophile elements (LILE) (e.g. 10–32 ppm Th. 8–15 ppm Ta), and have an initial 87Sr/86Sr of 0.70391 ± 5. The syenites and granites have moderate to high concentrations of LILE (e.g. 7–88 ppm Th, 4–25 ppm Ta), and initial 87Sr/86Sr ratios between 0.705 and 0.707. The Larvik larvikites and extrusive equivalents (rhomb porphyry lavas) have similar initial Sr isotope ratios to uncontaminated basalts and gabbros in the rift, and are believed to have a mantle origin. The higher initial 87Sr/86Sr ratios in the silicic than in the felsic rocks reflect a crustal component representing the intermediate or low crust. After intrusion into the upper crust, the major and traceelement concentrations of the silicic magmas were modified through fractional crystallization dominated by removal of alkali feldspar, and transport of elements with a fluid phase. The silicic magmas appear not to have interacted significantly with the side rock at this stage.

The plagioclase-alkali-feldspar geothermometer formulated by Stormer (1975) does not take into account the effect of small amounts of calcium in the alkali feldspar. This geothermometer has been reformulated using ternary regular solution model equations, and it is shown that as the Ca content of the alkali feldspar increases the temperature calculated using the Stormer geothermometer will be increasingly too high.

The development of protocols for the identification of metal phosphates in phosphate-treated, metalcontaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy.

Mixed-metal hydroxylapatites in the binary series Ca –Cd, Ca –Pb, Ca –Sr and Cd –Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca –Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd5(PO4)3OH end member could not be synthesized as a pure phase. Within the Ca –Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations.

In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.