Fluid inclusions in quartz from internally zoned barren and spodumene-bearing pegmatites associated with the Leinster granite of SE Ireland represent a variety of early and late hydrothermal fluids responsible for the development of pegmatites. Microthermometry and optical examination reveal two main populations of inclusions. The first (Type 1) comprises low-moderate salinity brines which homogenized at temperatures up to about 400 °C. The second (Type 2) appear to postdate the first population and are characteristically more saline and homogenized at temperatures mostly below 250 °C. Isochores for model type 1 inclusion fluids indicate that a late-magmatic/early-hydrothermal fluid developed from the Leinster granite at 675 °C. and 2.5 kbar and cooled isobarically into the spodumene stability field where complete crystallization of the pegmatites took place. Later, more saline, type 2 fluids of unknown origin may have contributed to the alteration of spodumene to muscovite and albite with the accompanying release of lithium from the lattice of spodumene.

In the Fen complex (Telemark, S.E. Norway), carbonatites of different compositions have penetrated feldspathic fenites (alkali feldspar(s) + aegirine augite ± alkali amphibole) or older carbonatites, inducing different types of contact metasomatic alterations in their wall-rocks. (1) Pyroxene søvite has induced alkali metasomatism (i.e. fenitization s.s.), with alkali feldspars remaining stable and aegirine-augite transformed to nearly pure aegirine. (2) Søvite and dolomite carbonatite with phlogopite and/or alkali or alkali-calcic amphibole have caused replacement of feldspathic fenite by phlogopite, i.e. magnesium metasomatism. (3) Granular (dyke facies) ferrocarbonatite has increased the ferromagnesian components in calcite in wall-rock søvite. (4) Heterogeneous (pyroclastic) ferrocarbonatite induced pseudomorphic replacement of phlogopite by chlorite (leaching of alkalis). The different contact metasomatic processes reflect contrasts in compositional character among carbonatite magmas in the Fen complex, which may be evaluated in terms of differences in alkali and magnesium carbonate activities. The different types of carbonatite magma represent the products of local evolutionary trends, and are genetically related to spatially associated silicate rocks, rather than to a single ‘primitive’ carbonatite parent magma.

In ion microprobe analysis the specimen is bombarded with a focussed ion beam a few µm in diameter and the secondary ions produced are accelerated into the entrance slit of a mass spectrometer. An outline of the salient features of the instrument is given here, together with an account of the methods used for quantitative elemental and isotopic analysis.

The major part of this paper consists of a comprehensive account of the geological applications of ion microprobe analysis. These include elemental analysis, especially for trace elements (down to sub-ppm levels in many cases) and light elements (H-F) which are beyond the scope of the electron microprobe. The other main area of geological interest is isotopic analysis, where the ion microprobe has the advantage over conventional mass spectrometry of being capable of in situ analysis of selected points on polished sections, obviating the need for laborious specimen preparation, and enabling spatially-resolved data to be obtained, with a resolution of a few µm. The ion microprobe has been especially successful in U-Pb zircon dating and the study of isotope anomalies in meteorites. Other significant applications include diffusion and stable isotope studies.

The mechanism by which secondary porosity in sandstone reservoirs is produced is poorly understood. Previous hypotheses to account for the increased dissolution of framework silicates have invoked the introduction of acidic and/or organic-rich fluids capable of complexing metals. In order to evaluate the relative effects of these factors, the rates of K-feldspar dissolution have been measured at 70°C and 95°C, at pH values of 1, 4, and 9, with and without oxalic acid, at a total pressure of 50 MPa, using direct sampling autoclaves. The presence of oxalic acid increased the dissolution rate of Kfeldspar at pH 4 and 9, but decreased the rate at pH 1 at both temperatures. The maximum increase in dissolution rate was observed at pH 4, 95°C by a factor ∼4. In oxalic-free experiments, the rate of dissolution increased an order of magnitude with each unit decrease in pH in the pH regime 1–4. In the presence of oxalic acid, this dependency of dissolution upon pH decreased to approximately an order of magnitude increase with each decrease in pH by 2pH units. The dissolution process was observed to be stoichiometric under all conditions, indicating that the mechanism by which rates are increased was not due to preferential complexation of aluminium, but rather by an increase in the overall solubility of feldspar in the neutral pH region. This regime of increased rate of reaction of feldspar coincides with that expected to be naturally buffered by the introduction of organic acids into a sandstone reservoir system.

The Little Michiru complex is a composite intrusion of pyroxenite and pyroxene syenite which is located at the boundary between amphibolite and granulite facies gneisses in the Shire rift valley. Pyroxene and feldspar chemistry shows that the intrusion consolidated from two magmatic fractions, one a pyroxenite cumulate that equilibrated at 870–1000 °C, the other a partly anatectic pyroxene syenite magma which metasomatized the surrounding gneisses during granulite-facies metamorphism and equilibrated at a temperature of 730–830 °C at 7 kbar.

Spectral measurements of sunlight reflected from planetary surfaces, when correlated with experimental visible-near-infrared spectra of rock-forming minerals, are being used to detect transition metal cations, to identify constituent minerals, and to determine modal mineralogies of regoliths on terrestrial planets. Such remote-sensed reflectance spectra measured through earth-based telescopes may have absorption bands in the one micron and two micron wavelength regions which originate from crystal field transitions within Fe2+ ions. Pyroxenes with Fe2+ in M2 positions dominate the spectra, and the resulting 1 μm versus 2 µm spectral determinative curve is used to identify compositions and structure-types of pyroxenes on surfaces of the Moon, Mercury, and asteroids, after correcting for experimentally-determined temperature-shifts of peak positions. Olivines and Fe2+-bearing plagioclase feldspars also give diagnostic peaks in the 1 µm region, while tetrahedral Fe2+ in glasses absorb in the 2 µm region as well. Opaque ilmenite, spinel and metallic iron phases mask all of these Fe2+ spectral features. Laboratory studies of mixed-mineral assemblages enable coexisting Fe2+ phases to be identified in remote-sensed reflectance spectra of regoliths. Thus, noritic rocks in the lunar highlands, troctolites in central peaks of impact craters such as Copernicus, and high-Ti and low-Ti mare basalts have been mapped on the Moon's surface by telescopic reflectance spectroscopy. The Venusian atmosphere prevents remote-sensed spectral measurements of its surface mineralogy, while atmospheric CO2 and ferric-bearing materials in the regolith on Mars interfere with pyroxene characterization in bright- and dark-region spectra. Reflectance spectral measurements of several meteorite types, including specimens from Antarctica, are consistent with a lunar highland origin for achondrite ALHA 81005 and a martian origin for shergottite EETA 79001, although source regions may not be outermost surfaces of the Moon and Mars. Correlations with asteroid reflectance spectra suggest that Vesta is the source of basaltic achondrites, while wide ranges of olivine/pyroxene ratios are inconsistent with an ordinary-chondrite surface composition of many asteroids. Visible-near-infrared spectrometers are destined for instrument payloads in future spacecraft missions to neighbouring solar system bodies.

Three voluminous Quaternary phonolitic pumice fall deposits erupted from the compositionally-zoned Tenerife magma chamber exhibit variability in Sr and Pb isotope ratios. It has been previously argued that the Sr isotope variations are due to syn-eruptive interaction between magma and hydrothermal fluids (Palacz and Wolff, 1989). Pb compositions are not correlated with Sr, and are believed to reflect magmatic values. Pb isotope ratios exhibit regular variation with degree of fractionation, and one zoned deposit is heterogeneous in Pb. The highest values seem to characterize the most fractionated upper parts of the zoned system. This is unlikely to be a consequence of magmatic recharge. Isotopic and trace element behaviour is instead consistent with combined assimilation and fractional crystalliza- tion, involving the recycling of material containing relatively radiogenic Pb, from within the volcanic edifice. Assimilation of sediment intercalated within the submarine portion of the pile is ruled out by the isotopic data. The most probable contaminant is a felsic igneous rock. Early trachytes reported by Sun (1980) have the required Pb isotope compositions and may approximately represent the assimilant.

An apparatus is described for the measurement of the rates of fast precipitation reactions. It consists of a T-tube, where reactants are added to the arms of the T, mixed rapidly at the junction, and the rates of disappearance of reactants or appearance of products are measured along the stem of the T. The geometry of the system results in a steady state being established in the apparatus, enabling detailed analysis of reaction progress. The apparatus has been used to investigate the kinetics and mechanism of iron sulphide precipitation reactions. It has enabled measurements to be made with relatively high precision and good accuracy of the first 130 ms of reaction time.

X-ray photoelectron spectroscopy can be used to measure the ionization energies of electrons in both valence band and core orbitals. As core vacancies are the initial states for X-ray emission, a knowledge of their energies for all atoms in a mineral enables all the X-ray spectra to be placed on a common energy scale. X-ray spectra are atom specific and are governed by the dipole selection rule. Thus the individual bonding roles of the different atoms are revealed by the fine structure of valence X-ray peaks (i.e. peaks which result from electron transitions between valence band orbitals and core vacancies). The juxtaposition of such spectra enables the composition of the molecular orbitals that make up the chemical bonds of a mineral to be determined.

Examples of this approach to the direct determination of electronic structure are given for silica, forsterite, brucite, and pyrite. Multi-electron effects and developments involving anisotropic X-ray emission from single crystals are also discussed.

A combination of ion-microprobe (for Li) and electron-microprobe (for other major elements including F) methods has been used to analyse Li-rich micas from the S.W. England batholith (mainly the St Austell granite) and the Massif Central, France. Rocks showing various degrees of hydrothermal alteration were studied in order to separate the original compositional trends from alteration trends. The original compositional trend is essentially one of increasing Li with increasing degree of evolution. The main atomic substitution in the original micas is 3Li substituting for A1 and 2 vacancies in octahedral sites; substitution of Li for R2+ (Fe, Mn, Mg) in octahedral co-ordination is generally subordinate. Alteration trends involve a loss of Li, Fe, F, Rb and Cs, and a gain in A1. The effects of volatile elements on phase relations of granites are reviewed and it is concluded that the original Li-micas were primary, i.e. crystallized from the melt. It is suggested that the late-magmatic stage passed transitionally into the hydrothermal stage leading inevitably to subsolidus recrystallization (autometasomatism) of the primary minerals, so introducing further textural and mineralogical complexities to the rocks.

Homogeneous and heterogeneous phase relationships in the alkali feldspars are reviewed, and behaviour diagrams developed. Al,Si ordering is almost certainly continuous and higher order in both albite and potassium feldspar and has been established reversibly or nearly so down to below 500°C in albite and possibly to ∼ 200°C in potassium feldspar. The degree of order in intermediate albite changes strongly over a range of ∼ 75–150°C depending on pressure, low albite being stable up to about 620–650°C and high albite above about 725°C at low pressure. Symmetry is broken at ∼ 980°C mainly by a cooperative shearing of the whole framework and not by Al,Si ordering alone; there is a thermal crossover near 700°C shearing being dominant above (high albite) and ordering dominant below (intermediate albite).

In potassium feldspar symmetry is broken by Al,Si ordering at a temperature of about 500°C The change in degree of order with respect to temperature has been followed easily and reversibly in sanidine from ∼ 1075 to ∼ 550°C and to a lesser extent in microcline from 450 to 200°C. Ordering rates in sanidine down to 500°C and ordering rates in microcline between 450 and 200°C are almost as fast as in albite. Ordering in sanidine at 500°C and below slows and then stops with the development of the tweed orthoclase domain texture. The tweed texture acts as a barrier to further order because the strain energy associated with the (incipient) twin domain texture balances or nearly balances the free energy decrease resulting from ordering. Ordering stops not because of the kinetics of Al,Si diffusion, but because the total driving force is very small or nil. Ordering can readily proceed to completion, with the formation of low microcline, only if the domain-texture barrier is overcome by processes involving fluids or strong external stresses. There is no barrier in albite.

The symmetry-breaking process in alkali feldspar changes with composition from mainly shearing in albite to ordering in potassium feldspar. Symmetry is broken equally at a compositional crossover (metastable with respect to exsolution) near Ab80-75 at low pressure and progressively displaced towards Or at higher pressures. Ordering in pure albite occurs by a (nearly) one-step path which progressively becomes two-step with substitution of Or. Diagrams showing the near-equilibrium variation of the order parameters at low pressure with composition and T are given, as well as two extreme phase and behaviour diagrams for complete coherent and complete incoherent (strain-free) relationships. These diagrams can be used to understand feldspar relationships and microtextures in hypersolvus and subsolvus rocks, the occurrence of orthoclase, and of intermediate and low microcline.

Ore microscope and electron microprobe investigations on Zn-Pb-Ag ores from B Zone in Silvermines, Ireland, have shown the presence of two As-Sb-Ag phases; a tetrahedrite-group mineral with composition Cu6.3Ag3.7Fe0.9Zn1.2As2.2Sb2.1S12.7 and proustite-pyrargyrite (Ag3As0.5Sb0.5S3). It is postulated that both phases inherited their As and Sb from primary geocronite (Pb14.5As3.4Sb2.6S23) and that they are metastable. An enrichment in Ni in the ores is due to very fine to submicroscopic intergrowths of gersdorffite (Ni0.6Fe0.4AsS) with geocronite and with galena.

Several examples of magma mixing exist within the undersaturated alkaline magma series of the Tertiary/Quaternary volcanics in the French Massif Central. This study describes magma mixing in the Puy Griou/Griounot area of the Cantal volcano (10-3 Ma). Petrographic evidence for injection of blebs of basic magma into phonolitic host magmas is abundant (cauliform inclusions, liquid-liquid contacts, vesiculation and chilling). Compositions of the inclusions are basic tephrite, whereas the hosts are miaskitic phonolites. Petrographic examination reveals the presence of disequilibrium mineralogical features (e.g. Mg-rich olivine in phonolites) and strong zoning in many clinopyroxenes. Transfer of phenocrysts between basic inclusions and phonolite hosts was common, and can be seen clearly in the wide range of compositions of clinopyroxene. Hornblende, magnetite and olivine were also transferred from inclusions to host.

Sr and Nd isotope data indicate that, unlike most other fractionated magmas of the region, phonolites which show evidence for magma mixing are uncontaminated by the continental crust and have isotopic ratios similar to local primitive basic magmas. This leads to the suggestion that the magma mixing event took place at great depth, rather than being a high-level phenomenon. The phonolites were thus generated by high-pressure fractional crystallisation of an earlier basanitic or tephritic parent, perhaps at upper-mantle depths. This conclusion may explain why some phonolites elsewhere in the world have entrained spinel Iherzolite mantle xenoliths.

Titanomaghemite occurs in a relatively fresh doleritic intrusion in an area of Precambrian gneiss in Minas Gerais, Brazil. It hosts exsolution lamellae of ilmenite and contains more than 90% of the iron in the ferric form. It is more resistant to weathering than the ilmenite and is inherited virtually unaltered by the resulting soils. Titanomaghemite, extracted as grains from a weathered rind of the rock, has lattice parameter a0 = 0.8348(3) nm and has a canted spin structure due to substitution of non-magnetic ions on tetrahedral and octahedral sites of the spinel structure. The average canting angle is 32 ± 3° and canting occurs predominantly on the octahedral iron sublattice. Its formula, based on microprobe analysis and Mössbauer spectroscopy may be expressed as:

where [] and {} denote ions on tetrahedral and octahedral sites, respectively. The spontaneous magnetization of the mineral is 36(3) J/T/kg.

Compositional data are presented for Nb-Ba-K-V titanates from micaceous kimberlite (Star mine, S. Africa). These data significantly extend the previously known range of solid solutions in naturally occurring members of the hollandite group. Two distinct suites of crystals occur. One is a suite of primary groundmass prismatic crystals that are Ba-K-V-rich and represent solid-solutions from the priderite series towards mannardite. The second suite consists of anhedral xenocrysts that are Ba-free. In this suite relatively Nb-rich varieties (>4.0% Nb2O5) represent solid-solution towards a niobian-bearing potassian analogue of mannardite, whereas relative Nb-poor (<3.0% Nb2O5) varieties are Nb-bearing vanadian priderites. These hollandite-group minerals have compositions that differ significantly from priderites found in lamproites.

A wide range of natural K-, Na-, Ca- or (K + Li)-micas have been systematically examined by Raman spectrometry. The spectra are interpretable in terms of regular variations in peak positions and chemical parameters. Several vibrations give higher wavenumbers for Na-micas compared to K-micas, in accord with the smaller ionic size of Na+ than K+. The ≈195 cm-1 and ≈270 cm-1 peak wavenumbers and intensities vary as functions of the chemistry of the octahedral sites, i.e. the replacement of Mg2+ by Mn2+, Zn2+, Cr3+, Fe3+, Ti4+, and especially by Al3+, or by a vacancy, and the replacement of (OH)- by F-. The group of ≈700 cm-1 peaks vary in wavenumber and intensity with the replacement of Si by Al in the tetrahedra; distinct Si-O-Si and Si-O-Al vibrations can be recognized. Di- and tri-octahedral micas are distinguished on the basis of certain relative peak intensities which vary considerably with polarization direction, and of trends with increasing Al(iv), Al(vi) or Al(tot.). Calibration of these trends for the chemical analysis of mica microinclusions seems feasible once the uncertainties in the data set are resolved by the determination of further samples selected to highlight the effect of specific elements.

The new mineral bernardite has been identified on one specimen from Allchar, Macedonia, Yugoslavia, together with orpiment and realgar. It forms black crystals, the size of which may exceed 1 mm. The streak is deep red; on an arbitrarily oriented section R(589nm) ranges from 23.8 to 24.7% in air, from 10.2 to 11.6% in oil. Microprobe analyses together with an X-ray structure analysis suggest the ideal formula TlAs5S8, with a possible replacement of As by Sb up to 15 wt. %. Monoclinic; a 15.647(4), b 8.038(3), c 10.750(3) Å, β 91.27(3)°; space group P21/c; Z = 4; R = 0.049, wR = 0.036 for 2410 reflections. The atomic arrangement consists of a 3-dimensional As5S8 framework with eight-coordinated T1 in its holes. The mineral is named for Doc. Dr Jan H. Bernard, Prague, Czechoslovakia.