Lapilli from the August 1966 eruption of the carbonatite volcano Oldoinyo Lengai consist of carbonate-cemented aggregates of (i) mono- and poly-mineralic fragments of ijolitic rocks, (ii) single grains and clusters of euhedral nepheline, Ti-andradite, and Ti-magnetite, and (iii) corroded pyroxene and wollastonite grains surrounded by coronas containing combeite, melilite, Ca-silicates (possibly larnite and rankinite), and rounded bodies of submicrometre intergrowths with complex bulk compositions dominated by Na,K,Ca-phosphate-carbonate and alkali-iron-sulphide-carbonate. The (ii,iii) materials, together with abundant Na-carbonate, sylvite and fluorite occurring as cement and shells in the lapilli, are attributed to mixing and incomplete reaction of ijolite and carbonatite magmas during the explosive eruption. The rounded submicrometre intergrowths are interpreted as the quench products of two types of immiscible liquids whose properties should be studied by controlled synthesis.

Fragments of a hydrothermal deposit, partly moulded on pieces of basalt lava, were dredged from the edge of the median valley in the centre of the Gulf of Aden. The deposit consists of two main components, manganese oxide in the form of spongy brown to hard black lumps and coatings, and friable green massive smectite. There are smaller amounts of an iron-oxide component, and mixed manganese-oxide-smectite material. Contents of the less mobile trace elements in the smectite are too low for it to have formed by alteration of basalt glass, and it is interpreted as a direct precipitate from hydrothermal solution. None of the components is enriched in Cu or Zn, or contains appreciable amounts of sulphur. If there are sulphides in this deposit, they must lie beneath the parts sampled.

Analytical transmission electron microscopy (ATEM) and X-ray absorption spectroscopy (XAS) have been used to determine the mineralogy of Pb-P deposits in the roots of the heavy metal tolerant grass cultivar Agrostis capillaris L. cv. Parys Mountain. The deposits have a pyromorphite (Pb5(PO4)3Cl)-type structure and composition although some of the Cl may be substituted by OH. Energy-dispersive mapping under the scanning electron microscope demonstrated that the majority of these deposits are present in the outer cell wall of the epidermis (the outermost layer of root cells). The phosphate composition of these grains contrasts with the phytate (C6H18O24P612−) composition of Zn-P deposits observed in similar electron microscopy studies. The physiological role of heavy metal P deposits is unclear. Heavy metal P precipitates may form actively as a tolerance mechanism to heavy metals or passively, sequestering P in a metabolically inactive form.

Granitic pegmatites are exceptional igneous rocks and the possible role of an immiscibility process in their origin is strongly debated. To investigate metal and metalloid behaviour in hydrous peraluminous systems (aluminium saturation index, ASI >1), we analysed 15 quartz-hosted primary melt and fluid inclusions from pegmatites in the Ehrenfriedersdorf Complex (Erzgebirge, Germany) and 26 primary melt inclusions from leucogranites of the Ehrenfriedersdorf district (Germany), Kymi (Finland) and Erongo (Namibia) by femtosecond laser ablation inductively coupled plasma quadrupole mass spectrometry. The results presented here for 32 elements provide evidence for metal and metalloid fractionation between two types of immiscible melts (A and B) and NaCl – HCl-rich brine in the pegmatite system. No evidence for the boundary layer effect was observed in the 40 – 500 μm size melt inclusions that were investigated. The data on the Ehrenfriedersdorf pegmatites allow quantification of the metal and metalloid partitioning between natural NaCl-rich brine and the two types of melt (e.g. KAsbrine/type-A,B melts = 0.01 – 1.7; KSbbrine/type-A,B melts = 10 – 285; KZnbrine/type-A,B melts ≥ 50; KPbbrine/type-A melt ≥ 50; KAgbrine/type-A melt = 46). These data are in accord with existing natural and experimental data on equilibrium fluid – melt partitioning as well as spectroscopic data on the metal and metalloid complexation in hydrous aluminosilicate melts and NaCl – HCl-rich fluids.

Gold mineralization at the Viceroy Mine is hosted in extensional veins in steep shear zones that transect metabasalts of the Archaean Arcturus Formation. The gold mineralization is generally made up of banded or massive quartz carrying abundant coarse arsenopyrite. However, most striking is a distinct suite of Au-Bi-Te-S minerals, namely joseite-A (Bi4TeS2), joseite-B (Bi4Te2S), hedleyite (Bi7Te3), ikunolite (Bi4S3), ‘protojoseite’ (Bi3TeS), an unnamed mineral (Bi6Te2S), bismuthinite (Bi2S3), native Bi, native gold, maldonite (Au2Bi), and jonassonite (AuBi5S4). The majority of the Bi-Te-S phases is characterized by Bi/(Se+Te) ratios of >1. Accordingly, this assemblage formed at reduced conditions at relatively low fS2 and fTe2. Fluid-inclusion thermometry indicates depositional temperatures of the main stage of mineralization of up to 342°C, in the normal range of mesothermal, orogenic gold deposits worldwide. However, melting temperatures of Au-Bi-Te phases down to at least 235°C (assemblage (Au2Bi + Bi + Bi7Te3)) imply that the Au-Bi-Te phases have been present as liquids or melt droplets. Furthermore, the close association of native gold, native bismuth and other Bi-Te-S phases suggests that gold was scavenged from the hydrothermal fluids by Bi-Te-S liquids or melts. It is concluded that a liquid/melt-collecting mechanism was probably active at Viceroy Mine, where the distinct Au-Bi-Te-S assemblage either formed late as part of the main, arsenopyrite-dominated mineralization, or it represents a different mineralization event, related to rejuvenation of the shear system. In either case, some of the gold may have been extracted from pre-existing, gold-bearing arsenopyrite by Bi-Te-S melts, thus leading to an upgrade of the gold ores at Viceroy. The Au-Bi-Te-S assemblage represents an epithermal-style mineralization overprinted on an otherwise mesothermal (orogenic) gold mineralization.

Quartz from different zones within five granitic pegmatites of the rare-element class from the Borborema Pegmatite Province in northeast Brazil were analysed for fourteen trace elements using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The concentrations of Li (6—150 ppm), B (1—9 ppm) and Ge (1—23 ppm) in quartz show a positive correlation with Al (30—770 ppm). The concentrations of these elements increase from the border zone to the quartz core of pegmatites of the spodumene or lepidolite subtypes. The Ge concentrations in the quartz core are the highest so far reported in igneous quartz. In the less evolved pegmatites of the beryl-columbite subtype, the Al, Li, B, and Ge concentrations in quartz from all zones remain at the same level as the border and wall zones. The Ti concentrations in quartz from the core of the more evolved pegmatites are below 3 ppm (with Al >250 ppm), contrasting with 7—25 ppm (with Al <280 ppm) in samples from the border and wall zones of the less evolved and more evolved pegmatites. The concentrations of Al. Li, B, Ge, and Ti in quartz are therefore confirmed as good indicators of the degree of magma fractionation and analyses of pegmatite quartz cores can be used for exploration purposes to distinguish pegmatites with high metallogenic potential. Atoms of Li and Al are incorporated into quartz such that Li/Al ranges between 0.75 and 1.0. This suggests a coupled substitution of the form Si4+ ↔ (Li+ + Al3+). The other elements analysed either showed an erratic distribution (e.g. Be and P) or were below the respective limits of detection (Na, K, Rb, Ca, Sr, Mn, Fe) in most samples.

A recent database and world distribution map of carbonatites supports previous observations of the spatial and temporal aspects of these rocks, and provides new observations that are important for understanding their petrogenesis. These data reveal that there is an overwhelming concentration of carbonatites in Precambrian cratonic areas, most of which are elevated topographically. Thus, although approximately two-thirds of carbonatites are Phanerozoic in age, at least 88% of all dated carbonatites are located in the cratons, demonstrating a remarkable tendency for a Precambrian host. This observation suggests a link with kimberlites as diamond-bearing kimberlites are confined to the Archaean areas of cratons. The age data show that in many carbonatite-bearing provinces there has been repetition of carbonatite emplacement, with up to five episodes separated by hundreds of millions of years. In at least three provinces such activity extends from the late Archaean to relatively recent times and, because of the drift of the plates, this would seem to preclude any direct role for mantle plumes in carbonatite genesis. Magmatism is activated when lithosphere lesions are reopened in response to major changes in global plate movement patterns.

This paper is based on microprobe analysis (Ta, Nb, Fe, Mn, Ti, W, Sn) and Fe3+ EPR spectra of cassiterite samples from 14 tin deposits from the Iberian Hercynian Massif. The interpretation of microprobe data, atomic ratios (Fe+Mn)/(Nb+Ta), and Fe3+ EPR spectra reveal that the coupled substitution: 3Sn4+ = (Fe,Mn)2+ + 2(Nb,Ta)5+ is dominant in cassiterites from pegmatites, and high-temperature quartz veins and in the dark zones of cassiterites.

The mechanisms:

2Sn4+ = Fe3+ + (Nb,Ta)5+ and

Sn4+ + O2− = Fe3+ + OH−

are dominant in those from medium-low temperature quartz veins and in the light zones of cassiterites.

Atoll garnet has been found in metabasites and quartz- and mica-rich rocks that have experienced low- to medium-temperature, high-pressure eclogite facies metamorphism in the Krušné Hory (Erzgebirge). They occur in several localities but are restricted to thin, texturally distinct zones, even on a thin-section scale. The mechanism of atoll garnet formation is documented by a series of micrographs and compositional maps and profiles of atoll garnet in combination with textural relations to other phases in the rocks. The core of full garnet or its relics in the atoll garnet have larger Ca and Fe, but smaller Mg contents, compared with the thin rim (ring). In addition to quartz, Na-Ca amphibole and phengite, the atoll cores are filled by a new garnet that has a composition similar to the outer rim. Formation of the atoll garnet is interpreted as resulting from fluid infiltration and element exchange between the garnet core and matrix, a process facilitated by a temperature increase during eclogite facies metamorphism. In addition to fluid access, the primary textures, mainly grain size, were also effective for the atoll garnet formation. Small grain fractions with thin rims were easily infiltrated by fluid, which used the short distance for element exchange between core and matrix. The core garnet was gradually dissolved and replaced by new garnet having the same crystallographic orientation as the rim or relics in the core.

This paper is primarily concerned with the interpretation of phenomena associated with phase transformations in single crystals, as observed by current experiments using electron-optical techniques. An analysis of permissible metastable behaviour in such single crystals, in terms of lattice theory, is provided. The dominant role of symmetry in defining the constraints on permissible be-haviour of this kind is explained. The resulting theory indicates that, at low temperatures, permissible thermal fluctuations in local chemical composition, or order, become strongly degenerate and lead to the development of non-Bragg diffraction effects. The theory and practical study of the phenomena by electron microscopy are also described.

The theory of metastable behaviour in a single crystal subject to symmetry constraints is then tested by re-examining the experimental data available for two systems that have been studied recently where such behaviour might be suspected. The first of these concerns the low-temperature behaviour of adularia, and the second deals with incipient exsolution phenomena in the alkali feldspar from a pantellerite. The data in each case appear to be compatible with the general theory proposed. Finally the theory is used to analyse the low-temperature behaviour of the intermediate plagioclase feldspars. In this case the theory indicates that both antiphase phenomena and schiller effects are associated with metastable behaviour in a system subject to strong symmetry constraints at low temperature. The implications of the analysis in relation to peristerite exsolution phenomena are discussed.

Infrared absorption spectra of the precipitated solids separated from aluminium-hydroxide solutions below the pH of minimum solubility of Al(OH)3 demonstrate the slow ageing of polymeric Al complexes to gibbsite. On comparison with the spectra of natural gibbsites, shifts in absorption frequency during crystal growth are interpreted in terms of changes in hydrogen bonding as a consequence of deprotonation and stacking of aluminium hydroxide layers to form gibbsite. In alkaline solutions the bayerite polymorph precipitates and IR frequencies are compatible with protonation as aluminate ions associate with the bayerite crystal having a lower crystal energy than its low pH polymorph. The infrared spectrum of nordstrandite, which is probably the stable polymorph in alkaline solution, shows evidence of strongly polarized hydroxyl ions similar to gibbsite.

Ferritchromite is rarely reported in forearc mantle peridotites. This contribution describes ferritchromite alteration and zoned Cr-spinel in serpentinites from the Rio San Juan Complex in the Dominican Republic. These rocks originated from the forearc mantle and protruded along lithosphere-scale faults in the mid Eocene. The cores of the Cr-spinel grains have Cr# ratios [i.e.atomic Cr/(Cr + Al)] between 0.48 and 0.66; such values are relatively high and are considered to represent primary compositions. Relatively high Zn contents in the grain cores (0.46 c 0.95 wt.% ZnO) are also thought to be primary; they reflect exceptionally cool conditions in the northern Caribbean forearc mantle. A progressive change in the zoning of Cr-spinel is recorded in the samples. Weakly zoned grains of Cr-spinel have rims with lower Mg# ratios [i.e.atomic Mg/(Mg + Fe2+)] and slightly higher Cr# ratios than the cores. More strongly zoned grains of Cr-spinel, in addition to low Mg# and high Cr# in their rims, have a marked increase in Fe3+# [i.e.Fe3+/(Fe3+ + Al + Cr)] of up to 0.35 in their rims and are partially coated by Mg-rich chlorite. All grains show core-to-rim decreases in their Zn content and increases in Ti, Mn and V. The association with Mg-rich chlorite and the compositional zoning are reminiscent of those reported for ferritchromite. Ferritchromite (with Fe3+# >0.5) is common in ultramafic rocks in amphibolite-grade terranes; however, the serpentinite samples described herein show little evidence of high-grade metamorphism. The lowtemperature serpentine-group mineral lizardite is dominant and high-temperature antigorite is either very rare or absent; other high-temperature minerals, such as talc, tremolite and cummingtonite, are trace constituents. The observed zoning in the Cr-spinel is thought to represent 'immature' ferritchromite, probably formed in response to a short-lived thermal event. This event appears to have been on too short a timescale to produce either proper ferritchromite or significant quantities of high-temperature minerals. It may be related to the emplacement of the nearby Rio Boba Intrusion, or the upward protrusion of the serpentinites along the lithosphere-scale Septentrional fault zone from the base of the mantle wedge through its hotter interior. We suggest that such alteration is rare in forearc serpentinites because they are not commonly heated during exhumation along the plane of subduction. This work demonstrates that Cr-spinel compositions can be modified by relatively low-grade metamorphism.

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 changes in olivine morphology and grain size upwards through comb-layered olivine eucrite and peridotite varieties of harrisite in the Rhum layered pluton are systematic, from abundant small granular crystals, to fewer and larger hopper crystals, to highly elongate branching crystals, which are preferentially elongate along the a axis and perpendicular to the plane of the layering. These changes have been reproduced in the laboratory by cooling water-bearing melts (P = 5 kb) of harrisite at 14 and 30 °/hr. These cooling rates represent maximum values for natural crystallization of comb-layered harrisite. Other experiments suggest that the oriented branching olivines in the rock crystallized at 30–50 °C supercooling. The results indicate that continuous, rather than abrupt, changes in the degree of supercooling and supersaturation of the magma can cause formation of comb layers. They also indicate that while field relations point to growth of most comb layers along a thermal gradient in the magma, this is not an essential condition for comb layer formation. Growth could be along a compositional gradient instead. During crystallization of a comb layer, both nucleation rate and the number of crystals suspended in magma close to the layer are essentially zero. Conditions initiating and terminating comb layer formation and the origin of the rapid vectorial crystallization are discussed. It is suggested that some comb layers could form without change in degree of supercooling, due to rapid removal of crystals suspended in the magma causing the enhanced growth rate and branching style of growth of the remaining crystals. Multiple origins of comb-layered rocks may therefore be possible.

W-bearing rutile formed during alteration of jarosite by resurgent hydrothermal fluids in the oxide zone of the Kori Kollo gold deposit. The rutile shows sector zoning in basal sections and well developed multiple growth zones, both defined in backscatter electron images by variations in the W content. The maximum WO3 content is 5.3 wt.% and W substitutes for Ti with double substitution of Fe to maintain charge balance. The causes of multiple growth bands are considered to be changes in externally controlled variables occurring in a shallow hydrothermal system. Whereas Ti is probably leached from biotite in dacitic rocks, the W is introduced by hydrothermal fluids.

Using high intensity beams of fast electrons, the transmission electron microscope (TEM) and scanning transmission electron microscope (STEM) enable comprehensive characterization of rocks and minerals at micrometre to sub-nanometre scales. This review outlines the ways in which samples of Earth and planetary materials can be rendered sufficiently thin for TEM and STEM work, and highlights the significant advances in site-specific preparation enabled by the focused ion beam (FIB) technique. Descriptions of the various modes of TEM and STEM imaging, electron diffraction and X-ray and electron spectroscopy are outlined, with an emphasis on new technologies that are of particular relevance to geoscientists. These include atomic-resolution Z-contrast imaging by high-angle annular dark-field STEM, electron crystallography by precession electron diffraction, spectrum mapping using X-rays and electrons, chemical imaging by energy-filtered TEM and true atomic-resolution imaging with the new generation of aberration-corrected microscopes. Despite the sophistication of modern instruments, the spatial resolution of imaging, diffraction and X-ray and electron spectroscopy work on many natural materials is likely to remain limited by structural and chemical damage to the thin samples during TEM and STEM.

Vaterite, the third unstable polymorph of CaCO3, is recognized by optical and X-ray powder techniques as a major constituent in a carbonated calcium silicate hydrogel complex formed from larnite at Ballycraigy, Lame, Northern Ireland. Re-indexed X-ray powder data obtained on synthetic vaterite are provided indicating a hexagonal unit cell with dimensions a = 7·135 Å. and c = 8·524 Å., Z = 6CaCO3. The re-indexing is endorsed by the results of electron diffraction study of synthetic vaterite. Vaterite is shown to correspond to the hypothetical CaCO3 member of the bastnäsite-synchisite mineral series on the basis of extrapolated cell dimensions and optical properties. A structural scheme for vaterite is proposed in which Ca layers replace the CeF layers in bastnäsite, and near-vertical CO3 groups are present. The stability relations of natural vaterite are discussed and comment made on the recent observation of vaterite, in a like environment, in carbonated cements and mortars.

The water-undersaturated melting relationships of an orendite (with 1.23% H2O as shown by chemical analysis) from the Leucite Hills, Wyoming, have been determined at pressures up to 30 kbar. The dominant liquidus and near-liquidus phases are leucite, olivine, orthopyroxene, clinopyroxene, and garnet. Leucite is stable only at pressures below 5 kbar, but at 27 kbar, minor olivine, orthopyroxene, clinopyroxene, and garnet crystallize simultaneously at or near the liquidus. The following reaction relationships occur with falling temperature in the orendite magma: (a) a reaction between olivine and melt to yield orthopyroxene at pressures above 12 kbar; (b) a reaction between olivine and melt to yield phlogopite at pressures below 12 kbar; (c) a reaction between olivine, orthopyroxene and melt to yield phlogopite and probably clinopyroxene at pressures above 12 kbar; (d) a reaction between leucite and melt to yield sanidine at pressures below 5 kbar. Electron microprobe analyses demonstrate that the ortho- and clinopyroxenes crystallized from orendite are aluminium-poor; the clinopyroxenes contain insufficient aluminium to balance sodium and titanium (Al < Na+2Ti) and these elements must either be partly balanced by (undetermined) chromium or ferric iron or be involved in substitutions which do not require trivalent ions for charge balance. The experimental results indicate that relatively silica-rich potassic magmas such as orendite form under water-undersaturated (essentially carbon dioxide free) conditions at pressures of about 27 kbar by small degrees of melting of phlogopite-garnet-lherzolite or by larger degrees of melting of peridotite which has been enriched in potassium and incompatible elements. The peralkalinity of some potassic magmas (such as orendite and wyomingite) could reflect a primary geochemical characteristic of the source rock, but could also result from the melting of phlogopite in the presence of residual pyroxenes. The association of silica-poor, mafic madupites and relatively silica-rich orendites and wyomingites in the Leucite Hills can be explained in terms of the relative effects of water and carbon dioxide on melting processes within the upper mantle.

Serpentine minerals and brucite in ultramafic rocks from the South Chamorro Seamount were characterized chemically to investigate the serpentinization of the Mariana forearc mantle. Relict primary minerals of the serpentinites are olivine, enstatite and minor Cr-spinel and diopside. The secondary minerals are mostly serpentine and brucite with minor magnetite. The serpentine minerals, mostly lizardite and chrysotile, display large compositional variations. Al2O3 and Cr2O3 contents depend generally upon the nature of the primary mineral from which the serpentine was derived. Both serpentine minerals and brucite exhibit wide Mg, Fe and Mn substitution: the Mg# ranges are 95.1–77.2 and 88.9–60.8, respectively. These mineralogical and chemical features allowed us to estimate an upper temperature limit for serpentinization of ∼200–300°C, in agreement with recent thermal models which suggest that the serpentinized mantle wedge of the Izu-Bonin-Mariana subduction zone is cold. The high degree of serpentinization (40–100%, average >75%), and the serpentine + brucite paragenesis of these ultramafics imply that the Mariana forearc mantle has a significantly reduced density and strength down to ∼30 km, which provides a driving mechanism for serpentinite diapirism. Pervasive serpentinization of the forearc by fluids released from the décollement zone also explains the low seismicity of the Izu-Bonin-Mariana subduction zone.

The structural and thermodynamic properties of minerals are strongly affected by cation site-ordering processes. We describe methods to determine the main interatomic interactions that drive the ordering process, which are based on parameterizing model Hamiltonians using empirical interatomic potentials and/or ab initio quantum mechanics methods. The methods are illustrated by a number of case study examples, including Al/Si ordering in aluminosilicates, Mg/Ca ordering in garnets, simultaneous Al/Si and Mg/Al ordering in pyroxenes, micas and amphiboles, and Mg/Al non-convergent ordering in spinel using only quantum mechanical methods.