Tritin(II)dihydroxyoxosulphate, Sn3O(OH)2SO4, is a rare corrosion product found on the surfaces of certain tin alloys. A new synthesis based on the hydrolysis of SnSO4 is described. The stability constant determination of Sn3O(OH)2SO4,s, at 298.2K and 105Pa is determined using direct measurements via electrodes, of the activities of tin(II) and sulphate ions. ΔfG0(298.2K) is equal to −1563.1 ± 0.9 KJ mol−1.

Magnetite—apatite deposits associated with the Atacama Fault Zone of northern Chile are interpreted here, on field criteria, as being the products either of hydrothermal fluids with a strong magmatic signature, or of late-stage Fe-rich magmas mixed with an aqueous fluid. Even in the Chilean iron belt, apatite-rich magnetite deposits are a rarity. Variations in F- and Cl- contents in apatites, strongly zoned with respect to halogens, are indicative of primary variations in fHF and fHCI in the hydrothermal fluids. Small variations in halogen fugacities in the aqueous fluid are capable of buffering large variations in halogen content within apatite crystals in equilibrium with that fluid. The recorded halogen zonation profiles are inconsistent with crystallization of the apatites simply from a volatile-rich, late-stage fractionation Fe-rich magma, or its derived magmatic vapour. It is more likely that they are the result of mineral—fluid buffering with a fluid that represents the mixing of a magmatically-derived aqueous fluid with a meteoric fluid that has variably scavenged Ca and Cl from within the country rocks. The source magma of the former is probably an Fe-P enriched acidic magma, derived by fractionation of primary calc-alkaline basic magmas.

Wedge-shaped layers of ultramafic and mafic cumulates in Intrusion II of the Caledonian Honningsvåg Intrusive Suite suggest crystallization on an inclined magma chamber floor from a compositionally-zoned and density-stratified magma.

Cyclic unit 8 (140–100 m thick) consists of a distally-thinning olivine gabbro (denoted paoC) macrolayer overlain by a distally-thickening gabbronorite, pahC. New mineral data in four traverses across cyclic unit 8 show systematic compositional changes; the Mg# of the mafic phases decreases upwards through the unit and distally, both along the base and along the paoC/pahC interface.

A crystallization model based on an effectively continuously-zoned magma chamber with numerous, relatively thin, double-diffusive magma layers is proposed. Differential migration of horizontal isopleths (e.g. Mg# and aSiO2) in response to fractional crystallization and assimilation of country rock can explain the variations in the Mg# of the cumulates.

The crystal-chemical relationships occurring within a single grain of monazite-(Ce) from Vetralla, Vico Volcanic Complex, north of Rome, are outlined. The sample is from a miarolitic cavity in a holocrystalline ejectum consisting of K-feldspar plus minor plagioclase, mica and Fe-oxides, collected from a pyroclastic explosive level. The Gandolfi film (Cu-Kα radiation) can be indexed in space group P21/n with a = 6.816(4); b = 6.976(4); c = 6.471(3) Å; β = 103.63(3)°; V = 299.0(6) Å3. Electron-probe microanalyses plot within the field of monazite along the huttonite-monazite edge of the huttonite-monazite-brabantite triangle. Despite patchy and irregular zoning, the grain shows a clear enrichment towards pure monazite at the outer rim. A constant Th:Si ratio of 1:1 indicates the existence of a simple solid-solution between huttonite and monazite. The substitution can be written as Th4+ + Si4+ → REE3+ + P5+ without requiring any electrostatic compensation by divalent cations, or by anionic groups. The REE distribution pattern is compatible with that of monazites from syenitic rocks.

Frankamenite, K3Na3Ca5[Si12O30]F3(OH)1H2O, from the Yakutian charoitic rocks, has a triclinic unit cell with the dimensions: a = 10.094(3), b = 12.691(3), c = 7.240(1) Å, α = 90.00(2)°, β = 111.02(2)°, γ = 110.20(2)°, sp.gr. = P1, Z = 1. Its crystal structure has been refined to Raniso= 0.059 (Rw = 0.060) using the intensities of 2563 reflections.

The bases of the structure are zig-zag walls of Ca, Na octahedra joined by infinite octagonal cross-sectioned tubes of SiO4 of the composition (Si12O30). Unlike canasite from the Khibini Mountains, the triclinic cell of frankamenite contains only one silicate tube. The atomic coordinates, interatomic distances and angles are topologically similar to those of canasite. Major differences are observed in the distribution of octahedral cations, which reflect the different anion compositions. Frankamenite exhibits six mixed Ca-Na positions, whereas canasite has only one such position. The H2O molecule is located in the centre of the silicate tube between K+ cations.

Silicate minerals grown from glasses, and rapidly cooled melts, often have non-compact branching or ‘spherulitic’ morphology. The branching patterns are observed in volcanic rocks, glasses, meteorites, slags and sometimes in shallow level intrusive rocks. Experiments, observations, theory and simulations all support the concept that the crystal morphology is the result of growth under diffusion limited conditions. We show that in a silicate melt under appropriate conditions the equations for heat transfer and chemical-diffusion reduce to the Laplace equation. This means that the temperature or chemical gradient is a steady state field. Interaction between this field and a random variable (Brownian motion of growth species) is modelled and yields complex branching objects. The growing cluster affects the field such that an in-filled structure cannot be formed. The branching structures of the model crystal are remarkably similar to those formed in nature, and to those produced in laboratory experiments, implying that the model captures the essence of the branching-growth process.

Chernikovite and meta-ankoleite were synthesized with a relatively high crystallinity and the compounds were identified by means of chemical analysis and X-ray diffraction. The infrared spectra were recorded and the bands assigned. From the luminescence spectra, the band-gap energy for both compounds was calculated as 2.35 eV, indicating that they must be considered as insulators. The dependence of the solubilities of these compounds on the acidity of the solution was studied, and the dominant ionic species were determined. The pKsp values of chernikovite and meta-ankoleite were found to be 22.73±0.24 and 24.30±0.81 respectively.

Field relations in the upper part of Intrusion II of the Caledonian Honningsvåg Intrusive Suite show that some peridotite sheets transgress, and include in situ rafts of, the adjacent gabbroic cumulates. Modal and textural analyses of three olivine melagabbro sheets show non-cotectic mineral proportions that are likely to result from crystal-melt reactions. Discordant, replacive fingers and pipes of feldspathic peridotite along interfaces between peridotite and overlying olivine melagabbro also suggest crystal-melt reactions.

It is proposed that several picritic sills intruded porous gabbroic cumulates in the upper part of Intrusion II. Lateral infiltration of picritic magma led to crystal-melt reactions, mainly assimilation of plagioclase and precipitation of olivine, resulting in the formation of olivine melagabbro and peridotite sheets, and replacive fingers and pipes of feldspathic peridotite.

Pyrrhotites in polished sections from more than twenty stratabound massive sulphide and magmatic nickel-copper deposits in Norway were studied under the microscope using the magnetic colloid method. In both types of deposits, two distinct styles of intergrowths between monoclinic and hexagonal pyrrhotites were found: crystallographically-controlled lamellar intergrowths and fissure-controlled irregular intergrowths.

Lamellar intergrowths consist of crystallographically oriented monoclinic lamellae occurring in a hexagonal matrix and were produced originally by exsolution from hexagonal pyrrhotite on cooling. Irregular intergrowths comprise blades and patches of monoclinic pyrrhotite occurring along fissures and grain boundaries of hexagonal pyrrhotite, and were formed by interactions between hexagonal grains and sulphur-rich hydrothermal solutions.

Increase in lamella thickness and spacing, development of lamella zonations, wedge-shaped composite ends, boxworks and composite lamellae were caused by progressive lamellae coarsening and maturation during natural annealing, which could have been promoted by anisotropic stress. Metamorphic recrystallization and annealing tend to homogenize pyrrhotite and erase preexisting exsolution lamellae.

Electron-microprobe analyses of muscovite, biotite, and feldspar are reported for the stratiform Yindongzi—Daxigou Pb—Zn—Ag and Fe deposits of Qinling, northwestern China. The micas are characterized by high Ba levels in banded albite-carbonate rocks that host the deposits. The biotite is also rich in Cl, as is biotite in the nearby Tongmugou Pb-Zn deposit, although biotite and muscovite from this deposit lack Ba enrichment. It is likely that the Ba-rich micas in the Yindongzi-Daxigou deposits formed contemporaneously from the diagenesis and/or regional metamorphism of hydrothermally altered clay minerals, with the barium being derived from entrained pore fluids that may represent relict hydrothermal fluids associated with ore deposition. During the formation of coexisting muscovite and biotite, barium is preferentially partitioned into muscovite and chloride into biotite. Together with the presence of baryte rocks in the bedded ores, these data suggest that ore deposition in the Yindongzi—Daxigou deposits took place in a more oxidising environment than in the nearby Tongmugou deposit. This difference is attributed to the contrasting sedimentary environments of the two deposits, with the Yindongzi—Daxigou deposits having formed under shallow, oxic conditions and the Tongmugou deposit under deeper, anoxic conditions.

The Shiant Isles Main Sill, of Tertiary age, is a classic example of a composite, differentiated alkaline basic sill. The first unit to be intruded was a 2 m thick olivine teschenite which was emplaced with phenocrysts of olivine (mg > 83) [mg ≡ Mg#] and, perhaps, plagioclase. This was intruded by a 24 m thick picrite sill consisting of a mush of melt and suspended olivine phenocrysts (mg > 83) with a D-shaped modal profile. The 140 m thick picrodolerite-crinanite unit was formed by a magma carrying ∼ 10% olivine (mg > 83) as the main phenocryst phase, together with some calcic plagioclase phenocrysts, being emplaced into the top of the picrite unit before the host rock was completely solidified. The olivine phenocrysts settled towards the bottom to form the picrodolerites. In-situ differentiation processes occurred under conditions of almost perfect fractional crystallization, during which very strongly zoned ophitic crystals of olivine (fayalitic rims) and clinopyroxene (hedenbergitic rims), and zoned laths of plagioclase (anorthoclase rims), formed. The last unit consists of ∼ 2 m of granular olivine picrodolerite which was intruded into the upper crinanites, again before the host rock was fully solid.

The mineral zoning patterns are interpreted using published cation diffusion coefficient data, and used to show that the picrite unit might have cooled to the blocking temperatures for Mg and Fe diffusion in < 5 years, and that even the relatively thick crinanite unit cooled very fast, so preserving the zoned Fe-Mg olivine and pyroxene compositions. The compositions of coexisting ilmenites and spinels define a redox trend which initially lies close to fayalite-magnetite-quartz buffer conditions, but later becomes more reducing and approaches magnetite-wustite buffer conditions. The final stages of development occurred during sub-solidus deuteric processes and involved formation of analcime and zeolites, as well as localized sulphide mineralization.

Pyroxene and mica found in plutonic rocks of the Little Murun ultrapotassic pluton exhibit trends of compositional evolution that permit evaluation of the differentiation sequence of the complex. Pyroxene evolves from diopside in kalsilite and phlogopite pyroxenites through aegirine-diopside in shonkinite to aegirine in late stage charoitite and evolved hypabyssal rocks. The compositional trend is unusual in that the hedenbergite content of the pyroxenes never exceeds 15 mol.% and is thus unlike pyroxene compositional trends found in sodic alkaline complexes. Mica is Al- and Ti-poor and ranges in composition from Fe-rich phlogopite through biotite towards tetraferriannite. Compositional trends of mica found in ‘lamproite-like’ hypabyssal rocks are identical to those observed in the micaceous plutonic rocks; hence the former are considered to be representatives of the lamprophyric facies of the magmas which formed the plutonic series.

Bismuthinite-bearing quartz veins from the Alston Block of the North Pennine Orefield are all close to, or above, the Rookhope and Tynehead cupolas of the buried Weardale Granite. They are uniform in composition and paragenesis and are earlier than the main fluorite-baryte-galena-sphalerite mineralization of the orefield. Rhythmical crystallization of quartz, chalcopyrite and minor pyrite is followed by fluorite-quartz-chalcopyrite-minor sphalerite-altered pyrrhotite mineralization. Early tin-bearing (up to 0.29 wt.% Sn) chalcopyrite encloses trace amounts of bismuthinite (Bi2S3), synchysite (CaREE(CO3)F2), argentopentlandite (Ag(FeNi)8S8) (close to being stoichiometric), pyrrhotite, cubanite and cosalite (Pb2Bi2S5), while early pyrite carries monoclinic pyrrhotite (close to Fe7S8) and tungsten-bearing cassiterite (up to 1.03 wt.% WO3). Bismuthinite is macroscopically visible and is associated with native bismuth and small, fine-grained, spherical aggregates that qualitative analysis suggests may be cosalite crystals. Synchysite and more rarely monazite, xenotime and adularia are intergrown with bismuthinite. These mineralogical data form part of the basis for an increasing awareness of the contribution of the Weardale Granite to the early phases of mineralization in the Alston Block.

A natural Mg-Al-Fe spinel from the Balmuccia peridotite (Italian Western Alps) was annealed at T between 650 and 1150°C, under controlled oxygen activity, and quenched in H2O. Twenty-three cation distributions were calculated from XRD structural refinements in tandem with microprobe analysis, and verified by Mössbauer spectroscopy in the case of unheated samples.

Unheated crystals showed essentially ordered distribution of Fe3+ in octahedral and Fe2+ in tetrahedral sites, the only intracrystalline disorder being represented by ∼0.12 atoms per formula unit of [4]Al and [6]Mg. Thermal runs and quenching maintained substantially ordered distribution of Fe2+ and Fe3+ up to ∼990°C and produced continuous [4]Mg-[6]Al exchange. Between 990 and 1150°C, the previous order of Fe2+-Fe3+ appeared to change slightly, [6]Fe2+ reaching ∼0.04 afu and [6]Mg ≅ [4]Al ≅ 0.24 afu at the highest T. After quenching from this temperature, Fe2+ still resided mainly in the T site. Some previously heated crystals underwent reordering on lowering of the temperature.

Experimental data, integrated with existing literature, enabled cation-oxygen distance in this structure to be improved. Results from annealed samples allowed the formulation of an experimental thermometric function based on Mg-Al intracrystalline disorder.

We document the occurrence of Fe-bearing trioctahedral micas in the Poudrette quarry in the Mont Saint-Hilaire alkaline intrusion, characterize them by microprobe analysis, Mössbauer spectroscopy, X-ray diffraction, and optical measurements, describe their mineral chemistry, and discuss their petrological significance. In the nepheline and sodalite syenite, biotite and annite occur as coarse crystals characterized by low Al content (typically 2 atoms per formula unit, a.f.u.), high Mn content (typically 0.2 to 0.8 a.f.u.) and variable Fe/(Fe+Mg) values from 0.61 to 0.97. In the gabbro, biotite is less Fe-rich, has lower Mn content and high Ti content. Phlogopite is found as small metamorphic crystals in marble xenoliths within the syenite and siderophyllite occurs as large crystals in a metasomatized albitite dyke. Fe3+/Fetot values extend from 0.079 in the siderophyllite to 0.282 in a high-Fe3+ annite. All of the micas except for the phlogopite have high contents of (Fe3+)iv (∼0.13 to 0.45 a.f.u.) despite the high availability of Al in the rocks. We suggest that the high (Fe3+)iv amounts are caused by the high Mn abundance via a local structural mechanism. The great variety of mica encountered at Mont Saint-Hilaire reflects the highly heterogeneous conditions that prevailed during magmatic and postmagmatic crystallization in this intrusion.

In the Fregeneda area different pegmatitic types can be distinguished on the basis of their mineralogy, internal structure and field relationships. The most common type corresponds with simple pegmatites with a homogeneous internal structure, but Li and Sn-bearing pegmatites are also relatively widespread, besides a minority group of Fe-Mn phosphate-bearing pegmatites that has recently been characterized. These pegmatites are located in an intermediate zone, between the barren pegmatites and the most evolved Li and Sn-bearing bodies, and they carry a complex association of phosphate minerals. The study of these phosphates has allowed the identification of the primary phases as wyllieite, graftonite, sarcopside, triplite-zwieselite and ferrisicklerite; the secondary phosphates are rosemaryite, heterosite-purpurite, alluaudite and väyrynenite. In this study, the main characteristics of these phosphate minerals are reported, including their chemical composition, analysed by electron microprobe, and their unit-cell parameters, calculated using X-ray powder diffraction techniques.

A common transformation mechanism in this phosphate association is the oxidation of the transition metal cations at the same time as Na-leaching in wyllieite to generate rosemaryite, and Li-leaching in ferrisicklerite to generate heterosite. The occurrence of sarcopside lamellae in ferrisicklerite and heterosite is evidence of the replacement processes of the former by the latter. A Na-metasomatic replacement of the early phosphates as ferrisicklerite and graftonite, producing alluaudite, is also a well developed process.

Phosphate minerals occur in pegmatites with an intermediate degree of fractionation, appearing between the barren and the more evolved pegmatites with Li and Sn, which is in agreement with the pegmatite field zonation established in the literature.

Petrographic features and compositions of titanites in eclogites within the ultra-high pressure metamorphic terrane in central Dabieshan are documented and phase equilibria and thermobarometric implications discussed. Carbonate-bearing eclogite pods in marble at Shuanghe contain primary metamorphic aluminous titanites, with up to 39 mol.% Ca(Al,Fe3+)FSiO4 component. These titanites formed as part of a coesite-bearing eclogite assemblage and thus provide the first direct petrographic evidence that AlFTi−1O−1 substitution extends the stability of titanite, relative to rutile plus carbonate, to pressures within the coesite stability field. However, it is emphasised that A1 and F contents of such titanites do not provide a simple thermobarometric index of P—T conditions but are constrained by the activity of fluorine, relative to CO2, in metamorphic fluids — as signalled by observations of zoning features in these titanites.

These ultra-high pressure titanites show unusual breakdown features developed under more H2O-rich amphibolite-facies conditions during exhumation of these rocks. In some samples aluminous titanites have been replaced by ilmenite plus amphibole symplectites, in others by symplectitic intergrowths of secondary, lower Al and F, titanite plus plagioclase. Most other coesite-bearing eclogite samples in the central Dabieshan terrane contain peak assemblage rutile often partly replaced by grain clusters of secondary titanites with customary low Al and F contents.

Transmission electron microscopy (TEM) was used to study the aluminate sodalite, Ca8[Al12O24](CrO4)2. This aluminate sodalite has four polymorphs: one cubic, one modulated, one tetragonal, and an orthorhombic cell that arise from ordering of [Ca4·CrO4]6+ clusters that occur in the cages of the structure. The transition temperatures are 432, 453, and 610 K. The cell parameters for the orthorhombic phase, with the cubic cell parameter of a = b = c = 9.222 Å, are 3a × 2b × c. Transformation twins are formed at 432 K during the transition from the tetragonal to the orthorhombic phase. The twin plane is {110} in the cubic cell, and {320} in the orthorhombic cell.

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

Sericitization in three separate pulses of the Rosses Granite Ring Complex, Co. Donegal, Ireland, has been investigated texturally and chemically using electron microscopy, electron microprobe and fluid inclusion thermometry. The sericitization, which is restricted to the cores of plagioclase, is associated with pores which are abundant in the cores, but absent in the margins. Alkali feldspar, although porous, is unaltered. Associated with the sericitization is alteration of the adjacent primary plagioclase within the cores of grains to a more sodic composition.

It is postulated that the sericitization resulted from the action of externally derived secondary hydrothermal fluids, which gained access to the pores in the plagioclase via now sealed microfractures, formed either by contraction during cooling of the Rosses Complex, or more likely by hydraulic fracturing by the fluids themselves. Limited fluid/rock ratios restricted the degree of sericitization within the host plagioclase, whilst an absence of alteration in alkali feldspar may have been due to the inaccessibility of pores in the alkali feldspar to the hydrothermal fluids at the time of alteration. Fluid inclusion data suggest that the fluids were of low salinity, and that the sericitization took place at an early stage in the cooling history of the Rosses Complex at temperatures between 400 and 600°C. It is further contended that greisenization in the Rosses Complex predated the sericitization and that the greisenization may have been due solely to volatile-rich late-stage magmatic fluids.