In order to aid the graphical presentation of analyses of igneous rocks, a pseudo-quaternary system R2O3XO-YO-ZO2 has recently been used (O'Hara, 1968, fig. 4). To test its ability to present the analytical data of tholeiitic basalts, the analyses of selected lavas have been projected into the system and then sub-projected into two planes. Lines, which represent the loci of liquid compositions in certain isobaric, pseudo-univariant equilibria, have been drawn on the basis of the melting relations of the basalts. After reading the pseudo-ternary phase diagrams resulting from the sub-projections, some genetic aspects of the lavas of Kilauea and Mauna Loa are discussed from a phase equilibrium standpoint.

This paper presents an extended version of the local lattice deformation model of solid solutions (J. T. Iiyama, 1974b). It has been assumed previously that a foreign atom fixed in a crystal causes local lattice deformation, which prevents another foreign atom from occupying the deformed zone. The resulting entropy of the solid solution from this model can explain the particular behaviour of ion-exchange reactions observed with alkali and alkali-earth elements in feldspars and in muscovite. The present version assumes that the deformed zone does not prohibit foreign atoms, but that the number of foreign atoms acceptable in this region depends on the total numbers of foreign atoms already fixed in the crystal. The model is applied successfully to explain ion-exchange isotherms observed with Cs, Na, and Li in micas and permits an estimation of the apparent reaction constant of the ion exchange. This is otherwise impossible because of the lack of ideal dilute-solution behaviour in exchange isotherms even at the IO ppm range of the foreign element fixed into the crystal. It is demonstrated that the model can explain the particular behaviour of Li in sanidine.

Knowledge of the solid-phase speciation of As in Bengali sediments associated with hazardous As-rich groundwaters is crucial to understanding the processes controlling As release. The local coordination environment of As in such a sediment has been probed using K-edge As EXAFS. This revealed that As exists predominantly in its oxidized form, As(V), probably adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of As into a metal oxide structure cannot be ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (<10 μg g–1) of As in the sediment prevented the unambiguous assignment of the second coordination sphere. The EXAFS analysis of the sediment after incubation under anaerobic conditions in the presence of added electron donor for metal reduction indicated changes in the relative concentrations of different solid-phase As species, providing circumstantial evidence for differential susceptibility to microbial action.

Barium feldspar and barian muscovite are major constituents of the Aberfeldy Ba-Zn mineralization. Celsian varies from equigranular to a platy habit in quartz-celsian rock and forms porphyroblasts in schist and marble. Hyalophane is less common. Barian muscovite is a major component of the schist in the mineralized zone. Celsian (> 80 % Cn) and/or hyalophane coexist with muscovite containing c.6% Ba, and c.8.5% Ba was measured in muscovite from one feldspar-free specimen. Cymrite separated from foliated quartz-celsian rock conformed to the formula BaAl2Si2O8·H2O. The rock textures reflect regional metamorphism, but it is believed that the barium silicates are ultimately authigenic in origin. The platy habit of much of the celsian may have been inherited from cymrite formed during the development of tectonic fabrics.

This paper discusses the relationship between the chemical composition of basic melts and the temperatures at which olivine, clinopyroxene, and plagioclase begin to crystallize at one atmosphere. Diagrams are given which show the correlation between crystallization temperature and melt composition and which allow some of the temperatures to be estimated. Because the relationship between melt composition and crystallization temperature is virtually linear over short compositional ranges, the data available can be subdivided and examined by linear multivariate statistical techniques. The result is a set of equations which permit the crystallization temperatures to be calculated with an average error of less than 6 °C and a maximum error of 27 °C. These equations have been tested by experimental determination of crystallization temperatures for a range of rocks from the Marquesas Islands.

The structure and elastic properties of MgSiO3, a major mantle-forming phase, have been simulated using computer models which predict the minimum energy structure by using interatomic pair potentials to describe the net forces acting between the atoms. Four such interatomic potentials were developed in this study, and are compared with potential N1 of Miyamoto and Takeda (1984). The most successful potential (W3) was derived by fitting the short range potential parameters to both the experimentally obtained structural and elastic properties of MgSiO3 perovskite. The relative stabilities of some of the possible perovskite polymorphs, the orthorhombic, cubic, and tetragonal phases and hexagonal polytypes, were evaluated at 0 K and between 1 bar and 2 Mbar. The orthorhombic phase is found to be stable at all but the highest pressures, where the cubic phase may be stable. The temperature of the ortho-rhombic to cubic transition may decrease with increasing pressure. The energy of a stacking fault on (110) in the cubic phase was estimated using the ANNNI model and found to be about 1.95 J m−2 using potential W3. The distance of separation of partial dislocations of this type is predicted to increase with increasing pressure from 8.4 Å at 1 bar to 9.2 Å at 1 Mbar.

Many of the experiments described in this paper were made in the course of an examination of problems arising in connexion with technical uses of fibrous asbestos, undertaken about three years ago at the request of Dr. W. Francis, at that time Director of Research for Messrs. Turner Brothers Asbestos Company Limited, Rochdale. We have recently been able to investigate in a little more detail certain points which seemed likely to be of fairly general interest, and we now present our results in the hope that they may be of use to other researchers in this field. We are indebted to Dr. Francis and his colleagues for valuable discussions on questions arising in the course of the work, and to the Directors of Messrs. Turner Brothers for financial assistance in connexion with the earlier experiments, and for permission to publish this paper.

Transmission electron microscopy shows that normal chrysotile and polygonal serpentine occur together and in parallel association with balangeroite, within the slip-veins of the Balangero serpentinite. Chrysotile substitutes for balangeroite and it is later replaced by the polygonal serpentine.

The chrysotile fibres are packed together according to a rod close-packing scheme, with defects. Lattice images of the polygonal serpentine confirm the structure model proposed by Middleton and Whittaker (1976), consisting of polygonally arranged fiat layers. This structural type is probably common for serpentine minerals and constitutes a fourth main type of layer configuration in 1:1 layer silicates.

Tetrahedral framework compounds, as defined in this paper, generally exist as tilted and distorted versions of ideal fully expanded structures at room temperature and atmospheric pressure. How pressure, temperature, and composition (P, T, and X) affect the tilting and distortion is critically reviewed. It is shown that although the effects of P, T, and X on the cell parameters are broadly analogous, the underlying structural changes are generally different. An important, and frequently neglected thermal effect is the apparent shortening of the framework bonds by the anisotropic thermal motion of the framework oxygens. Tilting models of framework compounds are critically examined and their failure to match the observed structural behaviour is attributed to changes in tetrahedral distortion. For quartz it appears that during compression the change in tetrahedral distortion is virtually all angular (O-Si-O angles), whereas during thermal expansion the change in distortion is in the Si-O distances. Such behaviour may typify the behaviour of many other framework compounds but the structural data needed to establish this are lacking. The review is illustrated by reference to the quartz and cristobalite analogues; to the sodalite, leucite, nepheline, scapolite, and feldspar families; and to the nitrides and oxynitrides of silicon and germanium. It is concluded that our understanding of the structural behaviour of framework compounds is still superficial and that much theoretical and experimental work remains to be done.

Small ophiolitic bodies are enclosed in the calcschists of the Piemont zone (western Alps). They have been metamorphosed in the blueschist facies during the alpine orogeny. One of them, the Roche Noire massif, includes gabbro breccias. The magmatic mineralogy of the gabbro was plagioclase + clinopyroxene + minor chromite. There was no chemical homogenization during metamorphism because of the lack of penetrative deformation and on the site of previous chromites, chromium-rich high-pressure and low-temperature minerals (jadeite, phengite, pumpellyite, and lawsonite) were formed. The Al ⇌ Cr substitution does not affect other P- and T-dependent substitutions.

The constituent manganese minerals of an ore body located at the Lecht mines near Tomintoul include cryptomelane and lithiophorite. The latter, now known to occur extensively in soils, was characterized by X-ray, thermal, and electron microscope techniques. Lithiophorite yields a distinctive differential thermal curve and this was studied in some detail. A platy morphology is revealed under the electron microscope and from selected-area electron diffraction patterns it was concluded that the b parameter of the mineral is 8·73 Å, three times the value determined by Wadsley (1952). As suggested by Wadsley, this could arise from the distribution of lithium ions. Chemical analysis shows that the Lecht lithiophorite is slightly unusual in that it has a high iron and zinc content but is relatively low in cobalt. The associated cryptomelane contains a significant amount of thallium.

The new mineral saranchinaite, ideally Na2Cu(SO4)2, was found in sublimates of the Saranchinaitovaya fumarole, Naboko Scoria Cone, Tolbachik volcano, Kamchatka, Russia. Its discovery and study has enabled the characterization of the thermal decomposition of kröhnkite and provided an insight into the high-temperature behaviour of other kröhnkite-type materials. Saranchinaite is monoclinic, P21, a = 9.0109(5), b = 15.6355(8), c = 10.1507(5) Å, β = 107.079(2)°, V = 1367.06(12) Å3, Z = 8 and R1 = 0.03. Saranchinaite is a unique mineral in that two of its four independent Cu sites display a very unusual Cu2+ coordination environment with two weak Cu–O bonds of ~2.9–3.0 Å, resulting in [4+1+2] CuO7 polyhedra. Each of the Cu-centred polyhedra shares common corners with SO4 tetrahedra resulting in a [Cu4(SO4)8]8– framework with a complex channel system occupied by Na atoms. Saranchinaite is sensitive to moisture and transforms into kröhnkite within one week when exposed to open air at 87% relative humidity and 25°C. High-temperature X-ray diffraction studies were performed for both kröhnkite (from La Vendida mine, Antofagasta Region, Chile) and saranchinaite. During thermal expansion kröhnkite retains its strongly anisotropic character up to its full dehydration and the formation of saranchinaite at ~200°C, which then transforms back into kröhnkite after exposure to open air. The thermal expansion of saranchinaite is more complex than that of kröhnkite. Saranchinaite is stable up to 475°C with subsequent decomposition into tenorite CuO, thénardite Na2SO4 and unidentified phases.

Manganese (Mn) oxides have been prevalent on Earth since before the Great Oxidation Event and the Mn cycle is one of the most important biogeochemical processes on the Earth's surface. In sunlit natural environments, the photochemistry of Mn oxides has been discovered to enable solar energy harvesting and conversion in both geological and biological systems. One of the most widespread Mn oxides is birnessite, which is a semiconducting layered mineral that actively drives Mn photochemical cycling in Nature. The oxygen-evolving centre in biological photosystem II (PSII) is also a Mn-cluster of Mn4CaO5, which transforms into a birnessite-like structure during the photocatalytic oxygen evolution process. This phenomenon draws the potential parallel of Mn-functioned photoreactions between the organic and inorganic world. The Mn photoredox cycling involves both the photo-oxidation of Mn(II) and the photoreductive dissolution of Mn(IV/III) oxides. In Nature, the occurrence of Mn(IV/III) photoreduction is usually accompanied with the oxidative degradation of natural organics. For Mn(II) oxidation into Mn oxides, mechanisms of biological catalysis mediated by microorganisms (such as Pseudomonas putida and Bacillus species) and abiotic photoreactions by semiconducting minerals or reactive oxygen species have both been proposed. In particular, anaerobic Mn(II) photo-oxidation processes have been demonstrated experimentally, which shed light on Mn oxide emergence before atmospheric oxygenation on Earth. This review provides a comprehensive and up-to-date elaboration of Mn oxide photoredox cycling in Nature, and gives brand-new insight into the photochemical properties of semiconducting Mn oxides widespread on the Earth's surface.

Jurassic limestones occurring in a screen between two ring dykes are shown to have undergone two periods of thermal metamorphism; the first characterized by a high ratio of CO2:H2O and the second by a high ratio of H2O:CO2 in the vapour phase. The first metamorphism produced minerals characteristic of Bowen's decarbonation series. Some of these minerals became unstable in the second metamorphism and (OH, F) bearing minerals were produced. A stage of fracture-controlled replacement veins with mineral assemblages which indicate a varying CO2:H2O ratio in the vapour and a general falling temperature sequence terminate the metamorphic history. Three new minerals, rustumite (Ca3Si2O7.Caterminate (OH)2), dellaite (Ca12Si6O22(OH)4), and kilchoanite (Ca3Si2O7), of which the last has previously been described, are characteristic of the second episode of metamorphism.

Cu-bearing elbaite from Paraíba (Brazil) is a highly-prized gem tourmaline. Specimens of similar quality from localities in Mozambique and Nigeria are being sold, and reliable provenance tools are required to distinguish specimens from the original locality from ‘Paraíba-type’ tourmaline from Africa. Here we present Li and B isotope analyses of Cu-bearing elbaite from all three localities and demonstrate the suitability of these isotope systems as a provenance tool. Isotopic profiles across chemically zoned grains revealed homogenous B and Li isotopic compositions, demonstrating a strong advantage of their application as a provenance tool as opposed to major, minor or trace element signatures.

Li and B isotopes of all investigated samples of Cu-bearing elbaites from the three localities are within the range of previously published granitic and pegmatitic tourmaline. Anomalous isotope compositions published previously for these samples are corrected by our results.

Ion probe data for zircons from tuffs within the Llfynant flags (Arenig) and the Serw Formation (lower Llanvirn) of north Wales have been revised using better statistical methods for separating detrital ages, making allowance for recently-found variability in radiogenic 206Pb/238U in the reference zircon SL13, and testing the sensitivity of the ages to the secondary ion discrimination slope. The revised ages are options of 469.2 ± 2.1 (σ) or 472.9 ± 2.9 Ma for the Llfynant flags dependent on mixture modelling, and 465.3 ± 1.4 Ma for the Serw Formation. All ages are within error of previous SHRIMP results and the Serw age now has the same numerical value as a previous MSID age for the same sample. It is shown that an MSID age of 483 ± 0.5 Ma with interpreted Pb loss for a late Tremadoc bentonite is dependent on the correction for common Pb, and that a slightly more radiogenic choice for the common Pb composition places nearly all data on Concordia. The latter would indicate that the bentonite might contain two zircon populations: inherited grains at 482 Ma and tuff magmatic grains at 473 Ma, which is more compatible with the SHRIMP Arenig result. Interpretations of other MSID zircon ages from the Ordovician are also sensitive to choice of common Pb, and raise the likelihood that many multigrain ages might be too old owing to admixture with slightly older inherited zircon. A supposed 1–2% technical bias of SHRIMP 206Pb/238U ages relative to MSID is refuted.

Tertiary ultrapotassic volcanic rocks from Serbia occasionally display low levels of K2O and K2O/ Na2O. In these rocks, analcime regularly appears as pseudomorphs after pre-existing leucite microphenocrysts. The process ofleucite transformation in Serbian ultrapotassic rocks is very thorough: fresh leucite survives only in ugandites from the Koritnik lava flows as well as in rare inclusions in Cpx. This paper focuses on the impact of ‘analcimization’ on the mineralogy and geochemistry ofthe Serbian ultrapotassic rocks, using the samples where leucite survived as a monitor for the process.

Analcimization has had a great impact on the geochemistry of the rocks, but affects only a restricted number of chemical parameters. These are the falsification of the original K2O/Na2O ratio, the decoupling oflarge-ion lithophile elements resulting in considerable depletion of Rb and K2O, but not ofBa, and sporadic, but extreme enrichment ofCs in some analcime-bearing samples (up to 900 ppm). Analcimization is also recognized by an increase in whole-rock δ18O values of ∼3% compared to fresh rocks, which correlates with the level of whole-rock hydration. Finally, the 87Sr/86Sr enrichment at nearly constant 143Nd/144Nd demonstrated by some rocks can also be explained by the analcimization ofleucite. For samples with variable 87Sr/86Sr from the same lava flow, 87Sr/86Sr values correlate with modal analcime abundance (ex-leucite), loss on ignition of whole-rock and whole-rock δ18O values. The extreme depletion in K and enrichment in Na, together with modification of other geochemical parameters, may have led to the misinterpretation of the origin and geodynamic affiliations of the Serbian ultrapotassic rocks, had the effects of analcimization not been taken into account.

The new minerals manganvesuviante and tweddillite, both formed by hydrothermal alteration of primary manganese ores, are described from the Kalahari manganese fields (Republic of South Africa). In addition, single-crystal X-ray structure refinements of both new minerals are presented.

Manganvesuvianite is a tetragonal vesuvianite mineral with the simplified formula Ca19Mn3+(Al,Mn3+,Fe3+)10(Mg,Mn2+)2Si18O69(OH)9, characterized by Mn3+ occupying the five-coordinated position (square pyramid). The crystals simple prismatic forms: {100}, {110} terminated by {101} and exhibit deep maroon red colour. With polarized light the crystals are strongly pleochroic, yellowish parallel to E and dark red to lilac parallel to O.

Tweddillite is an epidote-group mineral (space group P21/m, a = 8.932(5), b = 5.698(4), c = 10.310(5) Å, β = 114.56(4), V = 477.3(8) Å3) with the simplified formula CaSr(Mn3+,Fe3+)2Al[Si3O12](OH), closely related to strontiopiemontite. The difference between strontiopiemontite and tweddillite is the concentration of octahedral Mn3+. Strontiopiemontite has Mn3+ mainly on the M3 site whereas tweddillite has Mn3+ with minor Fe3+ on M3 and M1. Tweddillite forms aggregates of very thin dark red {001} blades characterized by striking pleochroism. The crystals appear dark red parallel to b and orange-yellow parallel to a. Perpendicular to (001) the blades appear magenta to red.

Coexisting scapolite, biotite and hornblende in scapolite-biotite rocks from the Tongmugou Pb-Zn deposit, Qinling, northwestern China are characterized by high levels of chlorine. Scapolite composition varies from EqAn27 to EqAn47 with 47–80 wt.% Cl. The scapolite composition is a sensitive indicator of the NaCl activity in coexisting hydrothermal fluid. Biotite contains 0.3–1.2 wt. % Cl and also has high F contents (0.2–0.7 wt.%). The hornblende is a Cl-rich hastingsite with Cl>3.5 wt.% and high (Na2O + K2O) contents (3.2–3.9 wt. %), high Xk [= K/(K + Na)] values (0.45–0.55) and high XFc [= Fe/(Fe + Mg)] values (0.76–0.79). The chlorine within these minerals is thought to be derived from evolved seawater. The scapolite-biotite rocks are products of Cl-rich alteration of volcanoclastic sedimentary rocks during submarine hydrothermal processes. Multiple-stage hydrothermal activity culminated with the circulation of a high-NaCl fluid that was also responsible for the formation of the massive sulphide deposits.

The first comprehensive assessment of the dissolution kinetics of simulant Magnox–ThORP blended UK high-level waste glass, obtained by performing a range of single-pass flow-through experiments, is reported here. Inherent forward rates of glass dissolution were determined over a temperature range of 23 to 70°C and an alkaline pH range of 8.0 to 12.0. Linear regression techniques were applied to the TST kinetic rate law to obtain fundamental parameters necessary to model the dissolution kinetics of UK high-level waste glass (the activation energy (Ea), pH power law coefficient (η) and the intrinsic rate constant (k0)), which is of importance to the post-closure safety case for the geological disposal of vitreous products. The activation energies based on B release ranged from 55 ± 3 to 83 ± 9 kJ mol–1, indicating that Magnox–THORP blend glass dissolution has a surface-controlled mechanism, similar to that of other high-level waste simulant glass compositions such as the French SON68 and LAW in the US. Forward dissolution rates, based on Si, B and Na release, suggested that the dissolution mechanism under dilute conditions, and pH and temperature ranges of this study, was not sensitive to composition as defined by HLW-incorporation rate.