Perovskite compositions are used to investigate the relationship between the minor components (i.e. LREE, Fe3+ and Nb) and the oxygen fugacity (fo2) of perovskite in four different kimberlite lithofacies from the Dutoitspan pipe, Kimberley, South Africa, which range from diamondiferous to barren. The perovskite textures and chemical variations provide insight into magmatic and eruptive processes. Some crystals display cores with rims separated by a sharp boundary. The cores contain larger Na and LREE contents relative to the rims, which show a large increase in Fe3+ and Al. The mid-grade and barren kimberlites have bi-modal cores, reflected in the mineral chemistry, signifying multiple batches of magma and magma mixing. The fo2 of the magma is determined by an Fe-Nb oxygen barometer. The most diamondiferous kimberlite has the greatest Fe3+ content and highest fo2 (NNO –3.6 to –1.1). The kimberlite containing large diamonds has the smallest Fe3+ content and lowest fo2 (NNO –5.2 to –3.0). The barren and mid-grade kimberlites display a wide range of fo2,(NNO –5.3 to –1.5) as a result of perovskites forming in different melts and subsequently mixing together. Chemical and petrological evidence suggests that the volatile content, degassing, decompression and rate of crystallization can influence the rate at which the magma is erupted. One possibility is that the most oxidized magma, containing the highest volatile content, is therefore erupted much more rapidly, preserving diamond as a consequence.

The presence of garnet in acid rocks of the charnockite series south of Madras is reported. Petrographic deseriptions of garnetiferous enderbites and related pyroxene-granulites, khondalites, and leptynites are accompanied by new chemical analyses of 6 rocks, 8 garnets, and 5 orthopyroxenes from the type area near Madras, and from Ceylon, Varberg, and Uganda. The garnets show a considerably higher FeO/MgO ratio than the coexisting ortbopyroxenes and the host rocks. The presence or absence of garnet appears to be related to the bulk chemistry of the rocks. Basic garnetiferous granulites associated with these rocks are considered to represent an unstable mineral assemblage and may be genetically unrelated to the acid types. Attention is drawn to the prevalence of enderbitic rocks in the type area.

It is argued on crystal-chemical grounds that Si deficiency is compensated by the entering of Al, Fe3+, or Ti4+, in this order of preference, into tetrahedral sites. It is pointed out that Ti4+ occurs in tetrahedral coordination in exceptional circumstances only, while Fe3+ relatively easily takes a tetrahedral coordination.

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.

Contrasting distribution patterns of Fe and Ca have been found by electron microprobe analysis (EMPA) mapping of alkali feldspar in a quartz syenite from the Patagonian Andes, Chile. They comprise mainly mantle zoning (Fe-rich, Ca-poor rims and Fe-poor, Ca-rich interiors) and corresponding patchy zoning in grain interiors. The rims are dominantly of turbid, patch microperthites associated with abundant micropores, but there remain clear, optically featureless regions almost free of micropores. The interiors are intricate mixtures of optically clear, featureless regions, and turbid, patch microperthite regions. The clear, featureless regions (Or31 –47) are of remaining exsolution lamellar cryptoperthites. The zoning patterns of Fe and Ca formed by large-scale transport over the feldspar grain during the high-temperature fluid stage. They have been modified by successive transport of Fe and Ca during the later hydrothermal development of patch microperthites and finally by K-feldspathization and albitization. Cathodoluminescence images correspond to the spatial distribution patterns of Fe overprinted by these multi-stage reactions. The original composition of the alkali feldspar before the subsolidus reactions is estimated to have been ~Or34Ab65An1, and the present bulk composition after the reactions is Or40Ab59An0.5.

Mr. A. Steiner has kindly invited the present writer to study by X-ray methods the new mineral wairakite described by him in the preceding pages. The material provided includes an incomplete octahedron 15 ram. across with small modifying ieositetrahedron-like faces, and some smaller partial icositetrahedra. Faces are dull and give diffuse reflections oil the optical goniometer, but, by attaching small pieces of glass cover-slip to improve the reflections, interfacial angles approximating to those of the cubic forms {111} and {211} were measured. As pointed out by Mr. Steiner, however, the mineral is birefring'ent, biaxial, and finely twinned. A preliminary small-diameter X-ray powder photograph taken by Mr. N. Wells of the Soil Bureau, Wellington, showed an apparently cubic, analeime-like pattern (personal communication).

Several complex Cu-Pb-Bi, Cu-Pb-Bi-Sb and Ag-Pb-Bi sulphosalt minerals have been identified in samples from hydrothermal vein mineralisation associated with the Toroiaga sub-volcanic body in the Baia Borşa area of Maramureş County, northwest Romania. This is the first chemically-documented report of Bi-sulphosalts in the Neogene metallogenic province around Baia Mare. The investigated samples contain abundant amounts of matildite solid solution within galena, the Cu-Pb/Bi sulphosalts aikinite, friedrichite, krupkaite, hammarite, lindströmite and gladite as well as nuffieldite and berryite. Within the Ag-Pb/Bi group, the majority of analysed grains can be regarded as members of the lillianite homologous series. Three distinct lillianite homologues were identified, which correspond to (i) phases along the lillianite-gustavite solid solution join (Pb3Bi2S6-AgPbBi3S6), (ii) phases within solid solution field of heyrovskyite, and (iii) compositions which best correspond to ‘schirmerite’, sensu Makovicky and Karup-Møller (1977b), but may represent disordered gustavite, vikingite or eskimoite. Some of the analysed lillianite homologues contain excess Cu, which may occupy interstitial sites. Furthermore, a large proportion of the lillianite homologues display significant substitution of Sb for Bi within the limits predicted by experimental investigations. Cosalite, also showing a range of compositions including Sb-rich varieties is recognised. Izoklakeite, Cu2Pb22(Sb,Bi)22S57, is an abundant phase throughout the analysed samples, its composition is in good agreement with previously published analyses, except for excess Cu and Fe beyond the limits previously reported. The description of several minerals from this new occurrence and compositional data on them, including the Sb-bearing varieties, provides valuable additional information on compositional limits in natural samples.

Basalts from the volcano-sedimentary Eriksfjord Formation (Gardar Province, South Greenland) were erupted at around 1.2 Ga into rift-related graben structures. The basalts have compositions transitional between tholeiite and alkaline basalt with MgO contents <7 wt.% and they display LREE-enrichment relative to a chondritic source. Most of the trace element and REE characteristics are similar to those of basalts derived from OIB-like mantle sources. Initial 87Sr/86Sr ratios of clinopyroxene separates range from 0.70278 to 0.70383 and initial ϵNd values vary from –3.2 to +2.1. The most unradiogenic samples overlap with the field defined by carbonatites of similar age and can be explained by mixing of isotopically depleted and enriched mantle components. Using AFC modelling equations, the Sr-Nd isotope data of the more radiogenic basalts can successfully be modelled by addition of <5% lower crustal granulite-facies gneisses as contaminants. δ18Ov-smow values of separated clinopyroxene range from +5.2 to +6.0% and fall within the range of typical mantle-derived rocks. However, up to 10% mixing with an average lower crustal component are permitted by the data.

The turquoise group has the general formula: A0–1B6(PO4)4−x(PO3OH)x(OH)8.4H2O, where x = 0–2, and consists of six members: planerite, turquoise, faustite, aheylite, chalcosiderite and an unnamed Fe2+-Fe3+ analogue. The existence of ‘coeruleolactite’ is doubtful. Planerite is revalidated as a species and is characterized by a dominant A-site vacancy. Aheylite is established as a new member of the group, and is characterized by having Fe2+ dominant in the A-site.

Chemical analyses of 15 pure samples of microcrystalline planerite, turquoise, and aheylite show that a maximum of two of the (PO4) groups are protonated (PO3OH) in planerite. Complete solid solution exists between planerite and turquoise. Other members of the group show variable A-site vacancy as well. Most samples of ‘turquoise’ are cation-deficient or are planerite. Direct determination of water indicates that there are 4 molecules of water.

Planerite, ideally ☐Al6(PO4)2(PO3OH)2(OH)8.4H2O, is white, pale blue or pale green, and occurs as mamillary, botryoidal crusts as much as several mm thick; may also be massive; microcrystalline, crystals typically 2–4 micrometres, luster chalky to earthy, H. 5, somewhat brittle, no cleavage observed, splintery fracture, Dm 2.68(2), Dc 2.71, not magnetic, not fluorescent, mean RI about 1.60. a 7.505(2), b 9.723(3), c 7.814(2) Å, α 111.43°, β 115.56°, γ 68.69°, V 464.2(1) Å3, Z = 1.

Aheylite, ideally Fe2+Al6(PO4)4(OH)8.4H2O, is pale blue or green, and occurs as isolated and aggregate clumps of hemispherical or spherical, radiating to interlocked masses of crystals that average 3 micrometres in maximum dimension; porcelaneous-subvitreous luster, moderate to brittle tenacity, no cleavage observed, hackly to splintery fracture, not magnetic, not fluorescent, biax. (+), mean RI is about 1.63, Dm 2.84(2), Dc 2.90. a 7.400(1), b 9.896(1), c 7.627(1) Å, α 110.87°, β 115.00°, γ 69.96°, V 460.62(9) Å3, Z = 1.

Silvialite, ideally Ca4Al6Si6O24SO4, is tetragonal, I4/m, Z = 2, with a = 12.160(3), c = 7.560(1) Å, V = 1117.9(8) Å3, c:a = 0.6217:1, ω = 1.583, ε = 1.558 (uniaxial negative), Dm = 2.75 g/cm3, Dcalc = 2.769 g/cm3 and H (Mohs) = 5.5. It is transparent and slightly yellow, has a good {100} cleavage, chonchoidal fracture, white streak and a vitreous lustre. It occurs in upper-mantle garnet-granulite xenoliths hosted by olivine nephelinite, from McBride Province, North Queensland, Australia. The empirical formula, derived from electron-microprobe analysis, is (Na1.06Ca2.86)(Al4.87Si7.13)O24 [(SO4)0.57(CO3)0.41]. Crystal-structure refinement shows disordered carbonate and sulfate groups along the fourfold axis. Silvialite is a primary cumulate phase precipitated from alkali basalt at 900–1000°C and 8–12 kbar under high fSO2 and fO2. The name silvialite, currently used in literature to describe the sulfate analogue of meionite, was suggested by Brauns (1914).

Materials designed for nuclear waste disposal include a range of ceramics, glass ceramics and glass waste forms. Those with crystalline phases have provided the momentum for studies of minerals as a means to understand aspects of waste-form crystal chemistry, behaviour in aqueous systems and radiation damage over geological periods of time. Although the utility of natural analogue studies varies, depending upon the degree of analogy to the proposed geological repository and other factors such as chemical composition, the available data suggest that Th-U host phases such as brannerite, monazite, pyrochlore, zircon and zirconolite are resistant generally to dissolution in aqueous fluids at low temperatures. Geochemical durability may or may not extend to hydrothermal systems depending on the specifics of fluid composition, temperature and pressure. At elevated temperatures, for example, davidite may break down to new phase assemblages including titanite, ilmenite and rutile. Perovskite is generally less resistant to dissolution at low temperatures and breaks down to TiO2, releasing A-site cations to the aqueous fluid. Studies of radiation damage indicate that the oxide and silicate phases become amorphous as a result of the gradual accumulation of alpha-recoil collision cascades. Monazite tends to remain crystalline on geological time scales, a very attractive property that potentially eliminates major changes in physical properties such as density and volume, thereby reducing the potential for cracking, which is a major concern for zircon. In spite of recent success in describing the behaviour of Th-U minerals in geological systems, considerable work remains in order to understand the P-T-X conditions during alteration and T-t history of the host rocks.

This paper presents wet chemical analyses of forty-one pyroxenes (thirty-nine of them new) from pyroxene granulites and a few neighbouring rocks from Swat Kohistan and the adjoining Indus Valley. The granulites, considered to be derived from plutonic norites of an island arc tholeiitic nature, constitute one of the most extensive belts of its kind in the world. The pyroxenes are not unusual in any respect but they bear a closer resemblance to metamorphic than to igneous pyroxenes crystallized from deep-seated tholeiitic magmas. The distribution of Mg, Fe, and Mn (average KDMg−Fe=0.57) and the tie-line intersections on the Wo-En join (generally from Wo80.5 to Wo76.5) between the coexisting eighteen pyroxene pairs from the granulites are discussed. Based on eight different methods of geothermometry and other considerations, it is concluded that the pyroxene granulites were metamorphosed at around 800 °C and 7 to 8 kbar.

Arsenic-rich scales are widely associated with geothermal fields and constitute a potential hazard to human health. Such arsenic has hitherto been reported to be almost exclusively hosted by sulphide or oxide phases or occurring as surface species. We report here, however, the occurrence of an arsenic-rich (1500 to 4000 mg kg—1 As) smectite from geothermal precipitates from a geothermal field in northwestern Japan and present evidence that the arsenic is predominantly hosted within this silicate mineral.

Consistently ∼80% of the total arsenic determined in these geothermal precipitates was found by selective chemical extractions to be associated with an operationally defined clay mineral fraction, with lesser proportions being associated with operationally defined amorphous silica, Fe oxide and sulphide fractions. Analysis by XRD, ATR IR and XRF showed the clay fraction to be dominated by Mg-rich trioctahedral smectite.

Arsenic K-edge XAS spectra of the smectite suggested the dominance of As(III)-O coordinated species with significant contributions from As(V)-O coordinated species. Both XPS and a magnesium chloride chemical extraction indicated minimal adsorption of arsenic on smectite surfaces suggesting that the arsenic was predominantly either dissolved within the smectite or occurred within mineral occlusions. No such occlusions greater than 1 μm in size were observed in the As-rich smectites.

The potential occurrence of arsenic-bearing clays should be considered when determining remediation strategies for geothermal environments or evaluating risks associated with the industrial usage of geothermal precipitates.

Conversion of randomly ordered illite-smectite to ordered illite-smectite in the Upper Jurassic Kimmeridge Clay Formation from the North Sea has been recorded in the literature as occurring within the ‘oil window’ and has been suggested as an indicator of oil source rock maturity. Studies of authigenic clay minerals in the fine fraction (>0.5 µm) of the Kimmeridge Clay Formation mudstones from fourteen locations along the UK onshore outcrop between Dorset and North Yorkshire show that they comprise mainly ordered illite-smectites. The onshore Kimmeridge Clay section is organically immature, suggesting that the illite-smectite ordering reaction cannot be extrapolated between basins as an inorganic indicator of ‘oil window’ levels of maturity. These results also have important implications in source rock hydrocarbon expulsion and migration models which involve shale dewatering as a flushing agent. However, dewatering of shales may aid migration as it could cause fracturing of the shale bands separating the organic-rich layers within the source rock, prior to hydrocarbon generation.

This study documents the textures and chemical evolution of igneous quartz (Qz) in granite from the Oslo Rift (Norway) during the magmatic-hydrothermal transition. Contrary to the other major igneous phases, primary quartz is well preserved. SEM-CL imaging documents four types of quartz (Qz1— Qz4). Qz1: bright primary magmatic quartz that grew under H2O-undersaturated conditions and developed a conspicuous sector zoning. Qz2: light grey luminescent secondary quartz that surrounds Qz1 and altered Qz1 in a ‘non-destructive’ process. Qz3: is usually darker than Qz2 and intersects Qz1 and Qz2. It is formed by dissolution/recrystallization processes involving saline deuteric fluids. Qz4: found in narrow cracks and patches of black quartz intersecting all the other types. EPMA in situ analyses of the different quartz generations confirm that the intensity of luminescence of quartz is positively correlated with the Ti content of the quartz. Aluminium and K are mostly incorporated in quartz in the form of [AlO4/K+]0 centre defects. In the Drammen granite, the Ti and Al contents of Qz1 averages 200 ppm and 80 ppm respectively. Titanium in Qz1 varies from 50 to 95 ppm in the peralkaline granite known as ekerite, whereas Al is irregular and ranges between 100 ppm and values below the limit of detection (LODAl at 2σ = 14 ppm). In all samples, Qz2 and Qz3 are strongly depleted in Ti and Al compared to Qz1. Either the Ti content in Qz2 is falling gradually towards Qz1 or more abruptly, whereas it is sharp from Qz3 towards Qz1 and Qz2. Potassium is variable in all four quartz types and samples, and ranges from values below the detection limit (LODk, at 2σ = 8 ppm) to 120 ppm. Grains in Qz4, being only 1–2µm wide, could not be resolved with the EPMA beam. In all granites, quartz crystallized from haplogranitic melts at P ~1.5 kbar and T = 700—750°C. SEM-CL and EPMA studies of igneous Oslo Rift quartz illustrate vividly the complex chemical and physical processes that characterize the magmatic-hydrothermal transition in shallow granitic systems and show that the chemistry of primary aqueous fluids is strongly modified from its primary igneous composition before eventually being expelled from the granitic system and perhaps incorporated in ore-forming hydrothermal convection systems.

The crystal chemistry characteristics of a hydroxyl-fluor apatite from a recently discovered kalsilite-bearing leucitite from Abruzzi, Italy, were investigated by electron microprobe, single crystal X-ray diffraction, IR, Raman and micro-Raman spectroscopy. The apatite has exceptionally high S and relatively high Si, Sr and LREE, whereas the HREE content is negligible. The IR spectra confirm the presence of OH calculated from formula difference. A high positive correlation between Ca-site Substitution Index (CSI = 100(10-Ca)/Ca) and Tetrahedral Substitution Index (TSI = 100 (Si+C+S)/P atom/a.p.f.u.) and a systematic parallel increase in REE, S and Si indicate two substitution mechanisms, i.e. REE3+ + Si4+ = Ca2+ + P5+ and Si4+ + S6+ = 2 P5+. Site occupancy data and bond lengths, determined from structural refinements on selected samples, demonstrate that LREE and Sr show a marked preference for the Ca2 site, even though in the LREE-rich samples a partial substitution of LREE for Ca in the Cal site was observed.

Tetrahedral distances (from 1.535 to 1.541 Å.) reflect the substitution of Si4+ and S6+ for P5+, which is also confirmed by vibrational spectra. As (SiO4)4− and (SO4)2− substitute for (PO4)3−, the relative intensity of v1 Raman bands of (SO4)2− (at 1007 cm−1) and (SiO4)4− (at 865 cm−1) increase systematically, while that of phosphate decreases and the five components of phosphate v3 modes disappear. Moreover, the (PO4)3− Raman peak broadening is linearly correlated with the Si and S concentrations.

Apatite crystals are sometimes zoned with compositions varying from SiO2 = 1.15–2.07 wt.%, Σ(LREE2O3) = 0.56–1.08 wt.% and SrO = 0.58–1.02 wt.% in the core to 3.98–5.03, 4.14–6.73 and 1.97–2.17, respectively, in the rim. A sharp, strong enrichment in Sr and LREE in the rim indicate that the apatite suddenly became an acceptor of these elements in the late stages of crystallization.

An occurrence of silica-glass in lumps up to 10 lb. in weight, smaller fragments being scattered over an area at least 80 by 25 kilometres, has been discovered in the course of the work of the Egyptian Desert Surveys. A Survey expedition under Mr. P. A. Clayton was sent out in December 1932 to work in the unexplored area of the Sand Sea and Gill Kebir, west of Major R. A. Bagnold's 1930 route, and found the glass on December 29, 1932.

The alkaline volcanic rocks of Tenerife comprise a compositionally continuous series of ankaramites, alkali basalts, trachybasalts, trachyandesites, trachytes, phonolites, and peralkaline phonolites. Ca-rich pyroxenes occur as phenocrysts throughout the series. They show a limited range of composition from diopside and Ti-rich samite in the basic and intermediate rocks, to sodic sahlite in some phonolites. Features of both the sahlite-aegirine and sahlite-hedenbergite trends are present. Sodic ferrosahlites occur as xenocrystal 'green cores' in phenocrysts from some basic and intermediate rocks. The latter are associated with kaersutite xenocrysts and are similar to pyroxenes in some plutonic xenoliths from Tenerife. During the formation of the 'green cores' conditions were more reducing allowing pyroxene compositions to extend through the range sahlite-hedenbergite.

Aegirine-angite and Ti-rich aegirine are present in the groundmass of some phonolites and in pyroclastic boulders of nepheline syenite. The aegirines are associated with magnesioarfvedsonite and aenigmatite, and it is considered that they crystallized under conditions of low oxygen fugacity.

Polarized spectra (2000 to 25000 Å) have been obtained for fifteen analysed trioctahedral micas covering a wide range of compositions, and including four phlogopites, nine biotites, and two lepidomelanes. Three main contributions to the absorption have been noted: charge transfer from oxygen to ferrous iron throughout the visible and near ultraviolet, charge transfer from ferrous to ferric ions at the red end of the visible spectrum and internal d-d transitions of ferrous ions in the near infrared.

Substitutions in the brucite layer (especially Ti) cause the O → Fe2+ band to broaden, and thus to encroach on the visible region for vibration directions in the plane of the cleavage flake. The transmission window between these bands is further blocked by the Fe2+ → Fe3+ charge-transfer band, which is polarized in the plane of the flake. The overall effect is to produce very strong absorption throughout the visible region for (β, γ) vibration directions, and relatively weak absorption for α, i.e. the observed very strong pleochroism of biotite.

Many features of the spectra of chlorite, amphiboles, and tourmaline, which contain octahedral ions in brucite-like sheets, strips, and fragments respectively, may be interpreted by analogy with biotite.

Two types of solid solution effect are described: substitutional broadening, which is responsible for the extension of the O → Fe2+ band into the visible region in biotites and aluminous ortho-pyroxenes, and substitutional intensification, which permits in solid solutions transitions that are forbidden by the conventional selection rules.