Of the metals in the series Sc, V, Cr, Mn, Fe, and Ga pyroxenes of the type LiM3+Si2O6 were obtained only from Sc, V, Cr, and Fe in dry synthesis experiments near 1000 °C. Ga and A1 gave keatite derivatives (so-called ‘β-spodumenes’) by dry heating; α-Ga-eucryptite was obtained from Ga hydrothermally at pressures between 4·5 and 6·5 kb. Mn gave Mn2O3. The lattice parameters of the pyroxenes vary irregularly with atomic number. This variation and the failure to produce a Mn3+-pyroxene can be explained by the crystal-field theory. At high temperatures A1 and Ga are too small to stabilize a silicate pyroxene phase even at moderately high pressures and form less dense tectosilicates. The octahedral stabilization energy for Cr3+ ensures that Cr, which has the same size as Ga, forms a pyroxene.

Balićžunićite, ideally Bi2O(SO4)2, is a new mineral found as a high-temperature fumarole sublimate (T = 600°C) at La Fossa crater, Vulcano, Aeolian Islands, Italy. It occurs as aggregates of mm-sized prismatic and elongated crystals (∼50 μm across and up to 200 μm long) associated with anglesite, leguernite, one other potentially new Bi-oxysulfate mineral, lillianite, galenobismutite, bismoclite, Cd-rich sphalerite, wurtzite, pyrite and pyrrhotite. Balićžunićite is colourless to white or pale brown, transparent and non-fluorescent. It has a vitreous lustre and a white streak. Electron microprobe analysis gives the following average chemical composition (wt.%): Bi2O3 68.68 and SO3 23.73, total 92.41. The empirical chemical formula, calculated on the basis of 9 anions p.f.u., is Bi1.99S2O9. The calculated density is 5.911 g/cm3.

Balićžunićite is triclinic, space group P , with a 6.7386(3), b 11.1844(5), c 14.1754(7) Å, α 80.082(2)°, β 88.462(2)°, γ 89.517(2)°, V = 1052.01(8) Å3 and Z = 6. The six strongest reflections in the X-ray powder-diffraction data [d in Å(I) (hkl)] are: 3.146 (100) (033), 3.486 (21) (004), 3.409 (12) (01), 3.366 (7) (200), 5.562 (4) (11), 5.433 (4) (111). Balićžunićite is the natural analogue of the stable low-temperature a form of synthetic Bi2O(SO4)2. The name is in honour of Tonci Balić-Žunić(born 1952), Professor of Mineralogy at the Natural History Museum of the University of Cophenagen. Both the mineral and the mineral name have been approved by the IMA-CNMNC Commission (IMA2012-098).

Djerfisherite [K6(Cu,Fe,Ni)25S26Cl] has been found as a daughter mineral in melt inclusions in melilite from a Kugda melilitolite. The inclusion mineral assemblage includes pyrrhotite, pentlandite, forsterite, diopside, monticellite, phlogopite, wollastonite, nepheline, sodalite, combeite, calcite, Na-K-Ca carbonate, and hydrated calcium silicates. The djerfisherite is Ni-rich rather than Cu-rich consistent with an ultimate upper mantle magma source. The djerfisherite-bearing assemblage formed from primary carbonate/alkali-rich, melilititic melt inclusions which underwent extreme, closed-system, magmatic to postmagmatic fractionation over a temperature range of >1000° to <500 °C.

The concept of the algorithmic complexity of crystals is developed for a particular class of minerals and inorganic materials based on orthogonal networks, which are defined as networks derived from the primitive cubic net (pcu) by the removal of some vertices and/or edges. Orthogonal networks are an important class of networks that dominate topologies of inorganic oxysalts, framework silicates and aluminosilicate minerals, zeolites and coordination polymers. The growth of periodic orthogonal networks may be modelled using structural automata, which are finite automata with states corresponding to vertex configurations and transition symbols corresponding to the edges linking the respective vertices. The model proposed describes possible relations between theoretical crystallography and theoretical computer science through the theory of networks and the theory of deterministic finite automata.

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. Although P, T, and X are generally regarded as analogous variables in their effect on framework structures there is reason to believe that they have different structural effects. In particular, an important, and frequently neglected, thermal effect is the apparent shortening of the framework bonds by the anisotropic thermal motion of the framework oxygens. The effects of P, T, and X on displacive transformations in framework compounds are reviewed with particular reference to the disordered alkali feldspars and the leucites. It seems probable from the available evidence that displacive transformations do not take place at a critical size of the framework. Displacive transformations can take place with or without a volume discontinuity and hysteresis. Furthermore, the effects of P, T, and X on a solid-solution series with a displacive transformation can be different, one variable causing a volume discontinuity and another a smooth transition.

Baotite occurs as an accessory mineral in carbonatites, fenites, and carbothermal veins associated with a lamprophyre dyke swarm in the Haast River area of south Westland, New Zealand. Carbonatites are petrogenetically evolved, with assemblages dominated by ankerite, siderite and Ba-Sr-REE carbonates. Microprobe analysis indicates baotite compositions more Nb-rich than previously recorded, with compositions close to Ba4[Ti3(Nb,Fe)5]Si4O28Cl. Ti must be partially replaced in both crystallographically-independent octahedral sites. Compositional zoning, and stoichiometric considerations suggest that the dominant octahedral substitution is the same as that described in rutile, namely 3Ti4+ ⇌ 2Nb5+ + Fe2+. Contrary to previous suggestions, Fe in the octahedral site should, therefore, be dominated by Fe2+.

The presence of baotite further documents the involvement of halogens in carbonatite magmas. In the New Zealand occurrences it is suggested that the chlorine originates from associated phonolitic magmas and is partitioned into carbonatite during liquid immiscibility.

A wide range of volcanic sublimates and alteration products from the Johnston-Lavis collection has been analysed for major elements plus copper, lead, and zinc. 'Aphthitalite' and 'natrikalite' from Mount Vesuvius and an 'alum' from the island of Vulcano all proved to be enriched in copper and selected analyses are tabulated. The process leading to copper and lead enrichment of the Vesuvian material may be vapour phase transport as chloride followed by sulphation on sublimation. It is suggested that the source of the copper found in the alum sample from Vulcano could be of interest to economic geologists.

Industrial minerals, particularly bentonites, have long been used in treatments to improve the stability and shelf life of white wines. We evaluated a new combination of rocks and minerals, including steam-treated bentonites and natural zeolites (chabazite and phillipsite), to greatly reduce the risk of protein and tartaric instability of wines. Detailed mineralogical, chemical and electrokinetic studies of these materials were conducted using powder X-ray diffraction (PXRD), X-ray fluorescence (XRF), microporosimetry, BET surface-area analysis and zeta-potential measurements. Several model wine solutions containing Bovine Serum Albumin (BSA) were prepared to evaluate the oenological performance of the rock/mineral combinations. UV-VIS spectrophotometry and ion chromatography were used to evaluate the degree of wine stabilization from the protein and tartaric point of view.

The experimental results showed that steam treatment modifies both the microporosity and external surface area of the bentonite. These changes in surface area, along with creation of hydrophobic surfaces, significantly modified the behaviour of the steam-treated bentonites, requiring an increase in the amount of material necessary to bring the protein content to required levels. An important benefit derived from the use of steam-treated bentonites is that the pre-mixing with water before addition to wine is not necessary, as the material is readily dispersed. Finally, the addition of natural zeolites effectively decreased the potassium content, thereby improving the tartaric stability of white wines. In addition, this procedure results in minimal waste, as the bentonite-zeolite mixture can be reused as soil amendments in agriculture.

The carbonatites at Loe Shilman, near Khyber in NW Pakistan, fenitize their country rocks to form a metasomatic zone c.100 m wide of alternate dark blue (mafic) and pale grey (felsic) banded fenites which grade into unfenitized bedded slates and phyllites. The Na-amphiboles in the banded fenites form a complete solid solution series between magnesio-arfvedsonite and magnesio-riebeckite which coexist with varying proportions of aegirine, albite, and K-feldspar, with or without phlogopite or biotite.

The amphiboles show a gradual decrease in Na2O, K2O, Mg ratio [100Mg/(Mg + FeT + Mn)] and iron oxidation ratio, and an increase in total iron away from the carbonatite contact. The pleochroism correlates with the chemistry and distance from the carbonatite contact.

The Mg ratio decreases from 74 to 35 away from the carbonatite contact. The iron oxidation ratio [100Fe3+/ (Fe3+ + Fe2+)] decreases in the magnesio-arfvedsonite for the first 30 metres from the carbonatite contact, and then increases in the magnesio-riebeckite from 40 to 60 metres from the carbonatite contact. K relative to Na decreases away from the contact in the amphibole, and the decrease in K causes an increase in vacancy in the A site. The main variation in the chemistry in this solid solution series is due to (K,Na)A+(Mg,Fe2+)c ⇌ □ + (Fe3+)c substitution.

Full chemical analysis, cell dimensions, γ refractive index, density, and infra-red absorption spectrum have been determined for fourteen stilpnomelanes. Coupled with data from previously described material and electron probe analyses of three further samples, the new information shows that γ = 1·616+0·0047 Fe3+ −0·0037 Mg; substitution of Mn for Fe appears to have little effect on γ. For ferrostilpnomelane, D = 2·85−0·011 Mg, for ferristilpnomelane, D = 2·89−0·011 Mg. Cell dimensions clearly distinguish ferro-, ferri-, and man-ganstilpnomelanes; for ferri-stilpnomelane a = 22·03−0·00446 Mg−0·00786 Fe3+ (Å). A convenient approximation to the structural formula using a ⅛ subcell, is K0·6(Mg, Fe2+Fe3+)6Si8Al(O,OH)27 2–4 H2O.

Sazhinite-(La) is a new mineral from the Aris phonolite, Windhoek, Namibia. It occurs in vesicles within the phonolite, together with other species crystallized from late-stage hydrothermal fluids: natrolite, aegirine, microcline, apophyllite, sphalerite, analcime, fluorite, villiaumite, hydroxylapatite, galena, makatite, quartz, eudialyte, kanemite, tuperssuatsiaite and korobitsynite. Sazhinite-(La) forms small euhedral crystals up to 1 mm long and 0.4 mm wide, elongated along [001] and flattened on (010), exhibiting the forms {h0l}, {100} and {001}. It has good cleavage parallel to {010} and {001}. Twinning was not observed. Crystals are brittle with a Mohs hardness of 3, creamy white with a white streak, vitreous to pearly lustre, and translucent to transparent. In plane-polarized light, crystals are colourless with a = Z, b = Y, c = X. It is biaxial positive with α = 1.524, β = 1.528, γ = 1.544, all ±0.002, 2Vz(obs) = 46(1)°, and 2Vz(calc.) = 53.6°.

Sazhmite-(La) is orthorhombic Pmm2, a = 7.415(2), b = 15.515(3), c = 7.164(1) Å, and V = 824.2 Å3. One crystal was studied by X-ray diffraction, electron microprobe and secondary ion mass spectrometry (SIMS) microanalysis, leading to the average composition (Na2.87K0.02Sr0.01)Σ2.90 [La0.41Ce0.35Pr0.02Nd0.04(Sm,Gd,Dy,Er,Yb)Σ0.01Th0.09U0.01Y0.01Zr0.01Ca0.08Li0.01]Σ1.04 (S15.87S0.06B0.01) (O14.86F0.14).(H2O)2.

Weighted full-matrix least-squares refinement on 3369 reflections yielded Rall = 3.8%. The structure is built of corrugated [Si6O15]6- layers linked by [7]-coordinated REE and R4+ cations. This framework leaves channels that contain three [5]- and [6]-coordinated Na cations per formula unit that compensate for the residual charge on the silicate layers. The SIMS analyses confirm a Na content of 3 atoms per formula unit, leading to an ideal formula of Na3LaSi6O15(H2O)2. The third Na atom is bonded to H2O groups and therefore the total content of both Na and H2O may be reduced to 2 and 1 per formula, respectively. The depletion in Na allows for the entrance of high-charge cations such as Th4+.

Perovskite group minerals, general formula ABX3, from the intrusive ultramafic alkaline Gardiner Complex, East Greenland, range from almost pure CaTiO3 (perovskite, sensu stricto), to the rare earth element (REE) variety, loparite-(Ce). Chemical zonation in the perovskites (sensu lato), is described by the substitutions 2Ca2+ = (Na+ + REE3+) on the A-site and 2Ti4+ = (Fe3+ + Nb5+) on the B-site. Other trace elements detected include Th, Sr, Al, Si, Zr, Ta and Sn. Excellent agreement was found between the determinations of the REE by electron microprobe and neutron activation analysis. Chondrite-normalized REE patterns display enrichment in the light rare earths for perovskite, loparite, apatite, melilite and diopside. Mean perovskite/apatite partition coefficients from four of the Gardiner rocks were calculated as La = 10.4, Ce = 13.8, Nd = 13.9, Sm = 9.9, Eu = 7.7, Gd = 5.2, Tb = 5.6, Tm = 5.5, Yb = 2.7 and Lu = 1.6, indicating that perovskite concentrates all REE to a much greater extent than apatite. Light-REE enrichment occurs in both perovskite and apatite.

The crystal structure of galeite from Searles Lake (California) has been determined by means of X-ray diffraction data on a single crystal. A possible structure was derived from that of schairerite on the basis of chemical and lattice analogies and was confirmed by comparison of the observed diffractometric structure factors with the calculated ones. The refinement was performed by least-squares methods employing isotropic thermal parameters and assuming that atoms related by translational pseudosymmetry exhibit equal thermal parameters. The final R value is 0·09. The cell content is 3[Na15(SO4)5F4Cl]; the space group is P31m The lattice dimensions are a 12·197(4)Å, c 13·955(10) Å The marked subcell has P3m1 symmetry and a 7·042Å, c 13·955 Å. The crystal structure of galeite consists of a three-dimensional framework, formed by coordination octahedra around Na+ ions, including tetrahedral holes with sulphur atoms at the centres. The three-dimensional framework can be considered built up by five octahedral sheets (seven sheets can be recognized in schairerite and six in sulphohalite). The very close analogies occurring in the structures of galeite and schairerite are discussed.

The weathering and oxidation of mine tailings has the potential to contaminate water and soil with toxic elements. To understand the mechanisms, extent and products of the long-term weathering of complex Bolivian tailings from the Cerro Rico de Potosí, and their effects on As, Pb, P and Sb cycling, three-year long laboratory column experiments were carried out to model 20 years of dry- and wet-season conditions in the Pilcomayo basin. Chemical analysis of the leachate and column solids, optical mineralogy, X-ray diffraction, scanning electron microscopy, electron probe microanalysis, microscale X-ray absorption near edge structure spectroscopy, Bureau Commun de Référence sequential extraction and water-soluble chemical extractions, and speciation modelling have shown that the weathering of As-bearing pyrite and arsenopyrite, resulted in a loss of 13–29% of the original mass of As. By contrast, Pb and Sb showed much lower mass losses (0.1–1.1% and 0.6–1.9%, respectively) due to the formation of insoluble Pb- and Sb(V)-rich phases, which were stable at the low pH (~2) conditions that prevailed by the end of the experiment. The experiment also demonstrated a link between the cycling of As, Sb, and the oxidation of Fe(II)-bearing sphalerite, which acted as a nucleation point for an Fe-As-Sb-O phase. Phosphorus was relatively immobile in the tailings columns (up to 0.3% mass loss) but was more mobile in the soil-bearing columns (up to 10% mass loss), due to the formation of soluble P-bearing minerals or mobilization by organic matter. These results demonstrate the influence of mine tailings on the mobility of P from soils and on the potential contamination of ecosystems with As, and strongly suggest that these materials should be isolated from fluvial environments.

Naujakasite (Na6(Fe,Mn)Al4Si8O26) is a characteristic, rock-forming mineral of hyperagpaitic naujakasite lujavrite (arfvedsonite + naujakasite + steenstrupine + albite ± relict nepheline ± microcline ± ussingite) from the Ilímaussaq complex, South Greenland, and is only known from this complex. The qualitative stability relationships of naujakasite-bearing, low-variance liquidus mineral assemblages at near-solidus conditions in lujavritic magma can be modelled within the six-component system Si-Al-Fe-Na-O-H. The modelling suggests that an uncommon combination of elevated water activity and low oxygen fugacity is needed to stabilize arfvedsonite + naujakasite mineral assemblages in highly sodic liquids. These conditions are incompatible with the stable coexistence of aegirine and arfvedsonite. They are met in the arfvedsonite-bearing lujavrites of Ilímaussaq, but apparently not in rocks of similar composition in the Khibina and Lovozero complexes, Kola Peninsula, where aegirine- or aegirine-arfvedsonite-bearing mineral assemblages are characteristic. Liquid lines of descent leading to crystallization of naujakasite have to pass through the albite+nepheline+arfvedsonite liquidus field in the Si-Al-Fe-Na-O-H system, reaching this field at the high-Na side of the albite-nepheline-arfvedsonite plane.

An orbicular diorite from Fisher Lake, California, USA, contains multi-shelled, magmatic orbicules with branching and budding orthopyroxene crystals as well as feather and acicular plagioclase crystals that are oriented perpendicular to the growth horizon. Plagioclase and orthopyroxene show gradual, reverse compositional zoning along the long axes and normal zoning along the short axes. The reverse zoning varies from An87 to An93 and Mg68 to Mg74 over distances of 4 mm and 8 mm respectively. The close proximity of these two minerals makes it likely that only one mechanism is responsible for the reverse zoning. This zoning can be explained by using relevant temperature-composition diagrams and Gibbs free energy-composition plots. Under sudden and moderate undercoolings, which produce high growth but low nucleation rates, the difference in Gibbs free energy (ΔG) between the crystals and liquid is not initially maximized, i.e. initial compositions are not near-to-equilibrium. This results in crystal compositions that are closer to that of the bulk liquid than expected for crystallization under near-to-equilibrium conditions (i.e. very small ΔT). Over time, and under isothermal crystallization conditions, ΔG gradually increases to a maximum producing crystal compositions that also gradually attain near-to-equilibrium compositions. Subsequent to attaining these conditions, normal zoning occurs perpendicular to the crystal growth axes.

The single crystal X-ray methods for the study of exsolution phenomena in pyroxenes previously described by the authors have been applied to the pyroxenes of the Skaergaard intrusion. The results for about fifty pyroxene crystals, selected from various levels between the chilled margin and a height of 2600 metres in the layered series, are presented and are correlated with previous optical descriptions. Whilst the correlation between the results of the optical and X-ray examinations is in general satisfactory, the present investigation shows that the X-ray techniques can in some cases extend our knowledge of the Skaergaard pyroxenes.

The Good Hope carbonatite is located adjacent to the Prairie Lake alkaline rock and carbonatite complex in northwestern Ontario. The occurrence is a heterolithic breccia consisting of diverse calcite, dolomite and ferrodolomite carbonatites containing clasts of magnesio-arfvedsonite + potassium feldspar, phlogopite + potassium feldspar together with pyrochlore-bearing apatitite clasts. The apatitite occurs as angular, boudinaged and schlieren clasts up to 5 cm in maximum dimensions. In these pyrochlore occurs principally as euhedral single crystals (0.1–1.5 cm) and can comprise up to 25 vol.% of the clasts. Individual clasts contain compositionally- and texturally-distinct suites of pyrochlore. The pyrochlores are hosted by small prismatic crystals of apatite (~100–500 μm × 10–25 μm) that are commonly flow-aligned and in some instances occur as folds. Allotriogranular cumulate textures are not evident in the apatitites. The fluorapatite does not exhibit compositional zonation under back-scattered electron spectroscopy, although ultraviolet and cathodoluminescence imagery shows distinct cores with thin (<50 μm) overgrowths. Apatite lacks fluid or solid inclusions of other minerals. The apatite is rich in Sr (7030–13,000 ppm) and rare earth elements and exhibits depletions in La, Ce, Pr and Nd (La/NdCN ratios (0.73–1.14) relative to apatite in cumulate apatitites (La/NdCN > 1.5) in the adjacent Prairie Lake complex. The pyrochlore are primarily Na–Ca pyrochlore of relatively uniform composition and minor Sr contents (<2 wt.% SrO). Irregular resorbed cores of some pyrochlores are A-site deficient (>50%) and enriched in Sr (6–10 wt.% SrO), BaO (0.5–3.5 wt.%), Ta2O5 (1–2 wt.%) and UO2 (0.5–2 wt.%). Many of the pyrochlores exhibit oscillatory zoning. Experimental data on the phase relationships of haplocarbonatite melts predicts the formation of apatite and pyrochlore as the initial liquidus phases in such systems. However, the texture of the clasts indicates that pyrochlore and apatite did not crystallise together and it is concluded that pyrochlores formed in one magma have been mechanically mixed with a different apatite-rich magma. Segregation of the apatite–pyrochlore assemblage followed by lithification resulted in the apatitites, which were disrupted and fragmented by subsequent batches of diverse carbonatites. The genesis of the pyrochlore apatitites is considered to be a process of magma mixing and not simple in situ crystallisation.

Electron-probe data are presented for coexisting magnetite and ilmenite from seven gabbro cumulates and a gabbro pegmatite, and bulk FeO-Fe2O3-TiO2 analyses for ten magnetite-ilmenite assemblages. The oxides equilibrated at 580 to 720 °C and oxygen fugacities of 10−15·0 to 10−20·5 bar. Late-stage alteration, associated with growth of hydrothermal silicates, resulted in the breakdown of ilmenite to rutile and the dissolution of magnetite. Higher levels in the intrusion equilibrated at lower temperatures than deeper levels. All features described are consistent with the retention of the initial water content of the magma within the walls of the intrusion.