The stability field of analcime solid solutions in the system NaAlSi3O8-NaAlSiO4-H2O has been previously determined by Kim and Burley (1971a). These experiments are re-examined with a view to determining the variations of the room-temperature cell parameters of analcime as a function of temperature of synthesis and composition. It is shown from this evidence that most of the analcime solid solutions in these experiments are equilibrium compositions. The increase in the cell dimension of quenched analcime solid solution is found to be 5 × 10−5 Å/°C. It is suggested that birefringence in analcime is induced by low water-pressure relative to total pressure. A phase transition appears to be observed in quenched analcimes of this study and is thought to be the same as that in the Golden analcime reported by Yoder and Weir (1960).

Three new minerals in the dumortierite supergroup were discovered in the Szklary pegmatite, Lower Silesia, Poland. Nioboholtite, endmember (Nb0.6☐0.4)Al6B3Si3O18, and titanoholtite, endmember (Ti0.75☐0.25)Al6B3Si3O18, are new members of the holtite group, whereas szklaryite, endmember ☐Al6BAs3+3O15, is the first representative of a potential new group. Nioboholtite occurs mostly as overgrowths not exceeding 10 μm in thickness on cores of holtite. Titanoholtite forms patches up to 10 μm across in the holtite cores and streaks up to 5 μm wide along boundaries between holtite cores and the nioboholtite rims. Szklaryite is found as a patch ∼2 μm in size in As- and Sb- bearing dumortierite enclosed in quartz. Titanoholtite crystallized almost simultaneously with holtite and other Ta-dominant minerals such as tantalite-(Mn) and stibiotantalite and before nioboholtite, which crystallized simultaneously with stibiocolumbite during decreasing Ta activity in the pegmatite melt. Szklaryite crystallized after nioboholtite during the final stage of the Szklary pegmatite formation. Optical properties could be obtained only from nioboholtite, which is creamy-white to brownish yellow or grey-yellow in hand specimen, translucent, with a white streak, biaxial (–), nα = 1.740 – 1.747, nβ ∼ 1.76, nγ ∼ 1.76, and Δ < 0.020. Electron microprobe analyses of nioboholtite, titanoholtite and szklaryite give, respectively, in wt.%: P2O5 0.26, 0.01, 0.68; Nb2O5 5.21, 0.67, 0.17; Ta2O5 0.66, 1.18, 0.00; SiO2 18.68, 21.92, 12.78; TiO2 0.11, 4.00, 0.30; B2O3 4.91, 4.64, 5.44; Al2O3 49.74, 50.02, 50.74; As2O3 5.92, 2.26, 16.02; Sb2O3 10.81, 11.48, 10.31; FeO 0.51, 0.13, 0.19; H2O (calc.) 0.05, –, –, Sum 96.86, 96.34, 97.07, corresponding on the basis of O = 18–As–Sb to {(Nb0.26Ta0.02☐0.18)(Al0.27Fe0.05Ti0.01)☐0.21}Σ1.00Al6B0.92{Si2.03P0.02(Sb0.48As0.39Al0.07}Σ3.00(O17.09OH0.04☐0.87)Σ18.00, {(Ti0.32 Nb0.03 Ta0.03☐0.10)(Al0.35 Ti0.01 Fe0.01)☐0.15 }Σ1.00 Al6 B0.86 {Si2 . 3 6 (Sb0.5 1 As0.14 )}Σ3.01(O17.35☐0.65)Σ18.00 and {☐0.53 (Al0.41 Ti0.02 Fe0.02 )(Nb0.01☐0.01 )}Σ1.00Al6 B1.01 {(As1.07 Sb0.47 Al0.03 ) Si1.37 P0.06 }Σ3.00(O16.46☐1.54 )Σ18.00. Electron backscattered diffraction indicates that the three minerals are presumably isostructural with dumortierite, that is, orthorhombic symmetry, space group Pnma (no. 62), and unit-cell parameters close to a = 4.7001, b = 11.828, c = 20.243 Å, with V = 1125.36 Å3 and Z = 4; micro-Raman spectroscopy provided further confirmation of the structural relationship for nioboholtite and titanoholtite. The calculated density is 3.72 g/cm3 for nioboholtite, 3.66 g/cm3 for titanoholtite and 3.71 g/cm3 for szklaryite. The strongest lines in X-ray powder diffraction patterns calculated from the cell parameters of dumortierite of Moore and Araki (1978) and the empirical formulae of nioboholtite, titanoholtite and szklaryite are [d, Å, I (hkl)]: 10.2125, 67, 46, 19 (011); 5.9140, 40, 47, 57 (020); 5.8610, 66, 78, 100 (013); 3.4582, 63, 63, 60 (122); 3.4439, 36, 36, 34 (104); 3.2305, 100, 100, 95 (123); 3.0675, 53, 53, 50 (105); 2.9305, 65, 59, 51 (026); 2.8945, 64, 65, 59 (132), respectively. The three minerals have been approved by the IMA CNMNC (IMA 2012-068, 069, 070) and were named for their relationship to holtite and occurrence in the Szklary pegmatite, respectively.

Experiments in the system NaAlSiO4(Ne)−KAlSiO4(Ks)−SiO2(Qz)−H2O at 100 MPa show that the maximum content of NaAlSi2O6 in leucite is ∼4 wt.% and that analcime is close to the stoichiometric composition (NaAlSi2O6.H2O). Analcime forms metastably on quenching the higher-temperature experiments; it is secondary after leucite in experiments quenched from 780°C, while from 850°C it forms by alteration of leucite, and by devitrification of water-saturated glass. Both processes involve reaction with Na-rich aqueous fluids. Stable analcime forms at 500°C, well below the solidus, and cannot form as phenocrysts in shallow volcanic systems. New data for natural analcime macrocrysts in blairmorites are presented for the Crowsnest volcanics, Alberta, Canada. Other researchers have suggested that primary analcime occurs as yellow-brown, glassy, analcime phenocrysts. Our microprobe analyses show that such primary analcime is close to stoichiometric, with very low K2O (<0.1 wt.%), minor Fe2O3 (0.5−0.8 wt.%) and CaO (∼0.5 wt.%). An extrapolation of published experimental data for Ne−Ks−Qz at >500 MPa PH2O, where Anl + melt coexist, suggests that at >800 MPa two invariant points are present: (1) a reaction point involving Kf + Ab + Anl + melt + vapour; and (2) a eutectic with Kf + Anl + Ne + melt + vapour. We suggest that the nepheline-free equilibrium mineral assemblage for Crowsnest samples is controlled by reaction point (1). In contrast, blairmorites from Lupata Gorge, Mozambique, form at eutectic (2), consistent with the presence of nepheline phenocrysts. Our conclusions, based on high- vs. low-pressure experiments, confirm the suggestion made by other authors, that Crowsnest volcanic rocks must have been erupted explosively to preserve glassy analcime phenocrysts during very rapid, upward transport from deep in the crust (H2O pressures ≫500 MPa). Only rare examples survived the deuteric and hydrothermal alteration that occurred during and after eruption.

Deep azure-blue beryl is reported from veins in Upper Devonian conglomerate from southeast Ireland. Microprobe analysis, Mössbauer spectroscopy and loss on ignition suggest an unusual chemistry with an exceptionally high degree of substitution of Fe and Mg for Al, and extreme amounts of Na and water held within channel sites in the structure. The calculated structural formula is:

Refractive indices (1.603 and 1.595) and the cell edge, a, (9.292 Å) are also unusually high. Colourless beryl from the same locality, some of which forms cores to blue beryl prisms, has less octahedral substitution and a lower Fe/Mg ratio. The origin of the beryl is tentatively linked to contemporaneous volcanic activity.

Since its discovery by Tilley in 1930, scawtite has been recognized in several locations in regions of metamorphosed siliceous limestones. Scawtite is believed to be the same as CSH(A) and, as such, has been synthesized sporadically many times during runs in the CaO-SiO2-H2O system where slight contamination from CO2 has occurred. Attempts to synthesize scawtite were successfully carried out at low partial pressures of CO2 in an excess of water. The stability of selected scawtite compositions lies between 140 and 300° C, and above saturated steam pressures is not pressure-dependent, at least up to 50 000 psi. The scawtite facies (2) lies between the tobermorite-calcite facies (3) and the xonotlite-calcite facies (1). A hydration series exists from (1) to (2) to (3).

Grandidierite has been found in hornfelses around a diorite stock on Cuvier Island. Physical properties and electron microprobe analyses are given for two Cuvier Island and two Madagascan grandidierites. The Cuvier Island grandidierite has crystallized under conditions of the K-feldspar-cordierite hornfels facies at temperatures of approximately 600°C. and pressures (Pload) of less than 300 bars.

The thermal disintegration of crocidolite has been investigated with X-ray powder and rotation photographs. Initial disintegration products include monoclinic pyroxene, iron oxide phases, and eristobalite as a pseudomorph of the original fibre bundles but at about 1000° C fusion occurs due to incongruent melting of the pyroxene. The products are strongly oriented along the fibre axis and full orientation relationships have been deduced with the aid of structural models. From these relationships it is suggested that regions of the amphibole structure on (100) are retained in the product phases without change in orientation.

The near field, together with the containment and isolation provided by the geosphere, contributes to the long-term safety provided by a geological disposal facility (GDF) after closure. The different engineered barriers can prevent or limit the release of radionuclides and their migration to the undisturbed host rock or geosphere and are expected to fulfil their post-closure safety functions for many thousands to hundreds of thousands of years. They will continue to contribute to containment after their eventual degradation when there would no longer be confidence that they would continue to fulfil all of their safety functions in their totality. By that time, significant radioactive decay will have occurred, substantially reducing the hazard associated with the wastes. Therefore, demonstration of long-term safety requires an understanding of the evolution of the engineered barriers and the consequences for the generic safety functions that the different barriers provide. This paper provides an overview of the research of the Nuclear Decommissioning Authority Radioactive Waste Management Directorate into the evolution of the near field of a GDF.

A study of phase equilibria among the orthosilicates on the Ca2SiO4—CaMgSiO4 join was undertaken with the use of hydrothermal techniques in the temperature range 600–900°C. at water pressures from 1000 to 15000 psi. Monticellite, merwinite, and Ca2SiO4 crystallize as pure phases throughout this temperature range, and intermediate compositions contain mixtures of the end members. Powder X-ray diffraction data obtained on the mixtures indicate no change in lattice dimensions from the end members. Hence, very little or no solid solution is indicated at these temperatures. Ca2SiO4 was crystallized as the γ-form below 675°C. (at 2000 psi) and the β-form above this temperature (presumably having inverted from the α′-form on cooling to room temperature). Infra-red absorption spectra obtained on the compounds γ-Ca2SiO4, β-Ca2SiO4, merwinite, and monticellite show characteristic differences in the pattern within the 9–13 micron region. All the data thus appear to confirm merwinite as a unique compound stable in the temperature range studied.

Five turquoise samples, belonging to the XVII century historical collection of the Real Museo Mineralogico (University of Naples Federico II), were investigated by a multi-methodological approach based on powder X-ray diffraction, electron microprobe analysis in wavelength-dispersive spectroscopy mode, backscattered electron images from scanning electron microscopy in energy-dispersive spectroscopy mode, laser ablation inductively coupled plasma mass spectrometry, Fourier transform infrared and Raman spectroscopy.

The samples originate from Sinai (Egypt), Santa Fè S. Miguel (New Mexico), Saxony (Germany), Montebras Creuse (France) and Nishapur (Khorassan, Iran) and display different mineralogical compositions and various mineral associations. The study has shown the presence of: (1) four minerals of the turquoise group: turquoise, faustite, chalcosiderite and planerite; (2) other phosphates from different groups: wavellite, crandallite, goyazite, gorceixite, variscite, metavariscite, fluorapatite; and (3) other minerals: voltaite, adularia and quartz.

The present investigation is intended to show the mineralogical and geochemical variability of the samples with particular attention to the mineralogical parageneses, textural analyses and trace-element concentrations.

Present-day facies schemes are reviewed in relation to their definitions and applicability: a simplification is proposed based on assemblages in basaltic rocks, with secondary facies defined subsequently on pelitic assemblages.

Germanium abundances, determined by laser ablation-inductively coupled plasma-mass spectrometry, are presented for phenocrysts and glass matrices from a metaluminous trachyte and four peralkaline rhyolites from the Greater Olkaria Volcanic Complex, Kenya Rift Valley, Africa. Abundances (in ppm) are: sanidine 0.45–0.61; fayalite 4.8–11.7; hedenbergite 5.1–9.0; titanomagnetite 2.7; ilmenite 0.48; amphibole 8.3–8.9; biotite 7.0; chevkinite-(Ce) 309; trachyte glass 3.0; rhyolitic glasses 2.3–3.9. These values are generally greater than those recorded for silicic rocks in the literature, whilst the chevkinite-(Ce) value is the largest yet found in a magmatic mineral. Apparent partition coefficients range from 0.15–0.26 in sanidine to 124 in chevkinite-(Ce). Those for fayalite and hedenbergite increase with whole-rock peralkalinity and Fe content. The possibility of a role for accessory phases in influencing Ge distribution in rock-forming minerals is also raised.

The thermal decomposition of caledonite has been examined by simultaneous differential thermal analysis, thermogravimetry and mass spectrometry. Structural H2O and CO2 are liberated endothermically between 300 and 400°C leaving a residue of lead sulphate, oxysulphate, and Cu(I) and Cu(II) oxides. A series of sharp endothermic peaks between 850 and 950°C correspond to phase transition and melting reactions of the PbO-PbSO4 mixture. The sulphate anion breaks down above 880 °C. Mass spectra of the gaseous decomposition products show SO2, SO, and O2, although SO is an artefact arising from ion fragmentation of the SO2 within the mass spectrometer. The residue at 1060 °C is composed predominantly of 2PbO · PbSO4 and Cu(I) and Cu(II) oxides.

An ideal solution model has been used to calculate the effect of the substitutions on the stability fields of the Al2SiO5 minerals. The results show that divariant assemblages of andalusite+sillimanite and sillimanite + kyanite solid solutions can coexist over ranges of 0·1 to 0·4 kbar at 527° C, but that kyanite+andalusite would be stable over a much narrower range. On adding (Fe, Mn)3+ to the system, the andalusite/sillimanite curve can be considered to rotate about the invariant point, first eliminating the sillimanite field, and then penetrating the kyanite field. Wide zones of viridine+sillimanite and viridine+kyanite are thus formed.

In view of the ease with which epitaxial nucleation occurs in the Al2SiO5 system, it is considered that extensive metastable growth of andalusite, sillimanite, and kyanite is improbable in nature. Metastable persistence is likely to occur in dry systems, or in the presence of an ‘armour’ of the stable phase, but reaction of millimetre-sized crystals should be completed in geologically short times when aqueous or silicate liquids are present. The combination of the effects of metastable persistence and solid solution seems adequate to account for essentially all the examples of kyanite + sillimanite and kyanite + andalusite, and for many sillimanite +andalusite assemblages. In addition, if small supersaturations develop during metamorphism, simultaneous growth of andalusite + sillimanite could occur over a restricted temperature range.

Rinkite-(Y), ideally Na2Ca4YTi(Si2O7)2OF3, is a new rinkite-group (seidozerite-supergroup) TS-block mineral from the Darai-Pioz alkaline massif, Tian-Shan mountains, Tajikistan. The mineral is of hydrothermal origin. It occurs as aggregates (up to 1.5 cm long) of acicular crystals 0.1–1.0 mm thick, and as separate elongated columnar, flattened-prismatic crystals up to 1 cm long with rectangular or rhombic sections up to 0.5 mm across. Associated minerals are quartz, aegirine, microcline, neptunite, pectolite, calcite, eudialyte-group minerals, fluorite, titanite, turkestanite, kupletskite, galena, albite and pyrochlore-group minerals. Crystals are transparent and colourless to occasionally white, with a vitreous lustre. Rinkite-(Y) has a white streak, uneven, conchoidal fracture and does not fluoresce under a cathode or ultraviolet light. Cleavage is very good on {100}, no parting was observed, Mohs hardness is ~5, and it is brittle, Dmeas. = 3.44(2) g/cm3, Dcalc. = 3.475 g/cm3. It is biaxial (+) with refractive indices (λ = 590 nm) α = 1.662(2), β = 1.666(2), γ = 1.685(5); 2Vmeas. = 50(3) and 2Vcalc. = 49.7°. It is nonpleochroic. Rinkite-(Y) is monoclinic, space group P21/c, a = 7.3934(5), b = 5.6347(4), c = 18.713(1) Å, β = 101.415(2)° and V = 764.2(2) Å3. The six strongest reflections in the X-ray powder diffraction data [d(Å), I, (hkl)] are: 3.057, 100, (006, $\bar{2}$12, 210); 2.688, 28, (016); 9.18, 24, (002); 2.929, 17, ($\bar{2}$13, 211); 3.559, 15, (104, 014) and 2.783, 14, (021). The empirical formula calculated on 18 (O + F) is Na2.11(Ca3.74Sr0.03Mn0.03)Σ3.80(Y0.50Nd0.16Ce0.16Gd0.07Dy0.06Sm0.05Pr0.03La0.03${\rm U}_{0.01}^{{\rm 4 + }} {\rm )}_{\Sigma 1.07}{\rm (T}{\rm i}_{0.85}{\rm N}{\rm b}_{0.17}{\rm W}^{6+}_{0.01}{\rm T}{\rm a}_{0.01}{\rm )}_{\Sigma 1.04}\left( {{\rm S}{\rm i}_{4.03}{\rm O}_{14}} \right){\rm O}_{1.40}{\rm F}_{2.60}$ with Z = 2. The ideal formula is Na2Ca4YTi(Si2O7)2OF3. The crystal structure was refined on a twinned crystal to R1 = 4.59% on the basis of 1489 unique reflections (F > 4σF) and is a framework of TS (Titanium-Silicate) blocks. The TS block consists of HOH sheets (H – heteropolyhedral, O – octahedral) parallel to (100). In the O sheet, the Ti-dominant [6]MO1 site ideally gives 1 Ti apfu. The [8]MO2 and [6]MO3 sites are ideally occupied by Na and (NaCa) apfu. In the H sheet, the [7]MH site is occupied by Ca1.13Y0.50REE0.37, (REE = rare-earth element), ideally (CaY), <MH–φ> = 2.415 Å and the [7]AP site is occupied by Ca1.81REE0.19, ideally Ca2, <AP–φ> = 2.458 Å. The MH + AP sites ideally give (Ca3Y) apfu. The MH and AP polyhedra and Si2O7 groups constitute the H sheet. Linkage of H and O sheets via common vertices of MH and AP polyhedra and Si2O7 groups with MO1–3 polyhedra results in a TS block. The TS block in rinkite-(Y) exhibits linkage 1 and stereochemistry typical for the rinkite group (Ti = 1 apfu) of the seidozerite supergroup. For rinkite-(Y), the ideal structural formula of the form AP2MH2MO4(Si2O7)2$ \left( {{\rm X}_{\rm M}^{\rm O} } \right)_2\left( {{\rm X}_{\rm A}^{\rm O} } \right)_2{\rm is }\;\left( {{\rm C}{\rm a}_3{\rm Y}} \right){\rm Na}\left( {{\rm NaCa}} \right){\rm Ti}\left( {{\rm S}{\rm i}_2{\rm O}_7} \right)_2\left( {{\rm OF}} \right){\rm F}_2 $ with Z = 2. The mineral is named rinkite-(Y) as it is structurally identical to rinkite-(Ce) and Y is the dominant rare-earth element.

Microprobe analysis of marshite and miersite from Broken Hill, Australia, demonstrate extensive solid solution between the end-members CuI and AgI, indicating the possibility of a complete solid-solution series. Unit-cell parameters increase from 6.054 Å for marshite to 6.504 Å for miersite, closely following Vegard's Law. The Cu content of iodargyrite is generally below the limit of detection, but one zoned crystal contained 0.28 wt.% Cu. Crystallization of either miersite or iodargyrite at Broken Hill appears to be dependent upon the local availability and ratio of copper, silver and iodine ions.

The new mineral alwilkinsite-(Y) (IMA2015-097), Y(H2O)7[(UO2)3(SO4)2O(OH)3]·7H2O, was found in the Blue Lizard mine, San Juan County, Utah, USA, where it occurs as a secondary alteration phase.The mineral is slightly flexible before brittle failure with splintery fracture and perfect cleavage parallel to [010], has Mohs hardness of ∼2–2½, exhibits dull greenish-grey fluorescence and has a calculated density of 3.371 g cm–3. Alwilkinsite-(Y) occursas yellowish-green needles, elongate on [010], with domatic terminations and exhibits the forms {102}, {301} and {124}. It is optically biaxial (+) with α = 1.573(1), β = 1.581(1), γ = 1.601(1) (white light), the measured 2V is 65.3(1)°, the dispersion is r<v (weak), the optical orientation is X = c, Y = a, Z = b and there is no pleochroism. Electron microprobe analyses yielded the empirical formula (Y0.66Dy0.08Gd0.06Er0.05Nd0.03Yb0.03Sm0.02Ce0.01)∑0.94(H2O)7[(UO2)3(S1.01O4)2O(OH)3]·7H2O.The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 9.88(100)(101,002), 7.47(13)(102), 5.621(17)(103,201), 4.483(18)(104), 3.886(14)(130,222), 3.322(46)(multiple), 3.223(13)(multiple) and 3.145(16)(034). Alwilkinsite-(Y) is orthorhombic,P212121, a = 11.6194(5), b = 12.4250(6), c = 19.4495(14) Å, V = 2807.9(3) Å3 and Z = 4. The structure of alwilkinsite-(Y) (R1 = 0.042 for 4244 Fo > 4σF)contains edge-sharing chains of uranyl bipyramids with outlying sulfate tetrahedra that are similar to the chain linkages within the uranyl sulfate sheets of the zippeite structure. Short segments of the uranyl sulfate chains in the alwilkinsite-(Y) structure have the same topology as portionsof the uranyl sulfate linkages in uranopilite. Alwilkinsite-(Y) is named for Alan (Al) J. Wilkins, MD (born 1955), the discoverer of the mineral.

Johnsomervilleite, Na10Ca6Mg18(Fe, Mn)25 (PO4)36 has Z = 3, a 15.00 Å, c 42.75 Å and cell volume 8330 Å3 and is a new rhombohedral species occurring in two metamorphic segregation pods in Moine gneiss of kyanite-sillimanite grade. Associated minerals are apatite, jahnsite, graftonite, mineral A, phosphosiderite, rockbridgeite, mitridatite, and vivianite. It is dark brown, brittle, and glassy, H = 4½, D = 3·35 (calc. 3.41) with a perfect basal (?) cleavage. Eight electron probe analyses are given and d spacings for 50 lines. The mineral, which is a Mg-Fe analogue of fillowite, is named after the late Mr J. M. Somerville who presented a specimen of garnet-quartz rock, which contained the new species, to the Royal Scottish Museum.

Of the results which have so far been achieved by study of the packing of equal spheres one of the most remarkable, both by reason of its simplicity and of its fundamental importance, was that announced by Barlow in 1883. He called attention to the fact that equal spheres can be most densely packed in two ways, one possessing cubic symmetry and the other hexagonal (fig. 1).

Already in 1862 Tait had investigated the piling of marbles of equal size and had noticed that ‘there are two obvious ways of constructing the layers, and two of applying layer to layer’: nevertheless his two densest arrangements are in fact identical. He saw that the cubic structure could be begun either upon a square base or a triangular base but failed to perceive the possibility of the hexagonal arrangement.