The development of the morphology of baryte crystals grown in a silica gel medium is related to the changes in supersaturation. Nucleation occurs when the supersaturation in the system exceeds a threshold value which depends on the supersaturation rate, i.e. the rate at which the supersaturation is changing at the nucleation site. During growth the supersaturation decreases, although a high level of supersaturation is maintained throughout. These experimental results compare well with the morphological development predicted from theoretical models based on the periodic bond chain theory. The ontogeny of natural harytes corresponds, in considerable detail, to the experimental observations made here and strongly suggests that similarly high supersaturations have prevailed in nature. This correspondence indicates that the technique of crystal growth in a porous silica gel medium provides a good experimental model of studying natural growth processes.

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.

Irinarassite, Ca3Sn2SiAl2O12, a new mineral species of the garnet supergroup was discovered in metasomatically altered carbonate-silicate xenoliths in ignimbrites of the Upper Chegem Caldera, Northern Caucasus, Kabardino-Balkaria, Russia. It occurs as small zones and irregular spots in kimzeyite-kerimasite or rarely as single crystals not exceeding 10 μm in size, within complex pseudomorphs after zircon. Lakargiite, tazheranite, baddeleyite, kerimasite, kimzeyite, baghdadite and rarely magnesioferrite are associated with irinarassite in the pseudomorphs which are confined to larnite-cuspidine zones immediately adjoining the ignimbrite. Larnite, cuspidine, rondorfite, fluor- and hydroxylellestadite, fluorite and secondary minerals such as ettringite, hillebrandite and bultfonteinite are associated with irinarassite. Irinarassite is pale brown to yellow colour. The mineral is characterized by the absence of cleavage and by an irregular fracture. The calculated density is 4.3 g cm–1. The mineral is isotropic with a calculated refractive index of 1.9. The empirical crystal chemical formula of irinarassite from the holotype specimen is as follows (Ca2.965Fe2+0.035)Σ3(Sn1.016Zr0.410Ti0.262Sb5+0.237Fe2+0.035U6+0.017Sc0.014Hf0.006Nb0.004)Σ2.001(Al1.386Fe3+0.804Si0.446Ti4+0.364)Σ3O12. Electron backscatter diffraction patterns of irinarassite are fitted to the garnet model with a = 12.50(3) Å with excellent MAD (mean angular deviation) = 0.16°. The Raman spectrum of irinarassite is analogous to those of kerimasite and other Zr-Sn-garnets of the schorlomite and bitikleite groups.

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.

A combination of hydrogen and oxygen isotope analyses and fluid inclusion studies has defined the composition of fluids involved in the metamorphism of Lower Palaeozoic rocks in the English Lake District. Three fluid fields have been defined from secondary phases: 1, syn-burial metamorphic D-enriched fluids from epidote and chlorite at a temperature between 250 and 350°C; D-depleted fluid measured from groundmass and quartz inclusions; 3, a mixed magmatic-meteoric fluid with an intermediate H-isotopic composition estimated from W/R granite data and calculated from illite.

The synthesis of monazite was first reported by Radominsky (1875). Since then various methods have been used to synthesize various end members of the monazite solid solution series, mainly CePO4 and LaPO4 (e.g. Anthony, 1957, 1965). As part of an experimental study dealing with the solubility of monazite in granitic melts (Montel, 1986, 1987, and in prep.), the synthesis of some of the end members, as well as solid solutions, was achieved.

Aluminium-bearing strunzite, [Mn0.65Fe0.26Zn0.08Mg0.01]2+[Fe1.50Al0.50]3+(PO4)2(OH)2·6H2O, occurs as fibrous aggregates in a crystallographically oriented association with jahnsite on altered zwieselite samples from the phosphate pegmatite at Hagendorf Süd, Bavaria, Germany. Synchrotron X-ray data were collected from a 3 μm diameter fibre and refined in space group P to R1 = 0.054 for 1484 observed reflections. The refinement confirmed the results of chemical analyses which showed that one quarter of the trivalent iron in the strunzite crystals is replaced by aluminium. The paragenesis revealed by scanning electron microscopy, in combination with chemical analyses and a crystal-chemical comparison of the strunzite and jahnsite structures, are consistent with strunzite being formed from jahnsite by selective leaching of (100) metal—phosphate layers containing large divalent Ca and Mn atoms.

The new mineral jakobssonite, ideally CaAlF5, was first found in crusts collected in 1988 from a fumarole on the Eldfell volcano, Heimaey Island, Iceland. It was subsequently found in similar crusts collected in 1991 from a fumarole on the Hekla volcano, Iceland. It is associated with leonardsenite (IMA2011-059), ralstonite, heklaite, anhydrite, gypsum, jarosite, hematite, opal and several fluoride minerals that have not been fully characterized. Jakobssonite occurs as soft white fragile crusts of acicular crystals <50 μm long. Its calculated density is 2.89 g cm–3. Chemical analyses by energy-dispersive spectrometry on a scanning electron microscope produced a mean elemental composition as follows: Ca, 18.99; Al, 18.55; Mg, 1.33; Na, 0.33; F, 50.20; O, 10.39; total 99.79 wt.%. The empirical chemical formula, calculated on the basis of 7 atoms per formula unit with all of the oxygen as OH, is (Ca0.73Mg0.09Na0.02)Σ0.84Al1.06F4.09(OH)1.01. Jakobssonite is monoclinic, space group C2/c, with a = 8.601(1), b = 6.2903(6), c = 7.2190(7) Å, β = 114.61(1)o, V = 355.09(8) Å3and Z = 4. The crystal structure contains chains of [AlF6] octahedra which run parallel to the c axis. These chains are interconnected by chains of [CaF7] pentagonal bipyramids. Jakobssonite is isostructural with several other CaMIIIF5 compounds. The eight strongest lines in the powder diffraction diagram [d in Å (I) (hkl)] are as follows: 4.91 (18) (110), 3.92 (76) (200), 3.15 (68) (020), 3.13 (100) (1), 2.27 (22) (2), 1.957 (21) (400), 1.814 (20) (1), 1.805 (22) (20). The chemical and crystal-structure analyses of jakobssonite are similar to synthetic CaAlF5 with minor substitutions of light elements (e.g. Na) or vacancies for Ca, and OH for F.

The concept of effective stress is one of the basic tenets of rock mechanics where the stress acting on a rock can be viewed as the total stress minus the pore water pressure. In many materials, including clay-rich rocks, this relationship has been seen to be imperfect and a coefficient (χ) is added to account for the mechanical properties of the clay matrix. Recent experimental results during the flow testing (both gas and water) of several rocks (Callovo-Oxfordian claystone, Opalinus Clay, Boom Clay) and geomaterials (bentonite, kaolinite) has given evidence for stable high pressure differentials. The design of the experiments allows multiple measurements of pore pressure, which commonly shows a complex distribution for several different experimental geometries. The observed stable high pressure differentials and heterogeneous pore pressure distribution makes the describing of stress states in terms of effective stress complex. Highly localized pore pressures can be sustained by argillaceous materials and concepts of evenly distributed pore pressures throughout the sample (i.e. conventional effective stress) do not fit many clay-rich rocks if the complexities observed on the micro-scale are not incorporated, especially when considering the case of gas flow.

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.

The crystal structure of kraisslite, orthorhombic (pseudo-hexagonal), a = 8.1821(1), b = 14.1946(3), c = 43.9103(8) Å, V = 5099.8(2) Å3, Z = 4 and d calc = 4.083 g cm–3, has been solved bydirect methods and refined in the space group C2221 to an R 1 index of 1.68% for 7432 observed (|F o| > 4σ|F|) reflections. Electron-microprobe analysis gave the following chemical composition: As2O510.86,As2O36.18, SiO213.39, Al2O30.25, Fe2O32.06, MnO 51.14, ZnO 7.39, MgO 2.13, CaO 0.05, H2Ocalc = 4.50, sum 97.95 wt.%; and empirical formula: Zn2.91(Mn23.07Mg1.69Ca0.03)Σ=24.79(Fe0.83 3+Al0.16)Σ=0.99(As3+O3)2[(Si0.71As0.30 5+)O4]10(OH)16 calculated on the basis of 62 anions with (OH) = 16 and As3+/(As3++ As5+) taken from the refined crystal structure. The general formula, [4]Zn3(Mn,Mg)25(Fe3+,Al)(As3+O3)2[(Si,As5+)O4]10(OH)16, differs from those given previously.

There is one As3+ site with a <As–O> distance of 1.780 Å and a stereochemistry typical of a stereoactive lone-pair of electrons. There are five tetrahedrally coordinated T sites with <T–O> distances from 1.635 to 1.692 Å; the T(1)site is fully occupied by As5+, and the T(2)–T(5) sites are occupied by both Si and As5+. There are two tetrahedrally coordinated Zn sites with <T–O> distances of ∼1.996 Å, both of which are occupied by dominantZn and minor Mn2+. There are thirteen octahedrally coordinated M sites, twelve of which are occupied by dominant Mn2+ with lesser Mg and minor Zn; <M–O> distances are in the range 2.197–2.284 Å. The <M(13)–O> distanceis 2.083 Å and its lower site scattering indicates occupancy by Fe3+, Mn2+, Mg and Al. The structure consists of five crystallographically distinct layers of polyhedra, labelled m = 0 – 4. Layer m = 0 consists of corner-sharing Zn and (Si, As5+)tetrahedra, and layers m = 1–4 each consist of trimers of Mn2+ octahedra linked by (Si, As5+) tetrahedra and intrasheet hydrogen bonds (m = 1, 3) or (Si, As5+) tetrahedra and (Fe3+,Al) octahedra (m = 2) or (As5+)tetrahedra and (As3+O3) triangular pyramids and intrasheet hydrogen bonds (m = 4). The layers stack along [001] with reversals of the sequence m = 1, 2, 3, 4 at z = 0, ¼, ½ and ¾. Kraisslite is a member of the mcgovernite family.

Over 100 samples of ‘pegmatite’ and associated host rocks from the Cree Lake Zone of northern Saskatchewan have been studied. The degree of U and Th enrichment of the pegmatites appears to depend on the parent material of the anatectic melts produced during the Hudsonian thermotectonic event. Evidence for Archaean granulite-facies depletion of U and Th is inconclusive; however, important enrichment of U and Th in the basal Aphebian is associated with metamorphosed black shales and possibly evaporates.

Many evolved peraluminous granite plutons contain either andalusite (Al2SiO5) or topaz (Al2SiO4(OH,F)2), but some plutons contain both of these A/NK [mol. Al2O3/(Na2O+K2O)] = ∞ phases. We present the results of experiments conducted to locate the andalusite-topaz boundary in water-saturated peraluminous haplogranite melts in T-P-Xspace, where T = 700—650°C, P = 200 MPa. andX(A/NK = 1.1, 1.2, 1.3, 1.4, and F = 0, 1, 2, 4 wt.%).The starting materials are synthetic K-Na-Al-Si gels, with added H2O and AgF, with seeds of natural andalusite and topaz, and with run times of 5—7 days. Phase identification is by electron microprobe. All experimental run products contained quartz. For all values of bulk A/NK, F concentrations ⩽ 1 wt.% favour andalusite stability, whereas F concentrations ⩾ 1 wt.% favour topaz stability. For bulk A/NK ⩽ 1.2 and intermediate F concentrations, no A/NK = phase is present; for bulk A/NK ⩾ 1.3, quench or metastable mullite formed. Topaz reaction rims on naturally occurring andalusite, frequency of naturally occurring assemblages, general chemical considerations, and experimental evidence all suggest that some topaz is the product of a peritectic reaction between an early primary magmatic andalusite and a late F-enriched melt. The appearance of such topaz is an important mineralogical expression of F activity in the melt, and may be an indicator for high field-strength Sn-W-U-Mo polymetallic mineralization.

The lead isotope systematics, zircon uranium concentrations and whole-rock rubidium concentrations of 11 Scottish Caledonian granites are examined for clues to the origin of their uranium. A positive correlation between U in zircon and initial lead isotope ratios suggests that U and Pb were derived from the same source which, as some of these granites contain their U in inherited zircons, is likely to have been within the crust. It is argued, therefore, that most of the uranium in these granites had a crustal derivation but lead isotope ratios indicate that any Lewisian contribution was minor in comparison with those from postulated Grenville, Morarian or Caledonian metamorphic reservoirs. However, additional data are required before this conclusion can be extended to include uraniferous Caledonian granites such as Cairngorm.

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.

Lacking the pronounced modal layering of the underlying Critical Zone, the Main Zone of the Bushveld Complex nevertheless displays well-developed cryptic layering, expressed in a series of iron-enrichment trends, each defining a unit of the order of 100 to 200 m thick. At the base of one such unit, 1100 m above the Main Zone — Critical Zone contact, a 10 m thick pyroxenitic layer was intersected in an exploration borehole from the southern sector of the western Bushveld.

Within the pyroxenitic layer, mineral chemistry defines a series of five cycles of upward Mg and Cr enrichment in pyroxenes, and Ca enrichment in plagioclase. The mineral chemistry, supported by textural evidence, suggests the influx of successive surges of magma. Sustained streaming of magma gave rise to adcumulate textures in the central portion of each cycle, with orthocumulate textures at bases and tops of cycles representing waxing and waning stages of magma surges.

Kingstonite, ideally Rh3S4, is a new mineral from the Bir Bir river, Yubdo District, Wallaga Province, Ethiopia. It occurs as subhedral, tabular elongate to anhedral inclusions in a Pt-Fe nugget with the associated minerals isoferroplatinum, tetraferroplatinum, a Cu-bearing Pt-Fe alloy, osmium, enriched oxide remnants of osmium, laurite, bowieite, ferrorhodsite and cuprorhodsite. It is opaque with a metallic lustre, has a black streak, is brittle and has a subconchoidal fracture and a good cleavage parallel to [001]. VHN25 is 871–920 kg/mm2. In plane-polarized reflected light, kingstonite is a pale slightly brownish grey colour. It is weakly pleochroic and displays a weak bireflectance. It does not possess internal reflections. The anisotropy is weak to moderate in dull greys and browns. Reflectance data and colour values are tabulated. Average results of twenty electron microprobe analyses on four grains give Rh 46.5, Ir 16.4, Pt 11.2, S 25.6, total 99.7 wt.%. The empirical formula is (Rh2.27Ir0.43Pt0.29)Σ2.99S4.01, based on 7 atoms per formula unit (a.p.f.u.). Kingstonite is monoclinic (C2/m) with a = 10.4616(5), b = 10.7527(5), c = 6.2648(3) Å, β = 109.000(5)°, V = 666.34(1) Å3 (Z = 6). The calculated density is 7.52 g/cm3 (on the basis of the empirical formula and unit-cell parameters refined from powder data). The seven strongest X-ray powder-diffraction lines [d in Å(I) (hkl)] are: 3.156 (100) (310), 3.081 (100) (31), 2.957 (90) (002), 2.234 (60) (202), 1.941 (50) (23), 1.871 (80) (41) and 1.791 (90) (060, 33). The structure of kingstonite was solved and refined to Rp = 3.8%. There are four distinct metal sites with Rh occupancies of 0.64–0.89. Two metal sites are regular RhS6 octahedra that share edges to form a ribbon running parallel to c. The other two metal sites are coordinated by 4 S + 2 Rh and 5 S + 2 Rh and define a puckered Rh6 ring. The ribbons of regular RhS6 octahedra alternate with the columns of Rh6 rings linked by S atoms. S–S bridges also connect the ribbons and columns. As such, the kingstonite structure is essentially that of synthetic Rh3S4. Minor differences in the unit-cell parameters, atom coordinates and displacement parameters of kingstonite and synthetic Rh3S4 arise from the considerable substitution of Ir for Rh. The mineral name honours Gordon Kingston (formerly of Cardiff University) in recognition of his contributions to platinum group element mineralogy and the geology of their mineral deposits.

The crystal structure of comancheite, Hg2+55N3–24(OH, NH2)4(Cl,Br)34, orthorhombic, space group Pnnm, a = 18.414(5), b = 21.328(6), c = 6.6976(19) Å, V = 2630(2) Å3, Z = 1, was solved by direct methods and refined to an R1 index of 4.3% based on 4160 unique observed reflections. In the structure of comancheite, there are nine crystallographically distinct Hg2+ cations, each of which is coordinated by two N3– anions to form near-linear N3––Hg2+–N3– groups. Four other crystallographically distinct Hg2+ cations are coordinated by a mixture of N3–, O2–, (OH)– and (NH2)– anions, and there is a small amount of [Hg–Hg]2+ dimer. In addition, there are eight crystallographically distinct halogen sites, three of which are completely occupied by Cl–, and five of which are occupied by both Cl– and Br–. The principal anion, N3–, shows a strong preference for tetrahedral coordination by Hg2+, which results in a strongly bonded three-dimensional {–Hg2+–N3––} framework. This framework is both interrupted and contains large interstices that incorporate additional Hg2+ cations, a very small amount of [Hg+–Hg+]2+ dimer and additional anion species, O2–, (OH)– and (NH2)–, that coordinate Hg2+.

Comancheite was described originally as an Hg-oxide mineral. The major change in chemical composition indicated by the present work was approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (Voting Proposal 13-B). The presence of N provides some analytical challenges, particularly in the presence of Hg. New bond-valence parameters were derived for Hg2+–N3– bonds [Ro(N3–) = 1.95] using well refined Hg2+ structures, and this allows discrimination between Hg2+–O2– and Hg2+–N3– bonds based on the valence-sum rule. Comparison of the Raman spectra of several Hg-bearing minerals shows that peaks in the range 500–700 cm–1 are characteristic of Hg2+–N3– stretching vibrations whereas peaks in the range 350–500 cm–1 are characteristic of Hg2+–O2– stretching vibrations; Hg2+–O2– and Hg2+ – N3– bonds may be discriminated on this basis.