Taking advantage of the bent uranyl-peroxide-uranyl interaction found in studtite, 26 nanoscale clusters have been synthesized using uranyl hexagonal bipyramids. Sixteen of these clusters are built from uranyl hexagonal bipyramids only. Eight contain pyrophosphate groups that bridge between uranyl polyhedra, and two contain oxalate groups that adopt a similar structural role. These clusters contain from 20 to 60 uranyl polyhedra and have diameters in the range ∼1.5 to 3 nm. All spontaneously selfassemble in aqueous solution under ambient conditions.

Capranicaite, ideally (K,☐)(Ca,Na)Al4B4Si2O18, is a new inosilicate mineral from the Vico volcanic complex collected at Capranica, Viterbo Province, Latium, Italy. It occurs in miarolitic cavities of a feldspathoid-bearing syenite ejectum and formed by late-stage metasomatic processes related to the activity of theVico volcano.

Capranicaite occurs as thin, tabular crystals no larger than 0.1 mm. Crystals are colourless, with a white streak and a vitreous lustre; they are brittle and their Mohs hardness is certainly <6. Capranicaite is non-fluorescent with good {001} cleavage and no observable parting. The calculated density is 2.41 g/cm3. Crystals are biaxial negative, non pleochroic, with α = 1.495(1), β = 1.543(1), γ = 1.544(1), 2Vobs = 7.3(2)°, 2Vcalc = 16.0°.

Capranicaiteis monoclinic P21/n, with a = 4.8507(2), b = 16.6156(6), c = 20.5445(7) Å, β = 90.245(1)°, V = 1655.82(17) Å3, Z = 4. The strongest six X-ray diffraction lines in the simulated powder pattern are [d in Å (I) (hkl)]: 3.234 (10) (124; 044), 4.104 (9) (1̄21; 121), 3.424 (8) (006), 2.184 (4) (048; 1̄64), 2.405 (4) (160), 2.425 (3) (200). EMP-WDS analysis gives: SiO2 20.70, Al2O3 32.91, B2O3 22.90, K2O 5.36, CaO 11.04, Na2O 4.08, Cs2O 2.20, sum 99.19%; the formula, based on 18 oxygens, is: (K0.69Cs0.10)Σ0.79(Ca1.19Na0.80)Σ1.99Al3.91B3.99Si2.09O18, corresponding to the ideal formula: (K,☐)(Ca,Na)Al4B4Si2O18. The crystal structure shows three overlapping layers of polyhedra parallel to (001): (1) the A layer contains periodic single chains formed by Si2O6 units with a topology not previously observed; (2) the B layer contains isolated AlO4 tetrahedra and BO3 triangles forming a sheet of six-fold rings (3Al + 3B); (3) the C layer contains two octahedral sites: M(1) and M(2), with a mixed (Ca, Na) population. Two B layers and an intermediate A layer are vertex-connected to form a bi-dimensional B-A-B network characterized by large channels not completely populated and accommodating K and minor Cs. Along c from the origin the following layer sequence results: C-[B-A-B]-C-[B-A-B]-C.

The (110) surfaces of arsenopyrite (FeAsS) and enargite (Cu3AsS4) have been modelled using a Density Functional Theory (DFT) plane-wave pseudopotential method (CASTEP) in order to better understand aspects of the geometric and electronic structures of these minerals, which have important implications for the release of arsenic in acid mine drainage environments. In this study, bulk calculations of these minerals have been conducted to give consistent geometries for surface models and to establish reference states for changes at the surfaces in these models. Surface structure experimental data for enargite were collected using low-energy electron diffraction which confirmed an unreconstructed 161 (110) lattice, with a and b values of 6.38±0.3 Å and 9.92±0.5 Å, respectively. Surface calculations demonstrate geometric and electronic relaxation of both arsenopyrite and enargite (110) surfaces. Changes in atomic positions, interatomic distances, Mulliken charges and electronic configurations are reported. Enargite has a surface energy of ∼0.02 eV/Å2 compared with arsenopyrite which has a surface energy of ∼0.11 eV/Å2, indicating that the enargite (110) surface is more energetically stable than that of arsenopyrite. The most stable surfaces are those which relax to restore the surface coordination and partial charge balance. For both minerals this is achieved by the formation of covalent bonds. Arsenic has the most positive Mulliken charge of all the surface atoms and is, therefore, predicted to be the most reactive atom at the arsenopyrite and enargite (110) surfaces. This implies that, according to these calculations, arsenic is most likely to react with oxidative species such as O2 and H2O in environments such as those associated with acid mine drainage, potentially releasing oxides and acids of arsenic into the environment.

Tourmalines of unusual (mushroom) habit are common in granitic pegmatites of Momeik, northeast of Mogok, Myanmar. Here, we examine a sample of elbaite of significantly different habit, consisting of a series of diverging crystals, resembling a sheaf of wheat and ranging in colour from light purplish-red at the base to dark purplish-red at the tip with a thin green cap at the termination. The crystal structures of eight crystals are refined to R1-indices of ∼2.5% using graphite-monochromated Mo-Kα X-radiation; the same crystals were analysed by electron microprobe. 11B and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra were collected on four regions of the wheatsheaf crystal, and show ∼0.3 a.p.f.u. [4]B and <0.1 a.p.f.u. [4]Al in the structure. 57Fe Mössbauerspectr oscopy was done on the dark green rim at the termination of the crystal, showing all Fe in this region (∼0.6 a.p.f.u.) to be Fe2+. Detailed electron-microprobe traverses show that the principal compositional variation involves the substitutions [4]B + YAl → Si + YFe*, where transition metals are present, and [4]B2 + YAl → Si2 + YLi, where transition metals are not present, although several other minor substitutions also affect crystal composition. Successive microscopic bifurcation of crystallites causes divergence of growth directions along the c axis, imparting the overall ‘wheatsheaf’ shape to the crystal aggregate. We suggest that such bifurcation is common in pegmatitic elbaite crystals, resulting in their common divergent habit.

Eudialyte-group minerals (EGM) represent the most important index minerals of persodic agpaitic systems. Results are presented here of a combined EPMA, Mössbauer spectroscopy and LA-ICP-MS study and EGM which crystallized in various fractionation stages from different parental melts and mineral assemblages in silica over- and undersaturated systems are compared. Compositional variability is closely related to texture, allowing for reconstruction of locally acting magmatic to hydrothermal processes. Early-magmatic EGM are invariably dominated by Fe whereas hydrothermal EGM can be virtually Fe-free and form pure Mn end-members. Hence the Mn/Fe ratio is the most suitable fractionation indicator, although crystal chemistry effects and co-crystallizing phases play a secondary role in the incorporation of Fe and Mn into EGM. Mössbauer spectroscopy of EGM from three selected occurrences indicates the Fe3+/ΣFe ratio to be governed by the hydration state of EGM rather than by the oxygen fugacity of the coexisting melt. Negative Eu anomalies are restricted to EGM that crystallized from alkali basaltic parental melts while EGM from nephelinitic parental melts invariably lack negative Eu anomalies. Even after extensive differentiation intervals, EGM reflect properties of their respective parental melts and the fractionation of plagioclase and other minerals such as Fe-Ti oxides, amphibole and sulphides.

Experimental breakdown of staurolite + inclusions of albite and muscovite (representing an aluminous Fe-rich metapelitic composition) occurs within the KNFMASH system at 800°C and 0.1 GPa under fluid-present conditions over periods of 2 days to 8 weeks. The overall melt-producing reaction is staurolite + muscovite + plagioclase + vapour = hercynite + corundum + mullite + quartz + liquid, and involves three reactions; staurolite + vapour = hercynite + corundum + quartz + liquid, albite + vapour = mullite + liquid, and muscovite + vapour = mullite + liquid. Melt (glass) compositions are siliceous (77.2–64.5 wt.% SiO2), peraluminous (A/CNK = 1.5–5.5), and have granite-trondjhemite compositions in terms of normative Ab-Ab-Or contents. Textures indicate that quartz formed later than corundum. The corundum + quartz + hercynite assemblage after staurolite is considered to be metastable and only likely to be found in nature where staurolite-bearing rocks have undergone rapid heating and melting followed by quenching.

Bariopharmacoalumite, ideally Ba0.5Al4(AsO4)3(OH)4·4H2O, is a new mineral from Cap Garonne, France. It occurs in several places within the mine as colourless to pale yellow interpenetrating cubes up to 0.5 mm across. Bariopharmacoalumite is transparent to translucent, with a white streak, has an adamantine lustre and imperfect cleavage on {001}. The Vickers hardness is 234.35 and the Mohs harness is 3.5. Bariopharmacoalumite is isotropic, with n = 1.573 (upper estimate) [calculated from reflectance values at 589 nm using Fresnel Equations]. The empirical formula, based on 20 oxygen atoms, is: (Ba0.54Cu0.03K0.01)Σ0.58(Al3.99Fe0.02)Σ4.01(AsO4)3.00(OH)3.85O0.15·4H2O and the calculated density (on the basis of the empirical formula and single-crystal unit cell) is 2.580 g/cm3. The four strongest lines in the X-ray powder diffraction pattern are [dobs(Å), Iobs,(hkl)]: 7.759, 100, (001); 5.485, 27, (011); 3.878, 27, (002); 4.454, 18, (011). Bariopharmacoalumite from Cap Garonne is cubic, space group P4̄3m with a = 7.742(4) Å, V = 464.2(4) Å3 and Z = 1. The crystal structure was solved by direct methods and refined to R1 = 0.0705 for 215 reflections with I > 4σ(I) and is consistent with members of the pharmacosiderite supergroup. Data are also presented from zoned bariopharmacoalumite–bariopharmacosiderite crystals found at the Mina Grande mine, Chile.

Non-stoichiometric, carbon-containing crandallite from Guatemala and plumbogummite from Cumbria have been characterized using electron microprobe (EMPA) and wet-chemical analyses, Rietveld analysis of powder X-ray diffraction (PXRD) patterns, and infrared (IR), Raman and cathodoluminescence (CL) spectroscopies. The samples contain 11.0 and 4.8 wt.% CO2, respectively. The IR spectra for both samples show a doublet in the range 1410–1470 cm–1, corresponding to CO3 vibrations. Direct confirmation of CO3 replacing PO4 was obtained from difference Fourier maps in the Rietveld analysis. Carbonate accounts for 67% of the C in the plumbogummite and 20% of the C in the Guatemalan crandallite, the remainder being present as nano-scale organic carbon. The CO3 substitution for PO4 is manifested in a large contraction of the tetrahedral volume (14–19%) and by a contraction of the a axis, analogous to observations for carbonate-containing fluorapatites. Stoichiometric crandallite from Utah was characterized using the same methods, for comparison with the non-stoichiometric, carbon-bearing phases.

The pre-Caledonian NYF Skoddefjellet pegmatite in Wedel Jarlsberg Land, Svalbard, contains xenotime-(Y) that is partly replaced by fluorapatite-hingganite-(Y) reaction coronas. Hingganite-(Y) contains up to 2.0 wt.% of Gd2O3, 4.7 wt.% of Dy2O3, 3.3 wt.% of Er2O3 and 5.5 wt.% of Yb2O3. Such unusual, previously undescribed, xenotime-(Y) breakdown was caused by Ca- and F-bearing fluids interacting with the pegmatite. The occurrence of hinnganite-(Y) as a breakdown product of xenotime-(Y) implies that a Be-bearing phase (beryl in this case) was also involved in the reaction. There are few Ca-bearing primary phases in the pegmatite, indicating that the source of fluid was probably located in the generally Ca-richer host rocks (metasediments), though the fluid composition was modified during metasomatism of the pegmatite (i.e. beryl dissolution).

Oscillatory zoning in solid solutions of alums ((K,NH4)Al(SO4)2·12H2O, K(Al,Cr)(SO4)2·12H2O, (K,Rb)Al(SO4)2·12H2O) and nitrates of divalent metals ((Sr,Pb)(NO3)2, (Ba,Pb)(NO3)2) grownfrom low-temperature aqueous solutions is considered. The zoning is detected by means of X-ray diffraction topography, crystal optics and electron probe microanalysis and involves variations of the crystal composition and degree of the growth ordering of atoms. The zoning patterns are very different in the predominant ﹛111﹜ and ﹛1̄11﹜ and subordinate ﹛100﹜ and ﹛110﹜ growth sectors. The different types of micromorphological instabilities of a growing face are suggested to explain the origin of the observed zoning.

Several bodies of moderately foliated and porphyroblastic metabasites crop out on the SE side of the metamorphic cover of the Karkonosze granite within metapelites of the Sowia Dolina area (West Sudetes, Saxothuringian zone). Depending on the microstructural setting of the Ca-amphiboles in the rocks, different mineral-chemical trends have been determined for Si, XMg, AlVI, A[Na+K] which serve as semi-quantitative indicators of temperature and pressure changes. Porphyroblasts and prisms oblique to the main foliation in schistose metabasites show zoning from Mg-hornblende and actinolite to tschermakite, and then to Mg-hornblende (or actinolite). Matrix amphiboles and those in pressure shadows around some porphyroblasts have tschermakitic cores and actinolitic rims. Rarely, Ca-amphibole is accompanied in schists by late- to post-tectonic cummingtonite. Thermobarometric calculations involving empirically calibrated amphibole equilibria enable a reconstruction of P-T paths for individual rocks and the unravelling of the metamorphic evolution of the metabasites. Peak metamorphic temperatures of 615–640°C and pressures of 7.3–8.2 kbar were preceded by a variably preserved earlier stage (T = 370–550°C, P = 2.8–6.2 kbar). The final metamorphic episode took place at 450–550°C and 2.5–4.8 kbar and is recorded particularly in rocks close to the Karkonosze pluton. The metabasites shed new light on the history of metamorphism in the Sowia Dolina area. The first two stages of MP-MT metamorphism, coeval with Variscan deformation events (continental collision, burial and subsequent exhumation), took place under epidote-amphibolite then amphibolite facies conditions. The last stage partly concurred with the final stages of Variscan deformation and overlapped the onset of thermal activity associated with the Karkonosze granite. This metamorphic event is documented by metabasites (occasionally cummingtonite-bearing) outcropping close to the granite. Finally, a prehnitebearing assemblage reflects retrograde re-equilibration under greenschist/sub-greenschist facies conditions (T <300–350°C, P <2.5–3 kbar), which might also be partly due to hydrothermal activity around the pluton.

Bavenite is an orthorhombic calcium beryllium aluminosilicate, a ≈ 23.2, b ≈ 5.0, c ≈ 19.4 Å, V ≈ 2250 Å3, Z = 4, that crystallizes in the space group Cmcm. The crystal structures of 24 bavenite samples from various localities worldwide were refined to R1 values from 2.4 to 7.5% based on ∼1330 unique reflections collected with Mo-Kα X-radiation on a Bruker P4 CCD single-crystal diffractometer. The composition of each crystal was determined by electron microprobe analysis. There is extensive solid-solution in bavenite according to O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+, such that the general formula may be written Ca4BexSi9Al4–xO28–x(OH)x, where x ranges from 2.00 to ∼3.00 a.p.f.u. Small amounts of additional Be may be incorporated into bavenite via the substitution T(3)Be + O(2)OH– + Na + T(4)Si2 ⇌ T(3)Si + O(2)O2– + Ca + T(4)Al2. Local (short-range) bond-valence considerations indicate that Short-Range Order (SRO) should be extensive in the bavenite structure, and this is confirmed by Fourier Transform Infrared (FTIR) spectroscopy in the principal OH-stretching region and by 27Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Short-range bond-valence considerations indicate that the T(3)–T(4)–T(3)–T(4) rings of the framework can incorporate any short-range arrangement of cations consonant with their site populations [T(3) = Be,Si; T(4) = Si,Al], and 27Al MAS NMR spectroscopy confirms this, showing the presence of the local clusters T(3)Be–T(4)Al–T(3)Be, T(3)Si–T(4)Al–T(3)Be and T(3)Si–T(4)Al–T(3)Si. Incorporation of Be at the T(3) site is accompanied by local replacement of O2– by (OH)– at the O(2) site and hydrogen bonding to the adjacent O(3) anion; the latter promotes Be → Si substitution at the T(3) tetrahedron adjacent in the b direction. T(3)–T(4)–T(3)–T(4) rings link in the c direction through a T(3)–(1)–(3) linkage [T(1) = Si]. Local bond-valence considerations show that occupancy of both T(3) tetrahedra by Be violates the valence-sum rule, and that the linkage T(3)Be–T(1)Si–T(3)Si provides the constraint whereby Be does not exceed 3 a.p.f.u. in bavenite when incorporated via the substitution O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+.

Sodic pyroxene is reported from an Ordovician metatrachyte of the Kaczawa Mountains, SW Poland. Its composition ranges from Jd0.98Ae0.02 to Jd0.15Ae0.85. Relict jadeite and phengite (up to 3.75 Si atoms per fomula unit) belong to the peak-pressure assemblage of an early HP-LT event. Later greenschist-facies stages are represented by riebeckite, biotite, chlorite, low-Si potassic white mica and actinolite. P-T pseudosections calculated for the range 200–450°C, 3–13 kbar allow evaluation of the conditions of formation of jadeite in the metatrachyte and derivaton of a P-T path. Considering the position of prograde, peak and retrograde metamorphic assemblages and respective mineral compositions, we can derive the following equilibration stages: 8.5±0.5 kbar, 270±20°C for the pressure maximum, 6.0±1.0 kbar, 310±20°C for the temperature maximum and 3.5±0.5 kbar, 280±20°C as well as <3.5 kbar, <280°C for the retrograde stages.

The metamorphic gradient for the peak-pressure is estimated at ∼10°C/km, which is typical of a subduction setting involving subducted continental crust, in particular of an exhumation channel within a collision zone of a microplate. Based on earlier structural observations, the ESE-oriented subduction in the NE Bohemian Massif was confined with WNW thrusting and followed by extension and ESE backward normal faulting during Devonian–Early Carboniferous times.