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.

The crystal structure of mendeleevite-(Ce), (Cs,☐)6(☐,Cs)6(☐,K)6(REE,Ca,☐)6(Si70O175) (H2O,OH,F,D)35, a new mineral from the moraine of the Darai-Pioz glacier, the Alai mountain ridge. Tien-Shan mountains, northern Tajikistan, was solved by direct methods and refined to Ri = 4.15% based on 2274 observed [Fo > 4σ|F|] unique reflections measured with Mo-Kα. radiation on a Bruker PA diffractorneter equipped with a CCD detector. Mendeleevite-(Ce) is cubic, space group Pm3̄, a 21.9148(4) Å, V 10525(1) Å3, Z = 2, Dcalc = 3.066 g/cm3. The empirical formula (electron microprobe) is CS5.94K2.22[(Ce11.35La5.86Nd3.23Pr1.54Sm0.32Gd0.20)Σ22.50(Ca4.68Sr1.00)Σ5.68]Σ28.18 Si70.12O203.17H45.67F6.83, Z = 2, calculated on the basis of 210 (O + F) a.p.f.u., with H2O and OH calculated from structure refinement (OH + F = 17 p.f.u.; H2O = 17.75 p.f.u.).

The structural formula is (Cs4.65☐1.35)Σ6(☐4.71Cs1.29)Σ6(☐3.78K2.22)Σ6﹛[(Ce11.35La5.86Nd3.23 Pr1.54Sm0.32Gd0.20)Σ22.50(Ca4.68Sr1.00)Σ5.68]Σ28.18☐1.82﹜Σ30(Si70O175)[(OH)10.17F6.83]Σ17(H2O)17.75. Simplified and endmember formulae are as follows: (Cs,☐)6(☐,Cs)6(☐,K)6(REE,Ca,☐)30(Si70O175) (H2O,OH,F,☐)35 and Cs6(REE22Ca6)(Si70O175)(OH,F)14(H20)21. The crystal structure of mendeleevite-(Ce) is an intercalation of two independent Si—O radicals and an M framework of (REE,Ca) polyhedra. The Si—O radicals are an (Si140O260)104– framework and an (Si36O90)36– cluster which do not link directly. The M framework is located between the Si—O framework and the Si—O clusters. Interstitial cations occupy two types of cages and channels. Cages I and II are 78 and 22% occupied by Cs. Channels along [100↻] contain K atoms and H2O groups. Mendeleevite-(Ce) has no natural or synthetic structural analogues. Mendeleevite-(Ce) is a framework mineral with large cavities and it has the potential to be used as a model for the synthesis of microporous materials of industrial interest.

Cement and concrete will be used as fracture grouts, shotcrete, tunnel and borehole seals, and as matrices for waste encapsulation inter alia in geological repositories for radioactive wastes. Alteration of the host rock and/or swelling clay in waste package buffers and tunnel backfills by hyperalkaline solutions from cement/concrete may be deleterious to system performance through changes in the physicochemical properties of these barrier materials.

Analogue systems (and timescales) relevant to the understanding of the alkaline disturbed zone include: industrial analogues, such as alkaline flooding of hydrocarbon reservoirs (up to 30 y), cement-aggregate reactions (up to 100 y) and the Tournemire tunnel (up to 125 y); and natural analogues, including the hyperalkaline springs at Maqarin, Jordan (more than 100,000 y), saline, alkaline lakes (more than 1,000,000 y) and certain fracture fillings in granites (more than 1,000,000 y).

These systems show that alkaline alteration can be observed for thousands of years over distance scales of hundreds of metres under extreme conditions of hydraulic gradients in fractured rocks (Maqarin), but may be limited to a few centimetres over tens to a hundred years in mudstone (Tournemire). Important reaction mechanisms for retardation of alkaline fluids include: fluid mixing (alkaline oil floods, Maqarin), ion exchange (alkaline oil floods, Tournemire) and kinetic mineral dissolution-precipitation reactions (all systems studied). Qualitative and quantitative kinetic data for mineral reactions are available from cement aggregate reactions and the Searles Lake analogue, respectively. Short-term alteration observed in cement-aggregates is characterized by calcium silicate hydrate (C-S-H) minerals and incipient zeolite formation, whereas evidence from the Tournemire tunnel shows the growth of K-feldspar after relatively short time intervals (tens to a hundred years). There is a tendency for alkaline alteration to result in porosity decreases, but locally, porosity may be enhanced (e.g. near-injection well interactions in alkaline oil floods, or at fracture margins at Maqarin, Jordan). Data from industrial and natural analogues may thus supply some key data for bridging time and space scales between laboratory and in situ experiments on one hand and the requirements for safety assessment on the other.

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.

The Szklary holtite is represented by three compositional varieties: (1) Ta-bearing (up to 14.66 wt.% Ta2O5), which forms homogeneous crystals and cores within zoned crystals; (2) Ti-bearing (up to 3.82 wt.% TiO2), found as small domains within the core; and (3) Nb-bearing (up to 5.30 wt.% Nb2O5,) forming the rims of zoned crystals. All three varieties show variable Sb+As content, reaching 19.18 wt.% Sb2O3 (0.87 Sb a.p.f.u.) and 3.30 wt.% As2O3 (0.22 As a.p.f.u.) in zoned Ta-bearing holtite, which constitutes the largest Sb+As content reported for the mineral. The zoning in holtite is a result of Ta-Nb fractionation in the parental pegmatite-forming melt together with contamination of the relatively thin Szklary dyke by Fe, Mg and Ti. Holtite and the As- and Sb-bearing dumortierite, which in places overgrows the youngest Nb-bearing zone, suggest the following crystallization sequence: Ta-bearing holtite → Ti-bearing holtite → Nb-bearing holtite → As- and Sb-bearing, (Ta,Nb,Ti)-poor dumortierite → As- and Sb-dominant, (Ta,Nb,Ti)-free dumortierite-like mineral (16.81 wt.% As2O3 and 10.23 wt.% Sb2O3) with (As+Sb) > Si. The last phase is potentially a new mineral species. Al6□☐(Sb,As)3O15, or Al5☐2B(Sb,As)3O12(OH)3, belonging to the dumortierite group. The Szklary holtite shows no evidence of clustering of compositions around ‘holtite I’ and ‘holtite II'. Instead, the substitutions of Si4+ by Sb3++As3+ at the Si/Sb sites and of Ta5+ by Nb5+ or Ti4+ at the Al(l) site suggest possible solid solutions between: (1) (Sb,As)-poor and (Sb,As)-rich holtite; (2) dumortierite and the unnamed (As+Sb)-dominant dumortierite-like mineral; and (3) Ti-bearing dumortierite and holtite. i.e. our data provide further evidence for miscibility between holtite and dumortierite, but leave open the question of defining the distinction between them. The Szklary holtite crystallized from the melt along with other primary Ta-Nb-(Ti) minerals such as columbite-(Mn), tantalite-(Mn), stibiotantalite and stibiocolumbite as the availability of Ta decreased. The origin of the parental melt can be related to anatexis in the adjacent Sowie Mountains complex, leading to widespread migmatization and metamorphic segregation in pelitic-psammitic sediments metamorphosed at ∼390—380 Ma.

Monoclinic, non-stoichiometric natrojarosite—hydroniumjarosite solid solution phases have been synthesized hydrothermally over a range of temperatures, starting compositions and reaction times, and have been characterized using Rietveld refinement of synchrotron X-ray diffraction data, and chemical and thermal analyses. The H atom locations have been obtained from refinement of neutron diffraction data on a deuterated sample. The results confirm a direct relationship between the monoclinic distortion and the ordering of iron site vacancies in one of two independent iron sites. Ordering of iron vacancies gives rise to domains containing butlerite-like 7 Å chains of corner-connected octahedra and tetrahedra. The formation of these chains within (100) planes results in an expansion of the monoclinic a lattice parameter and a contraction of the c parameter relative to stoichiometric jarosites. The results support a recent model for iron deficiency, whereby an iron vacancy is compensated by the replacement of four coordinated OH– ions by H2O molecules, with one of the H2O molecules coming from deprotonation of H3O+. The general formula, based on intergrowth of stoichiometric jarosite and non-stoichiometric, butlerite-like regions, is [(Na,H3O)Fe3(SO4)2(OH)6]1–y[(H2O)Fe2(SO4)2(OH)2(H2O)4]y.

The thermal diffusivity of diopside, jadeite and enstatite were measured at simultaneous pressures and temperatures of up to 7 GPa and 1200 K using the X-radiographic Ångström method. The measurements herein show that the pressure dependency of thermal diffusivity in pyroxenes is significantly greater than in olivine or garnet and that in the MORB-layer of a subducting slab the thermal diffusivity of pyroxenes are a factor of 1.5 greater than that of olivine. The temperature dependence of all the data sets is well described by a low-order polynomial fit to 1/K and the pressure dependence is exponential in 1/K, formulations which are consistent with the damped harmonic oscillator model for thermal properties.

X-ray absorption spectroscopy, scanning electron microscopy (SEM) and X-ray diffractometry (XRD) have been used to study the solid-phase speciation of Zn in urban road dust sediments (RDS) in Manchester, UK. X-ray absorption near-edge structure (XANES) analysis using linear combination modelling suggest that the soluble species Zn(NO3)2·6H2O and ZnCl2 represent 70—83%, and Zn-sorbed goethite 17—30%, of the Zn species present. The presence of goethite is not corroborated by extended X-ray absorption fine structure (EXAFS) modelled first shell scattering Zn—O distances of 2.01—2.03 Å, but this may be due to distortion of the Zn octahedra on the goethite surface, or the existence of Zn-sorbed species with other metal hydrous oxides, as inferred by the EXAFS-modelled second shell Fe and Al scatterers. Analysis by EXAFS also suggests that metallic Zn-Cu-Sn-Pb and Zn-silicate phases are present in the RDS, and this is corroborated by SEM and XRD. Other phases suggested by EXAFS include ZnO, franklinite, Zn-sorbed birnessite and zinc formate. Differences between the XANES and other results suggest that model compounds such as Zn-bearing phyllosilicates and metallic Zn phases may have been missing from the XANES fitting. Long-term low-level exposure to the RDS Zn phases identified may lead to an increased risk of cardiovascular or pulmonary diseases.

Iron minerals influence the environmental redox behaviour and mobility of metals including the long-lived radionuclide technetium. Technetium is highly mobile in its oxidized form pertechnetate (Tc(VII)O4–), however, when it is reduced to Tc(IV) it immobilizes readily via precipitation or sorption. In low concentration tracer experiments, and in higher concentration XAS experiments, pertechnetate was added to samples of biogenic and abiotically synthesized Fe(II)-bearing minerals (bio-magnetite, bio-vivianite, bio-siderite and an abiotically precipitated Fe(II) gel). Each mineral scavenged different quantities of Tc(VII) from solution with essentially complete removal in Fe(II)-gel and bio-magnetite systems and with 84±4% removal onto bio-siderite and 68±5% removal onto bio-vivianite over 45 days. In select, higher concentration, Tc XAS experiments, XANES spectra showed reductive precipitation to Tc(IV) in all samples. Furthermore, EXAFS spectra for bio-siderite, bio-vivianite and Fe(II)-gel showed that Tc(IV) was present as short range ordered hydrous Tc(IV)O2-like phases in the minerals and for some systems suggested possible incorporation in an octahedral coordination environment. Low concentration reoxidation experiments with air-, and in the case of the Fe(II) gel, nitrate-oxidation of the Tc(IV)-labelled samples resulted in only partial remobilization of Tc. Upon exposure to air, the Tc bound to the Fe-minerals was resistant to oxidative remobilization with a maximum of ∼15% Tc remobilized in the bio-vivianite system after 45 days of air exposure. Nitrate mediated oxidation of Fe(II)-gel inoculated with a stable consortium of nitrate-reducing, Fe(II)-oxidizing bacteria showed only 3.8±0.4% remobilization of reduced Tc(IV), again highlighting the recalcitrance of Tc(IV) to oxidative remobilization in Fe-bearing systems. The resultant XANES spectra of the reoxidized minerals showed Tc(IV)-like spectra in the reoxidized Fe-phases. Overall, this study highlights the role that Fe-bearing biogenic mineral phases have in controlling reductive scavenging of Tc(VII) to hydrous TcO2-like phases onto a range of Fe(II)-bearing minerals. In addition, it suggests that on reoxidation of these phases, Fe-bound Tc(IV) may be octahedrally coordinated and is largely recalcitrant to reoxidation over medium-term timescales. This has implications when considering remediation approaches and in predictions of the long-term fate of Tc in the nuclear legacy.

The structure of perloffite, ideally BaMn22+Fe23+(PO4)3(OH)3, has been solved and refined from single-crystal X-ray data collected on a Sr-bearing sample from the Spring Creek copper mine, near Wilmington, South Australia. A fragment of the crystal used for the collection of the X-ray intensity data was analysed by electron microprobe. The resulting unit formula is (Ba1.00,Sr0.03Σ1.03) (Mn2+1.15,Fe2+0.76Ca0.05Mg0.02,Na0.01)Σ1.99(Fe3+1.94,Al0.06)Σ2.00(PO4)2.99(OH)3.04. The structure is monoclinic. space group P21/m, a = 9.2425(18), b = 12.470(3), c = 5.002(1) Å, 0 = 100.19(3)°, V = 567.41(19) Å3, Z = 2, and was refined to R1 = 4.71% for 1568 unique observed reflections. The X site is [11]-coordinated and is occupied by dominant Ba and minor Sr, with an <X—O< distance of 2.953 Å. The Ml site is octahedrally coordinated and is occupied by Mn2+and Fe2+ plus minor Ca, Mg and Na with an observed <M1—O> distance of 2.208 Å. The M2 site is also octahedrally coordinated and is occupied by Fe3+ plus minor Al with a <M2—O> distance of 2.018 A. Perloffite is isostructural with other members of the bjarebyite group. Edge-linked [M22O6(OH)4] dimers link via corners to form chains along [010]. Chains are decorated with PO4 tetrahedra and link in the a direction via [M1O5(OH)] octahedra and (Ba,Sr) atoms to form a complex framework. The H2 atom hydrogen-bonds strongly to the O3 anion, providing additional linkage between chains.

A lenticular metagabbro crops out in an early Palaeozoic metasedimentary sequence at Nurra, northwest Sardinia. The metagabbro consists of variable proportions of early-formed coarse-grained albite, chlorite, epidote and apatite, later biotite and amphibole, and late stilpnomelane. Clinopyroxene and ilmenite are rare relict igneous minerals; albite has completely replaced primary plagioclase.

The metamorphic evolution of the Nurra metagabbro has been investigated by pseudosection modelling for a fixed bulk-rock composition in the Na2O—CaO—K2O—FeO—MgO—A12O3—SiO2—H2O (NCKFMASH) model system with added Ti and Mn in the P-T range 1-11 kbar and 150-450°C. The P—T path of the metagabbro is a loop with a prograde segment overprinted by later metamorphic re-equilibration. The pressure peak was at ⩽7 kbar and ∼400°C. The subsequent temperature peak, at ∼440°C, was accompanied by a decrease in pressure to ∼3 kbar. The final P—T evolution of the metagabbro is characterized by near-isobaric cooling to 250—300°C, with the formation of stilpnomelane. The P—T path of the Nurra gabbro is typical of continental orogenic belts that have undergone crustal thickening.

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.

The Environment Agency is the environmental regulator for the nuclear industry in England and Wales. We aim to ensure that any future Geological Disposal Facility (GDF) will meet our standards for protecting people and the environment during development, operation and following closure. We shall only grant an environmental permit for such a facility if the GDF developer submits an Environmental Safety Case (ESC) to the Environment Agency demonstrating that the proposed GDF will meet our standards. The ESC should be based on sound science and supported by appropriate research and development. The Environment Agency undertakes its own research programme to inform its regulatory decisions.

Iangreyite, ideally Ca2Al7(PO4)2(PO3OH)2(OH,F)15·8H2O, is a new mineral (IMA2009-087) from the Silver Coin mine, Nevada, USA and the Krásno ore district, Horní Slavkov, Czech Republic. At Silver Coin, iangreyite occurs as thin, colourless to white or cream, hexagonal tablets up to 0.4 mm in diameter and 0.02 mm thick associated with meurigite-Na, plumbogummite, kidwellite, lipscombite. strengite, chalcosiderite, wardite, leucophosphite, wavellite, goethite, barite, quartz and F-rich perhamite. At Krásno, white, yellowish or light pink iangreyite coatings consist of 0.3 mm wide clusters of minute and very thin intergrown tabular crystals with a maximum diameter of 0.2 mm. Individual iangreyite crystals are transparent with a vitreous lustre, while iangreyite clusters tend to be pearly and translucent. The estimated hardness is 3 on the Mohs scale, the fracture is irregular and the mineral is non-fluorescent under SW and LW ultraviolet light. Individual crystals are somewhat flexible and there is perfect cleavage on ﹛001﹜. The density (Silver Coin), measured by the sink-float method in an aqueous solution of sodium polytungstate, is 2.46(3) g/cm3, while the calculated density is 2.451 g/cm3. Crystals from Silver Coin are uniaxial (+), with the indices of refraction: ε = 1.544(2) and s = 1.554(2), measured in white light, and are non-pleochroic. The empirical formula for iangreyite from Silver Coin (calculated on the basis of 39 anions per formula unit) is: Ca1.42K0.22Na0.09Ba0.03 Sr0.01Al6.51Mg0.09Fe0.02Cu0.01Zn0.01P3.81F5.24H30.21O33.76, while the empirical formula from Krásno is: Ca2.15K0.10Na0.01Ba0.02Sr0.12Al6.28Mg0.01Fe0.12Cu0.08Zn0.01P3.64Si0.43F4.65H29.62O34.35. Iangreyite is trigonal, space group P321 and Z = 1, with the unit-cell parameters (Silver Coin): a = 6.988(1), c = 16.707(3) Å and V= 706.5(2) Å3 and (Krasno): a = 6.989(1), c = 16.782(4) Å and V = 709.8(2) Å3. The structure of iangreyite, modelled from powder data, consists of blocks of the crandallite-type structure that are interconnected along c via corner-sharing of crandallite-block PO4 tetrahedra with A1O2(OH)3 bipyramids. This linkage generates large channels along [110] bounded by 10-member rings of octahedra, tetrahedra and trigonal biyramids, that are occupied by Ca and water molecules.

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.

In addition to spurrite, Ca5(SiO4)2(CO3), and tilleyite, Ca5(Si2O7)(CO3)2, galuskinite, C is the third mineral in the CaO—SiO2—CO2 ternary system. Galuskinite, monoclinic, space group P21/c (a = 18.79, b = 6.72, c = 10.47 Å, β = 90.79°, V = 1322 Å3, Z = 4), occurs in thin veins which cut calcio-olivine, γ-Ca2SiO4, skarn with larnite, β-Ca2SiO4, relics. Pavlovskyite, Ca8(SiO4)2(Si3O10), and dellaite, Ca6(Si2O7)(SiO4)(OH)2, form a margin between the veins and the calcio-olivine skarn. The sanidinite facies high-temperature skarn formed ∼500 Ma ago when gabbroid rocks of the Birkhin complex (Baikal area, Eastern Siberia, Russia) intruded and contact-metamorphosed limestone xenoliths. Galuskinite is a retrograde product of skarn alteration and has neither been described from cement clinker production processes nor from studies of the CaO—SiO2—CO2 system. The crystal structure of galuskinite, refined from single crystal X-ray data to Ri = 3.1%, has a modular character. One may define a polysomatic series with spurrite and larnite as endmembers and galuskinite as a 1:1 polysome built from regular alternating spurrite and larnite modules. Differences between the X-ray powder patterns of galuskinite and spurrite are most obvious in the low 8 region. Galuskinite is named after the Russian mineralogists Irina O. Galuskina and Evgeny V. Galuskin, Faculty of Earth Sciences. University of Silesia, Poland, for their outstanding contributions to skarn mineralogy.

Cerianite-(Ce), ideally CeO2, occurs as rounded grains up to 5 μm across in a block of highly altered calcite carbonatite lava from the Kerimasi volcano, and as euhedral crystals up to 200 μm across in carbonatite-derived eluvial deposits in the Kisete and Loluni explosion craters in the Gregory Rift, northern Tanzania. X-ray powder diffraction data (a = 5.434(5) Å) and Raman spectroscopy (minor vibration modes at 184 and 571 cm—1 in addition to a strong signal at 449 cm—1) suggest the presence of essential amounts of large cations and oxygen vacancies in the Kisete material. Microprobe analyses reveal that the mineral contains both light and heavy trivalent rare earth elements (REE) (7.9-15.5 wt.% LREE2O3 and 4.9-9.7 wt.% HREE2O3), and that it is enriched in yttrium (7.1 — 14.5 wt.% Y2O3) and fluorine (2.2—3.5 wt.%). Single-crystal structure refinement of the mineral confirms a fluorite-type structure with a cation—anion distance of 2.3471(6) Å. The cerianite-(Ce) is considered to be a late-stage secondary mineral in the carbonatitic rocks.

One of the most important isotopes to be considered for disposal in the proposed UK Geological Disposal Facility (GDF) for higher-activity radioactive wastes will be 99Tc, due to its long half-life, high fission yield and ability to migrate through the geosphere as the pertechnetate ion. Much of the Tc is likely to be in the lower Tc(IV) oxidation state due to the low Eh in the near field. Batch Tc(IV) sorption experiments have been performed from pH 3–13, using 95mTc as a spike, in the presence of quartz, hematite, goethite, plagioclase feldspar, sand and shale. Solutions containing Tc(IV) were prepared at trace concentrations to avoid precipitation of TcO2. Values for the partition coefficient (Rd) were found to range from ∽4 up to ∽2 × 104 cm3 g–1. Rd was heavily dependent on pH in all cases, with the highest values being found in the circumneutral area. These data will inform the performance assessment for the near-field behaviour of technetium in the UK's planned higher-activity wastes GDF. Surface complexation modelling has been performed, fitting the data using both monodentate and bidentate binding models.

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.

The crystal structure of Fe2SiO4 spinel at room temperature was investigated at seven different pressures by X-ray diffraction, using a diamond anvil cell to examine the influence of Fe substitution on ringwoodite behaviour at high pressure. The results compared with those of a pure Mg endmember show that the substitution of Fe into the spinel structure causes only small changes in the compression rate of coordination polyhedra and the distortion of the octahedron. The data show that the compression rate for the octahedron and tetrahedron in (Mg,Fe)2SiO4 can be considered statistically equal for FeO6 and MgO6, as well as for SiO4 in both the endmembers. This shows why almost identical bulk moduli are reported along the solid solution in recent literature.