Large volumes of depleted natural and low-enriched uranium exist in the UK waste inventory. This work reports on initial investigations of the leaching performance of candidate glass and cement encapsulation matrices containing UO3 powder as well as that of uranium oxide powders. The surface areas of UO3 powder and the monolith samples of UO3 conditioned in the glass and cement matrices were very different making leaching comparisons difficult. The results showed that for both types of monolith conditioned samples a steady increase of uranium concentration in solution with time was generally not observed. The wt.% of uranium leached from UO3 conditioned in the lead borosilicate glass wasteform was approximately five orders of magnitude less than that leached from UO3 powder. Similarly, the quantities of uranium leached from UO3 conditioned in composite cement made with ordinary Portland cement, and from magnesium phosphate cement, were approximately four and three orders of magnitude, respectively, less than that leached from UO3 powder. The performance of a mixed oxide borosilicate glass wasteform was only slightly better than that of UO3 powder. This work shows that wasteforms based on encapsulation in lead borosilicate glass and cement matrices have the greatest potential for further development.

Room temperature Mössbauer and electron-probe measurements of Fe3+/ΣFe in chromite from the mantle section of the Oman ophiolite define two groups of samples: a low Fe3+/ΣFe group (with Fe3+/ΣFe = 0.21–0.36) have cr# = Cr/(Cr + Al) in the range 0.49–0.75, whereas a smaller more geographically localized high Fe3+/ΣFe group (with Fe3+/ΣFe = 0.71–0.78) have a more restricted range of cr# ratios of 0.72–0.75. The low Fe3+/ΣFe chromitites have very variable Fe3+/ΣFe ratios. They are thought to have crystallized from melts that have interacted with depleted mantle and thereby acquired their variable Fe3+/ΣFe ratio. The high Fe3+/ΣFe chromitites are restricted to one small area of the mantle and their high oxidation state is thought to be post magmatic. They are either the product of later heating, related to melt flux or interaction with a later oxidising melt. A difference in oxygen fugacity between the MORB-depleted harzburgite host, which is at the quartz–fayalite–magnetite (QFM) buffer and the later chromite-bearing melts (QFM + 2) implies that there is a real difference in the oxidation state of the MORB and arc-magma sources.

This paper reports an investigation of the crystallization products of K-rich silicate and carbonate melts trapped as melt inclusions in clinopyroxene phenocrysts from the Dunkeldyk alkaline igneous complex in the Tajik Republic. Heating experiments on the melt inclusions suggest that the carbonate melt was formed by liquid immiscibility at 1180°C and ∼0.5 GPa. The carbonate-rich inclusions are dominated by Sr-bearing calcite, and rich in incompatible elements. Most of the silicate minerals are SiO2-poor and rich in K, Ba and Ti. Leucite, kalsilite and aegirine are the earliest magmatic minerals. High Ba and Ti contents in the melt resulted in the crystallization of Ba-rich K-feldspar, titanite, perovskite and Ti-bearing garnet, and the rare Ba-Ti silicates fresnoite and delindeite. The last minerals to crystallize from volatile-rich melts and fluids were aegirine, götzenite, K-Ba- and Ca-Sr-bearing zeolites, fluorite and strontium-rich baryte. Interaction of the early minerals with residual melts and fluids produced Ba-rich phlogopite and Sr-rich apatite.

The high-pressure monazite – scheelite structure transition has been observed at P >4.57 GPa in CaSeO4 by synchrotron X-ray powder diffraction. It is a first-order transition with a 4.5% volume change and is severely hindered kinetically. Scheelite-type CaSeO4 remains to a maximum experimental pressure of 42.2 GPa and no (002) reflection, specifically indicative of a subgroup transition to a fergusonite-type structure, is observed. Scheelite-type CaSeO4 remains at ambient conditions, where the tetragonal unit cell has parameters of a = 5.04801(11) c = 11.6644(5) Å and V = 297.21(3) Å3 with Dcalc = 4.090 g cm–3. The diffraction pattern of the recovered material was refined in space group I41/a to Rp = 0.98%, wRp = 1.91%, GoF = 0.59, RFobs = 5.04%, wRFobs = 4.27%. The oxygen is located on the general 16f site at (0.2578(8) 0.3699(14) 0.5755(4)) and shares four identical bonds with Se (4a: ½ ½ ½) at 1.644(5) Å. The Ca (4b: 0, 0, ½) is eight-coordinated via O at 4 × 2.440(6) Å and 4 × 2.504(5) Å. This is further evidence of the dissimilarity of sulfate and selenate at high pressure and temperature conditions and the closer resemblance of the selenates to the orthophosphates, arsenates and vanadates, where this type of transition sequence has been described.

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

Transparent prismatic crystals of Pb2(AsO2OH)Cl2 were collected in black metallurgical slag on the coast in the Punta Zeza area, 3 km south of the town of Lavrion, Greece. Analyses by energy-dispersive X-ray spectrometry (EDS) provided the following chemical composition: PbO 73.04, As2O3 15.97, Cl 11.42, O=Cl –2.58, total 97.85 wt.%. The empirical formula calculated on the basis of As = 1 is HxPb2.03(AsO3)1.00Cl1.995 (x = 0.96). The infrared spectrum of Pb2(AsO2OH)Cl2 has characteristic AsO33– bands at 707 and 594 cm–1, O–H stretching vibrations at 3310 and 2900 cm–1 and a band at 1107 cm–1 which is assigned to As–O–H bending vibrations. The structure, which is monoclinic P21/m, a = 6.4235(8), b = 5.5399(7), c = 9.321(1) Å, β = 90.767(2)°, V = 331.67(7) Å3, R1 = 0.035, is identical to that of synthetic Pb2(AsO2OH)Cl2 and contains two symmetrically unique Pb sites and one As site. The crystal structure is based on [Pb2AsO2OH]2+ double chains interconnected via weak Pb–Cl bonds to produce a three-dimensional framework which is closely related to that of Pb oxysalt minerals containing [O2Pb3]2+ chains of oxocentred [OPb4]6+ tetrahedra including mendipite, damaraite, rickturnerite and plumboselite.

A pink-purple diamond crystal from the Internatsional'naya kimberlite pipe (Siberia) was studied by single-crystal X-ray diffraction techniques using an area detector. Direct indexing of the diffraction pattern suggested a primitive hexagonal unit cell [ahex = 2.513(4), chex = 6.172(11) Å], instead of the well known face-centred cubic unit cell (acub ∼3.567 Å). Theoretical considerations and diffraction pattern simulation showed that the hexagonal diffraction pattern is the result of the superposition of two diffraction patterns with cubic symmetry due to spinel-law twinning along (111). These data are in good agreement with previous analyses of deformation microtwins in natural pink-purple diamonds using electron paramagnetic resonance spectroscopy and optical microscopy. The results suggest that natural epigenetic plastic deformation of diamonds occurs not only by dislocation slipping but also as a result of mechanical twinning.

Stable perovskite and metastable post-perovskite NaCoF3 were deformed in pure-shear geometry in a deformation-DIA press with radiographic monitoring of the sample strain. In isothermal experiments where there was no transformation, post-perovskite was found to be 5 times weaker than perovskite. In temperature-ramping experiments where post-perovskite transformed to perovskite during the deformation experiment the initial post-perovskite sample was 5–10 times weaker than perovskite under comparable conditions and their strengths converged during the transformation, being equal on completion of the transformation. These results confirm recent findings which show that postperovskite is weaker than perovskite, regardless of the prior history of the sample.

Thirty pyrite samples from a wide range of localities were analysed using relative comparator and k0 neutron activation analysis (NAA) techniques at the University of Missouri Research Reactor, Columbia, Missouri, USA (MURR) and the Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW, Australia (ANSTO), respectively. Statistical analyses of the trace-element data produced by the two methods showed a generally good correlation, with the majority of elemental concentrations of paired data reported by MURR and ANSTO being indistinguishable at a 0.05 significance level. Trace-element analyses of pyrite from Navajún in Spain by both techniques compare well with published data. There is evidence for contamination by Al, Na and Ti in one set of samples, this is likely to have been introduced by contact with a plastic used in sample preparation.

The new minerals d'ansite-(Mn), Na21Mn2+(SO4)10Cl3, and d'ansite-(Fe), Na21Fe2+(SO4)10Cl3, occur as encrustations in fumaroles at Vesuvius, Naples, Italy and La Fossa crater, Vulcano, Aeolian Islands, Italy, respectively. Both minerals are cubic and crystallize in space group I3d. D'ansite-(Mn) forms colourless translucent tristetrahedral crystals up to 0.2 mm on edge; d'ansite-(Fe) forms aggregates of colourless to white complex isometric crystals of about the same size. Chemical analyses obtained by energy-dispersive spectrometry on an electron microprobe gave the following mean compositions: d'ansite-(Mn), Na2O 39.37, MnO 3.46, MgO 0.13, SO3 49.99, Cl 6.36, O=Cl–1.44, total 97.87 wt.%, corresponding to an empirical formula, on the basis of 43 anions, of Na20.61 (Mn2+0.79Mg0.05)Σ0.84S10.13O40.09Cl2.91; and d'ansite-(Fe), Na2O 39.12, FeO 4.18, MgO 0.12, SO3 49.91, Cl 6.81, O=Cl –1.54, total 98.60 wt.%, corresponding to an empirical formula of Na20.42(Fe2+0.94Mg0.05)Σ0.99S10.08O39.89Cl3.11. The six strongest reflections in the X-ray powder diffraction pattern of d'ansite-(Fe) [listed as dobs(Å) (I) (hkl)] are as follows: 2.807(100)(044), 2.570(37)(235), 1.714(29)(129), 3.384(27)(233), 3.113(26)(134), 2.108(15)(237). The unit-cell parameters obtained from single-crystal data are 15.9291(9) and 15.882(3) Å for d'ansite-(Mn) and d'ansite-(Fe), respectively. The structure of both minerals was refined, using single-crystal diffraction data, to final R parameters of 0.0309 and 0.0336 on reflections with I > 2σ(I). The structure contains three independent Na sites, one of which is partially occupied by Mn2+ or Fe2+, two independent sulfate anions and one chlorine site.

Intermediate-level wastes (ILW) include substantial quantities of fissile material and controls are required to ensure that its storage, transport and disposal does not present a nuclear criticality hazard. This paper describes the Radioactive Waste Management Directorate's research to develop package fissile material limits (in the form of screening levels) for four different categories of ILW, defined according to uranium or plutonium composition: (1) irradiated natural and slightly enriched uranium (uranium containing up to 1.9 wt.% 235U); (2) low-enriched uranium (uranium containing up to 4 wt.% 235U); (3) high-enriched uranium (uranium containing up to 100 wt.% 235U); and (4) separated plutonium (plutonium containing up to 100 wt.% 239Pu).

The derivation of package screening levels was supported by neutron transport calculations that addressed conditions during waste package transport to a geological disposal facility (GDF), during the GDF operational phase and after GDF closure. The analysis included consideration of combinations of events and processes that could result in fissile material accumulation and concentration after GDF closure, when waste packages have deteriorated sufficiently for fissile material to be mobilized. The results of the calculations have provided input to Radioactive Waste Management Directorate's decision making on setting waste package screening levels.

The low-temperature structural behaviour of natural cancrinite with a formula Na6.59Ca0.93[Si6.12Al5.88O24](CO3)1.04F0.41·2H2O has been investigated by means of in situ single-crystal X-ray diffraction and Raman spectroscopy. High quality structure refinements were obtained at 293, 250, 220, 180, 140, 100 and at 293 K again (at the end of the low-T experiments). The variation in the unit-cell volume as a function of temperature (T) exhibits a continuous trend, without any evident thermoelastic anomaly. The thermal expansion coefficient αV = (1/V)∂V/∂T is 3.8(7) × 10–5 K–1 (between 100 and 293 K). The structure refinement based on intensity data collected at ambient conditions after the low-T experiment confirmed that the low-T induced deformation processes are completely reversible. The extraframework population does not show significant variations down to 100 K. The strong positional disorder of the carbonate groups along the c axis persists within the T range investigated. The structural behaviour of cancrinite at low-T is mainly governed by the continuous framework rearrangement through the ditrigonalization of the six-membered rings which lie in a plane perpendicular to [0001], the contraction of the four-membered ring joint units, the decrease of the ring corrugation in the (0001) plane, and the flattening of the cancrinite cages. A list of the principal Raman active modes in ambient conditions is provided and discussed.

This study reports the discovery of inclusions, which are inferred to represent trapped primary silicate gels, in simple pegmatites genetically connected to the Precambrian Rønne granite of Bornholm Island, Denmark. These inclusions are randomly associated with more typical melt and alkali-carbonate-rich and bicarbonate-rich fluid inclusions. Their relationship to the latter and to the formation of the pegmatite bodies is discussed. The silicate gel inclusions become increasingly common towards the quartz cores of the pegmatites, and are considered to demonstrate increasing water and alkali carbonate concentrations in the pegmatite-forming liquid, and an accompanying tendency for sol/gel formation. This discovery may have important implications for the formation of the quartz cores of pegmatites. The possible origin of the alkali-carbonate concentrations in pegmatite-forming fluids is also briefly discussed.

Rumseyite, ideally [Pb2OF]Cl, is a new mineral species which is associated with calcite, cerussite, diaboleite, hydrocerussite and undifferentiated Mn oxides in a small cavity in 'hydrocerussite' from a manganese pod at Merehead quarry, Somerset, England. Rumseyite is tetragonal, I4/mmm, a = 4.065(1), c = 12.631(7) Å, V = 208.7(1) Å3, Z = 2. The mineral is translucent pale orange-brown with a white streak and vitreous lustre. It is brittle with perfect {100} cleavage; Dcalc = 7.71 g cm–3 (for the ideal formula, [Pb2OF]Cl). The mean refractive index in air at 589 nm is 2.15. The six strongest reflections in the X-ray powder-diffraction pattern [dmeas in Å, (Irel), (hkl)] are as follows: 2.923(100)(013), 2.875(68)(110), 3.848(41)(011), 6.306(17)(002), 1.680(14)(123), 2.110(12)(006). The crystal structure of rumseyite is based on alternating [OFPb2] and Cl layers. Rumseyite is related to other layered Pb oxyhalides. Fluorine and oxygen are statistically disordered over one crystallographic site. Rumseyite is named in honour of Michael Scott (Mike) Rumsey (1980– ), Curator and Collections Manager at the NHM (London), who discovered the mineral. The mineral and name have been approved by the IMA Commission on New Mineral Names and Classification (IMA 2011-091). The holotype specimen is in the collections of the Natural History Museum, London (specimen number BM1970,110).

Intermediate-level radioactive waste is normally encapsulated in cementitious grout. However, for some wastes, grout may not be suitable and polymeric encapsulants are being considered as an alternative. One concern with such encapsulants is their long-term chemical stability and the possibility that release of aggressive degradation products could cause corrosion.

This paper evaluates the potential for three polymeric encapsulants: two epoxy resins (the APS polymer system, (APS) and Alchemix 4760 (ALC)) and a vinyl-ester styrene (VES); to cause internal corrosion of stainless steel waste containers. The corrosion behaviour of stainless steel 316L in contact with each encapsulant was studied in saturated Ca(OH)2 solutions and deionized (DI) water, at 80°C, under non-irradiated and γ-irradiated conditions.

In aerated, alkaline conditions, 316L was resistant to corrosion in all the conditions tested. However, in DI water, the pH fell to values as low as three due to release of acidic species from the polymers. The two epoxy materials (particularly APS) also released significant levels of chloride; VES did not. Chloride release appeared to be increased by γ-irradiation. As a result of the low pH chloride-containing environment created by the APS encapsulant, 316L experienced localized corrosion, whereas coupons in Alchemix 4760 and VES did not. Weight loss measurements correlated with visual observations. γ-irradiation appeared to increase the degree of corrosion.

Arsenohopeite, ideally Zn3(AsO4)2·4H2O, is the arsenate analogue of hopeite, Zn3(PO4)2·4H2O (it is isostructural with α-hopeite). It was found as a single colourless to blue crystalline grain from the Tsumeb mine, Namibia. The holotype specimen is ∼1 × 1 × 1 mm in size. Arsenohopeite is associated with tiny white fibres of an unidentified Zn- and As-bearing phase. It is orthorhombic, space group Pnma, with a = 10.804(2), b = 19.003(4), c = 5.112(1) Å, V = 1049.5(4) Å3 and Z = 4. Electron microprobe analysis yielded: ZnO 44.92, Fe2O3 0.92, MnO 0.51, MgO 0.20, CuO 0.02, As2O5 45.84 (wt.%). The empirical formula is (Zn2.80Fe0.06Mn0.04Mg0.03)Σ2.93(As1.01O4)2·4H2O, based on 12 oxygen atoms. Optically, the mineral is biaxial negative, with α = 1.598(2), β = 1.606(2), γ = 1.613(2) (white light) and 2Vcalc = 86°. It is not pleochroic or fluorescent. Arsenohopeite is translucent with a vitreous lustre. It is brittle, has an uneven fracture and (by analogy with hopeite) a cleavage that is perfect on {010}, good on {100} and poor on {001}. The calculated density is 3.420 g cm–3. The five strongest calculated powder diffraction lines are [d in Å (I)(hkl)]: 9.502 (100)(020), 2.926 (95)(241), 4.937 (50)(011), 4.110 (48)(230) and 3.567 (31)(240). The crystal structure of arsenohopeite has been solved by direct methods and refined in space group Pnma to R1 = 0.0353. Raman spectroscopy confirms the crystal-structure data and indicates the presence of weak hydrogen bonds.

Synchrotron X-ray powder diffraction data have been collected on three synthetic leucite analogues with the general formula Cs2XSi5O12(X = Cd, Cu, Zn) between 295 and 1173 K. All three samples have the orthorhombic Pbca leucite structure at room temperature with ordered framework T-site cations. The sample with X = Cd retains the Pbca structure over the whole of the investigated temperature range. The sample with X = Cu also retains the Pbca structure, but there is a transition to a less distorted structure with a larger unit-cell volume at ∼333 K. The sample with X = Zn shows evidence for a transition to a previously unknown Pa cubic structure, with some T-site cation disorder, at 566 K, on heating. This transition is reversible on cooling to 633 K.