Further lines of the anomalous optical absorption spectrum in low metamict zircon have been observed in the infra-red. Low-temperature polarization studies have enabled a clear distinction to be made between lines due to the anomalous spectrum and those due to the normal spectrum of U4+ in zircon. Magnetic circular dichroism measurements showed, for the anomalous spectrum, only contributions due to the mixing of the energy levels by the magnetic field; thus the A spectrum results from singlet → singlet transitions. The anomalous spectrum appears to derive from U4+ incorporated in polycrystalline zirconia.

Assessing metal contamination of soils has been a difficult task because the metal concentration in soil is not directly correlated to its potential effects. We review an approach, termed the Terrestrial Biotic Ligand Model (TBLM), in which partitioning of metal from soil to soil solution is modelled and the metal in solution interacts with an organism, the biotic ligand, to cause toxicity. The toxicity is modulated by other cations in the soil solution, principally H+, Ca2+, and Mg2+. New results for the model using Ni as the toxic species and barley root elongation as the biological response are presented.

This study deals with the kyanite-staurolite assemblage from a metabasite (ortho-amphibolite) in the Chapada area of the Neoproterozoic Mara Rosa volcano-sedimentary sequence of Goiás state, Brazil. It is closely associated with hydrothermally altered rocks and contains the assemblage hornblende, epidote, quartz, kyanite, staurolite, plagioclase and rutile. The staurolite from the amphibolite shows lower values of SiO2 and higher values of MgO, MnO, ZnO and Xmg than those in staurolites from the metasediments of the same area. In the Al–Na–Ca–(Fe+Mg) diagram, the amphibolite plots in the aluminous part of the diagram and the phase volume encloses the area of mafic volcanic bulk compositions. Field relations and compositions in both kyanite-staurolite amphibolite and staurolite are consistent with formation of this amphibolite as a result of metamorphism of metasomatised basalts.

Hectorite was synthesized from a Eu(III)-bearing brucite precursor in a multistep procedure. In a separate experiment, Eu(III) ions were adsorbed onto hectorite in suspension. Colloids were extracted from both samples. The size distributions in the colloidal fractions were characterizedby application of the asymmetrical flow field-flow fractionation (AsFlFFF) method and the corresponding elemental compositions were obtained by ICP-MS. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to characterize the local chemical environment surrounding Eu in thebulk samples and in the colloidal fractions.

The EXAFS results show that Eu is associated with hectorite upon co-precipitation or adsorption. Results from AsFlFFF suggest that Eu is structurally associated with the colloidal fraction extracted from bulk Eu-bearing co-precipitated hectorite.The AsFlFFF data are different for the colloidal fraction containing Eu(III) adsorbed on hectorite; in this sample they are consistent with a surface retention mechanism. These small but significant differences enable surface sorbed Eu to be distinguished from co-precipitated Eu. Eu is verylikely located in a clay-like environment in the co-precipitation experiment, and it forms inner-sphere surface complexes in the adsorption experiment. The results obtained using the different experimental techniques agree, and show the benefits of using multiple methods of analysis.

Trivalent europium was used as non-radioactive chemical homologue for trivalent actinides. Similar retention mechanisms are expected for the trivalent actinides if they are co-precipitating with or adsorbing onto sheet silicates. The present study provides information which can be usefullyadded to the safety assessments required for deeply buried nuclear waste disposal sites.

Thermometric and D-ICP analysis of fluid inclusions in calcite and fluorite show that the fluids responsible for extensive carbonate-hosted copper mineralization in the Ecton Hill area were low-temperature (< 100 °C), high-salinity (19.5 to 23 wt. % NaCl equivalents) brines strongly enriched in calcium (mean Ca:Na wt. ratio = 1.9). Compared with the fluids responsible for classical ‘Mississippi Valley type’ lead-zinc deposits elsewhere in the south Pennine orefield, the Ecton ore-fluids were of lower temperature and slightly more enriched in potassium. Despite these subtle differences, the data are consistent with a basinal brine model for ore genesis in this western part of the orefield similar to that envisaged for the remainder of the orefield. These Ca-Na-K-Cl, copper-bearing brines were most probably derived from the Cheshire basin located to the west of the Derbyshire Dome.

Joteite (IMA2012-091), Ca2CuAl[AsO4][AsO3(OH)]2(OH)2·5H2O, is a new mineral from the Jote mine, Tierra Amarilla, Copiapó Province, Atacama, Chile. The mineral is a late-stage, low-temperature, secondary mineral occurring with conichalcite, mansfieldite, pharmacoalumite, pharmacosiderite and scorodite in narrow seams and vughs in the oxidized upper portion of a hydrothermal sulfide vein hosted by volcanoclastic rocks. Crystals occur as sky-blue to greenish-blue thin blades, flattened and twinned on {001}, up to ~300 μm in length, and exhibiting the forms {001}, {010}, {10}, {20} and {111}. The blades are commonly intergrown in wheat-sheaf-like bundles, less commonly in sprays, and sometimes aggregated as dense crusts and cavity linings. The mineral is transparent and has a very pale blue streak and vitreous lustre. The Mohs hardness is estimated at 2 to 3, the tenacity is brittle, and the fracture is curved. It has one perfect cleavage on {001}. The calculated density based on the empirical formula is 3.056 g/cm3. It is optically biaxial (–) with α = 1.634(1), β = 1.644(1), γ = 1.651(1) (white light), 2Vmeas = 78(2)° and 2Vcalc = 79.4°. The mineral exhibits weak dispersion, r < v. The optical orientation is X ≈ c*; Y ≈ b*. The pleochroism is Z (greenish blue) > Y (pale greenish blue) > X (colourless). The normalized electron-microprobe analyses (average of 5) provided: CaO 15.70, CuO 11.22, Al2O38.32, As2O546.62, H2O 18.14 (structure), total 100 wt.%. The empirical formula (based on 19 O a.p.f.u.) is: Ca1.98Cu1.00Al1.15As2.87H14.24O19. The mineral is slowly soluble in cold, concentrated HCl. Joteite is triclinic, P, with the cell parameters: a = 6.0530(2), b = 10.2329(3), c = 12.9112(4) Å, α = 87.572(2), β = 78.480(2), γ = 78.697(2)°, V = 768.40(4) Å3 and Z = 2. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 12.76(100)(001), 5.009(23)(020), 4.206(26)(120,003,121), 3.92(24)(022,02,02), 3.40(25)(13), 3.233(19)(031,023,123,03), 2.97(132,201) and 2.91(15)(22,13). In the structure of joteite (R1 = 7.72% for 6003 Fo > 4σF), AsO4 and AsO3 (OH) tetrahedra, AlO6 octahedra and Cu2+O5 square pyramids share corners to form sheets parallel to {001}. In addition, 7- and 8-coordinate Ca polyhedra link to the periphery of the sheets yielding thick slabs. Between the slabs are unconnected AsO3(OH) tetrahedra, which link the slabs only via hydrogen bonding. The Raman spectrum shows features consistent with OH and/or H2O in multiple structural environments. The region between the slabs may host excess Al in place of some As.

Danalite is the Fe2+ end-member of the minerals of the helvite group, which have the general formula M8(BeSiO4)6S2, with M = (Mn,Fe2+,Zn). These minerals are relatively uncommon, although limited amounts are known at many localities round the world (e.g. Ragu, 1994; Larsen, 1988; Kwak and Jackson, 1986, and references therein). Their typical host rocks are skams, but occurrences in mineralized veins pegmatites, and altered alkali granites have also been reported. Danalite is rarer than helvite (Mn endmember) and genthelvite (Zn end-member) and, unlike the other two end-members, has never been found nor synthesized as a pure mineral (Mel'nikov et al., 1968).

The structure of the mineral schultenite, PbHAsO4, has been studied using pulsed neutron single crystal diffraction. The low-temperature, low-symmetry structure is found to exhibit substantial ordering of the hydrogen atom onto one of two possible sites, which are equally occupied in the high-temperature phase above 313 K. The occupancies found at low temperature agree well with the normal behaviour for such a hydrogen ordering phase transition in this type of material. In addition the heavy atom lattice distortion has been characterised as a function of temperature and found to follow broadly the pattern of hydrogen ordering. Higher-temperature measurements at and above the phase transition confirm the high symmetry nature of the structure in this region, with no significant distortions from this within the resolution of the present data.

A natural olivenite single crystal was submitted to in situ high-temperature single-crystal X-ray diffraction from room temperature (RT) to 500°C. Unit-cell parameters were measured at regular intervals of 25°C, and complete datasets collected at T = 25, 50, 100, 150, 200, 250, 300, 400 and 500°C. Evolution of unit-cell parameters and structure refinements indicates that olivenite undergoes a structural phase transition from P21/n to Pnnm at ~200°C, and eventually becomes isostructural with the other members of the olivenite-mineral group. Volume expansion with temperature is larger in the monoclinic phase – where it follows a non-linear trend – than in the orthorhombic one. Axial and volume expansion coefficients of the orthorhombic olivenite phase are positive and linear and similar to those of the other Cu-bearing member of the mineral family, namely libethenite, but rather different from those of the Zn-analogue arsenate adamite.

Distortion of Cu polyhedra is quite high in the olivenite monoclinic phase at RT and goes towards a relative regularization with increasing T until the phase transition occurs. In the orthorhombic phase, no significant variation of the polyhedral distortion parameters is observed with increasing temperature, and maximum expansion is along the b direction and governed by corner-sharing. Landau potential provides a good representation of the macroscopic changes associated with the phase transition, coupling between the strains and the order parameter is responsible for the nearly tricritical character of the transition.

Calcium hexaluminate has recently been confirmed as a stable phase occurring within the system CaO-Al2O3. In the present investigation, this aluminate has been synthesized from the constituent oxides and its X-ray, optical, and physical (microhardness and reflectivity) properties determined. Similar data have also been obtained on the ferrian phase from the immediate hot-face zone of high-alumina bricks that had been in service in electric arc furnace roofs. An electron-probe microanalysis study revealed that between 12 and 13 % atomic replacement of Al by Fe had occurred in this ferrian calcium hexaluminate. The melting behaviour of the pure compound has been studied by firing pellets in a specially-constructed vacuum furnace. Results show the incongruent melting point to be 1870°C (±10° C), while the liquidus temperature is 1970° C (±10° C). These points were determined by examining polished sections of compacts heated within the range 1820 to 2000° C. A revised phase diagram of the high-alumina portion of the system CaO-Al2O2 is presented.

The rare uranyl lead carbonate widenmannite, Pb2(UO2)(CO3)3, was found at the Jánská vein, Příbram, Czech Republic, where two generations occur in several morphological types and mineral associations in hydrothermal veins. Alpha spectroscopy shows that these two generations have different ages, >220,000 and 118±12 y. ICP-MS analysis indicates that both widenmannites have a dominance of non-radiogenic Pb which originates from weathered galena. The older widenmannite I forms fine-grained, grey to beige aggregates in the highly altered supergene part of the hydrothermal ore vein in association with pyromorphite, cerussite and goethite. The younger widenmannite II occurs as white, yellow or greenish-yellow thin tabular crystals upto 0.5 mm long in association with cerussite, anglesite, limonite, kasolite and an unnamed Pb-U-O phase. Thermal analysis suggests that widenmannite decomposes in several steps, with Pb uranate as the final product. Infrared and Raman spectroscopy confirm the presence of non-equivalent (CO3)2– groups, bidentately coordinated in uranyl hexagonal polyhedra, forming the well known uranyl tricarbonate complex. Infrared spectroscopy shows conclusively that widenmannite does not contain molecular H2O.

The determination of reliable weathering/dissolution rates for cement phases is of fundamental importance for the modelling of the temporal evolution of both radioactive waste repositories and CO2 geological storage sites (e.g. waste matrix, plug in boreholes). Here, the dissolution kinetics of AFm-Cl (hydrated calcium aluminates containing interlayer Cl) has been studied using flow-through experiments conducted at pH values ranging from 9.2 to 13. Mineralogical (XRD) and chemical (EPMA, TEM) analyses have been performed to determine the evolution of the phases during the dissolution experiments. For pH values between 10 and 13, the dissolution of AFm-Cl is congruent (i.e. Ca/Al ratios close to 2 both for solids and outlet concentrations). In contrast, the precipitation of amorphous Al-phases and possibly amorphous mixed Al/Ca phases is observed at pH 9.2, leading to Ca/Al ratios in the outlet solutions higher than those of the initial solid. Therefore, at pH 9.2, even if Cl–/OH– exchange occurs, estimation of dissolution rate from released Cl appears to be the best proxy. Dissolution rates were normalized to the final specific surface areas (ranging from 6.1 to 35.4 m2 g−1). Dissolution rate appears to be pH-independent and therefore the far-from-equilibrium dissolution rate at room temperature is expressed as: logR(mol m–2 s–1) = –9.23 ± 0.18

The crystal structure of zoned philipsbornite – hidalgoite, hexagonal (rhombohedral), Rm , Z = 3: a = 7.1142(4), c = 17.0973(9) A ˚ , V = 749.4(1) Å3, from the Tsumeb mine, Namibia, has been refined to R1 = 1.68% for 301 unique reflections collected on a Bruker D8 three-circle diffractometer equipped with a rotating-anode generator, multilayer optics and an APEX-II CCD detector. Chemical analysis by electron microprobe showed zoned crystals with a rim enriched in S and Fe relative to the core. The core composition is SO3 3.31, As2O5 30.57, Al2O3 23.05, FeO 1.44, PbO 33.94, H2Ocalc 9.58, total 101.79 wt.%, corresponding to Pb0.982+(Al2.92Fe0.132+)(AsO4)[(As0.72S0.27)O3.14(OH)0.85](OH)6; and the rim composition is SO3 8.88, As2O5 22.63, Al2O3 22.90, FeO 2.57, PbO 34.91, H2Ocalc 9.27, total 101.16 wt.%, corresponding to Pb0.992+(Al2.85Fe0.232+)(AsO4)[(As0.25S0.70)O3.30(OH)0.50](OH)6. Philipsbornite – hidalgoite has the alunite-type structure, sheets of corner-sharing octahedra, decorated on top and bottom by [(As,S)O4] and (AsO3OH) tetrahedra, that are linked into a three-dimensional structure by [12]-coordinated Pb2+ cations and hydrogen bonds. A new hydrogen-bonding scheme for the D2+G33+(T5+O4)(TO3OH)(OH)6 minerals is proposed.

Free energies of formation of divalent metal ion zippeïtes, M2(UO2)6(SO4)3(OH)10 ·nH2O, M = Mg,Co,Ni,Zn have been determined from solution studies and metal speciation calculations, in water. It is found that in the compounds, the number of molecules of water of crystallization is equal to 8. This is at variance with a previous report (Frondel et al., 1976), but it has been found that some at least of the water content of zippeite is either nonessential or very loosely bound in the structure. Based on the octahydrate formulation, values are −3506, −12695, −12683 and −12870±4 kJ mol−1 for the Mg,Co,Ni and Zn end-members, respectively. Almost all of the differences in the values are accounted for by those values for the metal ions alone with the exception of Znzippeïte where a discrepancy of some 22 kJ mol−1 is found. Even this value is small however, and the chemical studies indicate that extensive mutual solid solution between all end members is to be expected. These findings agree perfectly with observations on the composition of naturally occurring zippeite minerals of this group.

At Mamandur, southern India, zincian spinel is associated with Zn-Pb-Cu sulphide ores, metamorphosed to the granulite facies. The Zn-spinel (XZn = 0.44–0.82) occurs in assemblages of: (a) cordierite + biotite + sillimanite + sphalerite + pyrite and/or pyrrhotite; (b) garnet + biotite + sphalerite + pyrite and/or pyrrhotite; (c) hornblende + biotite + sphalerite + pyrite and/or pyrrhotite; and (d) it also occurs in highly sheared quartz veins with sphalerite + pyrite/pyrrhotite. Two texturally and compositionally distinct modes of occurrence of Zn-spinel have been recorded from the metamorphic assemblages: one shows a polygonal, granular (equilibrium) fabric with Zn-spinel grains in textural equilibrium with cordierite in the granulite facies assemblage; the other which is involved in the formation of coronas in garnet- and hornblende-bearing assemblage of a younger paragenesis (presumably belonging to a late retrograde stage), shows distinct compositional zoning with depletion of Zn and enrichment in Fe and Mg from the rim inwards. A third mode of occurrence is as perfectly euhedral grains embedded in a quartzose matrix in quartz veins, often with sphalerite moulded over the Zn-spinel grains.

From textural evidence and consideration of stoichiometric balance, Zn-spinel occurring in association with cordierite is suggested to have formed by the prograde reactions: 0.46 biotite (Mg-rich) + 1.80 sillimanite + 3.01 quartz + 0.11 sphalerite = cordierite + 0.20 Zn-spinel + 0.80 K-feldspar + 0.06 pyrite + 4(OH,F) or 0.48 biotite (Mg-rich) + 2.08 sillimanite + 2.72 quartz + 0.26 sphalerite = cordierite + 0.50 Zn-spinel + 0.83 K-feldspar + 0.13 S2 + 4(OH,F) and, the Zn-spinels occurring in association with garnet and hornblende by the retrograde reactions: garnet + 4.53 Al2SiO5 + 4.17 sphalerite = 5.38 Zn (-Fe)-spinel + 0.22 Ca-feldspar + 0.92 pyrite + 7.06 quartz + 1.23 S2 and hornblende + 26.93 Al2SiO5 + 20.17 sphalerite + 0.88 pyrite = 25.93 Zn-spinel + 2 Ca-feldspar + 56.81 quartz + 11.32 S2 + 2(OH,F) Zn-spinel in the sheared quartz vein may be of (meta-) hydrothermal origin. Formation of sphalerite through sulphurization of gahnite is ruled out on the evidence of the perfectly euhedral nature of the spinel and the absence of any breakdown product from the spinel.

Iron-cross twins of pyrite are well known among mineralogists, however it is quite surprising that the conditions of their formation remain unexplored. To address this question we studied pyrite twins from the Upper Permian silts of Mt. Katarina near Ljubljana (Slovenia), which represent one of the most typical geological environments for twinned pyrite. Mineralization of pyrite starts with a reduction of the primary red-coloured hematite-rich sediment by sulfide-rich fluids that penetrated the strata. A short period of magnetite crystallization is observed prior to pyrite crystallization, which indicates a gradual reduction process. Sulfur isotope analysis of pyrite shows an enrichment in δ34S, suggesting its origin from the neighbouring red-bed deposit. Other sulfides, such as chalcopyrite and galena, formed at the end of pyrite crystallization. Remnants of mineralizing fluids trapped at the interfaces between the inclusions and host pyrite show trace amounts of Pb and Cu, indicating their presence in the solutions throughout the period of pyrite crystallization. An electron microscopy and spectroscopy study of twin boundaries showed that interpenetration twinning is accomplished through a complex 3D intergrowth of primary {110} Cu-rich twin boundaries, and secondary {100} boundaries that are pure. We show that approximately one monolayer of Cu atoms is necessary to stabilize the {110} twin structure. When the source of Cu is interrupted, the two crystal domains continue to form {100} interfaces, that are more favourable for pure pyrite.

In situ, high-temperature energy-dispersive X-ray powder diffraction (EDXRD) data have been collected on synthetic and a natural sample of mercury sulphide (HgS). These measurements were made between temperatures of 295 and 798 K. Synthetic samples of HgS were prepared by reaction between sulphide and mercury in aqueous solution. In a subsequently dried and aged synthetic HgS sample, heated in vacuo, there is a change from a poorly crystalline pseudocubic material into a well crystalline cubic material in the temperature region 583–623 K. At higher temperature (748 K), there is evidence for a partial phase transition to the high temperature hypercinnabar HgS structure. In a neoformed synthetic sample, heated in a sealed Ti container, the initial ‘pseudocubic’ metacinnabar phase partially transforms to a previously unknown phase (XHgS) in the temperature range 467–522 K. This phase disappears at 527 K, and the metacinnabar phase changes to a well crystalline cubic phase; cinnabar develops at 542 K. The proportion of cinnabar continues to increase up to 647 K. Both metacinnabar and cinnabar phases are retained on cooling. No phase transitions were observed for the natural cinnabar sample.