Hydroxylian pseudorutile in an adamellite from Cameroon has been identified using EPMA, FT-IR and single-crystal XRD analysis. TiO2 and Fe2O3 contents range between 60.6 and 67.9 wt.% and 22.2 and 36.5 wt.%, respectively, and totals vary from 90.1 to 98.1 wt.%. The SiO2 (0.03 —1.40 wt.%), Al2O3 (0.02—0.68 wt.%) and CaO (0.03—0.44 wt.%) contents increase systematically and MnO (0.04—0.69 wt.%) decreases slightly with decreasing Fe3+/Ti values. The MgO content is <0.06 wt.%. H2O contents (1.3—7.5 wt.%) are greater in parts of crystals with lower Fe3+/Ti, suggesting solid solution between the end-members Fe3+2Ti3O9 and Fe3+Ti3O6(OH)3. The lattice parameters are a = 2.85 Å and c = 4.57 Å with hexagonal symmetry and point group 6/mmm.

In an attempt to assemble together the sparse information regarding the eighty meteorites recorded as having fallen in Italy, tables have been prepared dealing respectively with chronology, name and generalities, synonymy, and literature, together with a distribution map. They are intended not only to help correct identification of pieces widespread in museums or private collections, but also to begin a labelling unification process, in order to avoid confusion arising from a wide variety of synonyms.

The crystal structure of the sheet oxychloride mineral parkinsonite, nominally Pb7MoO9Cl2, has been determined for synthetic and natural crystals of analysed compositions, (Pb7.28Mo0.72) O8.96Cl1.96 and (Pb7.23Mo0.40V0.37)O8.90Cl1.82, respectively. Parkinsonite is tetragonal, space group I4/mmm. Unit-cell parameters for synthetic and natural crystals are: asynthetic = 3.9773(4) Å, csynthetic = 22.718(4) Å, Vsynthetic = 359.38(5) Å3, and anatural = 3.9570(3) Å, cnatural = 22.634(5) Å, Vnatural = 354.40(5) Å3. Final agreement indices (R1, wR2) for refinements of the two crystals are 0.024, 0.067 (synthetic) and 0.036, 0.078 (natural). Although a superlattice has been identified by electron diffraction for crystals of both samples (Welch et al., 1996), only the substructure could be determined by X-ray diffraction. This X-ray invisibility of the superstructure has also been observed for the closely related sheet oxychlorides asisite and schwartzembergite, for both of which superstructure motifs have been identified by electron diffraction. The Pb(1) site of both parkinsonite crystals is fully occupied by Pb. Refinement of the Pb content of the Pb(2) site for the synthetic and natural crystals gives occupancies of 0.85(1) and 0.70(1) respectively, corresponding to 3.40 and 2.80 Pb(2) a.p.f.u. respectively. The substituent cation Mo (synthetic crystal) and [Mo+V] (natural crystal) was located at a distance of 0.5 Å from Pb(2), being displaced along the fourfold axis. The reduced occupancy of Pb(2) is due to substitution by Mo or [Mo+V]. No evidence for separate Mo and V sites in the substructure of natural parkinsonite was found. Refined occupancies of the Cl site are 0.84(4) and 0.91(5) for the synthetic and natural crystals, respectively, and are consistent with the 9:1 superstructure component identified by electron diffraction.

The distribution of uranium in a suite of variably deformed and metamorphosed rocks from the leucocratic member of the Glendessarry syenite has been determined using the fission track method. The uranium content of the magma increased during crystallization and uranium was concentrated in accessory minerals such as monazite, zircon, sphene, allanite, apatite, and microinclusions of a Zr- and Ti-rich phase. Contamination of the magma by pelitic metasediment enhanced the uranium content and monazite and zircon formed instead of sphene, allanite, and apatite.

Evidence of subsolidus uranium mobility in late stage magmatic or metamorphic fluids is presented here and shows: (a) Intracrystalline redistribution of uranium, especially in grains of sphene. (b) Intergranular mobility in a fluid phase, which affected the uraniferous accessory minerals in several ways.

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

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.

Petrographic, microscopic, and X-ray investigations of a uranium occurrence near Tiraun, Graubünden, Switzerland, are described. The uranium mineralization occurs in greenschist facies metamorphic rocks of the Tavetsch massif and consists essentially of uraninite of various habits with minor chalcopyrite, linnaeite, millerite, galena, marcasite, pyrite, hematite, magnetite, and skutterudite. The ore structure, characterized by concentrations along foliation planes, boudinage, and rotated (helicitic) textures of uraninite porphyroblasts, is indicative of a synmetamorphic (Alpine) remobilization, recrystallization and enrichment of the ore, which was probably derived from an original ‘protore’ in psephites and psammites (? sandstone-type mineralization) of at least Variscan age. The synmetamorphic emplacement of the ore took place under medium- to high-temperature conditions (approx. 350–400°C), as demonstrated by the lattice constants of the uraninite phases and by the ore paragenesis. Late to postmetamorphic tectonism resulted in a partial remobilization (over cm distances) and redistribution of the ore along veinlets that cut the foliation planes. The characteristics of the ore from Tiraun are similar to those from the synmetamorphic ore from Preit, northern Italy, as described by Cevales (1961).

The mole fractions of the silicons present in melilites as monomeric (SiO4) and dimeric (Si2O7) groups depends both upon the composition of the melilite and also upon the degree of Al-Si ordering. It is shown that the absolute numbers of monomeric and dimeric silicons in a 10 mg polycrystalline sample can be determined by a relatively rapid chromatographic method.

A statistical theory is developed to treat the data; this contains a variable k-parameter that describes the degree of ordering.

Experimental results are presented and interpreted for one natural and five synthetic melilites. The synthetic gehlenite-rich melilites are appreciably, but not completely disordered. The natural melilite is well ordered, but heating at 1050 °C introduces considerable disorder.

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.

The distribution of Mg and Ni over the octahedrally-coordinated sites M(l,2,3) in Ni-substituted potassic richterite solid solution, AKB(NaCa)c(Mg2.5Ni2.5)Si8O22(OH)2, synthesized at 0.1 GPa/750°C (25 days), has been studied in situ to 700°C by neutron powder diffraction with Rietveld structure refinement. Using a 2.7 g sample it was possible to make short data collections (3 h) at each temperature at intervals of 50° from 50 to700°C and locate the onset of cation exchange. Above 700°C the amphibole decomposes rapidly and so only an on-heating dataset was collected. Unit-cell parameters increase smoothly upon heating, with no discontinuities evident. Site occupancies of M(l), M(2) and M(3) sites were refined from site-scattering values. The initial XNi values of M(l), M(2) and M(3) sites, corresponding to the synthesis temperature of 750°C, are 0.57(1), 0.34(1) and 0.68(2), respectively. Above 400°C, there is initial ordering whereby thermal annealing allows the disordered Mg-Ni distribution of the quenched synthesis product to adjust to be closer to those appropriate for lower temperatures of the heating sequence. This ordering involves the exchange of Mg and Ni between M(l) and M(2), with no significant change in M(3) occupancy. At 700°C, XNi values of the M(l), M(2) and M(3) sites are 0.64(1), 0.27(1) and 0.69(2), respectively. No disordering was observed, due to the short duration of the high-temperature data collections and decomposition at 750°C. The results of this study indicate that divalent cations exchange between octahedral sites in amphiboles in a matter of hours.

Secondary minerals described from Tertiary amygdaloidal basalts in the Hunter Springs area, Barrington, New South Wales, are regarded as having been deposited from cold solutions some considerable time after consolidation of the basalts. The constituents in the solutions were evidently derived from the basalts by the action of circulating meteoric waters rather than by deuteric activity.

In the course of the routine X-ray examination of a number of lowgrade iron ores in order to determine their constitution, it was observed that the calcite phase had varying interplanar spacings. Since these variations could have been due to differing solid-solution contents of other carbonates, further consideration was given to this point. The existence of these generally small amounts of solid solution is of some technological interest.

A sample of 'specpure' calcite, supplied by Messrs. Johnson, Matthey & Co. Ltd., was used to provide accurate lattice parameters and interplanar spacings for pure calcite.

Canonite from Alfenza grows as crowded, radiating, acicular aggregates covering bismuthinite crystals. Individual crystals have a lozenge-shaped habit on {010}, the presumed cleavage plane of cannonite. Crystal structure refinements in the P21/c space group of two single crystals led to the following cell parameters: a = 7.7196(5) Å, b = 13.8856(9), c = 5.6980(4), b = 109.174(1)º (R1 = 0.0424); and a = 7.7100(8), b = 13.8717(14), c = 5.6939(6), b = 109.155(2)º (R1 = 0.0438). Hydrogen atoms were also localized in the density-difference Fourier map and refined with soft restraints on the bond distances. Raman and IR spectroscopy confirm the presence of OH groups and the absence of molecular water, and deliver OH···O geometry wholly comparable with the structure refinement. Electron microprobe analyses revealed no significant levels of elements other than those expected in the ideal formula except fluorine which was present up to 0.14 a.p.f.u. The crystal structure can be described in terms of anion-centred OBi4 edge-sharing tetrahedra forming chains running parallel to z and strongly cemented along x by isolated SO4 tetrahedra. Each OBi4 tetrahedron is further connected along y by OH groups, making walls of composition Bi4O2(SO4)2(OH)4 parallel to (010). These walls are tied to each other along y by fewer Bi–O–S bridges and weaker OH···O bonds.

Hydroniumpharmacosiderite, ideally (H3O)Fe4(AsO4)3(OH)4·4H2O, is a new mineral from Cornwall, UK, probably from the St. Day group of mines. It occurs as a single yellowish green, slightly elongated cube, measuring 0.17 mm ×0.14 mm ×0.14 mm. The mineral is transparent with a vitreous lustre. It is brittle with a cleavage on {001}, has an irregular fracture, a white streak and a Mohs hardness of 2–3 (determined on H3O-exchanged pharmacosiderite). Hydroniumpharmacosiderite has a calculated density of 2.559 g cm–3 for the empirical formula. The empirical formula, based upon 20.5 oxygen atoms, is: [(H3O)0.50K0.48Na0.06]1.04(Fe3.79Al0.22)4.01[(As2.73P0.15)2.88O12](OH)4·4H2.14O. The five strongest lines in the X-ray powder diffraction pattern are [dobs(Å),Iobs,(hkl)]: 8.050,100,(001); 3.265,35,(112); 2.412,30,(113); 2.830,23,(202); 4.628,22,(111). Hydroniumpharmacosiderite is cubic, space group with a = 7.9587(2) Å, V = 504.11(2) Å3 and Z = 1. The crystal structure was solved by direct methods and refined to R1 = 0.0481 for 520 reflections with I > 2σ(I). The structure is consistent with determinations for H3O-exhchanged pharmacosiderite and the general pharmacosiderite structure type.

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.

Fifteen widely separated occurrences of kimberlite and kimberlitic rocks are now known in south-eastern Australia. Those that have been satisfactorily dated isotopically give ages ranging from Permian to Late Jurassic. One occurrence exhibits an intimate spatial association with carbonatite. The classification of these rocks as ‘kimberlitic’ is partly based on their mode of emplacement, and particularly on the presence of crust/mantle inclusions. Compared with African kimberlitic magmas, the southeastern Australian examples have lower incompatible-element contents. These differences are interpreted as representing slightly greater degrees of partial melting of a four-phase Iherzolite assemblage at shallower depths (∼ 65 km) than typical African kimberlite magma.

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.