Ludwigite from B-bearing iron ores in the Bergslagen area of central Sweden and in the coastal area north of Stockholm has been studied using chemical and single-crystal diffraction techniques. Structure refinements, completed for three crystals showing slightly different Al contents, in the space group Pbam (agreement factor: 2.42 ≤ R ≤ 2.79) indicate that: (1) octahedral M1, M2 and M3 bond distances are similar, although the calculated site population suggests that M1 and M2 are nearly completely occupied by Mg whereas M3 also contains Fe2+ and Fe3+; (2) in the M4 octahedron Fe3+ and Al dominate over Mg (and Fe2+); and (3) the distortion parameter, BLD, indicates that M3 is the most regular, whereas M4 is the most distorted octahedron.

High-alumina subsilicic calcic amphiboles, including sadanagaite and subsilicic ferroan pargasite, are found in rock samples from the contact aureole in the Nōgō-Hakusan area, central Japan. They occur in the reaction zones between dark fragments and the surrounding crystalline limestone of the pyroxene hornfels facies zone. The dark fragments which underwent K-metasomatism are originally basaltic rocks. The sadanagaite and subsilicic ferroan pargasite have high Al2O3 (16–19 wt. %) and K2O (3.6–4.3 wt. %) contents. The Si value ranges from 5.38 to 5.64 and the total Al ranges from 3.10 to 3.43 when cation ratios are calculated on the basis of O = 23. The calculated unit cell parameters of sadanagaite are a 10.00 (1), b 18.06 (2), c 5.355 (4) Å, β105.52(7)°, V 932(1) Å3. The A-sites of the amphiboles is occupied almost entirely by K and Na; the amphiboles are saturated with the edenite component. The amphiboles show a larger extent of tschermakite-type substitution [(Mg,Fe)Si⇌AlAl] than does ordinary pargasite. Sadanagaite is probably stable at the temperature above the upper amphibolite facies.

Physical and chemical properties of lustrous black mica from greisen veins at the Bom Futuro tin mine indicate that it is a relatively Fe-F-rich, Li-poor zinnwaldite with a composition near the midpoint of the polylithionite-siderophyllite join. On the basis of 22 oxygens, the mica contains 1.28–1.73 atoms of Li with an average octahedral occupancy of 5.61 and a filled interlayer site. Compositional variation reflects the net effects of alteration, coupled tetrahedral-octahedral substitutions, and petrogenetic factors related to vein fluid chemistry. Geological constraints and compositional data suggest the Bom Futuro zinnwaldite crystallized at T ≈ 500°, P ≈ 1–500 bar, and fO2 ≈ 10−23. High Mn-Zn concentrations in the Bom Futuro mica appear to be a feature of Fe-Li micas from evolved anorogenic granitic systems not shared by orogenic counterparts.

Criddleite, ideally TlAg2Au3Sb10S10, is a rare constituent within the Hemlo gold deposit, Hemlo, Ontario, Canada. The mineral occurs as 20 to 50 µm-sized lath-like, tabular or anhedral grains usually surrounding or penetrating aurostibite, or associated with native antimony, native gold and stibnite. Criddleite is opaque with a metallic lustre and a black streak. It has been synthesized by reacting TlSbS2 and high purity Ag, Au, Sb and S in an evacuated silica glass tube at 400 °C. The measured density of the synthetic material is 6.86; the calculated density is 6.57 g/cm3. The difference is due to minor admixed aurostibite, native antimony and a dyscrasite-like phase within the charge. VHN25 is 94–129. Mohs hardness (calc.) = 3–3 ½. In reflected plane-polarized light in air, natural criddleite is weakly bireflectant with a discernible reflectance pleochroism from grey-blue to slightly greenish grey-blue. The mineral has a distinct to moderate anisotropy with rotation tints in shades of buff to slate grey. Reflectance spectra and colour values for both natural and synthetic criddleite are given. X-ray study showed that synthetic criddleite is monoclinic (pseudotetragonal) with refined unit-cell parameters a = 20.015(2), b = 8.075(2), c = 7.831(2) Å, β = 92.01(2)°, V = 1264.9 ± 1.0 Å3 and a:b:c = 2.4786: 1:0.9698. The space group choices are A2/m(12), A2(5) or Am(8), diffraction aspect A*/*. The seven strongest lines in the X-ray powder diffraction pattern [d in Å (I) (hkl)] are: 5.63(90) (011), 3.91(50) (002), 3.456(50) (320), 2.860(70) (700), 2.813(100) (022), 2.018(60) (040) and 1.959(70) (004). Electron microprobe analyses are reported of natural criddleite in five polished sections of drill core from four holes. The averaged empirical formulae, based on 26 atoms, are Tl0.92Ag1.99Au2.93Sb9.87S10.28 (natural) and Tl0.94Ag2.03Au2.89Sb9.76S10.38 (synthetic).

Abundant kiddcreekite grains were identified in the Zijinshan Cu-Au epithermal deposit in Fujian Province, China. The mineral occurs as polycrystalline grains, 5–300 μm in size, associated with colusite, enargite, stannoidite, mawsonite, vinciennite, hemusite, tennantite and wolframite in a predominantly covellite ore. Based on electron microprobe analysis, the empirical formula of the kiddcreekite is Cu6.2Sn0.97W0.95S7.83, without significant Se or Te contents. The crystal structure of kiddcreekite was solved using the direct-space method (EPCryst) from laboratory micro X-ray diffraction (μXRD) data and refined by the Rietveld method. The R values of the final Rietveld refinement were Rp = 9.06%, Rwp = 8.31%, RB = 3.16 and RF = 2.17%. Kiddcreekite has a cubic structure, space group F3m and lattice parameter a = 10.8178(3) Å (Z = 4, V = 1265.95(6) Å3). In the unit cell, W, Sn and Cu atoms occupy the 4a, 4c and 24f Wyckoff positions, respectively, and S atoms occupy two sets of 16e Wyckoff positions. The structure of kiddcreekite consists of stacked double MeS4 layers (giving a W–Sn–Cu tier and a Cu–vacancy tier) as in the sphalerite substructure. This study also demonstrates the possibility of using laboratory µXRD data coupled with the direct-space method to solve inorganic structures in cases where samples are too small for conventional powder and single-crystal diffraction.

A multi-methodological study, based on electron microprobe analysis (in wavelength dispersive mode), single-crystal X-ray diffraction (XRD), transmission electron microscopy and single-crystal Fourier transform infrared spectroscopy was performed in order to describe the crystal chemistry of four leucite samples from different localities of the Roman Comagmatic Province (central Italy). All the crystals examined were found to be tetragonal (space group I41/a with a = 13.076–13.103 Å and c = 13.744–13.784 Å) and characterized by a complex twinning (merohedric twins: on the tetragonal planes (110) and (1̄10) with the two individuals having parallel crystallographic axes with a and b interchanged; pseudo-merohedric twins: on the tetragonal planes (101), (011), (1̄01), (01̄ 1), with the two individuals having parallel a (or b) axes and the remaining two axes not parallel). The chemical analyses show that all the samples contain minor Na and Fe. Infrared spectroscopy shows that all samples contain structurally bound water molecules, up to unexpectedly large amounts (~0.4 wt.%) for a nominally anhydrous mineral, suggesting that ‘analcime-like’ substitution (K to Na + H2O) occurs in the leucite samples investigated here. The detection limits of the ‘analcime-like’ substitution by singlecrystal XRD are also discussed.

Sulphide and sulphosalt mineralization in the Hällefors silver mining district occurs as stratabound bodies in skarn-like black carbonates and other carbonates in the eastern part of the district, and as epigenetic, tectonically controlled vein mineralization in tuffaceous metavolcanics and, to a lesser extent in slates, in the western part.

Previous work has suggested that the Ag-bearing Hällefors deposits were formed by the action of metamorphic solutions on sediments of volcano-sedimentary origin. At the stages of sulphosalt and sulphide formation, temperature and pressure conditions were probably in the ranges 500–440 K and 4.5–3.5 kbar. Examination of a log aS2-1/T diagram and of Ag-Sb phase relations combined with study of the ores suggest the paragenesis of the Ag-bearing minerals is as follows: allargentum and dyscrasite as exsolution bodies in silver bearing galena; Ag-containing tetrahedrite → freibergite → miargyrite → pyrargyrite → stephanite (from hydrothermal solutions).

A Boring male at Iford Manor, 1½ miles S.E. of Lewes, Sussex, yieled the following section:

The lower sand contained numerous grains of glauconite, while the upper bed was black when wet and consisted almost entirely of dark-green glauconite, with a few shell fragments and large quartz grains. The glauconite grains were small and were separated in an almost pure state by sieving; the portion coarser than 76 [wires to the inch] mesh contained the shell fragments, &c., while that below was nearly all glauconite, with a few very small grains of magnetite present in the sand.

Chlorine is estimated in nine hornblendes (0·13–1·12%) and nine biotites (0·19–0·62%) from the Kondapalli charnockites for the first time, using the electron microprobe. The data obtained suggest that these Kondapalli minerals are unexpectedly and unusually rich in Cl, which is well equilibrated in the five available coexisting hornblende-biotite pairs.

Olivine (ol) leucitite lavas from Northeast China contain hyalophanes with contrasting Ba-zoning patterns. The hyalophanes occur: (1) in a magmatic inclusion (DZ2n), consisting of barian-titanian phlogopite + hyalophane + leucite + sodalite, and (2) as a mantle surrounding a sanidine megacryst (DZ19). Hyalophanes contain 4.6-20.2 mol.% celsian (Cn). The DZ2n hyalophane is normally zoned with respect to Ba (decreasing Ba toward rim), whereas the hyalophane mantle of megacryst DZ19 is reversely zoned. DZ2n probably crystallised from an extensively evolved (>80 wt.% crystallisation) potassic melt derived from a primitive magma chemically similar to the host, at relatively low temperatures and pressures (e.g. T-720°C P∼2 kbar). Competition with barian-titanian phlogopite for Ba, and limited Ba supply from the residual melt are the main cause for the normal Ba zonation. Sanidine megacryst DZ19 originated as a high P-T product (e.g. T > 950°C P > 15 kbar) of an evolved leucite (lc) basanite/trachybasalt genetically related to ol-leucitites. Subsequently, it was incorporated into the host ol-leucititic magma at which point it was partially resorbed and then mantled by hyalophane. An increase in KBaaf/liq values with decreasing temperature and pressure and cocrystallisation of the hyalophane mantle with Ba-free phases may have caused the unusual reverse zonation.

The international long-term cement studies (LCS) project aims to increase the understanding of the behaviour of cement within a radioactive waste disposal system and how hyper-alkaline leachates may interact with host rock. Such an understanding enables confident, robust and safety-relevant statements to be made concerning future system behaviour, irrespective of host rock, engineered barrier system, or waste type. The LCS project involves laboratory experiments, in situ tests and numerical modelling to address these issues. The agencies participating are Nagra (Switzerland), JAEA (Japan), the Nuclear Decommissioning Authority, Radioactive Waste Mangement Directorate (UK), Posiva (Finland) and SKB (Sweden).

Project activities have included: the development of conceptual and theoretical models of cement–rock interaction; testing of numerical models against data from laboratory experiments and industrial and natural analogues of cement–rock reaction; and the synthesis and incorporation of performance assessment (PA) relevant data from analogue studies. Key threads running through these studies include an analysis of issues relating to upscaling of processes and data to the greater temporal and spatial scales relevant to PA, and investigations of modelling the changes in physical properties that accompany geochemical reaction. Here we present examples of the results from model test cases, highlighting the important issues that have arisen.

From the microscopic examination of lightly etched, cleaved (111) surfaces of banded blue fluorite (Blue John, from Castleton, Derbyshire) it is concluded that the coloured lamellae are not necessarily or exclusively associated with lattice-line imperfections. Elemental analyses, by electron dispersive methods, of fresh cleavage (111) surfaces in the immediate vicinity of small inclusions (c. 10 µm diameter) possessing associated coloured haloes detected no appreciable concentrations of impurities. From the evidence available, it is suggested that the zones of blue colour consist of colloidal calcium resulting from radiation damage caused by the intermittent deposition of radioactive material on the surfaces of fluorite during crystal development. The dispersion of colloidal calcium produced is particularly stable as a consequence of the close correspondence between lattice spacings in calcium fluoride and in calcium metal.

Ktenasite from Glomsrudkollen zinc mine, Modum, Norway, is menoclinic, space group P21/c. The cell dimensions are a 5·598, b 6·121, c 23·762Å, β 95·55° The chemical formula is (Cu3·5Zn1·5)(SO4)2 (OH)6·6H2O with Z = 2; ρcale 2·96 g/cm3, ρobs 2·94 g/cm3. The mineral is biaxial negative with α (colourless) 1·574, β (bluish green) 1·615, γ (light green) 1·628, 2Vα 59°.

A new mineral, sasaite, occurs as white chalky nodules in the soil of a dolomitic cave and seems to be derived from the action of bat guano on clay minerals. Under the microscope it consists of an agglomeration of plates 10–20 µm on greatest dimension and with a rhombic shape. Its formula is (Al, Fe3+)14(PO411(OH)7SO4·83H2O and it is orthorhombic or quasi-orthorhombic. Preliminary crystallographic data based on an orthorhombic cell are a 21·50, b 30·04, c 92·06 Å, Z10, based on a calculated density of 1·747 (observed 1·75). The optical indices are α 1·465, β 1·473, γ 1·477 all ±0·001, and the principal vibration directions are parallel or quasi-parallel to the crystallographic axis.

Preferential removal of W relative to other trace elements from zoned, W–Sn–U–Pb-bearing hematite coupled with disturbance of U–Pb isotope systematics is attributed to pseudomorphic replacement via coupled dissolution reprecipitation reaction (CDRR). This hematite has been studied down to the nanoscale to understand the mechanisms leading to compositional and U/Pb isotope heterogeneity at the grain scale. High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF STEM) imaging of foils extracted in situ from three locations across the W-rich to W-depleted domains show lattice-scale defects and crystal structure modifications adjacent to twin planes. Secondary sets of twins and associated splays are common, but wider (up to ~100 nm) inclusion trails occur only at the boundary between the W-rich and W-depleted domains. STEM energy-dispersive X-ray mapping reveals W- and Pb-enrichment along 2–3 nm-wide features defining the twin planes; W-bearing nanoparticles occur along the splays. Tungsten and Pb are both present, albeit at low concentrations, within Na–K–Cl-bearing inclusions along the trails. HAADF STEM imaging of hematite reveals modifications relative to ideal crystal structure. A two-fold hematite superstructure (a = b = c = 10.85 Å; α = β = γ = 55.28°) involving oxygen vacancies was constructed and assessed by STEM simulations with a good match to data. This model can account for significant W release during interaction with fluids percolating through twin planes and secondary structures as CDRR progresses from the zoned domain, otherwise apparently undisturbed at the micrometre scale. Lead remobilisation is confirmed here at the nanoscale and is responsible for a disturbance of U/Pb ratios in hematite affected by CDRR. Twin planes can provide pathways for fluid percolation and metal entrapment during post-crystallisation overprinting. The presence of complex twinning can therefore predict potential disturbances of isotope systems in hematite that will affect its performance as a robust geochronometer.

Alstonite, BaCa(CO3)2, is a mineral described almost two centuries ago. It is widespread in Nature and forms magnificent cm-sized crystals. Notwithstanding, its crystal structure was still unknown. Here, we report the crystal-structure determination of the mineral and discuss it in relationship to other polymorphs of BaCa(CO3)2. Alstonite is trigonal, space group P31m, with unit-cell parameters a = 17.4360(6), c = 6.1295(2) Å, V = 1613.80(9) Å3 and Z = 12. The crystal structure was solved and refined to R1 = 0.0727 on the basis of 4515 reflections with Fo > 4σ(Fo) and 195 refined parameters. Alstonite is formed by the alternation, along c, of Ba-dominant and Ca-dominant layers, separated by CO3 groups parallel to {0001}. The main take-home message is to show that not all structure determinations of minerals/compounds can be solved routinely. Some crystals, even large ones displaying excellent diffraction quality, can be twinned in complex ways, thus making their study a crystallographic challenge.