Pyrrhotite Fe1–xS is the main sulfide component of platinum-group element (PGE) ores and commonly contains from a few tenths to a few dozen ppm of disseminated Pt. Here we report an X-ray absorption spectroscopy investigation into the state of Pt in synthetic pyrrhotite in combination with theoretical spectra modelling. The pyrrhotite crystals were obtained by means of the salt flux technique, using a eutectic mixture of alkali metal halides as the transport media. Analysis of the chemical composition of synthesised crystals showed that an increase of the temperature and sulfur fugacity yields higher concentrations of Pt in pyrrhotite. The Pt content reached 0.6 wt.% at the maximum temperature and sulfur fugacity (t = 720°C, log $f_{{\rm S}_ 2}$ = –0.1) achieved in a Pt-saturated system. X-ray absorption near-edge structure (XANES) analysis of Pt L3-edge spectra revealed that Pt is present in pyrrhotite in the 4+ and 2+ ‘formal’ oxidation states. Theoretical modelling of XANES and interpretation of extended X-ray absorption fine structure (EXAFS) spectra showed that Pt4+ substitutes for Fe in the crystal lattice of pyrrhotite, whereas Pt2+ forms PtS-like clusters disseminated in the pyrrhotite matrix. Atoms of isomorphous Pt4+ are surrounded by 6 S atoms at a distance of 2.39 ± 0.02 Å. According to theoretical simulations using the FDMNES program, the second coordination sphere of the solid-solution Pt contains one vacancy in the Fe sublattice within the Fe-layer. The Pt2+S-like clusters can be considered as a quench product. High sulfur fugacity stabilises the solid-solution Pt and prevents the formation of the PtS-like clusters during cooling. The maximum content of the solid-solution Pt in pyrrhotite is ca. 50 times lower than in pyrite and can be approximated by a straight line in the log C(Pt) vs. 1/T plot, it increases from 1 ppm at 350°C to 3 wt.% at 900°C.

The Icelandic crust is characterized by low δ18O values that originate from pervasive high-temperature hydrothermal alteration by 18O-depleted meteoric waters. Igneous rocks in Iceland with δ18O values significantly higher than unaltered oceanic crust (~5.7‰) are therefore rare. Here we report on rhyolitic intra-caldera samples from a cluster of Neogene central volcanoes in Borgarfjörður Eystri, Northeast Iceland, that show whole-rock δ18O values between +2.9 and +17.6‰ (n = 6), placing them among the highest δ18O values thus far recorded for Iceland. Extra-caldera rhyolite samples from the region, in turn, show δ18O whole-rock values between +3.7 and +7.8‰ (n = 6), consistent with the range of previously reported Icelandic rhyolites. Feldspar in the intra-caldera samples (n = 4) show δ18O values between +4.9 and +18.7‰, whereas pyroxene (n = 4) shows overall low δ18O values of +4.0 to +4.2‰, consistent with regional rhyolite values. In combination with the evidence from mineralogy and rock H2O contents, the high whole-rock δ18O values of the intra-caldera rhyolites appear to be the result of pervasive isotopic exchange during subsolidus hydrothermal alteration with 18O-enriched water. This alteration conceivably occurred in a near-surface hot spring environment at the distal end of an intra-caldera hydrothermal system, and was probably fed by waters that had already undergone significant isotope exchange with the country rock. Alternatively, 18O-enriched alteration fluids may have been produced during evaporation and boiling of standing water in former caldera lakes, which then interacted with the intra-caldera rock suites. Irrespective of the exact exchange processes involved, a previously unrecognized and highly localized δ18O-enriched rock composition exists on Iceland and thus probably within the Icelandic crust too.

An extensive set of porosity, ε, effective diffusion coefficient, D e, and hydraulic conductivity, K, data were obtained from 45 granitic samples from the Bohemian Massif, Czech Republic. The measured dataset can be used to define parameter ranges for data to be used in safety assessment calculations for a deep (>400 m) radioactive waste repository, even though the samples originated from shallower depths (<108 m). The dataset can also be used for other purposes, such as evaluating the migration of contaminants in granitic rock (e.g. from shallow intermediate-level radioactive waste repositories and chemical waste repositories).

Sample relaxation and ageing processes should be taken into account in research otherwise migration parameters might be overestimated in comparisons between lab results and those determined in situ.

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 presence of much native iron in Great Namaqualand was heard of in 1836 by the traveller Sir James E. Alexander, but he himself did not see any of the masses, and the material he acquired consisted only of small fragments that had been detached by the natives for pointing their weapons. An approximate chemical analysis of this material, made by Sir John Herschel, proved it to be meteoritic. A fragment weighing 2 grams which Alexander presented to the Geological Society of London in 1838 was transferred to the British Museum collection of meteorites in 1911. This appears to be all of his material that has been preserved.

Various other vague reports and travellers' tales have mentioned the presence of large masses of iron beyond the old mission station of Bethany, between there and Beersheba, and on the east side of the Great Fish River. A critical summary of these accounts was given by Sir Lazarus Fletcher in this magazine.

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.

Peridotite xenoliths 73–106 and 73–109 have coarse textures. All minerals in 73–106 are very Ti-rich, and include olivine (Fo 87.6), orthopyroxene (En 90.0), garnet (core TiO2 0.8, Cr2O3 7; rim 1.4, 4 wt. %), spinel (TiO2 5, Cr2O3 38), clinopyroxene (A12O3 1–8) secondary mica (TiO2 6, Cr2O3 2.5 near garnet 0.5 away from garnet), and serpentine (FeO 5–12) enclosing perovskite-rimmed ilmenite and minute apatites. All minerals in peridotite 73–109 are Ti-poor, and include olivine (Fo 92.6), orthopyroxene (En 93.6), garnet (Cr2O3 3.1–3.8), spinel (55), ureyitic diopside, primary mica (TiO2 0.06, Cr2O3 1.0, BaO 0.5, Cl 0.04), and serpentine (FeO 2–23). Various thermometers indicate ∼ 1350K (73–106) and 1100K (73–109). The low Al2O3 in the orthopyroxenes gives 39–47 kb for 73–109 from the Wood-Banno barometer. In 73–106, the spinel lies in secondary mica next to the garnet rim, whereas the spinel of 73–109 occurs in grains enclosed by garnet. The former assemblage indicates diffusion-dependent disequilibrium, whereas the latter is attributed to simultaneous growth of spinel and garnet, perhaps consequent upon exsolution from orthopyroxene. Complex behaviour was found for the Cr/Al distribution in published analyses of garnet and spinel. The 73–109 pair lies near the Thaba Putsoa trend, and the 73–106 assemblages are displaced towards the kelyphite region in which garnet and spinel have similar Cr/Al. Spinel and garnet may coexist over a 30 kb pressure interval ranging from ∼ 16 kb for low bulk Cr to ∼ 40 kb for high Cr.

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.

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.

Dargaite, ideally BaCa12(SiO4)4(SO4)2O3, is an additional member of the arctite group belonging to minerals with a modular intercalated antiperovskite structure derived from hatrurite. The holotype specimen was found at a small outcrop of larnite pseudoconglomerates in the Judean Mts, West Bank, Palestinian Autonomy. Larnite, fluorellestadite–fluorapatite, brownmillerite, fluormayenite–fluorkyuygenite and ye'elimite are the main minerals of the holotype specimen; ternesite, shulamitite and periclase are noted rarely. Dargaite, nabimusaite and gazeevite occur in linear zones with higher porosity within larnite rocks. Pores are filled with ettringite and Ca-hydrosilicates, less commonly with gibbsite, brucite, baryte, katoite and calciolangbeinite. Dargaite is colourless, transparent with a white streak and has a vitreous lustre. It exhibits pronounced parting and imperfect cleavage along (001). Mohs’ hardness is ~4.5–5.5. The empirical formula is (Ba0.72K0.24Na0.04)Σ1(Ca11.95Mg0.04Na0.01)Σ12([SiO4]0.91 [PO4]0.05[AlO4]0.03[Ti4+O4]0.01)Σ4([SO4]0.84[PO4]0.14[CO3]0.02)Σ2(O2.54F0.46)Σ3. Dargaite is trigonal R$\overline 3 $m, the unit-cell parameters are: a = 7.1874(4) Å, c = 41.292(3) Å, V = 1847.32(19) Å3 and Z = 3. The crystal structure of dargaite was refined from X-ray single-crystal data to R1 = 3.79%. The calculated density is 3.235 g cm–3. The following main Raman bands are distinguished on the holotype dargaite (cm–1): 122, 263, 323, 464, 523, 563, 641 and 644, 829 and 869, 947, 991 and 1116. The formation conditions of dargaite are linked to the local occurrence of pyrometamorphic by-products (gases, fluids and melts) transforming earlier mineral associations at ~900°C.

The crystal structure of nikmelnikovite, Ca12Fe2+Fe3+3Al3(SiO4)6(OH)20, a new member of the garnet supergroup from Kovdor massif, Kola Peninsula, Russia (R$\bar{3}$, a = 17.2072(6), c = 10.5689(4) Å, V = 2710.1(2) Å3 and Z = 3) has been refined to R1 = 0.046 on the basis of 1184 unique observed reflections. Nikmelnikovite is the first mineral species in the garnet supergroup that has a trigonal (rhombohedral) symmetry. The relationship between its unit cell and the pseudocubic (ideal garnet) unit cell can be described by the transformation matrix [1$\bar{1}$0 | 01$\bar{1}$ | ½½½]. The crystal-chemical relations between the ideal Ia$\bar{3}$d garnet and the nikmelnikovite structure type can be described by the following series of imaginary modifications: (1) the symmetry is lowered according to the Ia$\bar{3}$d → R$\bar{3}$ group–subgroup relationship; (2) the cation sites are split according to the following sequences: X → {X1, X2}; Y → {Y1, Y2, Y3, Y4}; Z → {Z1, Z2}; (3) the X sites remain fully occupied by Ca; (4) each Y site is occupied predominantly by a distinct chemical species: Y1 → Al (Al site), Y2 → Fe2+ (Fe1 site), Y3 → Fe3+ (Fe2 site), Y4 → vacancy (Mn site); (5) one of the Z sites (Z1) is occupied by Si, whereas the other site (Z2) is predominantly vacant. The crystal-chemical formula that takes into account the transition between the archetype and the nikmelnikovite structure type can be described as X{Ca12}Y[Fe2+Al4Fe3+2□]Z(Si6□6)O24(OH)20□4. The structural complexity of nikmelnikovite (4.529 bit/atom and 434.431 bit/cell, after H-correction) is higher than those for andradite, grossular and katoite, which is typical for low-temperature minerals formed after primary minerals with simpler structures.

Though the transitional members between the pyralspite and grandite series occur only very sporadically, there exists under favourable conditions a perfect miscibility between grossular on the one hand, and spessartine or almandine or pyrope on the other. The conditions favouring this miscibility are discussed.

Baron A. De Schulten, a political refugee from Finland, worked during the latter part of his life in the chemical laboratories of the Sorbonne in Paris. There he prepared in a crystallized form number of minerals and compounds analogous to them. These were determined crystallographlcally and compared in isonlorphous series. For example, having obtained crystals of artificial monetite, CaHPO4, he then proceeded to prepare the corresponding compounds in which strontium, barimn, or lead take the place of calcium, and arsenic the place of phosphorus. In this series he determined the crystallographic constants and optical data for CaHPO4, SrHPO4, BaHPO4, PbHPO4, SrHAsO4, and PbHAsO4. Crystals of CaHAsO4 were also obtained, but they were too small tbr measurement. Any of these compounds might be expected to occur in nature, but hitherto only monetite has been found as a mineral.

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.

Several field and laboratory studies have demonstrated that secondary Fe-bearing minerals such as goethite, lepidocrocite and mackinawite have a high capacity for the uptake of As, but little work has been carried out to examine the capacity of the mineral vivianite [Fe3(PO4)2·8H2O] for this element. We report here preliminary results of an experimental study designed to test the efficiency of As(III) and As(V) uptake by natural vivianite at acid, near-neutral and alkaline pH at T = 4ºC, which is representative of Lake Baikal-type environments, where natural vivianite is reported to occur. The vivianite takes up between 0 and 5% As(III), and between 21 and 45% As(V), from 200 ppb solutions of these As species. Further work at 25ºC and other solution concentrations, together with characterization of the post-sorption solids, will yield information on the efficiencies and mechanisms of As uptake by natural vivianite.

An unworked quartz vein-hosted gold deposit occurs in the Clew bay area of County Mayo, western Ireland. The veins are late-Caledonian in age and transect greenschist-facies poly-deformed Silurian quartzites. The veins contain disseminated arsenopyrite that may be a primary mineral source for elevated levels of arsenic (As) found in groundwater samples recovered from wells related spatially to the gold deposit. Levels from 5 to 188 μg/L (significantly above the 7.5 μg/L threshold for safe drinking water) have been detected. A series of element distribution maps using a scanning electron microscope (Hitachi model S-4700) linked to an energy-dispersive spectrometer (INCA® Oxford Instruments) and mineral distribution maps generated by QEMSCAN® (Quantitative Evaluation of Minerals by Scanning electron microscopy) were used to map the distribution of the primary arsenopyrite and related secondary As-bearing phases. Laser Raman microspectroscopy was used to identify the secondary As-bearing phases. 'Island weathering' of primary arsenopyrite together with hydrated pseudomorphs of arseniosiderite, pharmacosiderite and scorodite after arsenopyrite are recorded. Circulating groundwater hydrates the primary arsenopyrite, providing the release mechanism that forms the secondary As-bearing phases that occur as microfracture infills together with muscovite and biotite. The textural relationships between the primary and secondary As minerals indicate their potential as mineral sources of As that could enter transport pathways leading to its release into groundwater.

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.

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 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.

New chemical data show that the two main granite types (G1 and G2) cannot be discriminated, but that microgranite sheets/dykes (G3) are significantly different and more evolved, largely as a result of biotite, accessory mineral, and plagioclase fractionation. The Lundy granite is similar to other Tertiary granites of Scotland and Ireland, in age, setting, possible high-temperature mineralogy, relationship to basic magmatism, and REE patterns. These features and a highly evolved chemistry suggest derivation from an unexposed more ‘primitive’ granite that, in turn, had a basaltic parentage. However, similarities with the nearby S-type Hercynian granites, such as high aluminium saturation index (and normative corundum), high trace alkali, Nb, and F contents, low Zr, and high initial Sr ratio suggest a significant crustal component. The problem is resolved by proposing either mixing of silicic magma derived by strong fractionation of basaltic magma with anatectic magma from a pelitic/semi-pelitic crustal source, or fractionation of basaltic magma heavily contaminated by assimilated crustal material. Both origins would yield the high REE contents and fiat REE patterns of a ‘primitive’ granite magma. Fractionation, perhaps of hornblende initially, and later, of biotite and accessory minerals together with feldspars, would produce the small volume of highly fractionated Lundy granite.