The crystal structure of rabejacite from Jáchymov, ideally Ca2[(UO2)4O4(SO4)2](H2O)8, was solved by charge flipping from single-crystal data and refined to R1 = 11.94% for 1422 unique observed reflections [I > 3σ(I)]. According to single-crystal X-ray data, rabejacite is triclinic, space group P, with a = 8.7434(11), b = 8.309(3), c = 8.8693(10) Å , a = 77.86(2), b = 104.635(11), g = 82.935(18)°, V = 598.8(3) A˚ 3 and Z = 1, with Dcalc = 4.325 g cm–3. The structure refinement proved that rabejacite is related to the zippeite group of minerals, as it is based upon the structural sheets of the zippeite topology of composition [(UO2)4O4(SO4)2]4–. Located in the interlayer between the sheets, which are stacked perpendicular to [010], are Ca2+ cations and H2O groups. Ca2+ ions are [7]-coordinated, by three uranyl O atoms from adjacent sheets and four H2O groups. An additional H2O group, which is not bonded directly to any cation, is located in the interlayer. Along with rabejacite, its Cu-rich variety was found in the specimens examined and characterized structurally. Its crystal structure (R1 = 10.15% for 1049 reflections with I > 3s(I)) is practically the same as that of rabejacite, but there is an additional Cu2+ site located in between pairs of Ca polyhedra. The structural formula is (Ca1.56Cu0.40)Σ1.90[(UO2)4O4(SO4)2](H2O)8, Z = 1. Its existence suggests a greater diversity in zippeite crystal chemistry than was thought previously and also the possibility of a new Cu2+-dominant zippeite mineral besides pseudojohannite.

The current state of the lillianite homologous series is presented, with its two branches − the lillianite branch of the predominantly Pb-Bi-Ag sulfosalts and the andorite branch of predominantly Pb-Sb-Ag sulfosalts. Both the natural and synthetic members are discussed, especially from the structural and compositional point of view and the related, chemically distinct and structurally more complicated members of the series are described. A number of new published, or hitherto unpublished observations is given, together with fairly exhaustive tables of data. Relationships between the complex structures of different ‘andorite’ species and principal structural features of ‘oversubstituted’ As-Sb and Bi-Sb species are discussed. Contrary to many studies of this subject, synthetic phases form an integral part of the paper. It is concluded that research in this long-known homologous series still supplies new interesting phases, especially in the fields of synthetic products and in its andorite branch.

Markhininite, ideally TlBi(SO4)2, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Markhininite occurs as white pseudohexagonal plates associated with shcherbinaite, pauflerite, bobjonesite, karpovite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Markhininite is triclinic, P, a = 7.378(3), b = 10.657(3), c = 10.657(3) Å , α = 61.31(3), β = 70.964(7), γ = 70.964(7)º, V = 680.2(4) Å3, Z = 4 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 68/4.264/111, 100/3.441/113, 35/3.350/222, 24/3.125/122, 23/3.054/202, 45/2.717/022, 20/2.217/331, 34/2.114/204. Chemical composition determined by electron microprobe analysis is (wt.%): Tl2O 35.41, Bi2O3 38.91, SO3 25.19, total 99.51. The empirical formula based on 8 O a.p.f.u. is Tl1.04Bi1.05S1.97O8. The simplified formula is TlBi(SO4)2, which requires Tl2O 35.08, Bi2O3 38.48, SO3 26.44, total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.055 on the basis of 1425 independent observed reflections. The structure contains four Tl+ and two Bi3+ sites in holodirected symmetrical coordination. BiO8 tetragonal antiprisms and SO4 tetrahedra in markhininite share common O atoms to produce [Bi(SO4)2]– layers of the yavapaiite type. The layers are parallel to (111) and linked together through interlayer Tl+ cations. The mineral is named in honour of Professor Yevgeniy Konstantinovich Markhinin (b. 1926), Institute of Volcanology, Russian Academy of Sciences, Kamchatka peninsula, Russia, in recognition of his contributions to volcanology. Markhininite is the first oxysalt compound that contains both Tl and Bi in an ordered crystal structure.

Steady-state tremolite dissolution rates, at far-from-equilibrium conditions, were measured as a function of aqueous silica and magnesium activity, pH from 1.9 to 6.7, and temperature from 25 to 150ºC. Calcium is released from tremolite faster than either Mg or Si throughout most of the experiments even after these latter elements attained steady-state release rates. The preferential removal of Ca releases fine Mg-Si rich needle-like fibres from the tremolite, probably promoting its toxicity. In contrast, Mg was released in stoichiometric or near to stoichiometric proportion to Si once steady-state was attained. Measured steady-state tremolite dissolution rates based on Si release can be described using

where r+ signifies the BET surface area-normalized forward tremolite steady-state dissolution rate, AA refers to a pre-exponential factor = 6610–3 mol cm–2 s–1, EA designates an activation energy equal to 80 kJ mol–1, R represents the gas constant, T denotes absolute temperature, and ai refers to the activity of the subscripted aqueous species. This rate expression is consistent with tremolite dissolution rates at acidic pH being controlled by the detachment of partially liberated silica tetrahedra formed from the exchange of Mg2+ for two protons near the mineral surface after the near-surface Ca has been removed. Nevertheless, Mg release rates from tremolite are ~3 orders of magnitude slower than those from forsterite and enstatite suggesting that tremolite carbonation will be far less efficient than the carbonation of these other Mg-silicate minerals.

This study describes the occurrences of sulfate minerals in mines of the Czech part of the Upper Silesian Basin. This mineralization originates from the oxidation of Fe disulfides contained in the coal matrix and enclosing sediments. The oxidation occurs in the presence of formational brines and chemotrophic bacteria. The brines have a pH between 6.3 and 8.5 and total solute content of up to 300 g/l. They are rich in Na, Ca, K, Mg, Ba and Sr and Cl– is the major anion. The minerals of the pickeringite–halotrichite series with coexisting magnesiocopiapite are formed primarily in drier places and areas where the water is only slightly mineralized. In more humid places where the brines are more concentrated, a diverse assemblage of up to 20 different sulfates are found (e.g. natrojarosite, sideronatrite, metasideronatrite, tamarugite, magnesiocopiapite, bílinite, starkeyite, blödite, rozenite and siderotil). These sulfates are accompanied by halite, sulfur, goethite and a number of phases of uncertain identity, such as sulfates containing Sr and REE. This is an example of mineral paragenesis formed by weathering in a saline evaporite environment, which is extremely rare in Europe but is found in arid regions elsewhere (e.g. in the Atacama Desert in Chile).

Karpovite, ideally Tl2VO(SO4)2(H2O), was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Karpovite occurs as bundles of white, needle-like crystals associated with shcherbinaite, pauflerite, bobjonesite, markhininite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Karpovite is monoclinic, P21, a = 4.6524(4), b = 11.0757(9), c = 9.3876(7) Å , β = 98.353(2)º, V = 478.60(7) Å3, Z = 2 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 64/4.289/012, 81/4.253/110, 38/3.683/111, 47/3.557/022, 100/3.438/21, 52/2.982/013, 59/2.945/112, 54/2.354/132. The chemical composition determined by the electron microprobe analysis is (wt.%) Tl2O 61.43, VO2 11.53, SO3 23.55, H2O 2.61, total 99.12. The empirical formula (calculated on the basis of 10 O a.p.f.u.) is Tl2.00V0.96S2.03O9(H2O). The simplified formula of karpovite is Tl2VO(SO4)2(H2O), which requires Tl2O 61.93, VO2 12.09, SO3 23.34, H2O 2.62 total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.026 for 4196 independent observed reflections. The structure contains two symmetrically independent Tl+ sites, one V4+ site and two S6+ sites. VO5H2O octahedra and SO4 tetrahedra link together by sharing corners to form kröhnkite-type stripes parallel to the a axis with their planes oriented parallel to (021) and (02). Tl+ cations are located between the chains, linked into a three-dimensional structure. The new mineral is named in honour of Professor Gennadii Alexandrovich Karpov (b. 1938), volcanologist at the Institute of Volcanology, Russian Academy of Sciences, Petropavlovsk-Kamchatskii, Kamchatka Peninsula, Russia.

Experiments in the system NaAlSiO4(Ne)−KAlSiO4(Ks)−SiO2(Qz)−H2O at 100 MPa show that the maximum content of NaAlSi2O6 in leucite is ∼4 wt.% and that analcime is close to the stoichiometric composition (NaAlSi2O6.H2O). Analcime forms metastably on quenching the higher-temperature experiments; it is secondary after leucite in experiments quenched from 780°C, while from 850°C it forms by alteration of leucite, and by devitrification of water-saturated glass. Both processes involve reaction with Na-rich aqueous fluids. Stable analcime forms at 500°C, well below the solidus, and cannot form as phenocrysts in shallow volcanic systems. New data for natural analcime macrocrysts in blairmorites are presented for the Crowsnest volcanics, Alberta, Canada. Other researchers have suggested that primary analcime occurs as yellow-brown, glassy, analcime phenocrysts. Our microprobe analyses show that such primary analcime is close to stoichiometric, with very low K2O (<0.1 wt.%), minor Fe2O3 (0.5−0.8 wt.%) and CaO (∼0.5 wt.%). An extrapolation of published experimental data for Ne−Ks−Qz at >500 MPa PH2O, where Anl + melt coexist, suggests that at >800 MPa two invariant points are present: (1) a reaction point involving Kf + Ab + Anl + melt + vapour; and (2) a eutectic with Kf + Anl + Ne + melt + vapour. We suggest that the nepheline-free equilibrium mineral assemblage for Crowsnest samples is controlled by reaction point (1). In contrast, blairmorites from Lupata Gorge, Mozambique, form at eutectic (2), consistent with the presence of nepheline phenocrysts. Our conclusions, based on high- vs. low-pressure experiments, confirm the suggestion made by other authors, that Crowsnest volcanic rocks must have been erupted explosively to preserve glassy analcime phenocrysts during very rapid, upward transport from deep in the crust (H2O pressures ≫500 MPa). Only rare examples survived the deuteric and hydrothermal alteration that occurred during and after eruption.

The structure hierarchy hypothesis states that structures may be ordered hierarchically according to the polymerization of coordination polyhedra of higher bond valence. A mathematical hierarchy is an ordered set of elements where the ordering reflects a natural hierarchical relation between (or arrangement of) the elements. Here, I review the structure hierarchies for the borate, uranyl oxide, phosphate, sulfate, beryllate and oxide-centred Cu, Pb and Hg minerals (plus synthetics where appropriate). Structure hierarchies have two functions: (1) they serve to organize our knowledge of minerals (crystal structures) in a coherent manner; (2) if the basis of the classification involves factors that are related to the mechanistic details of the stability and behaviour of minerals, then the physical, chemical and paragenetic characteristics of minerals should arise as natural consequences of their crystal structures and the interaction of those structures with the environment in which they occur. We may justify the structure hierarchy hypothesis by considering a hypothetical structure-building process whereby higher bond-valence polyhedra polymerize to form the structural unit. The clusters constituting the FBBs (fundamental building blocks) may polymerize to form the following types of structural unit: (1) isolated polyhedra; (2) clusters; (3) chains and ribbons; (4) sheets; and (5) frameworks. The major advantage of this approach to structure hierarchy is the fact that the hypothetical structure-building process outlined above resembles (our ideas of) crystallization from an aqueous solution, whereby complexes in aqueous and hydrothermal solutions condense to form crystal structures, or fragments of linked polyhedra in a magma condense to form a crystal. Although our knowledge of these processes is rather vague from a mechanistic perspective, the foundations of the structure hypothesis give us a framework within which to think about the processes of crystallization and dissolution.

Results are reported here of an investigation into the effects of three carboxylic acid additives (tartaric, maleic and citric acids) on the precipitation of calcium sulfate phases. Precipitation reactions were followed at pH 7 in the pure CaSO4 system and in experiments with 0–20 ppm carboxylic acids added using in situ UV-VIS spectrophotometry (turbidity). The solid products were characterized in terms of their mineralogical composition, using X-ray diffraction, during and at the end of each reaction, and in terms of their morphological features, by scanning electron microscopy. All additives increased the time needed for turbidity to develop (induction time, start of precipitation) and the comparison between additive and additive-free experiments showed that, at equivalent concentrations, citric acid performed far better than the other two carboxylic acids. In all cases bassanite precipitated first and with time it transformed to gypsum. The addition of citrate stabilized bassanite and changed the final gypsum habit from typical needle-like crystals in the pure CaSO4 system to plates in the citrate-additive experiments.

The concept of the algorithmic complexity of crystals is developed for a particular class of minerals and inorganic materials based on orthogonal networks, which are defined as networks derived from the primitive cubic net (pcu) by the removal of some vertices and/or edges. Orthogonal networks are an important class of networks that dominate topologies of inorganic oxysalts, framework silicates and aluminosilicate minerals, zeolites and coordination polymers. The growth of periodic orthogonal networks may be modelled using structural automata, which are finite automata with states corresponding to vertex configurations and transition symbols corresponding to the edges linking the respective vertices. The model proposed describes possible relations between theoretical crystallography and theoretical computer science through the theory of networks and the theory of deterministic finite automata.

A third world occurrence of rouxelite, ideally Cu2HgPb22Sb28S64(O,S)2, has been identified from the baryte-pyrite-Fe oxides ore of Monte Arsiccio mine, near Sant’Anna di Stazzema (Apuan Alps, Tuscany, Italy). Rouxelite occurs as mm-sized acicular crystals, black in colour, with bluish-violet iridescence, in vugs of carbonate + baryte + quartz veins embedded in dolostones from the Sant’Olga tunnel. It is associated with Tl-bearing chovanite, sphalerite and valentinite. Its X-ray powder diffraction pattern gives unit-cell parameters a = 43.10(2), b = 4.060(2), c = 37.88(2) Å, β = 117.33(2)°, V = 5889(5) Å3. Electron-microprobe data reveal a complex chemistry, with additional minor elements (wt.%): Tl (0.6–1.7), Ag (0.4–0.6), As (0.2–0.6) and Bi (≤0.05). This indicates a widespread substitution of Hg by Ag, according to Hg + Pb = Ag + Sb and incorporation of Tl, with some Ag, according to 2Pb = Sb + (Tl, Ag). The occurrence of mixed (Hg, Ag) and (Hg, Cu) sites in natural sulfides and sulfosalts is briefly reviewed. The Tl-content of the samples studied is a characteristic fingerprint agreeing with the Tl-rich nature of the mineral assemblage from Monte Arsiccio. Rouxelite therefore constitutes a new example of a Tl-bearing sulfosalt.

Ultrahigh-pressure and -temperature (P-T) experimental techniques have progressed rapidly in recent years. By combining them with X-ray diffraction measurements at synchrotron radiation facilities, it is now possible to examine deep Earth mineralogy in situ at relevant high P-T conditions in a laser-heated diamond anvil cell (DAC). The lowermost part of the mantle, known as the D″ layer, has long been enigmatic because of a number of unexplained seismological features. Nevertheless, the discovery of a phase transition from MgSiO3 perovskite to ‘post-perovskite’ above 120 GPa and 2400 K indicates that post-perovskite is a principal constituent in the lowermost mantle, which is compatible with seismic observations. The ultrahigh P-T conditions of the Earth’s core have not been accessible by static experiments, but the structure and phase transition of Fe and Fe-alloys are now being examined up to 400 GPa and 6000 K by laser-heated DAC studies.

Twenty vapour-phase garnets were studied in two samples of the Topopah Spring Tuff of the Paintbrush Group from Yucca Mountain, in southern Nevada. The Miocene-age Topopah Spring Tuff is a 350 m thick, devitrified, moderately to densely welded ash-flow tuff that is zoned compositionally from high-silica rhyolite to latite. During cooling of the tuff, escaping vapour produced lithophysae (former gas cavities) lined with an assemblage of tridymite (commonly inverted to cristobalite or quartz), sanidine and locally, hematite and/or garnet. Vapour-phase topaz and economic deposits associated commonly with topaz-bearing rhyolites (characteristically enriched in F) were not found in the Topopah Spring Tuff at Yucca Mountain. Based on their occurrence only in lithophysae, the garnets are not primary igneous phenocrysts, but rather crystals that grew from a F-poor magmaderived vapour trapped during and after emplacement of the tuff. The garnets are euhedral, vitreous, reddish brown, trapezohedral, as large as 2 mm in diameter and fractured. The garnets also contain inclusions of tridymite. Electron microprobe analyses of the garnets reveal that they are almandinespessartine (48.0 and 47.9 mol.%, respectively), have an average composition of (Fe1.46Mn1.45Mg0.03Ca0.10)(Al1.93Ti0.02)Si3.01O12 and are comparatively homogeneous in Fe and Mn concentrations from core to rim. Composited garnets from each sample site have δ18O values of 7.2 and 7.4%. The associated quartz (after tridymite) has δ18O values of 17.4 and 17.6%, values indicative of reaction with later, low-temperature water. Unaltered tridymite from higher in the stratigraphic section has a δ18O of 11.1% which, when coupled with the garnet δ18O values in a quartz-garnet fractionation equation, indicates isotopic equilibration (vapour-phase crystallization) at temperatures of ∼600°C. This high-temperature mineralization, formed during cooling of the tuffs, is distinct from the later and commonly recognized low-temperature stage (generally 50−70°C) of calcite, quartz and opal secondary mineralization, formed from downward-percolating meteoric water, that locally coats fracture footwalls and lithophysal floors.

Three new valleriite-group minerals, ekplexite (Nb,Mo)S2·(Mg1−xAlx)(OH)2+x, kaskasite (Mo,Nb)S2·(Mg1−xAlx)(OH)2+x and manganokaskasite (Mo,Nb)S2·(Mn1−xAlx)(OH)2+x are found at Mt Kaskasnyunchorr, Khibiny alkaline complex, Kola Peninsula, Russia. They occur in fenite consisting of orthoclase−anorthoclase and nepheline with fluorophlogopite, corundum, pyrrhotite, pyrite, rutile, monazite-(Ce), graphite, edgarite, molybdenite, tungstenite, alabandite, etc. Ekplexite forms lenticular nests up to 0.2 mm × 1 mm × 1 mm consisting of near-parallel, radiating or chaotic aggregates of flakes. Kaskasite and manganokaskasite mainly occur as flakes and their near-parallel ‘stacks’ (kaskasite: up to 0.03 mm × 1 mm × 1.5 mm; manganokaskasite: up to 0.02 mm × 0.5 mm × 1 mm) epitaxially overgrow Ti-bearing pyrrhotite partially replaced by Ti-bearing pyrite. All three new minerals are opaque, ironblack, with metallic lustre. Cleavage is {001} perfect and mica-like. Flakes are very soft, flexible and inelastic. Mohs hardness is ∼1. D(calc.) = 3.63 (ekplexite), 3.83 (kaskasite) and 4.09 (manganokaskasite) g cm−3. In reflected light all these minerals are grey, without internal reflections. Anisotropism and bireflectance are very strong and pleochroism is strong. The presence of OH groups and an absence of H2O molecules are confirmed by the Raman spectroscopy data. Chemical data (wt.%, electron probe) for ekplexite, kaskasite and manganokaskasite, respectively, are: Mg 6.25, 5.94, 0.06; Al 4.31, 3.67, 3.00; Ca 0.00, 0.04, 0.00; V 0.86, 0.16, 0.15; Mn 0.00, 0.23, 11.44; Fe 0.44, 1.44, 2.06; Nb 18.17, 13.39, 14.15; Mo 15.89, 23.18, 20.08; W 8.13, 7.59, 9.12; S 27.68, 27.09, 24.84; O 16.33, 15.66, 13.36; H (calc.) 1.03, 0.99, 0.89; total 99.09, 99.08, 99.15. The empirical formulae calculated on the basis of 2 S a.p.f.u. are: ekplexite: (Nb0.45Mo0.38W0.10V0.04)S0.97S2· (Mg0.60Al0.37Fe0.02)S0.99(OH)2.36; kaskasite: (Mo0.57Nb0.34W0.10V0.01)S1.02S2· (Mg0.58Al0.32Fe0.06Mn0.01)S0.97(OH)2.32; manganokaskasite: (Mo0.54Nb0.39W0.13V0.01)S1.07S2· (Mn0.54Al0.29Fe0.10Mg0.01)S0.94(OH)2.28. All three minerals are trigonal, space groups Pm1, P3m1 or P321, one-layer polytypes (Z = 1). Their structures are non-commensurate and consist of the MeS2-type (Me = Nb, Mo, W) sulfide modules and the brucite-type hydroxide modules. Parameters of the sulfide (main) sub-lattices (a, c in Å, V in Å3) are: 3.262(2), 11.44(2), 105.4(4) (ekplexite); 3.220(2), 11.47(2), 102.8(4) (kaskasite); 3.243(3), 11.61(1), 105.8(3) (manganokaskasite). Parameters of the hydroxide sub-lattices (a, c in Å, V in Å3) are: 3.066(2), 11.52(2), 93.8(4) (ekplexite); 3.073(2), 11.50(2), 94.0(4) (kaskasite); 3.118(3), 11.62(1), 97.9(2) (manganokaskasite). Ekplexite was named from the Greek word έκπληξη meaning surprise, for its exotic combination of major chemical constituents, kaskasite after the discovery locality and manganokaskasite as a Mn analogue of kaskasite.

The new mineral therasiaite, ideally (NH4)3KNa2Fe2+Fe3+(SO4)3Cl5, was found in a mediumtemperature (∼250°C) intracrater active fumarole at La Fossa crater, Vulcano, Aeolian Islands, Sicily, Italy. It occurs on a pyroclastic breccia as brown to dark brown equant to short prismatic crystals up to 0.1 mm in length, in association with salammoniac, kremersite and adranosite. The mineral is monoclinic, space group: Cc (no. 9) with a = 18.284(4), b = 12.073(2), c = 9.535(2) Å, β = 108.10(3)°, V = 2000.6(7) Å3 and Z = 4. The six strongest reflections in the X-ray powder diffraction pattern are: [dobs in Å(I)(hkl)] 2.812(100)(23), 2.664(77)(13), 3.297(28)(33), 3.208(14)(2), 3.008(12)(040), 2.942(11)(331). The empirical formula (based on 17 anions per formula unit (p.f.u.)) is (NH4)2.68K1.32Na2.04Fe1.76Al0.12Mn0.12S2.98O11.95Cl5.05. The measured density is 2.41(1) g cm−3, dcalc = 2.395 g cm−3. The mineral is biaxial (−) with α= 1.585(3) β = 1.615(3) and γ = 1.630(3) (white light). Using single-crystal diffraction data, the structure was refined to a final R(F) = 0.0240 for 5574 independent observed reflections [I > 2σ(I)]. The structure of therasiaite displays a novel topology and contains two independent, distorted octahedral Fe sites, with the Fe atoms in oxidation state 3+ and 2+, respectively, each surrounded by three Cl atoms and three oxygens of the sulfate ions. The Fe octahedra and the three independent sulfate anions are connected to form chains running along [001]. Voids between the chains are occupied by three independent ammonium ions (partially replaced by K+), one K+ and two Na+ ions. The formula resulting from the structure refinement is [(NH4)2.25K0.75]KNa2Fe2(SO4)3Cl5.

The interaction of CO2-rich water with olivine was studied using geochemical reaction modelling in order to gain insight into the effects of temperature, acid supply (CO2) and extent of reaction on the secondary mineralogy, water chemistry and mass transfer. Olivine (Fo93) was dissolved at 150 and 250ºC and pCO2 of 2 and 20 bar in a closed system and an open system with secondary minerals allowed to precipitate. The progressive water–rock interaction resulted in increased solution pH, with gradual carbonate formation starting at pH 5 and various Mg-OH and Mg-Si minerals becoming dominant at pH>8. The major factor determining olivine alteration is the pH of the water. In turn, the pH value is determined by acid supply, reaction progress and temperature.

Arsenopyrite (FeAsS), gudmundite (FeSbS) and the rarer Fe sulfosalts berthierite (FeSb2S4) and garavellite (FeSbBiS4), were investigated by Raman spectroscopy. Whereas (Sb,Bi)S3 pyramids are responsible for the Raman spectra of berthierite and garavellite, the spectra of gudmundite and arsenopyrite arise from the stretching and bending modes of (Sb,As)S units. Internal vibrations for berthierite and garavellite occur between 400 and 50 cm–1, and those of the gudmundite and arsenopyrite between 500 and 100 cm–1. The longer bond distances of the SbS3 groups readily explain the lower frequencies for berthierite in comparison with garavellite. Similarly, the greater mass and the longer bond distances of the Sb–S units also explain the lower frequencies observed for gudmundite relative to arsenopyrite.

Evdokimovite, ideally Tl4(VO)3(SO4)5(H2O)5, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption of 1975–1976, Kamchatka Peninsula, Russia. Evdokimovite occurs as thin, colourless needles up to 0.09 mm long associated with shcherbinaite, pauflerite, bobjonesite, markhininite, karpovite and microcrystalline Mg, Al, Fe and Na sulfates. Evdokimovite is monoclinic, P21/n, a = 6.2958(14), b = 10.110(2), c = 39.426(11) Å , β = 90.347(6)º, V = 2509.4(10) Å3 and Z = 4 (from single-crystal diffraction data). The eight strongest lines of the powder X-ray diffraction pattern are (I/d/hkl): 57/9.793/011, 100/8.014/013, 26/6.580/006, 19/ 4.011/026, 29/3.621/118, 44/3.522/125, 19/3.010/036, 21/2.974/212. Chemical composition determined by the electron microprobe analysis is (wt.%): Tl2O 55.40, VO2 14.92, SO3 25.83, H2O 5.75, total 101.90. The empirical formula for evdokimovite calculated on the basis of (Tl + V + S) = 12 a.p.f.u. is Tl4.10V2.83S5.07H10.00O27.94. The simplified formula is Tl4(VO)3(SO4)5(H2O)5. The crystal structure was solved by direct methods and refined to R1 = 0.11 on the basis of 3660 independent observed reflections. V4+O6 octahedra and SO4 tetrahedra share common corners to form two types of vanadyl-sulfate chains, [(VO)(H2O)2(SO4)2]2– and [(VO)2(H2O)3(SO4)3]2–. Thallium atoms are located in between the chains. The structure can be described as a stacking of layers of two types, A and B. The A layer contains [(VO)2(H2O)3(SO4)3]2– chains and the Tl2 and Tl3 atoms, whereas the B layer contains [(VO)(H2O)2(SO4)2]2– chains and the Tl1 atoms. Stacking of the layers can be described as ...A’*BAA’B*A*..., where A and A’ denote A layers with opposite orientations of the [(VO)2(H2O)3(SO4)3]2– chains, and the A* and B* layers are rotated by 180º relative to the A and B layers, respectively. [(VO)2(H2O)3(SO4)3]2– chains are modulated and are arranged to form elliptical tunnels hosting disordered Tl(4), Tl(4A) and Tl(4B) sites. The new mineral is named in honour of Professor Mikhail Dmitrievich Evdokimov (1940–2010), formerly of the Department of Mineralogy, St Petersburg State University, for his contributions to mineralogy and petrology, and especially for teaching mineralogy to several generations of students at the University. Evdokimovite is the most complex V4+ sulfate known to date with structural information amounting to 1130 bits per unit cell, which places evdokimovite among minerals with the complexity of the vesuvianite group.

A single-crystal neutron diffraction study of oxy-dravite from Osarara (Narok district, Kenya) was performed. Intensity data were collected in Laue geometry at 10 K and anisotropic-structure refinement was undertaken. For the first time, two independent H sites were refined unambiguously for a mineral belonging to the tourmaline supergroup and located at 0.26, 0.13, 0.38 (labelled as H3, site occupancy ∼98%) and at 0, 0, 0.9 (labelled as H1, site occupancy ∼25%). The H-bonding scheme can thus be defined as follows: (1) the O at the O3 site acts as a ‘donor’ and the O at the O5 site as ‘acceptor’, the refined O3–H3 bond distance is 0.972(2) Å (and 0.9946 Å corrected for “riding motion”), H3⋯O5 = 2.263(2) Å, O3⋯O5 = 3.179(1) Å and O3–H3⋯O5 = 156.6(1)°; (2) the oxygen at the O1 site acts as a ‘donor’ and the O atoms at O4 and O5 as ‘acceptors’, the refined O1–H1 bond distance is 0.958(8) Å (and 0.9833 Å corrected for “riding motion”), H1⋯O4 = 2.858(6) Å, O1⋯O4 = 3.378(1) Å and O1–H1⋯O4 = 115.12(1)°, whereas H1⋯O5 = 2.886(6) Å, O1⋯O5 = 3.444(1) Å and O1–H1⋯O5 = 118.23(1)°. A further test refinement was performed with the H1 site out of the three-fold axis (at 0.02, 0.01, 0.90); this leads to O1–H1 = 0.995(8) Å (and 1.0112 Å corrected for “riding motion”), H1⋯O4 = 2.747(6) Å and O1–H1⋯O4 = 121.7(4)°, whereas H1⋯O5 = 2.654(9) Å and O1–H1⋯O5 = 136.5(6)°. Bond-valence analysis shows that the H-bonding strength involving O3 is stronger than that involving O1: ∼0.11 and <0.05 valence units, respectively.

The refined angle between the O3–H3 vector and [0001] is 3.40(9)°. Such a small angle is in line with a pleochroic scheme for the OH-stretching absorption bands measured by infrared spectroscopy.

The new mineral mössbauerite (IMA2012−049), Fe6 3+O4(OH)8[CO3]·3H2O, is a member of the fougèrite group of the hydrotalcite supergroup. Thus, it has a layered double hydroxide-type structure, in which brucite-like layers [Fe6 3+O4(OH)8]2+ are intercalated with CO3 2− anions and water molecules. Mössbauerite is the fully oxidized analogue of fougèrite and trébeurdenite, related to them chemically by the exchange of (Fe3+O2−) with (Fe2+OH−). Mössbauerite, intimately intergrown with trébeurdenite, was discovered in intertidal gleys from Mont Saint-Michel Bay, France, along with quartz, feldspars and clay minerals. Mössbauerite is formed by the oxidation of the other members of the fougèrite group. Like them, it occurs as μm-scale platelets in gleys with restricted access to atmospheric O and decomposes rapidly when exposed to air. Identification and characterization of these minerals has relied on an electrochemical study of synthetic analogues and Mössbauer spectroscopy, which inspired the name of the new mineral.

Unlike fougèrite and trébeurdenite, which are blue-green, pure synthetic mössbauerite is orange in colour. Detailed optical and other physical properties could not be determined because of the small platelet size and instability. The hardness is probably 2−3, by analogy with other members of the supergroup and the density, calculated from unit-cell parameters, is 2.950 g/cm3. Synchrotron X-ray data indicate that the natural material is a nanoscale intergrowth of 2T and 3T polytypes; the latter probably has the 3T7 stacking sequence. The corresponding maximum possible space group symmetries are P m1 and P3m1. Unit-cell parameters for the 3T cell are a = 3.032(7) Å, c = 22.258(4) = 367.420 Å and Z = ½.

Mössbauer spectroscopy at 78 K indicates that two distinct Fe3+ environments exist in a 2:1 ratio. These are interpreted to be ordered within each layer, but without the development of a threedimensional superlattice. Mössbauerite undergoes gradual magnetic ordering at 70−80 K to a ferromagnetic state, below which it splits into three sextets S 1m, S 2m and S 3m, as measured at 15 K, and shows the same intensity ratio ½:⅙:⅓ as the three doublets for fougèrite D 1f, D 2f, D 3f in the paramagnetic state at 78 K. This suggests that there is also short-range coupling of interlayer carbonate anions with respect to the octahedral layers and that the 2D long-range order of carbonates in interlayers remains unchanged.