Kihlmanite-(Ce), Ce2TiO2[SiO4](HCO3)2(H2O), is a new rare-earth titanosilicate carbonate, closely related to tundrite-(Ce). It is triclinic, P, a = 4.994(2), b = 7.54(2), c = 15.48(4) Å, α = 103.5(4), β = 90.7(2), γ = 109.2(2)o , V = 533(1) Å3, Z = 2 (from powder diffraction data) or a = 5.009(5), b = 7.533(5), c = 15.407(5) Å, α = 103.061(5), β = 91.006(5), γ = 109.285(5)°, V = 531.8(7) Å3, Z = 2 (from single-crystal X-ray diffraction data). The mineral was found in the arfvedsonite-aegirine-microcline vein in fenitized metavolcanic rock at the foot of the Mt Kihlman (Chil’man), near the western contact of the Devonian Khibiny alkaline massif and the Proterozoic Imandra-Varzuga greenstone belt. It forms brown spherulites (up to 2 cm diameter) and sheaf-like aggregates of prismatic crystals, flattened on {010} and up to 0.5 mm diameter. Both spherulites and aggregates occur in interstices in arfvedsonite and microcline, in intimate association with golden-green tundrite-(Ce). Kihlmanite-(Ce) is brown, with a vitreous lustre and a pale yellowish-brown streak. The cleavage is perfect on {010}, parting is perpendicular to c and the fracture is stepped. Mohs hardness is ∼3. In transmitted light, the mineral is yellowish brown; pleochroism and dispersion were not observed. Kihlmanite-(Ce) is biaxial (+), α = 1.708(5), β = 1.76(1), γ = 1.82(1) (589 nm), 2Vcalc = 89°. The optical orientation is Y ^ c = 5°, other details are unclear. The calculated and measured densities are 3.694 and 3.66(2) g cm−3, respectively. The mean chemical composition, determined by electron microprobe, is: Na2O 0.13, Al2O3 0.24, SiO2 9.91, CaO 1.50, TiO2 11.04, MnO 0.26, Fe2O3 0.05, Nb2O5 2.79, La2O3 12.95, Ce2O3 27.33, Pr2O3 2.45, Nd2O3 8.12, Sm2O3 1.67, Gd2O3 0.49 wt.%, with CO2 15.0 and H2O 6.0 wt.% (determined by wet chemical and Penfield methods, respectively), giving a total of 99.93 wt.%. The empirical formula calculated on the basis of Si + Al = 1 atom per formula unit is (Ca0.16Na0.11Mn0.02)∑0.29[(Ce0.98La0.47Pr0.09Nd0.29Sm0.06Gd0.02)∑1.91(Ti0.82Nb0.12)∑0.94O2 (Si0.97Al0.03)∑1O4.02(HCO3)2.01](H2O)0.96. The simplified formula is Ce2TiO2(SiO4)(HCO3)2·H2O. The mineral reacts slowly in cold 10% HCl with weak effervescence and fragmentation into separate plates. The strongest X-ray powder-diffraction lines [listed as d in Å(I) (hkl)] are as follows: 15.11(100)(00), 7.508(20)(00), 6.912(12)(01), 4.993(14)(00), 3.563(15)(01), 2.896(15)(1). The crystal structure of kihlmanite-(Ce) was refined to R1 = 0.069 on the basis of 2441 unique observed reflections (MoKα, 293 K). It is closely related to the crystal structure of tundrite-(Ce) and is based upon [Ce2TiO2(SiO4)(HCO3)2] layers parallel to (001). Kihlmanite-(Ce) can be considered as a cationdeficient analogue of tundrite-(Ce). The mineral is named in honour of Alfred Oswald Kihlman (1858–1938), a remarkable Finnish geographer and botanist who participated in the Wilhelm Ramsay expeditions to the Khibiny Mountains in 1891–1892. The mineral name also reflects its occurrence at the Kihlman (Chil’man) Mountain.

Nestolaite (IMA 2013-074), CaSeO3·H2O, is a new mineral species from the Little Eva mine, Grand County, Utah, USA. It is named in honour of the prominent Italian mineralogist and crystallographer Fabrizio Nestola. The new mineral was found on sandstone matrix as rounded aggregates up to 2 mm across and up to 0.05 μm thick consisting of tightly intergrown oblique-angled, flattened to acicular crystals up to 30 μm long and up to 7 μm (very rarely up to 15 μm) thick. Nestolaite associates with cobaltomenite, gypsum, metarossite, orschallite and rossite. The new mineral is light violet and transparent with a white streak and vitreous lustre. The Mohs hardness is 2½. Nestolaite is brittle, has uneven fracture and perfect cleavage on {100}. The measured and calculated densities are Dmeas. = 3.18(2) g/cm3 and Dcalc. = 3.163 g/cm3. Optically, nestolaite is biaxial positive. The refractive indices are α = 1.642(3), β = 1.656(3), γ = 1.722(6). The measured 2V is 55(5)° and the calculated 2V is 51°. In transmitted light nestolaite is colourless. It does not show pleochroism but has strong pseudoabsorption caused by high birefringence. The chemical composition of nestolaite (wt.%, electronmicroprobe data) is: CaO 28.97, SeO2 61.14, H2O (calc.) 9.75, total 99.86. The empirical formula calculated on the basis of 4 O a.p.f.u. (atoms per formula unit) is Ca0.96Se1.02O3·H2O. The Raman spectrum is dominated by the Se–O stretching and O–Se–O bending vibrations of the pyramidal SeO3 groups and O–H stretching modes of the H2O molecules. The mineral is monoclinic, space group P21/c, with a = 7.6502(9), b = 6.7473(10), c = 7.9358(13) Å, β = 108.542 (12)°, V = 388.37(10) Å3 and Z = 4. The eight strongest powder X-ray diffraction lines are [dobs in Å(hkl) (Irel)]: 7.277 (100)(100), 4.949 (110)(37), 3.767 (002)(29), 3.630 (200)(58), 3.371 (020)(24), 3.163 (02)(74), 2.9783 (21)(74) and 2.7231 (112)(31). The crystal structure of nestolaite was determined by means of the Rietveld refinement from the powder data to Rwp = 0.019. Nestolaite possesses a layered structure consisting of CaΦ–SeO3 sheets, composed of edge-sharing polyhedra. Adjacent sheets are held by H bonds emanating from the single (H2O) group within the sheets. The nestolaite structure is topologically unique.

Lithium micas of the zinnwaldite and phengite–Li-phengite series occur as characteristic minerals in Permian Li-F-(P) granites of the western Gemeric unit (Western Carpathians) accompanied by topaz, tourmaline, Nb, Ta, Ti, Sn oxides and aluminophosphates. The calculated Li2O contents of all the mica analysed, together with Rb2O and Cs2O were confirmed by LA-ICP-MS analyses for all the identified micas. Samples from three localities were investigated: two surficial (Surovec, Vrchsúl’ová); and one drill hole (Dlhá dolina). Zinnwaldite (polylithionite) occurs in the upper level of the Dlhá dolina granitic intrusion and in the nearby shallow satellite body of Surovec. The lower level porphyritic granites contain only siderophyllite. The Vrchsúl’ ová micas are closer in composition to Li-annite and siderophyllite. Dioctahedral micas are mostly phengites, although zinnwaldite-bearing granites are rich in late-crystallizing Li-phengite, which extensively replaces earlier zinnwaldite. The secondary Liphengite and phengite are interpreted as products of Alpine metamorphism during Cretaceous burial and subsequent exhumation of the Gemeric unit. Reactions are suggested explaining the formation of Li-phengite by reaction of zinnwaldite with phengite or with muscovite. All mica types were investigated by Mössbauer spectroscopy, which showed high degrees of oxidation (25–50% Fe3+ of total Fe) with the exception of zinnwaldite from Vrchsúl’ová, which may have preserved an original, reduced value of 10%. The metamorphic assemblage present permitted calculation of P-T-X conditions: T = 184°C, P = 320 MPa, with oxidation of siderophyllite to phengite + goethite and fO2 at ΔNN = 4.7, confirming the low-grade conditions of the Alpine metamorphism in agreement with previous estimates.

The natural hydroniumjarosite sample from Cerros Pintados (Chile) was investigated by electron microprobe, single-crystal X-ray diffraction and vibrational spectroscopy (Infrared and Raman). The chemical composition of studied specimens (wt.%, mean of seven analyses) obtained from electron microprobe (in wt.%): Na2O 1.30, K2O 0.23, CaO 0.04, Fe2O3 50.49, Al2O3 0.37, SiO2 0.33, SO3 33.88, H2O (calculated on the basis of Σ(OH–+H3O+) deduced from the charge balance) 13.32, total 99.98, corresponds to the empirical formula (H3O)0.77+(Na0.20K0.02)∑0.22(Fe2.95Al0.03)∑2.98 (OH)6.12[(SO4)1.97(SiO4)0.03]∑2.00 (calculated on the basis of S + Si = 2 a.p.f.u. (atoms per formula unit)). The studied hydroniumjarosite is trigonal, with space group Rm, with a = 7.3408(2), c = 17.0451(6) Å and V = 795.46(4) Å3. The refined structure architecture is consistent with known jarosite-series minerals, including synthetic hydroniumjarosite. However, in the current study the presence of H3O+ is well documented in difference Fourier maps, where characteristic positive difference Fourier maxima, with apparent trigonal symmetry, were localized in the vicinity of the O4 atom in the channel-voids of the structure. The structure of natural hydroniumjarosite, including the H atoms, was refined to R1 = 0.0166 for 2113 unique observed reflections, with Iobs>3σ(I). The present structure model, which includes the position of the H atom within the hydronium ion, is discussed with regard to the vibration spectroscopy results and earlier published density-functional theory (DFT) calculations for the alunite-like structure containing H3O+.

Tangdanite, ideally Ca2Cu9(AsO4)4(SO4)0.5(OH)9·9H2O and monoclinic, is a new mineral species (IMA No. 2011-096) occurring in the Tangdan and Nanniping mines, southeast Dongchuan copper mining district, Dongchuan County, Kunming City Prefecture, Yunnan Province, P. R. China (26°11’N 103°51’E). The mineral is found in the oxidized zone (gossan) of an As-bearing Cu sulfide deposit and is clearly of supergene origin. Associated minerals are chalcopyrite, bornite, chalcocite, covellite, tennantite, enargite, cuprite, malachite, azurite, copper and brochantite. Crystals form radiating or foliated aggregates of flaky crystals up to 3 mm, flattened parallel to (100) and elongated along [001]. It is emerald green with a light green streak, translucent and has a pearly to silky lustre. It is sectile having perfect cleavage on {100} although neither parting nor fracture was observed. No fluorescence in long- or short-wave ultraviolet radiation was observed. The hardness is VHN50 42.0−43.6, mean 42.8 kg mm−2 (2−2½ on the Mohs scale). The density measured by pycnometry is 3.22 g cm−3 (Ma et al., 1980). The calculated density from the empirical chemical formula is 3.32 g cm−3. The compatability index gives 1 − (Kp/Kc) = −0.041 (good). The empirical formula (based on 36 O a.p.f.u) of tangdanite is Ca2.05Cu9.08(As1.03O4)4(S0.63O4)0.5(OH)9·9H2.04O. The simplified formula is Ca2Cu9(AsO4)4(SO4)0.5(OH)9·9H2O. The strongest five reflections in the X-ray powder-diffraction pattern [d in Å(I) (hkl)] are: 4.782(100) ( 1 1), 4.333(71) (6 0 2), 5.263(54) ( 0 2), 3.949(47) (8 0 2) and 2.976(46) ( 1 1). The unit-cell parameters are a = 54.490(9), b = 5.5685(9), c = 10.4690(17) Å, β = 96.294(3)o, V = 3157.4(9) Å3, Z = 4. Its structure was solved and refined in space group C2/c, with R = 0.110.

The new mineral species vapnikite, Ca3UO6, was found in larnite pyrometamorphic rocks of the Hatrurim Formation at Jabel Harmun in the Judean desert, Palestinian Autonomy, Israel. Vapnikite is an analogue of the synthetic ordered double-perovskite β-Ca3UO6 and is isostructural with the natural fluorperovskite – cryolite Na3AlF6. Vapnikite Ca3UO6 (P21/n, Z = 2, a = 5.739(1), b = 5.951(1), c = 8.312(1) Å, β = 90.4(1)°, V = 283.9(1) Å3) forms yellow-brown xenomorphic grains with a strong vitreous lustre. Small grains up to 20−30 µm in size are wedged between larnite, brownmillerite and ye’elimite. Vapnikite has irregular fracture, cleavage and parting were not observed. The calculated density is 5.322 g cm−3, the microhardness is VHN25 = 534 kg mm−2 (mean of seven measurements) corresponding to the hardness of ∼5 on the Mohs scale. The crystal structure of vapnikite Ca3UO6 differs from that of its synthetic analogue β-Ca3UO6 by having a larger degree of Ca, U disorder. Vapnikite formed at the high-temperature retrograde stage of pyrometamorphism when larnite rocks were altered by fluids/melts of high alkalinity.

Tondiite, with the simplified formula Cu3Mg(OH)6Cl2, occurs as a rare supergene mineral in a phonolitic tephrite from the type locality, Vesuvius volcano, Italy, as well as associated with haydeeite in the Santo Domingo Mine, Arica Province, Chile. It is emerald green to bright green in colour and occurs in irregularly shaped crystals, often with stepped faces. Its calculated density is 3.503 g cm−3. Tondiite crystallizes with the herbertsmithite structure type, space group Rm. Lattice parameters are a = 6.8377(7) Å and c = 14.088(2)Å for the holotype material. The c parameter may vary with Mg/Cu ratio and the presence of impurity atoms. The five strongest lines in the calculated powder diffraction pattern are [d in Å(I)(hkil)]: 5.459(88)(101), 3.419(22)(110), 2.764(100)(112 3), 2.266(54)(024), 1.706(26)(220). Several tondiite crystals have been examined by single-crystal X-ray diffraction and by electron microprobe analysis. The observed Mg content ranges between 0.6 and 0.7 atoms per formula unit. The structural role of Mg is discussed.

The crystal structure of franconite, NaNb2O5(OH)·3H2O, has been characterized by single-crystal X-ray diffraction using material from Mont Saint-Hilaire, Québec, Canada. Results give a = 10.119(2), b = 6.436(1), c = 12.682(2) Å and β = 99.91(3)° and confirm the correct space group as P21/c. The crystal structure, refined to R = 4.63% and wR2 =11.95%, contains one Na site, two distorted octahedral Nb sites and nine O sites. It consists of clusters of four edge-sharing Nb(O,OH)6 octahedra, linked through shared corners to adjacent clusters, forming layers of Nb(O,OH)6 octahedra. These alternate along [100] with layers composed of NaO(H2O)4 polyhedra, the two being linked together by well defined H bonding. The predominance of H bonding, essential to the mineral, results in a perfect {100} cleavage. Chemical analyses (n = 7) of four crystals give the empirical formula (Na0.73Ca0.13☐0.14)∑=1.00(Nb1.96Ti0.02Si0.02Al0.01)∑=2.01O5(OH)·3H2O (based on nine oxygens) or ideally NaNb2O5(OH)·3H2O. Franconite is crystallo-chemically related to SOMS [Sandia Octahedral Molecular Sieves; Na2Nb2−xMxO6−x(OH)x·H2O with M = Ti, Zr, Hf], a group of synthetic compounds with strong ion-exchange capabilities. Both hochelagaite (CaNb4O11·nH2O) and ternovite (MgNb4O11·nH2O) have X-ray powder diffraction patterns and cation ratios similar to those of franconite indicating that these minerals probably have similar structures.

Hydrothermal treatment of quartz with 2 M K2CO3 solutions at 623 K and 1 kbar resulted in the formation of single crystals of the monoclinic polymorph of potassium hydrogen disilicate (KHSi2O5 or KSi2O4(OH)). Basic crystallographic data of this so-called phase I at room conditions are as follows: space group C2/m, a = 14.5895(10) Å, b = 8.2992(3) Å, c = 9.6866(7) Å, β = 122.756(10)°, V = 986.36(10) Å3, Z = 8. The structure was determined by direct methods and refined to a residual of R(|F|) = 0.0224 for 892 independent observed reflections with I > 2σ(I). The compound belongs to the group of chain silicates. It is based on crankshaft-like vierer double-chains running parallel to [010]. The H atoms are associated with silanol groups. Hydrogen bonding between neighbouring double-chains results in the formation of ∼5 Å wide slabs. The three crystallographically independent K cations with six to eight O ligands provide linkage (1) between the chains of a single slab or (2) between adjacent slabs. Structural investigations have been supplemented by micro-Raman spectroscopy. The interpretation of the spectroscopic data including the allocation of the bands to certain vibrational species has been aided by DFT calculations.

One of the major obstacles to our understanding of the growth of continental crust is that of estimating the balance between extraction rate of continental crust from the mantle and its recycling rate back into the mantle. As a first step it is important to learn more about how and when juvenile crust is preserved in orogens. The most abundant petrotectonic assemblage preserved in orogens (both collisional and accretionary) is the continental arc, whereas oceanic terranes (arcs, crust, mélange, Large Igneous Provinces, etc.) comprise <10%; the remainder comprises older, reworked crust. Most of the juvenile crust in orogens is found in continental arc assemblages. Our studies indicate that most juvenile crust preserved in orogens was produced during the ocean-basin closing stage and not during the collision. However, the duration of ocean-basin closing is not a major control on the fraction of juvenile crust preserved in orogens; regardless of the duration of subduction, the fraction of juvenile crust preserved reaches a maximum of ∼50%. Hafnium and Nd isotopic data indicate that reworking dominates in external orogens during supercontinent breakup, whereas during supercontinent assembly, external orogens change to retreating modes where greater amounts of juvenile crust are produced. The most remarkable feature of εNd (sedimentary rocks and granitoids) and εHf (detrital zircons) distributions through time is how well they agree with each other. The ratio of positive to negative εNd and eHf does not increase during supercontinent assembly (coincident with zircon age peaks), which suggests that supercontinent assembly is not accompanied by enhanced crustal production. Rather, the zircon age peaks probably result from enhanced preservation of juvenile crust. Valleys between zircon age peaks probably reflect recycling of continental crust into the mantle during supercontinent breakup. Hafnium isotopic data from zircons that have mantle sources, Nd isotopic data from detrital sedimentary rocks and granitoids and whole-rock Re depletion ages of mantle xenoliths collectively suggest that ≥70% of the continental crust was extracted from the mantle between 3500 and 2500 Ma.

The new mineral belakovskiite (IMA2013-075), Na7(UO2)(SO4)4(SO3OH)(H2O)3, was found in the Blue Lizard mine, Red Canyon, White Canyon district, San Juan County, Utah, USA, where it occurs as a secondary alteration phase in association with blödite, ferrinatrite, kröhnkite, meisserite and metavoltine. Crystals of belakovskiite are very pale yellowish-green hair-like fibres up to 2 mm long and usually no more than a few mm in diameter. The fibres are elongated on [100] and slightly flattened on {021}. Crystals are transparent with a vitreous lustre. The mineral has a white streak and a probable Mohs hardness of ∼2. Fibres are flexible and elastic, with brittle failure and irregular fracture. No cleavage was observed. The mineral is readily soluble in cold H2O. The calculated density is 2.953 g cm−3. Optically, belakovskiite is biaxial (+) with α = 1.500(1), β = 1.511(1) and γ = 1.523(1) (measured in white light). The measured 2V is 87.1(6)° and the calculated 2V is 88°. The mineral is non-pleochroic. The partially determined optical orientation is X ≈ a. Electron-microprobe analysis provided Na2O 21.67, UO3 30.48, SO3 40.86, H2O 6.45 (structure), total 99.46 wt.% yielding the empirical formula Na6.83(U1.04O2)(SO4)4(S0.99O3OH)(H2O)3 based on 25 O a.p.f.u. Belakovskiite is triclinic, P, with a = 5.4581(3), b = 11.3288(6), c = 18.4163(13) Å, α = 104.786(7)°, β = 90.092(6)°, γ = 96.767(7)°, V = 1092.76(11) Å3 and Z = 2. The eight strongest X-ray powder diffraction lines are [dobs Å(I)(hkl)]: 8.96(35)(002), 8.46(29)(011), 5.19(100)(01,101,10), 4.66(58)(013,02,0,110), 3.568(37)(120,023,005,03), 3.057(59)(06,15,31), 2.930(27)(multiple) and 1.8320(29)(multiple). The structure, refined to R1 = 5.39% for 3163 Fo > 4σF reflections, contains [(UO2)(SO4)4(H2O)]6− polyhedral clusters connected via an extensive network of Na−O bonds and H bonds involving eight Na sites, three other H2O sites and an SO3OH (hydrosulfate) group. The 3-D framework, thus defined, is unique among known uranyl sulfate structures. The mineral is named for Dmitry Ilych Belakovskiy, a prominent Russian mineralogist and Curator of the Fersman Mineralogical Museum.

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.

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.

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.

Wakabayashilite is a rare mineral with ideal formula [(As,Sb)6S9][As4S5]. Its structure consists of an [M6S9] bundle-like unit (M = As, Sb) running along the [001] axis and [As4S5] cage-like molecules. In this study, samples of wakabayashilite from different occurrences (Khaidarkan, Kyrgyzstan; Jas Roux, France; White Caps mine, USA; Nishinomaki mine, Japan) were selected to verify the possible presence of different molecular groups replacing the As4S5 molecule. Given the chemical (electron probe microanalysis-wavelength dispersive spectroscopy), spectroscopic (micro-Raman) and structural (single-crystal X-ray diffraction) results obtained, it appears evident that only the As4S5 molecular group is present in the wakabayashilite structure and that the apparent non-stoichiometry reported in literature is actually due to unreliable chemical analyses. The structural role of the minor elements (Cu, Zn and Tl) in wakabayashilite is also discussed.

The evolution of the trace-element patterns of quartz during crystallization of pegmatite melt was investigated using laser ablation inductively coupled plasma mass spectrometry. The contents of Al, B, Ba, Be, Cr, Fe, Ge, Li, Mn, P, Rb, Sn, Sr and Ti were analysed in quartz from the border, intermediate and core zones of four granitic pegmatites differing in degree of fractionation and origin. The material investigated originates from the pegmatite district of the Strážek Unit, Moldanubian Zone, Bohemian Massif, Czech Republic and includes: lepidolite LCT (Li-Cs-Ta) pegmatite from Rožná; berylcolumbite LCT pegmatite from Věžná; anatectic pegmatite from Znětínek; and intragranitic NYF (Nb-Y-F) pegmatite Vladislav from the Třebíč Pluton. The abundances of the elements analysed varied over wide intervals: <1 to 32 ppm Li, 0.5 to 6 ppm B, <1 to 10 ppm Ge, 1 to 10 ppm P, 10 to 450 ppm Al, 1 to 45 ppm Ti and <1 to 40 ppm Fe (average sample contents). Concentrations of Be, Rb, Sr, Sn, Ba, Cr and Mn are usually <1 ppm. Quartz from LCT pegmatites exhibits a distinct evolutionary trend with a decrease in Ti and an increase in Al, Li and Ge from the pegmatite border to the core. In comparison with the most fractionated rare-metal granites, pegmatitic quartz is relatively depleted in Al and Li, but strongly enriched in Ge. Quartz from simple anatectic and NYF pegmatites is poor in all trace elements with their evolution marked by a decrease in Ti and a small increase in Ge. There is little Al or Li and neither shows any systematic change with pegmatite evolution. Using the Ti-in-quartz thermobarometer, the outer zones of the Znětínek and Vladislav pegmatites crystallized at ∼670°C, whereas the border zone in the Rožná pegmatite yields a temperature near 610°C.

The crystal structure, H bonding and chemical composition of hydroxylherderite from the Bennett pegmatite, Buckfield, Oxford County, Maine, USA were investigated by single-crystal X-ray diffraction and neutron Laue diffraction, electron microprobe analysis in wavelength-dispersive mode, inductively coupled plasma-atomic emission spectrometry and polarized Raman spectroscopy [Ca(Na0.01Ca1.01)∑1.02Be(Be0.98Li0.01)∑0.99P(Si0.03P0.98)∑1.01O4(OH0.67F0.33)∑1, Z = 4, a = 9.7856(5), b = 7.6607(5), c = 4.8025(3) Å, β = 90.02(3)°, V = 360.02(4) Å3, space group P21/a]. The neutron-structure refinement converged with fully anisotropic displacement parameters to give a final agreement index R1 = 0.0363 for 85 refined parameters and 1614 unique reflections with Fo >4σ(Fo). The structure refinement was used to determine the H position and geometry of H bonding in the structure. One H site was found on the O5 anion with an O–H interatomic distance, corrected for “riding motion”, of 0.996(2) Å. The H bond of hydroxylherderite is bifurcated with O2 and O4 acceptors forming H bonds with O5⋯O2 = 3.163(1) Å, H⋯O2 = 2.544(2) Åand O5–H⋯O2 = 121.8(1)°; O5⋯O4 = 3.081(1) Å, H⋯O4 = 2.428(2) Å and O5–H⋯O4 = 124.4(1)°. The highly non-linear O–H⋯O hydrogen bonds in hydroxylherderite and in the isotypic datolite [ideally CaBSiO4(OH)] are constrained by the tetrahedral network topology. Two main O–H stretching modes were observed in the Raman spectra at 3565 and 3620 cm–1, which are attributed to the bifurcated H bond. Two additional weak bands at 3575 and 3610 cm–1 are attributed to Si–P disorder in the tetrahedral sites. Results of this study will contribute to the correlation of H-bonding geometry and O–H stretching frequencies of highly non-linear H bonds.

Kitagohaite, ideally Pt7Cu, is a new mineral from the Lubero region of North Kivu, Democratic Republic of the Congo. The mineral occurs as alluvial grains that were recovered together with other Pt-rich intermetallic compounds and Au. Kitagohaite is opaque, greyish white and malleable and has a metallic lustre and a grey streak. In reflected light, kitagohaite is white and isotropic. The crystal structure of kitagohaite is cubic, space group Fmm, of the Ca7Ge type, with a = 7.7891(3) Å, V = 472.57(5) Å3 and Z = 4. The strongest diffraction lines [d in Å(I)(hkl)] are: 2.246 (100)(222), 1.948(8)(004), 1.377 (77)(044), 1.174(27)(622), 1.123 (31)(444) and 0.893 (13)(662). The Vickers hardness is 217 kg mm−2 (VHN100), which is equivalent to a Mohs hardness of 3½ and the calculated density is 19.958(2) g cm−3. Electron-microprobe analyses gave a mean value (n = 13) of 95.49 wt.% Pt and 4.78 wt.%Cu, which corresponds to Pt6.93Cu1.07 on the basis of eight atoms. The new mineral is named for the Kitagoha river, in the Lubero region.

The new mineral torrecillasite (IMA2013-112), Na(As,Sb)43+O6Cl, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with anhydrite, cinnabar, gypsum, halite, lavendulan, magnesiokoritnigite, marcasite, quartz, pyrite, scorodite, wendwilsonite and other potentially new As-bearing minerals. Torrecillasite occurs as thin colourless prisms up to 0.4 mm long in jack-straw aggregates, as very thin fibres in puff balls and as massive intergrowths of needles. Prisms are elongated on [100] with diamond-shaped cross-section and irregular terminations. Crystals are transparent, with adamantine lustre and white streak. The Mohs hardness is 2½, tenacity is brittle and fracture is irregular. Cleavage on (001) is likely. The calculated density is 4.056 g cm−3. Optically, torrecillasite is biaxial (−) with α = 1.800(5), β = 1.96(1), γ = 2.03(calc.) (measured in white light). The measured 2V is 62.1(5)°, no dispersion or pleochroism were observed, the optical orientation is X = c, Y = b, Z = a. The mineral is very slowly soluble in H2O, slowly soluble in dilute HCl and rapidly soluble in concentrated HCl. The empirical formula, determined from electron-microprobe analyses, is (Na1.03Mg0.02)∑1.05(As3.39Sb0.62)∑4.01O6.07Cl0.93. Torrecillasite is orthorhombic, Pmcn, a = 5.2580(9), b = 8.0620(13), c = 18.654(3) Å, V = 790.7(2) Å3 and Z = 4. The eight strongest X-ray powder diffraction lines are [dobs Å(I)(hkl)]: 4.298(33)(111), 4.031(78)(014,020), 3.035(100)(024,122), 2.853(39)(115,123), 2.642(84)(124,200), 2.426(34)(125), 1.8963(32)(225) and 1.8026(29)(0·1·10,233). The structure, refined to R1 = 4.06% for 814 Fo >4σF reflections, contains a neutral, wavy As2O3 layer parallel to (001) consisting of As3+O3 pyramids that share O atoms to form six-membered rings. Successive layers are flipped relative to one another and successive interlayer regions contain alternately either Na or Cl atoms. Torrecillasite is isostructural with synthetic orthorhombic NaAs4O6Br.