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Leószilárdite (IMA2015-128), Na6Mg(UO2)2(CO3)6·6H2O, was found in the Markey Mine, Red Canyon, White Canyon District, San Juan County, Utah, USA, in areas with abundant andersonite, natrozippeite, gypsum, anhydrite, and probable hydromagnesite along with other secondary uranium minerals bayleyite, čejkaite and johannite. The new mineral occurs as aggregates of pale yellow bladed crystals flattened on ﹛001﹜ and elongated along , individually reaching up to 0.2 mmlong. More commonly it occurs as pale yellow pearlescent masses to 2 mm consisting of very small plates. Leószilárdite fluoresces green under both longwave and shortwave ultraviolet light, and is translucent with a white streak, hardness of 2 (Mohs), and brittle tenacity with uneven fracture. The new mineral is readily soluble in room temperature H2O. Crystals have perfect cleavage along ﹛001﹜, and exhibit the forms ﹛110﹜,﹛001﹜,﹛100﹜,﹛101﹜ and ﹛101﹜. Optically, leószilárdite is biaxial (-), α= 1.504(1), β= 1.597(1), γ= 1.628(1) (white light); 2V (meas.) = 57(1)°, 2V (calc.) = 57.1°; dispersion r > v, slight. Pleochroism: X= colourless, Y and Z= light yellow; X<Y ≈ Z The average of six wavelength dispersive spectroscopic analyses provided Na2O 14.54, MgO 3.05, UO3 47.95, CO2 22.13, H2O 9.51, total 97.18 wt.%. The empirical formula is Na5.60Mg0.90U2O28C6H12.60, based on 28 O apfu. Leószilárdite is monoclinic, C2/m, a = 11.6093(21), b = 6.7843(13), c = 15.1058(28) Å, β = 91.378(3)°, V= 1189.4(4) Å3 and Z = 2. The crystal structure (R1 = 0.0387 for 1394 reflections with Iobs > 4σI), consists of uranyl tricarbonate anion clusters [(UO2)(CO3)3]4- held together in part by irregular chains of NaO5(H2O) polyhedra sub parallel to . Individual uranyl tricarbonate clusters are also linked together by three-octahedron units consisting of two Na-centred octahedra that share the opposite faces of a Mg-centred octahedron at the centre (Na–Mg–Na), and have the composition Na2MgO12(H2O)4. The name of the new mineral honours the Hungarian-American physicist, inventor and biologist Dr. Leó Szilárd (1898–1964).
A comparative study is presented of the chemistry and crystallography of zinc-bearing strunzites from Hagendorf Süd, Bavaria, Germany and the Sitio do Castelo mine, Folgosinho, Portugal. Electron microprobe analyses of samples from the two localities show quite different cation substitutions. The Hagendorf Süd mineral is a Zn-bearing ferristrunzite, with compositional zoning due to Zn2+ replacing predominantly Fe3+ as well as minor Mn2+, whereas the Portugese mineral is a Zn-bearing strunzite, in which Zn2+ replaces Mn2+, with minor replacement of Fe3+ by Mn3+. Zincostrunzite, with dominant Zn in the interlayer octahedrally coordinated site, is a new strunzite-group mineral that has been characterized at both locations. Analysis of single-crystal synchrotron data for zinc-bearing ferristrunzite and zincostrunzite crystals from Hagendorf Süd show that the structures of both minerals contain zeolitic water in the interlayer region. The formula for strunzite-group minerals containing the zeolitic water is MFe23+(PO4)2(OH)2·6.5H2O, M=Fe, Mn, Zn. This formulation agrees with that found for zincostrunzite from the Sitio do Castelo mine, but differs from that reported previously for strunzite, MFe2+(PO4)2(OH)2·6H2O, which has no interlayer water. Interestingly, the zincostrunzites from the two localities differ in the location of the interlayer water molecule, with a corresponding difference in the H bonding.
This study presents the first crystal-structure determination of natural MgCO3·5H2O, mineral lansfordite, in comparison with previous structural works performed on synthetic analogues. A new prototype single-crystal X-ray diffractometer allowed us to measure an extremely small crystal (i.e. 0.020 mm × 0.010 mm × 0.005 mm) and refine anisotropically all non-hydrogen atoms in the structure and provide a robust hydrogen-bond arrangement. Our new data confirm that natural lansfordite can be stable for several months at room temperature, in contrast with previous works, which reported that such a mineral could be stable only below 10°C.
Dzierżanowskite, , a thiocuprate, was found in larnite pseudoconglomerate rocks of the Hatrurim Complex at Jabel Harmun, Palestinian Autonomy, Israel. Dzierżanowskite occurs in larnite pebbles, which are embedded in a low-temperature mineral matrix. Associated minerals are larnite, brownmillerite, fluorellestadite, ye'elimite, gehlenite, periclase, ternesite, nabimusaite, vorlanite, vapnikite, fluormayenite, fluorkyuygenite, oldhamite, jasmundite, covellite, chalcocite and pyrrhotite. Electron microprobe analyses yield an average composition of Cu 55.25, Fe 0.13, S 27.46 and Ca 16.99, total 99.83 wt.%. The empirical formula of dzierżanowskite, based on 5 atoms, is Ca0.98Cu2.02Fe0.01S1.99. Dzierżanowskite forms grains up to 15 μm in size or rims on oldhamite and laminar intergrowths with chalcocite and covellite. Dzierżanowskite is dark orange, has a cream streak and a submetallic lustre. In reflected light it is grey, with a cream tint and characteristic yellow-orange internal reflections. The calculated density of dzierżanowskite is 4.391 g cm -3. Three bands at 300, 103 and 86 cm -1 are observed in the Raman spectrum. The strongest lines of the calculated powder diffraction pattern are [d, Å (I) hkl]: 2.358(100) 102, 1.970(93)110, 3.023(78) 011, 6.523(36) 001, 3.412 (28) 100, 1.834(28) 103. Dzierżanowskite was also found in unusual jasmundite rocks, forming small ‘paleofumaroles’ within areas of low-temperature hydrothermal rocks bearing larnite pseudoconglomerates at Jabel Harmun. Dzierżanowskite is a superimposed phase of the high-temperature alteration of pyrometamorphic rocks subjected to by-products (melts/fluids and gases) of pyrometamorphism originating in the deeper levels of combustion.
Ilmenite–pyrophanite crystals from a garnet pegmatite dyke from the Upper Codera Valley (Sondrio, Italian Alps) showing exsolutions of titanohematite and columbite-tantalite were investigated by scanning and transmission electron microscopy. The titanohematite precipitates share the same crystallographic orientation of the ilmenite-pyrophanite host, are bean-shaped when observed on sections inclined to the pinacoidal section, and are elongated when observed on sections closer to the prism section, possibly because of their discoidal shape parallel to (001). The columbite-tantalite precipitates form a hexagonal network of needles elongated along ⟨110⟩ of the ilmenite–pyrophanite and titanohematite host. The following crystallographic relationship was established: Col//Ilm; Col//Ilm; , which can be explained in terms of preservation of the oxygen close packing between the ilmenite and columbite structures. The interfaces between any two of the three different phases are coherent but show lattice strain contrast and sometimes dislocations because of their different unit-cell dimensions. On the basis of textural observations, titanohematite is supposed to exsolve first, followed by columbite-tantalite at temperatures below 500°C. The addition of MnO to the Fe2O3–FeTiO3 system is supposed to considerably influence the topology of the related T-X phase diagram and the solubility of Nb2O5 and Ta2O5 in this system.
The new mineral centennialite (IMA 2013-110), CaCu3(OH)6Cl2·nH2O, was identified from three cotype specimens originating from the Centennial Mine, Houghton County, Michigan, USA, where it occurs as a secondary product, after acid water action upon supergene Cu mineralization in association with, and essentially indivisible from, other copper-containing minerals such as calumetite and atacamite family minerals. It forms as pale to azure blue encrustations, often taking a botryoidal form. Centennialite is trigonal, , a = 6.6606(9) Å, c = 5.8004(8) Å, V= 222.85(6) Å3, Z= 1. The strongest powder X-ray diffraction lines are dobs/Å [I%] (hkl), 5.799  (001), 2.583  (201), 2.886  (111), 1.665  (220), 1.605  (023), 1.600  (221), 1.444  (222). The X-ray refined structure forms a kagome net of planar coordinated CuO4 units with Jahn-Teller coordinated Cl apices to form octahedra that edge-share to in-plane adjacent and flattened CaO6 octahedra, which are centred about the lattice origin. All oxygen sites are protonated and shared between one Ca-octahedron and one CuO4 planar unit. Three protonated sites are linked, by hydrogen-bonding to Cl sites, which sit on the triad axis. Each lattice has one Cl above and one below the Ca-Cu polyhedral plane. Consequently, the layers are stacked, along ⟨001⟩, with two Cl sites between layers. In addition to this kapellasite-like topology, an extra c/2 site is identified as being variably water-hosting and extends the coordination of the Ca-site to 8-fold, akin to the body-diagonal Pb-Cu sheet in murdochite. Centennialite conforms to the description of the ‘Unidentified Cu-Ca-Cl Mineral’ noted in Heinrich's Mineralogy of Michigan and is almost certainly identical to the supposed hexagonal basic calcium-copper hydroxychloride monohydrate of Erdös et al. (1981). We comment upon relationships between calumetite and centennialite and propose a substructure model for a synthetic calumetite-like phase that is related directly to centennialite.
Girdite, a mineral described byWilliams in 1979 from the Grand Central mine, Tombstone, Cochise County, Arizona, USA, has been re-examined by powder X-ray diffraction, single-crystal X-ray diffraction and electron microprobe. Type material from The Natural History Museum, London and the United States National Museum of Natural History (Smithsonian Institution) was examined. The original description of girdite is shown to have been based upon data obtained from at least two and possibly three different phases, one corresponding to ottoite and another probably corresponding to oboyerite, although the latter itself appears to be a mixture. The discreditation of girdite as a valid mineral species has been approved by the IMA-CNMNC, Proposal 16-G.
A series of clinopyroxenes along the CaMgSi2O6–CaCoSi2O6 join was synthesized by quenching from melts at 1500°C and subsequent annealing at 1250°C (at 0.0001 GPa). This protocol proved to be the most effective to obtain homogenous, impurity-free and stoichiometric pyroxenes. Electron microprobe analyses in energy dispersive mode were conducted and single-crystal X-ray diffraction data were collected on Ca (CoxMg1-x)Si2O6 pyroxenes with x = 0.2, 0.4, 0.5, 0.6. Effects of cation substitution at the M1 site are described. The experimental findings of this study allow us to extend the comparative analysis of the structural features of pyroxenes with divalent cations at the M1 and M2 sites.
The new mineral currierite (IMA2016-030), Na4Ca3MgAl4(AsO3OH)12·9H2O, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with anhydrite, canutite, chudobaite, halite, lavendulan, magnesiokoritnigite, quartz, scorodite and torrecillasite. Currierite occurs as hexagonal prisms, needles and hair-like fibres up to ∼200 μm long, in sprays. The crystal forms are ﹛100﹜ and ﹛001﹜. Crystals are transparent, with vitreous to silky lustre and white streak. The Mohs hardness is ∼2, tenacity is brittle, but elastic in very thin fibres, and the fracture is irregular. Crystals exhibit at least one good cleavage parallel . The measured density is 3.08(2) g cm -3 and the calculated density is 3.005 g cm -3. Optically, currierite is uniaxial (–) with ω= 1.614(1) and ε= 1.613(1) (measured in white light). The mineral is slowly soluble in dilute HCl at room temperature. The empirical formula, determined from electron-microprobe analyses, is (Na3.95A12.96Ca2.74Mg1.28Fe0.633+Cu0.13K0.08Co0.03Σ11.80 (AS11.685+Sb0.325+Σ12(O56.96Cl0.04)Σ57H30.81. Currierite is hexagonal, P622, with a = 12.2057(9), c = 9.2052(7) Å, V= 1187.7(2) Å3 and Z = 1. The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 10.63(100)(100), 6.12(20)(110), 5.30(15)(200), 4.61(24)(002), 4.002(35)(210), 3.474(29)(202), 3.021(96)(212) and 1.5227(29)(440,334,612). The structure of currierite (R1 = 2.27% for 658 Fo > 4σF reflections) is based upon a heteropolyhedral chain along c in which AlO6 octahedra are triple-linked by sharing corners with AsO3OH tetrahedra. Chains are linked to one another by bonds to 8(4 + 4)-coordinated Na and 8-coordinated Ca forming a three-dimensional framework with large cavities that contain rotationally disordered Mg(H2O)6 octahedra. The chain in the structure of currierite is identical to that in kaatialaite and a geometrical isomer of that in ferrinatrite. The mineral is named in honour of Mr. Rock Henry Currier (1940–2015), American mineral dealer, collector, author and lecturer.
Omariniite, ideally Cu8Fe2ZnGe2S12, represents the Ge-analogue of stannoidite and was found in bornite-chalcocite-rich ores near the La Rosario vein of the Capillitas epithermal deposit, Catamarca Province, Argentina. The mineral is associated closely with three other Ge-bearing minerals (putzite, catamarcaite, rarely zincobriartite) and bornite, chalcocite, digenite, covellite, sphalerite, tennantite, luzonite, wittichenite, thalcusite and traces of mawsonite. The width of the seams rarely exceeds 60 μm, their length can attain several 100 μm. The mineral is opaque, orange-brown in polished section, has a metallic lustre and a brownish-black streak. It is brittle, and the fracture is irregular to subconchoidal. Neither cleavage nor parting are observable in the sections. In plane-polarized light omariniite is brownish-orange and has a weak pleochroism. Internal reflections are absent. The mineral is distinctly anisotropic with rotation tints varying between brownish-orange and greenish-brown. The average result of 45 electron-microprobe analyses is Cu 42.18(34), Fe 9.37(26), Zn 5.17(43), In 0.20(6), Ge 11.62(22), S 31.80(20), total 100.34(46) wt.%. The empirical formula, based on Σ(Me + S) = 25, is Cu8.04(Fe2.03In0.02)Σ2.05Zn0.96 Ge1.94S12.01, ideally Cu8+Fe2+Zn2+Ge24+S122-. Omariniite is orthorhombic, space group I222, with unit-cell parameters: a = 10.774(1), b = 5.3921(5), c = 16.085(2) Å, V = 934.5(2) Å3, a:b:c = 1.9981:1:2.9831, Z = 2. X-ray single-crystal studies (R1 = 0.023) revealed the structure to be a sphalerite derivative identical to that of stannoidite. Omariniite is named after Dr. Ricardo Héctor Omarini (1946–2015), Professor at the University of Salta, for his numerous contributions to the geology of Argentina.
Fluorine-, boron- and magnesium-rich metamorphosed xenoliths occur in the Campanian Ignimbrite deposits at Fiano (southern Italy), at ∼50 km northeast of the sourced volcanic area. These rocks originated from Mesozoic limestones of the Campanian Apennines, embedded in a fluid flow. The Fiano xenoliths studied consist of ten fluorophlogopite-bearing calc-silicate rocks and five carbonate xenoliths, characterized by combining mineralogical analyses with whole-rock and stable isotope data. The micaceous xenoliths are composed of abundant idiomorphic fluorophlogopite, widespread fluorite, F-rich chondrodite, fluoborite, diopside, Fe(Mg)-oxides, calcite, humite, K-bearing fluoro-richterite and grossular. Of the five mica-free xenoliths, two are calcite marbles, containing subordinate fluorite and hematite, and three are weakly metamorphosed carbonates, composed only of calcite. The crystal structure and composition of fluorophlogopite approach that of the end-member. The Fiano xenoliths are enriched in trace elements with respect to the primary limestones. Comparisons between the rare-earth element (REE) patterns of the Fiano xenoliths and those of both Campanian Ignimbrite and Somma-Vesuvius marble and carbonate xenoliths showthat the Fiano pattern overlaps that of Somma-Vesuvius marble and carbonate xenoliths, and reproduces the trend of Campanian Ignimbrite rocks. Values of δ13C and δ18O depict the same trend of depletion in the heavy isotopes observed in the Somma-Vesuvius nodules, and is related to thermometamorphism. Trace-element distribution, paragenesis, stable isotope geochemistry and data modelling point to infiltration of steam enriched in F, B,Mg and As into carbonate rocks at a temperature of ∼300–450°C during the emplacement of the Campanian Ignimbrite.
The crystal structure of karibibite, Fe33+(As3+O2)4(As23+O5)(OH), from the Urucum mine (Minas Gerais, Brazil), was solved and refined from electron diffraction tomography data [R1 = 18.8% for F > 4σ(F)] and further confirmed by synchrotron X-ray diffraction and density functional theory (DFT) calculations. The mineral is orthorhombic, space group Pnma and unit-cell parameters (synchrotron X-ray diffraction) are a = 7.2558(3), b = 27.992(1), c = 6.5243 (3) Å, V = 1325.10(8) Å3, Z = 4. The crystal structure of karibibbite consists of bands of Fe3+O6 octahedra running along a framed by two chains of AsO3 trigonal pyramids at each side, and along c by As2O5 dimers above and below. Each band is composed of ribbons of three edge-sharing Fe3+O6 octahedra, apex-connected with other ribbons in order to form a kinked band running along a. The atoms As(2) and As(3), each showing trigonal pyramidal coordination by O, share the O(4) atom to form a dimer. In turn, dimers are connected by the O(3) atoms, defining a zig-zag chain of overall (As3+O2)n-n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2)n-n chains. The simultaneous presence of arsenite chains and dimers is previously unknown in compounds with As3+. The lone-electron pairs (4s2) of the As(2) and As(3) atoms project into the interlayer located at y = 0 and y = ½, yielding probable weak interactions with the O atoms of the facing (AsO2) chain.
The DFT calculations show that the Fe atoms have maximum spin polarization, consistent with the Fe3+ state.
The three-dimensional distribution of melt in partially molten synthetic samples compositionally corresponding to diopside (90 wt.%)–anorthite (10 wt.%) and doped with PbO, WO3, MoO3, or Cs2O to enhance contrast was studied by X-ray computed tomography (CT) with synchrotron radiation. The heavy elements were strongly concentrated in the melt and contributed to an increase of the X-ray linear attenuation coefficient (LAC) of it. PbO was found to be compatible with silicate melt (>20 wt.% in solution) and incompatible with diopside crystals. Other oxides WO3 (∼10 wt.%), MoO3 (∼5 wt.%) and Cs2O (< 5 wt.%) are also soluble only in the melt. Such doping is useful not only for LAC control in X-ray CT measurements, but also for systematic control of the structure (wetting properties, distribution and connectivity) of partial melt. This technique gives basic information for discussion of the 3D distribution of partial melt having different wetting properties. As PbO was most effective in visualization of the diopside–anorthite partially molten system, CT images of the PbO-bearing sample were used for further 3D investigation of distribution. A distribution of dihedral angles at solid-melt-solid triple junctions ranging from 22 to 55° was observed with the 3D data. This range in angle distribution was probably caused by anisotropy of crystals and the result supports the argument that there is some limitation in a theoretical framework of stereology which estimates the 3D structure based on 2D observations. Investigators have begun to apply X-ray CT to the study of the 3D distribution of partial melts in rocks using synchrotron radiation. Our study on the effect of doping is one approach for developing a technique to investigate 3D melt distribution.
Dehydration of silanol and molecular water in 60 agates from 12 hosts with ages between 23 to 2717 Ma has been investigated using desiccators and high-temperature furnace heating. There are wide differences in the water data obtained under uncontrolled and fixed atmospheric water vapour pressure conditions. After agate acclimatization at 20°C and 46% relative humidity, the total water (silanol and molecular) was determined in powders and mini-cuboids by heating samples at 1200°C. Agates from hosts < 180 Ma all showed a greater mass loss using powders and demonstrate that after prolonged high-temperature heating, silanol water is partially-retained by the mini-cuboids. Desiccator dehydration of powders and slabs shows that powder preparation can produce water losses; this is particularly relevant in agates from hosts < 180 Ma. The identified problems have consequences for water quantification in agate and chalcedony using infrared or thermogravimetric techniques. Mobile and total water in agate is considered in relation to host-rock age, mogánite content and crystallite size. Links are observed between the various identified water contents allowing comment on quartz development and agate genesis. The water data also supports previous claims that agates from New Zealand and Brazil were formed long after their host.
The determination of reliable weathering/dissolution rates for cement phases is of fundamental importance for the modelling of the temporal evolution of both radioactive waste repositories and CO2 geological storage sites (e.g. waste matrix, plug in boreholes). Here, the dissolution kinetics of AFm-Cl (hydrated calcium aluminates containing interlayer Cl) has been studied using flow-through experiments conducted at pH values ranging from 9.2 to 13. Mineralogical (XRD) and chemical (EPMA, TEM) analyses have been performed to determine the evolution of the phases during the dissolution experiments. For pH values between 10 and 13, the dissolution of AFm-Cl is congruent (i.e. Ca/Al ratios close to 2 both for solids and outlet concentrations). In contrast, the precipitation of amorphous Al-phases and possibly amorphous mixed Al/Ca phases is observed at pH 9.2, leading to Ca/Al ratios in the outlet solutions higher than those of the initial solid. Therefore, at pH 9.2, even if Cl–/OH– exchange occurs, estimation of dissolution rate from released Cl appears to be the best proxy. Dissolution rates were normalized to the final specific surface areas (ranging from 6.1 to 35.4 m2 g−1). Dissolution rate appears to be pH-independent and therefore the far-from-equilibrium dissolution rate at room temperature is expressed as: logR(mol m–2 s–1) = –9.23 ± 0.18
This paper presents a microbeam (electron microprobe, Raman spectroscopic and X-ray microdiffraction) study of cancrinite-group minerals of relevance to alkaline igneous rocks. A solid solution is known to exist between cancrinite and vishnevite with the principal substitutions being CO32- by SO42- and Ca for Na. In the present study, several intermediate members of the cancrinite–vishnevite series from a syenitic intrusion at Cinder Lake (Manitoba, Canada), were used to examine how chemical variations in this series affect their spectroscopic and structural characteristics. The Cinder Lake samples deviate from the ideal cancrinite-vishnevite binary owing to the presence of cation vacancies. The only substituent elements detectable by electron microprobe are K, Sr and Fe (0.03-0.70, 0-0.85 and 0-0.45 wt.% respective oxides). The following Raman bands are present in the spectra of these minerals: ∼631 cm-1 and ∼984-986 cm-1 [SO42- vibration modes]; ∼720-774 cm -1 and ∼1045-1060 cm -1 [CO32- vibration modes]; and ∼3540 cm -1 and 3591 cm -1 [H2O vibration modes]. Our study shows a clear relationship between the chemical composition and Raman characteristics of intermediate members of the cancrinite-vishnevite series, especially with regard to stretching modes of the CO32- and SO42- anions. From cancrinite-poor (Ccn65) to cancrinite-dominant (Ccn913) compositions, the SO42- vibration modes disappear from the Raman spectrum, giving way to CO32- modes. X-ray microdiffraction results show a decrease in unit-cell parameters towards cancrinite-dominant compositions: a = 12.664 (1) Å, c = 5.173(1) Å for vishnevite (Ccn22); a = 12.613 (1) Å, c = 5.132(1) Å for cancrinite (Ccn71). Our results demonstrate that Raman spectroscopy and X-ray microdiffraction are effective for in situ identification of microscopic grains of cancrinite-vishnevite where other methods (e.g. infrared spectroscopy) are inapplicable. The petrogenetic implications of cancrinite-vishnevite relations for tracing early- to late-stage evolution of alkaline magmas are discussed.
IMA Commission on New Minerals, Nomenclature and Classification (CNMNC) Newsletter 39