The crystal structure of the fibrous mineral arangasite, Al2F(PO4)(SO4)·9H2O from the Alyaskitovoje deposit, Eastern Yakutiya, Russia, was solved using low-temperature single-crystal data from synchrotron radiation and refined against F2 to R = 9.8%. Arangasite crystallizes in the monoclinic space group P2/a, with unit-cell parameters a = 7.073(1), b = 9.634(2), c = 10.827(2) Å, β = 100.40(1)°, V = 725.7(7) Å3 and Z = 2. The positions of all the independent H atoms were obtained by difference- Fourier techniques and refined in an isotropic approximation. The arangasite crystal structure is built from one-dimensional chains of Al octahedra and PO4 tetrahedra sharing vertices, quasi-isolated SO4 tetrahedra and H2O molecules. All O atoms are involved in the system of H bonding, acting as donors and/or acceptors. Hydrogen bonding serves as the only mechanism providing linkage between the main structural fragments, thus maintaining the framework. Chains of corner-sharing Al octahedra and P tetrahedra in the arangasite structure are topologically identical to the chains built from (Fe, Al) octahedra and P tetrahedra in the crystal structure of destinezite, Fe2(OH)(PO4)(SO4)·6H2O. It has been shown that in spite of very similar chemical formulae, arangasite and sanjuanite, Al2(OH)(PO4)(SO4)·9H2O, are not isotypic.

Zeolites K-F and W (EDI and MER types) were synthesized hydrothermally using a natural rock as raw material. Chemical treatments were carried out on a diatomitic rock (containing opaline silica) from Crotone (Calabria, Italy) in order to separate/obtain potassium silicate, a reagent necessary for synthesizing zeolites. Synthesis experiments were performed by mixing the obtained siliceous solution with potassium hydroxide and alumina in varying proportions at 150°C and room pressure. Four synthesis series were performed to form zeolite K-F (EDI) and zeolite W (MER).

The chemical-physical and morphological characterization of the zeolite phases were carried out. Cell parameters were calculated using the Rietveld method. Infrared, thermal and nuclear magnetic resonance (29Si) experiments confirmed the high quality of the zeolite products. The amorphous phase in the synthesis powders was estimated with quantitative phase analysis using the combined Rietveld and reference intensity ratio methods.

The evolution with pressure of the CH4 vibrational modes related to C–H stretching has been followed by in situ Raman spectroscopy on a single crystal of cubic melanophlogite from Varano Marchesi (Parma, Italy) containing only CH4 in the cages. The sample was compressed hydrostatically in a diamond anvil cell up to 6.5 GPa, using a non-penetrating P-transmitting medium. Two modes at 2900 and 2910 cm–1 (ν1 and ν2) were followed in response to the applied pressure, corresponding to C–H stretching of CH4 enclathrated in the 51262 and 512 cages, respectively. A change in slope of the frequency vs. P linear trend of the sharper peak at 2900 cm–1, observed between 1 and 1.5 GPa, is interpreted as evidence of the P-induced cubic to tetragonal transition, previously observed by X-ray diffraction at P ≥ 1.2 GPa. At pressures below the transition, the shift with P of the CH4 modes is comparable to that observed in methane ice hydrate, which becomes hexagonal at P ≥ 0.9 GPa however. The ratio of the integrated areas of the two C–H stretching Raman peaks does not change significantly with pressure across the transition. At P ≥ 5.1 GPa, a shoulder appears, close to the n1 peak, along with a slight change in slope of peak shift and peak broadening. The shoulder is maintained in decompression down to P = 4.4 GPa, showing slight hysteresis. At the same pressures however, X-ray diffraction shows no evidence of a phase transition, suggesting that a rearrangement of CH4 configuration occurs, without any effect on the tetrahedral framework.

Synthesis and solubility studies of onoratoite have been undertaken to determine the role of this rare secondary phase in the immobilization of Sb and the conditions responsible for its formation in the supergene zone. Solubility studies were undertaken at 298.15 K. A value of ΔGfθ (Sb8O11Cl2, s, 298.15 K) = –2576 ±12 kJ mol–1 was derived. Calculations involving sénarmontite, Sb2O3, klebelsbergite, Sb4O4SO4(OH)2 and schafarzikite, FeSb2O4, show that onoratoite is a thermodynamically stable phase only at negligible activities of SO42–(aq) and low activities of Fe2+(aq), at low pH and very high activities of Cl–(aq). This explains why onoratoite is such a rare secondary phase and why it cannot exert any significant influence on the dispersion of Sb in the supergene environment.

Clay/polymer nanocomposites (CPN) exhibit improved technical properties compared to their microand macro-counterparts. Nevertheless, thermal degradation of CPN may limit the applicability of these hybrid materials. In this paper accelerated ageing (110°C and 150°C) was performed in injection moulded pure polyamide 66 (PA66-S-0 samples) and polyamide 66 reinforced with 5 wt.% sepiolite (PA66-S-5 samples) CPN. Polymer degradation was monitored by the amount of newly formed carbonyl bonds. The carbonyl indices obtained indicate that degradation occurs to a greater extent as the temperature of the ageing process increases. Moreover, the degradation increases with time at the highest treatment temperature (150°C). On the other hand, the occurrence of carbonaceous silicates in the nanocomposite samples at high temperatures yields greater thermal stability of sepiolite/PA66 nanocomposites compared to pure PA66. Furthermore, the sepiolite nanofibres maintain their position in the reticulated semicrystalline structure. In agreement with those results, differential scanning calorimetry and X-ray diffraction analyses show that the motion of the amide groups in the polymer chains are constrained by the well dispersed sepiolite.

A new mineral, yurmarinite, Na7(Fe3+,Mg,Cu)4(AsO4)6, occurs in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with hatertite, bradaczekite, johillerite, hematite, tenorite, tilasite and aphthitalite. Yurmarinite occurs as well-shaped, equant crystals up to 0.3 mm in size, their clusters up to 0.5 mm and thin, interrupted crystal crusts up to 3 mm × 3 mm on volcanic scoria. Crystal forms are {101}, {011}, {100}, {110} and {001}. Yurmarinite is transparent, pale green or pale yellowish green to colourless. The lustre is vitreous and the mineral is brittle. The Mohs hardness is ∼4½. One direction of imperfect cleavage was observed, the fracture is uneven. D(calc.) is 4.00 g cm−3. Yurmarinite is optically uniaxial (−), ω = 1.748(5), ε = 1.720(3). The Raman spectrum is given. The chemical composition (wt.%, electron microprobe data) is Na2O 16.85, K2O 0.97, CaO 1.28, MgO 2.33, MnO 0.05, CuO 3.17, ZnO 0.97, Al2O3 0.99, Fe2O3 16.44, TiO2 0.06, P2O5 0.12, V2O5 0.08, As2O5 56.68, total 99.89. The empirical formula, calculated on the basis of 24 O atoms per formula unit, is (Na6.55Ca0.28K0.22)S7.05(Fe2.483+Mg0.70Cu0.48Al0.23Zn0.14Ti0.01Mn0.01)S4.05(As5.94P0.02V0.01)S5.97O24. Yurmarinite is rhombohedral, Rc, a = 13.7444(2), c = 18.3077(3) Å, V = 2995.13(8) Å3, Z = 6. The strongest reflections in the X-ray powder pattern [d, Å (I)(hkl)] are: 7.28(45)(012); 4.375(33)(211); 3.440(35)(220); 3.217(36)(131,214); 2.999(30)(223); 2.841(100)(125); 2.598(43)(410). The crystal structure was solved from single-crystal X-ray diffraction data to R = 0.0230. The structure is based on a 3D heteropolyhedral framework formed by M4O18 clusters (M = Fe3+ > Mg,Cu) linked with AsO4 tetrahedra. Sodium atoms occupy two octahedrally coordinated sites in the voids of the framework. In terms of structure, yurmarinite is unique among minerals but isotypic with several synthetic compounds with the general formula (Na7–x☐x)(M3+x3+M1–x2+)(T5+O4)2 in which T = As or P, M3+ = Fe or Al, M2+ = Fe and 0 ≤ x ≤ 1. The mineral is named in honour of the Russian mineralogist, petrologist and specialist in studies of ore deposits, Professor Yuriy B. Marin (b. 1939). The paper also contains a description of the Arsenathaya fumarole and an overview of arsenate minerals formed in volcanic exhalations.

The effects of the presence of ten organic ligands and common pH buffering agents – acetate, oxalate, tartrate, citrate, phthalate, EDTA, carbonate, TRIS, phosphate and borate – on aqueous Si concentration measurements made using the common molybdate blue method were quantified. The concentrations of these additives ranged from 0.01 to 0.1 mol/kg in the measured aqueous solutions. Whereas measured Si concentrations were not affected by the presence of up to 0.1 mol/kg acetate, hydrogen phthalate or TRIS, the presence of 0.1 mol/kg of all other selected additives altered substantially the measured Si concentrations using the molybdate blue method. For example the presence of 0.1 mol/kg of citrate, EDTA, and hydrogen phosphate decreased the ratio of measured to true Si concentrations to ~0.05. These variations are interpreted to stem from the formation of competing aqueous complexes in the aqueous phase limiting the formation of the characteristically blue SiMo12O404– complex.

Putnisite, SrCa4Cr83+ (CO7)8SO4(OH)16·25H2O, is a new mineral from the Polar Bear peninsula, Southern Lake Cowan, Western Australia, Australia. The mineral forms isolated pseudocubic crystals up to 0.5 mm in size in a matrix composed of quartz and a near amorphous Cr silicate. Putnisite is translucent, with a pink streak and vitreous lustre. It is brittle and shows one excellent and two good cleavages parallel to {100}, {010} and {001}. The fracture is uneven and the Mohs hardness 1½−2. The measured density is 2.20(3) g/cm3 and the calculated density based on the empirical formula is 2.23 g/cm3. Optically, putnisite is biaxial negative, with α = 1.552(3), β = 1.583(3) and γ = 1.599(3) (measured in white light). The optical orientation is uncertain and pleochroism is distinct: X pale bluish grey, Y pale purple, Z pale purple. Putnisite is orthorhombic, space group Pnma, with a = 15.351(3), b = 20.421(4) Å, c = 18.270(4) Å, V = 5727(2) Å3 (single-crystal data), and Z = 4. The strongest five lines in the X-ray powder diffraction pattern are [d(Å)(I)(hkl)]: 13.577 (100) (011), 7.659 (80) (200), 6.667 (43) (211), 5.084 (19) (222, 230), 3.689 (16) (411). Electron microprobe analysis (EMPA) gave (wt.%): Na2O 0.17, MgO 0.08, CaO 10.81, SrO 5.72, BaO 0.12, CuO 0.29, Cr2O3 31.13, SO3 3.95, SiO2 0.08, Cl− 0.28, CO2calc 17.94, H2Ocalc 30.30, O=Cl−0.06, total 100.81. The empirical formula, based on O + Cl = 69, is: Cr8.023+Ca3.78Sr1.08Na0.11Cu0.072+Mg0.04Ba0.02[(SO4)0.96(SiO4)0.03]0.99 (CO3)7.98(OH)16.19Cl0.15·24.84H2O. The crystal structure was determined from single-crystal X-ray diffraction data (MoKα, CCD area detector and refined to R1 = 5.84% for 3181 reflections with F0 > 4σF. Cr(OH)4O2 octahedra link by edge-sharing to form an eight-membered ring. A 10-coordinated Sr2+ cation lies at the centre of each ring. The rings are decorated by CO3 triangles, each of which links by corner-sharing to two Cr(OH)4O2 octahedra. Rings are linked by Ca(H2O)4O4 polyhedra to form a sheet parallel to (100). Adjacent sheets are joined along [100] by corner-sharing SO4 tetrahedra. H2O molecules occupy channels that run along [100] and interstices between slabs. Moderate to weak hydrogen bonding provides additional linkage between slabs.

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.

A multi-anvil press was combined with monochromatic synchrotron X-ray radiation to investigate the synthesis, at high-pressure high-temperature conditions, of a recoverable bulk sample of Fe4O5, from an initial magnetite, Fe3O4, sample. Angle-dispersive diffraction patterns show that magnetite firstly breaks down, into an assemblage of hematite (Fe2O3) + Fe4O5. By increasing temperature at constant load, hematite disappears progressively by either reduction or by melting, or a combination of both. In the final product only Fe4O5 remains and, in the absence of hematite, can be kept stable and be recovered at ambient conditions. Refinement of the diffraction patterns at standard conditions demonstrate that Fe4O5 has the Sr2Tl2O5-type-structure with space group Cmcm and a = 2.8964(2) Å, b = 9.8225(6) Åand c = 12.5808(7) Å. This structure-type and related members of a homologous series, offer the possibility that the general sequence of AB(2+n)X(4+n) chemistries could, under certain conditions, be extended to accommodate prevalent oxygen fugacity or, indeed, other ordered stoichiometries through extension of the c axis by the addition of FeO6 octahedral blocks. This structural series, as in other systems, offers possibilities of hosting charge-transfer, Jahn-Teller and other electronic phenomena − as well as supporting metric distortions. Each of these possibilities is highlighted through illustration and extension to related structure-types, most notably from those of the spinels, post-spinels and post-perovskites.

We show how different aspects of a model of the complex disordered structure of wüstite, Fe1−xO, affect the pair distribution function (PDF) and powder diffraction pattern. The aim is to assess the efficacy of using these techniques to determine details of local structure. The different aspects include the nature of the individual defect clusters, the nature of the paracrystalline superlattice on which they are distributed and the ‘size-effect’ relaxation of the basic rocksalt FeO matrix around the defects. The results show that PDF data are sensitive to those aspects of the models that have a significant effect on the populations of interatomic spacings but are less able to determine correlation structures in the samples if these do not have a substantial interaction with interatomic separations.

Supersaturation-Nucleation-Time (S-N-T) diagrams are shown to be a useful tool to predict nucleation during reactive-transport processes in porous media. Such diagrams can be determined experimentally or estimated from theoretical calculations based on classical nucleation theory. With this aim, a ‘pragmatic’ understanding of the nucleation rate equation is adopted here and the meaning and magnitude of the interfacial tension and induction time discussed. Theoretical diagrams and experimental data are shown to match fairly well as long as there is an appropriate choice of the ‘relevant’ volume for induction-time calculations.

An atypical asbestiform sepiolite occurrence with exceptionally long fibres wrapped by a sheath of aliphatic hydrocarbons was found in the Gressoney Valley (Italian Western Alps) while monitoring asbestos presence in outcrops of serpentinite rocks. Microscopic and Fourier transform infrared analyses proved that these fibres, apparently up to several cm long, are formed by bundles of thinner fibrils (average length: 150 μm) potentially dispersible in the environment. When observed using transmission electron microscopy these fibrils show a rhomboidal to parallelogram cross section (<1 μm), of which surfaces are covered mostly by an aliphatic hydrocarbon film – an association not reported in the literature. The sepiolite fibrils and their organic coating probably originated in sequential steps from precipitation of Si/Mg rich hydrothermal fluids, resulting from serpentinization of olivine and clinopyroxene and a Fischer-Tropsch-type reaction. The presence of hydrocarbons has serious implications for the sepiolite habit, as the organic wrap interacts with the fibril’s surface reducing the amount of adsorbed water and favouring the fragmentation of thicker units into thinner ones, due to an ‘opening’ process implying separation along z and cleavage on (110). This defibrillation mechanism, coupled with the extraordinary length, further increases the aspect ratio of these fibrils (length/width ≫3) thus amplifying their potential danger for human health when dispersed in air and inhaled.

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.

Polycrystalline, cubic 13C diamond was synthesized from amorphous carbon in the Kawai-type multianvil apparatus at 21 GPa and at a temperature greater than 2350ºC. The polycrystalline diamond was homogeneous with a small grain size (10–20 μm) and a sharp Raman peak, and thereby was suitable as a pressure sensor for the experiments in a hydrothermal diamond anvil cell. Pressure- and temperature-dependence of the Raman shift of the synthesized 13C diamond was investigated in situ at simultaneous high pressures and high temperatures in the hydrothermal diamond anvil cell, using the ruby fluorescence line, quartz Raman shift and H2O phase transitions as pressure references. It was observed that the frequency shift with pressure is independent of temperature and vice versa up to 500ºC and 4.2 GPa. The present study indicates that the 13C diamond Raman shift can be used for pressure determination with an accuracy better than ±0.3 GPa under the conditions examined.

The 3.5 Ga Bon Accord Ni deposit occurs within the lowest serpentinized mafic–ultramafic lavas of the Barberton Greenstone Belt (South Africa). Though now completely mined out, it comprised a suite of rare Ni-rich minerals that led to its interpretation as either an extraterrestrial body or as an oxidized fragment of Fe-Ni alloy originating from the terrestrial core. In this study, we draw on detailed petrographic observation and mineral chemical data, as well as previous work, to re-evaluate these ideas. The balance of evidence, from thin section (<1 mm) to regional (∼10s of km) scales, appears to support an alternative origin for Bon Accord, possibly as an oxidized Ni-sulfide deposit formed in association with ocean floor komatiite eruptions.

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.

Ferromanganese nodules have been recognized widely as potentially important resources for strategic metals. However it remains unclear if the formation of these nodules is purely an abiotic process or if microorganisms are involved in their formation. To determine the microbial contributions, detailed organic geochemical analyses were performed on ferromanganese nodules collected from across the southwest Indian Ocean. These analyses reveal the presence of specific terrestrial, marine and petroleum derived biomarkers, consistent with formation in a marine setting with a substantial influx of terrestrially derived (higher plant detritus) and naturally occurring petroleum-related organic matter. In contrast, only trace amounts of general bacterial biomarkers, commonly present in these types of depositional environments, were present. This indicates that the formation of these ferromanganese nodules is predominantly an abiotic process although a minor contribution from microbial mediated processes to the growth of these nodules cannot be completely ruled out.