Calcium and Magnesium‐bearing Sabugalite from the Tono Uranium Deposit,Central Japan

Calcium and magnesium‐bearing sabugalite occurs as aggregations of yellowish platy crystals in veinlets or druses in conglomerate from the oxidized parts of the Tono uranium deposit, Central Japan. X‐ray powder diffractometry of this mineral has reflections consistent with previous powder diffraction data of sabugalite. It is included in the monoclinic system with space group C2/m and calculated cell parameters of a = 19.68Å, b = 9.89Å, c = 9.82Å α = γ = 90°, β‐96.93° and V = 1897.83ų. Chemical analysis yields a formula of (Ca_0.10 Mg_0.09)_Σ0.19Al_0.53(UO₂)_2.04((PO₄)_1.99(AsO₄)_0.01)_Σ2.00·11.22H₂O. EMPA mapping shows that the mineral is compositionally uniform with no micron‐scale layering. Charge of cations including Ca and Mg in the cation‐H₂O layer is 1.98 being identical to that of autunite group minerals. This suggests that the charge balance in the cation‐H₂O layer of the mineral could be made by the alkaline earth or alkaline elements rather than by hydrogen ions.     

Transformation of curite into metaautunite paragenesis and electrokinetic properties

Genesis of metaautinute [Ca(UO₂/PO₄)₂ · 7H₂O] starting from curite hints at the existence of an intermediate hydrogen autunite stage [HUO₂PO₄ · 4H₂O]. The substitution of protons in hydrogen autunite by Ca²⁺ ions is proved by electrokinetic measurements. As a consequence of the similarity between X-ray powder patterns of hydrogen autunite and meta-autunite a glycolation method has been applied in order to distinguish the two species. The cell dimensions have been determined from Guinier X-ray diffraction patterns. Both minerals are tetragonal with a=6.981±0.005 Å and c=8.448±0.005 Å for metaautunite and a=7.084±0.005 Å and c=8.777±0.005 Å for hydrogen autunite. For both minerals, the zeta-potential is mostly negative and is strongly influenced by temperature, pH and concentration of cations in the suspension. The surface conductivity has been calculated from the value of the zetapotential. The electrokinetic properties of metaautunite are very similar to those of metatorbernite.     

Synthesis,crystallographic data,solubility and electrokinetic properties of meta-zeunerite,meta-kirchheimerite and nickel-uranylarsenate

{M[UO₂¦AsO₄]₂ · nH₂O} with M=Cu²⁺, Co²⁺, Ni²⁺ has been synthesized from reagent grade chemicals and by ion exchange of trögerite {HUO₂AsO₄ · 4 H₂O}. Synthetic meta-zeunerite (M=Cu²⁺), meta-kirchheimerite (M=Co²⁺) and nickel-uranylarsenate are all tetragonal. The cell parameters determined from Guinier-Hägg diffraction data for {Cu[UO₂¦AsO₄]₂ · 8 H₂O} are a=b=7.10 Å and c=17.42 Å, with Z=2 and the measured density 3.70 g cm^?3. The cell parameters for {Co[UO₂¦AsO₄]₂ · 7 H₂O} and {Ni[UO²¦AsO⁴]² · 7 H₂O} are a=b=20.25 Å and c=17.20 Å, with Z=16 and the measured density 3.82 and 3.74 g cm^?3, respectively. The solubility products for synthetic Cu-, Co- and Ni-uranylarsenate at 25° C are 10^?49.20, 10^?45.34 and 10^?45.10, respectively. The zeta-potential remains negative between pH=2 and pH=9 and is strongly affected by the presence of different cations.     

Pseudosinhalite: discovery of the hydrous MgAl-borate as a new mineral in the Tayozhnoye, Siberia, skarn deposit

After its initial synthesis as the new compound Mg₂Al₃B₂O₉(OH) (Daniels et al. 1997) pseudosinhalite has now been discovered as a new mineral. It occurs, together with hydrotalcite, as a replacement product of sinhalite, MgAlBO₄, in an impure marble of the contact metasomatic iron boron deposit of Tayozhnoye in the Aldan Shield of Siberia. Its chemical composition determined by electron microprobe is (wt%): Al₂O₃ 46.88; MgO 25.12; FeO 1.99; B₂O₃ (calculated) 21.75; H₂O (calculated) 2.81 giving a total of 98.55 and leading to the empirical formula (Mg_2.00 Fe²⁺ _0.09)_Σ=2.09 Al_2.94 B₂O₉(OH). The small deviation from the ideal stoichiometry with (Mg?+?Fe²⁺):Al?≠?2:3 may be caused by either solid solution towards, or submicroscopic interlayering with lamellae of, the structurally similar mineral sinhalite. The underlying substitution involving also B and H would be (Mg?+?Fe)+?B=Al+2H. Pseudosinhalite is monoclinic, space group P2₁/c, with a=7.49(1), b=4.33(1), c=9.85(2) Å; β=110.7(1)°; V?=?299(1) ų; Z?=?2. Calculated density is 3.508?g/cm³. Pseudosinhalite is colourless with white streak and has a vitreous lustre. It is transparent; no fluorescence was detected. There is no cleavage and parting; fractures are concoidal. Optical constants could not be measured properly due to polysynthetic microtwinning, but α<1.72<γ. For synthetic pseudosinhalite α=1.691(1); β=1.713(1); γ=1.730(1); Δ=0.039; 2?V=80°. The temperature of pseudosinhalite formation was below about 400?°C at low pressures and with a hydrous, CO₂-bearing fluid participating in the reaction.     

Crystal chemical characteristics of α-CaSi2O5, a new high pressure calcium silicate with five-coordinated silicon synthesized at 1500°C and 10 GPa

The crystal structure of α-CaSi₂O₅ synthesized at conditions of 1500°C and 10 GPa, has been solved and refined in centrosymmetric space group P , using single crystal X-ray diffraction data. The composition (Z=4) and unit cell are Ca_1.02Si_1.99O₅ by EPMA analysis and a=7.243(2) Å, b=7.546(4) Å, c=6.501(4) Å, α=81.43(5)°, β=84.82(4)°, γ=69.60(3)°, V=329.5(3) ų, yielding the density value, 3.55 g/cm³. The structure is closely related to that of titanite, CaTiSiO₅ and features the square-pyramid five-fold coordination of silicon by oxygen. The ionic radius for five-coordinated Si calculated from the bond distances is 0.33 Å. The substantial deviation of valence sum for Ca indicates the existence of local strain and the instability of α-CaSi₂O₅ at room pressure.     

Crystal structure of xinganite

Xinganite is a new REE-Be-rich silicate discovered in China. Its ideal formula is: (Y, Ce)Be SiO₄ OH. The mineral is of monoclinic system. The intensity data were collected with a single-crystal four-circle diffractometer. The lattice parameters are: a=4.7681 (± 0.00263) Å,b=7.7657 (± 0.00686) Å, c=9.9301 (± 0.00639) Å; α =90°, β=90.171° (±0.0053°), γ=90° space group p2¹/c;,Z=4. The crystal structure has been determined by direct methods and electron density synthesis methods. The least squares refinement gave a final discrepancy indexR=0.086. The crystal structural analysis shows that xinganite is of datolite-type structure.     

Crystallographic,Mössbauer and electrokinetic study of synthetic lipscombite

The transformation of vivianite and the direct synthesis starting from pure chemicals lead to the formation of lipscombite {Fe _x ²⁺ Fe _3?x ³⁺ [(OH)_3?x/(PO₄)₂]} with varying Fe²⁺/Fe³⁺ molar ratios. The influence of this ratio on the Mössbauer spectra, solubility, electrokinetic potential and infrared spectra has been studied. By means of Mössbauer spectroscopy, the distribution of the Fe²⁺ and Fe³⁺ ions between the octahedral sites I and II has been investigated. The unit cell dimensions have been determined from Guinier-Hägg X-ray diffraction patterns. The crystal system is tetragonal for synthetic lipscombite with a=5.3020±0.0005 Å and c=12.8800±0.0005 Å. Lipscombite has been found to show a negative and time-dependent zeta-potential which, moreover, is influenced by the pH of the suspension and the Fe²⁺/Fe³⁺ molar ratio. An explanation of the time-dependence of the zeta-potential on variations of solubility is proposed. Infrared absorption spectrum only is characterized by two absorption bands: v _OH(3,500 cm^?1) and v _P?O(1,100-960 cm^?1). The density at 25° C is determined in toluene as 3.36±0.01 g·cm^?3.     

Celestite (SrSO4(s)) solubility in water,seawater and NaCl solution

Celestite solubility measurements have been conducted in pure water at temperatures from 10 to 90°C. Equilibrium was achieved with respect to a crystalline solid phase from both undersaturated and supersaturated solutions. The measurements show that the solubility undergoes a maximum near 20°C. LogK values for the solubility reaction are adequately described by the following expression over the temperature range 283.15 to 363.15 K: −logK= −35.3106+0.00422837T+318312/T²+14.99586 logT.The following thennodynamic values for the dissolution reaction of SrSO_4(s), at 25°C have been derived: ΔG_R⁰ = 37852 ± 30 Jmol⁻¹ΔH_R⁰ = −1668±920Jmol⁻¹ΔS_R⁰= −132.6±3.2JK^−1mol−1Celestite solubility measurements were also determined in NaCl solutions up to 5 m concentration and from 10 to 40°C. These data are in good agreement with the work of StrÜbel (1966), who reports solubility measurements to temperatures of 100°C.The application of the Pitzer relations and the solubility constants determined in this study to calculate celestite solubility in NaCl solutions yields excellent agreement between predicted values and experimental measurements over the entire range of temperature and NaCl concentration conditions. For the limited number of solubility measurements in seawater-type solutions and mixed-salt brines, the agreement using the Pitzer relations is within three percent of the measured solubility.     

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.     

The thermal expansion of anhydrite to 1000° C

The thermal expansion of anhydrite, CaSO₄, has been measured from 22° to 1,000° C by X-ray diffraction, using the Guinier-Lenné heating powder camera. The heating patterns were calibrated with Guinier-Hägg patterns at 25° C, using quartz as internal standard. Heating experiments were run on natural anhydrite (Bancroft, Ontario), which at room temperature has lattice constants in close agreement with those of synthetic material. The orthorhombic unit cell at 22° C (space group Amma) has a=7.003 (1) Å, b=6.996 (2) Å and c=6.242 (1) Å, V=305.9 (2) ų. At room temperature, the thermal expansion coefficients α and β (α in °C^?1×10⁴, β in °C^?2×10⁸) are for a, 0.10, ?0.69; for b, 0.08, 0.19; for c, 0.18, 1.60; for V, 0.37, 1.14. Second-order coefficients provide an excellent fit over the whole range to 1,000° C.     

The origin of space group violations in a lunar orthopyroxene

The space group of an orthopyroxene (En₈₆) from a deep crustal lunar rock (sample 76535) that was previously reported as having space group P2₁ ca has been re-examined on an automated X-ray diffractometer. In addition to diffractions violating the b-glide of the conventional space group, Pbca (0kl,k-odd) reported in the earlier study, diffractions violating the a-glide of Pbca are also present. Careful examination of both the a-glide- and b-glide-violations shows them to be sharp, with no evidence of diffuse streaks parallel to a ^*, and with consistent intensities at several rotations about ψ. Diffractions violating the b-glide are in registry with the host, however, those violating the a-glide appear to be out of registry and result from a cell with a slightly longer a of about 18.4 Å, consistent with previous electron diffraction studies. The most reasonable explanation for the observed space group violations is that both the a- and b-glide violations result from ordering of Ca into (100) Guinier-Preston (G-P) zones that possess orthopyroxene topology, but have space group P2₁/c and a cell of a=18.4 Å, b=8.83 Å, c=5.18 Å, and β=90.0°; whereas the Cadepleted host has space group Pbca and a cell of a= 18.230(6) Å, b = 8.828(2) Å, and c=5.1946(9) Å. In addition to the G-P zones which may compose 12% or more of the sample, the crystal contains (100) lamellae of pigeonite, and other samples from the same rock contain lamellae of augite.     

Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.     

Abramovite, Pb2SnInBiS7, a new mineral species from fumaroles of the Kudryavy volcano, Kurile Islands, Russia

Abramovite, a new mineral species, has been found as fumarole crust on the Kudryavy volcano, Iturup Island, Kuriles, Russia. The mineral is associated with pyrrhotite, pyrite, würtzite, galena, halite, sylvite, and anhydrite. Abramovite occurs as tiny elongated lamellar crystals up to 1 mm long and 0.2 mm wide (average 300 × 50 μ m), which make up chaotic intergrowths in the narrow zone of fumarole crust formed at ～600°C. Most crystals are slightly striated along the elongation. The new mineral is silver gray, with a metallic luster and black streak. Under reflected light, abramovite is white with a yellowish gray hue. It has weak bireflectance; anisotropy is distinct without color effects. The chemical composition (electron microprobe) is as follows, wt %: 20.66 S, 0.98 Se, 0.01 Cu, 0.03 Cd, 11.40 In, 12.11 Sn, 37.11 Pb, 17.30 Bi; the total is 99.60. The empirical formula calculated on the basis of 12 atoms is Pb_1.92Sn_1.09In_1.06Bi_0.89(S_6.90Se_0.13)_7.03. The simplified formula is Pb₂SnInBiS₇. The strongest eight lines in the X-ray powder pattern [d, Å (I)(hkl)] are 5.90(36)(100), 3.90(100)(111), 3.84(71)(112), 3.166(26)(114), 2.921(33)(115), 2.902(16)(200), 2.329(15)(214), 2.186(18)(125). The selected area electron diffraction (SAED) patterns of abramovite are quite similar to those of the homologous cylindrite series minerals. The new mineral is characterized by noncommensurate structure composed of regularly alternated pseudotetragonal and pseudohexagonal sheets. The structure parameters determined from the SAED patterns and X-ray powder diffraction data for pseudotetragonal subcell are: a = 23.4(3), b = 5.77(2), c = 5.83(1) Å, α = 89.1(5) °, β = 89.9(7)°, γ = 91.5(7)°, V = 790(8) ų; for pseudohexagonal subcell: a = 23.6(3), b = 3.6(1), c = 6.2(1) Å, α = 91(2)°, β = 92(1)°, γ = 90(2)°, V = 532(10) ų. Abramovite is triclinic, space group P(1). The new mineral is named in honor of Russian mineralogist Dmitry Abramov. The type material of abramovite has been deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

Scolecite, Part I: Refinement of high-order data, separation of internal and external vibrational amplitudes from displacement parameters

A single crystal of scolecite, CaAl₂Si₃O₁₀· 3H₂O, was studied by X-ray diffraction methods at room temperature. The intensities were measured with MoKα radiation (λ=0.71069?Å) in a complete sphere of reflection up to sinθ/λ=0.9?Å^?1. The structure was refined in the pseudo-orthorhombic setting of space group F1d1 instead of the conventional setting Cc for better comparison with natrolite (Fdd2). The cell parameters are: a=18.502(1)?Å, b=18.974(2)?Å, c=6.525(1)?Å, β=90.615(7)°, V=2290.6(3)?ų, Z=8. A refinement of high-order diffraction data yielded residuals of R(F)=0.9%, R _w (F)=0.9%, GoF=1.73 for 1831 high-angle reflections (0.7≤sinθ/λ≤0.9?Å^?1) and R(F)=1.2%, R _w (F)=1.4%, GoF=3.22 for all 3478 independent reflections. In comparison with natrolite, the replacement of 2 Na⁺ by 1 Ca²⁺ and 1 H₂O leads to a reduction of symmetry from Fdd2 to F1d1. Each general atomic position in natrolite (except of Na) splits into two crystallographically independent positions in scolecite. The T?O distances and T?O?T angles of these two sites differ distinctly from each other due to the influence of the calcium ions on the framework. An unexpected result of our detailed analysis of the data is that the additional water molecule (O7) disturbs the symmetry of the framework to a greater extent than the replacement of Na⁺ by Ca²⁺. As a comparison of the displacement parameters indicates, the bonds within the tetrahedral framework and to the extraframework cations are stronger in scolecite than in natrolite. The isotropic U(equ) values of the framework atoms and extraframework cations are about 10% smaller in scolecite compared to natrolite. The same tendency is shown by the analysis of the internal vibrational amplitudes ΔU. The corresponding force constants are in the range of F=358 to 3367?Nm^?1 for the T?O bonds in scolecite (in natrolite: F=354 to 824?Nm^?1). The values of the force constants which determine the vibrations of the Ca ions and water molecules against the framework oxygen atoms lie in the range of F=33 to 1757?Nm^?1 (in natrolite: F=57 to 293?Nm^?1).     

Kulkeite,a new metamorphic phyllosilicate mineral: Ordered 1∶1 chlorite/talc mixed-layer

Kulkeite occurs as platy, colorless, porphyroblastic, single crystals up to 2 mm in size in a low-grade dolomite rock associated with a Triassic meta-evaporite series at Derrag, Tell Atlas, Algeria, It is associated with sodian aluminian talc, unusual chlorite polytypes, and both K and Na phlogopite. Kulkeite is optically biaxial, negative, n _x=1.552, n _y=1.5605, n _z=1.5610, 2V_z=24° (obs.). Based on microprobe analysis the empirical formula is (Na_0.38K_0.01Ca_0.01)(Mg_8.02Al_0.99)[Al_1.43Si_6.57O₂₀](OH)₁₀ with some variation in Na, Si, and tetrahedral Al. The crystals are monoclinic with a=5.319(1), b=9.195(2), c=23.897(10) Å, β=97° 1(3)′; Z=2; the calculated density is 2.70 g cm^?3. The four strongest lines in the X-ray powder pattern are (d, I, hkl): 7.90, 100, 003; 1.533, 100, 060; 7.42, 80, 002; 3.38, 80, 007; the 001 reflection with 23.7 Å has intensity 10. Transmission electron microscopy confirms the nature of a regular 1∶1 mixed-layer, which consists of 14 Å chlorite (clinochlore) sheets alternating with sheets of one-layer (9.5 Å) talc characterized by the lattice substitution NaAl→Si just as in the talc occurring as a discrete mineral co-existing with kulkeite. Kulkeite is intergrown with lamellae of clinochlore that represent two-layer and five-layer (70 Å) polytypes with optical birefringence exceeding the normal value for clinochlore by a factor of 3. The origin of kulkeite is due to low-grade metamorphism with temperatures probably not exceeding 400° C. As the clinochlore lamellae and sodian aluminian talc are found in mutual contact, kulkeite seems to represent a metastable mineral at least during the latest phase of metamorphism. However, at an earlier stage, prior to clinochlore formation, kulkeite might have been stable, and the incorporation of Na and Al into its talc component could indeed be the decisive factor for the formation of the mixed-layer.     

Synthesis and thermal stability of 2 \frac{1}{2}-octahedral sodium mica,NaMg2.5 (OH)2∫i4O10]

A new 2 \(\frac{1}{2}\) -octahedral sheet silicate, NaMg_2.5 Si₄O₁₀ (OH)₂, has been synthesized from oxide mixtures in the temperature range 500–600°C at pressures between 1 and 5 kb. The lattice parameters are a ₀ = 5.298 Å, b ₀ = 9.047 Å, c ₀ = 9.479 Å and ß=99.55°. X-ray data are given in the text. At temperatures above 605° C/1 kb and 630° C/5 kb, it decomposes to magnesiorichterite plus quartz.     

Microsommite: crystal chemistry, phase transitions, Ising model and Monte Carlo simulations

Microsommite, ideal formula [Na₄K₂(SO₄)] [Ca₂Cl₂][Si₆Al₆O₂₄], is a rare feldspathoid that occurs in volcanic products of Vesuvius. It belongs to the cancrinite–davyne group of minerals, presenting an ABAB… stacking sequence of layers that contain six-membered rings of tetrahedra, with Si and Al cations regularly alternating in the tetrahedral sites. The structure was refined in space group P6₃ to R=0.053 by means of single-crystal X-ray diffraction data. The cell parameters are a=22.161?Å=√3a _dav, c=5.358?Å=c _dav; Z=3. The superstructure arises due to the long-range ordering of extra-framework ions within the channels of the structure. This ordering progressively decreases with rising temperature until it is completely lost and microsommite transforms into davyne. The order–disorder transformation has been monitored in several crystals by means of X-ray superstructure reflections and the critical parameters T _c?≈?750?°C and β?≈?0.12 were obtained. The kinetics of the ordering process were followed at different temperatures and the activation energy was determined to be about 125?kJ?mol^?1. The continuous order–disorder phase transition in microsommite has been discussed on the basis of a two-dimensional Ising model in a triangular lattice with nn (nearest neighbours) and nnn (next-nearest neighbours) interactions. Such a model was simulated using a Monte Carlo technique. The theoretical model well matches the experimental data; two phase transitions were indicated by the simulated runs: at low temperature only one of the three sublattices begins to disorder, whereas the second transition involves all three sublattices.     

Laihunite—A new iron silicate mineral

Laihuite reported in the present paper is a new iron silicate mineral found in China with the following characteristics:

1. This mineral occurs in a metamorphic iron deposit, associated with fayalite, hypersthene, quartz, magnetitc, etc.
2. The mineral is opaque, black in colour, thickly tabular in shape with luster metallic to sub-metallic, two perfect cleavages and specific gravity of 3.92.
3. Its main chemical components are Fe and Si with Fe³⁺>Fe²⁺. The analysis gave the formula of Fe Fe _1.00 ³⁺ ·Fe _0.58 ²⁺ ·Mg _0.03 ²⁺ ·Si_0.96O₄.
4. Its DTA curve shows an exothermic peak at 713°C.
5. The mineral has its own infrared spectrum distinctive from that of other minerals.
6. This mineral is of orthorhombic system; space group:C _2h ^/5 ?P2₁/c; unit cell:α=5.813ű0.005,b=4.812ű0.005,c=10.211ű0.005,β=90.87°.
7. The Mössbauer spectrum of this mineral is given, too.

     

Natural and synthetic ferroglaucophane

Amphiboles approximating the composition of the ferroglaucophane end member, Na₂Fe₃Al₂Si₈O₂₂(OH)₂, have not been found in nature prior to 1969. Chemical, physical and petrologic data of four specimens of that mineral are given, two from Southern Italy and two from New Caledonia (Black, 1970). The ferroglaucophane end member was synthesized in seeded runs at 500° C, 5000 bars fluid pressure with oxygen fugacity defined by the wüstite-magnetite (WM) buffer. X-ray data and cell dimensions (a=9.686 Å, b=17.89, c=5.317, β=103° 45.2′ V=894.9 ų) are presented along with microprobe data that confirm the end member composition. Under these conditions of synthesis the ferroglaucophane grew metastably, however. Stability relations of the synthetic end member and of one natural specimen were investigated in a temperature range from 250° C to 500° C and at 3 and 5 kb with different oxygen buffers. At relatively low oxygen fugacities (WM buffer, QFM buffer) ferroglaucophane breaks down above 350–360° C. Under more oxidizing conditions (HM buffer) ferroglaucophane may not be stable even at very low temperatures. Mineral facies and chemical bulk composition of rocks that would favor the natural occurrence of ferroglaucophane are discussed. As assemblages with ferroglaucophane can have crystallized only below a very specific upper temperature limit, it is proposed to direct some attention towards that mineral.