Distance least squares modelling of the cubic sodalite structure and of the thermal expansion of Na8(Al6Si6O24)I2

The Distance Least Squares (DLS) structure modelling technique is used to determine the room-temperature structures of the sodalites Li₈(Al₆Si₆O₂₄)Cl₂, Na₈(Al₆Si₆O₂₄)Cl₂, K₈(Al₆Si₆O₂₄)Cl₂, Na₈(Al₆Si₆O₂₄)Br₂, and Na₈(Al₆Si₆O₂₄)I₂. The technique is also used to calculate the thermal expansion behaviour of Na₈(Al₆Si₆O₂₄)I₂ assuming that the discontinuity in its thermal expansion curve occurred either when the ideal fully-expanded state was achieved (case 1) or when the x-coordinate of the sodium atom became 0.25 (case 2). The results are given as plots of bond lengths and bond angles as a function of temperature. Case 2 was preferred and analysis of the results implied that the driving force for the untwisting of the partially-collapsed sodalite framework was in the framework bonds with the cavity ion bonds resisting the untwisting. Best estimates indicate that the expansion of the Na-O and Na-I bonds are 9% and 27.4% respectively, between room temperature and 810° C, and there is an apparent shortening of the framework bond distances of about 1.5%.     

Uvarovite: Stability of uvarovite-grossularite solid solution at low pressure

Uvarovite (Ca₃Cr₂Si₃O₁₂) forms a complete solid solution series with grossularite (Ca₃Al₂Si₃O₁₂) below 855 ± 5 ° C at a total pressure of 1 atm. Pure uvarovite decomposes to pwo (CaSiO₃) + esk (Cr₂O₃) at 1385 ± 10 ° C. The incorporation of about 5 wt-% of Ca₃Al₂ Si₃O₁₂ component in the uvarovite structure raises the thermal stability of the garnet_ss to 1410 ± 5 ° C, and uvarovite₉₅ grossularite₀₅ melts incongruently to pwo (CaSiO₃) + coresk_ss ((Al, Cr)₂O₃) + L. Pure grossularite decomposes to wo (CaSi0₃) + geh (Ca₂Al₂SiO₇) + and (CaAl₂Si₂O₈) at 855 ± 5 ° C, grossularite thermal stability is increased by incorporation of Ca₃Cr₂Si₃O₁₂ component by 530 ° C. At 1280±5 ° C coresk_ss + L react to gar_ss + geh + an defining an invariant tequilibrium of the CaO-Cr₂O₃-Al₂O₃-SiO₂ quaternary system. Liquid reacts to gar_ss + pwo + geh + an at 1263 ±5 ° C terminating univariant and divariant liquid relations occurring along the join Ca₃Cr₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂. The unit-cell parameter for uvarovite is 11.996(2) Å, the refractive index 1.865(3). The substitution of Cr by Al decreases a and n almost linearly toward the grossularite end member which displays a unit-cell parameter of 11.848(2) Å and a refractive index of 1.732 (1).     

Jinshanjiangite and bafertisite from the Gremyakha-Vyrmes Alkaline Complex,Kola Peninsula

Jinshanjiangite (acicular crystals up to 2 mm in length) and bafertisite (lamellar crystals up to 3 × 4 mm in size) have been found in alkali granite pegmatite of the Gremyakha-Vyrmes Complex, Kola Peninsula. Albite, microcline, quartz, arfvedsonite, zircon, and apatite are associated minerals. The dimensions of a monoclinic unit cell of jinshanjiangite and bafertisite are: a = 10.72(2), b=13.80(2), c = 20.94(6) Å, β = 97.0(5)° and a = 10.654(6), b = 13.724(6), c = 10.863(8) Å, β = 94.47(8)°, respectively. The typical compositions (electron microprobe data) of jinshanjiangite and bafertisite are: (Na_0.57Ca_0.44)_Σ1.01(Ba_0.57K_0.44)_Σ1.01 (Fe_3.53Mn_0.30Mg_0.04Zn_0.01)_Σ3.88(Ti_1.97Nb_0.06Zr_0.01)_Σ2.04(Si_3.97Al_0.03O₁₄)O_2.00(OH_2.25F_0.73O_0.02)_Σ3.00 and (Ba_1.98Na_0.04K_0.03)_Σ2.05(Fe_3.43Mn_0.37Mg_0.03)_Σ3.83(Ti_2.02Nb_0.03)_Σ2.05 (Si_3.92Al_0.08O₁₄)(O_1.84OH_0.16)_Σ2.00(OH_2.39F_1.61)_Σ3.00, respectively. The minerals studied are the Fe-richest members of the bafertisite structural family.     

The thermal expansion of synthetic aluminosilicate-sodalites,M 8(Al6Si6O24)X 2

Thermal expansion data, determined by powder X-ray diffraction methods are presented for 11 members of the (Li,Na,K,Rb)₈(Al₆Si₆O₂₄)Cl₂ solid solution series, 3 members of the (Na,K)₈(Al₆Si₆O₂₄)Br₂ solid solution series and Na₈(Al₆Si₆O₂₄)I₂. Only the latter showed a discontinuity in its expansion curve at 810° C wigh a mean linear expansion coefficient of 22.0×10^?6 °C^?1 below and 7.7×10^?6 °C^?1 above the discontinuity. The mean expansion coefficients from 0° to 500° C decrease gradually over the range of room temperature cell edges from 8.4 to 8.89 Å, then increase up to a cell edge of 9.01 Å above which they decrease sharply and extrapolate to a zero coefficient at 9.4 Å. These variations may be related to the expansion characteristics of the bonds between the cavity cations and cavity anions in different sodalites. The aluminosilicate-sodalites which show a discontinuity in their thermal expansion curves are those with large cavity anions, I^? or SO ₄ ^2? ; the discontinuity is believed to occur at the point when the x-coordinate of the cavity cation becomes 0.25.     

Ion exchange between tectosilicates with the nepheline-kalsilite framework and molten MNO3 or MO (M = Li,Na, K,Ag)

Natural nepheline, a synthetic Na-rich nepheline, and synthetic kalsilite were ion exchanged in molten MNO₃ or MCl (M = Li, Na, K, Ag) at 220–800° C. Crystalline products were characterized by wet chemical and electron microprobe analysis, single crystal and powder X-ray diffraction, and transmission electron microscopy and diffraction. Two new compounds were obtained: Li-exchanged nepheline with a formula near (Li,K_0.3,□)Li₃[Al₃(Al,Si)Si₄O₁₆] and a monoclinic unit cell with a = 951.0(6) b = 976.1(6) c = 822.9(5)pm γ = 119.15°, and Ag-exchanged nepheline with a formula near (K,Na,□)Ag₃[Al₃(Al,Si)Si₄O₁₆] and a hexagonal unit cell with a = 1007.4(8) c = 838.2(1.0) pm. Both compounds apparently retain the framework topology of the starting material. Ion exchange isotherms and structural data show that immiscibility between the end members is a general feature in the systems Na-Li, Na-Ag, and Na-K. For the system Na-K, a stepwise exchange is observed with (K,D)Na₃[Al₃(Al,Si)Si₄O₁₆] as an intermediate composition which has the nepheline structure and is miscible with the sodian end member (Na,□)Na₃[Al₃(Al,Si)Si₄O₁₆], but not with the potassian end member (K,□)₄[Al₃(Al,Si)Si₄O₁₆] which shows the kalsilite structure; there was no indication for the formation of trior tetrakalsilite (K/(K + Na)≈0.7) at the temperatures studied (350 and 800° C). The exact amount of vacancies □ on the alkali site depends upon the starting material and was found to be conserved during exchange, with ca 0–0.2 and 0.3–0.4 vacancies per 16 oxygen atoms for the synthetic and natural precursors, respectively. Thermodynamic interpretation of the Na-K exchange isotherms shows, as one important result, that the sodian end member is unstable with respect to the intermediate at K/(K+Na)≈0.25 by an amount of ca 45 kJ/mol Na in the large cavity at 800° C (52 kJ/mol at 350° C).     

The diffusion of dissolved silica in dilute aqueous solution

The diffusion coefficient of dissolved silica at 25.5 ± .5°C was determined as a function of concentration using a non-steady-state method whereby agar-gelled solutions containing dissolved silica from 0.09 to 1.50 mM (pH = 5.5) were placed in contact with distilled water in glass cells. Diffusion coefficients were obtained by measuring the dissolved silica content of the distilled water after a given length of time. The measured diffusion coefficients decreased as a function of increasing dissolved silica concentration, which is thought to reflect an increase in dimeric silica according to the equilibrium: 2Si(OH)₄ = Si₂O(OH)₆ + H₂O. The tracer diffusion coefficients for Si(OH)₄ and Si₂O(OH)₆ and an association constant for the above reaction were determined by fitting the following equation to the experimental data: D_obs = αD_monomer + (1 − α)D_dimer where α is the fraction of total dissolved silica which is Si(OH)₄. The best fit yielded tracer D's for Si(OH)₄ and Si₂O(OH)₆ of 2.2 and 1.0 (in units of 10⁻⁵ cm² sec⁻¹), respectively, and an association constant of 330.     

A high pressure-high temperature study of TiO2 solubility in Mg-rich phlogopite: implications to phlogopite chemistry

The solubility of Tio₂ in phlogopites has been experimentally determined in the system K₂Mg₆Al₂Si₆O₂₀(OH)₄-K₂Mg₄TiAl₂Si₆O₂₀(OH)₄-K₂Mg₅TiAl₄Si₄O₂₀(OH)₄ between 825–1300°C and 10–30 kbar under vapour absent conditions. Starting compositions lie along the join K₂Mg₆Al₂Si₆O₂₀(OH)₄-K₂Mg_4.5TiAl₃Si₅O₂₀(OH)₄ which represents a combination of the Mg^[VI]2Si^[IV] = Ti^[VI]2Al^[VI] and $\text{2Mg}{}^{\mathrm{[VI]}}\text{=}\text{Ti}{}^{\mathrm{[VI]}}\text{□}{}^{\mathrm{[VI]}}$ substitution mechanisms for Ti in phlogopites. The results of the experiments indicate a systematic increase in solubility of Ti with increasing temperature and decreasing pressure for given bulk Tio₂ content. Under isobaric conditions high temperature Ti-saturated phlogopite breaks down to Ti-deficient phlogopite + rutile + vapour. Mass balance calculations suggest that the vapour phase may contain K₂O dissolved in H₂O and that the reaction is controlled by the vapour phase. Analyses of phlogopites coexisting with rutile and vapour can be represented in terms of the end-member components phlogopite [K₂Mg₆Al₂Si₆O₂₀(OH)₄], eastonite [K₂Mg₅Al₄Si₅O₂₀(OH)₄], an octahedral site deficient Ti-phlogopite (Ti-OSD) of composition K₂(Mg₄Ti□)Al₂Si₆)O₂₀(OH)₄, and Ti-eastonite [K₂Mg₅TiAl₄Si₄O₂₀(OH)₄]. With decreasing amounts of Ti in these phlogopites there is a decrease in the Ti-eastonite component and increase in the eastonite component.The general equation for the breakdown of Ti-phlogopite solid solution to Ti-free phlogopite + rutile + vapour is: 14 Ti-eastonite + 7 Ti-OSD ? 16 eastonite + 3 phlogopite + 21 rutile + 4 H₂O + 2 K₂O. Lack of knowledge of H₂O and K₂O activities in the vapour phase does not permit evaluation of thermodynamic constants for this reaction. The Ti solubility in phlogopites and hence its potential as a geothermobarometer under lower crustal to upper mantle conditions is likely controlled by common mantle minerals such as forsterite.     

Theoretical reaction pathways for the formation of [Si(OH)5]1− and the deprotonation of orthosilicic acid in basic solution

Ab initio, molecular orbital calculations at the 6-31G¹ level including second-order Møller-Plesset electron correlation predict that the species [Si(OH)₅]¹⁻ is dynamically stable in a distorted trigonal bipyramid configuration. Reaction pathways for Si(OH)₄ + (OH)⁻ → [Si(OH)₅]¹⁻ → [(OH)₃SiO]¹⁻—H₂O are also calculated. The first reaction represents the formation of pentacoordinate Si from orthosilicic acid and hydroxide. The activation energy for adding a fifth Si-(OH)⁻ bond to the Si(OH)₄ molecule is ≈0.1 eV /molec (≈10kJ/mol). The second reaction is the deprotonation of the Si(OH)₄ which forms as a hydroxyl group leaves the [Si(OH)₅]¹⁻ molecule. Removal of a bond from this complex requires 0.9 eV/molecule (≈85 kJ/mol). Lengthening the Si—OH₂ distance results in the isolated molecules [(OH)₃SiO]¹⁻ + H₂O. This represents dehydration of the deprotonated orthosilicic acid.[Si(OH)₅]¹⁻ and [(OH)₃SiO]¹⁻- H₂O have the same energetic stability within the accuracy of these calculations. The potential energies of the isolated molecular systems [(OH)₃SiO]¹⁻+ H₂O and Si(OH)₄ + (OH)⁻ are considerably higher. These results suggest that [Si(OH)₅]¹⁻ may be a stable species or reaction intermediate in dissolution of silicate minerals in basic aqueous solutions.     

Thermochemistry of (Fe2+, Mg)SiO3 orthopyroxene

Enthalpies of solution in eutectic (Li, Na)₂B₂O₄ melts at 1023 K were measured for five synthetic orthopyroxenes on the join MgSiO₃-FeSiO₃. The pyroxenes were synthesized at 1120°C and 20 kbar and thus were presumed to be highly disordered. The measurements indicate a small positive enthalpy of mixing, with W_H = 950 cal/MSiO₃.Enthalpy of solution measurements were made on a natural, well-ordered orthopyroxene near the composition En_52.5Fs_47.5 and on this material after heat-treatment at 1150°C and 20 kbar. Irreversible expansion of the unit-cell constants of the natural pyroxene after heat-treatment at various temperatures was used to characterize the degree of M-site disorder. The observed enthalpy of solution decrement of 0.85 kcal/MSiO₃ between the natural En_52.5 and the same material heated at 1150° corresponds to about half of the maximum possible disordering, or ΔX_Fe^M1? 0.25, which leads to a ΔH of 7.5 kcal/M₂Si₂O₆, for the exchange reaction: Fe(M2) + Mg(Ml) = Fe(Ml) + Mg(M2) if M-site interaction energy terms are ignored. This ΔH is larger than inferred from any of the analyses of site-occupancy data except that of Besancon (1981), who gave a very similar value. The measured ΔH of disorder and the W_H of mixing together indicate a large ΔH as great as 3.2 kcal for the reciprocal reaction: Fe₂Si₂O₆ + Mg₂Si₂O₆ = Fe(M2)Mg(M1)Si₂O₆ + Fe(M1)Mg(M2)Si₂O₆ as anticipated by Sack (1980).As a consequence of the inferred magnitudes of ΔHof the exchange and reciprocal reactions, departures from ideality of Gibbs energy of mixing of orthopyroxene are very small at 700°–1000°C. Activities of MgSiO₃ and FeSiO₃ may be replaced by their mol fractions at all temperatures in most petrologic calculations.     

Comprehensive physicochemical study of dioctahedral palygorskite-rich clay from Marrakech High Atlas (Morocco)

This study is devoted to the physicochemical and mineralogical characterizations of palygorskite from Marrakech High Atlas, Morocco. The raw clay and its Na⁺-saturated <2 μm fraction were characterized using chemical, structural, and thermal analytical techniques. Measurements of specific surface area and porous volume are reported. The clay fraction was found to be made up of 95 % of palygorskite and 5 % of sepiolite. An original feature of this palygorskite is its deficiency in zeolitic H₂O. The half-cell structural formula of its dehydrated form was determined on the basis of 21 oxygens to be (Si_7.92Al_0.08)(Mg_2.15Al_1.4Fe_0.4Ti_0.05 $ \square_{1} $ )(Ca_0.03Na_0.08K_0.04)O₂₁, while the hydrated form could be formulated as (Si_7.97Al_0.03)(Mg_2.17Al_1.46Fe_0.40Ti_0.05)(Ca_0.03Na_0.07K_0,03)O_20.18(OH)_1.94(OH₂)_3.88·2.43 H₂O. These formulas show that the (Al³⁺+Fe³⁺)/Mg²⁺ ratio is around 0.84, revealing a pronounced dioctahedral character. Further, inside its octahedral sheet, it was determined that the inner M₁ sites are occupied by vacancies, whereas the M₂ sites are shared between 90 % of trivalent cations (78 % for Al³⁺ and 22 % for Fe³⁺), 7.5 % of Mg²⁺, and 2.5 % of Ti⁴⁺, all of them linked to 1.94 of structural hydroxyls. The two remaining Mg²⁺ by half-cell occupy edge M₃ sites and are coordinated to 3.88 molecules of OH₂. Channels of this palygorskite are deficient in zeolitic H₂O since they contain only 2.43 H₂O molecules. A correlation was found between these results and the observation of very intense and well-resolved FTIR bands arising from dioctahedral domains (mainly Al₂OH, Fe₂OH, and AlFeOH) along with very small responses from a trioctahedral domain (Mg₃OH). Accordingly, a schematic representation of the composition of the octahedral sheet was proposed. The cation exchange capacity, specific surface area, and total pore volume were also assessed to be ca. 21.2 meq/100 g, 116 m²/g, and 0.458 cm³/g, respectively.     

Experimental determination of portlandite and brucite solubilities in supercritical H2O

Experimentally reversed portlandite and brucite solubilities were determined between 300° and 600°C and 1 to 3 kbar. In the portlandite runs the molality of Ca decreases with increasing pressure at constant temperature. For instance, at 2 kbar log molalities at 300°, 400°, 500° and 600°C give values of −2.34, −2.71, −3.18 and −4.18, respectively. At 500°C, pressures of 1, 2 and 3 kbar yield values of −4.40, −3.18 and −2.65. Distribution of species in solution can be calculated with the aid of data from Helgeson and co-workers assuming Ca⁺⁺ is the dominant Ca species. These calculated Ca concentrations are within ± 0.2 log units of experimental values in most cases. The solubility reaction is, in all likelihood: 2H⁺ + Ca(OH)₂ ↔a3 Ca⁺⁺ + 2H₂O.Although the computed pH's are close to 2 units greater than neutral, the solutions apparently contained no significant Ca(OH)⁺ or Ca(OH)_2sq.Concentrations of Mg in the brucite runs show a sigmoidal behavior at 2 kbar as a function of temperature with log molalities of Mg of −4.00, −4.28, −4.14 and −4.60 at 350°, 450°, 550° and 600°C, respectively. Values at 1 kbar are lower and decrease monotonically from 350° to 550°C. Based on available thermodynamic data for Mg⁺⁺ it appears that Mg(OH)⁺ is the dominant Mg species in solution. The solubility reaction is proposed to be: H⁺ + Mg(OH)₂↔a3 Mg(OH)⁺ + H₂O.With the aid of data of Helgeson and co-workers values of the equilibrium constant for H₂O + Mg⁺⁺ ↔a3 Mg(OH)⁺ + H⁺ necessary to account for the measured solution compositions can be calculated. These calculations indicate Mg(OH)⁺ becomes dominant at temperatures above 450°C at 2 kbar and above 360°C at 1 kbar at neutral pH.     

Anomalous optical variations in the grossular garnet from the Eden Mills,Belvidere Mountain (Vermont,USA)

The optical anomalies, and surface and lamellar textures of a birefringent grossular garnet crystal from the Eden Mills, Belvidere Mountain, Vermont, USA, have been investigated by optical polarizing microscope, electron-probe micro-analyzer, back-scattered electron imaging, infrared spectroscopy, and single-crystal X-ray diffractometer from the standpoint of crystal growth. This grossular shows one-to-one correlation between natural surface features and its internal textures under crossed polarizers. Electron-probe micro-analyzer (EPMA) gave average chemical composition in (110) thin section, of bright lamella {Ca_2.97Mn_0.06}_∑3.03 [Al_1.59Fe_0.37Ti_0.01]_∑1.97(Si_3.00)_∑3.00 (Gros_79.5And_18.9Sps_1.6) and of dark host {Ca_2.99Mn _0.06}_∑3.05 [Al_1.73Fe_0.26 Ti_0.01]_∑2.00(Si_2.97OH_0.03)_∑3.00 (Gros_85.4And₁₃Sps_1.6). The correspondence of surface features and the internal textures with spiral or pyramidal growth mechanism suggest that the internal textures of the Eden Mills grossular are formed during growth process. The optical vibrational orientations and the growth steps inclination along [001] and \( \left[\overset{-}{1}10\right] \) directions predict monoclinic symmetry. With X-ray diffractometer (XRD) method, pseudocubic parameters are a = 11.839(2) Å, b = 11.855(1) Å, and c = 11.868(2) Å with interaxial angles α = 90.00(1)°, β = 89.99(1)°, and γ = 90.02(2)° that show orthorhombic symmetry of this crystal. Lamellar texture of Al³⁺-rich host with Fe³⁺-rich lamella infers cation ordering at octahedral site of the garnet structure. IR data favors the non-cubic orientation of [(OH) ₄] at tetrahedral position in this grossular structure.     

Chemical composition and species attribution of tourmalines from a rare-metal pegmatite vein with scapolite, Sangilen Upland, Tuva

A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant and characterized by the ideal formula Ca(Mg₂Li)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg²⁺ → Fe²⁺, 2Mg²⁺ → Li⁺ + Al³⁺, and Mg²⁺ + OH → Al³⁺ + O²⁻. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al_1.5Li_1.5)Al₆(Si₆O₁₈)(BO₃)₃ (OH₂O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines allow us to regard them as new mineral species in the tourmaline group.     

Property Correlations and Statistical Variations in the Geotechnical Properties of (CH) Clay Soils

This study was focused on the correlations between the physical and mechanical properties and geostatistical analysis of the clay of high plasticity (CH) soil based on the experimental data and the data collected from various research studies. Four types of CH soil with liquid limit (LL) of 50, 62, 76 and 88% were collected from the field, tested, compared with the data from literature and qualified using hyperbolic model. X-ray diffraction analyses showed the major constituents of the CH soil with LL of 50% were calcium silicate (Ca₂SiO₄), aluminum silicate (Al₂SiO₅) and quartz (SiO₂) and the major constituents of the CH soil with LL of 88% were montmorillonite (Na, Ca) _0.33(Al, Mg) ₂(Si₄O₁₀) (OH)₂·nH₂O, kaolinite (Al₂Si₂O₅(OH)₄) and quartz (SiO₂). The index properties, compacted properties, free swelling and compressive strength of the CH soils were investigated and quantified with over 1000 data collected from the literature. Using the mean (μ), standard deviation (σ), variation (σ²) and coefficient of variation parameters of CH soils properties such as density (γ), index properties (LL and PL), compaction properties (OMC and γ_dmax), swelling index (FS), initial void ratio (e_o), compression index (Cc) and undrained shear strength (S_u) properties were also studied. Liquid limit of CH soils varied between 50 and 110% and plasticity index varied between 26 and 72%. The wet unit weight (γ_wet) for the CH soils varied from 1.30 to 2.19 g/cm³. Undrained shear strength (S_u) of CH soils were varied from 10 to 184 kPa and quantified very well as a function of liquid limit, plasticity index, moisture content and dry density using the experimental data and data collected from the literature.     

Perrierite-(La), (La,Ce,Ca)4(Fe2+,Mn)(Ti,Fe3+,Al)4(Si2O7)2O8, a new mineral species from the Eifel volcanic district, Germany

Non-metamict perrierite-(La) discovered in the Dellen pumice quarry, near Mendig, in the Eifel volcanic district, Rheinland-Pfalz, Germany has been approved as a new mineral species (IMA no. 2010-089). The mineral was found in the late assemblage of sanidine, phlogopite, pyrophanite, zirconolite, members of the jacobsite-magnetite series, fluorcalciopyrochlore, and zircon. Perrierite-(La) occurs as isolated prismatic crystals up to 0.5 × 1 mm in size within cavities in sanidinite. The new mineral is black with brown streak; it is brittle, with the Mohs hardness of 6 and distinct cleavage parallel to (001). The calculated density is 4.791 g/cm³. The IR spectrum does not contain absorption bands that correspond to H₂O and OH groups. Perrierite-(La) is biaxial (-), α = 1.94(1), β = 2.020(15), γ = 2.040(15), 2V _meas = 50(10)°, 2V _calc = 51°. The chemical composition (electron microprobe, average of seven point analyses, the Fe²⁺/Fe³⁺ ratio determined from the X-ray structural data, wt %) is as follows: 3.26 CaO, 22.92 La₂O₃, 19.64 Ce₂O₃, 0.83 Pr₂O₂, 2.09 Nd₂O₃, 0.25 MgO, 2.25 MnO, 3.16 FeO, 5.28 Fe₂O₃, 2.59 Al₂O₃, 16.13 TiO₂, 0.75 Nb₂O₅, and 20.06 SiO₂, total is 99.21. The empirical formula is (La_1.70Ce_1.45Nd_0.15Pr_0.06Ca_0.70)_Σ4.06(Fe _0.53 ²⁺ Mn_0.38Mg_0.08)_Σ0.99(Ti_2.44Fe _0.80 ³⁺ Al_0.62Nb_0.07)_Σ3.93Si_4.04O₂₂. The simplified formula is (La,Ce,Ca)₄(Fe²⁺,Mn)(Ti,Fe³⁺,Al)₄(Si₂O₇)₂O₈. The crystal structure was determined by a single crystal. Perrierite-(La) is monoclinic, space group P2₁/a, and the unit-cell dimensions are as follows: a =13.668(1), b = 5.6601(6), c = 11.743(1) Å, β = 113.64(1)°; V = 832.2(2) ų, Z = 2. The strong reflections in the X-ray powder diffraction pattern are [d, Å (I, %) (hkl)]: 5.19 (40) (110), 3.53 (40) ( $\overline 3 $ 11), 2.96 (100) ( $\overline 3 $ 13, 311), 2.80 (50) (020), 2.14 (50) ( $\overline 4 $ 22, $\overline 3 $ 15, 313), 1.947 (50) (024, 223), 1.657 (40) ( $\overline 4 $ 07, $\overline 4 $ 33, 331). The holotype specimen of perrierite-(La) is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, Russia, with the registration number 4059/1.     

A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece

Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO₂, 8 wt.% Cr₂O₃ and 4 wt.% ZrO₂, representing a solid solution of andradite (Ca₃Fe³⁺ ₂Si₃O₁₂ ≈46 mol%), uvarovite (Ca₃Cr₂Si₃O₁₂ ≈23 mol%), grossular (Ca₃Al₂Si₃O₁₂ ≈10 mol%), schorlomite (Ca₃Ti₂[Si,(Fe³⁺,Al³⁺)₂]O₁₂ ≈15 mol%), and kimzeyite (Ca₃Zr₂[Si,Al₂]₃O₁₂ ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al³⁺, Fe³⁺ and Ti⁴⁺. Cr³⁺ and Zr⁴⁺ are found at the octahedral site along with Fe³⁺, Al³⁺ and Ti⁴⁺. The measured H₂O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca_2.99Mg_0.03)_Σ=3.02(Fe³⁺ _0.67Cr_0.54Al_0.33Ti_0.29Zr_0.15)_Σ=1.98(Si_2.42Ti_0.24Fe_0.18Al_0.14)_Σ=2.98O₁₂OH_0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.     

Crystal chemistry, surface morphology and X-ray photoelectron spectroscopy of Fe-rich osumilite from Mt. Arci, Sardinia (Italy)

Microprobe analysis, single crystal X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray absorption spectroscopy were applied on Fe-rich osumilite from the volcanic massif of Mt. Arci, Sardinia, Italy. Osumilite belongs to the space group P6/mcc with unit cell parameters a = 10.1550(6), c = 14.306(1) Å and chemical formula (K_0.729)_C (Na_0.029)_B (Si_10.498 Al_1.502)_T1 (Al_2.706 Fe _0.294 ²⁺ )_T2 (Mg_0.735 Mn_0.091 Fe _1.184 ²⁺ )_AO₃₀. Structure refinement converged at R = 0.0201. Unit cell parameter a is related to octahedral edge length as well as to Fe²⁺ content, unlike the c parameter which does not seem to be affected by chemical composition. The determination of the amount of each element on the mineral surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si_2p, Al_2p, Mg_1s and Fe_2p core levels, suggests that Fe presents Fe²⁺ oxidation state and octahedral coordination. Two peaks at 103.1 and 100.6 eV can be related to Si⁴⁺ and Si¹⁺ components, respectively, both in tetrahedral coordination. The binding energy of Al_2p, at 74.5 eV, indicates that Al is mostly present in the distorted T2 site, whereas the Mg peak at 1,305.2 eV suggests that this cation is located at the octahedral site. X-ray absorption at the Fe L_2,3-edges confirms that iron is present in the mineral structure, prevalently in the divalent state and at the A octahedral site.     

Stability and composition relations of calcic amphiboles in ultramafic rocks

Calcic amphiboles are observed in ultramafic rocks that have equilibrated under a broad span of geological conditions and might prove to be good indicators of metamorphic grade if their stabilities could be determined as a function of their compositions. Experiments were performed on the stability of tremolite plus forsterite in the system H₂O-CaO-MgO-SiO₂ from 5 to 20 kbar. A univariant curve was fitted to the experimental brackets using volume, water fugacity, and heat capacity data. The results indicate that the maximum stability of tremolite in the presence of forsterite is about 825° C at 5 kbar. Addition of Al₂O₃ to this system increases the stability of tremolitic amphibole by only 20°–40° C and induces solubility of 5–7 wt.% Al₂O₃ in the amphibole, as determined from quantitative SEM analyses of individual amphibole crystals. Thus substitution of the tschermakite component (Ca₂(Mg₃Al₂) (Si₆Al₂) O₂₂(OH)₂) alone cannot lead to the greatly enhanced Al₂O₃ contents or thermal stability of natural calcic amphiboles. Comparison of the results from this study with experimental results from other studies on synthetic calcic amphiboles indicates that the high thermal stability of natural amphiboles is strongly linked with the substitution of alkalies (Na in particular) in the form of the component Na-Ca₂(Mg₄Al) (Si₆Al₂)O₂₂(OH)₂ (pargasite). Accordingly, experimental data from studies on pargasite have been combined with the appropriate univariant curves to obtain a phase diagram for amphibole-bearing ultramafic rocks modelled by the system H₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂.