The age of Kondyor massif dunites (Aldan Province, Russia): First U-Pb isotopic data

The material and isotope-geochemical peculiarities of zircons from dunites of the Kondyor massif (Aldan Province, Southeast Siberian Craton) have been described for the first time. This massif is associated with an economic platinum placer deposit. On the basis of detailed study of the morphology, internal structure, and geochemical characteristics, zircons have been subdivided into two types. The first type is represented by crystals of oval and rounded shapes, characterized by a bimodal distribution of ??ancient?? (2477 ± 18 and 1885 ± 52 Ma) U-Pb (SHRIMP-II) ages. The second type of zircons forms idiomorphic crystals and aggregates of prismatic habitus, forming two ??young?? age clusters (176 ± 1.2 and 143 ± 2.0 Ma). The obtained results allow us to make a conclusion about the long evolution of platinum-bearing dunites. The first type of zircons formed by metamictic cores and homogeneous peripheral rims indicates the time of metamorphism at the Archean-Proterozoic boundary (??2.5 Ga), implying an older age of porous zircon cores. Such zircons characterize the minimal age of the initial mantle substance or a close time when the platinum-bearing dunite was generated. Based on their formation time, the second type of zircons can be referred to the epoch of tectonic-magmatic activation of the Aldan Shield. The new geochronological data, along with the material identity of dunites from the Urals and the Aldan Province, argue for a common genetic origin of platinum-bearing dunites of the fold belts and ancient cratons.     

A single-crystal neutron and X-ray diffraction study of pezzottaite, Cs(Be2Li)Al2Si6O18

The chemical composition and the crystal structure of pezzottaite [ideal composition Cs(Be₂Li)Al₂Si₆O₁₈; space group: ${\it{R}} \overline{\text{3}} $ c, a?=?15.9615(6) ?, c?=?27.8568(9) ?] from the type locality in Ambatovita (central Madagascar) were investigated by electron microprobe analysis in wavelength dispersive mode, thermo-gravimetric analysis, Fourier-transform infrared spectroscopy, single-crystal X-ray (at 298?K) and neutron (at 2.3?K) diffraction. The average chemical formula of the sample of pezzottaite resulted ^Cs1,Cs2(Cs_0.565Rb_0.027K_0.017)_Σ0.600 ^Na1,Na2(Na_0.101Ca_0.024)_Σ0.125Be_2.078Li_0.922 ^Al1,Al2(Mg_0.002Mn_0.002Fe_0.003Al_1.978)_Σ1.985 ^Si1,Si2,Si3(Al_0.056Si_5.944)_Σ6O₁₈·0.27H₂O. The (unpolarized) IR spectrum over the region 3,800–600?cm^?1 was collected and a comparison with the absorption bands found in beryl carried out. In particular, two-weak absorption bands ascribable to the fundamental H₂O stretching vibrations (i.e. 3,591 and 3,545?cm^?1) were observed, despite the mineral being nominally anhydrous. The X-ray and neutron structure refinements showed: (a) a non-significant presence of aluminium, beryllium or lithium at the Si1, Si2 and Si3 sites, (b) the absence (at a significant level) of lithium at the octahedral Al1, Al2 and Al3 sites and (c) a partial lithium/beryllium disordering between tetrahedral Be and Li sites.     

Structure and compressibility of synthetic ZnAl2O4 (gahnite) under high-pressure conditions, from synchrotron X-ray powder diffraction

 The structural behavior of synthetic gahnite (ZnAl₂O₄) has been investigated by X-ray powder diffraction at high pressure (0–43 GPa) and room temperature, on the ID9 beamline at ESRF. The equation of state of gahnite has been derived using the models of Birch–Murnaghan, Vinet and Poirier–Tarantola, and the results have been mutually compared (the elastic bulk modulus and its derivatives versus P determined by the third-order Birch–Murnaghan equation of state are K ₀=201.7(±0.9) GPa, K ^′ ₀=7.62(±0.09) and K ^″ ₀=−0.1022 GPa⁻¹ (implied value). The compressibilities of the tetrahedral and octahedral bond lengths [0.00188(8) and 0.00142(5) GPa⁻¹ at P=0, respectively], and the␣polyhedral volume compressibilities of the four-␣and␣sixfold coordination sites [0.0057(2) and 0.0041(2) GPa⁻¹ at P=0, respectively] are discussed. Received: 15 January 2001 / Accepted: 23 April 2001     

Cation disorder in garnets along the Mg3Al2Si3O12-Mg4Si4O12 join: an infrared,Raman and NMR study

We have obtained infrared and Raman spectra for garnets synthesized at high (static) pressures and temperatures along the join Mg₃Al₂Si₃O₁₂ (pyrope) — Mg₄Si₄O₁₂ (magnesium majorite). The vibrational spectra of Mg-majorite show a large number of additional weak peaks compared with the spectra of cubic pyrope garnet, consistent with tetragonal symmetry for the MgSiO₃ garnet phase. The Raman bands for this phase show no evidence for line broadening, suggesting that Mg and Si are ordered on octahedral sites in the garnet. The bands for the intermediate garnet compositions are significantly broadened compared with the end-members pyrope and Mg-majorite, indicating cation disorder in the intermediate phases. Solid state ²⁷Al NMR spectroscopy for pyrope and two intermediate compositions show that Al is present only on octahedral sites, so the cation disorder is most likely confined to Mg-Al-Si mixing on the octahedral sites. We have also obtained a Raman spectrum for a natural, shock-produced (Fe,Mg) majorite garnet. The sharp Raman peaks suggest little or no cation disorder in this sample.     

A multinuclear,high-resolution solid-state NMR study of sorensenite (Na4SnBe2(Si3O9)·2H2O) and comparison with wollastonite and pectolite

This paper presents a solid state ¹H, ²³Na, ²⁹Si, and ¹¹⁹Sn nuclear magnetic resonance (NMR) study of sorensenite. New ²⁹Si NMR data for two related pyroxenoids, wollastonite and pectolite, are included for comparison. By more sensitively probing chemical bonding, the element-specific NMR observations both complement and reinforce the x-ray diffraction results. The role of hydrogen and its interactions with neighboring atoms in sorensenite is further clarified. The wollastonite and pectolite ²⁹Si spectra resolve for the first time all three crystallographic sites and their comparison with sorensenite reveals subtle, systematic differences in sites along the pyroxenoid chains. Effects of corner-shared BeO₄ tetrahedra on ²⁹Si shifts show that sorensenite may also be viewed as a more polymerized silicoberyllate. Contribution to the mineralogy of Ilimaussaq No. 86     

A New Compound of the (K,Na)3Ca8Si6[Si4O12]3 Charoite Substrate

Doklady Earth Sciences - As a result of experimental studies on the interaction between a charoite substrate and host lamprophyres of microcline-arfvedsonitic composition, a new...     

Phase transition of synthetic zinc ferrite spinel (ZnFe2O4) at high pressure, from synchrotron X-ray powder diffraction

 Synthetic Zn-ferrite (ideally ZnFe₂O₄; mineral name: franklinite) was studied up to 37 GPa, by X-ray powder diffraction at ESRF (Grenoble, France), on the ID9 beamline; high pressure was achieved by means of a DAC. The P-V equation of state of franklinite was investigated using the Birch-Murnaghan function, and the elastic properties thus inferred [K₀ = 166.4(±3.0) GPa K₀ ^′ = 9.3(±0.6) K₀ ^″ = −0.22 GPa⁻¹] are compared with earlier determinations for MgAl-spinel and magnetite. The structural behaviour of Zn-ferrite as a function of pressure was studied by Rietveld refinements, and interpreted in the light of a phase transition from spinel to either CaTi₂O₄- or MnFe₂O₄-like structure; this transformation occurs above 24 GPa. Received: 15 March 1999 / Accepted: 22 April 2000     

High-temperature X-ray diffraction study of Co3O4: Transition from normal to disordered spinel

A high-temperature x-ray powder diffraction structural refinement indicates that the room-temperature normal spinel, Co²⁺[Co ₂ ³⁺ ]O₄, transforms to a disordered spinel at temperatures above 1150±30 K, as shown by the decrease of the oxygen u parameter. It is also shown that this transition between normal and disordered spinel is a high order one, where the degree of disordering increases with increasing temperature up to the highest temperature of this study, 1201 K.     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

Synthesis and crystal structure of a triple chain silicate,Na2Mg4Si6O16(OH)2

In the system Na₂CO₃-MgO-SiO₂-H₂O a new sodium magnesium silicate was synthesized under hydrothermal conditions; 450–600 ° C and 300–1000 Kg/cm₂. The structure of the specimen was determined by X-ray powder methods, and its properties were studied by chemical, infrared and TG analyses. The specimen has a triple chain structure (space group, C2/c) with the ideal chemical composition, 4 (Na₂Mg₄Si₆O₁₆(OH)₂) and lattice parameters, a= 10.152(2), b=27.137(4), c=5.276(1) Å, and = 106.97(3) °.The essential feature of the structure is shown by the presence of SiO₄ tetrahedra linked to form chains which have three times the width of those in pyroxene. These triple chains have a periodicity, 5.27 Å, along their lengths, and are bonded to each other laterally by the brucite layer made up by eight Mg cations and sandwiched between two inward pointing bands of tetrahedra. These units are linked back to back by cations (Mg or Na) in the Na(2) site and by a large cation (Na) at the Na(1) site.     

Sulfur-Bearing Sodalite,Hackmanite, in Alkaline Pegmatites of the Inagli Massif (Aldan Shield): Crystal Chemistry,Photochromism, and Luminescence

Geology of Ore Deposits - Abstract—Sulfur-containing sodalite, hackmanite, has been found for the first time in alkaline pegmatites of the Inagli alkaline–ultramafic massif, South...     

High pressure X-ray diffraction study of ilvaite CaFe 2 2+ Fe3+[Si2O7/O/(OH)]

An in situ high pressure X-ray diffraction study on synthetic pure ilvaite powder has been performed using a diamond anvil cell. A phase transition from monoclinic to orthorhombic (Pbnm) has been observed at 2.25 Gpa, which can be described as a λ-transition.     

Synthesis and stability relations of wairakite,CaAl2 Si4 O12·2H2O

Hydrothermal investigation of the bulk composition CaO·Al₂O₃·4SiO₂ + excess H₂O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P _fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time.The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H₂O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P _fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process.The equilibrium dehydration of wairakite to anorthite, quartz and H₂O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H₂O to form laumontite. Reconnaissance experiments dealing with the effect of CO₂ on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO₂-bearing fluid phase.The determined P _fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher _CO2/_H2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of _CO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.     

Shonkinites and minettes of the Ryabinovyi massif (Central Aldan): composition and crystallization conditions

Dikes of biotitic shonkinites and minettes of the complex Ryabinovyi alkaline massif (Central Aldan) have been studied. The dikes are localized in a neck of K-picrites in the northeast of the massif, which intrudes gold-bearing microcline–muscovite metasomatites (Muscovitovyi site). The obtained data on the chemical and trace-element compositions of the rocks and minerals and study of melt inclusions in clinopyroxenes indicate that the biotitic shonkinites and minettes crystallized from the same deep-seated high-pressure alkaline ultrabasic magma during its evolution. Apparently, at the early stage of crystallization of diopside in the biotitic shonkinites, homogeneous carbonate–silicate melt was separated into immiscible fractions of silicate, carbonate–salt, and carbonate melts. The temperature of melt immiscibility was > 1120–1190 °C, i.e., higher than the homogenization temperature of silicate inclusions in the diopside. The contents of trace elements in the biotitic shonkinites and rock-forming clinopyroxenes were one or two orders of magnitude higher than the mantle values. The Eu/Eu* ratios of both the considered rocks and the clinopyroxenes were close to those of chondrites, which testifies to their crystallization from mantle magma. The HREE/LREE ratio indicates that the magma source was localized at the depths where garnet-spinel assemblages existed. The negative Nb and Ti anomalies in the trace-element spectra and the high (> 5) La/Nb ratios in the rocks and clinopyroxenes point to the influence of crustal material on the parental magma. Crystallization of magma took place in reducing conditions, which is evidenced by the low (4–7) Ti/V ratios in clinopyroxenes and the presence of chloride–sulfate inclusions in them. Since gold in the Ryabinovyi massif is associated with late sulfate–chloride and sulfate–carbonate fluids, it might have been transported by alkaline chloride–sulfate and carbonate (carbonatite) melts, found as inclusions in clinopyroxenes of the biotitic shonkinites, at the early stages of Mesozoic magmatism.     

Compression and amorphization of (Mg,Fe)2SiO4 olivines: An X-ray diffraction study up to 70 GPa

The effect of (Mg,Fe) substitution on the compression and pressure-induced amorphization of olivines has been investigated up to more than 50 GPa in a diamond anvil cell through energy-dispersive X-ray diffraction experiments with synchrotron radiation. For the four (Mg_1–x , Fe _x )₂SiO₄ olivines studied, the compressibility is the highest along the b axis and the smallest along the a axis. For compositions with x = 0, 0.17, 0.66, and 1, the slope of the volume-pressure curves shows a rapid decrease at pressures of around 42, 34, 20 and 10 GPa, respectively. Assuming K₀ = 4, we obtained at lower pressures with a Birch-Murnaghan equation of state essentially the same room-pressure bulk modulus for all olivines, namely K ₀ = 131 ± 6 GPa, in agreement with previous single-crystal compression and ultrasonic measurements. At higher pressures, the compression becomes nearly isotropic and the materials very stiff. These changes could precede partial transformation of olivines to a high-pressure polymorph related to the spinel structure. Only a small fraction of olivines seems to transform actually to this phase, however, because most of the material undergoes instead pressure-induced amorphization which take place at considerably higher pressures for Mg-than for Fe-rich olivines.     

Chemical composition of platinum-group minerals from the Bor-Uryakh massif (Maimecha-Kotui Province,Russia)

This contribution firstly presents particularities of mineral chemistry of platinum-group elements (PGE) mineralization from placer deposits linked to the Bor-Uryakh massif of the Maimecha-Kotui Province, northern part of the Siberian Craton. The chemical composition of PGE mineralization has been studied by electron microprobe analysis. At Bor-Uryakh, main platinum-group minerals (PGM) comprise Os-Ir and Pt-Fe alloys represented by individual crystals, and polyphase PGM assemblages. The majority (e.g., 12 out of 19) of the Os-rich nuggets are iridian osmium, with subordinate amounts of native osmium (Os) and chengdeite (Ir₃Fe). Pt-Fe alloys have a stoichiometric composition close to Pt₂Fe. According to the nomen-clature by L. Cabri and C. Feather [1975] these minerals correspond to ferroan platinum. Based on geological position and geochemical features of investigated PGE mineralization the particular rock sources have been established. This study has demonstrated the similarity of chemical characteristics of Os-Ir and Pt-Fe alloys of the Bor-Uryakh massif to those of PGM from the Guli massif (Maimecha-Kotui Province), platiniferous zoned-type ultramafic massifs (e.g., Kondyor, Inagli and Chad) of the Aldan Province and Platinum belt of the Urals (Nizhny Tagil, Kytlym, etc.).     

Sodium trisilicate: A new high-pressure silicate structure (Na2Si[Si2O7])

Crystals of sodium trisilicate (Na₂Si₃O₇) have been grown in the presence of melt at 9 GPa, 1200 °C using the MA6/8 superpress at Edmonton, and the X-ray structure determined at room pressure (R=2.0%). Na₂Si₃O₇ is monoclinic with a=8.922(2) Å, b= 4.8490(5) Å, c=11.567(1) Å, β=102.64(1)° (C2/c), D _x = 3.295 g·cm^-3. Silicon occurs in both tetrahedral and octahedral coordination (^[6]Si∶^[4]Si = l∶2). The SiO₄ tetrahedra form a diorthosilicate [Si₂O₇] group and are linked by the isolated SiO₆ octahedra via shared corners into a framework of 6-membered (^[4]Si-^[4]Si-^[6]Si^[4]Si-^[4] Si-^[6]Si) and 4-membered (^[4]Si-^[6]Si-^[4]Sr-^[6]Si) rings: 〈^[6]Si-O〉=1.789 Å, 〈^[4]Si-O〉= 1.625 Å, ^[4]Si-O-^[4]Si=132.9° and the bridging oxygen is overbonded (s = 2.22). Channels parallel to b-axis and [110] accommodate Na in irregular 6-fold coordination: 〈Na-O〉 = 2.511 Å.