β(Mg0.9, Fe0.1)2SiO4: Single crystal structure,cation distribution,and properties of coordination polyhedra

The synthesis boundaries of the phase transformation; ++ in (Mg_0.9, Fe_0.1)SiO₄, have been clarified at temperatures to 2000° C and pressures up to 20 GPa in order to synthesize single crystals of high quality. A single crystal of (Mg_0.9, Fe_0.1)₂SiO₄ was grown successfully to a size of 500 m. The crystal structure has been refined from single-crystal X-ray intensities. The ferrous ions prefer M1 and M3 sites to over the larger M2 site. The volume change of all the occupied polyhedra does not contribute to the decrease of total volume in the transformation; rather it tends to increase the bulk volume through the expansion of occupied tetrahedra. The volume reduction in the phase transformations is accounted for by unoccupied polyhedra, with the octahedra contributory 60% and the tetrahedra 40% to the V of the transition. The volume change in the transformation is caused also partly by the volume decrease of MO ₆ (25%), partly the unoccupied tetrahedra (45%) and octahedra (30%).     

The α-β phase transition in cristobalite,SiO2

Cristobalite, a high temperature phase of silica, SiO₂, undergoes a (metastable) first-order phase transition from a cubic, , to a tetragonal, P4₃2₁2 (or P4₁2₁2), structure at around 220° C. The cubic C9-type structure for -cristobalite (Wyckoff 1925) is improbable because of two stereochemically unfavorable features: a 180° Si-O-Si angle and an Si-O bond length of 1.54 Å, whereas the corresponding values in tetragonal -cristobalite are 146° and 1.609 Å respectively. The structure of the -phase is still controversial. To resolve this problem, a symmetry analysis of the (or P4₁2₁2) transition in cristobalite has been carried out based on the Landau formalism and projection operator methods. The starting point is the ideal cubic ( ) C9-type structure with the unit cell dimension a (7.432 Å) slightly larger than the known a dimension (7.195 Å at 205° C) of -cristobalite, such that the Si-O-Si angle is still 180°, but the Si-O bond length is 1.609 Å. The six-component order parameter driving the phase transition transforms according to the X₄ representation. The transition mechanism essentially involves a simultaneous translation and rotation of the silicate tetrahedra coupled along 110. A Landau free-energy expression is given as well as a listing of the three types of domains expected in -cristobalite from the transition. These domains are: (i) transformation twins from a loss of 3-fold axes, (ii) enantiomorphous twins from a loss of the inversion center, and (iii) antiphase domains from a loss of translation vectors 1/2 110 (FP). These domains are macroscopic and static in -cristobalite, and microscopic and dynamic in -cristobalite. The order parameter , couples with the strain components as ², which initiates the structural fluctuations, thereby causing the domain configurations to dynamically interchange in the -phase. Hence, the - cristobalite transition is a fluctuation-induced first-order transition and the -phase is a dynamic average of -type domains.     

31P solid-state nuclear magnetic resonance spectroscopy of aluminum phosphate minerals

This study examines the links between ³¹P solidstate NMR studies of aluminum phosphate minerals and their crystallographic structures. We found that ³¹P isotropic chemical shift values, _iso, carry little information about mineral structures. There seems to be no relation between the chemical shift anisotropy, =₃₃–₁₁ (₃₃>₂₂> ₁₁), and indicies of phosphate-tetrahedra distortion. ³¹P¹H heteronuclear magnetic dipole interactions, on the other hand, carry important information about hydrous phosphate mineral structures, information that should prove to be quite valuable in studies of phosphate adsorbed on mineral surfaces. This interaction can be measured through a variety of qualitative and quantitative experiments. It appears that spin diffusion is so rapid that subtle differences in hydrogen-bonding environments cannot be resolved.     

Tungsten-bearing baotite from Pierrefitte,Pyrenees, France

Summary Baotite occurs in the Garaoulére orebody, at Pierreftte, France, as an accessory mineral, included in alstonite and celsian, and associated with sphalerite, galena, pyrite, siderite and calcite in hydrothermal veins crosscutting calcareous, rutile-bearing, siltstones. Microprobe analyses revealed high W0₃ concentrations (up to 6 wt.%) in baotite. The empirical formula of W-rich baotite is Ba_3.959Ti₄(Ti_3.169W_0.393Fe_0.116Al_0.073 Cr_0.048Nb_0.024)_3.823 Si_4.05O₂₈Cl_1.166. The excess of charges due to the presence of W⁶⁺ and Nb⁵⁺ is compensated by the introduction of M³⁺ (Fe, Al, Cr) into Ti-octahedra, by the appearance of Al in Si-tetrahedra (for W-poor baotite) and by the appearance of vacancies in Ti-octahedra (3Ti⁴ -> 2W⁶⁺ + and in Ba-sites (Ti⁴⁺ Ba²⁺ W⁶⁺, ). The unit-cell parameters of W-rich baotite are: a = 19.92(2), c = 5.930(8) Å. Niobium-rich baotites (Baiyun-Obo,Semenov et al., 1961; Karlstein,Nmec, 1987) are characterized by substitutions: Ti⁴⁺(VI), Si⁴⁺(IV)Nb⁵⁺(VI), Al³⁺(IV) and 2Ti⁴⁺, Ba²⁺ 2Nb⁵⁺, .

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Wolfram führender Baotit von Pierrefitte, Pyrenäen, Frankreich

Zusammenfassung Baotit kommt in dem Garaoulére Erzkórper in Pierrefitte, Frankreich als ein akzessorisches Mineral in Einschlÿussen in Alstonit und Celsian vor. Er ist mit Zinkblende, Bleiglanz, Pyrit, Siderit und Calcit assoziiert. Diese Paragenese ist an hydrothermale Gänge gebunden, die kalkige rutil-führende Siltsteine durchsetzen. Mikrosondenanalysen zeigen hohe W0₃ Gehalte (bis zu 6 Gew.%) in Baotit. Die empirische Formel von wolfram-reichem Baotit ist: Ba_3.959Ti₄(Ti_3.169W_0.393Fe_0.116Al_0.073Cr_0.048Nb_0.024)_3.823 Si_4.05O₂₈Cl_1.66. Der durch die Anwesenheit von W⁶⁺ und Nb⁵⁺ erforderliche Ladungsausgleich ergibt sich durch das Eintreten von M³⁺ (Fe, Al; Cr) in Ti-Oktaeder, und von Al in Si-Tetraeder (für W-armen Baotit) und schließlich durch das Erscheinen von Leerstellen in Ti-Oktaedern (3Ti⁴⁺ 2W6+ + und in Ba-Stellen (Ti⁴⁺, Ba` W⁶⁺, Die Zellparameter von ldW-reichem Baotit sind: a = 19.92(2), c = 5.930(8) Å. Niob-reiche Baotite (Baiyun-Obo, Semenov et al., 1961; Karlstein, Nmec, 1987) sind durch Substitutionen charakterisiert: Ti⁴⁺(VI), Si⁴⁺(IV)Nb⁵⁺(VI), Al³⁺(IV) und 2Ti⁴⁺, Ba²⁺ 2Nb⁵⁺, .

     

Thermodynamics of the xanthoconite-proustite and pyrostilpnite-pyrargyrite phase transition as determined by abrasive stripping voltammetry

The electrochemical reduction of xanthoconite, proustite, pyrostilpnite, and pyrargyrite was studied by abrasive stripping voltammetry, a technique which is based upon a preliminary mechanical transfer of trace amounts of the mineral onto the surface of a paraffin impregnated graphite electrode. Because the electrochemical reduction proceeds near to reversibility and is very similar for each pair of minerals, the peak potentials in differential pulse voltammetry can be used to calculate the standard enthalpy of phase transformation of xanthoconite to proustite and of pyrostilpnite to pyrargyrite: _T H _{(xanth proust)} ^O = 35.46 ± 14.15 kJ/mol and _T H _{(pyrostilp pyrarg)} ^O = 38.85 ± 6.60 kJ/mol. These values are not accessible otherwise until now.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written:     

High-density CO2−N2 inclusions in eclogite-facies metasediments of the Münchberg gneiss complex,SE Germany

The eclogite-facies metasedimentary rocks in the Münchberg gneiss complex (T=630±30° C/P17–24 kbar) locally contain CO₂–N₂-rich fluid inclusions of extremely low molar volumes (32 cm³/mol) in quartz. These fluid compositions are mainly found in rocks intercalated with calcsilicate bands. Densities were determined from low-temperature phase transitions like stable or metastable homogenization (L+VL), partial homogenization (S+L+VS+L) and the transition S+LL (L = liquid, V = vapour, S = solid). The high fluid densities are in agreement with eclogite-facies pressure and temperature and subsequent amphibolite facies. CO₂–N₂ inclusions were not observed in adjacent eclogites nor in non-calcareous metasediments. These rock types contain predominantly H₂O-rich inclusions correlating with amphibolite-facies conditions. The variation of fluid composition with lithological differences indicates local fluid gradients and speaks against a pervasive fluid flow during eclogite-facies metamorphism.     

Phase transitions in leucite: X-ray diffraction studies

Lattice parameters, and intensities of selected X-ray reflexions, have been measured as a function of temperature for natural leucite, to characterise the phase transformation behaviour. At low temperatures leucite has a large ferroelastic distortion, but the temperature evolution of lattice parameters cannot be explained in terms of a purely ferroelastic phase transition; in particular, the considerable change in volume with temperature implies an additional transition mechanism, which we correlate with off-centring of K-ions in the low-temperature phase, and a collapse of the 111 structural channels. The transition behavior can therefore be rationalised in terms of two competing mechanisms: (I) Ferroelastic (consistent with the change m3m 4/mmm); (II) Volume-changing (consistent with m3m 4/m). Coupling of the two order parameters Q_I, and Q_II gives rise to the intermediate 4/mmm tetragonal phase.Our results confirm the existence of an I4 ₁/aI4 ₁/acd transition, but the non-disappearance of the 200 reflexion at high temperatures implies that the expected transition from I4₁/acd to Ia3d (cubic) symmetry does not occur. We attribute this to a residual strain field conjugated to the order parameter, due to defects (with possible Al/Si order). Nevertheless, within our experimental resolution, the lattice becomes metrically cubic at 665° C.     

An experimental investigation of olivine morphology

Olivine crystals can adopt ten types of shape. Experimental crystallization of eight rock melts shows that there is a systematic change from polyhedral or granular olivines hopper olivines branching olivines randomly oriented chain olivines parallel-growth chain olivines chain+lattice olivines plate or feather olivines, with increase in cooling rate and with increase in degree of supercooling. This sequence involves changes from complete to progressively less complete crystals and from equant habit to elongate bladed habit (c>ab) to tabular habit (ac b). The sequence is not affected by the phase relations of the melt. The larger the olivine content of a melt the slower the cooling rate at which a particular olivine shape grows, whereas the lower the melt viscosity, the greater the cooling rate. Irrespective of the melt composition, comparable crystal shapes grow at the same degrees of supercooling. By comparison of the shapes of olivine crystals in experiments with those in rocks of similar composition, it is possible to deduce the cooling rate through the olivine crystallization interval and the approximate degree of supercooling at which the olivine crystals nucleated and grew in the rocks. The various shapes of skeletal olivines in many picrites, olivine-rich basalts and the Archaean spinifex rocks are not due to rapid cooling, but to rapid olivine growth caused by the high normative olivine content of the magma.     

Mechanisms of the transformations between the α, β and γ polymorphs of Mg2SiO4 at 15 GPa

Data on the mechanisms of mantle phase transformations have come primarily from studies of analogue systems reacted experimentally at low pressures. In order to study transformation mechanisms in Mg₂SiO₄ at mantle pressures, forsterite () has been reacted in the stability field of -phase, at 15 GPa and temperatures up to 900° C, using a multianvil split-sphere apparatus. Transmission electron microscope studies of samples reacted for times ranging from 0.25–5.0 h show that forsterite transforms to -phase by an incoherent nucleation and growth mechanism involving nucleation on olivine grain boundaries. This mechanism and the resultant microstructures are very similar to those observed at much lower pressures in analogue systems (Mg₂GeO₄ and Ni₂SiO₄) as the result of the olivine to spinel () transformation. Metastable spinel () also forms from Mg₂SiO₄ olivine at 15 GPa, in addition to -phase, by the incoherent nucleation and growth mechanism. With time, the spinel progressively transforms to the stable -phase. After 1 h, spinels exhibit a highly striated microstructure along {110} and electron diffraction patterns show streaking parallel to [110] which indicates a high degree of structural disorder. High resolution imaging shows that the streaking results from thin lamellae of -phase intergrown with the spinel. The two phases have the orientation relationship [001]//[001] and [010]//[110] so that the quasi cubic-close-packed oxygen sublattices are continuous between both phases. These microstructures are similar to those observed in shocked meteorites and show that spinel transforms to -phase by a martensitic (shear) mechanism. There is also evidence that the mechanism changes to one involving diffusion-controlled growth at conditions close to equilibrium.     

Pressure-volume-temperature behavior of γ-Fe2SiO4 (spinel) based on static compression measurements at 400° C

Thirteen energy-dispersive x-ray diffraction spectra for -Fe₂SiO₄ (spinel) collected in situ at 400° C and pressures to 24 GPa constitute the basis for an elevated-temperature static compression isotherm for this important high-pressure phase. A Murnaghan regression of these molar volume measurements yields 177.3 (±17.4) GPa and 5.4(±2.5) for the 400° C, room pressure values of the isothermal bulk modulus (K _{P 0}) and its first pressure derivative (K _{P 0}), respectively. When compared to the room-Tdeterminations of K _{P 0} available in the literature, our 400° C K _{P 0} yields -4.1 (±6.2)×10^-2 GPa/degree for the average value of (K/T) _{P 0} over the temperature interval 25° C<><400°>A five-parameter V(P, T) equation for -Fe₂SiO₄ based on simultaneous regression of our data combined with the elevated P-Tdata of Yagi et al. (1987) and the extrapolated thermal expansion values from Suzuki et al. (1979) yields isochores which have very little curvature [(² T/P ²) _v 0], in marked contrast to the isochores for fayalite (Plymate and Stout 1990) which exhibit pronounced negative curvature [(T/P ²) _v <0]. along=" the=">-Fe₂SiO₄ reaction boundary V_Rvaries from a minimum of approximately 8.3% at approximately 450° C to approximately 8.9% at 1200° C. Extrapolation of the fayalite and -Fe₂SiO₄ V(P, T) relationships to the temperature and pressure of the 400 km discontinuity suggests a V _R of approximately 8.4% at that depth, approximately 10% less than the 9.3% V _R at ambient conditions.     

Sapphirine/kornenipine-bearing rocks and crustal uplift history of the Limpopo belt,Southern Africa

Sapphirine/kornerupine-bearing rocks occur within the anorthosites of the Messina layered intrusion in the Limpopo mobile belt of Zimbabwe. The X_Mg range of the major minerals is as follows: cordierite (0.98-0.93); enstatite (0.97-0.86); chlorite (0.98-0.92); phlogopite (0.98-0.90); sapphirine (0.98-0.86); kornerupine (0.94-0.88); gedrite (0.96-0.85); spinel (0.92-0.78). There are four rock types, the constituent minerals of which have different values, which decrease in the above mineral order; other minerals are corundum, sillimanite and relict kyanite. We recognise twenty reactions without phlogopite and nine reactions involving phlogopite. The textural relations and the plots of the microprobe data of coexisting minerals in the MgO-Al₂O₃-SiO₂-(H₂O) system are consistent with the following sequence of main reactions: (1) enstatite+corundum cordierite+sapphirine; (4) sapphirine+sillimanite cordierite+corundum; (8) kornerupine+corundum cordierite+sapphirine; (13) kornerupine cordierite+sapphirine+enstatite; (15) enstatite+spinel chlorite+sapphirine; (18) cordierite+sapphirine chlorite+corundum; (20) sapphirine chlorite+corundum+spinel. The early reactions are shown by coarse-grained reaction intergrowths, kornerupine and gedrite breakdown is shown by finer-grained symplectites, and the latest reactions by very fine-grained products in micro-fractures. These selected reactions illustrate a remarkably steep trajectory from thePT peak close to 10 kbar and 800° C to the minimum observable at 3.5–4.5 kbar and 700° C as indicated by the pure MASH system. Very rapid uplift took place under nearly isothermal conditions. The protolith of this material was possibly sedimentary, derived from altered volcanic rocks. The bulk composition is close to the composition of kornerupine or to a mixture of alunite, chlorite and pyrophyllite. These texturally and mineralogically complex rocks contain a wealth of relevant data for documenting crustal uplift history.     

Oxygen isotope geochemistry of hydrothermally-altered synmetamorphic granitic rocks from South-Central Maine,USA

Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock ¹⁸O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have ¹⁸O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of _Q–F ( ¹⁸O_quartz– ¹⁸O_feldspar)=2.4 and _Q–M ( ¹⁸O_quartz– ¹⁸O_muscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured _Q–F and _Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic ¹⁸O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock ¹⁸O>12.1 and contain quartz and feldspar with ¹⁸O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock ¹⁸O<11.4 and contain quartz and feldspar with ¹⁸O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO₂-H₂O fluids of and ¹⁸O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and ¹⁸O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO₂ were also enriched in ¹⁸O. Because CO₂ was added to the granites during hydrothermal alteration and because fluids enriched in CO₂ were enriched in ¹⁸O, some or all of the variation in ¹⁸O of altered granites may have been caused by addition of ¹⁸O to the rocks during the hydrothermal event. The source of both the CO₂ and ¹⁸O could have been high-¹⁸O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in ¹⁸O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.     

Electron paramagnetic resonance of Sc3+-stabilized CO 3 3− molecule-ion in natural calcite

Electron paramagnetic resonance (EPR) spectra of CO ₃ ^3– molecule-ions stabilized by Sc³⁺ in natural calcite were identified and studied at X-band frequencies and room temperature. The principal values of the g-tensor (g _xx= 1.9997, g _yy = 2.0030, g _zz = 1.9972) and the direction cosines of the g and A tensors for CO ₃ ^3– -Sc³⁺ center were found to be close to that for the well-known CO ₃ ^3– -Y³⁺ center. A quantitative comparison of different impurity contents in calcite samples and analysis of the intensities of forbidden transitions were used to identify Sc³⁺. An estimation of the unpaired electron spin density on the nuclei of paramagnetic centers confirms that both centers, CO ₃ ^3– -Sc³⁺ and CO ₃ ^3– -Y³⁺, have the same nature.     

The Al-Fe(III)epidote miscibility gap in a metamorphic profile through the penninic series of the Tauern window,Austria

The compositional variations in epidotes, Ca₂Al₂(Fe³⁺, Al)-Si₃O₁₂(OH), from a prograde Mesozoic rock series in the Eastern Alps, Austria, are systematically related to metamorphic grade and the oxidation state of the rock. With increasing metamorphic grade the average composition of the zoned epidotes shifts to Fe³⁺-poorer compositions reflecting not only the effect of temperature and total pressure but also the concomitant decrease of the oxidation state of the rocks. Oxidized hematite-bearing assemblages are: 90 mole % Al₂FeEp (greenschists) 70 mole % Al₂FeEp (garnet amphibolites) 58 mole % Al₂FeEp (eclogites); reduced sulfidebearing assemblages are: 42 mole % Al₂FeEp (greenschists) 24 mole % Al₂FeEp (garnet amphibolites) 23 mole % Al₂FeEp (eclogites).A similar compositional evolution of the epidotes as in the spatial sequence of the samples can be observed within the single zoned crystals, reflecting the temporal changes of temperature, total pressure and oxygen fugacity during the prograde crystallization. The Fe³⁺-contents of core and rim decrease with increasing metamorphic grade and decreasing oxidation state. Generally the zoned epidotes consist of a Fe³⁺-rich core (90 to 63 mole % Al₂FeEp) and a Fe³⁺-poorer rim (55 to 23 mole % Al₂FeEp). Core and rim of the epidote crystals are separated by a compositional gap the extension of which is independent of the bulk rock composition, the oxidation state, and the mineralogical composition of the assemblages but becomes smaller with increasing metamorphic grade: 7253 mole % Al₂FeEp (low grade greenschists, 400° C) 6355 mole % Al₂FeEp (higher grade greenschists, 500° C), and 6055 mole % Al₂FeEp (garnet amphibolites, 500–550° C). At the temperature conditions of the highest grade garnet amphibolites and eclogites (550° C) the compositional gap closes at a composition of 58 mole % Al₂FeEp.The data presented thus confirm clearly the existence of an asymmetric miscibility gap in the monoclinic Al-Fe(III)-epidote solid solution series, which, for the first time, has been assumed by Strens (1964, 1965).A model is proposed that describes the prograde compositional evolution of the epidotes studied through the competing mechanisms of growth and diffusional Al-Fe³⁺ exchange and their dependence on metamorphic grade and oxidation state.     

Oxygen isotopes in mantle related and geothermally altered magmatites of the Transhimalayan (Gangdese) ranges

In closed magma systems SiO₂ approximately measures differentiation progress and oxygen isotopes can seem to obey Rayleigh fractionation only as a consequence of the behaviour of SiO₂. The main role of ¹⁸O is as a sensitive indicator of contamination, either at the start of differentiation ( ¹⁸O_init) or as a proportion of fractionation in AFC. Plots of ¹⁸O vs SiO₂-allow to determine initial ¹⁸O values for different sequences for source comparison. For NBS-28=9.60, the ¹⁸O at 48% SiO₂-varies between a high 6.4 for Kiglapait (Kalamarides 1984), 5.9 for Transhimalaya, 5.8 for Hachijo-Jima (Matsuhisa 1979), 5.6 for Koloula (Chivas et al. 1982) and a low 5.3 for the Darran Complex, New Zealand. The Transhimalayan batholiths (Gangdese belt) were emplaced in the Ladakh-Lhasa terrane, between the present-day Banggong-Nujiang, and Indus-Yarlung Tsangbo suture zones, after its accretion to Eurasia. The gradient of the least contaminated continuous ( ¹⁸O vs SiO₂-igneous trend line is similar to that of Koloula, and AFC calculations suggest a low secondary assimilation rate of less than 0.05 times the rate of crystallisation. Outliers enriched in ¹⁸O are frequent in the Lhasa, and apparently rare in the Ladakh transsect. Low- ¹⁸O (5.0–0) granitoids and andesites on the Lhasa-Yangbajain axis are the result of present day or recent near-surface geothermal activity; their quartzes still trace the granitoids to the Transhimalaya ¹⁸O trend line, but the distribution of low total rock or feldspar ¹⁸O values could be a guide to more recent heat flow and thermally marked tectonic lineaments. Two ignimbrites from Maqiang show hardly any ¹⁸O-contamination by crustal material.     

Titania precipitation in sapphire containing iron and titanium

Titania, TiO₂, precipitation in natural blue sapphire (Fe, Ti: -Al₂O₃) has been investigated using high resolution and analytical transmission electron microscopy. The structure and habit of the TiO₂ precipitate depends on both the Ti⁴⁺ concentration and the temperature at which the precipitate formed. Tetragonal TiO₂ (Rutile) grows at 1350° C but at 1150° C an orthorhombic non-equilibrium TiO₂ polymorph precipitates. Both TiO₂ polymorphs nucleate in the (0001)s plane as lens shaped discs twinned along their diameter. The crystallographic alignment of each type of TiO₂ precipitate with respect to the -Al₂O₃ host matrix provides a high degree of structural coherency with minimal lattice mismatch. Electron diffraction analysis established the following precipitate/host orientation relationships: tetragonal TiO₂: {011}r {11 07B;100}r(0001)s and 01 r10 0s twinned along the (011)r planeand orthorhombic TiO₂: {021}{11 0}s, {100}(0001)s and 0 2 10 0s twinned along the (021) plane.     

Calibration of Al/Si order variations in anorthite

New single crystal diffraction data for natural and heat-treated anorthite crystals (Angel et al. 1990) allow the determination of their states of Al/Si order in terms of a macroscopic order parameter,Q _OD , for the transition. Numerical values ofQ _OD obtained from estimates of site occupancies are shown to vary with the scalar spontaneous strain, _s , as _s Q _OD ² , and with the ratio of the sums of typeb (superlattice) reflections and typea (sublattice) reflections asI _b/I _a Q _OD ² . An empirical calibration for pure anorthite is obtained giving varies between 0.92 and 0.87 in samples equilibrated at T1300° C, but then falls off relatively rapidly with increasing temperature, reaching 0.7 near the melting point ( 1557° C). The observed temperature dependence does not conform to the predictions of the simplest single order parameter models; coupling ofQ _OD withQ of the transition is suspeeted.     

Thermal expansion,heat capacity,and entropy of MgO at mantle pressures

The pressure dependence of the Raman spectrum of forsterite was measured over its entire frequency range to over 200 kbar. The shifts of the Raman modes were used to calculate the pressure dependence of the heat capacity, C _v, and entropy, S, by using statistical thermodynamics of the lattice vibrations. Using the pressure dependence of C _v and other previously measured thermodynamic parameters, the thermal expansion coefficient, , at room temperature was calculated from = K _S (T/P) _S C _V/TVK _T, which yields a constant value of ( ln / ln V)_T= 6.1(5) for forsterite to 10% compression. This value is in agreement with ( ln / ln V)_T for a large variety of materials.At 91 kbar, the compression mechanism of the forsterite lattice abruptly changes causing a strong decrease of the pressure derivative of 6 Raman modes accompanied by large reductions in the intensities of all of the modes. This observation is in agreement with single crystal x-ray diffraction studies to 150 kbar and is interpreted as a second order phase transition.     

Diamagnetic anisotropies of oxide minerals

The diamagnetic anisotropy of oxide minerals is analyzed in terms of a new model, in which the anisotropy is assigned to the individual chemical bond in the [MO₆] octahedral unit of the crystal. The diamagnetic principal axis of the individual M-O bond is assumed to be parallel to the direction of the bond. The calculated anisotropy based on this model shows a good correlation with the measured diamagnetic anisotropy, , for various minerals such as talc, sericite, kaolinite of the sheetsilicate group, forsterite of the orthosilicate group, and corundum of the hematite group. The values of many diamagnetic minerals are still unknown since the measurement is difficult to perform by means of conventional methods. The magnetic grain orientation recently observed in the mineral suspensions is effective for estimating the value, when the single crystal of the mineral cannot be obtained. The observation of fieldinduced crystal oscillation in the high magnetic fields can be applied for measuring the minerals with small values of less than 5 × 10^–10 emu/cc. The chemical bond model on the diamagnetic anisotropy can be confirmed, when the compiling of data on various mineral is made by means of the above two methods.