Preferred orientation in experimentally deformed limestone

Over sixty syntectonic deformation experiments in uniaxial compression have been done on fine-grained limestones in the stability fields of calcite I, calcite II and aragonite. X-ray techniques and spherical harmonic analysis of the data were used to determine preferred orientation quantitatively, and inverse pole-figures were derived for these axially symmetric specimens. They display in most cases strong preferred orientation which varies as a function of the experimental conditions, mainly temperature and pressure. At temperatures below 350° C recrystallization is lacking and flattened grains indicate that translation, twin gliding and kinking have been the dominant deformation mechanisms. The inverse pole-figure shows a maximum at c with a shoulder towards or a second maximum at e. This is in agreement with preferred orientation observed in experimentally deformed Yule marble and can be explained as the product of dominant twin gliding on e and translation gliding on r (Turner et al., 1956). At high temperatures (900–1000° C) strong grain growth (from 4 to 50 microns) indicates that the fabric recrystallized. Grains are equidimensional and clear with a marble-like texture. The inverse pole-figure shows a single maximum at r, and c-axes are oriented in a small circle around the axis of compression, ₁. Such a pattern of preferred orientation would be expected on thermodynamic grounds assuming that recrystallized grains will be oriented in such a way that the strain energy is a maximum (e.g. MacDonald, 1960). Decrease in confining pressure caused a decrease of the maximum at c and the formation of a secondary maximum at highangle positive rhombs in the inverse pole-figure. This can be interpreted as r translation dominating over e twinning. In all deformation experiments an equilibrium in preferred orientation was reached after 20 percent shortening. The strength of preferred orientation decreased with increasing temperature. Aragonite was produced within its hydrostatic stability field at temperatures above 500° C. Close to the phase boundary, coarse-grained textures showed preferred orientation with poles to (010) parallel to ₁. At higher pressures the fabric is fine-grained and [001] is aligned parallel to ₁. Evidence is given that the phase change from calcite to aragonite in these deformation experiments is a diffusive and not a martensitic transformation.Publication No. 1043, Institute of Geophysics and Planetary Physics, University of California, Los Angeles, California.     

Co2+ and Ni2+ diffusion in olivine determined by secondary ion mass spectrometry

Diffusion coefficients of Co²⁺ and Ni²⁺ in synthetic single crystal forsterite along the c-axis were determined in the temperature ranges, 700–1200?°C and 800–1300?°C, respectively. The synthesized forsterite specimens were coated with thin evaporated films of CoO and NiO on the c-surface and annealed for diffusion experiments. The short penetration distance of diffusing ions in forsterite was measured by secondary ion mass spectrometry using the depth profile method. The diffusion coefficients of Co (700–1200?°C) and Ni (800–1300?°C) are given by: and The observed diffusion coefficient values show good linear relationships in Arrhenius plots and the activation energy values obtained agree well with the previous values, although the diffusion coefficient values observed at the high temperature end of the experimental range deviate from the previous values. These results indicate that Co and Ni diffuse in olivine with a single mechanism within the temperature range observed, possibly with an extrinsic in nature as in the case of Mg tracer diffusion observed by Chakraborty et?al. 1994 and of Fe-Mg interdiffusion by Chakraborty.     

Dolomite microstructures between 390° and 700 °C: Indications for deformation mechanisms and grain size evolution

Dolomitic marble on the island of Naxos was deformed at variable temperatures ranging from 390 °C to >700 °C. Microstructural investigations indicate two end-member of deformation mechanisms: (1) Diffusion creep processes associated with small grain sizes and weak or no CPO (crystallographic preferred orientation), whereas (2) dislocation creep processes are related with larger grain sizes and strong CPO. The change between these mechanisms depends on grain size and temperature. Therefore, sample with dislocation and diffusion creep microstructures and CPO occur at intermediate temperatures in relative pure dolomite samples. The measured dolomite grain size ranges from 3 to 940 μm. Grain sizes at T_max >450 °C show an Arrhenius type evolution reflecting the stabilized grain size in deformed and relative pure dolomite. The stabilized grain size is five times smaller than that of calcite at the same temperature and shows the same Arrhenius-type evolution. In addition, the effect of second phase particle influences the grain size evolution, comparable with calcite. Calcite/dolomite mixtures are also characterized by the same difference in grain size, but recrystallization mechanism including chemical recrystallization induced by deformation may contribute to apparent non-temperature equilibrated Mg-content in calcite.     

Calcite texture development in experimentally induced ductile shear zones

Specimens of fine grained micritic limestone were deformed in plane strain geometry in pure shear, a combination of simple and pure shear, and in simple shear. Temperatures were 400° C and 500° C, confining pressure was 100 MPa. In the experiments with a simple shear component strain is concentrated and approximately homogeneous in a 2–3 mm wide shear zone. Shear displacement is documented by marker lines and circles. Shear strain γ varies between 0.84 and 1.56. Strain is recorded by flattening of individual grains, defining a foliation normal to the axis of principal finite shortening ε ₁. No twinning is observed on a macroscopic scale. X-ray and neutron diffraction techniques were used to characterize texture before and after deformation. All specimens display strong preferred orientation as documented by 0006, 10¯14 and 11¯220 pole-figures, c axes pole-figures display three maxima in the ε₁–ε₃ plane. If the axes of the strain ellipsoids are used as a coordinate system textures in pure and simple shear are similar but there is considerable monoclinic distortion in simple shear which is attributed to the noncoaxial strain path.     

Comparison of quartz microfabric with strain in recrystallized quartzite

The relationship between quartz c-axis microfabric and strain is examined in six specimens of recrystallized quartzite conglomerate in which strain was measured using pebble shapes. Four rocks subjected to plane strain display a direct relationship between the strength of preferred orientation and the strain intensity. The c-axis distributions in these rocks, as well as a rock subjected to moderate extensional strain, are crossed-girdles with maxima near the intermediate principal strain axis and connecting girdles at acute angles to the direction of maximum shortening. A rock subjected to moderate flattening strain has several maxima clustered near the direction of maximum shortening and a weak connecting girdle through the intermediate principal strain axis.These results are generally similar to those of other studies comparing strain and tectonite fabrics and also with experimental and computer simulation studies of fabrics. The degree of preferred orientation is related to total strain, and therefore microfabrics in quartzites may be cautiously interpreted as qualitative indicators of strain intensity. Uncertainties are greater, however, for correlations of fabric patterns with shapes of the strain ellipsoid. An observed increase in recrystallized grain sizes with increasing strain suggests that flow stress was lower in the more strained rocks.     

An experimental study of effect of pre‐existing fabric on deformation of foliated mylonite at high temperature and pressure

We performed deformation experiments on a foliated mylonite under high temperature and pressure conditions in this study. To investigate the effect of pre‐existing fabric on the rheology of rocks, our samples were drilled from natural mylonite with the cylinder axis parallel to the foliation (PAR) and perpendicular to the foliation (PER). We performed 25 tests on seven PAR samples and 21 tests on seven PER samples at temperatures ranging from 600 to 890 °C, confining pressures ranging from 800 to 1400 MPa, and steady‐state strain rates of 1 × 10⁻⁴, 1 × 10⁻⁵ and 2.5 × 10⁻⁶ s⁻¹. In the temperatures of 600–700 °C, the deformation is accommodated by semi‐brittle flow, with the average stress exponent being 6–7 assuming power law flow; in the temperature range of 800–890 °C, deformation is mainly by plastic flow, with an average stress exponent of n = 3 and activation energies of Q = 354 ± 52 kJ/mol (PER and PAR samples). The experimental results show that the strengths of PER samples are higher than those of PAR samples. Deformation microstructures have been studied by optical and electron microscopy. The original foliation of PER samples is destroyed by deformation and replaced by a new foliation, but the deformation of PAR samples followed the original foliation. Electron backscatter diffraction (EBSD) measurements show a strong lattice preferred orientation (LPO) of the quartz c axis fabrics of the starting samples and deformed PER and PAR samples. However, the c axis fabric of quartz in experimentally deformed PER and PAR samples varied with temperature and strain rate is different from that seen in the starting mylonite sample. The initial quartz c axis fabric of the starting mylonite sample has been transformed into a new fabric during experimental deformation. Dehydration melting of biotite and hornblende occurred in both PER and PAR samples at temperatures of 800–890 °C. Copyright © 2014 John Wiley & Sons, Ltd.     

Timing and rate of isothermal decompression in Pan-African granulites from Rundvågshetta, East Antarctica

Geochronological data, combined with field and petrological evidence, constrain the timing and rate of near‐isothermal decompression at granulite facies temperatures in rocks from the Lützow‐Holm Complex of East Antarctica. Granulite facies gneisses from Rundvågshetta in Lützow‐Holm Bay experienced a peak metamorphic temperature of over 900 °C at c. 11 kbar, as evidenced by primary orthopyroxene–sillimanite‐bearing assemblages, and secondary cordierite–sapphirine‐bearing assemblages in metapelites. Peak metamorphic assemblages show strong preferred mineral orientation, interpreted to have developed synchronously with pervasive ductile deformation. Zircon from a syndeformational leucosome has a U–Pb age of 517±9 Ma, which is interpreted as a melt crystallization age. This age provides the best estimate of the time of peak metamorphic conditions. The post‐peak metamorphic history is characterized by near‐isothermal decompression, recorded by mineral textures in a variety of rock compositions. Field and textural relations indicate that decompression post‐dated pervasive ductile deformation. K/Ar and ⁴⁰Ar/³⁹Ar ages from hornblende and biotite represent closure ages during cooling subsequent to decompression, and indicate cooling to temperatures between c. 350 and 300 °C by c. 500 Ma, thus placing a lower time limit on the duration of the high‐temperature isothermal decompression episode. The combination of the zircon age from a syndeformational melt with K/Ar and ⁴⁰Ar/³⁹Ar closure ages indicates that near‐isothermal decompression from c. 11 to c. 4 kbar at granulite facies temperatures, followed by cooling to c. 300 °C, took place within a time interval of 20±10 Myr. Simple one‐dimensional models for exhumation‐controlled cooling indicate that these data require exhumation rates of the order of c. 3 km Myr^?1 for several million years, then cessation of exhumation followed by relatively isobaric cooling during thermal re‐equilibration.     

Phase transition of potassium sulfate,K2SO4 (II); dielectric constant and electrical conductivity

The phase transition of K₂SO₄ has been investigated by measurements of the dielectric constant and electrical conductivity, correlated with the structural point of view. Using single crystals, the temperature dependences of the dielectric constants and electrical conductivities were measured at frequencies of 0.3, 1, 3, and 5 MHz in the temperature range from 20° to 640 °C. Within this range, the dielectric constant does not reach a maximum, but near the phase-transition temperature at 587° C, the dielectric constant along the c axis shows a larger discontinuity than those along the a and b axes. The temperature dependence of the dielectric constant is consistent with the disordered structure of the high temperature form. Based on the parabolic increase of the dielectric constant in the temperature range from 582° to 587° C, it is likely that the phase transition propagates through an intermediate state. The electrical conductivity coefficients of K₂SO₄ increase with increasing temperature, exhibiting semiconducting character above the phase-transition temperature. In the high-temperature form, the electrical conductivity along the a axis exceeds that along the c axis. Since the electrical conductivity of K₂SO₄ is mainly ionic in character, the migration of K⁺ ions makes a major contribution to the conduction process.     

Investigations of MX-1 tridymite by 29Si MAS NMR — Modulated structures and structural phase transitions

MX-1 tridymite is one of the room-temperature polymorphs of SiO₂ tridymite and has an underlying monoclinic structure (Cc) with incommensurate modulations along a ^* and c ^* (Hoffmann et al. 1983; Löns and Hoffmann 1987). With increasing temperature up to 500° C, MX-1 is reported to experience at least five structural phase transitions. However, its structures and the relationships to other tridymite polymorphs are unclear. We present here a ²⁹Si MAS NMR study of the room-temperature incommensurate structure of MX-1 and its structural phase transitions up to 540° C. Our results suggest that at room temperature, all the Si sites in MX-1 tridymite are in positions with similiar ∠Si-O-Si of ～150° and are consistent with the presence of two incommensurate modulations proposed by Hoffmann et al. (1983). Simulations of the spectra yield modulation amplitudes of 1.33 and 0.87 ppm, corresponding to 0.009 and 0.006 Å for Si-Si. The maximum atomic displacements along a and b due to the modulations appear to be ～0.01–0.02 Å. The structural phase transitions of MX-1 are significantly different from those of MC tridymite below 220° C. Our high temperature results confirm that MX-1 tridymite transforms to the H5 phase at about 65° C. The most important transition occurs near 110° C, where the H5 phase transforms to a phase yielding a single, narrow NMR peak, indicating the disappearance of the superstructure and possibly the onset of the dynamic averaging. The NMR lineshapes of H5 are consistent with the metrically orthorhombic unit cell and commensurate superstructure of 2a, 2b and 10c proposed by Graetsch and Flörke (1991). The phase present above 110° C is probably similar to the OC phase, but has a mean ∠Si-O-Si of ～152.0° at 113° C, 152.9° at 185° C and 154.1° at 500° C. The transitions at ～160 and 220° C for MX-1 are subtle and probably due to impurity MC. Analysis of the modulations in the OS phase of MC tridymite indicates that their amplitudes are of the order of 0.02 Å, significantly less than the value 0.3 Å proposed by Nukui et al. (1979).     

Estimation of dolomite formation: Dolomite precipitation and dolomitization

Reactive-transport models are developed here that produce dolomite via two scenarios: primary dolomite (no CaCO₃ dissolution involved) versus secondary dolomite (dolomitization, involving CaCO₃ dissolution). Using the available dolomite precipitation rate kinetics, calculations suggest that tens of meters of thick dolomite deposits cannot form at near room temperature (25-35°C) by inorganic precipitation mechanism, though this mechanism will provide dolomite aggregates that can act as the nuclei for dolomite crystallization during later dolomitization stage. Increase in supersaturation, Mg⁺²/Ca⁺² ratio and CO₃^-2 on the formation of dolomite at near room temperature are subtle except for temperature.This study suggests that microbial mediation is needed for appreciable amount of primary dolomite formation. On the other hand, reactive-transport models depicting dolomitization (temperature range of 40 to 200°C) predicts the formation of two adjacent moving coupled reaction zones (calcite dissolution and dolomite precipitation) with sharp dolomitization front, and generation of >20% of secondary porosity. Due to elevated temperature of formation, dolomitization mechanism is efficient in converting existing calcite into dolomite at a much faster rate compared to primary dolomite formation.     

The dolomitization of CaCO3: an experimental study at 252–295°C

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.     

Analbite → monalbite transition in a heat treated twinned amelia albite

Amelia albite annealed at > 1080 °C for 3200 hrs by Duba and Piwinskii (1974) shows very fine twin lamellae (～1 μm) after the albite law, suggesting that it once underwent transformation into monalbite. A fragment of this specimen was investigated at 27 °C, 300 °C, 550 °C, 800 °C and 930 °C using the high-temperature precession technique. As the temperature increases, the splitting angle of c ^*-axes (likewise c ^*-axes) of two twin individuals continues to decrease. The photographs taken at 930 °C show that these two splitting angles have converged to 0^o, indicating completion of the transformation into monalbite. The transition point we observe supports the results of MacKenzie (1952) (920±20 °C) and Grundy et al. (1967) (930 °C) rather than those of Sueno et al. (1973) and Prewitt et al. (1974) (> 1080 °C); the discrepancy is most likely due to the differences in the degree of Al-Si disorder of the samples used in the experiments.     

Transport properties of olivine grain boundaries from electrical conductivity experiments

Grain boundary processes contribute significantly to electronic and ionic transports in materials within Earth’s interior. We report a novel experimental study of grain boundary conductivity in highly strained olivine aggregates that demonstrates the importance of misorientation angle between adjacent grains on aggregate transport properties. We performed electrical conductivity measurements of melt-free polycrystalline olivine (Fo₉₀) samples that had been previously deformed at 1200 °C and 0.3 GPa to shear strains up to γ?=?7.3. The electrical conductivity and anisotropy were measured at 2.8 GPa over the temperature range 700–1400 °C. We observed that (1) the electrical conductivity of samples with a small grain size (3–6 µm) and strong crystallographic preferred orientation produced by dynamic recrystallization during large-strain shear deformation is a factor of 10 or more larger than that measured on coarse-grained samples, (2) the sample deformed to the highest strain is the most conductive even though it does not have the smallest grain size, and (3) conductivity is up to a factor of ~?4 larger in the direction of shear than normal to the shear plane. Based on these results combined with electrical conductivity data for coarse-grained, polycrystalline olivine and for single crystals, we propose that the electrical conductivity of our fine-grained samples is dominated by grain boundary paths. In addition, the electrical anisotropy results from preferential alignment of higher-conductivity grain boundaries associated with the development of a strong crystallographic preferred orientation of the grains.     

Texture development of polycrystalline anhydrite experimentally deformed in torsion

A polycrystalline aggregate of anhydrite was deformed in torsion to a maximum shear strain of 8.1 at 700°C and a maximum shear strain rate of 5᎒^-3 s^-1. The crystallographic preferred orientation (CPO or texture) was investigated as a function of shear strain/shear strain rate in a radial profile from the centre to the edge of the sample. A deformation texture developed at shear strains of 1.5-2 (corresponding to shear strain rates of 1 to 1.3᎒^-3 s^-1) and reached a stable position relative to the kinematic frame at a shear strain of 3.7 (2.3᎒^-3 s^-1). Further shear strain only led to a small increase in texture strength but no change in the orientation relative to the kinematic frame. The CPO is very similar to naturally observed textures and can be explained by the activity of the {001}<010> and {012}<121> slip systems. Although independent mechanical data indicate that a change of mechanism from dislocation- to diffusion-controlled creep occurred at a shear strain of approximately 1.5, the texture does not weaken, but rather increases, in strength with higher shear strains.     

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.     

Deformation mechanisms in experimentally deformed single crystals of pyrrhotite,Fe1−xS

Single crystals of hexagonal and monoclinic pyrrhotite, Fe_1?xS, have been experimentally deformed by uniaxial compression at 300 MPa confining pressure, and at a strain rate of 1 × 10^?5 s^?1 in the temperature range from 200° C to 400° C. Very high anisotropy characterizes the mechanical behaviour of the crystal structure. During compression parallel to thec-axis, when no slip system may be activated, the maximum strength is observed. One or two degrees of non-parallelism between [c] and σ₁ results in slip on the basal plane, illustrating the very low resistance of the lattice against shear in this plane. At σ₁ Λ(0001)=45°, i.e. when maximum resolved shear stress is attained on the basal plane, the strength reaches a minimum. Thecritical resolved shear stress (CRSS) increases from less than 4.7 MPa at 400° C to 52 MPa at 200° C. A new slip system, \((10\overline 1 0)\parallel \left\langle {1\overline 2 10} \right\rangle \) prism slip, is described. It is activated only at high angles (>70°) between σ₁ and [c]. The CRSS of the prism slip ranges from 7 MPa (400° C) to 115 MPa (200° C). Twinning on \((10\overline 1 2)[(10\overline 1 2):(1\overline 2 10)]\) , earlier reported by several authors, has been produced only at the highest temperature either as secondary feature during pressure release (compression ‖[c]) or in heterogeneously strained areas (compression ⊥[c]). As twinning and prism slip attain their maximum values of the Schmidt factor under nearly equal stress conditions it is postulated that the former of the two deformation modes has the higher shear resistance.     

The effect of cation ordering and temperature on the high-pressure behaviour of dolomite

Synchrotron single-crystal X-ray diffraction experiments at high-pressure and high-temperature conditions were performed up to 20 GPa and 573.0(2) K on a fully ordered stoichiometric dolomite and a partially disordered stoichiometric dolomite [order parameter, s = 0.26(6)]. The ordered dolomite was found to be stable up to approximately 14 GPa at ambient temperature and up to approximately 17 GPa at T = 573.0(2) K. The P–V data from the ambient temperature experiments were analysed by a second-order Birch–Murnaghan equation-of-state giving K ₀ = 92.7(9) GPa for the ordered dolomite and K ₀ = 92.5(8) GPa for the disordered dolomite. The high-temperature data, collected for the ordered sample, were fitted by a third-order Birch–Murnaghan equation-of-state resulting in K ₀ = 95(6) GPa and K′ = 2.6(7). In order to compare the three experiments results, a third-order Birch–Murnaghan equation-of-state was also calculated for the ambient temperature experiments giving K ₀ = 93(3) GPa, K′ = 3.9(6) for the ordered dolomite and K ₀ = 92(3) GPa, K′ = 4.0(4) for the disordered dolomite. The derived axial moduli show that dolomite compresses very anisotropically, being the c-axis approximately three times more compressible than the a-axis. The axial compressibility increases as T increases, and the a-axis is the most temperature-influenced axis. On the contrary, axial compressibility is not influenced by disordering. Structural refinements at different pressures show that Ca and Mg octahedra are almost equally compressible in the ordered dolomite with K(CaO₆) = 109(4) GPa and K(MgO₆) = 103(3) GPa. On the contrary, CaO₆ compressibility is reduced and MgO₆ compressibility is increased in the disordered crystal structure where K(CaO₆) = 139(4) GPa and K(MgO₆) = 89(4) GPa. Disordering is found to increase CaO₆ and to decrease MgO₆ bond strengths, thus making stiffer the Ca octahedron and softer the Mg octahedron. Cation polyhedra are distorted in both ordered and disordered dolomites and they increase in regularity as P increases. Ordered dolomite approaches regularity at approximately 14 GPa. The increase in regularity of octahedra in the disordered dolomite is strongly affected by the very slow regularization of MgO₆ with respect to CaO₆. The phase transition to the high-pressure polymorph of dolomite (dolomite-II), which is driven by a significant increase in the regularity of both cations polyhedra and mineral crystal structure, occurs in the ordered dolomite at ambient temperature at approximately 14 GPa; whereas no clear evidences of phase transition were observed as regards the disordered crystal structure.     

Thermal metamorphism of the Arunachal Himalaya, India: Raman thermometry and thermochronological constraints on the tectono-thermal evolution

Determination of the peak thermal condition is vital in order to understand tectono-thermal evolution of the Himalayan belt. The Lesser Himalayan Sequence (LHS) in the Western Arunachal Pradesh, being rich in carbonaceous material (CM), facilitates the determination of peak metamorphic temperature based on Raman spectroscopy of carbonaceous material (RSCM). In this study, we have used RSCM method of Beyssac et al. (J Metamorph Geol 20:859–871, 2002a) and Rahl et al. (Earth Planet Sci Lett 240:339–354, 2005) to estimate the thermal history of LHS and Siwalik foreland from the western Arunachal Pradesh. The study indicates that the temperature of 700–800 °C in the Greater Himalayan Sequence (GHS) decreases to 650–700 °C in the main central thrust zone (MCTZ) and decreases further to <200 °C in the Mio-Pliocene sequence of Siwaliks. The work demonstrates greater reliability of Rahl et al.’s (Earth Planet Sci Lett 240:339–354, 2005) RSCM method for temperatures >600 and <340 °C. We show that the higher and lower zones of Bomdila Gneiss (BG) experienced temperature of ~600 °C and exhumed at different stages along the Bomdila Thrust (BT) and Upper Main Boundary Thrust (U.MBT). Pyrolysis analysis of the CM together with the Fission Track ages from upper Siwaliks corroborates the RSCM thermometry estimate of ~240 °C. The results indicate that the Permian sequence north of Lower MBT was deposited at greater depths (>12 km) than the upper Siwalik sediments to its south at depths <8 km before they were exhumed. The ⁴⁰Ar/³⁹Ar ages suggest that the upper zones of Se La evolved ~13–15 Ma. The middle zone exhumed at ~11 Ma and lower zone close to ~8 Ma indicating erosional unroofing of the MCT sheet. The footwall of MCTZ cooled between 6 and 8 Ma. Analyses of P–T path imply that LHS between MCT and U.MBT zone falls within the kyanite stability field with near isobaric condition. At higher structural level, the temperatures increase gradually with P–T conditions in the sillimanite stability field. The near isothermal (700–800 °C) condition in the GHS, isobaric condition in the MCTZ together with T–t path evidence of GHS that experienced relatively longer duration of near peak temperatures and rapid cooling towards MCTZ, compares the evolution of GHS and inverted metamorphic gradient closely to channel flow predictions.     

Rutile/TiO<Subscript>2</Subscript>II phase equilibria

The transition between rutile and α-PbO₂ structured TiO₂ (TiO₂II) has been investigated at 700–1,200 °C and 4.2–9.6 GPa. Hydrothermal phase equilibrium experiments were performed in the multi-anvil apparatus to bracket the phase boundary at 700, 1,000, and 1,200 °C. The equilibrium phase boundary is described by the equation: P (GPa)=1.29+0.0065 T ( °C). In addition, growth of TiO₂II was observed in experiments at 500 and 600 °C, although growth of rutile was too slow to bracket unambiguously the equilibrium boundary at these temperatures. Water was not detected in either rutile or TiO₂II, and dry synthesis experiments at 1,200 °C were consistent with the phase boundary determined in the fluid-bearing experiments, suggesting that the equilibrium is unaffected by the presence of water. Our bracket of the phase boundary at 700 °C is consistent with the reversed, dry experiments of Akaogi et al. (1992) and the reversals of Olsen et al. (1999). The new data suggest that the phase boundary is linear, in agreement with Akaogi et al. (1992), but in striking contrast to the phase diagram inferred by Olsen et al. (1999). The natural occurrence of TiO₂II requires formation pressures considerably higher than the graphite–diamond phase boundary.     

Ionic conductivity in sodium magnesium silicates

Na₂MgSiO₄ crystals prepared hydrothermally at 700° C and 3,000 atm are related to carnegieite with SG Pmn2₁, a=7.015(2), b=10.968(2), and c=5.260(1). Na conductivity in Na₂MgSiO₄ is 3.0×10^?5 (ohm-cm)^?1 at 300° C but can be raised to 1.1×10^?3 (ohm-cm)^?1 by creating Na vacancies in the composition Na_1.9Mg_0.9Al_0.1O₄. Na₄Mg₂Si₃O₁₀ is also a cristobalite-related carnegieite with the orthorhombic cell a=10.584(7), b=14.328(7), and c=5.233(5). The Na conductivity of Na₄Mg₂Si₃O₁₀ is 4.8×10^?3 (ohm-cm)^?1 at 300° C.