Mineralogy,Mössbauer spectra and electrical conductivity of triphylite Li(Fe<Superscript>2+</Superscript>,Mn<Superscript>2+</Superscript>) PO<Subscript>4</Subscript>

The electrical conductivity of monocrystalline triphylite, Li(Fe²⁺,Mn²⁺)PO₄, with the orthorhombic olivine-type structure was measured parallel (∥) to the [010] direction and ∥ [001] (space group Pnma), between ～400 and ～700 K. Electrical measurements on triphylite are of technological interest because LiFePO₄ is a promising electrode material for rechargeable Li batteries. Triphylite was examined by electron microprobe, ICP atomic emission spectroscopy, X-ray diffraction, Mössbauer spectroscopy and microscopic analysis. The DC conductivity σ_DC was determined from AC impedance data (20 Hz–1 MHz) extrapolating to zero frequency. Triphylite shows σ_DC with activated behavior measured ∥ [010] between ～500 and ～700 K during the first heating up, with activation energy of E _A = 1.52 eV; on cooling E _A = 0.61 eV was found down to ～400 K and extrapolated σ_DC (295 K) ～10^?9 Ω^?1cm^?1; ∥ [001] E _A = 0.65 eV and extrapolated σ_DC(295 K) ～10^?9 to 10^?10 Ω^?1cm^?1, measured during the second heating cycle. The enhanced AC conductivity relative to σ_DC at lower temperatures indicates a hopping-type charge transport between localized levels. Conduction during the first heating up is ascribed to ionic Li⁺ hopping. DC polarization experiments showed conduction after the first heating up to be electronic related to lowered activation energy. Electronic conduction appears to be coupled with the presence of Li⁺ vacancies and Fe³⁺, formed by triphylite alteration. For comparison, σ_DC was measured on the synthetic compound LiMgPO₄ with olivine-type structure, where also an activated behavior of σ_DC with E _A ～1.45 eV was observed during heating and cooling due to ionic Li⁺ conduction; here no oxidation can occur associated with formation of trivalent cations.     

Experimental Study of the Melting Reaction and Genetic Mechanism of Mineral Phase Transformation in Granulite Facies Metamorphism

The high-temperature and high-pressure experiment on natural block rock indicates that dehydration-melting of hydrous biotite (Bi) and partial melting of felsic minerals in garnet-biotite-plagioclase gneiss are mainly controlled by temperature, while mineral phase transformation is not only controlled by temperature-pressure conditions but also genetically associated with hydrous mineral dehydration-melting and partial melting of felsic minerals. According to the characteristics of biotite dehydration-melting and garnet transformation reaction, three stages may be distinguished: (1) when the experimental temperature is 700℃, biotite transforms to ilmenite (Ilm) + magnetite (Mt) + H2O and garnet to magnetite (Mt); (2) when the temperature is 730-760℃, biotite is dehydrated and melted and transformed into K2O-rich melt + Ilm + Mt, and garnet, into hypersthene (Hy) + cordierite (Crd); (3) when the temperature is up to or higher than 790℃, biotite is dehydrated and melted and transformed into melt + Hy +     

Pressure and composition dependence of the electrical conductivity of iron-rich synthetic olivines to 200 kbar

The objectives of this study of olivines are, to calibrate the variation of electrical conductivity with pressure, up to 200 kbar in a diamond-anvil cell, and to determine how this is influenced by chemical composition. Experimentally, we have found that the variation of the electrical conductivity of three synthetic olivines containing 50, 75 and 100 mole percent of fayalite, is an exponential function of pressure P, closely represented at room temperature by:σ_xP=σ_x·exp ·(B _x·P) where x is the iron content of the olivine, σ _x the extrapolated value of conductivity at normal pressure and B _x the slope of the regression line in semi-logarithmic coordinates. It is thus possible to express the temperature dependence of conductivity through the Boltzmann relationship:σ_xPT= σ_αT· exp ·(-H*/RT)=σ_xT·exp ·[-(E*+PV _* ^x )/RT] where H* is the activation enthalpy, E* the activation energy and V _x ^* the activation volume. At constant temperature V _* ^x =B _x·RT and is approximately equal to 0,6 cm³/mole at 295 K. On the other hand, we have found that σ_xT is an exponential function of x and thus, B _x and of course V _x ^* are linear functions. The experimental procedure is described and the results discussed.     

High temperature creep of single crystal gadolinium gallium garnet

High temperature creep of single crystal gadolinium gallium garnet (GGG) was studied in the temperature range of 1723–1853 K (0.86–0.94 T_m, T_m: melting temperature) and strain rate from 9 · 10^?7 s^?1 to 2 · 10^?5 s^?1. The compression tests were made along the 〈100〉 and 〈111〉 orientations. We have performed both constant strain-rate and stress-dip tests. For the 〈100〉 orientation, deformation occurs via the 〈111〉 slip systems. For the 〈111〉 orientation, both the 〈100〉 {010} and the 〈111〉 slip systems can be activated. GGG garnet is very strong under these conditions: σ/μ=(1–3)×10^?3 (σ: creep strength, μ: shear modulus). The creep behavior is characterized by a power law with stress exponent n=2.9–3.3 and high activation energies E^*=612–743 kJ/mol (E^*～45×RT_m, at zero stress which decrease with the increase of stress). Stress-dip tests suggest a small internal stress (σ_i/σ～0.62; σ_i: internal stress, σ: applied stress) compared to other materials. These results suggest that the high creep strength of GGG is mainly due to difficulty of dislocation glide rather than dislocation climb.     

Water activity changes across an amphibolite-granulite facies transition,Broken Hill,Australia

Phase compositions in pelitic and mafic gneisses place tight constraints on pressure (ranging from 3 up to 6 kb), and, to a lesser extent, on temperature (500° up to 800° C) during prograde regional metamorphism of the Willyama Complex, Broken Hill, SE Australia. These limits allow an evaluation of water activity across the terrain using various equilibria in pelitic and mafic gneisses. The stability of cummingtonite and biotite over much of the terrain places upper limits on temperature, and the presence of syn-metamorphic partial melts in the metasediments places lower limits on a(H₂O). Garnet-biotitesillimanite-K feldspar-quartz relations combined with the partial melting data suggest a decrease in water activity from near 1.0 in the lower grade zones to 0.5±0.2 in the Broken Hill — Little Broken Hill part of the two pyroxene zone. This result is compatible with less precise hornblende-orthopyroxene-clinopyroxene-quartz relations.These P-T-a(H₂O) data from the Willyama Complex support a continuum from amphibolite to granulite facies, as proposed by Binns (1964) and suggest that the higher grade assemblages are formed in response to both higher temperature and lower water activity. The formation of granulite facies terrains by prior crustal dehydration is unsubstantiated in the present example. Instead, the decrease from a(H₂O)-1.0 in the andalusite/sillimanite-muscovite zones to a(H₂O) < 1.0 found at higher grades, is likely to reflect buffering by partial melting and dehydration reactions in the volumetrically dominant metasediments.     

An experimental study of grain scale melt segregation mechanisms in two common crustal rock types

Creation of pathways for melt to migrate from its source is the necessary first step for transport of magma to the upper crust. To test the role of different dehydration‐melting reactions in the development of permeability during partial melting and deformation in the crust, we experimentally deformed two common crustal rock types. A muscovite‐biotite metapelite and a biotite gneiss were deformed at conditions below, at and above their fluid‐absent solidus. For the metapelite, temperatures ranged between 650 and 800 °C at P_c=700 MPa to investigate the muscovite‐dehydration melting reaction. For the biotite gneiss, temperatures ranged between 850 and 950 °C at P_c=1000 MPa to explore biotite dehydration‐melting under lower crustal conditions. Deformation for both sets of experiments was performed at the same strain rate (ε.) 1.37×10^?5 s^?1. In the presence of deformation, the positive ΔV and associated high dilational strain of the muscovite dehydration‐melting reaction produces an increase in melt pore pressure with partial melting of the metapelite. In contrast, the biotite dehydration‐melting reaction is not associated with a large dilational strain and during deformation and partial melting of the biotite gneiss melt pore pressure builds more gradually. Due to the different rates in pore pressure increase, melt‐enhanced deformation microstructures reflect the different dehydration melting reactions themselves. Permeability development in the two rocks differs because grain boundaries control melt distribution to a greater extent in the gneiss. Muscovite‐dehydration melting may develop melt pathways at low melt fractions due to a larger volume of melt, in comparison with biotite‐dehydration melting, generated at the solidus. This may be a viable physical mechanism in which rapid melt segregation from a metapelitic source rock can occur. Alternatively, the results from the gneiss experiments suggest continual draining of biotite‐derived magma from the lower crust with melt migration paths controlled by structural anisotropies in the protolith.     

Significance of OH,F and Cl content in biotite during metamorphism of the Western Adamello contact aureole

The hydroxyl (O(4)) site composition of biotite can in principle be used to retrieve information about fluid composition during fluid–rock interaction; however, due to low F and Cl content, as well as difficulties involved with analyzing the H₂O content using in situ techniques, measuring these species in biotite has remained an elusive goal. Here we present high-precision secondary ion mass spectrometry (SIMS) OH–F–Cl measurements from biotite within metapelites from the Western Adamello Tonalite (WAT) contact aureole, Northern Italy. Fluorine, chlorine and hydrogen are analyzed on the SIMS sequentially by peak-hopping at the same biotite spot; H₂O, F and Cl content were measured with a precision (1σ) οφ 0.06 ωτ%, 50 ανδ 5 ππµ, ρεσπεχτι?ελψ. The compositions of isolated biotite crystals in andalusite are compared with that of biotite in the matrix, documenting that halogens and H₂O behave refractory in biotite during the time scale of contact metamorphism. The H₂O and halogen contents of biotite are mostly locked in during the prograde to peak formation of biotite, and are not reset during further heating or cooling, unless significant biotite recrystallization occurs. It also appears that both Ti content and X_Mg of the biotite from the Western Adamello contact aureole were not significantly reset during cooling. The concentration of F and Cl does not vary systematically with metamorphic grade, which indicates that these species reflect initial compositions. No significant Rayleigh fractionation behavior was observed for these elements. H₂O variations in the biotite from samples throughout the Western Adamello contact aureole suggest that Al-oxy substitution partially controls the variations in OH content through charge balance of the type R^2+,VI + OH^? = Al^3+,VI + O^2? + H₂, while the Ti-oxy substitution does not seem to influence the O(4) site occupation. The main titanium substitution appears to be the Ti-vacancy (\({\text{2}}{{\text{R}}^{{\text{2}}+}}~=~{\text{T}}{{\text{i}}^{{\text{4}}+}}~+\,{\square ^{{\text{VI}}}}\)) exchange. Variations in H₂O and halogen concentrations in biotite define sub mm-scale areas of localized equilibration, even for biotite recrystallized during dehydration reactions that produced large amounts of fluid (chlorite or muscovite breakdown). Similar systematics were observed for Ti⁴⁺ and Al³⁺. These findings further support the increasing number of observations that kinetics control much of the mineralogical reactions occurring in contact aureoles, and hence care is advised in using equilibrium thermodynamics in this environment.     

Geochronology and stable isotope signature of alteration related to hydrothermal magnetite ores in Central Anatolia,Turkey

Hydrothermal iron ores at Divri?i, east Central Anatolia, are contained in two orebodies, the magnetite-rich A-kafa and the limonitic B-kafa (resources of 133.8 Mt with 56% Fe and 0.5% Cu). The magnetite ores are hosted in serpentinites of the Divri?i ophiolite at the contact with plutons of the Murmano complex. Hydrothermal biotite from the Divri?i A-kafa yield identical weighted mean plateau ages of 73.75?±?0.62 and 74.34?±?0.83 Ma (2σ). This biotite represents a late alteration phase, and its age is a minimum age for the magnetite ore. Similar magnetite ores occur at Hasançelebi and Karakuz, south of Divri?i. There, the iron ores are hosted in volcanic or subvolcanic rocks, respectively, and are associated with a voluminous scapolite ± amphibole ± biotite alteration. At Hasançelebi, biotite is intergrown with parts of the magnetite, and both minerals formed coevally. The weighted mean plateau ages of hydrothermal biotite of 73.43?±?0.41 and 74.92?±?0.39 Ma (2σ), therefore, represent mineralization ages. Hydrothermal biotite from a vein cutting the scapolitized host rocks south of the Hasançelebi prospect has a weighted mean plateau age of 73.12?±?0.75 Ma (2σ). This age, together with the two biotite ages from the Hasançelebi ores, constrains the minimum age of the volcanic host rocks, syenitic porphyry dikes therein, and the scapolite alteration affecting both rock types. Pyrite and calcite also represent late hydrothermal stages in all of these magnetite deposits. The sulfur isotope composition of pyrite between 11.5 and 17.4‰ δ³⁴S_(VCDT) points towards a non-magmatic sulfur source of probably evaporitic origin. Calcite from the Divri?i deposit has δ¹⁸O_(VSMOV) values between +15.1 and +26.5‰ and δ¹³C_(VPDB) values between ?2.5 and +2.0‰, which are compatible with an involvement of modified marine evaporitic fluids during the late hydrothermal stages, assuming calcite formation temperatures of about 300°C. The presence of evaporite-derived brines also during the early stages is corroborated by the pre-magnetite scapolite alteration at Divri?i, and Hasançelebi-Karakuz, and with paleogeographic and paleoclimatic reconstructions. The data are compatible with a previously proposed genetic model for the Divri?i deposit in which hydrothermal fluids leach and redistribute iron from ophiolitic rocks concomitant with the cooling of the nearby plutons.     

Dehydration melting and the granulite transition in metapelites from southern Namaqualand,S. Africa

In a prograde amphibolite-granulite transition zone in the Namaqualand Metamorphic Complex, metapelites show an interbanding of the amphibolite facies association biotite+sillimanite+quartz with the granulite facies association garnet+cordierite+K-feldspar. Relict graded bedding shows that compositional banding is of sedimentary origin. The garnet-cordierite-K-feldspar gneisses contain quartzofeldspathic segregations surrounding garnets, and have more Fe-rich bulk compositions than the biotite-sillimanite schists.The contrasting asemblages could have formed at the same pressure and temperature provided that a(H₂O) was systematically lower in the garnet-cordierite-K-feldspar layers. The a(H₂O) reduction resulted from the production of silicate melt by a vapour-absent continuous Fe-Mg reaction such as biotite+sillimanite+quartz=garnet+K-feldspar+liquid which affects Fe-rich compositions before vapour-absent melting occurs in more Mg-rich rocks. The segregations represent the solid and liquid products of the reaction.Such processes imply local control of a(H₂O), and indicate that this granulite transition did not result from a regional influx of metasomatising fluids.     

Geochemical constraints on crustal anatexis: a case study from the Pan-African Damara granitoids of Namibia

 Major and trace element models of recently published vapour-absent mica dehydration melting experiments are used to identify granitoids generated by muscovite and biotite dehydration melting, and to distinguish between plagioclase-limited and biotite-limited, biotite dehydration melting. In the case of granitoids from the Pan-African Damara mobile belt (Namibia), many of the leucogranites and Salem-type granitoids may be modelled by biotite dehydration melting. The low Rb/Sr granitoids (e.g. Donkerhuk Onanis, Salem Onanis, Donkerhuk Nomatsaus, Salem Goas) probably reflect feldspar-limited, biotite dehydration melting (a pelitic source) whereas the high Rb/Sr suites (e.g. Bloedkoppie leucogranite, Stinkbank leucogranite, Salem Swakopmund, Leucocratic Stink bank granite) reflect biotite-limited, biotite dehydration melting (a greywacke source). Alaskites from the Damara belt have major element compositions which are consistent with muscovite dehydration melting, and their positive Eu anomalies are linked to high K₂O reflecting K-feldspar entrainment. Combined Zr and LREE (light rare earth element) solubility models indicate that insufficient time (probably less than 10⁴ years) had elapsed between melt generation and melt extraction to ensure that the alaskite melts attained their equilibrium concentrations of Zr and the LREEs. In contrast, the leucogranites and Salem-type granites have attained their equilibrium inventories of these trace elements. Combined Fe₂O₃ and MgO contents in some samples from two granitoids (the Salem Goas and Donkerhuk Onanis intrusions) are higher than those readily attainable by biotite dehydration melting indicating either: (1) that they contain a contribution from melts generated by incipient garnet breakdown or; (2) that they contain small amounts of an entrained ferromagnesian phase. Received: 24 April 1995/Accepted: 11 December 1995     

Wind dependence of quasi-specular sea scatter

Earlier investigations have shown that a power law relationship of the typeσ=aW ^b exists between the scattering coefficientσ and sea surface wind speedW at microwave frequencies. The coefficientsa andb are usually quoted for different frequencies, look angles, polarizations etc. This paper attempts to define the angular dependence using such a power law relationship in the quasi-specular range.     

Reversible hydration in synthetic mixite, BiCu6(OH)6(AsO4)3·nH2O (n≤3): hydration kinetics and crystal chemistry

 The presence of zeolitic water, with a reversible hydration behaviour, was determined by structural and kinetic studies on synthetic mixite BiCu₆(OH)₆(AsO₄)₃·nH₂O (n≤3). X-ray diffraction and infrared-spectroscopic investigations were performed on single crystals. Isothermal thermogravimetric experiments were carried out to determine the reaction kinetics of the de- and rehydration processes. The single-crystal structure refinement of a fully hydrated crystal yielded five partially occupied Ow positions (Ow=oxygen atom of a H₂O molecule) within the tube-like channels of the hexagonal [BiCu₆(OH)₆(AsO₄)₃] framework. For the partially dehydrated form, with n≈1, at least two of these sites were found to be occupied significantly. In addition, the structural investigations allowed two different intra-framework hydrogen bonds to be distinguished that are independent of the extra-framework water distribution and are responsible for the stability of the self-supporting framework. The kinetic analysis of the rate data in the 298–343K temperature range shows that the dehydration behaviour obeys a diffusion-controlled reaction mechanism with an empirical activation energy of E _a ^dehyd=54±4 kJ mol^–1. A two-stage process controls rehydration of which the individual steps were attributed to an initial surface-controlled (E _a ^hyd-I=6±1 kJ mol^–1) and subsequent diffusion-controlled reaction mechanism (E _a ^hyd-II=12±1 kJ mol^–1). The estimated hydration enthalpy of 42±5 kJ mol^–1 supports the distribution model of molecular water within the channels based on a purely hydrogen-bonded network. Received June 26, 1996 / Revised, accepted November 11, 1996     

Is there Link between the Type of the Volumetric Strain Curve and Elastic Constants, Porosity, Stress and Strain Characteristics ?

The stress [crack damage stress (σ _cd) and uniaxial compressive strength (σ _c)] and strain characteristics [maximum total volumetric strain (ε _cd), axial failure strain (ε _af)], porosity (n) and elastic constants [elastic modulus (E) and Poisson’s ratio (ν)] and their ratios were coordinated with the existence of two different types (type 1 and type 2) of volumetric strain curve. Type 1 volumetric strain curve has a reversal point and, therefore, σ _cd is less than the uniaxial compressive strength (σ _c). Type 2 has no reversal point, and the bulk volume of rock decreases until its failure occurs (i.e., σ _cd = σ _c). It is confirmed that the ratio between the elastic modulus (E) and the parameter λ = n/ε _cd strongly affects the crack damage stress (σ _cd) for both type 1 and type 2 volumetric strain curves. It is revealed that heterogeneous carbonate rock samples exhibit different types of the volumetric strain curve even within the same rock formation, and the range of σ _cd/σ _c = 0.54–1 for carbonate rocks is wider than the range (0.71 < σ _cd/σ _c < 0.84) obtained by other researchers for granites, sandstones and quartzite. It is established that there is no connection between the type of the volumetric strain curve and values of n, E, σ _cd, ν, E/(1 ? 2ν), M _R = E/σ _c and E/λ. On the other hand, the type of volumetric strain curve is connected with the values of λ and the ratio between the axial failure strain (ε _af) and the maximum total volumetric strain (ε _cd). It is argued that in case of small ε _af/ε _cd–small λ, volumetric strain curve follows the type 2.     

Dehydration melting of tonalites. Part I. Beginning of melting

 The beginning of dehydration melting in the tonalite system (biotite-plagioclase-quartz) is investigated in the pressure range of 2–12 kbar. A special method consisting of surrounding a crystal of natural plagioclase (An₄₅) with a biotite-quartz mixture, and observing reactions at the plagioclase margin was employed for precise determination of the solidus for dehydration melting. The beginning of dehydration melting was worked out at 5 kbar for a range of compositions of biotite varying from iron-free phlogopite to iron-rich Ann₇₀, with and without titanium, fluorine and extra aluminium in the biotite. The dehydration melting of phlogopite + plagioclase (An₄₅) + quartz begins between 750 and 770°C at pressures of 2 and 5 kbar, at approximately 740°C at 8 kbar and between 700 and 730°C at 10 kbar. At 12 kbar, the first melts are observed at temperatures as low as 700°C. The data indicate an almost vertical dehydration melting solidus curve at low pressures which bends backward to lower temperatures at higher pressures (> 5 kbar). The new phases observed at pressures ≤ 10 kbar are melt + enstatite + clinopyroxene + potassium feldspar ± amphibole. In addition to these, zoisite was also observed at 12 kbar. With increasing temperature, phlogopite becomes enriched in aluminium and deficient in potassium. Substitution of octahedral magnesium by aluminium and titanium in the phlogopite, as well as substitution of hydroxyl by fluorine, have little effect on the beginning of dehydration melting temperatures in this system. The dehydration melting of biotite (Ann₅₀) + plagioclase (An₄₅) + quartz begins 50°C below that of phlogopite bearing starting composition. Solid reaction products are orthopyroxene + clinopyroxene + potassium feldspar ± amphibole. Epidote was also observed above 8 kbar, and garnet at 12 kbar (750°C). The experiments on the iron-bearing system performed at ≤ 5 kbar were buffered with NiNiO. The f _{O 2} in high pressure runs lies close to CoCoO. With the substitution of octahedral magnesium and iron by aluminium and titanium, and replacement of hydroxyl by fluorine in biotite, the beginning of dehydration melting temperatures in this system increase up to 780°C at 5 kbar, which is 70°C above the beginning of dehydration melting of the assemblage containing biotite (Ann₅₀) of ideal composition. The dehydration melting at 5 kbar in the more iron-rich Ann₇₀-bearing starting composition begins at 730°C, and in the Ann₂₅-bearing assemblage at 710°C. This indicates that quartz-biotite-plagioclase assemblages with intermediate compositions of biotite (Ann₂₅ and Ann₅₀) melt at lower temperatures as compared to those containing Fe-richer or Mg-richer biotites. This study shows that the dehydration melting of tonalites may begin at considerably lower temperatures than previously thought, especially at high pressures (>5 kbar). Received: 27 December 1995 / Accepted: 7 May 1996     

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite-phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r_Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r_Fe=k_H(a_H+)^m+k_L(a_L)¹ where k is the apparent rate constant, a_H+ and a_L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.     

Fluid heterogeneities and hornblende stability in interlayered graphitic and nongraphitic schists (Tauern Window,Eastern Alps)

The assemblage hornblende+white mica occurs in graphite-free schists at two localities in the southwest corner of the Tauern Window, Eastern Alps. In interbedded graphitic layers (1 mm to 1 m thick), however, hornblende is typically replaced by pseudomorphs of biotite+plagioclase +epidote±chlorite+staurolite in the presence of white mica. Garnets adjacent to these pseudomorphs have pronounced growth discontinuities near their rims, in contrast to the continuously zoned garnets in nongraphitic layers. These observations imply that reactions of the type hbl+white micagar+bio+plag+epid±chl±staur +H₂O occurred in the graphitic samples, but that hbl+white mica remained stable in graphite-free layers.Calculation of the equilibrium constants for solid phases in five dehydration equilibria at locality 1 indicates thata(H₂O) in the nongraphitic layers was 6 to 11 times greater thana(H₂O) in the graphitic layers. Similar calculations involving six dehydration equilibria at locality 2 show no difference ina(H₂O) between layers at the conditions of final equilibration. Initial differences in fluid composition maintained between the graphitic and nongraphitic layers caused the hbl+white mica reaction to occur at differentP-T conditions in different horizons of the schists.These data indicate that systematic differences in fluid composition were generated during metamorphism of the interlayered graphitic and non-graphitic schists but were subsequently homogenized at locality 2. The heterogeneities could initially have been produced while the rocks were in theP-T field of CO₂-H₂O immiscibility. Development of a penetrative, layer-parallel shear foliation at this time would have prevented subsequent mixing of the fluids across layers after temperatures exceeded the consolute temperature in the CO₂-H₂O system. Late-stage homogenization of fluids at locality 2 is thought to reflect loss of the buffer capacity of the mineral assemblage in response to total consumption of hornblende.     

Mineralogy, Mössbauer spectroscopy and electrical conductivity of heterosite (Fe3+, Mn3+)PO4

Mineralogical analysis, electrical conductivity and thermopower are reported for monocrystalline heterosite (Fe³⁺, Mn³⁺)PO₄ with the orthorhombic olivine-type structure. The ⁵⁷Fe Mössbauer spectrum could be adequately described using two Fe³⁺ doublets. By impedance spectroscopy (20 Hz–1 MHz) the electrical DC conductivity σ_DC and AC conductivity σ_AC were determined parallel (∥) and perpendicular to the [001] direction (space group Pnma) in the range ～160–440 K. The graph log σ_DC?1/T shows a slightly bent curve in both directions with activation energies of E _A ～0.30 and ～0.15 eV in the high and low temperature ranges, respectively. The reduced E _A is associated with electronic conduction; σ_DC ∥ [001] follows Mott’s T ^1/4 variable range hopping law at lower temperatures with hopping between localized levels. The values of σ_AC are increased relative to σ_DC at high frequencies and low temperatures, obeying Jonscher’s universal dynamic response law; for σ_AC ∥ [001], the variation with temperature of the frequency exponent is in fair agreement with the model of small polaron hopping. The absolute thermopower Θ is negative and low between ～295 and ～440 K, Θ does hardly vary with temperatures in both directions; the temperature independency of Θ ∥ [001] is consistent with the small polaron hopping model.     

Paleoproterozoic migmatitic gneisses from the Tandilia belt (Argentina), Río de la Plata craton,record cooling at deep crustal levels

We studied high-grade metamorphic rocks of the El Cristo hill area of the Tandilia belt. Mineral analyses and thermodynamic calculations were carried out for two adjacent rock samples: an amphibole–biotite gneiss and a garnet–biotite-bearing migmatite. Peritectic garnets in the migmatite show core compositions of pyr_4.5(gro + andr)₁₀spes₆alm_79.5 changing to pyr_3.5(gro + andr)₁₇spes₆alm_73.5 at their thin rims. Garnet compositions in the gneiss are pyr_6.5(gro + andr)₂₆spes₁₂alm_55.5 and pyr_4.5(gro + andr)₃₄spes₁₂alm_49.5 for core and rim, respectively. A P–T path was constructed by calculating pseudosections in the 11-component system Si–Ti–Al–Fe–Mn–Mg–Ca–Na–K–O–H and contouring them by isopleths for garnet components using the PERPLE_X software package. Supra-solidus crystallization of garnet cores in the migmatite began at 5.8 kbar and 660 °C. Garnet rims equilibrated at 7.0 kbar and 640 °C compatible with garnet cores in the amphibole–biotite gneiss (7.6 kbar and 660 °C). The further chemical development of garnet in this rock points to P–T conditions of 11.6 kbar and 620 °C and 12.2 kbar and 595 °C (outermost garnet rim). At this high-pressure stage Ca-amphibole was not stable. Most biotite formed during exhumation whereas the high-pressure accessory minerals, titanite and epidote, persisted. According to the obtained anti-clockwise P–T path the originally partly melted material was tectonically transported from ∼22 km (middle crust) to ∼40 km (lower crust) depths reaching a geothermal gradient as low as 15 °C km⁻¹. This transport probably occurred along a major suture zone, which was active during the Paleoproterozoic (2.25–2.10 Ga), before a terminating collision of terranes near the SW boundary of the Rio de la Plata craton.     

Rectangular parallellepiped resonance method for piezoelectric crystals and elastic constants of alpha-quartz

A theory is presented on the free osculations of a rectangular parallelepiped of piezoelectric crystal, by extending the theory of the rectangular parallelepiped resonance (RPR) method to determine elastic constants of crystals, as exemplified by an alpha-quartz specimen. The piezoelectric contribution to resonance frequencies was examined numerically on the specimen, and it was revealed that piezoelectricity causes approximately 5 kHz increase around 1 MHz. The resonance frequencies of the specimen were measured and inverted to elastic constants by least squares inversion. The inversion was by both the previous non-piezoelectric or elastic theory and by the present piezoelectric theory. The use of the non-piezoelectric theory resulted in an overestimate of 2σ or 0.6% in c ₁₁ and underestimate of σ or 6% in c ₁₂. These are the constants expected to be most affected by piezoelectricity. Errors are less than σ in the other constants. During measurement, it was found that the force applied to hold the specimen caused deviations from free oscillation and experimental errors of 5 kHz. The correction for this force is of some importance in RPR studies of piezoelectric crystals.     

Ab initio calculations of 17O and nT NMR parameters (nT=31P, 29Si) in H3 TOTH3 dimers and T 3O9 trimeric rings

NMR shieldings (σ) and electric field gradients (eq) are calculated using ab initio methods at the O and T nuclei (where T=P, Si) in two different types of molecules-TH₃ dimers, i.e. H₃SiOSiH₃ and H₃POPH ₃ ²⁺ , and TO₄ trimeric rings, i.e., Si₃O ₉ ^6- and P₃O ₉ ^3- , which serve as models for assessing the effects of polymerization, bond length and bond angle variation on the NMR properties of polymerized silicates and phosphates. In agreement with earlier ab initio studies on H₃SiOSiH₃ we confirm that σ(²⁹Si), σ(³¹P), σ(¹⁷O) and eq(¹⁷O) all decrease as θ(SiOSi) decreases in the range from 180° to 100°. However, correction for artifacts due to distant core electrons leads to a considerably reduced value for the anisotropy in σ ^O, bringing it into better agreement with estimated experimental values. The qualitative change in σ(²⁹Si) with θ(SiOSi) can be understood on the basis of changes in the energies of the highest energy occupied MO's and consequent variations in their contributions to the paramagnetic part of the shielding. For H₃POPH ₃ ²⁺ we calculate a larger value of eq^O than for the analog Si compound but the same type of variation of σ(¹⁷O) with θ(TOT). The change in σ(³¹P) with θ(POP) is, however, calculated to be much smaller than in the Si case and a maximum is predicted for intermediate angles. For the trimeric rings we obtain energy optimized geometries in good agreement with x-ray structural data, with T-O terminal distances systematically shorter than the T-O bridging distances. Calculated σ(T) anisotropies are also in good agreement with experiment and can be simply related to the calculated structure. After correction for distant core effects we obtain a change in σ(³¹P) between PO ₄ ^3- and P₃O ₉ ^3- in reasonable agreement with experiment.