Anelasticity and microcreep in polycrystalline MgO at high temperature: an exploratory study

 The frequency dependence of the shear modulus and dissipation in polycrystalline MgO has been determined at high temperature using both microcreep (ɛ = 10⁻⁴) and seismic frequency forced-oscillation (ɛ = 10⁻⁵) measurements. The frequency-dependent and time-dependent data have been described in terms of the elastic, anelastic and viscous components of deformation using the Andrade model. The forced-oscillation measurements show that for temperatures above 700 °C the shear modulus begins to decrease dramatically and the modulus becomes frequency-dependent with increasing temperature. This is accompanied by an increase in dissipation, which also becomes frequency-dependent. The microcreep measurements resolve this frequency-dependent behaviour into an anelastic regime from 700–1050 °C, and a viscoelastic regime from 1100–1300 °C. At 1300 °C, the seismic frequency shear wave speed is ∼60% of the extrapolated low-temperature frequency-independent value, and the dissipation has risen to Q ⁻¹ = 10⁻¹ from 10⁻³ at temperatures below 600 °C. The mechanism by which this frequency-dependent rheology occurs appears to be diffusional creep, which produces viscous slip on the grain boundaries. It is proposed that the anelastic behaviour is due to viscous slip occurring on segments of grain boundaries, with the viscous deformation being accommodated by elastic distortion of adjacent unslipped regions of the grain boundary. At higher temperatures, slippage occurs across the entire grain boundary and viscoelastic behaviour begins to occur. Received: 11 April 2002 / Accepted: 9 January 2003 Acknowledgements Samples were precision-ground by Andrew Wilson, and polished sections prepared by Harri Kokkonen, who also did the SEM work. Uli Faul calculated the volume fraction of grain sizes. The density measurements were done by Lara Weston.     

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

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

Molecular dynamics simulations of the phase transition between low-temperature and high-temperature clinoenstatites

 Phase transition between low-temperature clinoenstatite (LT-CEn) and high-temperature clinoenstatite (HT-CEn) was studied by using molecular dynamics (MD) simulations, based on empirical potential parameters. Starting from LT-CEn, the MD calculations were carried out at atmospheric pressure and at elevated pressures (1–6 GPa). At elevated temperatures the transformation from the starting LT-CEn to HT-CEn occurred at any pressure. It was confirmed that the HT-CEn has the same space group C2/c as diopside but the M2 site is six-coordinated, unlike diopside. A significant difference in the MD-simulated cell volumes between LT-CEn and HT-CEn was also observed, showing a first-order transition. In addition, there were some temperature ranges where LT-CEN and HT-CEn would be coexistent and very small thermal hystereses between increasing and decreasing temperatures during the transition. These behaviors are consistent with the characteristic of a thermoelastic-martensitic transformation. The phase boundary between LT-CEn and HT-CEn was determined for the first time. Its positive dT/dP slope strongly shows that the high-pressure clinoenstatite is a significantly distinct phase from HT-CEn although the both phases have the same space group, C2/c. Received: 8 November 2000 / Accepted: 28 April 2001     

Crystal orbital contributions to the pyrrhotite valence band with XPS evidence for weak Fe–Fe π bond formation

 Synchrotron excited X-ray photoelectron spectra (SXPS) of hexagonal pyrrhotite reveal three distinct Fe 3d-derived photopeaks within its outer valence band. The t _2gα band (majority spin) is centered at about 2.5 eV, the e _g α band at about 1.0 eV and the t _2gβ (minority spin) contribution at about 0.25 eV. From these data the ligand field splitting energy is 1.5 (±0.2) eV and the majority spin pairing energy is 2.25 (±0.2) eV. These are the first such XPS measurements for this mineral. S 3p-derived bonding and non-bonding bands are identified, with the former centred at about 6.5 eV and the latter near 4.5 eV. The XPS results are remarkably consistent with SCF-Xα scattered wave molecular orbital calculations. Although the calculations and the collected spectra are consistent, they differ from a recent interpretation of the pyrrhotite valence band. An explanation for the discrepant results is provided. Auger resonant enhancement of Fe 3d photopeaks at 60 eV photon energy results in the t _2gα emission (at 2.5 eV) being strongly enhanced and broader than the t _2gβ emission (0.25 eV). The explanation of these observations requires the presence of weak Fe–Fe π and π^* crystal (molecular) orbitals located near 2.5 eV, and separated by no more than about 0.5 eV. The π-bonded crystal orbitals are derived from weak mixing of adjacent Fe t _2g atomic orbitals along the c crystallographic axis. Received: 15 June 2000 / Accepted: 11 June 2001     

An infrared and Raman spectroscopic study of gypsum at high pressures

 We present Raman and infrared spectra of gypsum to 21 GPa at 300 K. Our measurements encompass the internal modes of the (SO₄)⁻⁴ group that lie between 400 and 1150 cm⁻¹, hydroxyl-stretching vibrations between 3200 and 3600 cm⁻¹, and a libration and bending vibrations of the molecular H₂O group. All vibrations of the sulfate group have positive pressure shifts, while the hydroxyl-stretching and -bending vibrations have a mixture of positive and negative pressure shifts: the effect of pressure on the hydrogen bonding of the water molecule thus appears to be complex. Near 5 GPa, the two infrared-active bending vibrations of the water molecule coalesce, and the morphology of the hydroxyl-stretching region of the spectrum shifts dramatically. This behavior is consistent with a pressure-induced phase transition in gypsum in the vicinity of 5–6 GPa, which is observed to be reversible on decompression to zero pressure. The spectral observations are consistent with the onset of increased disorder in the position of the water molecule in gypsum: the sulfate vibrations are largely unaffected by this transition. The Raman-active symmetric stretch of the sulfate group undergoes an apparent splitting near 4 GPa, which is interpreted to be produced by Fermi resonance with an overtone of the symmetric bending vibration. The average mode Grüneisen parameter of the 20 vibrational modes we sample is less than 0.05, in contrast to the bulk thermal Grüneisen parameter of 1.20. Accordingly, the vibrations of both water and sulfate units within gypsum are highly insensitive to volumetric compaction. Therefore, in spite of the changes in the bonding of the water unit near 5 GPa, metastably compressed gypsum maintains strongly bound molecular-like units to over 20 GPa at 300 K. Received: 31 July 2000 / Accepted: 5 April 2001     

Hydrous olivine (Mg1? y? Fe2+y)2? x ?v x ? SiO4H2 x – a new DHMS phase of variable composition observed as nanometer-sized precipitations in mantle olivine

 An olivine grain from a peridotite nodule 9206 (Udachnaya kimberlite, Siberia) was investigated by TEM methods including AEM, HRTEM, SAED and EELS techniques. A previous study of the 9206 olivine sample revealed OH absorption bands in the IR spectrum and abundant nanometer-sized OH-bearing inclusions, of hexagonal-like or lamellar shape. Inclusions, which are several hundred nm in size, consist of 10 ? phase, talc and serpentine (chrysotile and lizardite). The lamellar (LI) and hexagon-like small inclusions of several ten nm in size (SI) are the topic of the present paper. AEM investigations of the inclusions reveal Mg, Fe and Si as cations only. The Mg/Si and Fe/Si atomic ratios are lower in the inclusions than in the host olivine. The Si concentration in the olivine host and both lamellar inclusions and small inclusions is the same. A pre-peak at 528eV was observed in EEL spectra of LI and SI, which is attributed to OH⁻ or Fe³⁺. From these data it is concluded that there is a OH⁻- or Fe³⁺-bearing cation-deficient olivine-like phase present. HRTEM lattice fringe images of LI and SI exhibit modulated band-like contrasts, which are superimposed onto the olivine lattice. Diffraction patterns (Fourier-transforms) of the HREM images as well as SAED patterns show that the band-like contrasts in HRTEM images of the inclusions are caused by periodic modulations of the olivine lattice. Three kinds of superperiodicity in the olivine structure such as 2a, 3a and 3c, were observed in SAED patterns. The corresponding olivine supercells labelled here as Hy-2a, Hy-3a and Hy-3c were derived. The M1-vacancies located in the (100) and (001) octahedral layers of the olivine lattice are suggested to form ordered arrays of planar defects (PD), which cause the band-like contrasts in HRTEM patterns as well as the superperiodicity in the SAED patterns. The vacancy concentrations as well as the chemical composition of Hy-2a, Hy-3a and Hy-3c olivine supercells were calculated using crystal chemical approaches, assuming either {(OH)^< _O−V^" _Me−(OH)^< _O}^↔, or {F e ^< _Fe −H _Me ^′}^↔ or {2F e ^< _Fe −V _Me ^"}^↔ point defect associates. The calculated theoretical compositions Mg_1.615Fe⁺² _0.135v_0.25SiO₄H_0.5 (Hy-2a) and Mg_1.54Fe²⁺ _0.12v_0.33SiO₄H_0.66 (Hy-3a and Hy-3c) are in a good agreement with the AEM data on inclusions. Hy-2a, Hy-3a and Hy-3c are considered to be a hydrous olivine with the extended chemical formula (Mg_1-yFe²⁺ _y)_2−xv_xSiO₄H_2x. The crystal structure of hydrous olivine is proposed to be a modular olivine structure with Mg-vacant modules. The crystal chemical formula of hydrous olivines in terms of a modular structure can be written as [MgSiO₄H₂] · 3[Mg_1.82Fe_0.18SiO₄] for Hy-2a, [MgSiO₄H₂] · 2[Mg_1.82Fe_0.18SiO₄] for Hy-3a and Hy-3c. Hydrous olivine is suggested to be exsolved from the olivine 9206, which has been initially saturated by OH-bearing point defects. The olivine 9206 hydration as well as the following exsolution of hydrous olivine inclusions is suggested to occur at high pressure-high temperature conditions of the upper mantle. Received: 15 January 2001 / Accepted: 2 July 2001     

Seismic Properties of Anita Bay Dunite: an Exploratory Study of the Influence of Water

As a pilot study of the role of water in the attenuation ofseismic waves in the Earth's upper mantle, we have performeda series of seismic-frequency torsional forced-oscillation experimentson a natural (Anita Bay) dunite containing accessory hydrousphases, at high temperatures to 1300°C and confining pressure(P_c) of 200 MPa, within a gas-medium high-pressure apparatus.Both oven-dried and pre-fired specimens wrapped in Ni–Fefoil within the (poorly) vented assembly were recovered essentiallydry after 50–100 h of annealing at 1300°C followedby slow staged cooling. The results for those specimens indicatebroadly similar absorption-band viscoelastic behaviour, butwith systematic differences in the frequency dependence of strain-energydissipation Q^–1, attributed to differences in the smallvolume fraction of silicate melt and its spatial distribution.In contrast, it has been demonstrated that a new assembly involvinga welded Pt capsule retains aqueous fluid during prolonged exposureto high temperatures—allowing the first high-temperaturetorsional forced-oscillation measurements under high aqueousfluid pore pressure P_f. At temperatures >1000°C, a markedreduction in shear modulus, without concomitant increase inQ^–1, is attributed to the widespread wetting of grainboundaries resulting from grain-scale hydrofracturing and themaintenance of conditions of low differential pressure P_d =P_c – P_f . Staged cooling from 1000°C is accompaniedby decreasing P_f and progressive restoration of significantlypositive differential pressure resulting in a microstructuralregime in which the fluid on grain boundaries is increasinglyrestricted to arrays of pores. The more pronounced viscoelasticbehaviour observed within this regime for the Pt-encapsulatedspecimen compared with the essentially dry specimens may reflectboth water-enhanced solid-state relaxation and the direct influenceof the fluid phase. The scenario of overpressurized fluids andhydrofracturing in the Pt-encapsulated dunite specimen may havesome relevance to the high Q^–1 and low-velocity zonesobserved in subduction-zone environments. The outcomes of thisexploratory study indicate that the presence of water can havea significant effect on the seismic wave attenuation in theupper mantle and provide the foundation for more detailed studieson the role of water. KEY WORDS: seismic wave attenuation; water; dunite; hydrous mineral; shear modulus; viscoelasticity; olivine; grain-scale hydrofracturing     

Crystal chemistry of iron in natural grandidierites: an X-ray absorption fine-structure spectroscopy study

 Fe–K edge XAFS spectra (pre-edge, XANES and EXAFS) were collected for eight grandidierites from Madagascar and Zimbabwe, as well as for Fe(II) and Fe(III) model compounds (staurolite, siderite, enstatite, berlinite, yoderite, acmite, and andradite). The pre-edge spectra for these samples are consistent with dominantly 5-coordinated ferrous iron. The analysis of the XANES and EXAFS spectra confirms that Fe(II) substitutes for Mg(II) in grandidierite, with a slight expansion of the local structure around Mg by ∼2%. In addition, ferric iron was also detected in some samples [5–10 mol% of the total Fe or 500–1100 ppm Fe(III)]. Based on theoretical calculations of the EXAFS region, Fe(III) appears to be located in the 5-coordinated sites of Mg(II) or in the most distorted 6-coordinated sites of Al (depending on the sample studied). Special attention is therefore required when using grandidierite as a model for ferrous iron in C_3v geometry, because of the possible presence of an extra contribution related to Fe(III). This additional contribution enhances significantly the Fe–K pre-edge integrated area [+40% for 1000 ppm Fe(III)]. Therefore, only a few grandidierite samples can be used as a robust structural model for the study of the Fe(II) coordination in glasses and melts. Received: 26 June 2000 / Accepted: 19 February 2001     

Octahedral cation ordering in olivine at high temperature. II: an in situ neutron powder diffraction study on synthetic MgFeSiO4 (Fa50)

 The partitioning of Fe and Mg between the M1 and M2 octahedral sites of olivine has been investigated by in situ time-of-flight neutron powder diffraction. The degree of M-cation order was determined from direct measurements of site occupancies in a synthetic sample of Fo50Fa50 heated to 1250 °C at the Fe-FeO oxygen buffer. Fe shows slight preference for M1 at temperatures below about 600 °C, progressively disordering on heating to this temperature. Above 630 °C, the temperature at which site preferences cross over (T _cr), Fe preferentially occupies M2, becoming progressively more ordered into M2 on increasing temperature. The cation-ordering behaviour is discussed in relation to the temperature dependence of the M1 and M2 site geometries, and it is suggested that vibrational entropy, crystal field effects and changes in bond characteristics play a part in the cross-over of partitioning behaviour. The temperature dependence of site ordering is modelled using a Landau expansion of the free energy of ordering of the type ΔG = −hQ + gTQ +  (T − T _c)Q ² +  Q ⁴, with a/h = 0.00406 K⁻¹, b/h = 2.3, T _c = 572 K and g/h = 0.00106 K⁻¹. These results suggest that the high-temperature ordering behaviour across the forsterite-fayalite join will have a bearing on the activity-composition relations of this important rock-forming mineral, and indicate that Fe-Mg olivine solid solutions become less ideal as temperature increases. Received: 12 August 1999 / Accepted: 25 April 2000     

Elasticity of the pyrope (Mg3Al2Si3O12)-majorite (MgSiO3) garnets solid solution

Dense isotropic polycrystalline specimens of majorite-rich garnets (Py₁₀₀, Py₆₂Mj₃₈, Py₅₀Mj₅₀, Py₂₁Mj₇₉ and Mj₁₀₀) along the pyrope (Mg₃Al₂Si₃O₁₂ = Py₁₀₀)-majorite (MgSiO₃ = Mj₁₀₀) join were fabricated in a 2000-ton uniaxial split-sphere anvil apparatus (USSA-2000) at pressures from 10 to 18.5 GPa and temperatures from 1200 to 1850 °C, within their stability fields in runs of 2–4-h duration, using hot-pressing techniques developed by Gwanmesia et al. (1993). These specimens are single-phased, fine-grained (≤5 mm), free of microcracks, and have bulk densities greater than 99% of the corresponding single-crystal X-ray density. Elastic compressional (P) and shear (S) wave velocities were determined at room pressure and temperature for these polycrystalline garnet specimens by phase comparison ultrasonic interferometry. For Mj₁₀₀, the P and S wave velocities are within 1% of the Hashin-Shtrikman averages calculated from the single crystal elastic moduli measured by Brillouin spectroscopy. Both the elastic bulk modulus (K) and the shear modulus (G) decrease continuously with increasing majorite content from pyrope garnet (Py₁₀₀) to pure majorite garnet (Mj₁₀₀). The compositional dependence of K and G are given by K = 172.3 (40) − 0.085X, and G = 91.6 (10) − 0.038X, where X = mol% majorite), respectively, indicating that substitution of Si for Mg and Al decreases both K and G by about 5% along the solid solution series. Received: 25 March 1999 / Accepted: 12 July 1999     

High-temperature creep in a Ni2GeO4: a contribution to creep systematics in spinel

 High-temperature creep behavior in Ni₂GeO₄ spinel was investigated using synthetic polycrystalline aggregates with average grain sizes ranging from submicron to 7.4 microns. Cylindrical samples were deformed at constant load in a gas-medium apparatus at temperatures ranging from 1223 to 1523 K and stresses ranging from 40 to 320 MPa. Two deformation mechanisms were identified, characterized by the following flow laws: where σ is in MPa, d is in μm and T is in Kelvin. These flow laws suggest that deformation was accommodated by dislocation creep and grain-boundary diffusion (Coble) creep, respectively. A comparison with other spinels shows that an isomechanical group can be defined for spinels although some differences between normal and inverse spinels can be identified. When creep data for olivine and spinel are normalized and extrapolated to Earth-like conditions, spinel (ringwoodite) has a strength similar to olivine in the dislocation creep regime and is considerably stronger than olivine in the diffusion creep regime at coarse grain size. However, when grain-size reduction occurs, spinel can become weaker than olivine due to its high grain-size sensitivity (Coble creep behavior). Analysis of normalized diffusion creep data for olivine and spinel indicate that spinel is weaker than olivine at grain sizes less than 2 μm. Received: 18 June 2000 / Accepted: 3 April 2001     

Viscoelastic behaviour of mica-based glass-ceramic aggregate

The present study deals with the small strain torsion deformation of MACOR glass-ceramic samples at high temperatures (450–850 °C) and over a range of low frequencies (20 Hz–5 mHz). The samples of MACOR ceramic consist of 55 vol% randomly oriented, sheet-like fluorophlogopite mica crystals (∼100–20 μm in planar size, 1–2 μm in thickness) and 45 vol% of isotropic alumino-borosilicate glass matrix. Measurements of the complex shear modulus show that the sample does not possess the relaxed shear viscosity even at temperatures above the glass transition temperature of the glass matrix. The maximum of the imaginary component G ^′′() of the shear modulus is ∼0.15 of the unrelaxed value G _∞, the relaxation strength Δ≈0.9. The activation energy of the peak of G ^′′() is ∼245 kJ mol⁻¹. Using this value of E _a , the data obtained at various frequencies and temperatures have been reduced to a master curve using the dimensionless variable ωτ, where ∼₀ exp(−E _a /RT). The internal friction Q⁻¹(ωτ) is ∝1/()^0.35−0.4 in the low-temperature high-frequency range (1); passes through a maximum at ∼1 and trends asymptotically to a value Q⁻¹∼0.25–0.30 at ≪1. The behaviour of Q ⁻¹(ωτ) differs from that of a Caputo body by the presence of the resolved peak which may be attributed to the slow mechanical relaxation of mica crystals due to rotation as well as flexing and bending modes of crystal deformation. Received: 26 June 1998 / Revised, accepted: 13 January 1999     

A high-temperature and high-pressure Raman spectroscopic study of CaGeO3 garnet

 High-pressure and high-temperature Raman spectra of CaGeO₃ tetragonal garnet have been collected to 11.5 GPa and 1225 K, respectively, in order to investigate possible intrinsic anharmonic behaviour in this phase. The Raman peak positions were observed to vary linearly with pressure and temperature within the ranges studied, with the higher-energy peaks showing larger P- and T-induced shifts than the low energy modes. The observed T-induced shifts are similar to those reported for grossular and andradite, while the observed P-induced shifts are generally larger than those of aluminosilicate and MgSiO₃ majorite garnets (Gillet et al. 1992; Rauch et al. 1996) due to the larger bulk modulus of CaGeO₃ garnet. The observed mode shifts of CaGeO₃ garnet were used to determine the isothermal and isobaric mode Grüneisen parameters for this phase. These parameters are similar in value to those reported previously for grossular and andradite (Gillet et al. 1992). The calculated intrinsic anharmonic parameters, a _i , for CaGeO₃ garnet were determined to be nonzero, indicating significant anharmonic behaviour for this phase. These values, which range from −3.8 × 10⁻⁵ K⁻¹ to −1.3 × 10⁻⁵ K⁻¹, are also similar to those reported for andradite and grossular, but smaller than those determined for pyrope (Gillet et al. 1992). Hence, we expect MgSiO₃ majorite to show greater anharmonicity than the germanate analogue studied by us. The anharmonic parameters determined for CaGeO₃ tetragonal garnet may now be introduced into quasiharmonic vibrational heat capacity models to account for the observed anharmonic behaviour. Received: 21 April 1999 / Revised, accepted: 11 September 1999     

X-ray powder diffraction study on the modulated high temperature forms of SiO2 tridymite between 110 and 220 °C

 The crystal structure of intermediate incommensurate tridymite was refined at 150 °C from powder data. Upon cooling from above 220 °C, the basic structure with space group symmetry C222₁ is gradually distorted from orthorhombic to monoclinic symmetry. With decreasing temperature, the monoclinic angle γ smoothly opens up to 90.3°, while a displacive modulation with temperature-dependent wavelength develops. The 3 + 1 dimensional superspace group of the incommensurate phase is C112₁(αβ0). The modulation mainly consists of two sinusoidal transverse displacement waves for the silicon atoms coupled to rotations of the rigid SiO_4/2 tetrahedra. The wave vector is r=0.1192(1)a* − 0.0043(1)b* at 150 °C. Below 150 °C tridymite discontinuously transforms to another orthorhombic phase and the modulation partially locks in at the wave vector r ₁=1/3a*. Simultaneously, an additional incommensurate modulation with r ₂= 0.0395(1)b* − 0.3882(1)c* is formed. The two-dimensional modulation does not vary significantly with the temperature. Received: 13 September 2000 / Accepted: 29 January 2001     

Thermoelastic properties of the high-pressure phase of SnO2 determined by in situ X-ray observations up to 30 GPa and 1400 K

 In situ synchrotron X-ray experiments in the system SnO₂ were made at pressures of 4–29 GPa and temperatures of 300–1400 K using sintered diamond anvils in a 6–8 type high-pressure apparatus. Orthorhombic phase (α-PbO₂ structure) underwent a transition to a cubic phase (Pa3ˉ structure) at 18 GPa. This transition was observed at significantly lower pressures in DAC experiments. We obtained the isothermal bulk modulus of cubic phase K ₀= 252(28) GPa and its pressure derivative K ^′=3.5(2.2). The thermal expansion coefficient of cubic phase at 25 GPa up to 1300 K was determined from interpolation of the P-V-T data obtained, and is 1.7(±0.7) × 10⁻⁵ K⁻¹ at 25 GPa. Received: 7 December 1999 / Accepted: 27 April 2000     

Single-crystal elastic constants of fluorite (CaF2) to 9.3 GPa

 The second-order elastic constants of CaF₂ (fluorite) have been determined by Brillouin scattering to 9.3 GPa at 300 K. Acoustic velocities have been measured in the (111) plane and inverted to simultaneously obtain the elastic constants and the orientation of the crystal. A notable feature of the present inversion is that only the density at ambient condition was used in the inversion. We obtain high-pressure densities directly from Brillouin data by conversion to isothermal conditions and iterative integration of the compression curve. The pressure derivative of the isentropic bulk modulus and of the shear modulus determined in this study are 4.78 ± 0.13 and 1.08 ± 0.07, which differ from previous low-pressure ultrasonic elasticity measurements. The pressure derivative of the isothermal bulk modulus is 4.83 ± 0.13, 8% lower than the value from static compression, and its uncertainty is lower by a factor of 3. The elastic constants of fluorite increase almost linearly with pressure over the whole investigated pressure range. However, at P ≥ 9 GPa, C ₁₁ and C ₁₂ show a subtle structure in their pressure dependence while C ₄₄ does not. The behavior of the elastic constants of fluorite in the 9–9.3 GPa pressure range is probably affected by the onset of a high-pressure structural transition to a lower symmetry phase (α-PbCl₂ type). A single-crystal Raman scattering experiment performed in parallel to the Brillouin measurements shows the appearance of new features at 8.7 GPa. The new features are continuously observed to 49.2 GPa, confirming that the orthorhombic high-pressure phase is stable along the whole investigated pressure range, in agreement with a previous X-ray diffraction study of CaF₂ to 45 GPa. The high-pressure elasticity data in combination with room-pressure values from previous studies allowed us to determine an independent room-temperature compression curve of fluorite. The new compression curve yields a maximum discrepancy of 0.05 GPa at 9.5 GPa with respect to that derived from static compression by Angel (1993). This comparison suggests that the accuracy of the fluorite pressure scale is better than 1% over the 0–9 GPa pressure range. Received: 10 July 2001 / Accepted: 7 March 2002     

A topo-geochemical sequence study of groundwater in Asa drainage basin, Kwara State, Nigeria

 A strong geochemical gradient was observed in the thick overburden aquifer of the Asa drainage basin. Different types of groundwater occur at different (downslope) locations and groundwater table depths. The following sequence was noticed with increasing distance downslope or with increasing groundwater table depth: 1. Ca–Mg–HCO₃ water at about 390-m groundwater table elevations or upslope locations. 2. Ca–Mg–HCO₃–Cl water at middle-slope locations or groundwater table elevations of about 350 m above sea level; 3. Ca–Mg–SO₄–Cl water at downslope locations or groundwater table elevations of about 300 m above sea level. In this basin, changes in the type of water are expected at about every 40–50 m depth from the surface. Statistical analysis via the determination of the correlation coefficient (r) and regression analysis shows that about 80–99% of the variation in groundwater chemistry is accounted for by the topography, using the model presented in this paper. The rate of change in the sequence will depend on the permeability of the aquifer, which determines the rate of groundwater flow and the residence time, and the nature of recharge. Received: 4 February 1997 · Accepted: 22 July 1997     

On the origin of inhomogeneity of anomalous birefringence in mixed crystals: an example of alums

 Optical anomalies (deviations of the symmetry of optical properties from the ideal symmetry of the crystal) occur in many minerals and synthetic compounds and have been under investigation since the last century. An important feature of optically anomalous mixed crystals is a high degree of optical inhomogeneity, whereas the optical patterns of mixed crystals without anomalies are usually rather uniform. This work is devoted to the study of this phenomenon. As a model object we have chosen mixed alum crystals, which were known for their anomalous birefringence and which revealed the following types of optical inhomogeneities: (1) sector zoning; (2) concentric zoning; (3) subsector zoning; (4) stripes normal to growth front. The inhomogeneity of anomalous birefringence of mixed crystals of alums can be explained by superposition of several effects: mismatch strain, strain along dislocations and growth ordering of isomorphous components. Optical inhomogeneities due to the sector zoning of crystals and their dislocation structure arise even under stationary growth conditions and stationary micromorphology of the growing face. Both variable growth conditions and the relief of the growing face strongly intensify the optical inhomogeneity due to three interrelated factors: (1) a significantly inhomogeneous mismatch strain; (2) a variable degree of ordering of isomorphous components due to the compositional inhomogeneities; (3) different degrees of ordering of isomorphous atoms caused by different orientations, heights and velocities of growth steps. These effects lead to the formation of subsector zoning and zoning superimposed on the optical sector zoning. These optical structures are crossed by birefringent stripes arising from dislocations. Received: 29 March 2000 / Accepted: 11 March 2001     

The enthalpy of transformation of Ca(OH)2-I (portlandite) to Ca(OH)2-II (EuI2 structure) by low-temperature DSC

 Thermodynamic properties of high-pressure minerals that are not recoverable from synthesis experiments by conventional quenching methods (“unquenchable” phases) usually are calculated from equation of state data and phase diagram topologies. The present study shows that, with cryogenic methods of recovery and sample treatment, phases with a suitable decomposition rate can be made accessible to direct thermodynamic measurements. A set of samples of Ca(OH)₂-II has been synthesized in a multianvil device and subsequently recovered by cooling the high-pressure assembly with liquid nitrogen. Upon heating from liquid nitrogen to room temperature, the material transformed back to Ca(OH)₂-I. The heat effect of this backtransformation was measured by differential scanning calorimetry. A commercial differential scanning calorimeter (Netzsch DSC 404), modified to allow sample loading at liquid nitrogen temperature was used to heat the material from −150 to +200 °C at rates varying between 5 and 15 °C min⁻¹. The transformation started around −50 °C very gradually, and peaked at about 0 °C. To obtain a baseline correction, each sample was scanned under exactly the same conditions after the backtransformation was complete. Because of the relative sluggishness, onset and offset temperatures were not well defined as compared to fast (e.g., melting) reactions. To aid in integration, the resulting signals were successfully fitted using a generic asymmetric peak model. The enthalpy of backtransformation was determined to be ΔH =−10.37 ± 0.50 kJ mol⁻¹. From previous in situ X-ray diffraction experiments, the location of the direct transformation in P-T space has been constrained to 5.7 ± 0.4 GPa at 500 °C (Kunz et al. 1996). With the reaction volume known from the same study, and assuming that ΔC _p of the transformation remains negligible between the conditions of our measurements and 500 °C, our result gives an estimate of the entropy of transition and the P-T slope of the reaction curve. To a first approximation, the values ΔS = −16.00 ± 0.65 J(mol · K)⁻¹ and dP/dT = 0.0040 ± 0.0002 GPa/K have been determined. These results need to be refined by equation of state data for Ca(OH)₂-II. Received: 30 December 1999 / Accepted: 10 April 2000     

Thermodynamic data of the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite)

 Calorimetric and P–V–T data for the high-pressure phase Mg₅Al₅Si₆O₂₁(OH)₇ (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B₂O₃) at T=700 ^∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol⁻¹ (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol⁻¹ (formation from the elements). The heat capacity of Mg₅Al₅Si₆O₂₁(OH)₇ has been measured from T=50 ^∘C to T=500 ^∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C _P (Mg-sursassite) =(1571.104 −10560.89×T ^−0.5−26217890.0 ×T ⁻²+1798861000.0×T ⁻³) J K⁻¹ mol⁻¹ (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ^∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ^′=4), V _T,0 =446.49 ³ exp[∫(0.33±0.05) × 10⁻⁴ + (0.65±0.85)×10⁻⁸ T dT], (K _T/T) _P  = −0.011± 0.004 GPa K⁻¹. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δ_f H ⁰ ₂₉₈ (Mg-sursassite) = −13901.33 kJ mol⁻¹, and S ⁰ ₂₉₈ (Mg-sursassite) = 614.61 J K⁻¹ mol⁻¹. Received: 21 September 2000 / Accepted: 26 February 2001