Electrical conductivity measurements on olivines and pyroxenes under defined thermodynamic activities as a function of temperature and pressure

Electrical conductivities of Ni₂SiO₄, Fe₂SiO₄, and MgSiO₃ were measured on synthetic powders in the temperature range 340° to 1,100° C and at pressures up to 20 kbars. For ternary compounds such as olivines and pyroxenes the control of two further variables, like the chemical activities of two components are needed, besides temperature and pressure. The activities of the corresponding binary oxides were controlled by equilibrating the samples with their neighbour-phases. Control of the oxygen partial pressure was achieved by buffer techniques. From the slopes of the lg σ vs. 1/T lines the activation energies were calculated for 10 kbar: 0.56 eV and 2.7 eV for Ni₂SiO₄ in equilibrium with SiO₂ and Ni/NiO-buffer for the temperature range 500°–800°C and 800°–1,000°C resp. 0.52 eV for Fe₂SiO₄ in equilibrium with SiO₂ and metallic iron, and 0.38 eV in equilibrium with SiO₂ and magnetite; 1.11 eV for MgSiO₃ in equilibrium with SiO₂, and 1.25 eV in equilibrium with Mg₂SiO₄.     

Synthetic Mn3+-kyanite and viridine, (Al2-xMn x 3+ ) SiO5, in the system Al2O3-MnO-MnO2-SiO2

Experiments on the join Al₂SiO₅-“Mn₂SiO₅” of the system Al₂O₃-SiO₂-MnO-MnO₂ in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn₂O₃, and high purity SiO₂ as starting materials and using /_O2-buffer techniques to preserve the Mn³⁺ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al_1.88Mn _0.12 ³⁺ )SiO₅ and, thus, equals approximately that on the join Al₂SiO₅-“Fe₂SiO₅” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn³⁺ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a _o, b _o, c _o, and V _o to increase by 0.015, 0.009, 0.014 Å, and 1.6 ų, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn³⁺-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusite_ss (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al_1.86Mn _0.14 ³⁺ )SiO₅-(Al_1.56Mn _0,44 ³⁺ )SiO₅. Thus, Al→Mn³⁺ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn³⁺ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a _o, b _o, c _o, and V _o to increase by 0.118, 0.029, 0.047 Å and 9.4 ų, resp. At “Mn₂SiO₅”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn₂SiO₅”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn²⁺Mn³⁺[O₈/Si0₄]), pyrolusite and SiO₂ were found to coexist with the Mn³⁺-saturated ky _ss or and _ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn³⁺). Pure synthetic braunites had the lattice constants a _o 9.425, c _o, 18.700 Å, V _o 1661.1 ų (ideal compn.) and a _o 9.374, c _o 18.593 ų, V _o 1633.6 ų (1 Al for 1 Mn³⁺). Stable coexistence of the Mn²⁺-bearing phase braunite with the Mn⁴⁺-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO₂-SiO₂.     

Infrared vibrational spectra of Beta-Phase Mg2SiO4 and Co2SiO4 to Pressures of 27 GPa

Infrared absorption spectra of the high-pressure polymorphs β-Mg₂SiO₄ and β-Co₂SiO₄ have been measured between 0 and 27 GPa at room temperature. Grüneisen parameters determined for 11 modes of β-Mg₂SiO₄ (frequencies of 300 to 1,050 cm^?1) and 5 modes of β-Co₂SiO₄ (490 to 1,050 cm^?1) range between 0.8 and 1.9. Averaging the mid-infrared spectroscopic data for β-Mg₂SiO₄ yields an average Grüneisen parameter of 1.3 (±0.1), in good agreement with the high-temperature thermodynamic value of 1.35. Similarly, we find a value of 1.05 (±0.2) for the average spectroscopic Grüneisen parameter of β-Co₂SiO₄.     

On the Relationship between Refractive Index and Density for SiO2-polymorphs

Five different refraction formulas were applied to SiO₂ polymorphs in order to determine the most suitable refractive index-density relation. 13 SiO₂ polymorphs with topological different tetrahedral frameworks are used in this study including eight new low density SiO₂ polymorphs — so called “guest free porosils”. These SiO₂ polymorphs cover a density range from 1.76 to 2.92 g/cm³. The mean refractive indices (ovn) of the porosils have been determined by the immersion method, the densities (ρ) were calculated from the unit cell parameters. Assuming the polarizability (α) of all SiO₂ polymorphs to be constant the general refractivity formula $$\{ 2\overline {11} 0\} \langle 0001\rangle $$ turned out to be the most suitable for SiO₂ polymorphs. Regression analysis yields an electronic overlap parameter b=1.2(1).     

Decomposition of fayalite (Fe2SiO4) in an oxygen potential gradient at 1,418 K

The decomposition of fayalite (Fe₂SiO₄) in oxygen potential gradients is studied at T=1,418 K. The compound will be decomposed into its component oxides wüstite, Fe_1?δO, and silica, SiO₂, by the simultaneous action of two different oxygen partial pressures, exceeding a critical ratio, despite the fact that fayalite is stable at both the lower and the higher oxygen potential. A quantitative analysis of the decomposition process caused by defect fluxes within the bulk Fe₂SiO₄ is given.     

Infrared spectra of olivine polymorphs: α, β phase and spinel

Infrared (IR) absorption spectra are presented for olivine (α) and spinel (γ) phases of A₂SiO₄ (A=Fe, Ni, Co) and Mg₂GeO₄. IR spectra of β phase (“modified spinel”) Co₂SiO₄ and of α Mg₂SiO₄ are also included. These results provide reference spectra for the identification of olivine high-pressure polymorphs. Isostructural and isochemical correlations are used to support a general interpretation of the spectra and to predict the spectrum of γ Mg₂SiO₄. A γ Mg₂GeO₄ sample equilibrated at 1,000° C shows evidence of partial inversion, but one equilibrated at 730° C does not. This suggests that partial inversion could occur in silicate spinels at elevated temperatures and pressures, however no evidence of inversion is seen in the ir spectra of the silicates in this study.     

Some physical properties of amorphous SiO2 synthesized by shock compression of α quartz

The amorphous phase of SiO₂ produced upon recovery of shock-compressed quartz demonstrates a wide range of refractive indices which can be correlated to the shock state. Both infra-red absorption spectra and X-ray diffraction patterns indicate that the shock-produced amorphous SiO₂ has a statistically more-random atomic distribution and longer Si-O and shorter Si-Si separation than does fused silica. By accounting for phase transformation, the calculated values of the shock and residual temperature are much higher than those obtained by Wackerle (1962) to a pressure of 700 kbar. Our results are consistent with experimental ones.     

Crystal structures of Ni2SiO4 and Fe2SiO4 as a function of temperature and heating duration

X-ray structure refinements of Ni₂SiO₄ and Fe₂SiO₄ spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni₂SiO₄ spinel linearly increased with temperature up to 1,000° C. However, Fe₂SiO₄ spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D _oct/D _tetr and between the shared and unshared edge distances (O-O)_sh/(O-O)_unsh in Fe₂SiO₄ spinel were both much larger than those in Ni₂SiO₄. These ratios increase with temperature. The Fe₂SiO₄ spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni₂SiO₄ spinel. The lattice parameter of Ni₂SiO₄ spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal.     

Phonon spectra and rigid-ion model calculations on andalusite

Polarised Raman and infrared spectra of (ir) andalusite (Al₂SiO₅) single crystals have been measured and interpreted on the basis of a rigid-ion model calculation. The Al-O bond strength is found to be about 70% ionic in character whereas the mainly covalently bound SiO₄ tetrahedra show ca. 40% ionicity. The interatomic short range forces are strongest between silicon and oxygen and rather weak around the fivefold coordinated aluminium. Thermal soft modes appear above 200°C and are correlated with a weakening of the Al-O bonds.     

Study of pocyclic aromatic hydrocarbons at a pressure of 6–9 GPa with X-ray diffraction and synchrotron radiation

This work is one of the stages of study of the deep C-O-H fluid and investigates the behavior of polycyclic aromatic hydrocarbons (PAHs) under conditions of the Earth’s mantle. The composition of the C-O-H fluid in the upper mantle is estimated as a mixture of H₂O and CH₄ with a minor amount of H₂ and heavier hydrocarbons. Some theoretical calculations show that the stability of heavy hydrocarbons (alkanes, alkenes, and PAHs) increases with an increase in temperature. This paper presents the results of an XRD study of PAHs stability in multianvil presses on a Spring-8 accelerator (Japan). The primary compositions were chosen according to the abundance of PAHs in nature. In situ diffraction spectrums were recorded to determine the PAHs stability field. It was established that the PAHs become unstable at a pressure of 6–9 GPa and a temperature of 873–1073 K.     

A thermochemical data base for phase equilibria in the system Fe-Mg-Si-O at high pressure and temperature

A thermochemical data base for phases in the system Fe-Mg-Si-O at high pressures up to 300 kbar is established by supplementing the available calorimetric data with data calculated from experimental high pressure synthesis studies. Phases included in the data base are the SiO₂ polymorphs, rock salt solid solutions (Fe-Mg-O), Fe₂O₃, Fe₃O₄, (Mg, Fe)₂SiO₄ olivine, spinel, modified spinel and (Mg, Fe)SiO₃ perovskite and pyroxene. Phases not included are the MgSiO₃-ilmenite and -garnet. Fe-Mg solution properties of olivine, spinel, perovskite and wustite (rock salt) are estimated. The wüstite solid solution has been modeled as a nonideal solution of three end members; FeO, FeO_1.5 and MgO. The new data base is made consistent with most of the available information on high pressure phase studies. The data base is useful in generating phase diagrams of various different compositions for the purpose of planning new experiments and analysing existing phase synthesis data.     

The lattice energy of forsterite. Charge distribution and formation enthalpy of the SiO 4 4− ion

In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z _o, the hardness parameter ρ and the repulsive radii r _Mg and r _Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO ₄ ^4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z _o=?1.34, ρ=0.27 Å, r _Mg=0.72 Å, r _Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol^?1 were obtained, respectively, for the lattice energy E _Land for its ionic component E _L ⁰ ,which accounts for interactions between Mg²⁺ and SiO ₄ ^4? ions only. The charge distribution calculated on the SiO ₄ ^4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO ₄ ^4? were estimated to be: ΔH _f(SiO ₄ ^4? )=2117.6 and E(SiO ₄ ^4? )=708.6 kJ mol^?1, respectively.     

A MEG study of the olivine and spinel forms of Mg2SiO4

In this paper we present a theoretical investigation of the structures and relative stability of the olivine and spinel phases of Mg₂SiO₄. We use both a purely ionic model, based on the Modified Electron Gas (MEG) model of intermolecular forces, and a bond polarization model, developed for low pressure silica phases, to investigate the role of covalency in these compounds. The standard MEG ionic model gives adequate structural results for the two phases but incorrectly predicts the spinel phase to be more stable at zero pressure. This is mainly because the ionic modeling of Mg₂SiO₄ only accounts for 95 percent of the lattice energy. The remainder can be attributed to covalency and many-body effects. An extension of the MEG ionic model using “many-body” pair potentials corrects the phase stability error, but predicts structures which are in poorer agreement with experiment than the standard ionic approach. In addition, calculations using these many-body pair potentials can only account for 10 percent of the missing lattice energy. This model predicts an olivine-spinel phase transition of 8 GPa, below the experimental value of 20 GPa. Therefore, in order to understand more fully the stability of these structures we must consider polarization. A two-shell bond polarization model enhances the stability of both structures, with the olivine structure being stabilized more. This model predicts a phase transition at about 80 GPa, well above the observed value. Also, the olivine and spinel structures calculated with this approach are in poorer agreement with experiment than the ionic model. Therefore, based on our investigations, to properly model covalency in Mg₂SiO₄, a treatment more sophisticated than the two-shell model is needed.     

Vibrational spectra of olivine composition glasses: The Mg-Mn join

The vibrational frequencies of a series of splatquenched, olivine glasses spanning the compositional range from Mg₂SiO₄ to Mn₂SiO₄ have been determined using both infrared and Raman spectroscopies. The spectra of all glasses show evidence of tetrahedral coordination of silicon (possibly with some slight distortions), and largely octahedral coordination of magnesium. Spectra of Mn-rich glasses indicate that there is some manganese in 4 or 5-fold coordination. The frequencies observed for the fundamental vibrations of the silica tetrahedra are similar to those previously observed for SiO₄ groups in both crystalline and glassy orthosilicates. Additionally, there is evidence for a small amount of silicate polymerization in all glasses characterized: vibrations attributable to Si₂O₇ groups are visible in both infrared and Raman spectra.     

Interaction between fluorine and silica in quenched melts on the joins SiO2-AlF3 and SiO2-NaF determined by raman spectroscopy

The solubility mechanism of fluorine in quenched SiO₂-NaF and SiO₂-AlF₃ melts has been determined with Raman spectroscopy. In the fluorine abundance range of F/(F+Si) from 0.15 to 0.5, a portion of the fluorine is exchanged with bridging oxygen in the silicate network to form Si-F bonds. In individual SiO₄-tetrahedra, one oxygen per silicon is replaced in this manner to form fluorine-bearing silicate complexes in the melt. The proportion of these complexes is nearly linearly correlated with bulk melt F/(F+Si) in the system SiO₂-AlF₃, but its abundance increases at a lower rate and nonlinearly with increasing F/(F+Si) in the system SiO₂-NaF. The process results in the formation ofnonbridging oxygen (NBO), resulting in stabilization of Si₂O ₅ ^2? units as well as metal (Na⁺ or Al³⁺) fluoride complexes in the melts. Sodium fluoride complexes are significantly more stable than those of aluminum fluoride.     

The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.     

Thermodynamic properties of the forsterite-fayalite (Mg2SiO4-Fe2SiO4) solid solution. determination of heat of formation

A high temperature calorimetric solution method involving the use of a sodium and lithium metaborate (NaBO₂+LiBO₂) molten bath at 1,180 K, has been developed in order to measure the enthalpy of formation of the forsterite-fayalite (Mg₂SiO₄-Fe₂SiO₄) system. The samples used for these measurements have been obtained by synthesis. They have been carefully controlled by chemical and X-ray analysis and Mössbauer spectroscopy. The results obtained for forsterite and fayalite agree closely with the data commonly found in the literature. Owing to the uncertainty of the experimental results, it is not possible to determine conclusively whether an enthalpy of mixing exists in this system.     

Polycyclic aromatic hydrocarbons in surface sediments of Binacional Itaipu Lake,Brazil: characteristics,sources and toxicity evaluation

Itaipu Lake, which includes the Itaipu hydroelectric power plant, is one of the largest dams in the world and has a strong relationship with its surroundings. The flooded area has multiple uses such as navigation, recreation, water abstraction for industrial, urban and agricultural irrigation. The lake is located at the frontier between Brazil, Argentina and Paraguay. In this study, superficial sediments collected from nine sampling sites were analysed for grain size, organic matter and 16 priority polycyclic aromatic hydrocarbons (PAHs) using high-performance liquid chromatography (HPLC) with fluorescence detector. The total concentration of PAHs in the dry sediment ranged from 35.21 to 685.37 µg kg^?1. Diagnostic ratios showed that the possible source of PAHs in the Itaipu Lake could be pyrolitic and petrogenic. The potential toxicity of sediment of PAHs varied from not detected to 127.70 µg g^?1, suggesting that some adverse ecological effects would arise due to PAHs in these sediments.     

The lattice dynamics and thermodynamics of the Mg2SiO4 polymorphs

We use an approach based upon the Born model of solids, in which potential functions represent the interactions between atoms in a structure, to calculate the phonon dispersion of forsterite and the lattice dynamical behaviour of the beta-phase and spinel polymorphs of Mg₂SiO₄. The potential used (THB1) was derived largely empirically using data from simple binary oxides, and has previously been successfully used to model the infrared and Raman behaviour of forsterite. It includes ‘bond bending’ terms, that model the directionality of the Si-O bond, in addition to the pair-wise additive Coulombic and short range terms. The phonon dispersion relationships of the Mg₂SiO₄ polymorphs predicted by THB1 were used to calculate the heat capacities, entropies, thermal expansion coefficients and Gruneisen parameters of these phases. The predicted heat capacities and entropies are in outstandingly good agreement with those determined experimentally. The predicted thermodynamic data of these phases were used to construct a phase diagram for this system, which has Clausius-Clapeyron slopes in very close agreement with those found by experiment, but which has predicted transformation pressures that show less close agreement with those inferred from experiment. The overall success, however, that we have in predicting the lattice dynamical and thermodynamic properties of the Mg₂SiO₄ polymorphs shows that our potential THB1 represents a significant step towards finding the elusive quantitative link between the microscopic or atomistic behaviour of minerals and their macroscopic properties.