Luminescence centers in anhydrite,barite, celestite and their synthesized analogs     

M. L. Gaft  L. V. Bershov  A. R. Krasnaya  V. Ya. Yaskolko 《Physics and Chemistry of Minerals》1985,11(6):255-260

The intrinsic luminescence center (LC) of SO ₄ ^2? appears at 360 nm in all types of sulfates, but is absent in sulfates with large quantities of impurities. Three nonequivalent Gd³⁺ LC have been observed in luminescence spectra of anhydrite. Gd³⁺, Ce³⁺ O ₂ ^? LC were established in celestite. Photoluminescence (PL) bands in the sulfates were assigned as follows: the band at 460 nm is related to Eu²⁺ (a connection with Al³⁺ or donor-acceptor pair is possible also) in sulfates of Ca and Ba; bands at 520 nm and 590 nm are related to VO₄, MoO₄ and TiO₄ substituting SO₄; the band at 660 nm is assigned to Ti³⁺ X-ray luminescence (XL) band at 620 nm is assigned to Ag⁺.  相似文献   

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

I. Abs-Wurmbach  Prof. Dr. K. Langer 《Contributions to Mineralogy and Petrology》1975,49(1):21-38

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.  相似文献   

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

Bjørn O. Mysen  David Virgo 《Physics and Chemistry of Minerals》1985,12(2):77-85

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.  相似文献   

Zircon and sphene as fission track geochronometer and geothermometer: A reappraisal     

K. D. Bal  N. Lal  K. K. Nagpaul 《Contributions to Mineralogy and Petrology》1983,83(3-4):199-203

The data published earlier on zircon and sphene fission track ages and annealing are discussed in the light of different etching conditions used for age determination and annealing experiments in order to explain the age discordances of some zircon and sphene pairs, as well as numerous closing temperatures obtained for individual minerals. Using the new set of simple etching conditions, zircon (KOH melt) and sphene (HF+HCl), the annealing experiments indicate that tracks in sphene are annealed more easily than in zircon. The closing temperature of zircon and sphene have been calculated at 300° and 250° C respectively. The study reveals that both the fission track age and the closing temperature of a mineral can vary considerably if different etchants are used. For different etching conditions the closing temperatures (T) of sphene have the following order: ^T NaOH> ^T HF+HCl+HNO₃+H₂O> ^THF+HCl>^THCl. An alternative method can be used to obtain thermal histories of rocks by selectively applying various etchants on the same mineral.  相似文献   

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

Michele Catti 《Physics and Chemistry of Minerals》1981,7(1):20-25

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.  相似文献   

Crystal chemistry of a natural schorlomite and Ti-andradites synthesized at different oxygen fugacities     

A. Kühberger  T. Fehr  H. G. Huckenholz  G. Amthauer 《Physics and Chemistry of Minerals》1989,16(8):734-740

Ti-andradites were synthesized at a pressure of P(H₂O)=3 kbar and temperatures of 700–800° C. Oxygen fugacities were controlled by solid state buffers (Ni/NiO; SiO₂ + Fe/Fe₂SiO₄). The Fe²⁺-and Fe³⁺-distribution was determined by low temperature Mössbauer spectroscopy. The water content was measured by a solid's moisture analyzer. The chemical composition of the synthetic and the natural sample has been determined by electron microprobe. Ti-andradites from runs at high oxygen fugacities have Fe³⁺ on octahedral and tetrahedral sites; Ti-andradites from runs at low oxygen fugacities have tetrahedrally and octahedrally coordinated Fe²⁺ as well. These “reduced” garnets must also contain Ti³⁺ on octahedral sites. Charge balance is maintained due to substitution of O^2? by (OH)^? by two mechanisms: (SiO₄)^4? ? (O₄H₄)^4? and (Fe³⁺O₆)^9? ? (Fe²⁺O₅OH)^9?. FTIR spectra of the synthetic samples do show the presence of structurally bound (OH)^?. In a natural sample tetrahedrally and octahedrally coordinated Fe³⁺ are observed together with Fe²⁺ on all three cation sites of the garnet structure.  相似文献   

The reaction forsterite+cordierite=aluminous orthopyroxene+spinel in the system MgO-Al2O3-SiO2     

Claude T. Herzberg 《Contributions to Mineralogy and Petrology》1983,84(1):84-90

Reversal experiments at 1,150–1,300°C on the reaction forsterite+cordierite=aluminous orthopyroxene+spinel in the system MgO-Al₂O₃-SiO₂ show the equilibrium to have a negativedT/dP. The slope andT-P location of this equilibrium have been modelled using available heat capacity data and various structural models which explore the configurational entropy contributions to the totalΔS. The experimental data are consistent with the aluminous orthopyroxene model of Ganguly and Ghose (1979) where limited Al disorder occurs between theM1 andM2 sites, Al-Si mixing occurs on the tetrahedralB site with the ‘aluminum avoidance’ principle maintained, and Mg-Al disorder occurs in spinel with an interchange enthalpy of 9–12 kcal mol^?1. Additionally, Al-Si disordering which occurs in the indialite structure of cordierite is inconsistent with the experimental data and all pyroxene and spinel mixing models; consequently, Si and Al in anhydrous cordierites to 1,300°C in the system MgO-Al₂O₃-SiO₂ must be largely ordered.  相似文献   

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

B. Marler 《Physics and Chemistry of Minerals》1988,16(3):286-290

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).  相似文献   

Clinopyroxene on the join CaMgSi2O6-CaFe3+AlSiO6-CaTiAl2O6 at low oxygen fugacity     

Masahide Akasaka 《Journal of Earth System Science》1990,99(1):39-48

Subsolidus phase relations on the join CaMgSi₂O₆-CaFe³⁺ AlSiO₆-CaTiAl₂O₆ were studied by the ordinary quenching method at \(f_{O_2 } = 10^{ - 11} \) atm and 1,100°C. Crystalline phases encountered are clinopyroxene_ss (ss:solid solution) (Cpx_ss), melilite (Mel), perovskite (Pv), spinel_ss (Sp_ss), magnetite_ss (Mt_ss) and anorthite (An). There is no Cpx_ss single phase field, and the following assemblages were found; Cpx_ss+Mel, Cpx_ss+Mel+Sp_ss, Cpx_ss+Mel+Pv, Cpx_ss+Mel+Sp_ss+Pv, Cpx_ss+Pv+Sp_ss+An, Sp_ss+Pv+Mel+An+Cpx_ss, Mel+Mt_ss+An+Sp_ss+Cpx_ss+liquid and Mel+Mt_ss+An+Sp_ss+Cpx_ss+Pv. Mössbauer spectral study revealed that Cpx_ss contains both Fe²⁺ and Fe³⁺ in the octahedral site, and it was confirmed that the CaFe³⁺ AlSiO₆ content in the Cpx_ss at low \(f_{O_2 } \) is considerably less than that in the Cpx_ss crystallized in air, whereas the CaFe²⁺Si₂O₆ component increases. The maximum solubility of CaTlAl₂O₆ component in the Cpx_ss at low \(f_{O_2 } \) is higher than that in air. The decrease of CaFe³⁺ AlSiO₆ in the Cpx_ss at low \(f_{O_2 } \) may cause increase of CaTial₂O₆ in the Cpx_ss.  相似文献   

A MEG study of the olivine and spinel forms of Mg2SiO4     

Mark D. Jackson  Roy G. Gordon 《Physics and Chemistry of Minerals》1988,15(6):514-520

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.  相似文献   

The geochemistry of pyroxenes from the lower layered series of the Jimberlana intrusion,Western Australia     

I. H. Campbell  G. D. Borley 《Contributions to Mineralogy and Petrology》1974,47(4):281-297

Most of the Al³⁺ entering the pyroxenes does so by substituting for tetrahedral Si⁴⁺. This creates a charge imbalance that requires the simultaneous entry of Cr³⁺, Ti⁴⁺, Fe³⁺ or Al³⁺ into octahedral sites. Cr³⁺, because of its high crystal field stabilisation energy (CFSE), is the most important of these elements to enter the early-formed pyrosenes but it is replaced by Ti⁴⁺ later in fractionation when the Cr³⁺ content of the melt becomes depleted. The dependence of Cr³⁺ and Ti⁴⁺ on charge balance controls their partition between coexisting pyroxenes and olivines. Ca-rich pyroxene which contains more Al³⁺ than Ca-poor pyroxene also has more Ti⁴⁺ and Cr³⁺ whereas olivine, which contains negligible Al³⁺, has low Cr³⁺ and Ti⁴⁺. The Al³⁺ content of pyroxenes is influenced by changes in P, T, \(a_{{\text{SiO}}_{\text{2}} }\) and \(a_{{\text{Al}}_{\text{2}} {\text{O}}_{\text{3}} }\) of the magma and by the nature of the ion providing charge balance in the octahedral site. Of these \(a_{{\text{SiO}}_{\text{2}} }\) is dominant and variations in the Al³⁺ content of the Jimberlana pyroxenes correspond closely with the expected changes in the \(a_{{\text{SiO}}_{\text{2}} }\) of the melt. The substitution of divalent ions, such as Mn²⁺ and Ni²⁺, in the pyroxene lattice is by replacement of Fe²⁺ or Mg²⁺ in the octahedral M ₃ and M ₂ sites and is therefore independent of charge balance. If there are no size restrictions, the principal factor to be considered is the CFSE the ion receives in octahedral co-ordination. Ni²⁺, which receives a high CFSE, partitions strongly between the early-formed pyroxenes and olivines and therefore becomes depleted in the magma with fractionation. Conversely Mn²⁺, which receives zero CFSE, concentrates in the magma with fractionation and becomes a more important substitute in the later-formed pyroxenes. Its geochemical behaviour is controlled by its size. The narrow miscibility gap of the Jimberlana pyroxenes and the high En content of the Ca-poor pyroxenes at the bronzite pigeonite changeover suggest that these pyroxenes crystallised at a higher temperature than pyroxenes of comparable composition from other intrusions.  相似文献   

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

Takamitsu Yamanaka 《Physics and Chemistry of Minerals》1986,13(4):227-232

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.  相似文献   

Computational modeling of the structure and elastic constants of the olivine and spinel forms of Mg2SiO4     

Masanori Matsui  William R. Busing 《Physics and Chemistry of Minerals》1984,11(2):55-59

  相似文献   

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

Quentin Williams  Raymond Jeanloz  M. Akaogi 《Physics and Chemistry of Minerals》1986,13(3):141-145

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.  相似文献   

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

Roger G. Burns  Chien-Min Sung 《Physics and Chemistry of Minerals》1978,2(4):349-364

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.  相似文献   

Effects of pH on isotherm modeling and cation competition for Cd(II) and Cu(II) biosorption on Myriophyllum spicatum from aqueous solutions     

Guoxin Li  Dandan Zhang  Qingsong Li  Guoyuan Chen 《Environmental Earth Sciences》2014,72(11):4237-4247

The biosorption characteristics of Cd(II) and Cu(II) ions from aqueous solutions obtained using submerged aquatic plant (Myriophyllum spicatum) biomass were investigated in terms of equilibrium, kinetics, thermodynamics, and cation competition. Langmuir and Freundlich models were applied to describe the biosorption isotherm of metal ions by M. spicatum biomass and isotherm constants considering the most important parameter, pH. The variation of sorption isotherm constants showed pH dependence. The Langmuir and Freundlich models fitted the equilibrium data well. The maximum biosorption capacity (q _m) of M. spicatum biomass was determined to be 29.07 mg/g for the Cd(II) ion at pH 5.0 and 12.12 mg/g for the Cu(II) ion at pH 6.0. Chi square analysis showed that the Freundlich model fitted the equilibrium data better than the Langmuir isotherm. Competition of Cd(II) and Cu(II) in a binary solution showed that the Langmuir monolayer capacity of Cd(II) decreased from 29.07 mg/g with only Cd(II) in solution to 12.02 mg/g in the presence of Cu(II). Kinetics results showed that the biosorption processes of both metal ions followed the pseudo-second-order kinetics well. The calculated thermodynamic parameters (?G ⁰, ?H ⁰, and ?S ⁰) showed that biosorption of Cd(II) and Cu(II) ions onto M. spicatum biomass was feasible, spontaneous, and endothermic in nature. Fourier transform infrared spectroscopy spectrum analysis revealed that Cd(II) and Cu(II) sorption was mainly ascribed to carboxyl, hydroxyl, amine, and C–N groups in M. spicatum.  相似文献   

Exoelectron spectroscopy of traps in surface layers of phenakite and quartz     

V. S. Kortov  A. F. Zatsepin  V. I. Ushkova 《Physics and Chemistry of Minerals》1985,12(2):114-121

The possibilities of exoelectron spectroscopy to investigate defects in dielectrics are demonstrated for phenakite Be₂SiO₄, its structural analogs Zn₂ SiO₄, Be₂GeO₄, solid solutions Be₂Si_1?x Ge _x O₄ (x=0÷1) and α-quartz. Emission maxima at 330 and 670 K in phenakite have been found to be due to [GeO₄]^5? andE' centers, respectively. Structural disturbances in the silicon and oxygen positions have been shown to control the exoemission activity of the crystals. Radiation induced decrease of exoemission activity connected with generation ofE' centers by neutron irradiation has been discovered. The energy level scheme of active centers in the subsurface region of Be₂SiO₄ has been established.  相似文献   

The structural role of Al2O3 and TiO2 in immiscible silicate liquids in the system SiO2-MgO-CaO-FeO-TiO2-Al2O3     

Marcus I. Wood  Paul C. Hess 《Contributions to Mineralogy and Petrology》1980,72(3):319-328

The effects of the addition of Al₂O₃ on the large stable two liquid field in the SiO₂-TiO₂-CaO-MgO-FeO system were experimentally determined. The increase of Al₂O₃ content in the starting composition results in the decrease of critical temperature, phase separation and liquidus temperature of the two liquid field until it is rendered completely metastable. The shrinkage of the two liquid field indicates that Al₂O₃ is acting in the role of a network former and homogenizes the structure of the two melts. In this alkali-free system Al⁺³ utilizes the divalent cations, Ca⁺² and Mg⁺², for local charge balance with a preference for Ca⁺² over Mg⁺². Thus, AlO₄ tetrahedra combine with SiO₄ tetrahedra to form an aluminosilicate framework which polymerizes the SiO₂-poor melt and makes it structurally more similar to the SiO₂-rich melt. However, Ca⁺² and Mg⁺² are not as efficient in a charge balancing capacity as the monovalent K⁺ and Na⁺ cations. The lack of alkalis in this system limits the stability of AlO₄ tetrahedra in the highly polymerized SiO₂-rich melt and results in the preference of Al₂O₃ for the SiO₂-poor melt. The partitioning systematics of Ti are virtually identical to those of Al. It is concluded that Ti occurs in tetrahedral coordination as a network forming species in both the high — and low — SiO immiscible melts.  相似文献   

Intrinsic oxygen Fugacity measurements on chromites from the Bushveld Complex and their petrogenetic significance     

Rolf Snethlage  Dietrich D. Klemm 《Contributions to Mineralogy and Petrology》1978,67(2):127-138

Oxygen Fugacity measurements were carried out on chromites from the Eastern Bushveld Complex (Maandagshoek) and are compared with former measurements on chromites from the western Bushveld Complex (Zwartkop Chrome Mine). These results together with those of Hill and Roeder (1974) yield the following conditions of formation for the massive chromitite layers: Western Bushveld Complex (Zwartkop Chrome Mine) $$\begin{gathered} Layer{\text{ }}T(^\circ C) p_{O_2 } (atm) \hfill \\ LG3{\text{ 1160}} - {\text{1234 10}}^{ - {\text{5}}} - 10^{ - 7.6} \hfill \\ LG4{\text{ 1175}} - {\text{1200 10}}^{ - 6.35} - 10^{ - 7.20} \hfill \\ LG6{\text{ 1162}} - {\text{1207 10}}^{ - 6.20} - 10^{ - 7.50} \hfill \\ \hfill \\ \end{gathered} $$ Eastern Bushveld Complex (Farm Maandagshoek) $$\begin{gathered} {\text{LXI 1115}} - {\text{1150 10}}^{ - 7.80} - 10^{ - 8.80} \hfill \\ ( = {\text{Steelpoort Seam)}} \hfill \\ {\text{LX 1125 10}}^{ - 8.25} \hfill \\ {\text{V 1120 10}}^{ - 8.55} \hfill \\ {\text{LII 1120 10}}^{ - 8.0} - 10^{ - 8.60} \hfill \\ \end{gathered} $$ The comparison of the data shows, that the chronitite layers within each particular sequence were formed under approximately identicalp _{o 2}- andT-conditions. The chromites from the western Bushveld Complex, however, were formed at higher temperatures and higher oxygen fugacities than the chromites from the eastern Bushveld Complex. Fromp _{o 2}-T-curves of disseminated chromites and the temperatures derived above, the following conditions of formation for the host rocks were obtained: Western Bushveld Complex $$T = 1200^\circ {\text{C; }}p_{{\text{o}}_{\text{2}} } = 10^{ - 7.25} - 10^{ - 7.50} $$ Eastern Bushveld Complex $$T = 1125^\circ {\text{C; }}p_{{\text{o}}_{\text{2}} } = 10^{ - 8.50} - 10^{ - 9.25} $$ Consequently, the host rocks in the Zwartkop-Chrome-Mine, were formed under higher temperatures and higher oxygen fugacities than the host rocks at Maandagshoek. The rock sequence in the Zwartkop-Chrome-Mine therefore originated in an earlier stage of the differentiation of the Bushveld magma. Comparison of the chromites from the host rocks with the chromites from massive layers supports Ulmer's (1969) thesis that an increase of the oxygen fugacity is responsible for the formation of massive chromitite layers. The values in this investigation show that increases of only about 0.5–1.0 log units are necessary to enhance chromitite layer formation.  相似文献   

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

G. Will  L. Cemič  E. Hinze  K. -F. Seifert  R. Voigt 《Physics and Chemistry of Minerals》1979,4(2):189-197

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.  相似文献