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   

On the nonstoichiometry and point defects of olivine     

A. Nakamura  H. Schmalzried 《Physics and Chemistry of Minerals》1983,10(1):27-37

This paper presents the point-defect thermodynamics for fayalite and olivine solid solutions (Fe _x Mg_1?x )₂SiO₄. By means of thermogravimetry, the metal-to-oxygen ratio of these silicates has been determined as a function of oxygen potential, compositionx and temperature. Experiments were performed in the range of 1,000° C≦T≦1,280° C and 0.2≦x≦1.0. It is found that V _Me ^″ , Fe _Me ^· and the associate {Fe′ _Si ^′ Fe _Me ^· } are the majority defects. With this knowledge it is possible to calculate the nonstoichiometry at given temperature as a function of \(p_{O_2 } \) and \(a_{SiO_2 } \) . The cation vacancy concentration shows a \(p_{O_2 }^{1/5} \) -dependence (forx≧0.2) and increases at givenT and \(p_{O_2 } \) almost exponentially with compositionx. In the composition range studied here, the silicates show an oxygen excess, and FeO is more soluble in the olivine than SiO₂.  相似文献   

Use of FePt alloys to eliminate the iron loss problem in 1 atmosphere gas mixing experiments: Theoretical and practical considerations     

T. L. Grove 《Contributions to Mineralogy and Petrology》1982,78(3):298-304

Theoretical and practical considerations are combined to place limits on the iron content of an FePt alloy that is in equilibrium with silicate melt, olivine and a gas phase of known \(f_{{\text{O}}_{\text{2}} }\) . Equilibrium constants are calculated for the reactions: (1) $$2{\text{Fe}}^{\text{o}} + {\text{SiO}}_{\text{2}} + {\text{O}}_{\text{2}} \rightleftharpoons {\text{Fe}}_{\text{2}} {\text{SiO}}_{\text{4}}$$ (2) $${\text{Fe}}^{\text{o}} + \frac{1}{2}{\text{O}}_{\text{2}} \rightleftharpoons {\text{FeO}}$$ . These equilibria may be used to choose an appropriate iron activity for the FePt alloy of an experiment. The temperature dependence of the equilibrium constants is calculated from experimental data. The Gibbs free energy of reaction (1) obtained using thermochemical data is in close agreement with ΔG_rxn calculated from the experimental data. Reaction (1) has the advantage that it is independent of the Fe²⁺/Fe³⁺ ratio of the melt, but is limited to applications where olivine is a crystallizing phase and requires a formulation for \(a_{{\text{SiO}}_{\text{2}} }^{{\text{liq}}}\) . Reaction (2) uses an empirical approximation for the FeO/Fe₂O₃ ratio of the liquid, and is independent of olivine saturation. However, it requires a formulation for a _FeO ^liq . Either equilibrium constant may be used to calculate the appropriate FePt alloy in equilibrium with a silicate melt. If experiments are conducted at an \(f_{{\text{O}}_{\text{2}} }\) parallel that of a buffer assemblage, a small range of FePt alloys may be used over a large temperature interval. For example, an alloy containing from 6 % to 9 % Fe by weight is in equilibrium with olivine-saturated tholeiites and komatiites at the quartzfayalite-magnetite buffer over the temperature interval 1,400° C to 1,100° C. Lunar basalt liquids in equilibrium with olivine at 1/2 log unit below the iron-wüstite buffer require an FePt alloy that contains 30–50 wt. % iron over a similar temperature interval.  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   

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   

Carbon Dioxide in igneous petrogenesis: I     

Frank J. Spera  Steven C. Bergman 《Contributions to Mineralogy and Petrology》1980,74(1):55-66

A number of experimental CO₂ solubility data for silicate and aluminosilicate melts at a variety of P- T conditions are consistent with solution of CO₂ in the melt by polymer condensation reactions such as SiO _4(m ^4? +CO_2(v)+Si _n O _3n+1(m) ⁽²ⁿ⁺¹⁾ ?Si _n+1O _3n+4(m) ^(2n+4)? +CO _3(m ^)2? . For various metalsilicate systems the relative solubility of CO₂ should depend markedly on the relative Gibbs free change of reaction. Experimental solubility data for the systems Li₂O-SiO₂, Na₂O-SiO₂, K₂O-SiO₂, CaO-SiO₂, MgO-SiO₂ and other aluminosilicate melts are in complete accord with predictions based on Gibbs Free energies of model polycondesation reactions. A rigorous thermodynamic treatment of published P- T-wt.% CO₂ solubility data for a number of mineral and natural melts suggests that for the reaction CO_2(m) ? CO_2(v)

1. CO₂-melt mixing may be considered ideal (i.e., { \(a_{{\text{CO}}_{\text{2}} }^m = X_{{\text{CO}}_{\text{2}} }^m \) );
2. \(\bar V_{{\text{CO}}_{\text{2}} }^m \) , the partial molal volume of CO₂ in the melt, is approximately equal to 30 cm³ mole^?1 and independent of P and T;
3. Δ C _p ⁰ is approximately equal to zero in the T range 1,400° to 1,650 °C and
4. enthalpies and entropies of the dissolution reaction depend on the ratio of network modifiers to network builders in the melt. Analytic expressions which relate the CO₂ content of a melt to P, T, and \(f_{{\text{CO}}_{\text{2}} } \) for andesite, tholeiite and olivine melilite melts of the form

$$\ln X_{{\text{CO}}_{\text{2}} }^m = \ln f_{{\text{CO}}_{\text{2}} } - \frac{A}{T} - B - \frac{C}{T}(P - 1)$$ have been determined. Regression parameters are (A, B, C): andesite (3.419, 11.164, 0.408), tholeiite (14.040, 5.440,0.393), melilite (9.226, 7.860, 0.352). The solubility equations are believed to be accurate in the range 3<P<30 kbar and 1,100°<T<1,650 °C. A series of CO₂ isopleth diagrams for a wide range of T and P are drawn for andesitic, tholeiitic and alkalic melts.  相似文献   

The role of water in the 1944 Vesuvius eruption     

Daniela Dolfi  Raffaello Trigila 《Contributions to Mineralogy and Petrology》1978,67(3):297-304

The P-T path of magma associated with the 1944 Vesuvius eruption has been outlined on the basis of probe mineralogy and the relationships between the crystallising phases. Equilibrium P-T values, obtained from the reactions:

1. CaMgSi₂O_6(liq) = CaMgSi₂O_6(cpx)
2. NaAlSi₃O_{8 (liq)} = NaAlSi₃O_{8 (plag)}
3. CaAl₂Si₂O_{8 (plag)}=CaAl₂SiO_6(cpx)+SiO_2(liq) have been established for three intracrustal crystallisation stages: I) 8.0 kbar and 1255 °C; II) 4.0 kbar and 1178 °C; III) 0.5 kbar and 1105 °C.

The H₂O content in the magma has been estimated from an experimental calibration of \(a_{^{CaMgSi_2 O_6 } }^{liq}\) as a function of \(X_{H_2 O}^{liq}\) at P _tot = 2 kbar. The estimated water contents of the magma for the three stages, I) 0.7%; II) 0.9%; III) 1.1%, are consistent with the pattern of activity of the 1944 Vesuvius eruption and with the relationship between the lavas. The shallow depth of H₂O-saturation of the magma, 0.24 kbar at 1100 °C, is consistent with the eruption sequence of lava flows followed by lava fountain activity.  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   

Mica-feldspar equilibria in supercritical alkali chloride solutions     

W. D. Gunter  H. P. Eugster 《Contributions to Mineralogy and Petrology》1981,75(3):235-250

The equilibrium position of the reaction $$\begin{gathered} 1.5 KAlSi_3 O_8 + HCl = 0.5 KAl_3 Si_3 O_{10} (OH)_2 \hfill \\ + 3SiO_2 + KCl \hfill \\ \end{gathered} $$ has been located at 1 and 2 kb pressure and temperatures between 600° and 670° C using the Ag-AgCl buffer. These data can be combined with information on the dissociation of KC1, HC1 and H₂O to determine species abundances in supercritical aqueous fluids in equilibrium with muscovite — K-feldspar — quartz assemblages. Chloride species become increasingly associated with increasingT, increasing total molality, (m _tot or \(m_{Cl_{tot} } \) ), and decreasing \(P_{H_2 O} \) . Master variable diagrams indicate that the pH of the solutions may vary from near neutral to quite acid. Published data on the paragonite-albite-quartz reaction and exchange reactions involving feldspars and micas were included to calculate speciation in mica-feldspar-NaCl-KCl-HCl-H₂O fluids at 2kb pressure and temperatures between 300° and 600° C. The data are not accurate enough to distinguish different feldspar structural states. Concentration gradients were calculated for individual species between K-feldspar+quartz, muscovite+quartz and andalusite+quartz assemblages at 500° C, 2 kb. Assuming that the proton diffuses most rapidly and that there are no [H⁺] gradients, the molality of the solution must vary 30-fold, with feldspar+quartz at the more concentrated side. The data on mica-feldspar-chloride equilibria are used to interpret the spacial distribution of micas, feldspar and quartz in microfolds. This distribution can be accounted for by pressure solution, due to the fact that non-hydrostatic pressure affects congruently dissolving minerals, auch as quartz, differently from minerals which dissolve incongruently, such as micas and feldspars. We postulate, that during folding at constant \(P_{H_2 O} \) ,T and \(m_{Cl - } \) , gradients in KC1 and SiO₂ are created by stress differences between hinge and limb of a microfold, such that both migrate to the hinge area where quartz precipitates and muscovite is converted to K-felspar, thus accounting for the observed mineral distribution.  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   

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

Yingwei Fei  Surendra K. Saxena 《Physics and Chemistry of Minerals》1986,13(5):311-324

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.  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   

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   

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   

A high pressure experimental study on a magnesian-rich leucite-lamproite from the West Kimberley area,Australia: petrogenetic implications     

Makoto Arima  Alan D. Edgar 《Contributions to Mineralogy and Petrology》1983,84(2-3):228-234

Liquidus and subliquidus phase relations of a leucite-lamproite (wolgidite) from the West Kimberley area, Australia have been studied experimentally under the volatile conditions of 3.22 wt.% H₂O ( \(X_{CO_2 }\) =0.11) and 13.0 wt.% H₂O ( \(X_{CO_2 }\) =0.03) between 10 to 40 kbar. Under these conditions, liquids are vapour undersaturated. In experiments with 13.0 wt.% H₂O, olivine is the liquidus phase up to 24 kbar and orthopyroxene above 24 kbar. Phlogopite and rutile occur close to the liquidus above 16 kbar. Crystallization temperatures of clinopyroxenes are 50–120° C below the liquidus. Based on these results, wolgidite magma is unlikely to be a partial melt of a garnet- or spinel-lherzolite mantle but could be derived from phlogopite+rutile±olivine±or-thopyroxene assemblages occurring as metasomatized mantle.  相似文献   

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

Raymond Jeanloz 《Physics and Chemistry of Minerals》1980,5(4):327-341

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.  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   

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   

Experimental study of the physico-chemical conditions of skarn formation     

Bin Zhao  Tongjin Li  Zhaopin Li 《中国地球化学学报》1985,4(2):114-126

Experimental results show that skarns can—800°C and 500–1,000 bars. Starting materials include intermediate-acidic igneous rocks, volcanic rocks, metamorphic rocks, carbonates of various purities and chemical reagents of analytical purity-grade. Experimental media are: NaCl, NaCl+CaCl₂, NaCl+CaCl₂+MgCl₂, Na₂CO₃ and Na₂SiO₃ solutions. Experimental results show that skarns can be formed under wide physico-chemical conditions:T=400°–800°C,P=500–1,000 bars,pH=4–11, and \(f_{O_2 } = 10^{ - 23} - 10^{ - 11} \) bar. The mineralogy of skarns and the chemical compositions of skarn minerals are generally controlled by the combined factors: the chemical composition of the original rocks, pH values, redox conditions, temperatures and pressures. Isomorphous substitution may have agreat effect on the temperature of formation andfo ₂ of some major skarn minerals. It is found that skarnization occurs preferentially in NaCl and NaCl+CaCl₂ solutions and subortinately in MaCO₃ and Na₂SiO₃ soiutions.  相似文献   

Molecular orbitals of Si2O 7 6− , Si3O 10 8− , etc., and mixed (B,Al,P,Si) m applied to clusters and X-ray spectroscopy data of silicates     

Yu. P. Dikov  E. I. Debolsky  Yu. N. Romashenko  S. P. Dolin  A. A. Levin 《Physics and Chemistry of Minerals》1977,1(1):27-41

The Si, Al L_{II, III} and OK_α emission and quantum yield spectra were obtained for 24 silicates. It was found that in minerals of a homogeneous anion composition the Si L_{II, III} line has double-humped structure, and when in addition to SiO ₄ ^4? ions of other composition (BeO ₄ ^6? , AlO ₄ ^5? etc.) are present it has triple-humped structure. The process of crystal-glass transition was studied by X-ray spectroscopy. The result is that in spite of the original form of the Si L_{II, III} line of the mineral this line changes its structure in glass and exhibits a typical double-humped structure. The CNDO/2 approach was used to calculate the electronic structure of basic structural groups of silicates from SiO ₄ ^4? to Si₅O ₁₆ ^12? by replacing one or two of the Si atoms by Be, B, Al and P. A qualitative interpretation of the X-ray spectra is presented.  相似文献