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1.
A nested design was used to analyze the variance of the proportions or percent species composition of shore-zone finfish assemblages in the vicinity of the Millstone Nuclear Power Station in eastern Long Island Sound. The relative importance of five selected shore-zone species was found to be significantly influenced by both station and season within a year. Also included in the nested ANOVA model were effects due to period of plant operation (no units operating, one unit operating and two units operating) and year within period. Neither of these two effects was found to influence the percent species composition. The results of this study suggest that a nested ANOVA of percent species composition can be useful for detecting changes in assemblages of finfish species over time and space.  相似文献   

2.
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   

3.
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 (Al1.88Mn 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 Å3, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn3+-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusitess (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al1.86Mn 0.14 3+ )SiO5-(Al1.56Mn 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 Å3, 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 Å3 (ideal compn.) and a o 9.374, c o 18.593 Å3, V o 1633.6 Å3 (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   

4.
The Gladstone-Dale law (specific refraction) and the Drude law (molecular refraction) for silica polymorphs, at “sodium light” (λ D =0.5893 μm), are derived from simple atomic properties of SiO2 complex (atomic weight, first ionization potential). The considerations are based on the Lorentz electron theory of solids. The characteristic frequency (or eigenfrequency) v 0 of elementary electron oscillators (in energy units, hv) is identified with the band gap E G of a solid; on the other hand, this E G -gap is identified with the single ionization potential \(\tilde U\) of non-free atoms. For \(\tilde U\) =E G =10.2 eV (energy gap of quartz, see Nitsan and Shankland 1976b) the Gladstone-Dale law, or specific refraction, is (n?1)/ρ=0.208 cm3/g, where n and ρ are the refractive index and the density of medium, respectively. According to empirical data, the average value of the specific refraction of pure SiO2 polymorphs (except stishovite-high density phase of silica) is (〈n〉?1)/ρ=0.207±0.001 (〈n〉 denotes the mean refractive index of crystal). For stishovite the Drude law (n 2?1)/ρ=0.542 cm3/g is valid under an assumption that the first ionization potential \(\tilde U\) =E G ≈9 eV; this result is good agreement with the empirical value (〈n〉2?1)/ρ=0.536 cm3/g.  相似文献   

5.
Stoichiometric anorthite, CaAl2Si2O8, Pˉ1, with sharp a, b, c, and d diffractions was grown, using a CaV2O6 solvent, by cooling at 2 ° C per hour from 1450 to 750 ° C in air. Euhedral crystals up to 5 × 3× 0.5 mm, with prominent {010} and well-developed {110} and {001}, were obtained by spontaneous nucleation. Nonstoichiometric anorthite with excess SiO2 (CaAl2Si2O8+Si2Si2O8) was grown on the join CaAl2Si2O8-SiO2. Chemical analysis of the synthetic anorthite, having the highest SiO2 content, with maximum vacancies on M-site gave □0.110 Na0.006Ca0.884Al1.80Si2.20O8, and X-ray diffraction showed a trend from stoichiometric Pˉ1 through diffuse Pˉ1 to body-centered Iˉ1 probably reflecting increasing disorder caused by a higher Si/Al ratio in the T-sites and the positional disorder accompanied by M-site vancancies. Annealing of the nonstoichiometric diffuse Iˉ1 anorthite in air at 1050 ° C for 14 days resulted in exsolution of minute SiO2 inclusions due to probable ordering in the T-sites and filling of M-sites by Ca. Stoichiometric Pˉ1 anorthite was not obtained by annealing at 1050 ° due to appreciable solubility of SiO2 in CaAl2Si2O8. Metastable hexagonal CaAl2Si2O8 was found to be a twinned monoclinic crystal with cell dimensions: a = 10.24 (2), b = 17.74 (3), c= 14.99 (5) ?, β = 92.05 (5) °, space group C2.  相似文献   

6.
Calcium-olivine, γ-Ca2SiO4, larnite, β-Ca2SiO4, merwinite, Ca3Mg(SiO4)2, and monticellite, CaMgSiO4, are considered. According to a rigid oxyanion scheme, eulerian orientation angles of the SiO4 tetrahedra and translation coordinates of Ca and Si atoms are specified as structural variables τk. All derivatives of the static energy (Born model) contain atomic charges and repulsive parameters as unknowns; the minimum energy conditions ?E L/?τk=0 yield 34 equations which are solved by a least-squares method. The set of energy parameters fitting structural properties of all four phases together is: z Ca=1.50, z o=?1.10 e, r Ca=1.05, ρ=0.25 Å; the Mg charge was fixed at 1.38 e, from a previous study on forsterite. An average shift of 0.04 Å is observed between experimental and least-energy calculated atomic positions. Results are compared with those of Mg2SiO4, where the fit was based both on thermoelastic and on structural properties. If no charge values were fixed “a priori”, just ratios between charges could be determined by fitting them to structural data only.  相似文献   

7.
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, Fe1?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.  相似文献   

8.
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   

9.
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 (Mg1?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   

10.
A relationship between the energy gap (E G) and density (ρ) for pure SiO2 polymorphs is derived from atomic weights and first ionization potentials of free silicon and oxygen atoms. Theoretical considerations are based on the Lorentz electron theory of solids. The eigenfrequency v0 of elementary electron oscillators, in energy units h v0, is identified with the energy gap of a solid. The numerical relation is expressed as \(E_G = \sqrt {139.24 - 13.8327\rho } \) is in eV. For low-quartz with a density of 2.65 g/cm3 and also for stishovite with a density of 4.28 g/cm3, the energy gap E G=10.1 eV and 8.9 eV, respectively. From laboratory measurements for low-quartz E G=10.2 eV. The energy gap-density relation suggests a critical density value of ρx ≈ 10.1 g/cm3 for an SiO2 phase when the energy gap vanishes (E G=0), which is consistent with estimated densities for a high pressure silica polymorph with the fluorite structure.  相似文献   

11.
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   

12.
The possibilities of exoelectron spectroscopy to investigate defects in dielectrics are demonstrated for phenakite Be2SiO4, its structural analogs Zn2 SiO4, Be2GeO4, solid solutions Be2Si1?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   

13.
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   

14.
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   

15.
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   

16.
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   

17.
New chemical and modal analyses are presented of magmatic rocks and pyroxenes nodules from the Somma-Vesuvius volcano and of trachytes from the surrounding area. Geochemical evidence is employed in checking the generally accepted suggestion that magma composition develops from that of trachyte into phonolitic tephrite and finally into tephritic leucitite (vesuvite) by assimilation of dolomite. At the Somma stage of the volcano, phonolitic tephrites (tephritic phonolites) alone have been produced. Vesuvius lavas (tephritic leucitites) are comparatively high in K2O, CaO, F, Cl, Mn, Cu, Sr and Ba and low in SiO2 and Nb. The formation of vesuvites by assimilation of dolomitic sedimentary rocks, combined with gravity-separation of early-formed pyroxenes from a trachytic or tephritic magma, is improbable as shown by chemical balances between the respective igneous and sedimentary rocks.  相似文献   

18.
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   

19.
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   

20.
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