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1.
We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl2O4 and MgCr2O4. The data also include new low-temperature heat capacity measurements for MgAl2O4 spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl2O4 spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)2O4 spinels. We suggest a standard entropy for MgAl2O4 of 80.9 ± 0.6 J mol−1 K−1. For the solid solution between MgAl2O4 and MgCr2O4, we observe a linear increase of the standard entropies from 80.9 J mol−1 K−1 for MgAl2O4 to 118.3 J mol−1 K−1 for MgCr2O4.  相似文献   

2.
 Raman spectra of a single-crystal fragment of hydrous γ-Mg2SiO4, synthesized in a multianvil press, have been measured in a diamond-anvil cell with helium as pressure-transmitting medium to 56.5 GPa at room temperature. All five characteristic spinel Raman modes shift continuously up to the highest pressure, showing no evidence for a major change in the crystal structure despite compression well beyond the stability field of ringwoodite in terms of pressure. At pressures above ∼30 GPa a new mode on the low-frequency site of the two silicate-stretching modes is clearly identifiable, indicating a modification in the spinel structure which is reversible on pressure release. The frequency of the new mode (802 cm−1 extrapolated to 1 bar) suggests the presence of Si–O–Si linkages and/or a partial increase in the coordination of Si. Direct determination of the subtle structural change causing the new Raman mode would require high-pressure, single-crystal synchrotron X-ray diffraction experiments. The Raman modes of hydrous and anhydrous Mg-end-member ringwoodite are nearly identical up to 20 GPa, suggesting that protonation has only minor effect on the lattice dynamics over the entire pressure stability range for ringwoodite in the mantle. Received: 7 December 2001 / Accepted: 16 April 2002  相似文献   

3.
 Cation tracer diffusion coefficients, DMe *, for Me=Fe, Mn, Co and Ti, were measured using radioactive isotopes in the spinel solid solution (Ti x Fe 1−x )3−δO4 as a function of the oxygen activity. Experiments were performed at different cationic compositions (x=0, 0.1, 0.2 and 0.3) at 1100, 1200, 1300 and 1400 °C. The oxygen activity dependence of all data for DMe * at constant temperature and cationic composition can be described by equations of the type DMe *=D∘ Me[V]. CV·a O2 2/3+DMe[I] ∘·a O2 −2/3·DMe[V] ∘ and DMe[I] ∘ are constants and CV is a factor of the order of unity which decreases with increasing δ. All log DMe * vs. loga O2 curves obtained for different values of x and for different temperatures go through a minimum due to a change in the type of point defects dominating the cation diffusion with oxygen activity. Cation vacancies prevail for the cation diffusion at high oxygen activities while cation interstitials become dominant at low oxygen activities. At constant values of x, DMe[V] ∘ decreases with increasing temperature while DMe[I] ∘ increases.  相似文献   

4.
Atomistic model was proposed to describe the thermodynamics of mixing in the diopside-K-jadeite solid solution (CaMgSi2O6-KAlSi2O6). The simulations were based on minimization of the lattice energies of 800 structures within a 2 × 2 × 4 supercell of C2/c diopside with the compositions between CaMgSi2O6 and KAlSi2O6 and with variable degrees of order/disorder in the arrangement of Ca/K cations in M2 site and Mg/Al in Ml site. The energy minimization was performed with the help of a force-field model. The results of the calculations were used to define a generalized Ising model, which included 37 pair interaction parameters. Isotherms of the enthalpy of mixing within the range of 273–2023 K were calculated with a Monte Carlo algorithm, while the Gibbs free energies of mixing were obtained by thermodynamic integration of the enthalpies of mixing. The calculated T-X diagram for the system CaMgSi2O6-KAlSi2O6 at temperatures below 1000 K shows several miscibility gaps, which are separated by intervals of stability of intermediate ordered compounds. At temperatures above 1000 K a homogeneous solid solution is formed. The standard thermodynamic properties of K-jadeite (KAlSi2O6) evaluated from quantum mechanical calculations were used to determine location of several mineral reactions with the participation of the diopside-K-jadeite solid solution. The results of the simulations suggest that the low content of KalSi2O6 in natural clinopyroxenes is not related to crystal chemical factors preventing isomorphism, but is determined by relatively high standard enthalpy of this end member.  相似文献   

5.
The temperature (T) evolution of the barium carbonate (BaCO3) structure was studied using Rietveld structure refinements based on synchrotron X-ray diffraction and a powdered synthetic sample. BaCO3 transforms from an orthorhombic, Pmcn, α phase to a trigonal, R3m, β phase at 811°C. The orthorhombic BaCO3 structure is isotypic with aragonite, CaCO3. In trigonal R3m BaCO3, the CO3 group occupies one orientation and shows no rotational disorder. The average <Ba–O> distances increase while the <C–O> distances decrease linearly with T in the orthorhombic phase. After the 811°C phase transition, the <Ba–O> distances increase while C–O distances decrease. There is also a significant volume change of 2.8% at the phase transition.  相似文献   

6.
Raman spectroscopy and heat capacity measurements have been used to study the post-perovskite phase of CaIr0.5Pt0.5O3, recovered from synthesis at a pressure of 15 GPa. Laser heating CaIr0.5Pt0.5O3 to 1,900 K at 60 GPa produces a new perovskite phase which is not recoverable and reverts to the post-perovskite polymorph between 20 and 9 GPa on decompression. This implies that Pt-rich CaIr1−xPtxO3 perovskites including the end member CaPtO3 cannot easily be recovered to ambient pressure from high P–T synthesis. We estimate an increase in the thermodynamic Grüneisen parameter across the post-perovskite to perovskite transition of 34%, of similar magnitude to those for (Mg,Fe)SiO3 and MgGeO3, suggesting that CaIr0.5Pt0.5O3 is a promising analogue for experimental studies of the competition in energetics between perovskite and post-perovskite phases of magnesium silicates in Earth’s lowermost mantle. Low-temperature heat capacity measurements show that CaIrO3 has a significant Sommerfeld coefficient of 11.7 mJ/mol K2 and an entropy change of only 1.1% of Rln2 at the 108 K Curie transition, consistent with the near-itinerant electron magnetism. Heat capacity results for post-perovskite CaIr0.5Rh0.5O3 are also reported.  相似文献   

7.
Mn2+Sb2S4, a monoclinic dimorph of clerite, and benavidesite (Mn2+Pb4Sb6S14) show well-individualized single chains of manganese atoms in octahedral coordination. Their magnetic structures are presented and compared with those of iron derivatives, berthierite (Fe2+Sb2S4) and jamesonite (Fe2+Pb4Sb6S14). Within chains, interactions are antiferromagnetic. Like berthierite, MnSb2S4 shows a spiral magnetic structure with an incommensurate 1D propagation vector [0, 0.369, 0], unchanged with temperature. In berthierite, the interactions between identical chains are antiferromagnetic, whereas in MnSb2S4 interactions between chains are ferromagnetic along c-axis. Below 6 K, jamesonite and benavidesite have commensurate magnetic structures with the same propagation vector [0.5, 0, 0]: jamesonite is a canted ferromagnet and iron magnetic moments are mainly oriented along the a-axis, whereas for benavidesite, no angle of canting is detected, and manganese magnetic moments are oriented along b-axis. Below 30 K, for both compounds, one-dimensional magnetic ordering or correlations are visible in the neutron diagrams and persist down to 1.4 K.  相似文献   

8.
The crystal structure of Pb6Bi2S9 is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb6Bi2S9 at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb2+ and Bi3+ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb6Bi2S9, is solved in Pna2 1 (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb3Bi2S6 (lillianite).  相似文献   

9.
We have used density functional theory to investigate the stability of MgAl2O4 polymorphs under pressure. Our results can reasonably explain the transition sequence of MgAl2O4 polymorphs observed in previous experiments. The spinel phase (stable at ambient conditions) dissociates into periclase and corundum at 14 GPa. With increasing pressure, a phase change from the two oxides to a calcium-ferrite phase occurs, and finally transforms to a calcium-titanate phase at 68 GPa. The calcium-titanate phase is stable up to at least 150 GPa, and we did not observe a stability field for a hexagonal phase or periclase + Rh2O3(II)-type Al2O3. The bulk moduli of the phases calculated in this study are in good agreement with those measured in high-pressure experiments. Our results differ from those of a previous study using similar methods. We attribute this inconsistency to an incomplete optimization of a cell shape and ionic positions at high pressures in the previous calculations.  相似文献   

10.
Suspended sediment was collected in the South Slough, National, Estuarine Research Reserve, Oregon, over 8 tidal cycles during and following a single runoff event. The sediment was analyzed for its radionuclide signature to determine the relative contributions of different sources of sediment to the efflux from the estuary. Suspended sediment in the estuary is a mixture of sediment from three potential sources: the river system, Coos Bay, and the estuarine bed. Each source material has a distinctive7Be:210Pbxs ratio. The ratios of the source sediments decreased, in magnitude in the following order: riverine >bay>bed. The ratios, of the suspended sediment collected within a subsection of the South Slough estuary reflected the relative mixture of the source areas. The7Be:210Pbxs ratios provided a means of not only differentiating, between resuspended bed sediment and freshly delivered sediment from both the river system and Coos Bay, but also calculating the relative amount of resuspended bed sediment in the suspended sediment collected in the estuary. The sampled subsection of the South Slough estuary was a net sink of sediment during a 100-h sampling period associated with the runoff event, but the radionuclide analysis suggests that approximately 39% of the sediment efflux was resuspended bed sediment.  相似文献   

11.
Zinclipscombite, a new mineral species, has been found together with apophyllite, quartz, barite, jarosite, plumbojarosite, turquoise, and calcite at the Silver Coin mine, Edna Mountains, Valmy, Humboldt County, Nevada, United States. The new mineral forms spheroidal, fibrous segregations; the thickness of the fibers, which extend along the c axis, reaches 20 μm, and the diameter of spherulites is up to 2.5 mm. The color is dark green to brown with a light green to beige streak and a vitreous luster. The mineral is translucent. The Mohs hardness is 5. Zinclipscombite is brittle; cleavage is not observed; fracture is uneven. The density is 3.65(4) g/cm3 measured by hydrostatic weighing and 3.727 g/cm3 calculated from X-ray powder data. The frequencies of absorption bands in the infrared spectrum of zinclipscombite are (cm?1; the frequencies of the strongest bands are underlined; sh, shoulder; w, weak band) 3535, 3330sh, 3260, 1625w, 1530w, 1068, 1047, 1022, 970sh, 768w, 684w, 609, 502, and 460. The Mössbauer spectrum of zinclipscombite contains only a doublet corresponding to Fe3+ with sixfold coordination and a quadrupole splitting of 0.562 mm/s; Fe2+ is absent. The mineral is optically uniaxial and positive, ω = 1.755(5), ? = 1.795(5). Zinclipscombite is pleochroic, from bright green to blue-green on X and light greenish brown on Z (X > Z). Chemical composition (electron microprobe, average of five point analyses, wt %): CaO 0.30, ZnO 15.90, Al2O3 4.77, Fe2O3 35.14, P2O5 33.86, As2O5 4.05, H2O (determined by the Penfield method) 4.94, total 98.96. The empirical formula calculated on the basis of (PO4,AsO4)2 is (Zn0.76Ca0.02)Σ0.78(Fe 1.72 3+ Al0.36)Σ2.08[(PO4)1.86(AsO4)0.14]Σ2.00(OH)1. 80 · 0.17H2O. The simplified formula is ZnFe 2 3+ (PO4)2(OH)2. Zinclipscombite is tetragonal, space group P43212 or P41212; a = 7.242(2) Å, c = 13.125(5) Å, V = 688.4(5) Å3, Z = 4. The strongest reflections in the X-ray powder diffraction pattern (d, (I, %) ((hkl)) are 4.79(80)(111), 3.32(100)(113), 3.21(60)(210), 2.602(45)(213), 2.299(40)(214), 2.049(40)(106), 1.663(45)(226), 1.605(50)(421, 108). Zinclipscombite is an analogue of lipscombite, Fe2+Fe 2 3+ (PO4)2(OH)2 (tetragonal), with Zn instead of Fe2+. The mineral is named for its chemical composition, the Zn-dominant analogue of lipscombite. The type material of zinclipscombite is deposited in the Mineralogical Collection of the Technische Universität Bergakademie Freiberg, Germany.  相似文献   

12.
The mineral ussingite, Na2AlSi3O8(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm–1, and a possible OH librational bending mode at 1295 cm–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the 1H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and 1H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and 1H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.  相似文献   

13.
Static lattice energy calculations (SLEC), based on empirical interatomic potentials, have been performed for a set of 800 different structures in a 2 × 2 × 4 supercell of C2/c diopside with compositions between diopside and jadeite, and with different states of order of the exchangeable Na/Ca and Mg/Al cations. Excess static energies of these structures have been cluster expanded in a basis set of 37 pair-interaction parameters. These parameters have been used to constrain Monte Carlo simulations of temperature-dependent properties in the range of 273–2,023 K and to calculate a temperature–composition phase diagram. The simulations predict the order–disorder transition in omphacite at 1,150 ± 20°C in good agreement with the experimental data of Carpenter (Mineral Petrol 78:433–440, 1981). The stronger ordering of Mg/Al within the M1 site than of Ca/Na in the M2 site is attributed to the shorter M1–M1 nearest-neighbor distance, and, consequently, the stronger ordering force. The comparison of the simulated relationship between the order parameters corresponding to M1 and M2 sites with the X-ray refinement data on natural omphacites (Boffa Ballaran et al. in Am Mineral 83:419–433, 1998) suggests that the cation ordering becomes kinetically ineffective at about 600°C.  相似文献   

14.
Using density functional simulations within the generalized gradient approximation and projector-augmented wave method together with thermodynamic modelling, the reciprocal solubilities of MgSiO3 and CaSiO3 perovskites were calculated for pressures and temperatures of the Earth’s lower mantle from 25 to 100 GPa and 0 to 6,000 K, respectively. The solubility of Ca in MgSiO3 at conditions along a mantle adiabat is found to be less than 0.02 atoms per formula unit. The solubility of Mg in CaSiO3 is even lower, and most important, the extent of solid solution decreases with pressure. To dissolve CaSiO3 perovskite completely in MgSiO3 perovskite, a solubility of 7.8 or 2.3 mol% would be necessary for a fertile pyrolytic or depleted harzburgitic mantle, respectively. Thus, for any reasonable geotherm, two separate perovskites will be present in fertile mantle, suggesting that Ca-perovskite will be residual to low degree melting throughout the entire mantle. At the solidus, CaSiO3 perovskite might completely dissolve in MgSiO3 perovskite only in a depleted mantle with <1.25 wt% CaO. These implications may be modified if Ca solubility in MgSiO3 is increased by other major mantle constituents such as Fe and Al.  相似文献   

15.
In order to illustrate different applications of the amphibole-albite-chlorite-epidote-quartz geothermobarometer, pressure-temperature-time ( P–T–t ) ± space ( P–T–t–s ) ± deformation ( P–T–t–d ) paths have been established from literature data. They are discussed as a function of the chemical, equilibrium and microstructural data available in each case, and compared with the conclusions already established by other methods. It is clear that it is necessary to know the relative chronology of the events (directions of zoning of minerals in successive microstructural positions) to establish precise P–T paths; this enables reconstruction of complex geodynamic histories. From this point of view, it is necessary to analyse the maximum possible number of minerals in a few well-chosen metabasic rocks showing different generations of blastesis. The rocks should belong to different tectonic units to obtain the best overall picture of a metamorphic complex.  相似文献   

16.
U-Pb systems were examined in samples (ranging from 4 to 10 cm3 in volume) of ore material taken from along a 3.5-m profile across a zone of U mineralization exposed in an underground mine at the Strel’tsovskoe U deposit in eastern Transbaikalia. The behaviors of two isotopic U-Pb systems (238U-206Pb and 235U-207Pb) are principally different in all samples from our profile. While the individual samples are characterized by a vast scatter of their T(206Pb/238U) age values (from 112 to 717 Ma), the corresponding T(207Pb/235U) values vary much less significantly (from 127 to 142 Ma) and are generally close to the true age of the U mineralization. The main reason for the distortion of the U-Pb system is the long-lasting (for tens of million years) migration of intermediate decay products in the 238U-206Pb(RD238U) in the samples. This process resulted in the loss of RD238U from domains with high U concentrations and the subsequent accommodation of RD238U at sites with low U concentrations. The long-term effect of these opposite processes resulted in a deficit or excess of 206Pb as the final product of 238U decay. The loss or migration of RD238U are explained by the occurrence of pitchblende in association with U oxides that have higher Si and OH concentrations than those in the pitchblende and a higher +6U/+4U ratio. The finely dispersed character of the mineralization and the loose or metamict texture of the material are the principal prerequisites for RD238U loss and an excess of 206Pb in adjacent domains with low U concentrations. Domains with low U contents in the zone with U mineralization serve as geochemical barriers (because of sulfides contained in them) at which long-lived RD238U(226Ra, 210Po, 210Bi, and 210Pb) were accommodated and subsequently caused an excess of 206Pb. The 235U-207Pb system remained closed because of the much briefer lifetime of the 235U decay products. This may account for the significant discrepancies between the T(206Pb/238U) and T(207Pb/235U) age values. RD238U was most probably lost via the migration of radioisotopes at the middle part and end of the 238U family (starting with 226Ra). The heavy Th, Pa, and U radioisotopes (234Th, 234Pa, 234U, and 230Th) that occur closer to the beginning of 238U decay, before 226Ra, only relatively insignificantly participated in the process. Our results show that the loss and migration of RD238U are, under certain conditions, the main (or even the only) process responsible for the distortion of the U-Pb system.  相似文献   

17.
Pyrrhotite (Fe7S8) is a natural iron sulphide that can participate in rock magnetisation. Its electronic structure is not yet surely described. X-ray magnetic circular dichroism (XMCD) at Fe L2,3 edges on Fe7S8, coupled with multiplet calculations, shows that iron is present only as Fe2+ in this magnetic iron sulphide. It reveals a strong magnetic orbital moment. XMCD at Fe and S K edges shows the quite strong polarization of both Fe and S in Fe7S8.  相似文献   

18.
 The magnetic behavior of the Jahn-Teller structure braunite, (Mn2+ 1−yM y )(Mn3+ 6− x Mx)SiO12, is strongly influenced by the incorporation of elements substituting manganese. Magnetic properties of well-defined synthetic samples were investigated in dependence on the composition. The final results are presented in magnetic phase diagrams. To derive the necessary data, ac susceptibility and magnetization of braunites with the substitutional elements M = Mg, Fe, (Cu+Ti) and Cu were measured. Whereas the antiferromagnetic ordering temperature, T N , of pure braunite is hardly affected by the substitution of nonmagnetic Mg, it is rapidly suppressed by the substitution of magnetic atoms at the Mn positions. Typically for a concentration (x, y) ≥ 0.7 of the substituted elements, a spin glass phase occurs in the magnetic phase diagrams. Additionally, for the braunite system with Fe3+ substitutions, we observe in the concentration range 0.2 < x< 0.7 a double transition from the paramagnetic state, first to the antiferromagnetic state, followed by a transition to a spin glass state at lower temperatures. The unusual change of the magnetic properties with magnetic substitution at the Mn positions is attributed to the peculiar antiferromagnetic structure of braunite, which has been resolved recently. Received: 19 April 2001 / Accepted: 6 September 2001  相似文献   

19.
The structure of CaGe2O5 between room temperature and 923 K has been determined by X-ray powder diffraction. A continuous phase transition from triclinic C1¯ to monoclinic C2/c symmetry at Tc=714±3 K is observed. The transition is accompanied by a weak heat capacity anomaly. This anomaly and the strain analysis based on the measured lattice parameters indicate a classical second-order phase transition. The order parameter, as measured by the strain component e23, is associated with the displacement of the Ca cation. Electronic structure optimization by density functional methods is used to verify the centric space group of the low-temperature structure of CaGe2O5.  相似文献   

20.
The study area is the N’zi watershed, sub-watershed of the Bandama River (Ivory Coast). The N’zi watershed is located between longitudes 3°49′ and 5°22′ West and latitudes 6°00′ and 9°26′ North and covers an area of 35,500 km2. This study aims to identify trends in the rainfall-runoff relationship by using a monthly conceptual model. The methodology has consisted on the one hand in highlighting the existence of interannual climate and hydrological variability by using the method of segmentation of Hubert, and on the other hand, in applying the crossed simulations method by using the GR2M model, over several 7-year sub-periods. The results of the application of the method of segmentation of Hubert have demonstrated the presence of a hydroclimatic variability in the N’zi watershed. The modifications of the climate and physical conditions of the flow resulted in a modification of the hydrological response of the watershed translated by a non-stationarity in the rainfall-runoff relation.  相似文献   

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