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1.
Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5–Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least ~?1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+?+?[6]Mg2+?=?2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298?=???1981.5 kJ mol??1. Solid solution is complete across the Fe4O5–Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg–Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.  相似文献   

2.
Tourmalines from the Kalinovka porphyry copper deposit with epithermal bismuth-gold-basemetal mineralization and the Michurino gold-silver-base-metal prospect have been studied in the South Urals. Tourmaline from the Kalinovka deposit occurs as pockets and veinlets in quartz-sericite metasomatic rock and propylite. The early schorl-“oxy-schorl” [Fetot/(Fetot + Mg) = 0.66?0.81] enriched in Fe3+ is characterized by the homovalent isomorphic substitution of Fe3+ for Al typical of propylites at porphyry copper deposits. The overgrowing tourmalines of the second and third generations from propylite and quartz-sericite metasomatic rock are intermediate members of the dravite-magnesio-foitite solid solution series [Fetot/(Fetot + Mg) = 0.05?0.46] with homovalent substitution of Mg for Fe2+ and coupled substitution of X ? + YAl for XNa + YMg. These substitutions differ from the coupled substitution of YAl + WO2? for YFe2+ + WOH? in tourmaline from quartz-sericite rocks at porphyry copper deposits. At the Michurino prospect, the tourmaline hosted in the chlorite-pyrite-quartz veins and veinlets with Ag-Au-Cu-Pb-Zn mineralization is an intermediate member of the dravite-magnesio-foitite solid solution series [Fetot/(Fetot + Mg) = 0.20?0.31] with homovalent substitution of Mg for Fe2+ and coupled substitutions of X ? + YAl for XNa + YMg identical to that of late tourmaline at the Kalinovka deposit. Thus, tourmalines of the porphyry and epithermal stages are different in isomorphic substitutions, which allow us to consider tourmaline as an indicator of super- or juxtaposed mineralization.  相似文献   

3.
The hydration of kotoite, suanite, and szaibelyite with ultimate brucitization was considered by the example of skarn deposits of endogenous magnesium borates. This process involves isomorphic substitution of hydroxyl groups for equivalent amounts of boron radicals. The degree of kotoite hydration varies from 2 to 40%. The hydration products reach Mg2[BO3](OH) and Mg3{[BO3]1.5(3OH)0.5}2, are isostructural with orthoborate, approach Mg3[BO3](OH)3, and do not contain szaibelyite. Kotoite in association with humites is replaced by Si-bearing pertsevite with variable F content. In contrast, suanite is directly replaced by szaibelyite, with preservation of its relics or inheritance of crystal shapes. The composition of szaibelyite also changes owing to the partial substitution of hydroxyl for boric radical (in hydroxylszaibelyite) or an increase in H2O content (in hydroszaibelyite), which does not rule out its brucitization. The hydration of borates is caused by a decrease in boron content in hydrothermal solutions with decreasing temperature. The borate assemblages studied are characterized by low F content, the increase of which leads to the appearance of F-bearing low-and moderate-Si pertsevites in humite-kotoite calciphyres. The investigation of hydration became possible owing to the direct determination of boron content in borates. The obtained data were compared with experimental studies on the hydrothermal synthesis of kotoite, suanite, szaibelyite, and fluoborates. The established geochemical tendencies in the hydration of boron minerals, which is accompanied by partial migration and loss of boron into the adjacent rocks, are important for estimating the quality of borate ores in magnesian-skarn deposits.  相似文献   

4.
Fe-Li云母化学成分的解释和分类   总被引：3，自引：0，他引：3       下载免费PDF全文
孙世华 《地质科学》1988,(3):213-228
用置换矢量概念解释了115个天然 Fe-Li 云母化学成分的变化。Fe-Li 云母是三八面体 Li-Fe-Al 云母,其基本置换是四锂云母置换。由于 Al-Li 白云母置换和白云母置换的影响,其化学组成变化的基本趋势呈明显的非线性,因而 Fe-Li 云母不是真正的二元系。作为 Fe-Li 云母,富铁黑云母和铁叶云母都是最富铁的成员,因而建议称 Fe-Li 云母为黑云母-锂云母系列。根据化学成分,晶胞参数和折光率的异常变化还提出了该系列自然分类的方案。  相似文献   

5.
Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe2+ and Mg in the octahedrally coordinated Y site, and Fe3+, Al and Fe2+ in the tetrahedrally coordinated Z site. Substitutions Ti4+Fe3+Fe3+–1Si–1 and Ti4+Al3+Fe3+–1Si–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe2+ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe2+ contents) for the presence of [6]Ti3+ or [4]Ti4+ in schorlomite. The simplified general formula of schorlomite can be written as Ca3Ti4+2[Si3-x(Fe3+,Al,Fe2+)xO12], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti4+ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe3+, Fe2+ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of [6]Ti4+, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: ([6]Ti4+–[6]Fe2+–[6]Mg2+– [8]Na+)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca3Fe3+2Si3O12), morimotoite (Ca3Fe2+TiSi3O12), and Ca3MgTiSi3O12. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.
A. R. ChakhmouradianEmail: Phone: +1-204-4747278Fax: +1-204-4747623
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6.
Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO2, 8 wt.% Cr2O3 and 4 wt.% ZrO2, representing a solid solution of andradite (Ca3Fe3+ 2Si3O12 ≈46 mol%), uvarovite (Ca3Cr2Si3O12 ≈23 mol%), grossular (Ca3Al2Si3O12 ≈10 mol%), schorlomite (Ca3Ti2[Si,(Fe3+,Al3+)2]O12 ≈15 mol%), and kimzeyite (Ca3Zr2[Si,Al2]3O12 ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al3+, Fe3+ and Ti4+. Cr3+ and Zr4+ are found at the octahedral site along with Fe3+, Al3+ and Ti4+. The measured H2O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca2.99Mg0.03)Σ=3.02(Fe3+ 0.67Cr0.54Al0.33Ti0.29Zr0.15)Σ=1.98(Si2.42Ti0.24Fe0.18Al0.14)Σ=2.98O12OH0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.  相似文献   

7.
Two synthetic series of spinels, MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 have been studied by Raman spectroscopy to investigate the effects of Fe2+ and Fe3+ on their structure. In the first case, where Fe2+ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A1g and Eg toward lower wavenumbers with the increase of the chromite component into the spinel, while the F2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe3+ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe3+ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe3+ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm?1, when observed, show little or negligible Raman shift.  相似文献   

8.
The Mössbauer spectra of 119Sn and 57Fe in three natural and a synthetic garnet were studied between 20 and 300 K. These spectra reveal the presence of octahedral Sn4+ as well as octahedral Fe3+ and Fe2+. Sn2+ could not be detected. On the basis of these results the following cation substitution can be derived for the tin-bearing Silicate garnets of this study: Sn4+ (oct)+Fe2+ (oct) ? 2 Fe3+ (oct).  相似文献   

9.
Synthetic melilites on the join Ca2MgSi2O7 (åkermanite: Ak)-Ca2Fe3+AlSiO7 (ferrialuminium gehlenite: FAGeh) were studied using X-ray powder diffraction and 57Fe Mössbauer spectroscopic methods to determine the distribution of Fe3+ between two different tetrahedral sites (T1 and T2), and the relationship between ionic substitution and incommensurate (IC) structure. Melilites were synthesized from starting materials with compositions of Ak100, Ak80FAGeh20, Ak70FAGeh30 and Ak50FAGeh50 by sintering at 1,170–1,350 °C and 1 atm. The average chemical compositions and end-member components, Ak, FAGeh and Geh (Ca2Al2SiO7), of the synthetic melilites were Ca2.015Mg1.023Si1.981O7 (Ak100), Ca2.017Mg0.788Fe 0.187 3+ Al0.221Si1.791O7 (Ak78FAGeh19Geh3), Ca1.995Mg0.695Fe 0.258 3+ Al0.318Si1.723O7 (Ak69FAGeh25Geh6) and Ca1.982Mg0.495Fe 0.449 3+ Al0.519Si1.535O7 (Ak49FAGeh44Geh7), respectively. Rietveld refinements using X-ray powder diffraction data measured using CuK α -radiation at room temperature converged successfully with goodness-of-fits of 1.15–1.26. The refined Fe occupancies at the T1 and T2 sites and the Mg and Si contents determined by electron microprobe analysis gave the site populations of [0.788Mg + 0.082Fe3+ + 0.130Al]T1[0.104Fe3+ + 0.104Al + 1.792Si]T2 for Ak78FAGeh19Geh3, [0.695Mg + 0.127Fe3+ + 0.178Al]T1[0.132Fe3+ + 0.144Al + 1.724Si]T2 for Ak69FAGeh25Geh6 and [0.495Mg + 0.202Fe3+ + 0.303Al]T1[0.248Fe3+ + 0.216Al + 1.536Si]T2 for Ak49FAGeh44Geh7 (apfu: atoms per formula unit), respectively. The results indicate that Fe3+ is distributed at both the T1 and the T2 sites. The mean T1–O distance decreases with the substitution of Fe3+ + Al3+ for Mg2+ at the T1 site, whereas the mean T2–O distance increases with substitution of Fe3+ + Al3+ for Si4+ at the T2 site, causing decrease in the a dimension and increase in the c dimension. However, in spite of the successful Rietveld refinements for the X-ray powder diffraction data measured using CuK α-radiation at room temperature, each Bragg reflection measured using CuK α1-radiation at room temperature showed weak shoulders, which were not observed in those measured at 200 °C. The Mössbauer spectra of the melilites measured at room temperature consist of two doublets assigned to Fe3+ at the T1 site and two or three doublets to Fe3+ at the T2 site, implying the existence of multiple T1 and T2 sites with different site distortions. These facts can be interpreted in terms of the IC structure in all synthetic melilites at room temperature, respectively. The results of Mössbauer analysis indicate that the IC structure in melilite is caused by not only known multiple T1 site, but also multiple T2 site at room temperature.  相似文献   

10.
A thermodynamic model for the Gibbs free energy of igneous pyroxenes with the general formula [Na, Ca, Fe2+, Mg]M2[Fe2+, Mg, Ti, Al, Fe3+]M1[Al, Fe3+, Si]TetSiO6 is calibrated from experimentally determined compositions of coexisting pyroxene and silicate melt. The model is based upon the general formulation, and relies upon the calibration of the “quadrilateral” subsystem, previously published by the present authors. The calibration database of pyroxene-liquid equilibria spans a broad spectrum of temperature, pressure and oxygen fugacity conditions, ranging from 1000°–1600°C, 0.001–30 kbar and iron-wüstite to air. Chemical potentials of endmember pyroxene components as well as exchange potentials between pyroxenes and coexisting liquids are defined utilizing the present authors' thermodynamic melt model. Model parameters are extracted from these relations by regression analysis. The resulting model and derivative endmember properties are internally consistent with an existing standard state thermodynamic database. The success of the model and its applicability to igneous petrogenesis are demonstrated by comparing calculated and experimentally determined liquidus compositions, temperatures and symmetry states for pyroxenes crystallizing from a variety of silicate melts, ranging in composition from tholeiites and angrites through rhyolites to potash ankaratrites.  相似文献   

11.
A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant and characterized by the ideal formula Ca(Mg2Li)Al6(Si6O18)(BO3)3(OH)3F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg2+ → Fe2+, 2Mg2+ → Li+ + Al3+, and Mg2+ + OH → Al3+ + O2−. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al1.5Li1.5)Al6(Si6O18)(BO3)3 (OH2O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines allow us to regard them as new mineral species in the tourmaline group.  相似文献   

12.
(Mg,Fe)(Si,Al)O3 perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe3+/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe3+/ΣFe with Al composition of (Mg,Fe)(Si,Al)O3 perovskite. The Fe3+/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O3 perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe3+/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe3+/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O3 perovskite.  相似文献   

13.
Summary The first natural tourmaline (because tourmaline with [4]B has also been synthesized, we distinguish here between natural and synthetic tourmaline) that has been unequivocally demonstrated to contain B as a substituent at the T sites was described from Koralpe, Styria, Austria. This colourless B-rich olenite occurs as rims overgrowing schorl (black crystals up to a few cm) that has not yet been structurally characterized. A crystal structure refinement (R = 0.019) of this Al-rich schorl shows that [4]B occurs in the overgrown schorl; the optimized occupants of the atomic positions yield X (Na0.64Ca0.10K0.06□0.20) Y (Fe2+ 1.72Al1.08Ti0.11Zn0.03□0.06) Z (Al5.70Mg0.20Fe0.08 2+Mn0.02) ([3]BO3)3.00 T (Si5.76 [4]B0.24)O18 [F0.11(OH)3.31O0.58]. This is the first known (Al-rich) schorl where a structure refinement has detected [4]B. Comparing the structure refinements and the chemical composition of the Koralpe schorl and other [4]B-bearing tourmalines with tourmalines which contain no [4]B, it is of interest that only structure refinements of tourmalines which are low in magnesium and with a higher component of olenite show substantial amounts of [4]B; the role of Mg in controlling the amount of [4]B is not known, but it seems that an Al-component on the Y site (olenite-component), a boron-enriched environment and special P-T-t conditions are necessary to get tourmaline with substantial amounts of [4]B. Received July 7, 2000; revised version accepted June 6, 2001  相似文献   

14.
The phase relations and the element partitioning in a mid-oceanic ridge basalt composition were determined for both above-solidus and subsolidus conditions at 22 to 27.5 GPa by means of a multianvil apparatus. The mineral assemblage at the solidus changes remarkably with pressure; majorite and stishovite at 22 GPa, joined by Ca-perovskite at 23 GPa, further joined by CaAl4Si2O11-rich CAS phase at 25.5 GPa, and Mg-perovskite, stishovite, Ca-perovskite, CF phase (approximately on the join NaAlSiO4-MgAl2O4), and NAL phase ([Na,K,Ca]1[Mg,Fe2+]2[Al,Fe3+,Si]5.5-6.0O12) above 27 GPa. The liquidus phase is Ca-perovskite, and stishovite, a CAS phase, a NAL phase, Mg-perovskite, and a CF phase appear with decreasing temperature at 27.5 GPa. Partial melt at 27 to 27.5 GPa is significantly depleted in SiO2 and CaO and enriched in FeO and MgO compared with those formed at lower pressures, reflecting the narrow stability of (Fe,Mg)-rich phases (majorite or Mg-perovskite) above solidus temperature. The basaltic composition has a lower melting temperature than the peridotitic composition at high pressures except at 13 to 18 GPa (Yasuda et al., 1994) and therefore can preferentially melt in the Earth’s interior. Recycled basaltic crusts were possibly included in hot Archean plumes, and they might have melted in the uppermost lower mantle. In this case, Ca-perovskite plays a dominant role in the trace element partitioning between melt and solid. This contrasts remarkably with the case of partial melting of a peridotitic composition in which magnesiowüstite is the liquidus phase at this depth.  相似文献   

15.
Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg3.40Fe0.23Al3.25Cr0.16)[6] Al 1.00 [6] [O2/Al4.53Si1.47O18] (N) and (Mg2.53Fe0.55 Mn0.04Ti 0.03 4+ Al3.55Cr 0.08 3+ )[6]Al 1.00 [16] [O2/Al4.28Si1.73O18] (Sl). Single crystal spectra in the range 35000–6000 cm1- showed a slightly polarization dependent absorption edge near 3200 cm1- (N) or 30000 cm1- (Sl) and unpolarized bands at 25300 and 17300 cm1-, typical of spin-allowed transitions, derived from 4A2g→4T1g and 4A2g→4T2g, of Cr3+ in octahedral sites, with point symmetry C1, of the structure. Another weak band at 23000 cm?1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited 4T1 (F)-State of Cr3+. These assignments lead to crystal field parameters Dq=1730cm?1 and B= 685cm?1 of Cr3+ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr3+ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr3+-transitions, spectra of Sl exhibit weak dd-bands of Fe2+ at 10000 and 7700 cm1-, which are unpolarized in consistency with the C1 site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv1/2～-5000 cm1-) at 15000 and 11000 cm1-, which occur in E//Y(//b) and E//Z(//c=12°) only and exhibit an intensity ratio αY∶αz close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe2+[6]-Fe3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe2+-Fe3+ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of the websterite from the Noyabrskaya pipe compared to that from the Sludyanka pipe.  相似文献   

16.
A revised regular solution-type thermodynamic model for twelve-component silicate liquids in the system SiO2-TiO2-Al2O3-Fe2O3-Cr2O3-FeO-MgO-CaO-Na2O-K2O-P2O5-H2O is calibrated. The model is referenced to previously published standard state thermodynamic properties and is derived from a set of internally consistent thermodynamic models for solid solutions of the igneous rock forming minerals, including: (Mg,Fe2+,Ca)-olivines, (Na,Mg,Fe2+,Ca)M2 (Mg,Fe2+, Ti, Fe3+, Al)M1 (Fe3+, Al,Si)2 TETO6-pyroxenes, (Na,Ca,K)-feldspars, (Mg,Fe2+) (Fe3+, Al, Cr)2O4-(Mg,Fe2+)2 TiO4 spinels and (Fe2+, Mg, Mn2+)TiO3-Fe2O3 rhombohedral oxides. The calibration utilizes over 2,500 experimentally determined compositions of silicate liquids coexisting at known temperatures, pressures and oxygen fugacities with apatite ±feldspar ±leucite ±olivine ±pyroxene ±quartz ±rhombohedral oxides ±spinel ±whitlockite ±water. The model is applicable to natural magmatic compositions (both hydrous and anhydrous), ranging from potash ankaratrites to rhyolites, over the temperature (T) range 900°–1700°C and pressures (P) up to 4 GPa. The model is implemented as a software package (MELTS) which may be used to simulate igneous processes such as (1) equilibrium or fractional crystallization, (2) isothermal, isenthalpic or isochoric assimilation, and (3) degassing of volatiles. Phase equilibria are predicted using the MELTS package by specifying bulk composition of the system and either (1) T and P, (2) enthalpy (H) and P, (3) entropy (S) and P, or (4) T and volume (V). Phase relations in systems open to oxygen are determined by directly specifying the f o 2 or the T-P-f o 2 (or equivalently H-P-f o 2, S-P-f o 2, T-V-f o 2) evolution path. Calculations are performed by constrained minimization of the appropriate thermodynamic potential. Compositions and proportions of solids and liquids in the equilibrium assemblage are computed.  相似文献   

17.
Zusammenfassung Die Kristallstruktur von künstlichem Voltait, K2Fe5 2+Fe3 3+Al[SO4]12· ·18 H2O, kubisch hexakisoktaedrisch,Fd3c–O h 8,a 0=27,254 ,Z-16, wurde mittels photographischer Röntgendaten bestimmt. Die Aufklärung der Struktur erfolgte mit Patterson- und Fouriermethoden unter Zuhilfenahme des multiplen isomorphen Ersatzes. Die Verfeinerung nach der Methode der kleinsten Quadrate ergab mit anisotropen Temperaturfaktoren für 726 beobachteteF hkl R=0,033. Das Hauptmerkmal der Struktur ist ein 3dimensionales Gerüst aus [Fe3+O6]-Oktaedern, [Fe 5 6/2+ Fe 1 6/3+ O4(H2O)2]-Oktaedern und [K+O12]-Polyedern, die durch SO4-Tetraeder verknüpft werden. Hohlräume dieses Gerüstes werden von ungeordnet orientierten [Al(H2O)6]-Oktaedern eingenommen. Es wird gezeigt, daß Al als wesentlicher Bestandteil dieses Voltaits angesehen werden muß.
The crystal structure of voltaite, K2Fe5 2+Fe3 3+Al[SO4]12·18H2O
Summary The crystal structure of synthetic voltaite, K2Fe5 2+Fe3 3+Al[SO4]12· · 18 H2O, cubic hexakis-octahedral, space groupFd3c–O h 8,a 0=27.254 ,Z=16, was determined from photographic X-ray data. The structure was solved by Patterson and Fourier-methods with the aid of multiple isomorphic substitution. Least squares refinement with anisotropic temperature factors resulted inR=0.033 for 726 observedF hkl . The dominant structural feature is a continous framework composed of [Fe3+O6]-octahedra, [Fe 5 6/2+ Fe 1 6/3+ O4(H2O)2]-octahedra and [K+O12]-polyhedra linked by SO4-tetrahedra. The arrangement gives rise to cages occupied by disordered [Al(H2O)6]-octahedra. It is shown that Al must be considered to be a essential constituent of such voltaites.

Mit 2 Abbildungen  相似文献   

18.
Fifteen samples of (Mg,Fe)SiO3 majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O3 majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe3+ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe2+–Fe3+ charge transfer, where band intensity increases with increasing Fe3+ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe3+ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO3 majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe3+ concentration of (Mg,Fe)(Si,Al)O3 majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O3 perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.  相似文献   

19.
Synchrotron radiation boron K-edge XANES spectra collected in fluorescence yield mode are reported for monoclinic metaboric acid [HBO2(II)], sinhalite (MgAlBO4), and a selection of boron oxides in which B is exclusively in trigonal coordination ([3]B). The anomalously high divergence of tetrahedral ([4]B–O) bond lengths in HBO2(II) and sinhalite is used to resolve fine structure at the [4]B K edge due to splitting of σ*(t2) antibonding orbitals. For HBO2(II), XANES peaks at 196.9 and 199.3?eV are assigned to [4]B–O distances of 1.564 and ～1.440 (×3) Å, respectively, and, for sinhalite, peaks at 196.8, 197.9, and 199.6?eV are assigned to distances of 1.586, 1.483 (×2), and 1.442?Å, respectively. A correlation between peak splitting at the [4]B K edge and divergence of tetrahedral bond length is established for borates and borosilicates using data for sinhalite, HBO2(II), ferroaxinite, danburite, datolite, and BPO4. B K-edge XANES spectra collected in total electron yield mode, which probes to <60?Å, show that almost all [4]B in HBO2(II) and about one-third of the [4]B in sinhalite are converted to [3]B in the near-surface structure. Moreover, HBO2(II), HBO2(III), sassolite (boric acid; H3BO3), and v-B2O3, which have markedly different bulk structures, have a similar near-surface layer composed of a relaxed anhydrous network of BO3 groups.  相似文献   

20.
Three iron-rich 1:1 clay minerals, greenalite [Si2]{Fe 3 2+ }O5(OH)4, berthiérine [Si, Al]2{Fe2, Mg, Fe3+, Al}3 O5(OH)4 and cronstedtite [Si, Fe3+]2{Fe2+, Fe3+}3O5(OH)4 have been studied by Mössbauer spectroscopy, magnetization measurements and neutron diffraction to determine their magneticproperties. The predominant magnetic coupling is ferromagnetic for pairs of ferrous ions in the octahedral sheet, but antiferromagnetic for ferric pairs. The crystal field at Fe2+ sites in greenalite and berthiérine is effectively trigonal with an orbital singlet l z=0 as ground state. These mainly ferrous minerals order magnetically at 17K and 9K respectively. The magnetic structure of greenalite consists of ferromagnetic octahedral sheets, with the moments lying in the plane, coupled antiferromagnetically by much weaker interplane interactions. The ratio of intraplane to interplane coupling is of order 50, so the silicate has a two-dimensional aspect, both structurally and magnetically. Although the overall magnetic order is established as antiferromagnetic by neutron diffraction, the magnetization curves resemble those of a ferromagnet because of the very weak interplane coupling. Cronstedtite orders antiferromagnetically around 10K. Moments within the planes are antiferromagnetically coupled. The magnetism has no particular two-dimensional character because exchange paths between the layers are provided by the ferric cations present in the tetrahedral sheets.  相似文献   

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