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1.
Experimental observations using transmission electron microscopy (TEM) indicate that Fe3+-rich grossular–andradite solid solutions with oscillatory zoning tend to occur as separate lamellae of andradite and intermediate compositions (Hirai and Nakazawa 1986; Pollok et?al. 2001). From one lamella to the next, the Fe3+ concentration can change significantly within a few nm. In order to understand the Fe3+ and Al content of each phase and the thermodynamics, chemistry, structure, and stability at the interfaces, Monte Carlo simulations were performed. According to our calculations, there is an ordered structure with a 1:1 ratio of Al and Fe3+ with alternating Al and Fe octahedra along the main cubic crystallographic axes. Even though this ordered grandite is more energetically favorable than a 1:1 mixture of the end members grossular and andradite [by ≈1.6?kJ (mol exchangeable cations)?1], this structure is stable only at temperatures below ≈500?K. Enthalpies, free energies, configurational and vibrational entropies of mixing, and the long-range order parameter are influenced by the formation of ordered grandite below 500?K. These data also explain why interfaces are stable only between grossular and grandite or between andradite and grandite but not between the end members. The interface energies between the end members and ordered grandite are comparably low [0.16?meV?Å?2∥(1?0?0), 0.55?meV?Å?2∥(1?1?0), 0.63?meV?Å?2∥(1?1?1)] and, therefore, do not hinder the formation of lamellae. Our calculations on the free energies of mixing indicate that there are miscibility gaps between grossular and grandite and between grandite and andradite only below ≈430?K. Since most of these solid solutions are formed at higher temperatures for which we did not find evidence of a miscibility gap, the formation of compositional oscillations is probably due to kinetic hindering of thermodynamically stable complete solid solutions. ?A new methodological aspect is the incorporation of zero-point energies of vibrations and the vibrational entropies into the calculation of the free energy of mixing. In case of the grossular–andradite solid solution, these vibrational effects change the free energy of mixing by only a few percent.  相似文献   

2.
Ab initio LDF theory has been used to study the structure of the hydrogarnet defect in α-quartz. The predicted structure is in good agreement with the available sexperimental data. The techniques employed also yield a good model for the structure of α-quartz, giving an average Si-O bond length of 1.62 Å and average Si-O-Si angle of 142°.  相似文献   

3.
Atomistic computer simulation techniques have been employed to model mechanisms of hydrogen incorporation in the clinopyroxenes diopside and jadeite. Calculation of solution reaction energies for the pure phases indicates that hydrogen is most easily incorporated via the formation of [VSi(OH)4] x hydrogarnet type defects. When components of the two phases are mixed, then solution energies can become exothermic. The substitution of Al for Si in diopside and of Mg or Ca for Al in jadeite, provides favourable routes for hydrogen incorporation, with exothermic values of solution energy. Thus the amount of water present in these minerals in the Earth’s upper mantle will vary with composition. Simulation of IR frequencies associated with O–H stretching at specific defect clusters has also been carried out. An analysis of hydrogen–oxygen bond lengths gives good agreement, although comparison of experimental and calculated IR frequencies are problematic. This is partly due to the complexity of experimental spectra, but may also be due in part to deficiencies in the ability of the model to accurately describe the O–H stretching frequency.  相似文献   

4.
The phase relations in the system grossular-spessartine-H2O were investigated at 2.0 Kb aqueous fluid pressure and at subsolidus temperatures down to 420 ° C. Despite metastable persistence of a compositional gap found in some intermediate members, a complete solid solution between grossular and spessartine exists.Linear relations between the unit cell edge, a 0, and composition were readily observed down to 620 ° C with a 0=11.849(2) Å and 11.613(2) Å for grossular and spessartine, respectively. Hydrated garnets began to appear at higher temperature for the Ca-rich members. Grossular and spessartine formed at 420 ° C have a 0=11.901(2) Å and 11.632(2) Å, indicating the presence of 0.6 and 0.2 mol H2O, respectively. Intermediate members show varying degrees of hydration. Infrared spectra of the more hydrated members show a major and minor absorption bands at 3,620 cm–1 and 3,660 cm–1, respectively, in addition to a broad band around 3,430 cm–1. All the hydrogarnets formed at 420 ° C were proven to be metastable.The rare occurrence of the intermediate grossular-spessartine garnets may be attributed to the lack of appropriate bulk chemistry of the rock rather than to the P-T conditions to which the rock is subjected. There may be a stability field for hydrogrossular below 420 ° C at 2 Kb, but not for hydrospessartine. Any occurrence of hydrogarnet may be used as a temperature indicator setting the maximum of formation for the hydrogarnet-bearing assemblage below 420 ° C at 2 Kb.  相似文献   

5.
《Chemical Geology》2006,225(3-4):360-372
Powder IR absorption spectroscopy has been used to characterise cation substitutions in three garnet solid solutions: grossular–andradite, skiagite–andradite and skiagite–almandine. The wavenumber shift of the highest energy mode associated with tetrahedral vibrations depends on the type of cation occupying the adjacent sites in the structure. The wavenumber shifts exhibit positive deviations from linearity that correlate closely with the variations of the Si–O bond distances for all three garnet solid solutions. The autocorrelation function has been used to determine an effective line width (Δcorr) of the absorption bands over a given spectral region. Non-linear behaviour of Δcorr was found for all three solid solutions. An empirical calibration between Δcorr excess and calorimetric enthalpy of mixing data gives an estimate for the symmetric Margules parameters WspecH of the three solid solutions. Comparison with the systematics of aluminosilicate garnets in terms of WspecH vs. ΔV2, where ΔV represents the difference in molar volume between the end members in a binary system, reveals that such a relationship is not generally applicable to garnet solid solutions with an octahedral cation other than Al.  相似文献   

6.
A suite of 11 gem-quality, optically completely clear garnet crystals with a broad variety of compositions in the space of the end members pyrope–almandine–spessartine–grossular–andradite–goldmanite were analyzed for trace amounts of “water” by nuclear reaction analysis, NRA, based on the reaction 1H(15N, αγ)12C, and by single-crystal absorption spectroscopy in the νOH vibrational range using microscope-FTIR-spectroscopic methods. The aim was to establish a calibration of the highly sensitive IR method with high areal resolution for “water” determination in garnets, by studying garnets of a wide compositional range, and to check for compositional dependencies of the integral molar absorptivities of the “water” component, ?int[1molH2O?1cm?2], in the nominally “water”-free garnets. The results of NRA show a broad variation of water contents in the range (14 ± 3) to (950 ± 80) wt ppmH2O, the values being low and very high for the garnet solid solutions (PyrAlm)SS and close-to-end-member GrossSS, respectively. There were no indications of inhomogeneities in the OH distribution, except possibly for one of the garnets (grossular, variety hessonite, from Tanzania). The quantitative evaluation of the complex νOH spectra, which showed similar shape only for members of the (PyrAlm)SS, yielded integral absorption coefficients, αint (cm?2), which allowed the calculation of integral molar absorptivities, ?int, using the “water” values of NRA. The ?int values obtained varied in a wide range but with no obvious correlation with the composition of the garnet except for the extremely high values, in the 104 range, of the two specimen with compositions close to end-member grossular. In all other garnets, ?int was in the 103 range with an average of ?int=3630±1580[1molH2O?1cm?2]. Therefore, this value is proposed for the use in routine “water” determinations of compositionally different garnets by the micro-IR method, except for garnets near to end-member grossular.  相似文献   

7.
The incorporation of OH defects in quartz from the systems quartz–water, quartz–albite–water and granite–water at pressures between 5 and 25?kbar and temperatures between 800 and 1,000?°C was investigated by IR spectroscopy. The two most important OH absorption features can be assigned to hydrogarnet defects (absorption band at 3,585?cm?1) and coupled substitutions involving Al3+ (Al–H defects, absorption bands at 3,310, 3,378 and 3,430?cm?1). Al incorporation in quartz is controlled by mineral/melt partitioning (D Al Qz/Melt ?=?0.01) and exhibits a negative pressure dependence. This trend is not clearly reflected by the concentration of Al–H defects, which shows positive deviations from the theoretical 1:1 correlation of Al/H for some samples. In contrast to the Al–H defects, formation of hydrogarnet defects appears to be positively correlated to pressure and water activity, and may be used a petrological indicator. The overall water concentration exhibits only minor changes with pressure and temperature, but a clear correlation of water activity (controlled by various amounts of dissolved salts) and hydrogarnet substitution could be established.  相似文献   

8.
The partitioning of samarium and thulium between garnets and melts in the systems Mg3Al2-Si3O12-H2O and Ca3Al2Si3O12-H2O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D Sm (D Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10–13 cm2 s–1 at 1,300 ° C and 2 × 10–12 cm2 s–1 at 1,500 ° C, and for grossular, 8.3 × 10–12 cm2 s–1 at 1,200 ° C and 4.6 × 10–11 cm2 s–1 at 1,300 ° C. The equilibrium values of D Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm3Al5O12 in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) DREE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg3Al2Si3O12-H2O at low Sm concentrations. These change D Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature.  相似文献   

9.
In polymetamorphic pelites of the Rappold complex in the Wölz crystalline basement (Eastern Alps) reaction rim garnets at staurolite-quartz interfaces (type I) and single grain garnets along previous staurolite-white mica interfaces (type II) were formed. The garnet reaction rims were formed during the Cretaceous amphibolite facies metamorphic overprint of the pre-existing mineral assemblages comprising garnet, staurolite, and kyanite from an amphibolite facies metamorphic event probably of Variscian age. The newly formed garnet may take the form of reaction rims along the margins of large pre-existing staurolite blasts. The initial growth increments of garnet have low grossular content, and reaction rim growth was controlled by the transfer of Fe, Mg and Mn components from the staurolite-garnet interface to the quartz-garnet interface. Later garnet growth increments have relatively high grossular content due to consumption of matrix plagioclase, which was destabilized by successive pressure increase. The grossular content of newly formed garnet shows systematic increase towards sites where plagioclase breaks down indicating that transport of calcium through the matrix was sluggish. On the basis of reaction microstructures it is demonstrated that the mineral assemblage garnet?+?kyanite?+?biotite?+?paragonite was formed at the conditions of eo-alpine amphibolite facies overprint while staurolite and plagioclase broke down successively with increasing pressure.  相似文献   

10.
Scapolite–wollastonite–grossular bearing calc-silicate rocks from the Vellanad area in the Kerala Khondalite Belt (KKB) of Southern India preserve a number of reaction textures which help to deduce their P–T–fluid history. Textures include calcite+plagioclase±quartz symplectites after scapolite, grossular+quartz coronas between wollastonite and plagioclase, grossular coronas between wollastonite and plagioclase+calcite that replace former scapolite, and grossular blebs replacing anorthite+calcite+quartz pseudomorphs of scapolite. Garnet coronas are also observed between clinopyroxene and wollastonite or scapolite or plagioclase. The reactions, apart from those involving clinopyroxene, can be modelled in the simple CaO–Al2O3–SiO2–CO2 system and interpreted using partial reaction grids constructed for the activities of end-members in the analysed phases. The reaction topologies produced are good approximations for the peak as well as retrograde mineral assemblages and reaction textures. For the compositions of the phases present in this study, the medium pressure calc-silicate assemblages are defined by the stable pseudo-invariant points [Qtz], [Mei] and [Grs]. The textural features interpreted using these activity-corrected grids indicate a phase of isobaric cooling from about 835°C to 750°C at 6 kbar in the Vellanad area. This is inconsistent with earlier studies on other lithologies from the KKB, most of which imply a post-peak P–T path involving near-isothermal decompression. However, as the temperatures obtained for the KKB from the calc-silicates are higher than those previously deduced from metapelites and garnet–orthopyroxene assemblages, the phase of near-isobaric cooling reported here is inferred to have proceeded prior to the onset of the decompression documented from studies of other rock types.  相似文献   

11.
We present an X-ray absorption near-edge structure study performed at the Yb LI- and LIII-edges on synthetic pyrope (Mg3Al2Si3O12) and grossular (Ca3Al2Si3O12) garnets containing about 1% wt of Yb. For the first time Yb L-edge XANES spectra are analyzed by full multiple scattering theory using clusters of different sizes and different final-state potentials. A comparison between experimental spectra and model calculations indicates that Yb3+ enters the dodecahedral X-site in both pyrope and grossular, in agreement with the results of an EXAFS study. Based on the present results, the charge balancing substitution mechanism required by the replacement of divalent Mg and Ca cations with trivalent Yb3+ is discussed in terms of vacancies in dodecahedral sites surrounding the central Yb3+ absorber. Received: 7 December 1998 / Revised, accepted: 7 May 1999  相似文献   

12.
利用钾长石合成雪硅钙石纳米粉体的反应机理研究   总被引：2，自引：2，他引：0  
刘贺  马鸿文  聂轶苗  王蕾 《现代地质》2006,20(2):347-353
采用CaO为助剂,在水热条件下分解钾长石,进而合成雪硅钙石。影响反应的主要因素为：n(CaO)/n(SiO2+AlO1.5)、晶化温度和晶化时间等。在n(CaO)/n(SiO2+AlO1.5)为0.75～1.00、晶化温度为230～250 ℃、晶化时间为5～8 h的条件下,可以合成结晶良好的雪硅钙石晶体。反应机理分析表明：在钾长石-氧化钙的水热体系中,钾长石的分解并不是简单的离子交换作用或铝硅酸盐解聚作用,而是在碱金属离子与水作用的基础上,反应物中H+与矿物表面的碱金属离子K+、Na+、Ca2+作用,首先形成表面富硅贫铝的前驱聚合体（SiO2·nH2O）;然后这些前驱聚合体分解,与溶液中的Ca2+作用,生成C-S-H凝胶和水钙铝榴石;随着反应时间的延长,C-S-H凝胶和水钙铝榴石进一步转变为雪硅钙石。  相似文献   

13.
 The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various bulk Ca/(Ca+Mn) compositions: Ca3Al2Si3O12+3Mn2+(aq) ⇔ Mn3Al2Si3O12+3Ca2+(aq) The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving grossular grains. The first garnet to crystallize is spessartine rich (X gt Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn) zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24 hours. Plots of ln KD versus X gt Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters ΔG° (600 °C, 2 kbar)=−8.0±0.8 kJ/mol and w gt CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated data. Grossular activities calculated using the w gt CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al2SiO5-quartz barometer will not be increased by more than 0.2 kbar. Received: 18 January 1995/Accepted: 4 June 1996  相似文献   

14.
The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K?1 mol?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K?1 mol?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10?3T ? 15.27 × 105T?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10?3T ? 30.24 × 105T?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10?3T ? 25.02 × 105T?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10?3T ? 24.08 × 105T?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al2O3-SiO2-H2O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H2O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.  相似文献   

15.
Single-crystal Raman spectra of synthetic end-member uvarovite (Ca3Cr2Si3O12) and of a binary solution (59% uvarovite, 41% andradite) have been measured using single crystal techniques. For each of these garnets, 22 and 21 of the 25 Raman modes were located, respectively. The spectra for uvarovite garnets closely resemble those of the other calcic garnets, grossular, and andradite. The modes for uvarovites do not fit into the same trends as established by the other five anhydrous end-member garnets: the high energy “internal” Si–O modes do not depend on lattice constant in uvarovite. They exceed frequencies for both andradite and grossular. This is likely due to the large crystal field stabilization energy of trivalent chromium. The low energy and midrange modes are at similar frequencies to the other calcic garnets.  相似文献   

16.
This study describes the microstructural and chemical development of symplectites, obtained in fluid‐mediated mineral replacement experiments. During the experiments polymineralic feldspar‐rich samples were exposed to aqueous Na–SiO2 solution at 600 °C and 2 kbar confining pressures for durations of 12 h to 20 days. The resulting reaction rims display high mineralogical and structural complexity and contain two varieties of symplectites, represented by nanometre‐scale intergrowths of gehlenite–zeolite and grossular–zeolite grains. The experimental fluid was enriched in 18O isotope in order to trace oxygen redistribution during the reaction. The elevated 18O concentration in the reaction products and the heterogeneity in its distribution suggest that symplectite formation was controlled by dissolution–precipitation mechanisms rather than volume‐diffusion processes. Microstructural and chemical observations suggest that symplectite formation occurred in multiple stages in response to spatially heterogeneous and temporarily evolving fluid composition at the reaction interfaces. Hence, our results shed light on the fundamental processes involved in symplectite formation improving our ability to interpret symplectite microstructures.  相似文献   

17.
Recent low temperature, adiabatic calorimetric heat capacity measurements for grossular have been combined with DSC measurements to give entropies up to 1000 K. In conjunction with enthalpy of solution values for grossular, these data have yielded H f o (298.15K) and G f o (298.15K) values of –1583.2 ± 3.5 and –1496.74 ± 3.7 kcal mol–1 respectively. For 15 reactions in the CaO-Al2O3-SiO2-H2O system, thermodynamically calculated P-T curves have been compared with experimental reversals and have shown good agreement in most cases. Calculations indicate that gehlenite is probably totally disordered. Estimates of zoisite and lawsonite entropies are consistent with the phase equilibrium and grossular data, but estimates of the entropies of pyrope and andradite show large discrepancies when compared with experimental reversals.Contribution no. 600 from the Mineralogical Laboratory, The Department of Geology and Mineralogy, The University of Michigan, Ann Arbor, Michigan 48109, USA  相似文献   

18.
The incorporation mechanisms and diffusional loss of hydrogen in garnet have been experimentally investigated. A suite of gem-quality hydrous spessartine- and grossular-rich garnets were analysed by Fourier transform infrared spectroscopy (FTIR) and by ion microprobe (SHRIMP-SI) to determine the calibration coefficients for quantification of FTIR data. The excellent agreement between measured absorption and OH/O indicates that the same molar extinction coefficient can be used for spessartine and grossular. The coefficient of 14400 l mol??1 cm??2 proposed by Maldener et al. (Phys Chem Miner 30:337–344, 2003) seems the most appropriate for both minerals. A grossular with 6.4% andradite and 1.6% almandine containing 834 ppm H2O, and an almost pure spessartine with 282 ppm H2O, were selected for diffusion experiments. 1.5-mm cubes of garnets were heated between 12 h and 10 days at 1 atm under various temperature (750–1050 °C) and oxygen fugacity (\({f_{{{\text{O}}_2}}}\)) conditions, (ΔQFM +?15.2 to ??3.0). Diffusion profiles were acquired from sections through the cubes using FTIR, with a deconvolution algorithm developed to assess peak-specific behaviour. Different families of peaks have been identified based on their diffusive behaviour, representing hydrogen incorporated in different H-bearing defects. A dominant, fast, strongly \({f_{{{\text{O}}_2}}}\)-dependent oxidation-related diffusion mechanism is proposed \(\left( {\{ {{\text{M}}^{2+}}+{{\text{H}}^+}\} +\frac{1}{4}{{\text{O}}_2}={{\text{M}}^{3+}}+\frac{1}{2}{{\text{H}}_2}{\text{O}}} \right)\) (M=Fe, Mn) with a relatively low activation energy (158?±?19 kJ mol??1). This diffusion mechanism is likely restricted by availability of ferrous iron in grossular. At low oxygen fugacity, this diffusion mechanism is shut off and the diffusivity decreased by more than three orders of magnitude. A second, slower hydrogen diffusion mechanism has been observed in minor bands, where charge balance might be maintained by diffusion of cation vacancies, with much higher activation energy (≈?200–270 kJ mol??1). Spessartine shows clear differences in peak retentivity suggesting that up to four different H sites might exist. This opens exciting opportunities to use hydrogen diffusion in garnet as speedometer. However, it is essential to constrain the main diffusion mechanisms and the oxygen fugacity in the rocks investigated to obtain timescales for metamorphic or igneous processes.  相似文献   

19.
 We have performed atomistic computer simulations on trace element incorporation into the divalent dodecahedral X-sites of pyrope (Py — Mg3Al2Si3O12) – grossular (Gr — Ca3Al2Si3O12) solid solutions. An ionic model and the Mott–Littleton two-region approach to defect energies were used to calculate the energetics of substitution by a range of divalent trace-elements and of charge-balanced substitution by trivalent ions in the static limit. Results are compared with experimental high-temperature, high-pressure garnet-melt trace element partitioning data obtained for the same garnet solid solution to refine our understanding of the factors controlling element partitioning into solid solutions. Defect energies (U def,f), relaxation (lattice strain) energies (U rel), and solution energies (U sol) were derived using two different approaches. One approach assumes the presence of one type of hybrid X-site with properties intermediate between pure Mg and Ca sites, and the other assumes discrete Mg and Ca X-sites, and thus two distinct cation sublattices. The hybrid model is shown to be inadequate, since it averages out local distortions in the garnet structure. The discrete model results suggest trace elements are more soluble in Py50Gy50 than in either end-member compound. Physically this is due to small changes in size of the X-sites and the removal of unfavourable interactions between third nearest neighbours of the same size. Surprisingly, depending on the local order, large trace element cations may substitute for Mg2+ and small trace elements for Ca2+ in Py50Gr50. These solubilities provide an explanation for the anomalous trace-element partitioning behaviour along the pyrope–grossular join observed experimentally. Received: 27 January 2000 / Accepted: 14 February 2003  相似文献   

20.
The incorporation and site preference of minor amounts (about 1 wt%) of Yb3+ in synthetic pyrope (Mg3Al2Si3O12) and grossular (Ca3Al2Si3O12) garnet were studied by X-ray Absorption Fine-Structure (XAFS) Spectroscopy. The measurements, performed in the temperature range 77–343 K at both Yb LI- and LIII-edges, demonstrate that Yb3+ enters the garnet structure and is located in the dodecahedral site in both samples. The coordination environment of Yb3+ in the two samples was compared to that of the X-site cation in end-member synthetic pyrope and grossular and in Yb3Al5O12 as determined by single-crystal X-ray diffraction. The local geometry around Yb3+ is different from that of Mg and Ca in the bulk of the garnet, and also from that of Yb3+ in Yb3Al5O12. Τhe XAFS results indicate that, (1) structural relaxation occurs around Yb3+ in the garnet structure; (2) the host garnet matrix exerts a major structural control on the incorporation of Yb3+, and (3) minor amounts of Yb3+ in garnet are located in structural sites and not in ill-defined defects. Received: 15 January 1998/ Revised, accepted: 21 July 1998  相似文献   

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