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1.
Lath-shaped and highly crystalline trioctahedral smectites were synthesized under hydrothermal conditions. The quenched glasses with stoichiometrically dehydrated Na-smectite compositions were treated at （a） 500℃ and 100 MPa for 1 and 11 days; and （b） 300℃ and 100 MPa for 7 days. The crystallinity and particle size of products were dependent on the chemical composition of the starting glass, synthetic temperature and duration of hydrothermal treatment. The high structural ordering and large dimensions of the products were confirmed from the sharpness of XRD peaks; and hydration behavior under controlled relative humidity. Transmission electron microscopy was also performed for the characterization of the particle size of product. Particle sizes vary from ca. 10 nm to a few pm by changing the chemical compositions of the starting materials. The product with the highest structural ordering and largest dimension was obtained from Nao.33（Mg1.83Al0.67）Si4O11 glass treated at 500℃ and 100 MPa for 1 day. The obtained results also confirmed the metastability and compositional dependency in the formation of highly crystalline trioctahedral smectite at hydrothermal conditions.  相似文献   

2.
Si+4 Content of natural phengites   总被引：2，自引：0，他引：2  
The chemical compositions of white micas separated from adjacent rocks of glaucophane and greenschist facies are compared with respect to their Si+4 content. The micas are predominantly phengitic, i.e. between muscovite, K[Al2Si3AlO10(OH)2] and celadonite, K[(R+2R+3)Si4O10(OH)2] in composition. Constancy of Si content in micas coming from rocks of different bulk chemical composition but closely similar physical conditions indicates that the silica content of a potassic dioctahedral mica can be used to indicate the pressure and temperature conditions of its formation. This conclusion is in part based upon previous experimental data obtained for synthetic phengites.  相似文献   

3.
It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al2O3-FeO-Fe2O3-MgO-Na2O-SiO2-H2O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if fO2(g) values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If fO2(g) exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.  相似文献   

4.
As part of a study of the effect of geologically common network modifiers on polymerization in silicate melts, glasses, and silica-rich aqueous solutions, we have studied the energies, electronic structures, and inferred chemical properties of IVT-O-IVT linkages in the tetrahedral dimers H6,Si2O7, H6AlSiO71?, and H6Al2O72? using semi-empirical molecular orbital theory (CNDO/2). Our results indicate that the electron donating character of the bridging oxygen, O(br), linking two tetrahedra increases with increasing T-O(br) bond length but decreases with decreasing T-O(br)-T angles and increasing O-T-O(br) angles. This increase or decrease of the donor character of O(br) coincides with an increase or decrease of the affinity of O(br) for hard acceptors. The calculated electronic structure for the H6Si2O7 molecule is compared with the observed X-ray emission, absorption, and photoelectron spectra of quartz and vitreous silica; the reasonable match between calculated and observed oxygen Kα emission spectra of vitreous silica supports our assertion that non-bonded O(br) electron density energetically at the top of the valence band controls the chemical reactivity of IVT-O-IVT linkages in polymerized tetrahedral environments.  相似文献   

5.
Equations for the configurational entropy and homogeneous equilibria in Ca2MgSi2O7-Ca2SiAl2O7 melilites are derived for a site constraint that does not permit Mg on the smaller T2 tetrahedral sites. This constraint leads to one ordering parameter and one composition parameter. The maximum configurational entropy for perfectly ordered crystalline solutions is 3.795 cal K–1 mol–1, corresponding to the structural formula Ca2(Mg0.33Al0.67) (Si0.67Al0.33)2O7 and not the equimolar composition Ca2(Mg0.5Al0.5)(Si0.75Al0.25)2O7. Similarly, the configuration Ca2(Si0.33Al0.67)(Si0.33Al0.67)2O7 has the maximum entropy for the gehlenite end-member composition. The tabulated entropy of end-member gehlenite at 298.15 K must be corrected by at least 2Rln2, which corresponds to a substantial correction to its Gibbs energy at high temperature. The same corrections are applicable to other minerals having two crystallographically distinct sites in a 21 ratio and where the same configurational entropy equation applies: MgFe2O4 (magnesioferrite), NiFe2O4 (trevorite), TiFe2O4 (ulvospinel), TiMg2O4, TiZn2O4, CuFe2O4, and TiFe2O5 (pseudobrookite) inasmuch as these substances prefer the same inverse ordered state as gehlenite at low temperatures. The effects of the ideal enthalpy and entropy on temperatures of homogeneous equilibria in gehlenite and MgTi2O5 are evaluated. Geological-thermometer phase diagrams of the long-range ordering parameter plotted against temperature have a sigmoidal shape for these minerals owing to the fact that this type of disordering is non-convergent.  相似文献   

6.
?-Na2Si2O5, ζ-Na2Si2O5, Na2Si[Si2O7], and Na6Si3[Si9O27] have been synthesized using an MA6/8 superpress. Densification in high-pressure sodium silicates is effected largely by changes in packing. In the relaxed (1 bar) structures, cation polyhedra and thermal/displacement parameters are similar to those of low-pressure silicates, but the extra-framework cation positions are oversized. The two mixed [4]Si and [6]Si framework silicates of known structure (Na2Si[Si2O7] and Na6Si3[Si9O27]) belong to the limited homologous series Na2mSim[Sin–mO2n+m], with m<n. The structure-composition relationships of wadeite-type, A2Ge4O9-type, and Na6Si3[Si9O27] silicates and germanates depend on T-O distance and size of the large extra-framework cation. Characteristic features of the SiO4 tetrahedral units are present in micro-Raman spectra of mixed [4]Si and [6]Si framework silicates, but bands uniquely attributable to SiO6 octahedra are weak or obscured. However, [6]Si has a profound indirect influence on the Raman spectra, resulting in intense and complex low-frequency bands, assigned to symmetric bending modes with coupled displacements at both bridging oxygens and nonbridging oxygens bonded to [6]Si, and a shift to higher frequency and reduction in intensity of the high-frequency bands assigned to symmetric [4]Si-Onbr stretching vibrations. Raman spectroscopy does not appear to be a useful structural probe for small amounts of [6]Si in silicate glasses and melts.  相似文献   

7.
The heat capacity of åkermanite solid solutions was measured by a small scale adiabatic calorimeter near the incommensurate-normal (I-N) transition. The heat capacity anomalies caused by the I-N transition show the type characteristic behavior implying the presence of dynamical fluctuations. The heat capacity anomalies were observed over the whole range of the åkermanite solid solutions Ca2Mg1-xCoxSi2O7 and Ca2Mg1-x-ZnxSi2O2. With increase of Co or Zn atoms, the transition temperature, Ti, rises linearly from ca. 83° C to 220° C and to 130° C, respectively. In the system Ca2CoSi2O7-Ca2FeSi2O7 and Ca2MgSi2O7-Ca2-FeSi2O7 electronic microscopy revealed that the temperature of the heat capacity anomaly decreases with increasing Fe content, whereas the Ti rises. This unusual behavior is ascribed to the microdomains observed in high resolution lattice images.  相似文献   

8.
A series of alumina-free micas was synthesized hydrothermally in the potassium-poor portion of the system K2O-MgO-SiO2-H2O. One end member of this series has the composition KMg2.5[Si4O10](OH)2, which, because of its octahedral occupancy, is intermediate between the dioctahedral and trioctahedral micas.From this end member a series of mica solid solutions extends towards more Mg-rich compositions. Single phase micas were obtained along the substitution line 2Mg for Si which appears to involve incorporation of part of the Mg in tetrahedral sites. It leads to a theoretical end member with a structural formula KMg3[Si3.5Mg0.5O10](OH)2. Solid solutions containing up to 75 mole % of this theoretical end member could be synthesized. The observed densities, water contents, and a one-dimensional Fourier synthesis are consistent with the assumed substitution.At 1 kb fluid pressure and 620° C the Si-rich end member KMg2.5[Si4O10](OH)2 decomposes to a more Mg-rich mica, the roedderite phase K2Mg5Si12O30, liquid, and H2O-rich vapor. With increasing Mg-content the thermal stability of the mica solid solutions increases up to 860°C at a composition of about K2O·6.2MgO·7.4SiO2·2H2O, i.e. KMg2.8[Si3.7Mg0.3O10](OH)2. This mica disintegrates directly into forsterite + liquid + H2O-rich vapor. The mica phase richest in Mg with a composition of about K2O·6.5MgO·7.25SiO2·2H2O, i.e. KMg2.875 [Si3.625Mg0.375O10](OH)2, breaks down at 765° C into forsterite, a more Si-rich mica, liquid, and H2O-rich vapor.This binary series of alumina-free micas forms a complete series of ternary solid solutions with normal phlogopite, KMg3[Si3AlO10](OH)2. Analyses of some natural phlogopites showing Si in excess of 3.0 (up to 3.18) per formula unit can be explained through this ternary miscibility range.  相似文献   

9.
Infrared reflectance (IR) and Raman spectra were collected on small (ca. 500 micron) single crystals of 5 natural garnets with nearly end-member compositions: pyrope (98% Mg3Al2Si3O12), almandine (83% Fe3Al2Si3O12), spessartine (98% Mn3Al2Si3O12), grossular (97% Ca3Al2Si3O12), and andradite (99% Ca3Fe2Si3O12). Frequencies and symmetry assignments were determined for all 17 IR modes and all 25 Raman modes. By using factor group analysis and by correlating the bands by their intensities, bands were assigned to either one of the SiO4 internal motions, as a rotation, or to a type of translation. The assignments are supported by (1) the distinct trends of frequencies with cell size and cation masses for each of the different types of motion, (2) the similarity of garnet energies for each of the different types of motion to those of olivine with the same cation, and (3) the closeness of the T 1 u IR frequencies to the T 2 g Raman frequencies. Mode mixing appears to be weak. Correlations between frequencies and structural parameters suggests a direct dependence of force constants on lattice parameter. This relationship arises from bond lengths in the garnet structure being constrained by the size and compressibility of adjacent polyhedra through edge-sharing. Comparison of our endmember data with previous powder IR studies of intermediate garnets indicates that dodecahedral (X) and octahedral (Y) sites alone exhibit two-mode behavior for those solid solutions involving two ions with considerably different masses. However, for solid solutions involving cations of much different ionic radii, two-mode behavior is found for the translations of SiO4 groups. This is the first report of two-mode behavior that is unrelated to mass, and instead is due to significantly different force constants in the pyralspites compared to the ugrandites.Anomalies in mixing volumes are linked to two-mode behavior of the SiO4 translations, which leads to the suggestion that the mixing volume behavior is caused by the resistance of the Si-O bond to expansion and compression, as well as to changes in the dodecahedral site. Crystal-field effects may also play an important role within the ugrandite series. Deviation of molar volume dependence on composition from a linear to a asymmetric, non-linear (sometimes sigmoidal) dependence can be linked to solid solutions that possess slightly non-equivalent cation sites.  相似文献   

10.
Sursassite is monoclinic, space group P2 1/m, a=8.70, b=5.79, c=9.78 Å, β=108.9°. The crystal structure was determined with X-rays and refined to R=0.065, obtaining Mn2Al3[(OH)3(SiO4)(Si2O7)] as ideal crystal chemical formula. Sursassite, isostructural with macfallite Ca2Mn3[(OH)3(SiO4)(Si2O7)], is closely related to pumpellyite Ca2Al3[(OH)3(SiO4)(Si2O7)]. In fact both sursassite and pumpellyite, apart from the different chemical composition, are built up by common structural layers, which are repeated by different stacking vectors. As a result, faulted stacking sequences are energetically possible. Examination by high resolution transmission electron microscopy (HRTEM) shows that frequent (001) pumpellyite-like lamellae are intergrown with thicker (001) sursassite lamellae. Usually, the guest lamellae are a few unit cells thick along [001] and continuous along the (001) plane, although also rare interrupted lamellae are found.  相似文献   

11.
Rare metal mineralization of oceanic carbonatites was studied for the first time by the example of calcite carbonatite from Fogo Island in the Cape Verde Archipelago. The following evolutionary sequence of rare metal minerals was established: zirconolite-Th-calciobetafite-betafite + Th-pyrochlore-thorite + Ti-Zr-Nb silicates + zircon.Schematic reactions were proposed for zirconolite transformation to secondary phases: (Ca,Th,U)Zr(Ti,Nb)2O7 (zirconolite) + SiO2 + Ca(F,OH)2 → ZrSiO4 (zircon) + (Ca,Th,U)2(Ti,Nb)2O6(OH,F) (Th-calciobetafite) and (Ca,Th,U)2(Ti,Nb)2O6(OH,F) + Na2Si2O5 → ThSiO4 (thorite) + (Ca,Na,Th)2(Nb,Ti)2O6(OH,F) (Th-pyrochlore), where SiO2, Ca(F,OH)2, and Na2Si2O5 are the components of melt-solution coexisting with the carbonatite.It was shown that the distribution and behavior of rare and radioactive elements in oceanic carbonatites show the same tendencies as in continental carbonatites. The contents and distribution of Ti, Ta, and Th in zirconolites and pyrochlores from oceanic and continental carbonatites are different: the minerals of oceanic carbonatites are enriched in Ti and Th and strongly depleted in Ta.  相似文献   

12.
The local structure around Co, Zn and Sr atoms in incommensurately modulated, melilite-type X2T1 T 2 2 O7 (X=Ca and Sr, T1=Mg, Co and Zn, T2=Si) solid-solutions has been investigated by EXAFS analyses. The modulated structure was confirmed in Ca2-xSrxCoSi2O7 solid-solutions with X=0.0 to 0.6 and for both Ca2Mg1-YCoYSi2O7 and Ca2Mg1-YZnYSi2O7 solid-solutions over the whole compositional range at room temperature. The actual bond-distances determined by the EXAFS method for the T1 site (Co-, Zn-O) in the modulated structure are longer than the mean bond-distances obtained from the X-ray diffraction method. This is attributable to the libration of the T1 tetrahedra. In the Ca1-XSrXCoSi2O7 solid-solution both the Sr-O and Co-O distances by the EXAFS method for the X-site increase from Ca end-member to Sr end-member. These increases are respectively 0.8% and 0.6%. This means the local expansions of the tetrahedral sheets and of the XO polyhedra are well matched. In the modulated Ca2Co1-YMgYSi2O7 and Ca2Zn1-YMgYSi2O7 solid-solutions, the actual Co-O and Zn-O distances for the T1-sites are nearly constant in the whole compositional range. The compositional variations of the local structure around the cations in the solid-solution are different for the X and T1 sites. It is concluded that the local geometric restriction for the size of substituted cation in X site is larger than that in T1 site. The dimension of the tetrahedral sheet puts restriction on the size of the cations situated at the interlayer X sites. In other words, the different behavior of the local geometric restriction between the X and T1 sites is an important feature of the melilite structure and is also related to the modulated structure.  相似文献   

13.
Three minerals of the mayenite supergroup have been found in fluorellestadite-bearing metacarbonate rock (former fragment of petrified wood of ankeritic composition) from the dump at the Baturinskaya-Vostochnaya-1-2 mine. These are eltyubyuite Ca12Fe1°Si4O32Cl6, its fluorine analog Ca12Fe103+Si4O30F10, and chlormayenite-wadalite Ca12(Al,Fe)14O32Cl2-Ca12(Al,Fe)10Si4O32Cl2. The first two phases occur in the reaction mantle around hematite, magnesioferrite, and Ca-ferrite aggregates (“calciohexaferrite” CaFe12O19, “grandiferrite” CaFe4O7, and “dorrite phase” Ca2(Fe53 +Mn00.5Mg0.5)(Si0.5Fe5.53+)O20) and, rarely, as individuals in grained aggregates of fluorellestadite-cuspidine (± lar- nite ± rusinovite Ca10(Si2O7)3Cl2). Assemblages of zoned chlormayenite-wadalite crystals are found in grained aggregates of fluorellestadite- cuspidine, which lack Ca-ferrite. Also, harmunite CaFe2O4, chlorellestadite, fluorapatite, anhydrite, rondorfite CasMg(SiO4)4Cl2, fluorine analog of rondorfite CasMg(SiO4)4F2, “Mg-cuspidine” Ca3.5(Mg,Fe)0.5(Si2O7)F2, fluorite, barioferrite BaFe12O19, zhangpeishanite BaFCl, and other rare phases are identified in this rock. Data on the chemical composition and Raman spectroscopy of the mayenite-supergroup minerals are given. The genesis of metacarbonate rock is considered in detail: “oxidizing calcination” of Ca-Fe-carbonates with the formation of hematite and lime; reaction between hematite and lime with the formation of different Ca-ferrites; formation of larnite as a result of reaction between SiO2 and lime or CaCO3; and reactionary impact of hot Cl-F-S-bearing gases on early assemblages. Eltyubyuite and its fluorine analog crystallized at the stages of gas impact. It is presumed that the maximum temperature during the formation of rock reached 1200–1230 °C. © 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.  相似文献   

14.
Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1–0.5 GPa and 200–850 °C for durations of 18–1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg10Si12O32(OH)4), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na4Mg8Si12O32(OH)4. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO2, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F− for OH−, Mn2+, Ca2+, or Fe2+ for Mg2+, and 2Li+ for Mg2+ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440–630 °C and 0.2 GPa from the composition Na4Mg8Si12O32(OH)4, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na4Mg8Si12O32F4 at 550–750 °C and 0.2–0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na+ for Na+ + H+ and of Mg2+ + vacancy for 2Na+. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na2.5Mg8Si12O30.5(OH)5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na1.1Mg9.4Si12O31.9(OH)4.1 based on a fixed number of Si cations. Further investigation involving Mg for Na cation exchange may provide a pathway for the synthesis of Na-free clinojimthompsonite. Fairly extensive solid solution was also observed for triple-chain silicates made along the compositional join Na4Mg8Si12O32(OH)4–Ca2Mg8Si12O32(OH)4 where the limit of Ca substitution at 450 °C and 0.2 GPa corresponds to Na0.7Ca1.8Mg7.8Si12O31.9(OH)4.1 (with the OH content adjusted to achieve charge balance). Aside from the Na content, this composition is similar to that observed as wide-chain lamellae in host actinolite. The relative ease with which Na-rich triple chains can be made experimentally suggests that these phases might exist in nature; this study provides additional insights into the range of compositions and formation conditions at which they might occur.  相似文献   

15.
Due to their potential retention capacity, clay minerals have been proposed for use in the engineered barriers for the storage of high-level radioactive actinides in deep geological waste repositories. However, there is still a lack of data on the sorption of actinides in clays in conditions simulating those of the repositories. The present article examines the sorption of two lanthanides (actinide analogues) in a set of smectitic clays (FEBEX bentonite, MX80 bentonite, hectorite, saponite, Otay montmorillonite, and Texas montmorillonite). Distribution coefficients (Kd) were determined in two media: water and 0.02 mol L−1 Ca, the latter representing the cement leachates that may modify the chemical composition of the water in contact with the clay. The Kd values of the lanthanides used in the experiments (La and Lu) varied greatly (25-50 000 L kg−1) depending on the ionic medium (higher values in water than in the Ca medium), the initial lanthanide concentration (up to three orders of magnitude decrease inversely with lanthanide concentration), and the examined clay (up to one order of magnitude for the same lanthanide and sorption medium). Freundlich and Langmuir isotherms were used to fit sorption data to allow comparison of the sorption parameters among smectites. The model based on the two-site Langmuir isotherms provided the best fit of the sorption data, confirming the existence of sorption sites with different binding energies. The sites with higher sorption affinity were about 6% of the total sorption capacity in the water medium, and up to 17% in the Ca medium, although in this latter site sorption selectivity was lower. The wide range of Kd values obtained regarding the factors examined indicated that the retention properties of the clays should also be considered when selecting a suitable clay for engineered barriers.  相似文献   

16.
The crystal structure and chemical composition of crystals of (Mg1?x Cr x )(Si1?x Cr x )O3 ilmenite (with x = 0.015, 0.023 and 0.038) synthesized in the model system Mg3Cr2Si3O12–Mg4Si4O12 at 18–19 GPa and 1,600 °C have been investigated. Chromium was found as substitute for both Mg at the octahedral X site and Si at the octahedral Y site, according to the reaction Mg2+ + Si4+ = 2Cr3+. Such substitutions cause a shortening of the <X–O> and a lengthening of the <Y–O> distances with respect to the values typically observed for pure MgSiO3 ilmenite and eskolaite Cr2O3. Although no high Cr contents are considered in the pyrolite model, Cr-bearing ilmenite may be the host for chromium in the Earth’s transition zone. The successful synthesis of ilmenite with high Cr contents and its structural characterization are of key importance because the study of its thermodynamic constants combined with the data on phase relations in the lower-mantle systems can help in the understanding of the seismic velocity and density profiles of the transition zone and the constraining composition and mineralogy of pyrolite in this area of the Earth.  相似文献   

17.
Infrared absorption spectra are presented for four hydrous magnesian silicates which are stable at high pressures and high temperatures characteristic of the earth's mantle: phase A (Mg7Si2O14H6), phase B (approx. Mg23Si8O42H6), chondrodite (Mg5Si2O10H2), clinohumite (Mg9Si4O18H2). The results show that phase B as well as phase A, chondrodite and clinohumite contain hydroxyl groups in their structures. It is also suggested that phase B, in addition to phase A, could be of potential importance in the upper mantle and transition zone as a dense host mineral for hydroxyl ions. Chemical composition of phase A was reexamined by microprobe analysis: it agrees well with Mg7Si2O14H6, estimated by Yamamoto and Akimoto (1974, 1977), but disagrees with a newly proposed formula Mg2SiO5H2 by Benimoff and Sclar (1984).  相似文献   

18.
Preiswerkite and Na-(Mg,Fe)-margarite are two unusual micas very rare in Nature. They have been observed together in two eclogite occurrences (La Compointrie, France; Liset, Norway) as retrogression products in coronae or symplectites around kyanite. The chemical compositions and some physical properties of these micas are presented. The possible solid solutions and the conditions of stability are discussed. The preiswerkites display slight solid solution towards phengitic muscovite and Na-phlogopite. On the other hand, there is negligible solid solution towards more aluminous compositions; AlIV ≤ 4 appears to be a composition limit for natural (K,Na)-micas. The margarites have an unusual Na-(Mg,Fe)-rich composition. They can be considered as a solid solution of about 2/3 mol% of margarite and 1/3 mol% of the theoretical end-member Na2(Mg,Fe)1AlVI 4[Si4AlIV 4]O20(OH)4 (“Mica L”), with a possible substitution towards paragonite. The Marg2/3 Mica L1/3 composition (i.e. NaCa2(Mg,Fe)0.5 AlVI 6 [Si6AlIV 6]O30(OH)6) might represent a particularly stable crystallographic configuration and could be considered as a true end-member. Many “sodian” margarites described in the literature are, in fact, complex solid solutions between margarite, paragonite and Marg2/3 Mica L1/3. The rarity of these micas is not related to extreme or unusual P-T conditions. They seem to be related to unusual chemical compositions, appearing in H2O-saturated Na-Al-rich Si-poor systems, principally, if not only, at greenschist- or amphibolite-facies P-T conditions. Moreover, they are subject to crystallographic constraints whereby the high proportion of Al-tetrahedra create considerable distortion which prevents the entry of K into the interlayer site, thus necessitating Na (preiswerkite or ephesite) or Ca (margarite or clintonite) instead. Received: 21 April 1998 / Accepted: 25 January 1999  相似文献   

19.
A crystallographic and m?ssbauer spectroscopy study of Fe   总被引：1，自引：0，他引：1  
The crystal chemistry of garnet solid solutions on the Fe 3 2+ Al2Si3O12-Fe 3 2+ Fe 2 3+ Si3O12 (almandine-“skiagite”) and Ca3Fe 2 3+ Si3O12-Fe 3 2+ Fe 2 3+ Si3O12 (andradite-“skiagite”) joins have been investigated by single-crystal X-ray structure refinements and M?ssbauer spectroscopy. Together, these two solid solution series encompass the complete range in Fe3+/ΣFe from 0.0 to 1.0. All garnets are isotropic and were re0fined in the Ia d space group. Small excess volumes of mixing are observed in andradite-“skiagite” solid solutions (W v =1.0±0.2 cm3 mol-1) and along the almandine-“skiagite” join (W v =-0.77±0.17cm3 mol-1). The octahedral (Al, Fe3+)-O bond lengths show a much greater variation across the almandine-skiagite join compared to the andradite-skiagite garnets. The dodecahedral (X)-O bond lengths show the opposite behaviour. In andradite-“skiagite” solid solutions, the octahedral site passes from being flattened to elongated parallel to the 3 axis of symmetry with increasing “skiagite” content. A perfect octahedron occurs in a composition of ≈35 mol% “skiagite”. The occupancy of the neighboring dodecahedral sites has the greatest effect on octahedral distortion and vice versa. The M?ssbauer hyperfine parameters of Fe2+remain constant in both solid solutions. The hyperfine parameters of Fe3+ (at room temperature: centre shift=0.32–0.40 mm/sec, quadrupole splitting (QS)≈0.21–0.55 mm/ sec) indicate that all Fe3+ is in octahedral coordination. The Fe3+ parameters are nearly constant in almandine-“skiagite” solid solutions, but vary significantly across the andradite-“skiagite” join. The structural unit that contributes to the electric field gradient of the octahedral site is different from that of the coordinating oxygen polyhedron, probably involving the neighboring dodeca-hedral sites.  相似文献   

20.
The phase relations of glaucophanic amphiboles have been studied at 18–31 kbar/680–950°C in the synthetic system Na2O–MgO–Al2O3–SiO2–SiF4 (NMASF) using the bulk composition of fluor-glaucophane, Na2Mg3Al2Si8O22F2. Previous experimental studies of glaucophane in the water-bearing system (NMASH) have been hampered by problems of fine grain size (electron microprobe analyses with low oxide totals and contamination by other phases), and consequently good compositional data are lacking. Fluor-amphiboles, on the other hand, generally have much higher thermal stabilities than their hydrous counterparts. By using the fluorine-analogue system NMASF, amphibole crystals sufficiently coarse for electron microprobe analysis have been obtained. Furthermore, NMASH amphibole phase relations are directly analogous to those of the NMASF system because SiF4 fills the role of H2O as the fluid species. High-pressure NMASF amphibole parageneses are comparable to those obtained for NMASH amphiboles under similar pressure-temperature conditions, except that the NMASF solidus was not encountered. In the pressure-temperature range of the NMASF experiments, fluor-glaucophane is unstable relative to glaucophanenyböite-Mg-magnesio-katophorite amphiboles. Variations in synthetic fluor-amphibole composition with P and T are discussed in terms of changes in the thermodynamic activities of the principal amphibole end-members, such as glaucophane (aGp) and nyböite (aNy) using an ideal-mixing-on-sites model. The most glaucophanic amphiboles analysed have aGp=0.50–0.60 and coexist with jadeite and coesite at 30 kbar/800°C. Amphiboles become increasingly nyböitic with decreasing pressure through the NaAlSi-1 exchange, which is the principal variation observed. The most nyböitic amphiboles have aNy =0.65–0.70 and coexist with fluor-sodium-phlogopite and quartz at 21–24 kbar/800–850°C. At 800°C amphiboles are essentially glaucophane-nyböite solid solutions. At 850°C there is some minor displacement along MgMgSi-1, but Mg-magnesio-katophorite activities are very low (<0.06). Activities of the eight other NMASF amphibole end-members are <0.001, except for eckermannite activity which varies from 0.01–0.11. Our results indicate that: (a) synthetic amphiboles mimic the essential stoichiometries observed in blueschist amphiboles; (b) synthetic studies should be relevant to petrologically important high-pressure parageneses and reactions involving glaucophanicamphiboles, sodic pyroxenes, albite and talc; (c) the high-pressure stability limit of fluorglaucophane lies at pressures higher than those reached in this study (31 kbar); (d) in natural systems an approach to glaucophane stoichiometry should be favoured by high water activities as well as high pressures.Abbreviations and formulae used in this paper Glaucophane (Gp) oNa2(Mg3Al2)Si8O22(OH,F)2 - Nyböite (Ny) NaNa2(Mg3Al2)Si7AlO22(OH,F)2 - Eckermannite (Ek) NaNa2(Mg4Al)Si8O22(OH,F)2 - Magnesio-cummingtonite (MC) oMg2(Mg5)Si8O22(OH,F)2 - Sodium-magnesio-cummingtonite (SMC) NaNaMg(Mg5)Si8O22(OH,F)2 - Sodium-anthophyllite (SAn) NaMg2(Mg5)Si7AlO22(OH,F)2 - Gedrite (Gd) oMg2(Mg3Al2)Si6Al2O22(OH,F)2 - Sodium-gedrite (SGd) NaMg2(Mg4Al)Si6Al2O22(OH,F)2 - Mg-magnesio-aluminotaramite (MAT) NaNaMg(Mg3Al2)Si6Al2O22(OH,F)2 - Mg-magnesio-katophorite (MKt) NaNaMg(Mg4Al)Si7AlO22(OH,F)2 - Mg-magnesio-barroisite (MBa) oNaMg(Mg4Al)Si7AlO22(OH,F)2 - Jadeite (Jd) NaAlSi2O6 - Enstatite (En) Mg2Si2O6 - Forsterite (Fo) Mg2SiO4 - Nepheline (Ne) NaAlSiO4 - Albite (Ab) NaAlSi3O8 - Quartz/Coesite (Qz/Co) SiO2 - Sodium-phlogopite (Sphl) NaMg3Si3AlO10(OH,F)2 - Talc (Tc) oMg3Si4O10(OH,F)2 - o vacant A-site in amphiboles and interlayer site in talc. Octahedral cations in amphiboles are bracketted  相似文献   

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