XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets

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 L_I- and L_III-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     

Trace element incorporation into pyrope–grossular solid solutions: an atomistic simulation study

 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     

Trace-element partitioning between garnet,clinopyroxene and Fe-rich picritic melts at 3 to 7 GPa

We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py₆₃Al₂₅Gr₁₂) and clinopyroxene (∼Ca_0.2Mg_0.6Fe_0.2Si₂O₆) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D ^cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca_0.3–0.5Mg_0.3–0.6Fe_0.07–0.2Si₂O₆) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca_0.2Mg_0.7Fe_0.1Si₂O₆). D ^grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py_70–88Al_l7–20Gr_8–14). 97SB68 D _LREE^grt/liq values are higher and D _HREE^grt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py_20–70Al_10–50Gr_10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.     

Cation disorder in garnets along the Mg3Al2Si3O12-Mg4Si4O12 join: an infrared,Raman and NMR study

We have obtained infrared and Raman spectra for garnets synthesized at high (static) pressures and temperatures along the join Mg₃Al₂Si₃O₁₂ (pyrope) — Mg₄Si₄O₁₂ (magnesium majorite). The vibrational spectra of Mg-majorite show a large number of additional weak peaks compared with the spectra of cubic pyrope garnet, consistent with tetragonal symmetry for the MgSiO₃ garnet phase. The Raman bands for this phase show no evidence for line broadening, suggesting that Mg and Si are ordered on octahedral sites in the garnet. The bands for the intermediate garnet compositions are significantly broadened compared with the end-members pyrope and Mg-majorite, indicating cation disorder in the intermediate phases. Solid state ²⁷Al NMR spectroscopy for pyrope and two intermediate compositions show that Al is present only on octahedral sites, so the cation disorder is most likely confined to Mg-Al-Si mixing on the octahedral sites. We have also obtained a Raman spectrum for a natural, shock-produced (Fe,Mg) majorite garnet. The sharp Raman peaks suggest little or no cation disorder in this sample.     

An experimental investigation of the partitioning of REE between garnet and liquid with reference to the role of defect equilibria

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) D_REE 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.     

Partition coefficients for REE between garnets and liquids: implications of non-Henry's Law behaviour for models of basalt origin and evolution

Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg₃Al₂Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), D^{garnet liquid}_REE increases as the REE concentration in the garnet decreases. At higher concentrations, D_REE is constant. D^{grossular liquid}_REE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which D_REE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of D_REE^{garnet/liquid} for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (D^{pyrope/liquid} = 0.067(Ce), 0.108(Sm), 0.155(Tm) and D^{grossular/Liquid} = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined.     

Low-temperature single-crystal Raman spectrum of pyrope

 The single-crystal polarized Raman spectra of synthetic pyrope, Mg₃Al₂Si₃O₁₂, were measured at room temperature and 5 K, as were the room-temperature unpolarized spectra of two natural pyrope-rich crystals. No major differences in the spectra between room temperature and 5 K are observed or are present between the synthetic and the natural crystals. The spectra are consistent with the proposal that the Mg cation is dynamically disordered and not statically distributed over subsites in the large triangular-dodecahedral E-site in pyrope. A low-energy band at about 135 cm⁻¹ softens and shows a large decrease in its line width with decreasing temperature. The presence of a weak, broad band at about 280 cm⁻¹ may be due to anharmonic effects, as could the one at 135 cm⁻¹. The latter is assigned to the rattling motion of Mg in pyrope in the plane of the longer Mg-O(4) bonds (Kolesov and Geiger 1998). The successful modeling of the anisotropic motion of the Mg cation in pyrope, which has an anharmonic character, provides a valuable test of the validity of empirical or semi-empirical lattice-dynamic calculations for silicates. Received: 10 May 1999 / Accepted: 10 April 2000     

Single-crystal hydrostatic compression of synthetic pyrope, almandine, spessartine, grossular and andradite garnets at high pressures

The compression of synthetic pyrope Mg₃Al₂ (SiO₄)₃, almandine Fe₃Al₂(SiO₄)₃, spessartine Mn₃Al₂ (SiO₄)₃ grossular Ca₃Al₂(SiO₄)₃ and andradite Ca₃Fe₂ (SiO₄)₃ was studied by loading the crystals together in a diamond anvil cell. The unit-cell parameters were determined as a function of pressure by X-ray diffraction up to 15 GPa using neon as a pressure transmitting medium. The unit-cell parameters of pyrope and almandine were measured up to 33 and 21 GPa, respectively, using helium as a pressure medium. The bulk moduli, K _{T 0}, and their first pressure derivatives, K _{T 0} ^′, were simultaneously determined for all five garnets by fitting the volume data to a third order Birch-Murnaghan equation of state. Both parameters can be further constrained through a comparison of volume compressions between pairs of garnets, giving for K _{T 0} and K _{T 0} ^′ 171(2) GPa and 4.4(2) for pyrope, 185(3) GPa and 4.2(3) for almandine, 189(1) GPa and 4.2 for spessartine, 175(1) GPa and 4.4 for grossular and 157(1) GPa and 5.1 for andradite, where the K _{T 0} ^′ are fixed in the case of spessartine, grossular and andradite. Direct comparisons of the unit-cell volumes determined at high pressures between pairs of garnets reveal anomalous compression behavior for Mg²⁺ in the 8-fold coordinated triangular dodecahedron in pyrope. This agrees with previous studies concerning the compression behaviors of Mg²⁺ in 6-fold coordinated polyhedra at high pressures. The results show that simple bulk modulus–volume systematics are not obeyed by garnets. Received: 29 July 1998 / Revised, accepted: 7 April 1999     

On the mechanisms for H and Al incorporation in stishovite

The solubility and incorporation mechanisms of hydrogen in synthetic stishovite as a function of Al₂O₃ content have been investigated. Mechanisms for H incorporation in stishovite are more complex than previously thought. Most H in stishovite is incorporated via the Smyth et al. (Am Mineral 80:454–456, 1995) model, where H docks close to one of the shared O–O edges, giving rise to an OH stretching band in infrared (IR) spectra at 3,111–3,117 cm⁻¹. However, careful examination of IR spectra from Al-stishovite reveals the presence of an additional OH band at 3,157–3,170 cm⁻¹. All H is present on one site, with interstitial H both coupled to Al³⁺ substitutional defects on adjacent octahedral (Si⁴⁺) sites, and decoupled from other defects, giving rise to two distinct absorption bands. Trends in IR data as a function of composition are consistent with a change in Al incorporation mechanism in stishovite, with Al³⁺ substitution for Si⁴⁺ charge-balanced by oxygen vacancies at low bulk Al₂O₃ contents, and coupled substitution of Al³⁺ onto octahedral (Si⁴⁺) and interstitial sites at high bulk Al₂O₃ contents. Trends in OH stretching frequencies as a function of Al₂O₃ content suggest that any such change in Al incorporation mechanism could alter the effect that Al incorporation has on the compressibility of stishovite, as noted by Ono et al. (Am Mineral 87:1486–1489, 2002).     

A crystallographic and m?ssbauer spectroscopy study of Fe

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.     

A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece

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: (Ca_2.99Mg_0.03)_Σ=3.02(Fe³⁺ _0.67Cr_0.54Al_0.33Ti_0.29Zr_0.15)_Σ=1.98(Si_2.42Ti_0.24Fe_0.18Al_0.14)_Σ=2.98O₁₂OH_0.11. 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.     

Vibrational spectroscopy of end-member silicate garnets

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.     

The transition of pyrope to perovskite

The stability field of Mg₃Al₂Si₃O₁₂-pyrope was examined for the first time under hydrostatic pressure conditions in a CO₂-laser heated diamond cell in the pressure range 21–30 GPa between 2300 and 3200 K. The phases were characterized using Raman and fluorescence spectroscopy. With increasing pressure pyrope transforms to an ilmenite phase above ∼21.5 GPa, to perovskite plus ilmenite above ∼24 GPa, and to perovskite above 29 GPa. The pressures of the first occurrence of perovskite in this study are about 2 GPa above the corresponding phase boundary between end-member MgSiO₃-ilmenite and perovskite. A small amount of Al₂O₃ coexists with perovskite up to 43 GPa, as evident from fluorescence spectra resembling those of ruby, but above 43 GPa the entire Al₂O₃ content of the pyrope starting material is accommodated in the perovskite structure. Received: 6 March 1997 / Revised, accepted: 23 July 1997     

再论花岗岩按照Sr-Yb的分类:标志

2006年作者曾经按照Sr=400×10~(-6)和Yb=2×10~(-6)作为标志将花岗岩分为埃达克岩、喜马拉雅型花岗岩、浙闽型花岗岩和广西型花岗岩,在浙闽型中又分出南岭型(Sr100×10~(-6)和Yb2×10~(-6)),于是花岗岩被分为5类。Sr=400×10~(-6)和Yb=2×10~(-6)是根据阿留申群岛中的Adak岛的资料得出来的。本文统计了全球花岗岩6000多个数据(其中,埃达克型花岗岩为2810个,喜马拉雅型花岗岩636个,浙闽型花岗岩1183个,南岭型花岗岩1518个,广西型花岗岩142个,总共6289个),统计的结果,各类花岗岩的地球化学特征大致如下:(1)埃达克型花岗岩富Al_2O_3和Sr,贫Y和Yb,具较高和变化的铕异常,绝大多数样品的Sr300×10~(-6),Yb2.5×10~(-6)(当Sr=400×10~(-6)～600×10~(-6)时Yb值最大,Sr超过600×10~(-6),Yb降低至2×10~(-6)),Al_2O_3在14%～18%之间,Eu/Eu~*大多在0.6～1.2范围;(2)喜马拉雅型花岗岩贫Sr和Yb,具中等的Al_2O_3和变化的Eu/Eu~*,Sr300×10~(-6)和Yb2×10~(-6)(少数Sr300×10~(-6)),Al_2O_3为13%～17%,Eu/Eu~*为0.2～1.0;(3)浙闽型花岗岩贫Sr富Yb,Sr在40×10~(-6)～400×10~(-6)之间,Yb1.5×10~(-6),Al_2O_3和Eu/Eu~*的变化类似喜马拉雅型花岗岩,Al_2O_3为12%～17%,Eu/Eu~*为0.4～1.0;(4)南岭型花岗岩以很低的Sr、Al_2O_3和Eu/Eu~*以及很高的Yb而不同于上述各类花岗岩,通常Yb1.5×10~(-6),Sr100×10~(-6)(Yb变化大,绝大多数2×10~(-6);当Yb在2×10~(-6)～8×10~(-6)时,部分样品Sr可100×10~(-6),但很少200×10~(-6));Al_2O_314%,集中在11%～13%之间,Eu/Eu~*0.7,大多0.4;Yb越大,Sr越低,负铕异常越明显。文中讨论了花岗岩Sr-Yb分类的意义,指出本分类适用于产于大陆和海洋的绝大多数中酸性岩浆岩(可能不适用于一部分特别富铁和钾的花岗岩,如具有高Sr和Yb特征的广西型花岗岩)。不同类型的花岗岩主要反映了源区压力的不同,而源区成分、温度、部分熔融程度、水和挥发分的加入以及岩浆混合等的影响可能是次要的。文中指出,该分类的依据、其实质,是熔体与残留相平衡的理论。与浙闽型花岗岩平衡的残留相是斜长石,与喜马拉雅型花岗岩平衡的是斜长石+石榴石,与埃达克型花岗岩平衡的是石榴石,与南岭型花岗岩平衡的是富钙的斜长石。文中指出,加强实验岩石学研究,将年代学和地球化学研究密切结合起来是深化花岗岩研究的关键。     

Study on Al2O3 content and phase stability of aluminous-CaSiO3 perovskite at high pressure and temperature

 In order to clarify Al₂O₃ content and phase stability of aluminous CaSiO₃-perovskite, high-pressure and high-temperature transformations of Ca₃Al₂Si₃O₁₂ garnet (grossular) were studied using a MA8-type high-pressure apparatus combined with synchrotron radiation. Recovered samples were examined by analytical transmission electron microscopy. At pressures of 23–25 GPa and temperatures of 1000–1600 K, grossular garnet decomposed into a mixture of aluminum-bearing Ca-perovskite and corundum, although a metastable perovskite with grossular composition was formed when the heating duration was not long enough at 1000 K. On release of pressure, this aluminum-bearing CaSiO₃-perovskite transformed to the “LiNbO₃-type phase” and/or amorphous phase depending on its Al₂O₃ content. The structure of this LiNbO₃-type phase is very similar to that of LiNbO₃ but is not identical. CaSiO₃-perovskite with 8 to 25 mol% Al₂O₃ was quenched to alternating lamellae of amorphous layer and LiNbO₃-type phase. On the other hand, a quenched product from CaSiO₃-perovskite with less than 6 mol% consisted only of amorphous phase. Most of the inconsistencies amongst previous studies could be explained by the formation of perovskite with grossular composition, amorphous phase, and the LiNbO₃-type phase. Received: 11 April 2001 / Accepted: 5 July 2002     

Ca–Mn exchange between grossular and MnCl2 solutions at 2 kbar and 600°°C: reaction mechanism and evidence for non-ideal mixing in spessartine-grossular garnets

 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 K_D 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     

Thermochemistry of high pressure garnets and clinopyroxenes in the system CaO-MgO-Al2O3-SiO2

The enthalpies of solution of several synthetic garnets on the join Mg₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ (pyrope-grossular) and of several synthetic clinopyroxenes on the join CaMgSi₂O₆-CaAl₂SiO₆ (diopside-Ca-Tschermak's molecule) were measured in a melt of composition 2PbO · B₂O₃ at 970 K. The determinations were made with sufficient precision so that thermochemical characterizations of the solid solutions could be achieved.The pyrope-grossular solutions show positive enthalpies of mixing. The non-ideality in the range 0–30 mole % grossular is relatively the largest and is in good agreement with the predictions of Ganguly and Kennedy (1974) based largely on cation partitioning of natural high grade metamorphic garnets with biotite, and with the deductions of Hensenet al. (1975) based on measurement of the compositions of synthetic pyrope-rich garnets equilibrated with anorthite, Al₂SiO₅ and quartz. However, the garnets show smaller excess enthalpies at higher grossular contents. This would lead to an asymmetric solvus with a critical temperature lower than predicted by the symmetrical regular solution model of Ganguly and Kennedy (1974). The composition-dependent non-ideality can be understood by simple ionic size considerations in solid substitution and is analogous to the situations for the calcite-dolomite and enstatite-diopside solvi.The heats of solution of pyropes crystallized in the range 1000–1500°C were all the same, within the precision of measurement, and thus we have found no evidence for temperature-dependent cation disordering as a possible explanation of the high entropy of pyrope, as suggested by Charluet al. (1975). Positional disorder of dodecahedral Mg is a more probable reason.The diopside-CaTs join is also non-ideal, with the larger positive enthalpy deviations near the diopside end. The calorimetric data in the magnesian range are consistemt with the model for completely disordered tetrahedral Si and Al which results from the free energy derivations of wood (1975) based on syntheses of diopside-rich aluminous pyroxenes in the presence of anorthite and quartz. At higher Al concentrations the calorimetric data seem more consistent with the ‘local charge-balance’ model of Wood (1975).No evidence for temperature-dependent disorder was found for either the diopside or CaTs end-members.     

Raman spectra of silicate garnets

The single-crystal polarized Raman spectra of four natural silicate garnets with compositions close to end-members almandine, grossular, andradite, and uvarovite, and two synthetic end-members spessartine and pyrope, were measured, along with the powder spectra of synthetic pyrope-grossular and almandine-spessartine solid solutions. Mode assignments were made based on a comparison of the different end-member garnet spectra and, in the case of pyrope, based on measurements made on additional crystals synthesized with ²⁶Mg. A general order of mode frequencies, i.e. R(SiO₄)>T(metal cation)>T(SiO₄), is observed, which should also hold for most orthosilicates. The main factors controlling the changes in mode frequencies as a function of composition are intracrystalline pressure (i.e. oxygen-oxygen repulsion) for the internal SiO₄-vibrational modes and kinematic coupling of vibrations for the external modes. Low frequency vibrations of the X-site cations reflect their weak bonding and dynamic disorder in the large dodecahedral site, especially in the case of pyrope. Two mode behavior is observed for X-site cation vibrations along the pyrope-grossular binary, but not along the almandine-spessartine join. Received: 3 December 1996 / Revised, accepted: 13 April 1997     

Chemical composition and species attribution of tourmalines from a rare-metal pegmatite vein with scapolite, Sangilen Upland, Tuva

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(Al_1.5Li_1.5)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.     

Low-temperature heat capacities of synthetic pyrope,grossular, and pyrope60grossular40

The heat capacities of synthetic pyrope (Mg₃Al₂Si₂O₁₂), grossular (Ca₃Al₂Si₃O₁₂) and a solid solution pyrope₆₀grossular₄₀ (Mg_1.8Ca_1.2Al₂Si₃O₁₂) have been measured by adiabatic calorimetry in the temperature range 10–350 K. The samples were crystallized from glasses in a conventional piston-cylinder apparatus.The molar thermophysical properties at 298.15 K (J mol^?1 K^?1) are:

     

	Cop	So298?So0	Ho298?Ho0/T
Pyrope	325.31	266.27	47852
Grossular	333.17	260.12	47660
Py60Gr40	328.32	268.32	47990