Crystal field stabilization energies of almandine-pyrope and almandine-spessartine garnets determined by FTIR near infrared measurements

The band positions of three partially overlapping Fe²⁺ spin-allowed transitions located between 4000 and 9000 cm^–1 in almandine-pyrope and almandinespessartine garnets solid solutions were measured using near-infrared (NIR) spectroscopy. The crystal field stabilization energies (CFSE) along both binaries were calculated assuming a splitting of 1100 cm^–1 for the lower orbitals. The CFSE show a slight increase along the almandine-spessartine binary from 3730 to 3810 cm^–1 and a larger increase from 3730 to 3970 cm^–1 for the almandine-pyrope binary. Dodecahedral Fe²⁺-site distortion increases with an increase in spessartine component and decreases with increasing pyrope component, in agreement with average dodecahedral site distortions determined from diffraction experiments. The excess CFSE's along both joins are negative. For the almandinespessartine binary they are small, but are about 3.5 times larger in magnitude along the join almandine-pyrope, where an interaction parameter of W= -2.9 KJ/mole has been derived from a symmetric mixing model. The excess CFSE are relatively small compared to the magnitudes of the excess enthalpies of mixing that have been assigned to garnet solid solutions. Moreover, they give no indication which could support the positive and asymmetric excess enthalpies of mixing that have been proposed for almandine-pyrope solid solutions.     

Isomorphism of actinides and REE in synthetic ferrite garnets

The reprocessing of spent nuclear fuel (SNF) is accompanied by the formation of liquid high-level radioactive waste (HLW). To increase the safety of handling HLW, it is proposed to extract actinide isotopes (An) and REE from them. These elements may be incorporated into crystalline matrices, e.g., based on ferrites with garnet structure, and then disposed in a geologic repository. The actinide-REE fraction is characterized by a complex composition. In addition to major components (An and REE), Al, Si, Na, and Sn occur therein in small amounts (a few wt %). Possible incorporation of the admixtures into ferrite garnets, as well as their effect on the phase composition of matrices and Th, Ce, Gd, and La contents were studied. It was shown that admixtures enter into garnet by means of isomorphic replacement. The properties of samples change only when admixtures are added in amounts exceeding their concentrations in HLW. The ability of ferrite garnets to accumulate significant amounts of An, REE, and admixture elements makes them suitable for use as matrices in immobilizing actinide-REE HLW of complex composition.     

Enthalpy of formation of forsterite,enstatite, akermanite,monticellite and merwinite at 1073 K determined by alkali borate solution calorimetry

Enthalpies of solution of synthetic enstatite (Mg₂Si₂O₆), forsterite (Mg₂SiO₄), akermanite (Ca₂MgSi₂O₇), monticellite (CaMgSiO₄), and merwinite (Ca₃MgSi₂O₈) and their component oxides were determined in eutectic (Li, Na)BO₂ at 1073 K. Resulting enthalpies of formation at 1073 are enstatite: $\text{?8.10 ± 0.42}\text{kcal}$; forsterite: $\text{?14.23 ± 0.45}\text{kcal}$; akermanite: $\text{?42.60 ± 0.39}\text{kcal}$; monticellite: $\text{?25.05 ± 0.41}\text{kcal}$; and merwinite: $\text{?51.10 ± 0.49}\text{kcal}$. The value for the synthetic monticellite of composition Mo_.965Fo_.035 was corrected slightly for non-stoichiometry based on experimental monticellite-forsterite phase equilibrium relations.The enthalpies of formation of enstatite and forsterite are somewhat less negative than yielded by several other solution calorimetric studies but are in good agreement with the recent Pb₂B₂O₅ solution calorimetry of Kiselevaet al. (1979), and are in good agreement with values to be derived from reliable phase equilibrium data in the system MgO-Al₂O₃-SiO₂. The enthalpies of formation of akermanite, monticellite and merwinite are all much less negative than values tabulated by robieet al. (1978) and helgesonet al. (1978) but are shown to be compatible with reliable phase equilibrium data for the system CaO-MgO-SiO₂, whereas the tabulated values are not. Several methods of analysis yield an entropy of monticellite at 1000 K of $\text{69.9 ± 0.2 cal/K}$.     

Molecular simulations of interfacial and thermodynamic mixing properties of grossular–andradite garnets

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.     

X-ray and electron-optical investigation of synthetic high-temperature plagioclases

High-temperature plagioclases NaAlSi₃O₈(Ab)-CaAl₂Si₂O₈(An) have been prepared by dry devitrification of glasses. X-ray powder photographs were taken to follow the time-temperature dependence of indicators of structural state and to determine the lattice parameters of the plagioclases as well as their K-exchanged equivalents. Transmission electron microscopy (TEM) has been used to study the anorthite-type antiphase domain textures. The results are as follows:

1. TEM and X-ray powder data suggest to subdivide the high-temperature plagioclase series into three structural regions: (a) An0 to An30–40: monalbite/analbite to high albite-type structures, (b) An60–70 to An100: anorthite-type structures, (c) An30–40 to An60–70: transitional structures assumed to represent the early stages in the development of the structural complexities found in chemically intermediate low temperature plagioclases.
2. b-Antiphase domains typical for the anorthite-type structure could be imaged in samples ranging between An100 and An67.5, whereas c-antiphase domains have only been found in An90 and An100. The b-domains developed during isothermal crystallization, rather than cooling. The transition from the anorthite-type structure (S.G.I \(\bar 1\) ) to an intermediate C \(\bar 1\) -type structure at An60–70 appears to be a gradual one.
3. The relative contribution of various structural and chemical influences on the cell edges and angles is discussed in detail. It is shown that the nonlinear variation of γ with An content is due to incomplete Al,Si disorder in the high series.

     

Compressions of synthetic pyrope,spessartine and uvarovite garnets up to 25 GPa

The volumes of the pure synthetic pyrope, spessartine and uvarovite garnets have been determined by powder x-ray diffraction as a function of pressure up to 25 GPa in a diamond anvil cell at room temperature. Experiments in different pressure transmitting media have been systematically carried out to determine the effects of anisotropic stress components, which were found to be substantial and have been taken into account. Assuming that the bulk moduli determined from ultrasonic experiments have the lowest uncertainties, the following values for the pressure derivatives of the bulk modulus of uvarovite, spessartine and pyrope were respectively obtained: 4.7±0.7, 7?7.3±1 and 3.4±1. The value for pyrope can be attributed to the small size of the Mg²⁺ cation in its dodecahedral site.     

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     

Formation of garnets in a rock from Mallaig

A garnet-mica schist from Mallaig, Invernessshire, Scotland, contains two textural varieties of almandine garnet. Microprobe analyses show that there are significant chemical differences between them. A sequence of garnet-forming reactions is suggested from the chemical and textural evidence, and related to the thermal history of the rock.     

Chrome-rich garnets from the kimberlites of yakutia and their parageneses

The chrome-rich magnesian garnets (6.6–18.9% Cr₂O₃) of kimberlitic concentrates and some peridotite xenoliths contain variable admixtures of CaO: from 0.69 to 26.0% (1.7–72% Ca-component). All the garnets both in respect of Ca and Cr-contents make up a continuous series.The variability in the Ca-content is caused by differences in paragenesis. Most of the Ca-poor pyropes are related to a paragenesis without clinopyroxene (mostly dunitic). Garnets rich in calcium are related to a paragenesis without entstatite. All the parageneses listed are of an ultramafic type, i.e. contain magnesian olivine. The solubility of knorringite—Mg₃Cr₂(Si₃O₁₂)—in kimberlitic garnets is possibly limited by pressure and does not exceed 50–60% mol.     

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     

Energetics of anhydrite, barite, celestine, and anglesite: a high-temperature and differential scanning calorimetry study

The thermochemistry of anhydrous sulfates (anglesite, anhydrite, arcanite, barite, celestine) was investigated by high-temperature oxide melt calorimetry and differential scanning calorimetry. Complete retention and uniform speciation of sulfur in the solvent was documented by (a) chemical analyses of the solvent (3Na₂O · 4MoO₃) with dissolved sulfates, (b) Fourier transform infrared spectroscopy confirming the absence of sulfur species in the gases above the solvent, and (c) consistency of experimental determination of the enthalpy of drop solution of SO₃ in the solvent. Thus, the principal conclusion of this study is that high-temperature oxide melt calorimetry with 3Na₂O · 4MoO₃ solvent is a valid technique for measurement of enthalpies of formation of anhydrous sulfates. Enthalpies of formation (in kJ/mol) from the elements (ΔH_f^o) were determined for synthetic anhydrite (CaSO₄) (−1433.8 ± 3.2), celestine (SrSO₄) (−1452.1 ± 3.3), anglesite (PbSO₄) (−909.9 ± 3.4), and two natural barite (BaSO₄) samples (−1464.2 ± 3.7, −1464.9 ± 3.7). The heat capacity of anhydrite, barite, and celestine was measured between 245 and 1100 K, with low- and high-temperature Netzsch (DSC-404) differential scanning calorimeters. The results for each sample were fitted to a Haas-Fisher polynomial of the form C_p(245 K < T < 1100 K) = a + bT + cT⁻² + dT^−0.5 + eT². The coefficients of the equation are as follows: for anhydrite a = 409.7, b = −1.764 × 10⁻¹, c = 2.672 × 10⁶, d = −5.130 × 10³, e = 8.460 × 10⁻⁵; for barite, a = 230.5, b = −0.7395 × 10⁻¹, c = −1.170 × 10⁶, d = −1.587 × 10³, e = 4.784 × 10⁻⁵; and for celestine, a = 82.1, b = 0.8831 × 10⁻¹, c = −1.213 × 10⁶, d = 0.1890 × 10³, e = −1.449 × 10⁻⁵. The 95% confidence interval of the measured C_p varies from 1 to 2% of the measured value at low temperature up to 2 to 5% at high temperature. The measured thermochemical data improve or augment the thermodynamic database for anhydrous sulfates and highlight the remaining discrepancies.     

Enthalpy of formation of Fe3Al2Si3O12 (almandine) by high temperature alkali borate solution calorimetry

A high-temperature solution calorimetric method suitable for thermochemical studies of anhydrous minerals containing Fe²⁺ ions has been developed. The method is based on an oxide melt solvent with 52 wt% LiBO₂ and 48 wt% NaBO₂ maintained at a temperature of 750°C. In a first application of this method the enthalpies of solution of synthetic almandine, fayalite, a mixture of fayalite plus quartz on FeSiO₃ composition, and natural quartz were measured. For the reaction:

the enthalpy change at 1023 K is ?3.82 ± 0.87 kcal, based on fayalite, quartz, corundum and almandine, and ?5.96 ± 0.90 kcal based on the fayalite plus quartz mixture, corundum, and almandine. These values lead to standard molar enthalpies of formation of almandine from the oxides at 1023 K of ?14.10 ± 1.22 kcal and ?16.24 ± 1.74 kcal, respectively. The measured enthalpy of formation of almandine is less negative by several kilocalories than values derived from analysis of the phase equilibrium work of Hsu (1968), but in closer agreement with the phase equilibrium study of O'Neill and Wood (1979) and similar to the phase equilibrium deduction of Froese (1973).The agreement of the present almandine enthalpy of formation with O'Neill and Wood (1979) and Froese (1973) suggests that almandine entropies at 298 K to be obtained from their studies, in the range 79–81 cal/K, are more nearly correct than the several estimates based on oxide sum and volume-entropy systematics, most of which are much lower.     

Genesis of garnets in some magmatic rocks from Hungary

Summary Garnets from Miocene di-normative, medium-K andesites as well as from a Mesozoic fine-grained albite granite have been petrologically investigated. The chemical compositions of the garnets from the andesites as determined by electron microprobe (alm 57–65,pyr 14–22,gross 10–24,spess 2–5, -all in mol.-%) are compatible with the garnets being high pressure megacrysts. Garnets from the granite (alm 71–74,pyr 12–18,gross 3.5–5.5,spess 5.6–11) apparently crystallized in a low pressure environment. They are believed to have formed in an autometasomatic event.

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Die Genese von Granaten in einigen magmatischen Gesteinen Ungarns

Zusammenfassung Granate aus miozänen di-normativen, medium-K Andesiten und aus einem mesozoischen feinkörnigen Albit-Granit wurden petrologisch untersucht. Die chemische Zusammensetzung der Granate, (Alm 57–65,Pyr 14–22,Gross 10–24,Spess 2–5 Mol.-%), gemessen mittels Elektronenstrahl-Mikrosonde, macht es wahrscheinlich, daß diese Granate Hochdruck-Megakristalle sind. Die Granate im Granit (Alm 71–74,Pyr 12–18,Gross 3,5–5,5,Spess 5,6–11) kristallisierten bei niedrigen Drücken und sind wahrscheinlich das Produkt autometasomatischer Vorgänge.

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With 7 Figures     

东蒙地区夕卡岩石榴石稀土元素地球化学及其成因

东蒙地区为我国北方重要的夕卡岩型锡银铜铅锌多金属成矿区，不仅矿床发育，而且成矿种类较多，典型矿床有黄岗梁Fe（Sn）、白音诺Pb-Zn-Ag等金属和浩布高Fe（Sn）－PbZnAg（Cu）矿床。研究表明，它们都是中生代岩浆岩与本区二叠系地层相互作用的产物。本文通过对黄岗梁、白音诺和浩布高3个矿床中不同阶段的石榴石夕卡岩矿物学研究，划分出早晚两期夕卡岩石榴石矿物。早期以浅色、他形细粒、均质的钙铁榴石为主，多形成环带的核心；晚期以深色、半自形中粗粒、弱非均质的钙铝榴石为主，多构成环带的边部。同时采用ICP－MS方法对3其中石榴石比较发育的黄岗梁和浩布高2个矿床中石榴石单矿物进行了稀土元素含量的测定。结果表明，矿区早期的石榴石具有岩浆成因的特征，晚期石榴石具有热液交代成因特征，即东蒙地区既有早期岩浆阶段的岩浆型夕卡岩，又有晚期热液交代型夕卡岩的多成因认识。     

Thermodynamic mixing behavior of synthetic Ca-Tschermak–diopside pyroxene solid solutions: I. Volume and heat capacity of mixing

The unite cell parameters and heat capacities of a series of synthetic clinopyroxenes on the join Ca-Tschermak (CaTs)−diopside (Di) were measured using X-ray powder diffraction and calorimetric methods, respectively. The volume of mixing at 298 K shows a negative asymmetric deviation from ideality. A two-parameter Margules fit to the data yields W _CaTs−Di ^V = −0.29 ± 0.11 cm³ mol⁻¹ and W _Di−CaTs ^V = −1.14 ± 0.14 cm³ mol⁻¹. Heat capacities were determined between 5 and 923 K by heat-pulse at 5−302 K and differential-scanning calorimetry at 143−923 K. The precision of the low and high temperature C _p data is better than ±1%. Polynomials of the form C _p = a + bT ^−1/2 + cT ⁻² + dT ⁻³ were fitted to the C _p data in the temperature range between 250 and 925 K. Thermal entropy values [S ₂₉₈ − S ₀] and [S ₉₀₀ −S ₀] as well as enthalpies [H ₂₉₈ − H ₀] and [H ₉₀₀ − H ₀] were calculated for all members of the solid solution series. No significant deviation from ideal mixing behavior was observed.     

A study of garnets from eclogite and peridotite xenoliths found in kimberlite

The chemical compositions of garnets from 58 eclogite, 72 peridotite and 4 pyroxenite xenoliths in kimberlites have been estimated from their unit cell edge length and refractive indices. The samples studied were obtained from 17 kimberlite occurrences and include all those of known source which remain in the famous Williams (1932) collection which is stored at the University of Cape Town. Every suitable sample available to the authors has been examined.A gap in the range of garnet volume percentages occurs in the samples studied between approximately 15 and 30%. Garnet peridotites characteristically have <15% garnet and eclogites >30% garnet. Very rare exceptions occur. Our collection contains no eclogites with olivine and only one with orthopyroxene. All but two of the peridotite-pyroxenite group contain orthopyroxene. The garnets from the peridotites and pyroxenites plot on a pyrope-almandine-uvarovite triangle in a narrow band with a remarkably constant almandine/uvarovite ratio. Garnets from the eclogites are plotted on a pyrope-almandine-grossularite triangle and have a wide spread of compositions. These fall into 4 groups viz. eclogite I, eclogite II, kyanite eclogite and corundum eclogite.The reasons for the differences in garnet chemistry are considered and a tentative evolutionary scheme suggested by partial melting of the garnet peridotite which is assumed to occur in the upper mantle. Recent models of upper mantle composition and the genesis of garnet-bearing xenoliths in kimberlite are briefly and critically examined.S.A. UMP Publication No. 9.     

Entropies and enthalpies of aluminosilicate garnets

Activity-composition data have been used to obtain excess entropies and enthalpies of mixing for almandine-grossular and Mg-rich pyrope-grossular solid solutions. Excess free energies of Fe-rich almandine-grossular garnets are negative and imply the formation of a stable garnet compound with a different structure from the end members in this series.X-ray investigations of natural and synthetic calcium-poor aluminosilicate garnets indicate a lower space group symmetry than Ia3d, that of the end members. The most probable space group is I2₁3 in which there are two crystallographically distinct 8-coordinate sites present in equal numbers in the garnet structure.Excess entropies of mixing for almandine-grossular garnets are asymmetric and can be explained by Fe-Ca ordering in calcium-poor garnets together with Fe positional disorder on sub-sites within the 8-coordinate polyhedra. In the middle of the series and towards the Ca-rich end, a high degree of sub-site disorder with little or no Fe-Ca ordering may be responsible for the high positive entropies. Excess entropies of calcium-poor pyrope-grossular garnets show a similar trend, but are slightly more positive. Excess enthalpies of mixing for Mg-rich pyropegrossular garnets are in good agreement with the high-temperature calorimetric measurements of other workers.