Abstract Three reactions are calibrated as geothermobarometers for garnet–orthopyroxene–plagioclase–quartz assemblages, namely: 1/2 ferrosilite + 1/3 pyrope ± 1/2 enstatite + 1/3 almandine (A): ferrosilite + anorthite ± 2/3 almandine + 1/3 grossularite + quartz (B); and enstatite + anorthite ± 2/3 pyrope + 1/3 grossularite + quartz (C). The internally consistent geothermobarometers based on reactions (A), (B) and (C) are calibrated from experimental data only. The thermodynamic parameters of reaction (A) are derived from published experimental data in the FMAS system (n= 104) in the range 700–1400°C and 5–50 kbar, while those for reaction (B) are derived by summation of the existing reversed experimental data of the mineral equilibria: ferrosilite ± fayalite + quartz (D) and anorthite + fayalite ± 2/3 almandine + 1/3 grossularite (E). The retrieved thermodynamic parameters for reactions (A), (B) and (C) are, respectively: (ΔH0, cal) -3367 ± 209, -2749 ± 350 and +3985 ± 545; (ΔS0, cal K?1) -1.634 ± 0.163, -8.644 ± 0.298 and -5.376 ± 0.391; and (ΔV01,298, cal bar?1) -0.024, -0.60946 and -0.5614. On a one-cation basis, the derived Margules parameters of the ternary Ca–Fe–Mg in garnet are: WFe–Mg= -1256 + 1.0 (～0.23) T(K), WMg–Fe= 2880 -1.7 (～0.13) T(K), WCa–Mg= 4047 (～77) -1.5 T(K), WMg–Ca= 1000 (～77) -1.5 T(K), WCa–Fe= -723 + 0.332 (～0.02) T(K), WFe–Ca= 1090, (cal) and the ternary constant C123= -4498 + 1.516 (～0.265) T(K) cal (subregular solution model of non-ideal mixing); and Fe–Mg–Al in orthopyroxene: WFe–Mg= 948 (～200) -0.34 (～0.10) T(K), WFe–Al= -1950 (～500) and WMg–Al= 0 (cal) (regular solution model of non-ideal mixing). The anorthite activity in plagioclase is calculated by the ‘Al-avoidance’model of subregular Ca–Na mixing commonly used for geobarometry based on reactions (B) and (C). When the geothermobarometers are applied to garnet–orthopyroxene–plagioclase–quartz assemblages (n= 45) of wide compositional range from the Precambrian South Indian granulites, temperature ranges of 690–860°C (X= 760 ± 45°C) and pressure ranges of 5–10 kbar were obtained. The P–T values were estimated simultaneously and there is no difference in the pressure calculated from PMg (reaction C) and PFe (reaction B). In the existing calibrations this difference is 1 kbar or more. Furthermore, there is no compositional dependence of the ln K of the experimental data in the FMAS (n= 104) and the CFMAS (n= 78) systems at different temperatures and the estimated temperatures of the South Indian granulites. 相似文献
The i.r. spectrum of 13 analyzed garnets of the pyralspite group has been investigated in the 1400-200 cm–1 region, and correlations have been found between the spectrum and the chemical composition. The results include: typical features in the spectrum of the end-members pyrope, almandine and spessartine; relationships between the spectrum and the pyrope percentage in pyrope-almandine solid solutions; and the influence of the CaO (grossularite) amount on the shape of the low-frequency absorption bands. These data allow a semiquantitative determination of the pyrope percentage in pyrope-almandine solid solutions. 相似文献
Principal component analysis, using eigenvalues and eigenvectors, of the encountered variation in the chemistry of 153 garnets indicates the following: (1) In low grade metamorphic rocks, spessertite and almandine are distinctly isomorphous. The variability of pyrope content does not influence the binary Fe-Mn relationship. However there may be some influence of the grossularite content. (2) In high grade metamorphic rocks, pyrope and almandine are distinctly isomorphous. Variability of grossularite content does not affect the binary Mg-Fe relationship. However, variability in spessertite content may influence the linearity particularly when there is little pyrope.Similar statistical analysis of the chemical data on 119 samples of clinopyroxenes indicates that only significant changes in the concentrations of Al in octahedral and/or of Al in tetrahedral sites and Ti could cause some change in the FeMg ratio in the mineral.Principal component analysis of the data on coexisting garnet and clinopyroxene could be used to classify rocks into their petrogenetic types.Distribution coefficient calculated by assuming ideal binary solution of Mg and Fe members in pyroxene and garnet is useful to indicate the P-T of the formation of the rocks. 相似文献
Local heterogeneities in pyrope-almandine, almandine-grossular and pyrope-grossular solid solutions have been investigated using IR-powder absorption spectroscopy. Correlations of the wavenumber shifts and line broadening systematics with the thermodynamic mixing properties were found. Wavenumber shifts of the highest energy modes correlate closely with the Si-O bond distances and give an indirect view of the average distortions across the three solid solutions. They have a linear behaviour for Py-Alm, but show positive variations from linearity for Alm-Gr and Py-Gr systems. An effective line width (Δcorr) of the absorption bands over a given wavenumber interval was obtained using the autocorrelation function. Line broadening is associated with local heterogeneities arising from cation substitution in the structure of samples at intermediate compositions. Non-linearities of the line broadening were found for Alm-Gr and Py-Gr and have a shape similar to the enthalpy of mixing, ΔHmix. An empirical analysis was therefore carried out to compare ΔHmix and Δcorr quantitatively. Low-temperature far-IR spectra were recorded for the end-members pyrope, almandine and grossular and far-IR and mid-IR low-temperature spectra for Py60Gr40 in the temperature range 292–44 K. Softening of the lowest energy band with decreasing temperature was observed in the spectrum of pyrope and more enhanced in the spectrum of Py60Gr40. The same softening occurs by substitution of grossular component into pyrope. High energy modes of Py60Gr40 show the effect of saturation below 110–130 K, which correlates with the volume saturation at low temperature. This could provide an alternative explanation for the heat capacity anomaly found for Py-Gr solid solution at low-temperatures. 相似文献
Uvarovite (Ca3Cr2Si3O12) forms a complete solid solution series with grossularite (Ca3Al2Si3O12) below 855 ± 5 ° C at a total pressure of 1 atm. Pure uvarovite decomposes to pwo (CaSiO3) + esk (Cr2O3) at 1385 ± 10 ° C. The incorporation of about 5 wt-% of Ca3Al2 Si3O12 component in the uvarovite structure raises the thermal stability of the garnetss to 1410 ± 5 ° C, and uvarovite95 grossularite05 melts incongruently to pwo (CaSiO3) + coreskss ((Al, Cr)2O3) + L. Pure grossularite decomposes to wo (CaSi03) + geh (Ca2Al2SiO7) + and (CaAl2Si2O8) at 855 ± 5 ° C, grossularite thermal stability is increased by incorporation of Ca3Cr2Si3O12 component by 530 ° C. At 1280±5 ° C coreskss + L react to garss + geh + an defining an invariant tequilibrium of the CaO-Cr2O3-Al2O3-SiO2 quaternary system. Liquid reacts to garss + pwo + geh + an at 1263 ±5 ° C terminating univariant and divariant liquid relations occurring along the join Ca3Cr2Si3O12-Ca3Al2Si3O12. The unit-cell parameter for uvarovite is 11.996(2) Å, the refractive index 1.865(3). The substitution of Cr by Al decreases a and n almost linearly toward the grossularite end member which displays a unit-cell parameter of 11.848(2) Å and a refractive index of 1.732 (1). 相似文献
The thermoelastic parameters of synthetic Mn3Al2Si3O12 spessartine garnet were examined in situ at high pressure up to 13 GPa and high temperature up to 1,100 K, by synchrotron radiation energy dispersive X-ray diffraction within a DIA-type multi-anvil press apparatus. The analysis of room temperature data yielded K0 = 172 ± 4 GPa and K0′ = 5.0 ± 0.9 when V0,300 is fixed to 1,564.96 Å3. Fitting of P–V–T data by means of the high-temperature third-order Birch–Murnaghan EoS gives the thermoelastic parameters: K0 = 171 ± 4 GPa, K0′ = 5.3 ± 0.8, (?K0,T/?T)P = ?0.049 ± 0.007 GPa K?1, a0 = 1.59 ± 0.33 × 10?5 K?1 and b0 = 2.91 ± 0.69 × 10?8 K?2 (e.g., α0,300 = 2.46 ± 0.54 × 10?5 K?1). Comparison with thermoelastic properties of other garnet end-members indicated that the compression mechanism of spessartine might be the same as almandine and pyrope but differs from that of grossular. On the other hand, at high temperature, spessartine softens substantially faster than pyrope and grossular. Such softening, which is also reported for almandine, emphasize the importance of the cation in the dodecahedral site on the thermoelastic properties of aluminosilicate garnet. 相似文献
We present results of high temperature, high pressure atomistic simulations aimed at determining the thermodynamic mixing properties of key binary garnet solid solutions. Computations cover the pressure range 0–15 GPa and the temperature range 0–2000 K. Through a combination of Monte-Carlo and lattice-dynamics calculations, we derive thermodynamic mixing properties for garnets with compositions along the pyrope–almandine and pyrope–grossular joins, and compare these with existing experimental data. Across the pressure–temperature range considered, simulations show virtually ideal mixing behaviour in garnet on the pyrope–almandine join, while large excess volumes and enthalpies of mixing are predicted for garnet along the pyrope–grossular join. Excess heat capacities and entropies are also examined. These simulations shed additional light on the link between the behaviour at the atomic level and macroscopic thermodynamic properties: we illustrate the importance of certain atomistic Ca–Mg contacts in the pyrope–grossular solid solutions. For simulation techniques of this type to become sufficiently accurate for direct use in geological applications such as geothermobarometry, there is an urgent need for improved experimental determinations of several key quantities, such as the enthalpies of mixing along both joins. 相似文献
In contrast to Ferry (1980) (XCa)-values in garnet even lower than 0.1 have a significant effect on the calculated equilibrium temperature using the experimental calibration of the Fe and Mg paritioning between garnet and biotite. Garnet compositions and Mg/Fe — distribution coefficients from samples of the Eoalpine staurolite — in zone in the southern Ötztal are related by the quadratic regression equation: InKD= -1.7500 (±0.0226) + 2.978 (±0.5317)XCaGt
-5.906(±2.359)(XCaGt
)2 Temperatures derived by the Ferry and Spear (1978) calibration using chemistry — correctedKD values are petrologically realistic.Analysis of our data supports non ideal mixing of grossular with almandine — pyrope solid solution. The derived excess mixing energies are quite small for the almandine — pyrope solution (WFeMg= –133 cal/mole) and about +2775 cal/mole for the difference between pyrope-grossular and almandine-grossular solutions (WMgCa —WFeCa) at metamorphic conditions of 570° C and 5,000 bar. The mixing parameters proposed by Ganguly and Saxena (1984) are not confirmed by our data as they would result in significantly lower temperatures. 相似文献
P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at Pf=1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly
In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at Pf=1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles. 相似文献
High-temperature oxide-melt calorimetry and Rietveld refinement of powder X-ray diffraction patterns were used to investigate the energetics and structure of the hematite–corundum solid solution and ternary phase FeAlO3 (with FeGaO3 structure). The mixing enthalpies in the solid solution can be described by a polynomial ΔHmix=WXhem(1?Xhem) with W=116 ± 10 kJ mol?1. The excess mixing enthalpies are too positive to reproduce the experimental phase diagram, and excess entropies in the solid solution should be considered. The hematite–corundum solvus can be approximately reproduced by a symmetric, regular-like solution model with ΔGexcess=(WH?TWS)XhemXcor, where WH= 116 ± 10 kJ mol?1 and WS=32 ± 4 J mol?1 K?1. In this model, short-range order (SRO) of Fe/Al is neglected because SRO probably becomes important only at intermediate compositions close to Fe:Al=1:1 but these compositions cannot be synthesized. The volume of mixing is positive for Al-hematite but almost ideal for Fe-corundum. Moreover, the degree of deviation from Vegard's law for Al-hematite depends on the history of the samples. Introduction of Al into the hematite structure causes varying distortion of the hexagonal network of oxygen ions while the position of the metal ions remains intact. Distortion of the hexagonal network of oxygen ions attains a minimum at the composition (Fe0.95Al0.05)2O3. The enthalpy of formation of FeAlO3 from oxides at 298 K is 27.9 ± 1.8 kJ mol?1. Its estimated standard entropy (including configurational entropy due to disorder of Fe/Al) is 98.9 J mol?1 K?1, giving the standard free energy of formation at 298 K from oxides and elements as +19.1 ± 1.8 and ?1144.2 ± 2.0 kJ mol?1, respectively. The heat capacity of FeAlO3 is approximated as Cp(T in K)= 175.8 ? 0.002472T ? (1.958 × 106)/T 2? 917.3/T 0.5+(7.546 × 10?6) T 2 between 298 and 1550 K, based on differential scanning calorimetric measurements. No ferrous iron was detected in FeAlO3 by Mössbauer spectroscopy. The ternary phase is entropy stabilized and is predicted to be stable above about 1730 ± 70 K, in good agreement with the experiment. Static lattice calculations show that the LiNbO3-, FeGaO3-, FeTiO3-, and disordered corundum-like FeAlO3 structures are less stable (in the order in which they are listed) than a mechanical mixture of corundum and hematite. At high temperatures, the FeGaO3-like structure is favored by its entropy, and its stability field appears on the phase diagram. 相似文献
The Raman spectra of the natural end members of the garnet-group minerals,which include pyrope, almandine and spessarite of Fe-Al garnet series and grossularite ,andradite and uvarovite of Ca-Fe garnet series, have been strdied.Measured Raman spectra of these minerals are reasonably and qualitatively assigned to the internal modes, translational and rotatory modes of SiO4 tetrahedra, as well as the translational motion of bivalent cations in the X site.The stretch and rotatory A1g modes for the Fe-Al garnet series show obvious Raman shifts as compared with those for the Ca-Fe garnet series ,owing to the cations residing in the Xsite connected with SiO4 tetrahedra by sharing the two edges.The Raman shifts of all members within either of the series are attributed mainly to the properties of cations in the X site for the Fe-Al garnet series andin the Y site for the Ca-Fe garnet series. 相似文献
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. 相似文献
Enthalpies of solution in 2PbO· B2O3 at 712°C have been measured for glasses in the systems albite anorthite diopside, NaAlO2-SiO2, Ca0.5AlO2-SiO2 and albite-anorthite-quartz. The systems albite-anorthite and diopside-anorthite show substantial negative enthalpies of mixing, albite-diopside shows significant positive heats of mixing. For compositions up to NaAlO2 = 0.42 (which includes the subsystem albite-silica) the system NaAlO2-SiO2 shows essentially zero heats of mixing. A negative ternary excess heat of mixing is found in the plagioclase-rich portion of the albite-anorthite-diopside system. The join Si4O8-CaAl2Si2O8 shows small but significant heats of mixing. In albite-anorthite-quartz. ternary glasses, the ternary excess enthalpy of mixing is positive.Based on available heat capacity data and appropriate consideration of the glass transition, the enthalpy of the crystal-glass transition (vitrification) is a serious underestimate of the enthalpy of the crystal-liquid transition (fusion) especially when the melting point, Tf, is many hundreds of degrees higher than the glass transition temperature, Tg. On the other hand, the same heat capacity data suggest that the enthalpies of mixing in albite-anorthite-diopside liquids are calculated to be quite similar to those in the glasses. The enthalpies of mixing observed in general support the structural models proposed by Taylor and Brown (1979a, b) and others for the structure of aluminosilicate glasses. 相似文献
An unusual magmatic three-feldspar syenogabbro occurs 3 m inside the contact of the Klokken gabbro-syenite stock. It contains plagioclase, mesoperthite and cryptoperthite, together with a low temperature symplectite intergrowth. Textural relationships have been investigated by cathodoluminescence, bulk chemistry by microprobe, and exsolution microtextures and intracrystalline boundaries by TEM. The mesoperthite has a bulk composition around Or26Ab52An22, well outside accepted limits of ternary feldspar solid solution. It is a mainly coherent, lamellar intergrowth of sodic andesine and orthoclase with incipient Mtwinning. The cryptoperthite, bulk composition around Or61Ab33An6, is a coherent lamellar intergrowth of orthoclase and sodic low oligoclase. The compositions of the exsolved phases have been estimated. The meso- and cryptoperthite crystals have sharp boundaries with each other. Plagioclase (zoned An 55-35, with 2–3% Or) defines a solidus fractionation path. It behaved as an inert phase during crystallization of the perthites, which grew as homogeneous monoclinic phases in equilibrium on the strain-free ternary solvus, defining a solvus isotherm at ～ 950° C. Both of the monoclinic phases exsolved on reaching the coherent ternary spinodal at temperatures estimated to be close to 800–850° C and 700–830° C respectively. Lamellar periodicities (529±149 nm and 148±18 nm respectively) are considerably finer scale than predicted by coarsening experiments, suggesting that An and/or Al-Si order greatly inhibit coarsening. The symplectite is a coarse, incoherent intergrowth of sodic andesine and nearly pure K-feldspar, probably produced by simultaneous crystallization at <400° C. The new data and literature analyses are used to construct the geometry of the ternary feldspar system. Solvus isotherms implied by existing experimental data approach the Ab apex too closely at high temperature. The critical solution curve becomes slightly more albitic after leaving the binary Ab-Or join, and then turns sharply towards the An-Or join. It intersects the proposed new limit of feldspar solid solution near Or36Ab44An20 at 1,060° C. This probably approximates to the highest temperature on the ternary critical curve at 1 bar. 相似文献
The pyroxene saturation surface in the system diopside-albite-anorthite may be calculated to ±10°C from thermochemical data over most of its composition range. The thermochemical data used are the experimentally determined enthalpies of mixing of the ternary liquids and the enthalpy of fusion of diopside. These are combined with a mixing model for the configurational entropy in the melt and the activity of CaMgSi2O6 in the clinopyroxene, which is less than unity due to departures from CaMgSi2O6 stoichiometry. The ‘two-lattice’ melt model appears to work satisfactorily throughout the pyroxene primary phase field but probably needs modification at more anorthite-rich compositions. 相似文献
The cation exchange equilibrium has been investigated by hydrothermal experiments at 700 and 800°C at 200 MPa. To avoid equilibration problems of conventional exchange experiments, we synthesized amphiboles with an excess fluid allowing exchange between solid and fluid during the experiment. The exchangeable cations Na and K were provided as excess 1 to 2n chloridic solution. These exchange syntheses can be described by the reaction equation with (aq) for hydroxides and chlorides in aqueous solutions and (s) and (p)?=?start and product fluid. The amphiboles grew in presence of the exchange fluid and adjusted their stoichiometry in equilibrium with the fluid phase. The solid products consist of more than 99% amphibole (Na,K-richteritess) with traces of diopside and quartz. The amphiboles are up to 1?mm long and often ≈ 40 μm thick. Detailed EMP- and HRTEM-observations show that they are chemically homogeneous and structurally wellordered. The experimental results give consistent phase relations in the reciprocal ternary system Na-richterite–K-richterite–NaCl–KCl. We analysed the product fluid with AAS- and ICP-methods. The Na-K distribution coefficients between fluid and amphiboles of the richterite–K-richterite join are close to unity at 700°C and 800°C at 200 MPa. Small systematic deviations are explained by a symmetric solution model for the A-position of the amphiboles. Using ideal mixing for H2O-NaCl-KCl fluids, a mixing model for the system richterite–K-richterite is presented. We suggest that the composition of richterite solid solutions can be used as a sensor for NaCl/KCl-ratios in metamorphic fluids. 相似文献
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. 相似文献
Approximate mixing properties of the dominant calcium silicate end-member components of natural garnets, namely grossularite, andradite and uvarovite, have been derived through theoretical thermodynamic and crystal chemical analysis, and appropriate reduction of the available experimental data. The stability of the solid solution with respect to phase separation in the ternary system has been analyzed. Finally, a general model is presented as to the approximate mixing properties of multicomponent natural garnet solid solution involving substitutions in both eight and six coordinated sites. 相似文献
Raman and infrared spectroscopic data at ambient and high pressures were used to compute the lattice contribution to the heat capacities and entropies of six endmember garnets: pyrope, almandine, spessartine, grossular, andradite and uvarovite. Electronic, configurational and magnetic contributions are obtained from comparing available calorimetric data to the computed lattice contributions. For garnets with entropy in excess of the computed lattice contribution, the overwhelming majority is found in the subambient temperature regime. At room temperature, the non-lattice entropy is approximately 11.5 J/mol-K for pyrope, 49 J/mol-K for almandine, and 19 J/mol-K for andradite. The non-lattice entropy for pyrope and some for almandine cannot be accounted for by magnetic or electronic contributions and is likely to be configurational in nature. Estimates of low temperature non-lattice entropies for both spessartine and uvarovite are made in absence of calorimetric measurements and are based on low temperature calorimetry of other minerals containing the Mn2+ and Cr3+ cations as well as on solid solution garnets containing these cations. The estimate for uvarovite non-lattice entropy is approximately 18 J/mol-K, while for spessartine, approximately 45 J/mol-K. Neither of these cations is expected to provide electronic contributions to the entropy. For both iron-bearing garnets, a small electronic or magnetic entropy contribution continues above ambient temperatures. High pressure data on pyrope, grossular and andradite permit calculation of the thermodynamic parameters at high pressures, which are important for computation of processes in the Earth’s mantle. Thermal expansion coefficients of these materials were found to be 1.6, 1.5, 1.6×10−5 K−1 at 298 K, respectively, using a Maxwell relation. These closely match the literature values at ambient conditions. 相似文献
Pan‐African high‐pressure granulites occur as boudins and layers in the Lurio Belt in north‐eastern Mozambique, eastern Africa. Mafic granulites contain the mineral assemblage garnet + clinopyroxene + plagioclase + quartz ± magnesiohastingsite. Garnet porphyroblasts are zoned with increasing almandine and spessartine contents and decreasing grossular and pyrope contents from core (Alm46Prp32Grs21Sps2) to rim (Alm52Prp26Grs19Sps3). This pattern is interpreted as a retrograde diffusion zoning with the preserved core chemistry representing the peak metamorphic composition. Mineral reaction textures occur in the form of monomineralic and composite plagioclase ± orthopyroxene ± amphibole ± biotite ± magnetite coronas around garnet porphyroblasts. Thermobarometry indicates peak metamorphic conditions of up to 1.57 ± 0.14 GPa and 949 ± 92 °C (stage I), corresponding to crustal depths of ～55 km. Zircon yielded an U–Pb age of 557 ± 16 Ma, inferred to date crystallization of zircon during peak or immediately post‐peak metamorphism. Formation of plagioclase + orthopyroxene‐bearing coronas surrounding garnet indicates a near‐isothermal decompression of the high‐pressure granulites to lower pressure granulite facies conditions (stage II). Development of plagioclase + amphibole‐coronas enclosing the same garnet porphyroblasts shows subsequent cooling into amphibolite facies conditions (stage III). Symplectitic textures of the corona assemblages indicate rapid decompression. The high‐pressure granulite facies metamorphism of the Lurio Belt, followed by near‐isothermal decompression and subsequent cooling, is in accordance with a long‐lived tectonic history accompanied by high magmatic activity in the Lurio Belt during the late Neoproterozoic–early Palaeozoic East‐African–Antarctic orogeny. 相似文献
