Theoretical phase relations involving cordierite and garnet in the system MgO-FeO-Al2O3-SiO2

Theoretical stability relations have been derived between the phases cordierite (Cd), garnet (Ga), hypersthene (Hy), olivine (Ol), sapphirine (Sa), spinel (Sp), sillimanite (Si) and quartz (Qz) in the system MgO-FeO-Al₂O₃-SiO₂. Natural rock data and experimental evidence suggest that the Mg/Mg+Fe²⁺ ratio (X) of coexisting ferromagnesian phases decreases as follows: X _Cd>X _Sa>X _Hy>X _Ol>X _Sp>X _Ga. By use of this information four stable invariant points are proposed involving the phases: Cd, Hy, Sa, Ga, Si, Qz; Cd, Sa, Ga, Sp, Si, Qz; Cd, Hy, Sa, Ga, Sp, Qz; Cd, Ga, Hy, Ol, Sp, Qz. All univariant curves in the system are nonterminal, representing the breakdown of a join rather than the stability limit of an individual phase. A detailed treatment of divariant equilibria involving two and three ferromagnesian solid solutions illustrates the potential of these equilibria as Pressure-Temperature indicators. Interactions between solid-solid reactions and dehydration reactions involving biotite in the system MgO-FeO-Al₂O₃-SiO₂-K₂O-H₂O have been graphically analysed. The addition of biotite to anhydrous divariant assemblages does not affect the composition of coexisting phases at constant P and T but can affect their relative proportions.     

The stability of sapphirine-quartz and hypersthene-sillimanite-quartz assemblages: an experimental investigation in the system FeO−MgO−Al2O3−SiO2 under H2O and CO2 conditions

Phase relations and mineral chemistry involving the phases garnet (Gt), spinel (Sp), hypersthene (Hy), sapphirine (Sa), cordierite (Cd), sillimanite (Sil) and quartz (Qz) have been experimentally determined in the system FMAS (FeO−MgO−Al₂O₂−SiO₂) under low fO₂ and for various H₂O/CO₂ conditions. Several compositions were studied with 100 (Mg/Mg+Fe) ratio ranging from 64 to 87 with excess quartz and sillimanite. Our data do not show any differences in Gt−Cd stability and composition as a function of H₂O, CO₂ and H₂O−CO₂ (±CH₄) content, in good agreement with a previous experimental study at lower temperature (Aranovich and Podlesskii 1983). At 1,000° C and 11 kbar, under CO₂-saturated conditions, cordierite grew from a crystalline mix unseeded with cordierite. Thus, under water-absent conditions, cordierite will have a high-P stability field in the presence of CO₂. If water has a pressure stabilizing effect on cordierite, then our results would indicate that the effects of H₂O and CO₂ are of the same magnitude at high temperature. Our data support the theoretical P-T grid proposed by Hensen (1986) for high-T metapelites and are largely consistent with the high-temperature experimental data of Hensen and Green (1973). The univariant boundary Gt+Cd=Hy+Sil+Qz, which marks the disappearance of Hy−Sil−Qz assemblages, has a negative dP/dT slope above 1,000° C and a positive one below this temperature. Extrapolation of our data to iron-free systems shows that the high-P breakdown limit of Mg-cordierite has a negative slope in the range 1,025–1,300° C and probably positive below 1,000° C. This indicates a maximum of stability for Mg-cordierite at around 1,000° C and 13 kbar. Because of the curvature of the univariant reactions En+Sil=Py+Qz, Mg−Cd=En+Sil+Qz and Gt+Cd=Hy+Sil+Qz, the iron-free invariant point involving the phases Py, En, Cd, Sil and Qz probably does not exist. Sapphirine—Qz-bearing assemblages are stable only at temperatures above 1,050° C. At 1,075° C, the joint Gt−Sa is stable up to 11 kbar. At higher pressure, garnet, sapphirine and quartz react according to the reaction Gt+Sa+Qz=Hy+Sil. Reequilibrated sapphirines are more aluminous than the theoretical endmember Mg₂Al₄SiO₁₀ due to AlAl=MgSi substitutions [100(Al₂O₃/Al₂O₃+FeO+MgO) in experimental sapphirines ranges from 50.5 to 52.2]. Sapphirine in the assemblage Sa−Cd−Sil−Qz shows a decrease in Al content with decreasing temperature and pressure, such that the alumina isopleths for sapphirine have a slight negative dP/dT slope. A similar decrease in Al content of sapphirine with temperature is also observed in Sa−Sil−Qz assemblages.     

P-T grids for silica-undersaturated granulites in the systems MAS (n+ 4) and FMAS (n+ 3)-tools for the derivation of P-T paths of metamorphism

Abstract Considering the minerals cordierite (Cd), sapphirine (Sa), hypersthene (Hy), garnet (Ga), spinel (Sp), sillimanite (Si) and corundum (Co) in the system FeO-MgO-Al₂O₃-SiO₂ (FMAS), the stable invariant points are [Co], [Ga], [Cd] and [Sa]. Constraints imposed by experimental data for the system MAS indicate that under low P _H2o conditions the invariant points occur at high temperature (> 900° C) and intermediate pressure (7-10 kbar). This temperature is higher than that commonly advocated for granulite facies metamorphism. In granulites Fe-Mg exchange geothermometers may yield temperatures of 100–150° C below peak metamorphic conditions and evidence for peak temperatures is best preserved by relict high-temperature assemblages and by Al-rich cores in orthopyroxene. Application of the FMAS grid to some well-documented granulite occurrences introduces important constraints on their P-T histories. Rocks of different bulk compositions, occurring in close proximity in the field, may record distinct segments of their P-T paths. This applies particularly to rocks with evidence for reaction in the form of coronas, symplectites and zoned minerals. Consideration of curved reaction boundaries and _XMs isopleths may explain apparently contradictory results for the stability of cordierite obtained from low-temperature experiments and thermochemical calculations on the one hand and hightemperature experimental data on the other.     

假蓝宝石(Sapphirine)的矿物学特征及其在超高温变质作用研究中的应用

假蓝宝石是Mg-Al质麻粒岩中一种特殊的高温矿物,对超高温变质作用的研究有重要的意义。本文通过对全球66个超高温麻粒岩中47个含假蓝宝石麻粒岩地区的文献调研,总结了几种最常见的含假蓝宝石矿物组合产出的结构位置和变质反应关系,以及假蓝宝石的矿物化学特征。假蓝宝石的化学成分一般位于7∶9∶3端元左右,X_(Mg)大于0. 7,XFe_(3+)变化范围很宽,为0～0. 7。含假蓝宝石矿物组合的形成和演化指示了岩石经历的P-T轨迹。岩石中保留的假蓝宝石取代尖晶石、Grt/Opx+Sil取代Spr+Qz组合,以及随后的Spr+Crd±Opx后成合晶取代Grt/Opx+Sil组合的结构,一般可能指示了逆时针P-T轨迹中冷却和随后减压的部分;岩石中Grt/Opx+Sil/Ky或富Mg十字石反应形成Spr+Qz组合的结构可能指示了顺时针P-T轨迹中减压升温的部分。超高温变质岩不同的P-T轨迹暗示着它们的成因机制并不单一,前者可能是幔源基性岩浆底侵或增生作用的结果,后者可能与长期的热造山作用相关。     

Pressure-temperature and evolution of fluid compositions of Al2SiO5-bearing rocks,Mica Creek,B.C., in light of fluid inclusion data and mineral equilibria

Metamorphosed pelitic rocks from Mica Creek, British Columbia contain sillimanite, kyanite with minor fibrolite and andalusite-bearing quartz pods. Mineral equilibria were used to infer peak P-T conditions and fluid compositions in equilibrium with the solid phases. Fluid inclusions in three schist samples appear to be good indicators of conditions affecting those rocks during and after peak metamorphic conditions. In samples from two localities, fluid inclusions from schist and quartz-rich segregations have densities appropriate to the peak metamorphic conditions. The observed compositions for these fluids (low salinity with 12 mole % dissolved CO₂) agree with calculated values of 0.84 to 0.85, based upon paragonite-quartz-albite-Al₂SiO₅ equilibria. The fluids unmixed as the schists were uplifted and cooled; fluid inclusions trapped during this stage outline a solvus in the CO₂-H₂O-NaCl system. A later influx of fluids containing CH₄ and N₂ accompanied formation of andalusite-bearing plagioclaserich segregations. The restricted association of andalusite-bearing pods and low density fluids suggest a localized but pervasive fluid influx during uplift. Preservation of high density fluid inclusions during uplift and erosion, coupled with evidence for unmixing of H₂O- and CO₂-rich fluids on the solvus, provide constraints on the P-T uplift path.     

Sapphirine bearing granulites from the Sipiwesk Lake area of the late Archean Pikwitonei granulite terrain,Manitoba, Canada

Sapphirine occurs in the orthopyroxene-cordierite and feldspar-sillimanite granulites in the Sipiwesk Lake area of the Pikwitonei granulite terrain, Manitoba (97°40W, 55°05N). The orthopyroxene-cordierite granulites have extremely high Al₂O₃ (24.5 wt%) and MgO (24.6 wt%) contents and contain sapphirine (up to 69.2 wt% Al₂O₃), aluminous orthopyroxene (up to 8.93 wt% Al₂O₃), cordierite, spinel, phlogopite, and corundum. Sapphirine forms coronas mantling spinel and corundum. Corona sapphirine is zoned and its composition varies through the substitution (Mg, Fe, Mn) Si=2 Al as a function of the phases with which it is in contact. Textural and chemical relationships of sapphirine with coexisting phases indicate that spinel + cordierite reacted to form orthopyroxene + sapphirine under conditions of increasing pressure. Moreover, decreasing core to rim variation of Al₂O₃ in orthopyroxene porphyroblasts suggests decreasing temperature during sapphirine formation. On the basis of experimentally determined P-T stability of the assemblage enstatite + sapphirine + cordierite, and the Al content of hypothetical Fe²⁺-free orthopyroxene associated with sapphirine and cordierite, metamorphic temperatures and pressures are estimated to be 860–890° C and 3.0–11.2 kbar.In the feldspar-sillimanite granulites, sapphirine occurs as a relict phase mantled by sillimanite and/or by successive coronas of sillimanite and garnet. These textural relations suggest the reaction sapphirine + garnet + quartz = orthopyroxene + sillimanite with decreasing temperature. Compositions of minerals in the assemblage garnet-orthopyroxene-sillimanite-plagioclase-quartz, indicate metamorphic P-T conditions of 780–880° C and 9±1 kb.The metamorphic conditions estimated in this study suggest that the sapphirine bearing granulites in the Sipiwesk Lake area represent Archean lower crustal rocks. Their formation might be related to the crustal thickening processes in this area as suggested by Hubregtse (1980) and Weber (1983).     

Osumilite-bearing Granulites in the Eastern Grenville Province, Eastern Labrador, Canada: Mineral Parageneses and Metamorphic Conditions

Osumilite-bearing metasedimentary gneiss occurs in the contactaureole of the Sand Hill Big Pond gabbronorite complex of Labradorianage in eastern Grenville Province, eastern Labrador, Canada.The osumilite (Os) occurs in association with cordierite (Cd),orthopyroxene (Opx), sillimanite (Sil), sapphirine (Sa), spinel(Sp), K-feldspar (Kf), plagioclase (PI), phlogopite (Ph), hematite(Hm),magnetite (Mt), corundum (Co), and quartz (Q) in zones adjacentto the gabbronorite intrusion. The osumilite-in isogard is delineatedat a distance of 1-3km from the intrusive contact. The osumiliteis characterized by enhanced Mg/(Mg + Fe) ratios (0.89-0.92)and relatively high K₂O contents (4. 13-4.78 wt. % ) The compositionalvariation of the osumilite is best understood by the substitutions(Mg+Fe+Mn)+St=2A1 and (K+Na)+(Mg +Fe+Mn)=Al+vacancy. Symplectiticintergrowth of Opx-Cd-Kf-Q, which partly of completely replacedosumilite, is ubiquitously present. The stable osumilite-bearingassemblages (all with Hm, Mt, and P1) deduced from petrographicfeatures and from the phase relations in the KMAS system areOs-Sa-Cd, Os-Cd-Sil-Q, Os-Cd-Kf-Q, Os-Cd-Opx-Q, and Os-Opx-Kf-Q.The saphirine-bearing assemblages are restricted to silica-deficient(quartz-absent) zones of the gnesis, which include Sa-Os-Cd,Sa-Sil-Cd, Sa-Opx-Sp, Sa-Sp-Cd, and Sa-Sp-Co. Orthopyroxenecoronas mantling phologite reflect the breakdown reaction Ph+ Q= Opx+Kf+vapor under extremely low water activity in thevapour. Petrogenetic grids in MAS, KMAS, and KMAS-H₂O-CO₂appropriateto the mineral assemblages in the metasedimentary gneisses suggestthat the changes of the mineral assemblages in the area studiedreflect dehydration reactions Ph+Sil+Q=Cd+Kf+V and Ph+Q=Opx+Kf+V, and osumilite and sapphirine-forming reactions Opx+Cd+Kf+Q=Os,Cd+Kf+Q=Os+Sil+, Opx+Sil+Kf=Os+Sa, and Opx+Sil =Sa+ Cd. Relativelyhigh Mg/(Mg+Fe²⁺) (0. 64-0.88) in the whole-rock compositionand high oxygen fugacity (near hematite-magnetite buffer), togetherwith exceptionally high temperature ( 1000?C) and extremelylow water activity (0.2) at peak meta-morphic conditions mightstabilize the osumilite- and sapphirine-bearing assemblagesat middle or lower crustal levels. Relatively low water activityis probably caused by the relatively dry precursor, which hadbeen metamorphosed at upper amphibolite facies metamorphic conditionsbefore gabbronorite emplacement.     

P-T-X Relationships Deduced from Corona Textures in Sapphirine--Spinel--Quartz Assemblages from Paderu, Southern India

The sapphirine (Sa)-spinel (Sp)-quartz (Qz)-bearing rocks fromPaderu occur as lenticular enclaves within the Precambrian khondalite-charnockiteterrane of southern India. In addition these rocks contain orthopyroxene(Opx), sillimanite (Sill), garnet (Gt), cordierite (Cd), biotite,potash feldspar (Kf), plagioclase, and symplectites of Cd-Kf-Qz-Opx.The symplectites may have formed from the breakdown of osumilite.Grain contacts of sapphirine and spinel with quartz are rarelyobserved and the incompatibility with quartz during later stagesis displayed by the development of several types of polymineralicreaction coronas. The coronas in the different rock types A,B, etc. are (minerals listed from core to rim of corona): (A-1) sapphirine-bearing rock type without spinel: Sa-Sill-Opx,Sa-Sill-Cd, Sa-Cd-Opx (A-2) sapphirine and spinel-bearing: Sp-Sa-Sill-Opx-Qz, Sp-Sa-Sill,Sp-Sa-Opx, Sp-Sill-Opx, Sp-Sa-Sill-Gt-Qz, Sa-Sill-Opx, Sp-Sa-Sill-Opx,Sa-Sill-Opx-Gt, Sp-Sa-Opx-Gt, Sp-Sa-Sill-Gt; and (B) spinel-bearingbut sapphirine free: Sp-Sill-Opx, Sp-Sill-Gt, Sp-Cd. Commonlythe coronas in the rock type A 2 and B also contain ilmeno-hematite?corundumin the core in association with spinel. These rock types alsoprovide textural evidence for later crystallization of Cd, Cd+ Sa, and Gt + Qz from Opx+Sill?Qz and Gt+Sill+Qz. Sapphirine is aluminous (near 7(Mg, Fe²⁺)O?9(Al, Fe³⁺)₂O₃?3SiO₂)and contains up to 12?2 wt. per cent iron as FeO. Orthopyroxeneis also aluminous, containing up to 10?4 wt. per cent Al₂O₃.Sapphirine and spinel have relatively high contents of Fe₂O₃.X_Mg in the Fe-Mg minerals increases from rock type B to A2 toA1. A sequence of reactions has been deduced from coronas and otherreaction textures, and from the phase compatibility relationsin the FeO-MgO-Al₂O₃-SiO₂-H₂O system. The P-T-X relationshipsfrom geothermobarometry and petrogenetic grids, viz. µ_Fe2O3vs. µ_FeO and µ_H2O vs. µ_Fe2O3, suggest: (1)a retrograde, mildly decompressive trajectory from 900?60?C/65?0?7kb (core) to 760?50?C/5 ? 0?6 kb (rim); and (2) the observedmineralogy of the coronas and reactions deduced from them aredependent on the relative FeO, Fe₂O₃, and H₂O contents of therocks (µ_FeO3, µ_Fe2O3), and µ_H2O).     

Petrology of spinel granulites from Araku, Eastern Ghats, India, and a petrogenetic grid for sapphirine-free rocks in the system FMAS

Abstract Spinel-quartz-cordierite and spinel-quartz are found as relic prograde assemblages in Fe-rich granulites from the Araku area, Eastern Ghats belt, India. Subsequent reactions produced orthopyroxene + sillimanite in the former association and garnet + sillimanite in the latter. The first reaction is univariant in the FMAS system, but is trivariant in the present case because of the presence of Zn and Fe³⁺ in spinel. The second reaction also has high variance because of Zn and Fe³⁺, but also because of the presence of Ca in garnet. Thermobarometry shows that the metamorphic conditions were approximately 950° C and 8.5 kbar and the fo ₂ was near the NNO buffer. In Fe-rich bulk compositions and low- P -high- T conditions of metamorphism, two of the univariant reactions around the invariant point [Sa], namely (Sa, Hy) and (Sa, Cd), change topology due to reverse partitioning of Fe-Mg between coexisting garnet and spinel. An alternative partial petrogenetic grid in the system FMAS is constructed for such conditions and is applied satisfactorily to several sapphirine-free spinel granulites. It is shown that bulk composition ( X _Fe and Zn) exerts greater control on the stability of spinel + quartz than fo ₂. The effect of the presence of Zn and Fe³⁺ in spinel on the proposed grid is evaluated. Reaction textures in the Araku spinel granulites can be explained from the petrogenetic grid as due to near-isobaric cooling.     

Solubility of Ca and Al in orthopyroxene from spinel peridotite: an improved version of an empirical geothermometer

Geothermometric equations for spinel peridotites by Fujii (1976), Gasparik and Newton (1984), and Chatterjee, and Terhart (1985) based on the reaction enstatite (en)+spinel (sp)Mg–Tschermaks (mats)+forsterite (fo) were tested using a nearly isothermal suite of mantle xenoliths from the Eifel, West Germany. In spite of using activities of MgAl₂O₄, en, and mats to allow for the non-ideal solution behaviour of the constituent phases, temperatures calculated from these equations systematically change as a function of Cr/(Cr+AL+Fe³⁺) in spinel. We propose an improved version of the empirical geothermometer for spinel peridotites of Sachtleben and Seck (1981) derived from the evaluation of the solubilities of Ca and Al in orthopyroxene from more than 100 spinel peridotites from the Rhenish Volcanic Province. A least squares regression yielded a smooth correlation between

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.

Ferric iron partitioning between plagioclase and silicate liquid: thermodynamics and petrological applications

A series of Fe and Mg partition experiments between plagioclase and silicate liquid were performed in the system SiO₂-Al₂O₃-Fe₂O₃-FeO-MgO-CaO-Na₂O under oxygen fugacities from below the IW buffer up to that of air. A thermodynamic model of plagioclase solid solution for the (CaAl,NaSi,KSi)(Fe³⁺,Al³⁺)Si₂O₈-Ca(Fe²⁺,Mg)Si₃O₈ system is proposed and is calibrated by regression analysis based on new and previously reported experimental data of Fe and Mg partitioning between plagioclase and silicate liquid, and reported thermodynamic properties of end members, ternary feldspar and silicate liquid. Using the derived thermodynamic model, FeO^t, MgO content and Mg/(Fe^t+Mg) in plagioclase can be predicted from liquid composition with standard deviations of ǂ.34 wt% (relative error =9%) and ǂ.08 wt% (14%) and ǂ.7 (8%) respectively. Calculated Fe³⁺-Al exchange chemical potentials of plagioclase, m_{Fe^{3 +} ( Al )- 1} ^Pl{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Pl}} agree with those calculated using reported thermodynamic models for multicomponent spinel, m_{Fe^{3 +} ( Al )- 1} ^Sp{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Sp}} and clinopyroxene, m_{Fe^{3 +} ( Al )- 1} ^Cpx{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Cpx}} . The FeO^t content of plagioclase coexisting with spinel or clinopyroxene is affected by Fe³⁺/(Fe³⁺+Al) and Mg/(Fe+Mg) of spinel or clinopyroxene and temperature, while it is independent of the anorthite content of plagioclase. Three oxygen barometers based on the proposed model are investigated. Although the oxygen fugacities predicted by the plagioclase-liquid oxygen barometer are scattered, this study found that plagioclase-spinel-clinopyroxene-oxygen and plagioclase-olivine-oxygen equilibria can be used as practical oxygen barometers. As a petrological application, prediction of plagioclase composition and f_O2 are carried out for the Upper Zone of the Skaergaard intrusion. The estimated oxygen fugacities are well below QFM buffer and consistent with the estimation of oxidization states in previous studies.     

Petrology of garnet — cordierite — sillimanite gneisses from the El Tormes thermal dome,Iberian Hercynian foldbelt (W Spain)

The core of the El Tormes thermal dome, situated in the central part of one of the main metamorphic belts of the Iberian Peninsula, is formed by garnet-cordierite-biotite-sillimanite pelitic gneisses. These rocks, that very often are cut by minor intrusions of Al-rich S-type granites, are metatexitic gneisses in which there exists garnet showing different stages of resorption and transformation into an aggregate of cordierite±plagioclase±biotite. The garnet, mantled and corroded mainly by cordierite, has never been found to occur in contact with the prismatic sillimanite of the matrix, thus indicating that the continuous reaction Gr+Sill+Q = Cd has taken place. The presence of corroded biotite inside the garnet-rimming cordierite of the aggregates as well as inside the cordierite of the matrix, which usually includes remmants of sillimanite, indicates that the continuous reaction Bi+Sill+Q = Cd+FK+H₂O has occurred too. Therefore, a realistic net reaction for these aggretates should be represented by the univariant, at a given , equilibrium: Biotite+Sillimanite+Garnet+Quartz = Cordierite+K-feldspar+H₂O (1)The important garnet resorption near the anatectic granitic veins implies that this process is favoured by a decrease in , this factor being otherwise buffered by the reaction (1) assemblage.The most probable P-T path, assuming these conditions, consistent with the AFM projection of the former (inferred) and present assemblages in the aggregates and in the matrix, implies a decrease in P coeval with a decrease in T (Fig. 4, path 2).The most reliable P-T determination for the final stage of garnet breakdown through reaction (1), based on the coexistence of the seven phase assemblage garnet — cordierite — biotite — sillimanite — plagioclase — potash feldspar — quartz plus melt, gives 695° C, 4.3 kbar, = 0.5, The maximum pressure for this process, obtained from the garnet — plagioclase equilibrium, is 6.5±1 kbar at the same temperature.The estimates of the T for the garnet core-garnet included biotite pairs are consistently lower, ca. 550° C, than those obtained for the garnet rim-biotite in aggregates, ca. 645° C, or garnet rim-adjacent cordierite pairs, ca. 695° C.It may, therefore, be supposed that, during their evolution these rocks underwent first an increase in T and then, during the last stages, as garnet and biotite brokedown, a decrease in P and T. This represents an uplift of the core of El Tormes dome under high grade amphibolite to low pressure granulite facies conditions, accompanied by a process of partial melting with local decrase in . It is suggested, from mineral growth-deformation relationships, that this process took place during the late hercynian deformation phases, P-3 or doming stage.     

Optimized standard state and solution properties of minerals

 An internally consistent set of standard state and mixing properties has been derived for olivine, orthopyroxene, garnet, cordierite, and ilmenite in the system FeO-MgO-CaO-Al₂O₃-TiO₂-SiO₂-H₂O from analysis of relevant phase equilibrium and thermophysical data. Solubility of Al₂O₃ in orthopyroxene is accounted for in addition to Fe-Mg mixing. Added confidence in the retrieved properties stems from the representation within reasonable uncertainties of data for seven linearly dependent Fe-Mg exchange equilibria, as well as net transfer equilibria, among the above phases. Critical to successful analysis was the extension of the mathematical programming technique to include bulk composition constraints which force an observed assemblage of fixed composition to be stable at experimentally studied conditions. The final optimization reproduces the extremely tight constraints on endmember properties while invoking very simple macroscopic solution models that afford an excellent opportunity for extrapolation beyond the data considered in this study. Compatibility among the experimental data is improved markedly by incorporation of recently published C_p data on pyrope and forsterite. Electrochemical data defining the oxygen fugacity of Fe-Fa-Qz, Fa-Mt-Qz, and Mt-Hm allow excellent compatibility of almandine thermochemical properties derived from phase equilibrium data obtained at both reducing (Fe-Wst) and oxidizing (Hm-Mt) conditions. Analysis of the combined data involving endmembers and solid solutions removes many of the ambiguities in mixing property magnitudes that arise in analyses of more restricted sets of data. In addition, the consideration of the solid solution data allows further refinement of some endmember properties. Nonideal mixing parameters, although correlated, are well defined by the combination of experimental data, with GOlex>GIlmex>GGtex >GOpxex>GCdex, and 0.7<WOlG<4.1 kJ/atom of isomorphous Fe-Mg at 1000 K. Experiments defining the Al₂O₃ solubility of Opx in equilibrium with Gt and Cd+Qz define negative Fe-Al interactions that have an important effect on Fe-Mg partitioning in Opx. Applications of this data set to high-grade metamorphic rocks are described in a companion paper, published as part II of the present work. Received: 14 September 1994 / Accepted: 20 March 1996     

Thermodynamic mixing properties of Mg(Al,Cr)2O4 spinel crystalline solution at high temperatures and pressures

Three Al-Cr exchange isotherms at 1,250°, 1,050°, and 796° between Mg(Al, Cr)₂O₄ spinel and (Al, Cr)₂O₃ corundum crystalline solutions have been studied experimentally at 25 kbar pressure. Starting from gels of suitable bulk compositions, close approach to equilibrium has been demonstrated in each case by time studies. Using the equation of state for (Al, Cr)₂O₃ crystalline solution (Chatterjee et al. 1982a) and assuming that the Mg(Al, Cr)₂O₄ can be treated in terms of the asymmetric Margules relation, the exchange isotherms were solved for Δ G ^*, and . The best constrained data set from the 1,250° C isotherm clearly shows that the latter two quantities do not overlap within three standard deviations, justifying the choice of asymmetric Margules relation for describing the excess mixing properties of Mg(Al, Cr)₂O₄ spinels. Based on these experiments, the following polybaric-polythermal equation of state can be formulated: , P expressed in bars, T in K, G _m ^ex and W _G,i ^Sp in joules/mol. Temperature-dependence of G _m ^ex is best constrained in the range 796–1,250° C; extrapolation beyond that range would have to be done with caution. Such extrapolation to lower temperature shows tentatively that at 1 bar pressure the critical temperature, T _c, of the spinel solvus is 427° C, with dT_c/dP≈1.3 K/kbar. The critical composition, X _c, is 0.42 , and changes barely with pressure. Substantial error in calculated phase diagrams will result if the significant positive deviation from ideality is ignored for Al-Cr mixing in such spinels.     

A redox profile of the Slave mantle and oxygen fugacity control in the cratonic mantle

The authors report a redox profile based on Mössbauer data of spinel and garnet to a depth of 210 km from mantle xenoliths of the northern (N) and southeastern (SE) Slave craton (northern Canada). The profile transects three depth facies of peridotites that form segments of different bulk composition, represented by spinel peridotite, spinel–garnet peridotite, low-temperature garnet peridotite, high-temperature garnet peridotite, and pyroxenite. The shallow, more depleted N Slave spinel peridotite records lower oxygen fugacities compared to the deeper, less depleted N Slave spinel–garnet peridotite, consistent with their different spinel Fe³⁺ concentrations. Garnet peridotites show a general reduction in log fO₂ (FMQ)s with depth, where values for garnet peridotites are lower than those for spinel–garnet peridotites. There is a strong correlation between depletion and oxygen fugacity in the spinel peridotite facies, but little correlation in the garnet peridotite facies. The strong decrease in log fO₂ (FMQ) with depth that arises from the smaller partial molar volume of Fe³⁺ in garnet, and the observation of distinct slopes of log fO₂ (FMQ) with depth for spinel peridotite compared to spinel–garnet peridotite strongly suggest that oxygen fugacity in the cratonic peridotitic mantle is intrinsically controlled by iron equilibria involving garnet and spinel.

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The mobility of U and Th in subduction zone fluids: an indicator of oxygen fugacity and fluid salinity

The solubility of U and Th in aqueous solutions at P-T-conditions relevant for subduction zones was studied by trapping uraninite or thorite saturated fluids as synthetic fluid inclusions in quartz and analyzing their composition by Laser Ablation-ICPMS. Uranium is virtually insoluble in aqueous fluids at Fe-FeO buffer conditions, whereas its solubility increases both with oxygen fugacity and with salinity to 960 ppm at 26.1 kbar, Re-ReO₂ buffer conditions and 14.1 wt% NaCl in the fluid. At 26.1 kbar and 800°C, uranium solubility can be reproduced by the equation: log\textU = 2.681 + 0.1433logf\textO₂ + 0.594\textCl, \log {\text{U}} = 2.681 + 0.1433\log f{\text{O}}_{2} + 0.594{\text{Cl,}} where fO₂ is the oxygen fugacity, and Cl is the chlorine content of the fluid in molality. In contrast, Th solubility is generally low (<10 ppm) and independent of oxygen fugacity or fluid salinity. The solubility of U and Th in clinopyroxene in equilibrium with uraninite and thorite was found to be in the order of 10 ppm. Calculated fluid/cpx partition coefficients of Th are close to unity for all conditions. In contrast, D^fluid/cpx for uranium increases strongly both with oxygen fugacity and with salinity. We show that reducing or NaCl-free fluids cannot produce primitive arc magmas with U/Th ratio higher than MORB. However, the dissolution of several wt% of oxidized, saline fluids in arc melts can produce U/Th ratios several times higher than in MORB. We suggest that observed U/Th ratios in arc magmas provide tight constraints on both the salinity and the oxidation state of subduction zone fluids.     

The interpretation of reaction textures in Fe‐rich metapelitic granulites of the Musgrave Block,central Australia: constraints from mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

Fe‐rich metapelitic granulites of the Musgrave Block, central Australia, contain several symplectic and coronal reaction textures that post‐date a peak S2 metamorphic assemblage involving garnet, sillimanite, spinel, ilmenite, K‐feldspar and quartz. The earliest reaction textures involve spinel‐ and quartz‐bearing symplectites that enclose garnet and to a lesser extent sillimanite. The symplectic spinel and quartz are in places separated by later garnet and/or sillimanite coronas. The metamorphic effects of a later, D3, event are restricted to zones of moderate to high strain where a metamorphic assemblage of garnet, sillimanite, K‐feldspar, magnetite, ilmenite, quartz and biotite is preserved. Quantitative mineral equilibria calculations in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) using Thermocalc 3.0 and the accompanying internally consistent dataset provide important constraints on the influence of TiO₂ and Fe₂O₃ on biotite‐bearing and spinel‐bearing equilibria, respectively. Biotite‐bearing equilibria are shifted to higher temperatures and spinel‐bearing equilibria to higher pressures and lower temperatures in comparison to the equivalent equilibria in K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH). The sequence of reaction textures involving spinel is consistent with a D2 P–T path that involved a small amount of decompression followed predominantly by cooling within a single mineral assemblage stability field. Thus, the reaction textures reflect changes in modal proportions within an equilibrium assemblage rather than the crossing of a univariant reaction. The D3 metamorphic assemblage is consistent with lower temperatures than those inferred for D2.     

The bearing of the system CaMgSi2O6CaAl2SiO6CaFeAlSiO6 on fassaitic pyroxene

The system CaMgSi₂O₆CaAl₂SiO₆CaFeAlSiO₆ has been studied in air at 1 atm. The phase assemblage at subsolidus temperatures in the CaMgSi₂O₆-rich portion is Cpx + An + Mel and that in the CaMgSi₂O₆-poor portion Cpx + An + Mel + Sp. At subsolidus temperatures the sigle-phase field of clinopyroxene increases with an increase in the CaFeAlSiO₆ component of the system. The Al₂O₃ content of clinopyroxene, however, continues to increase beyond the single-phase field and attains at least 16.04 wt.% Al₂O₃ with 3.9 wt.% Fe₂O₃. The stability field of fassaite in the system over a range of pressures and oxygen fugacities has been estimated from data in the literature as well as the present data. The CaFeAlSiO₆ content of fassaite is dependent on oxygen fugacity, but is not influenced by pressure. The stability field is strongly influenced by oxygen fugacity at low and high pressure, and decreases with decreasing oxygen fugacity. Clinopyroxenes in both volcanic and metamorphic rocks from various localities, when plotted on the CaMgSi₂O₆CaAl₂SiO₆CaFeAlSiO₆ triangle, show that there is no compositional gap between diopside and fassaitic pyroxene in metamorphic rocks, and that the fassaitic pyroxene in alkalic rocks becomes richer in both CaAl₂SiO₆ and CaFeAlSiO₅ components as crystallization proceeds. These results agree with those obtained in the experimental study.     

Ulvöspinel in native iron-bearing assemblages and the origin of these assemblages in basalts from Ovifak,Greenland, and Bühl,Federal Republic of Germany

Euhedral crystals of ulvöspinel are found in many of the native-iron-bearing xenoliths from the basalt of Bühl near Kassel (West Germany) and Ovifak on Disko Island (West Greenland). The typical assemblage of these xenoliths at both localities is: native Fe, troilite, cohenite, ulvöspinel, ilmenite, olivine, and plagioclase, as well as silicate glass containing droplets of former Fe and troilite melt. The ulvöspinel subsolidus textures and intergrowths also indicate identical cooling histories for the xenoliths in both cases. Ulvöspinel crystallized after the formation of iron, but still above the Fe-FeS eutectic at 988° C. A subsequent strong drop in oxygen fugacity revealed partial breakdown of ulvöspinel according to the reaction .Microprobe analyses of a Bühl xenolith indicate that ulvöspinel contains up to 4.7 w.t.% MnO, while olivine compositions correspond to Fa_64–74Fo_12–24Te_12–15. The entire xenolith contains 1.9 w.t.% MnO. This fact, together with the geological evidence and the occurrence of corroded quartz relicts within some of the xenoliths provides clear evidence for reduction under near-surface conditions in a blast-furnace-like process. The reducing agent was coal from the Tertiary seams cut by the erupting basalt, while the xenolith source material most probably was spherosiderite, which is very common in the coals and would explain the high MnO content. Consequently, the presence of cohenite is not necessarily an indicator of high pressure.The analogies between the Bühl and Ovifak localities and their xenoliths strongly suggest a similar formation through near surface reduction and not derivation from the mantle.