Enthalpies of formation at 970 K of compounds in the system MgO-Al2O3-SiO2 from high temperature solution calorimetry

The enthalpies of solution of petrologically important phases in the system MgO-Al₂O₃-SiO ₂ were measured in a melt of composition 2PbO · B₂O₃ at 970 ± 2K. The substances investigated included synthetic and natural (meteoritic) enstatite (MgSiO₃), synthetic aluminous enstatite (MgSiO_30.9Al₂O_30.1), synthetic and natural cordierite (Mg₂Al₄Si₅O₁₈), synthetic and natural sapphirine (approx. 7MgO·9Al₂O₃ · 3SiO₂), synthetic spinel (MgAl₂O₄), natural sillimanite (Al₂SiO₅), synthetic forsterite (Mg₂SiO₄), synthetic pyrope (Mg₃Al₂Si₃O₁₂), natural quartz (SiO₂), synthetic periclase (MgO) and corundum (Al₂O₃). Improvement in standardization of the calorimeter solvent made possible greater precision in this study than obtainable in former work in this laboratory on some of the same substances.The enthalpies of formation of enstatite, synthetic cordierite, forsterite and spinel are in reasonable agreement with values previously determined by solution calorimetry. The enthalpy of formation of enstatite is about 0.7 kcal less negative than the value for clinoenstatite resulting from the HF calorimetry of Torgesen and Sahama (J. Amer. Chem. Soc.70. 2156–2160, 1948), and is in accord with predictions based on analysis of published pyroxene equilibrium work. Aluminous enstatite with 10 wt.% Al₂O₃ shows an enthalpy of solution markedly lower than pure MgSiO₃: the measurements lead to an estimate of the enthalpy of formation at 970 K for MgAl₂SiO₆ (Mg-Tschermak) orthopyroxene of + 9.4 ± 1.5 kcal/mole from MgSiO₃ and Al₂O₃.Comparison of the enthalpies of formation of synthetic cordierite and anhydrous natural low-iron cordierite shows that they are energetically quite similar and that the synthetic cordierite is not likely to have large amounts of (Al, Si) tetrahedral disorder. Comparison of the enthalpies of formation of synthetic sapphirine and natural low-iron sapphirine shows, on the other hand, that the former is not a good stability model for the latter. The lower enthalpy of formation of the high-temperature synthetic sample is undoubtedly a consequence of cation disordering.The enthalpy of formation of natural sillimanite is considerably less negative than given by the tables of Robie andWaldbaum (U.S. Geol. Surv. Bull.1259 1968).The measured enthalpy of formation of synthetic pyrope is consistent with that deduced from published equilibrium diagrams in conjunction with the present measured enthalpy of formation of aluminous enstatite. Calculation of the entropy of synthetic pyrope from the present data yields surprisingly high values and suggests that synthetic pyrope is not a good stability model for natural pyrope-rich garnets. Hence, considerable doubt exists about the direct quantitative application of experimental diagrams involving pyropic garnet to discussions of the garnet stability field in the Earth's outer regions.     

U–Cr-rich high Mg-Al granulites from Karimnagar Granulite Belt, India: implications for Neoarchean-Paleoproterozoic events in southern India

High Mg-Al granulite occurs as enclave within granite gneisses at Karimnagar, southern India, and it contains coarse granoblastic aggregates of orthopyroxene and sapphirine with minor amount of cordierite, spinel and phlogopite. An important chemical characteristic of these minerals is their extremely high MgO content and the high Cr₂O₃ in sapphirine and spinel. Textural analysis shows sapphirine + orthopyroxene + cordierite as the peak-metamorphic assemblage that possibly evolved though the breakdown of a spinel-bearing assemblage. Cation exchange geothermometers involving orthopyroxene, sapphirine and spinel yield temperatures of 600–800 °C with a maximum of 860 °C implying an event of high temperature (HT) metamorphism. Pseudosection analysis in the FeO–MgO–Al₂O₃–SiO₂ chemical system shows the stability of the peak- assemblage below 6.2 kbar. Subsequently, the rock underwent hydration and cooling with the appearance of phlogopite in the assemblage. Chromium enrichment is possibly inherited from the protolith and its presence presumably stabilized sapphirine and spinel below their high-temperature stability field. The recorded Rb–Sr age of ca. 2,500 Ma in host granite gneiss marks the upper age limit of HT metamorphism. Presence of patchy, lobate grains as well as veinlets of uraninite and brannerite is also a characteristic feature of the rock. Uranium mineralization took place during the post peak metamorphic stage, sulfide mineralization represented by tiny grains and veinlets of pyrite, millerite and pentlandite coincided with, and outlasted the uranium mineralization. The U–Th–Pb chemical ages of uraninite grains suggest ca. 2,200?±?12 Ma for the age of uranium mineralization in the granulite. Based on the field relations, it is surmised that the granulite metamorphism in the study area is older than ca. 2,500 Ma and is comparable with an event in the other parts of Eastern Dharwar Craton. It can be conceived as a widespread event in southern India.     

The stability of osumilite in high grade metamorphic rocks

Osumilite, approximate composition K(Mg,Fe)₂ Al₅Si₁₀O₃₀, has been reported recently from two granulite localities. The mineral has been synthesised in a model pelitic composition at 1000 and 1100 ° C and 3.6–6.3 kb under conditions of low water and oxygen fugacity. Osumilite coexists, apparently stably, with hypersthene, cordierite and quartz (?) thus duplicating the mineral assemblage of one of the natural occurrences. Osumilite is in a divariant reaction relationship with cordierite and hypersthene i.e. osumilite ? cordierite + hypersthene + orthoclase+quartz. This reaction runs to the right with increasing pressure. Experimental data and field observations suggest that the joins osumilite-garnet and osumilite-sillimanite are not stable. It is suggested osumilite is involved in an invariant point in the system K₂O-MgO-FeO-A1₂O₃-SiO₂ with the phases cordierite, hypersthene, sapphirine, spinel, orthoclase and quartz. The invariant point should occur at 1000 ± 100 °C and 7± 2kb.     

Experimental study of phase relations involving osumilite in the system K2O-FeO-MgO-Al2O3-SiO2-H2O at high pressure and temperature

Abstract Phase relations and mineral chemistry for garnet (Grt), orthopyroxene (Opx), sapphirine (Spr), water-undersaturated cordierite (Crd), osumilite (Osu), sillimanite (Sil), K-feldspar (Kfs), quartz (Qtz) and a water-undersaturated liquid (Liq) have been determined experimentally in the system KFMASH (K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O) under low P_H2O and f_O2 conditions. Four compositions have been studied with 100 [Mg/(Mg + Fe)] ranging from 65.6 to 89.7. Based on our experimental data, a P-T grid is derived for the KFMASH system in the presence of quartz, orthopyroxene and liquid. Osumilite has been found in various mineral assemblages from 950 to 1100°C and 7.5 to 11 kbar. In the temperature range 1000-1100°C, the pair Os-Grt is stable over a pressure range of about 3kbar. The divariant reaction Os + Opx = Grt + Kfs + Qtz runs to the right with increasing pressure. Because osumilite is the most magnesian phase it is restricted to Mg-rich compositions at high pressure. The reaction defining the upper pressure stability limit of Os-Grt is located around 11 kbar with a nearly flat dP/dT slope over the temperature range 950–100°C. Over the entire temperature range investigated osumilite is not stable beyond 12 kbar. The data imply a restricted pressure range between 11 and 12 kbar for the stability of the assemblage Os-Opx-Sil-Kfs-Qtz. At 1050°C and above, osumilite occurs in various mineral assemblages together with the high-T pair Spr-Qtz. When coexisting with garnet, orthopyroxene or sapphirine, osumilite is always the most magnesian phase. At 1050 and 1100°C, liquid is invariably the most Fe-rich phase in the run product. Our data support a theoretical P-T grid for the KFMAS system in which osumilite is stable outside the field of the high-T assemblage Spr-Qtz. Moreover, our grid indicates that Os-Opx-Sil-Kfs-Qtz has a more restricted pressure and compositional stability domain than Os-Grt, in agreement with natural occurrences. Osumilite is stable over a large pressure range, such that in Mg-rich rocks, and at high temperature, it can occur at any depth in normal thickness continental crust.     

Stability of sapphirine-bearing mineral assemblages in the system FeO-MgO-Al2O3-SiO2 and metamorphic P-T parameters of aluminous granulites

Consistent thermodynamic data on the properties of pure mineral end members and the mixing properties of solid solutions in the system FeO-MgO-Al₂O₃-SiO₂ were employed to simulate phase relations of sapphirine, garnet, spinel, orthopyroxene, cordierite, quartz, Al silicates, and corundum. Compositional variations of the solid solutions with temperature notably modify the topology of the P-T diagrams, which differ from the petrogenetic grids widely used in the literature. It is worth noting that the evaluation of P-T metamorphic conditions based on reaction relations in sapphirine-bearing assemblages cannot be so far considered reliable enough. The lower stability limit of the sapphirine + quartz assemblage in the system in question is possibly located at much lower P-T parameters: at least 835°C and ∼6 kbar. The sapphirine + kyanite assemblage can be stable at temperatures below 860°C and a pressure of ∼11 kbar, and the stability field of the sapphirine + olivine assemblage is narrow and constrained to temperatures no higher than ∼800°C.     

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).     

Silica-undersaturated sapphirine, spinel and kornerupine granulite facies rocks, NE Strangways Range, Central Australia

Small pods of silica-undersaturated Al-rich and Mg-rich granulite facies rocks containing sapphirine, pleonastic spinel, kornerupine, cordierite, orthopyroxene, corundum, sillimanite and gedrite are scattered throughout the NE Strangways Range, Central Australia. These are divided into four distinct rock types, namely orthopyroxene-rich aluminous granofels and metapelitic gneisses containing sapphirine, spinel or kornerupine. Two granulite facies metamorphic events are recognized, of which only the first (M1) is considered in this paper. Peak metamorphic mineral parageneses indicate that the M1 thermal maximum occurred at approximately 900–950 °C and 8–9 kbar. All samples are characterized by profuse and diverse coronitic and symplectic reaction textures. These are interpreted as evidence for the sequential crossing of the following reactions in the system FMAS: cordierite + spinel + corundum = sapphirine + sillimanite, cordierite + spinel = orthopyroxene + sapphirine + sillimanite, sapphirine + spinel + sillimanite = orthopyroxene + corundum, sapphirine + sillimanite = cordierite + orthopyroxene + corundum. Phase stability relationships in FMAS and MASH indicate an anticlockwise P–T path terminated by isobaric cooling. Such a path is exemplified by early low-P mineral parageneses containing spinel, corundum and gedrite and the occurrence of both prograde and retrograde corundum. Reaction textures preserve evidence for an increase in aH₂O and aB₂O₃ with progressive isobaric cooling. This hydrous retrogression resulted from crystallization of intimately associated M1 partial melt segregations. There is no evidence for voluminous magmatic accretion giving rise to the high M1 thermal gradient. The M1 P–T path may be the result of either lithospheric thinning after both crustal thickening and burial of the supracrustal terrane, or concomitant crustal thickening and mantle lithosphere thinning.     

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.     

Cordierite-garnet-H2O equilibrium: A geological thermometer,barometer and water fugacity indicator

The high-grade assemblage Cd-Ga-Si-Qz can be thermodynamically modelled from available calorimetric data on the metastable reaction: (I) $$3 MgCd \rightleftarrows 2 Py + 4 Si + 5 Qz$$ naturalK _D ^Fe-Mg between garnet and cordierite and experimental results on cordierite hydration. In the system SiO₂-Al₂O₃-MgO-H₂O, reaction (I) becomes (II) $$3 MgCd \cdot nH_2 O \rightleftarrows 2 Py + 4 Si + 5 Qz + 3 nH_2 O$$ . However, hydrous cordierite is neither a hydrate nor a solid solution between water and anhydrous cordierite and when nH₂O (number of moles of H₂O in Cd) is plotted against \(P_{H_2 O} \) , the resulting isotherms are similar to adsorption isotherms characteristic of zeolitic minerals. Reaction (II) can thus be considered as a combination of reaction (I) with a physical equilibrium of the type nH₂O (in Cd)?nH₂O (in vapor phase). Starting from a point on equilibrium (I), introduction of H₂O into anhydrous Mg-cordierite lowers the chemical potential of MgCd and hence stabilizes this mineral to higher pressure relative to the right-hand assemblage in reaction (I). The pressure increment of stabilization,ΔP, above the pressure limit of anhydrous cordierite stability at constantT, has been calculated using the standard thermodynamics of adsorption isotherms. Cordierite is regarded as a mixture of Mg₂Al₄Si₅O₁₈ and H₂O. The activity of H₂O in the cordierite is evaluated relative to an hypothetical standard state extrapolated from infinite H₂O dilution, by using measured hydration data. The activity of Mg₂Al₄Si₅O₁₈ in the cordierite is then obtained by integration of the Gibbs-Duhem equation, and the pressure stabilization increment,ΔP, computed by means of the relation: $$\Delta V_s \Delta P \cong - RT\ln a_{MgCd}^{MgCd \cdot nH2O} \left( {\Delta V indepentdent of P and T} \right)$$ . Thus, one may contour theP-T plane in isopleths of nH₂O=constant within the area of Mg-cordierite stability allowed by the hydration data for \(P_{H_2 O} = P_{total} \) . The present model indicates greater stabilization of cordierite by H₂O than the model of Newton and Wood (1979) and the calculated curve for metastable breakdown of hydrous MgCd is consistent with experimental data on cordierite breakdown at \(P_{H_2 O} = P_{total} \) . Mg/(Mg+Fe) isopleths have been derived for cordierites of varying nH₂O in the SiO₂-Al₂O₃-MgO-FeO-H₂O system using the additional assumptions that (Fe, Mg) cordierite and (Fe, Mg) garnet behave as ideal solutions, and that typical values of the distribution coefficient of Fe and Mg between coexisting garnet and cordierite observed in natural parageneses can be applied to the calculations. The calculated stable breakdown curve of Fe-cordierite under conditions of \(P_{H_2 O} = P_{total} \) to almandine, sillimanite, quartz and vapor has a positive slope (dP/dT) apparently in contrast to the experimental negative slope. This may be explained by hydration kinetics, which could have allowed systematic breakdown of cordierites of metastable hydration states in the experiments. The bivariant Cd-Ga fields calibrated from the present model are, potentially, good petrogenetic indicators, as, given the iron-magnesium ratio of garnet and cordierite and the hydration number of cordierite, the temperature, pressure and water fugacity are uniquely determined. As this geothermobarometer is in part based on the water content of cordierite, it can be used only if there is some assurance that the actual hydration is inherited from high-grade metamorphic conditions. Such conditions could be realised if the slope of unloading-cooling retrograde metamorphism is more or less parallel to a cordierite isohydron.     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

The stability of cordierite and garnet relative to their anhydrous breakdown products, i.e. hypersthene, sapphirine, olivine, spinel, sillimanite and quartz, has been studied experimentally in model pelitic compositions (system MgO-FeO-Al₂O₃-CaO-K₂O-SiO₂). Below 1000° C cordierite breaks down according to the divariant reaction cordierite garnet+sillimanite+quartz (1) for most values of the MgO/MgO + FeO ratio (X). At very high values of X (ca. X0.9) garnet in reaction (1) is replaced by hypersthene. The position and width of the divariant field (in terms of pressure and temperature) in which cordierite and garnet coexist, is a function of the MgO/MgO + FeO ratio. If this ratio is increased then the stability field of garnet is reduced and that of cordierite extended towards higher pressure. Compositions of coexisting cordierite and garnet in divariant equilibrium have been analysed by electron probe micro-analyser. These compositions are unique functions of pressure and temperature. Above ca. 1000° C the breakdown of cordierite involves the phases sapphirine and hercynite-rich spinel in Mg-rich and Fe-rich compositions respectively.     

Petrology of phlogopite-sapphirine-bearing Al-Mg granulites from Ihouhaouene, In Ouzzal, Hoggar, Algeria: an example of phlogopite stability at high temperature

Al-Mg granulites, with cordierite, garnet, sapphirine, orthopyroxene, sillimanite, spinel, phlogopite, K-feldspar, plagioclase and variable quartz from Ihouhaouene (In Ouzzal, Algeria), display a range of decompression textures involving the breakdown of orthopyroxene and sillimanite, and of garnet. The succession of parageneses suggests that the P–T–t evolution corresponds to decompression with cooling from peak conditions of about 950°C and 10 kbar. This decompression path is obtained from the paragenetic analysis in the FMAS system. However, according to current KFMASH grids, this P–T–t evolution should take place outside the stability field of phlogopite+quartz; yet this assemblage is probably stable during most of the P-T evolution, notably during peak metamorphism. This discrepancy is interpreted as the effect of the high content of F in phlogopite which should shift its stability limit towards higher temperature. The consequences of this shift on the phase relationships in the KFeMASH system are investigated and it is concluded that a topological inversion could exist in the F-bearing system.     

A sapphirine-cordierite-garnet-sillimanite granulite from Enderby Land,Antarctica: implications for FMAS petrogenetic grids in the granulite facies

A quartz-absent magnesian paragneiss layer from Mount Sones, in the Archaean Napier complex of Enderby Land, Antarctica, contains the stable divariant FMAS assemblage sapphirine (X _Mg=78) — cordierite (X _Mg=87) — garnet (X _Mg=51) — sillimanite. Rare green spinel (X _Mg=53.5, ZnO=2.65wt%) occurs as inclusions mainly within sapphirine, but also within sillimanite and garnet. Late thin coronas of cordierite (X _Mg=90.5) mantle sapphirine in contact with extensively exsolved anorthoclase. The mineral textures are interpreted to indicate the former stability of a hypersthene-quartz absent assemblage followed by the development of the FMAS equilibrium assemblage sapphirine-cordierite-garnet-sillimanite (sp, hy, qz) and further divariant reaction involving the consumption of sapphirine. The (sp, hy, qz) assemblage uniquely defines the stable P-T reaction topology appropriate to granulites from the Napier Complex, as this paragenesis is allowed in the grids of Hensen (1971, 1986) but is not possible in other grids which assume the stability of a sapphirine-absent ([sa]) FMAS invariant point involving the phases spinel, garnet, hypersthene, cordierite, sillimanite and quartz. The observed mineral assemblages and textures are consistent with peak metamorphism between the [sp] and [hy] invariant points of Hensen (1971), at temperatures of 930–990° C, followed by cooling on a lower dP/dT trajectory towards the (sp, qz) univariant line. The initial spinel-bearing assemblage was stabilized by Zn and to a lesser extent by Ni and Cr, and hence does not require a marked decrease in temperature and increase in pressure to produce the (sp, hy, qz) assemblage. It is inferred that fO ₂ conditions substantially lower than those used in the experiments of Annersten and Seifert (1981) prevailed in the high-grade metamorphism in the Napier Complex.     

Instability of sapphirine at high pressures

The stability field of Mg-sapphirines is limited at high pressures through the solid-solid breakdown reaction sapphirine?pyrope = corundum+spinel, the univariant curve originating from an invariant point located at 22 kb, 880°C to 30 kb, 1350°C. Under water pressures less than 22 kb sapphirines exhibit the same low-temperature breakdown into the assemblage chlorite+corundum+spinel as determined by Seifert (1974) between 1 kb and 7 kb thus resulting in one continuous univariant lower stability limit extending from 1 kb, about 650°C through 10 kb, 770°C to the invariant point at 22 kb, 880°C. If \(P_{{\text{H}}_{\text{2}} {\text{0}}} < P_{{\text{total}}} \) , the stability field of sapphirine will expand towards lower temperatures. The occurrence of sapphirine in mantle depths requires rather aluminous bulk compositions, high geothermal gradients and/or \(P_{{\text{H}}_{\text{2}} {\text{0}}} < P_{{\text{total}}} \) , with total pressures not exceeding 30 kb. Thus sapphirine is probably not a stable phase in the lower portions of lithospheric plates and the underlying asthenosphere.     

Sapphirine/kornenipine-bearing rocks and crustal uplift history of the Limpopo belt,Southern Africa

Sapphirine/kornerupine-bearing rocks occur within the anorthosites of the Messina layered intrusion in the Limpopo mobile belt of Zimbabwe. The X_Mg range of the major minerals is as follows: cordierite (0.98-0.93); enstatite (0.97-0.86); chlorite (0.98-0.92); phlogopite (0.98-0.90); sapphirine (0.98-0.86); kornerupine (0.94-0.88); gedrite (0.96-0.85); spinel (0.92-0.78). There are four rock types, the constituent minerals of which have different values, which decrease in the above mineral order; other minerals are corundum, sillimanite and relict kyanite. We recognise twenty reactions without phlogopite and nine reactions involving phlogopite. The textural relations and the plots of the microprobe data of coexisting minerals in the MgO-Al₂O₃-SiO₂-(H₂O) system are consistent with the following sequence of main reactions: (1) enstatite+corundum cordierite+sapphirine; (4) sapphirine+sillimanite cordierite+corundum; (8) kornerupine+corundum cordierite+sapphirine; (13) kornerupine cordierite+sapphirine+enstatite; (15) enstatite+spinel chlorite+sapphirine; (18) cordierite+sapphirine chlorite+corundum; (20) sapphirine chlorite+corundum+spinel. The early reactions are shown by coarse-grained reaction intergrowths, kornerupine and gedrite breakdown is shown by finer-grained symplectites, and the latest reactions by very fine-grained products in micro-fractures. These selected reactions illustrate a remarkably steep trajectory from thePT peak close to 10 kbar and 800° C to the minimum observable at 3.5–4.5 kbar and 700° C as indicated by the pure MASH system. Very rapid uplift took place under nearly isothermal conditions. The protolith of this material was possibly sedimentary, derived from altered volcanic rocks. The bulk composition is close to the composition of kornerupine or to a mixture of alunite, chlorite and pyrophyllite. These texturally and mineralogically complex rocks contain a wealth of relevant data for documenting crustal uplift history.     

Sapphirine + quartz assemblage in contrasting textural modes from the Eastern Ghats Belt, India: Implications for stability relations in UHT metamorphism and retrograde processes

Stability of the assemblage sapphirine + quartz in Mg–Al-rich granulites implies ultrahigh temperature (UHT) condition of metamorphism but their direct contact is rarely preserved in natural rocks. The present study shows contrasting textural relations between sapphirine and quartz in different parts of the same occurrence of a Mg–Al-rich granulite, Eastern Ghats Belt, India. Textural data suggest stabilization of the assemblage sapphirine + quartz with orthopyroxene and cordierite during the metamorphic peak. Thermometric estimates yield temperature exceeding 950 °C for the stability of this assemblage. Most of such sapphirine grains (Spr₁) are texturally separated from quartz and cordierite grains by double corona of sillimanite + orthopyroxene that results due to isobaric cooling during the post-peak stage. Sapphirine (Spr₂) also forms a symplectic intergrowth with quartz and orthopyroxene at the fringe of coarse orthopyroxene. This textural feature can be explained by the breakdown of (Fe, Mg)-Tschermak components of orthopyroxene during the same isobaric cooling episode from UHT peak condition. The preservation of grain contact of this intergrown sapphirine and quartz can be attributed to a problem in reaction kinetics. In the other mode, sapphirine (Spr₃) occurs with quartz with a thin skin of cordierite near a quartz vein. Such texture could result from isothermal decompression of the cooled crust. Alternatively and more possibly, cordierite could form from ingress of CO₂–H₂O rich fluid during terminal stage of cooling. Finally, sapphirine (Spr₄) and quartz show direct contact close to the quartz vein. Direct contact of such sapphirine and quartz represents textural disequilibrium as this particular quartz is introduced as a vein much later than the peak metamorphism but prior to the major foliation-forming deformation. Coarse sapphirine and vein quartz, therefore, accidentally came in contact with each other and persisted metastably. Therefore, though coexistence of sapphirine and quartz is considered to be a strong evidence for ultrahigh temperature condition, care should be taken to decipher their stable coexistence. Different types of textural relations involving this mineral pair could originate in a single rock, probably in different stages of its metamorphic history.     

Synthetic gedrite: a stable phase in the system MgO-Al2O3-SiO2-H2O (MASH) at 800 °C and 10 kbar water pressure, and the influence of FeNaCa impurities

Seeded, solid-media piston-cylinder runs of unusually long duration up to 31 days indicate growth or persistence of synthetic gedrite of the composition □Mg₆Al[AlSi₇O₂₂](OH)₂(=6:1:7), prepared from the purest chemicals available, at 10 kbar water pressure and 800 °C. Conversely, breakdown was observed at 11 kbar and 850 °C to aluminous enstatite, Al₂SiO₅, and a melt of the composition MgO·Al₂O₃·8SiO₂. Thus, pure gedrite free of iron, sodium, and calcium is likely to have only a small PT stability field in the MASH system, estimated as 10 ± 1 kbar, 800 ± 20 °C, even though metastable growth of gedrite can be observed over a larger PT range. A second starting material with the anhydrous composition 5MgO · 2Al₂O₃ · 6SiO₂ also yielded gedrite of the composition 6:1:7, together with more aluminous phases such as kyanite, corundum or sapphirine, thus suggesting that the end-member gedrite defined as □Mg₅Al₂[Al₂Si₆O₂₂](OH)₂(=5:2:6) by the IMA Commission on New Minerals and Mineral Names probably does not exist. With the use of this second starting material, which contains FeNaCa impurities, growth of 6:1:7-gedrite was observed over a still wider PT-range. Seeded runs indicate that the true stability field of such slightly impure 6:1:7-gedrites may also be larger than that of the pure MASH phase and extend at least to 15 kbar, 800 °C. There is, thus, a remarkable stabilization effect on the orthoamphibole structure by impurities amounting only to a total of less than one weight percent of oxides in the starting material. The gedrites synthesized are structurally well ordered amphiboles nearly free of chain multiplicity faults, as revealed by HRTEM. The X-ray diffraction work on the gedrites synthesized yielded the smallest cell volume yet reported for this phase. The small stability field of the pure MASH gedrite is intersected by the upper pressure stability limit of hydrous cordierite for excess-H₂O conditions, thus leading to complicated phase relations for both gedrite and cordierite involving the additional phases aluminous enstatite, talc, quartz, Al₂SiO₅, melt and perhaps boron-free kornerupine. Received: 29 July 1998 / Accepted: 7 January 1999     

Cordierite breakdown under high-pressure,hydrous conditions

Clear evidence exists for a cordierite breakdown reaction to amphibole-kyanite-quartz in high-grade metamorphic rocks of the Arunta Complex, Australia. Using the natural minerals this reaction has been duplicated experimentally. It proceeds over a divariant band with a slope of 12±4 bars/°C, occurring between 8 and 10.4 kb at 750° C and between 9.5 and 11.3 kb at 850°C. The reaction is cut off at low temperature by the appearance of talc and at high temperature by the appearance of orthopyroxene. The maximum pressure stability of the amphibole-kyanite-quartz assemblage is about 20 kb. These data suggest that the natural rock was subjected to pressures of at least 8 kb at 750–850° C for high water fugacities. Other experimental data on the hydration of hypersthene and cordierite-hypersthene stability, point to a temperature below 820° C and an upper pressure limit of 9.5 kb at 750–820°C. Experiments at \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) total indicate that the breakdown of cordierite to amphibole-kyanite-quartz is a hydration reaction, and occurred in the natural rock as a result of an increase of water fugacity at constant total pressure (8–9.5 kb) and temperature (750–820°C).     

First Report of Sapphirine+Quartz Assemblage from Southern India: Implications for Ultrahigh-temperature Metamorphism

We report here for the first time, the occurrence of sapphirine+quartz assemblage in textural equilibrium from quartzo-feldspathic and pelitic granulites from southern India. The sapphirine-bearing rocks occur as layered gneisses associated with pink granite within massive charnockite in Rajapalaiyam area in the southern part of Madurai Block. Sapphirine occurs in three associations: (i) fine-grained subhedral mineral associated with quartz enclosed in garnet, (ii) intergrowth with Al-rich orthopyroxene (up to 9.7 wt.% Al₂O₃), and (iii) in symplectitic intergrowth with orthopyroxene (Al₂O₃= 5.9–6.7 wt.%) and cordierite surrounding garnet. The sapphirine in association with quartz is slightly magnesian (X_Mg = 0.79–0.80) and low in Si content (1.55–1.56 pfu) as compared with those associated with orthopyroxene and cordierite (X_Mg= 0.77–0.79, Si = 1.59–1.63 pfu). The sapphirine+quartz assemblage suggests that the granulites underwent T>1050 °C peak metamorphism. Cores of porphyroblastic orthopyroxene in the sapphirine-bearing rocks shows high-Al₂O₃ content of up to 9.7 wt.%, suggesting T = 1040–1060°C and P = 8 kbar. FMAS reaction of sapphirine+quartz→garnet+sillimanite+cordierite indicates a cooling from sapphirine+quartz stability field after the peak ultrahigh-temperature metamorphism. Slightly lower temperature estimates from ternary feldspar and sapphirine-spinel geothermometers (T = 950–1000°C) also support a post-peak isobaric cooling. Corona textures of orthopyroxene+cordierite (±sapphirine), orthopyroxene+sapphirine, and cordierite+spinel around garnet suggest subsequent decompression. The sapphirine-quartz association and related textures reported in this study have important bearing on the ultrahigh-temperature metamorphism and exhumation history of the Madurai Block as well as on the tectonic evolution of the continental deep crust in southern India.     

Cordierite gneisses of southern Kerala,India: petrology,fluid inclusions and implications for crustal uplift history

The cordierite-bearing gneisses occurring as elongate patches in an 8- to 10-km-wide zone along the Achankovil fault-lineament at the northern margin of the southern Kerala crustal segment represent an important lithological unit in the Archaean granulite terrane of south India. The textural relationships in these rocks are consistent with the following main reactions: (1) garnet+quartz=cordierite+hypersthene; (2) garnet+sillimanite+quartz=cordierite; (3) hypersthene+sillimanite+quartz=cordierite; (4) sillimanite+spinel=cordierite+corundum; and (5) biotite+quartz+sillimanite=cordierite+K-feldspar. Many of the mineral associations and reaction textures, including the remarkable preservation of symplectites, are indicative of partial replacement of high-pressure assemblages by cordierite-bearing lower-pressure ones during an event of rapid decompression. Temperature estimates from coexisting mineral phases show 710° (garnet-biotite), 791° (garnet-cordierite) and 788° C (garnet-orthopyroxene). Pressure estimates from mineral assemblages range from 5.4 to 7 kb. Detailed fluid inclusion studies in quartz associated with cordierite show high-density CO₂ (0.80–0.95 g/cm³) as the dominant fluid phase, with traces of probable CH₄ (?) in the sillimanite-bearing rocks. The isochore for the higher-density fluid inclusions defines a pressure of 5.5 kb. The fracture-bound CO₂ and CO₂-H₂O (±CH₄?) inclusions indicate simultaneous entrapment at 400° C and 1.7 kb in the cordierite-hypersthene assemblage and 340° C and 1.2 kb in the cordierite-sillimanite assemblage. The P-T path delineated from combined solid and fluid data corresponds to the piezothermic array of the gneisses and is characterized by T-convex nature, indicative of rapid and virtually isothermal crustal uplift, probably aided by extensional tectonics.     

Al zoning in orthopyroxene in a sapphirine quartzite: evidence for >1120 °C UHT metamorphism in the Napier Complex, Antarctica, and implications for the entropy of sapphirine

A unique sapphirine + orthopyroxene + quartz granulite from Mt. Riiser-Larsen in the Tula Mountains of Enderby Land, East Antarctica, preserves two generations of coarse and texturally equilibrated orthopyroxene and sapphirine coexisting with quartz. Initial subhedral orthopyroxene porphyroblasts retain core compositions enriched in Al₂O₃ (12.2 ± 0.5 wt%) compared with their rims and finer orthopyroxene (9.6 ± 0.5 wt% Al₂O₃) that forms granoblastic textures with sapphirine. Sapphirine and quartz also form symplectites on and along cleavage planes within orthopyroxene. These compositional and textural features are consistent with the reaction [2MgAl₂SiO₆=Mg₂Al₄ SiO₁₀ + SiO₂] leading to the formation of sapphirine + quartz at the expense of aluminous orthopyroxene. Calculations in the MAS and FMAS systems and theoretical considerations involving the phases enstatite, sapphirine, sillimanite, quartz and cordierite indicate that the reaction above progresses from left to right with decreasing temperature in the orthopyroxene + sapphirine + quartz field, at pressures of ca. 8–10 kbar. The temperature difference required to account for the ca. 2.5–3 wt% decrease in Al₂O₃ in orthopyroxene is at least 60–80 °C, and implies peak temperatures for the initial assemblage of at least 1120 °C if the second granoblastic assemblage equilibrated at 1040 °C, the P–T conditions required by the sapphirine + quartz association and other P–T-sensitive assemblage indicators in the Napier Complex. It is not possible to distinguish whether the two assemblages are simply related by cooling and re-equilibration or reflect a polyphase evolution involving the superposition of a second UHT event on an earlier, even higher temperature, UHT metamorphism. Preliminary thermodynamic modelling of the reaction above incorporating the observed range in orthopyroxene Al₂O₃ zoning indicates that present estimates for the entropy of high-temperature sapphirine are potentially too high by 15–18% compared with sapphirine entropy estimates that are consistent with MAS system experiments. The Mt. Riiser-Larsen sapphirine–quartz rocks preserve the first definitive record of regional metamorphic temperatures in excess of 1120 °C in the Napier Complex, or indeed any UHT granulite terrain worldwide. Similarly high peak temperatures may be retrieved from detailed studies of sapphirine–quartz granulites from other regions, further expanding the thermal realm of crustal metamorphism, but progress will critically depend on the experimental acquisition of new entropy data for sapphirine. Received: 3 September 1998 / Accepted: 8 November 1999