Theoretical phase relations involving cordierite and garnet revisited: the influence of oxygen fugacity on the stability of sapphirine and spinel in the system Mg-Fe-Al-Si-O

The theoreticalP-T grid for stability relations of the phases cordierite (Cd), sapphirine (Sa), hypersthene (Hy), garnet (Ga), spinel (Sp), sillimanite (Si), and quartz (Qz) of Hensen (1971), has proved useful in the interpretation of metamorphic mineral assemblages formed at low oxygen fugacity. Both experimental data and evidence from natural rocks indicate that at high oxygen fugacity compatability relations change as a result of the enlargement of the stability field of spinel, which causes a topological inversion and the stabilisation of the invariant points [Sa], [Ga], and [Cd]. This implies the stable existence of the univariant equilibria (for buffered conditions): Sp+Qz=Ga+Hy+Si+O₂ (Sa, Cd), Cd+Sp+Qz=Hy+Si+O₂ (Sa, Ga) and Sa+Sp+Qz=Hy+Si+O₂ (Ga, Cd) and the divariant reaction: Sp+Qz=Hy+Si+O₂ (Sa, Ga, Cd). These redox equilibria are restricted to conditions of high oxygen fugacity. The proposed theoreticalP-T grids, for both low and high oxygen fugacity, satisfactorily explain all experimental data and metamorphic mineral assemblages so far found in granulites.     

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.     

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

The stability of cordierite and garnet has been studied experimentally in complex, silica oversaturated compositions (in the systems MgO-FeO-Al₂O-CaO₃-Na₂O-K₂OSiO₂) in which the molecular ratio Al₂O₃/FeO+MgO<1. Compositions with 100 Mg/Mg+Fe²⁺ ratios (X) of 0, 30, 50, 70 and 100 have been used to investigate the role of this ratio in determining phase assemblages and P, T coordinates of reactions. The minimum pressure for appearance of garnet at a given temperature is strongly dependent on X _{total rock}.The X-values of co-existing phases (chiefly garnet, cordierite, hypersthene) in divariant equilibrium are a function of temperature and pressure and have been experimentally determined at 900° C, 1000° C and 1100° C. At high temperature (>1050° C) the phases sapphirine and spinel are stable with quartz in Mg-rich and Fe-rich compositions respectively. Experiments in the system MgO-FeO-Al₂O₃-SiO₂ show that for a given X-value and temperature the pressure required to produce Ca-free garnet from hypersthene-cordierite assemblages is 1–2 kb greater than that required to produce garnet containing 6±2 mol percent grossular solid solution in the more complex Ca-bearing system.     

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.     

Experimental Study on the Solubility of Cr^2 in Olivine,Orthopyroxene and Spinel Solid Solutions

Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

Paragenetic relations in gedrite — cordierite — staurolite — biotite sillimanite — kyanite gneisses at Ajitpura,Rajasthan, India

Aluminous parageneses containing gedrite, cordierite, garnet, staurolite, biotite, sillimanite, kyanite, quartz or spinel plus corundum are found as dark colored lenses in the polymetamorphic, multideformed Archean complex at Ajitpura in northwest peninsular India. Staurolite, like kyanite, is a relict phase of earlier metamorphism and is excluded as a paragenetic mineral in view of its incompatibility with quartz and gedrite and its lower X _Mg values than for garnet of the assemblage. Its stability here is attributed to zinc content of up to 3 wt%. The XMg in other ferromagnesian minerals decreases in the order: cordierite, biotite, gedrite, garnet, as found elsewhere in high grade rocks.The textural criteria and systematic partitioning of Fe and Mg in the ferromagnesian phases, excluding staurolite, indicate attainment of equilibrium during the second metamorphism. From tie line configurations in the phase diagrams, X _Mg ratios in the constituent minerals, and other petrographic criteria, it is suggested that gedrite — cordierite-garnet — sillimanite — biotite assemblage has been produced by the reactions: Biotite+Sillimanite+Quartz = Cordierite+Garnet+K-feldspar+Vapor (1) and Biotite+Sillimanite+Quartz = Cordierite +Gedrite+K-feldspar+Vapor (2) which occurred during partial melting of the rocks at fixed P and T conditions.By isothermal P-X(Fe-Mg) sections it has been demonstrated that release of FeO, SiO₂ and other components modified the composition of the reactant biotite presumably by the substitution FeSi2 Al, whereby reaction 1 was replaced by reaction 2. Cordierite with higher X _Mg was produced with gedrite instead of with garnet, whose X _Mg is less than X _Mg of gedrite. Reaction 2 has been tentatively located in T-P space from the intersection of some continuous loops in the P-X(Fe-Mg) diagram at 700°C and also by other constraints. The discontinuous reaction 2 is located about 1–2 kilobars higher than reaction 1, which implies that it is difficult to distinguish between effects of pressure and those of melting on the X _Mg ratios of the reaction phases.The P-T calibrations of garnet — cordierite, garnet — biotite and garnet — plagioclase equilibria and the calibrations from other dehydration curves give temperatures near 700°C and pressure (assuming ) about 6 kilobars.     

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.     

Tholeiitic basalt magmatism of Mount Etna and its relations with the alkaline series

Mount Etna is composed for the most part of intermediate alkaline products, most of them porphyritic-the etnaïtes-, that may be defined as sodic trachybasalts or trachyandesites. The strato-volcanio itself overlies tholeiitic basalts (usually aphyric, except for olivine) belonging to three major types: olivine tholeiites (normative Ol+Hy; modal olivine and augite, titanomagnetite and ilmenite), pigeonite tholeiites (normative Hy+minor Ol or Qz; modal pigeonite and augite with minor olivine, ilmenite and titanomagnetite), transitional tholeiites, i.e. transitional between pigeonite tholeiites (aphyric) and alkali basaltic etnaïtes (porphyritic, with normative Ol+Ne or minor Hy; modal augite and olivine, titanomagnetite alone). An analcite basalt, chemically close to alkali basaltic etnaïtes, forms the small Cyclopean Islands, SE of Etna, and an alkali olivine basalt composes a neck at Paterno, SW foot of Etna.Both pigeonite tholeiites and alkali basaltic etnaïtes may be derived from a primitive olivine tholeiite magma by subtraction or addition of phases crystallized at moderate and low pressure (kaersutite±olivine, calcic plagioclase and clinopyroxene). The differentiation process implies crystal fractionation of the primitive olivine tholeiite magma at varying levels of the crust. The speed of ascent of the magma is thought to be the factor controlling the level at which differentiation may take place: in low velocity regimes, fractionation takes place at deeper levels of the crust. Slow ascent speeds would be the consequence of a developing crustal extension episode, induced by mantle diapirism that generated the olivine tholeiite magma below the Mount Etna area.     

An enlarged and updated internally consistent thermodynamic dataset with uncertainties and correlations: the system K2O–Na2O–CaO–MgO–MnO–FeO–Fe2O3–Al2O3–TiO2–SiO2–C–H2–O2

We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end-members made consistent with over 200 P–T–X_CO2–f_O2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron-bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H₂O and CO₂ contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak-substituted end-members have been derived for iron and magnesium end-members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end-members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end-members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.     

P–T–X relationships in the Precambrian Al–Mg-rich granulites from In Ouzzal, Hoggar, Algeria

The Al–Mg-rich granulites from the In Ouzzal craton, Algeria, show a great diversity of mineral reactions which correspond to continuous equilibria as predicted by phase relationships in the FeO–MgO–Al₂O₃–SiO₂ system. The sequence of mineral reactions can be subdivided into three distinct stages: (1) a high-P stage characterized by the growth of coarse mineral assemblages involving sapphirine and the disappearance of early corundum and spinel-bearing assemblages; (2) a high-T stage characterized by the development of Sa–Qz-bearing assemblages; and (3) a later stage, in which garnet-bearing assemblages are replaced by more or less fine symplectites involving cordierite. During the course of early mineral reactions, the distribution coefficient, K_d, between the various ferromagnesian phases decreased significantly whereas Al₂O₃ in pyroxene increased concomitantly. These observations, when combined with topological constraints, clearly indicate that the high-P stage 1 was accompanied by a significant rise in temperature (estimated at 150 ± 50° C) under near isobaric conditions, in agreement with the reaction textures. By stage 2, pressure and temperature were extreme as evidenced by the low K_d value between orthopyroxene and garnet (K_d= 2.06–1.99), the high alumina content in pyroxene (up to 11.8%) and the high magnesium content in garnet [100 Mg/(Mg + Fe) = 60.6]. Mineral thermometry based on Fe–Mg exchange between garnet and pyroxene and on Al-solubility in pyroxene gives temperatures close to 970 ± 70° C at 10 ± 1.5 kbar. These results are in agreement with the development of Sa–Qz assemblages on a local scale. Late mineral reactions have been produced during a decompression stage from about 9 to 6 kbar. Except for local re-equilibration of Mg and Fe at grain boundaries, there is no evidence for further reactions below 700° C. We interpreted the whole set of mineral reactions as due to changes in pressure and temperature during a tectonic episode located at c. 2 Ga. Because of the lack of evidence for further uplift after the thermal relaxation which occurred at c. 6 kbar, it is possible however that the exhumation of this granulitic terrane occurred in a later tectonic event unrelated to its formation.     

Thermodynamic calculation of peridotite phase relations in the system MgO-Al2O3-SiO2-Cr2O3, with some geological applications

The system MgO-Al₂O₃-SiO₂(MAS) comprises 88–90% of the bulk composition of an average peridotite. The MAS ternary is thus a suitable starting point for exploring peridotite phase relations in multicomponent natural systems. The basic MAS phase relations may be treated in terms of the reactions (see list of symbols etc).

1. py (in Gt)=en (in Opx)+mats (in Opx),
2. en (in Opx)+sp (in Sp)=mats (in Opx)+fo (in Ol), and
3. py (in Gt)+fo (in Ol)=en (in Opx)+sp (in Sp).

Extensive reversed phase equilibria data on these three reactions by Danckwerth and Newton (1978), Perkins et al. (1981), and Gasparik and Newton (1984) employing identical experimental methods in the same laboratory have been used by us to deduce the following internally consistent thermodynamic data applying the technique of linear programming:ΔH ₂₉₈₍₁₎ ⁰ = 2536 J, ΔS ₂₉₈₍₁₎ ⁰ =? 6.064 J/K;ΔH ₂₉₈₍₂₎ ⁰ = 29435 J, ΔS ₂₉₈₍₂₎ ⁰ = 8.323 J/K; andΔH ₂₉₈₍₃₎ ⁰ =?26899 J, ΔS ₂₉₈₍₃₎ ⁰ =?14.388 J/K.These data are also found to be consistent with results of calorimetry. Figure 2 shows the calculated phase relations based on our thermodynamic data; they are consistent with the phase equilibria experiments. Successful extension of the MAS phase relations to multicomponent peridotites pivots on the extent to which the effects of the “non-ternary” (i.e. other than MAS) components can be quantitatively handled. Particularly hazardous in this context is Cr₂O₃, although it barely makes up 0.2 to 0.5 wt% of such rocks. This is because Cr⁺³ fractionates extremely strongly into Sp. This study focuses on the peridotite phase relations in the MgO-Al₂O₃-SiO₂-Cr₂O₃ (MASCr) quaternary. Thermodynamic calculations of the MASCr phase relations have been accomplished by using ΔH ₂₉₈ ⁰ and ΔS ₂₉₈ ⁰ values for the reactions (1) through (3) indicated above, in conjunction with data on thermodynamic mixing properties of

1. binary Sp (sp-pc) crystalline solution (Oka et al. 1984),
2. ternary Opx (en-mats-mcts) crystalline solution (this study), and
3. binary Gt (py-kn) crystalline solution (this study).

The results are shown in P-T projections (Figs. 3a and b) and isobaric-isothermal sections of MASCr in a projection through the component fo onto the SiO₂-Al₂O₃-Cr₂O₃ ternary (Figs. 4a and b). The most important results of this work may be summarized as follows:

1. With increasing incorporation of Cr⁺³ into Sp and Gt, the X _mats isopleths of the reactions (1) and (2) are shifted to higher temperatures (Fig. 3a); simultaneously, the spinel-peridotite to garnet-peridotite phase transition is moved to higher pressures (Fig. 3b).
2. At identical P and T, the X _mats values of Opx coexisting in equilibrium with Ol and Sp is strongly dependent upon the X _pc value in the latter phase (Figs. 4a and b). Accurate correction for the composition of Sp is, therefore, a necessary precondition for geothermometry of the spinelperidotites.
3. The discrepant temperatures reported by Sachtleben und Seck (1981, Fig. 5) from the spinel-peridotites of the Eifel area (systematically too high temperatures as a function of X _pc in Sp) are demonstrated to be the result of ignoring the nonideality in the chromian spinels.

     

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).     

Continuous reactions with amphibole, garnet and plagioclase

Abstract End-member, continuous and degenerate reactions are derived for the multisystem with the six components Na₂O, CaO, (Mg/Fe)O, Al₂O₃, SiO₂, H₂O among the phases plagioclase_ss, garnet_ss, amphibole_ss, cpx, opx, olivine, spinel, quartz and an aqueous fluid. The chemography of this system is degenerate due to the co-linearity 2Opx = Ol + Qtz. This co-linearity has its implications both on reaction space and phase equilibria. From a total of 28 reaction systems, reaction space is derived for nine subsystems (phases in parentheses are absent): Case A₁: (Cpx,Ol) (Cpx,Opx) and (Cpx,Qtz), Case A₂: (Spl,Ol) (Spl,Opx) and (Spl,Qtz), Case B: (Ol,Opx) (Ol,Qtz) and (Opx,Qtz). In the absence of either cpx or spl (case A), three reactions form an invariant point, either [Cpx] or [Spl], where the co-linear phases olivine, opx and quartz coexist on the transformation line 2Opx = Ol + Qtz. Changing mineral compositions force invariant points to move along the line with the different reaction curves changing their relative position according to Schreinemakers’rules. Zero contours, i.e. the location where (a) phase(s) disappear(s) in reaction space correspond to singular points in phase diagrams. Two types are distinguished; singular points of indispensable and of substitutable phases. In the first case the phase disappears from the entire bundle while in the second it disappears from a single reaction. In the specific case where the substitutable phases are also the co-linear ones, two of the three co-linear phases disappear simultaneously. Two of the three reaction curves coincide. In the system including Cpx and Spl (Case B) three reactions, (Ol,Opx) (Ol,Qtz) and (Opx,Qtz), oppose three invariant points, [Ol], [Opx] and [Qtz]. Invariant points no longer move along the line 2Opx = Ol + Qtz. The coincidence of the zero contours of all three co-linear phases in reaction space-the result of the chemographic degeneracy-causes the respective singular points to coincide in the phase diagrams. This is the location where curves must be rearranged in a bundle to conform Schreinemakers’rules. The reaction Grs₁Prp₂= 2 Ol + An is fourth order degenerate and part of all nine subsystems (cases A and B). It can be used to relate the different phase diagrams to one another.     

Low-Pressure Phase Relationships in the System Na2O--CaO--FeO--MgO--Al2O3--SiO2 at 1100C, with Implications for the Differentiation of Basaltic Magmas

Experiments were performed on the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂at 1100C, with the interest focused on the assemblage Liq+Aug+Pl+Oland its boundaries. Glass synthesized in a very reducing atmospherewas used as starting material. To avoid sodium loss during theexperiment, the starting material was loaded into iron capsules,and the experiments were carried out in evacuated silica glasstubes. All phases in the products were identified and analysedwith an electron microprobe. The probe analyses indicate thatthe assemblage Liq+Aug+Pl+Ol is stable over a wide range ofcompositions, and is bounded by the appearance of pigeonitein the silica-rich compositions. In the silica-poor compositions,the assemblage is successively bounded by the appearance ofkirschsteinite, melilite, and nepheline with increasing sodiumcontent. Owing to the isothermal and ‘isobaric’divariant nature of the assemblage Liq+Aug+Pl+Ol in the studiedsystem, a numerical method has been used to describe the phasecompositions with Si and Na contents in the liquid as two arbitrarilychosen independent variables. This procedure results in quantitativecharacterization of the assemblage Liq+Aug+Pl+Ol over a rangeof compositions. ^*Present address: Geochemistry Group, Geology Dept., Beijing University, Beijing, 100871, P.R. China.     

Phase relations, singularities and thermobarometry of metamorphic assemblages containing phengite, chlorite, biotite, K-feldspar, quartz and H2O

The phase relations of divariant and trivariant assemblages involving combinations of phengite, chlorite, biotite, K-feldspar, quartz and H₂O in the KFASH, KMASH and KFMASH systems were calculated using a single thermodynamic data set (Holland and Powell 1998). The stability fields of the various equilibria are represented in P-T projections by contouring sets of compositional isopleths for the Tschermak (Al₂(Fe,Mg)₋₁Si₋₁) and FeMg₋₁ exchanges controlled by the coexisting phases. Five multivariant continuous equilibria, which occur in different regions of P-T-X space, are calibrated as thermobarometers in metamorphic rocks of pelitic to quartzofeldspathic composition. More subtle P-T information, relating to the trajectories (dT/dz) along which reacting rocks have been buried or exhumed, can be extracted from the continuous reactions by investigating the recorded compositional trends in the Al₂(Fe,Mg)₋₁Si₋₁ and FeMg₋₁ solutions. Singularities in P-T space are associated with some of these reactions and may result in unusual mineral textures and compositional trends. A fluid-absent singularity has particular petrological significance because it marks the transition between hydration and dehydration along a single reaction with increasing pressure and temperature. This behaviour causes the sequence of reactions among these minerals observed during metamorphism to be critically dependent on the P-T trajectory. Thermobarometric calculations show good agreement with respect to experimental and field-based data for phengite compositions less than about 50 mol% celadonite (<∼3.5 Si p.f.u. phengite). Received: 15 November 1999 / Accepted: 3 April 2000     

Phase equilibria in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2 and the stability limit of stilpnomelane in metamorphosed Precambrian iron-formations

The phase relations of Al- and Fe-bearing silicates in the system K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O-CO₂, in the presence of quartz and magnetite, are discussed on the basis of mineralogic and petrologic data from Precambrian iron-formations and blueschist facies meta-ironstone from the Franciscan Formation, California. These relations allow an estimation of the physiochemical conditions during low-grade metamorphism of iron-formations. Petrologic data together with available experimental and predicted thermodynamic data on the associated minerals place the upper stability limit of stilpnomelane in iron-formations at about 430–470° C and 5–6 kilobars. Fe-end member stilpnomelane can persist to a maximum temperature of 500° C and pressures up to 6–7 kilobars, although it is unlikely to occur in metamorphosed iron-formations. In iron-formation occurrences the stilpnomelane stability field is bordered by four equilibrium reactions with the assemblages stilpnomelane-zussmanite-chlorite-minnesotaite, stilpnomelane-zussmanite-chlorite-grunerite, stilpnomelane-biotite-chlorite-grunerite, and stilpnomelane-biotite-almandine-grunerite. The stability field is reduced by increasing X(CO₂) and X _Mg ^Stil , and is also a function of a(K ⁺)/ a(H ⁺) in the metamorphic fluid. If the value of a(K ⁺)/ a(H ⁺) is smaller than that defined by the above assemblages, stilpnomelane decomposes to chlorite, but if larger, it is replaced by biotite. At pressures less than 4 kilobars, the zussmanite field is restricted to a very high value of a(K ⁺)/a(H ⁺) (> 5.0 in log units at 1.0 kilobar) where iron-formation assemblages are not stable.     

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.     

Osumilite-sapphirine-quartz granulites from Enderby Land Antarctica — Mineral assemblages and reactions

The pre-Cambrian granulites of Enderby Land Antarctica, contain coexisting spinel-quartz, sapphirine-quartz, hypersthene-sillimanite-quartz and osumilite on a regional extent. Osumilite is present in a variety of mineral assemblages, most of which are documented in granulites for the first time. The mineral assemblages, reactions and compositional zoning in minerals are discussed in terms of continuous and discontinuous reactions in response to changing conditions of metamorphism. The development of many of the mineral coronas can be explained by continuous rather than discontinuous reactions, due to the effects of Mg-Fe and (Mg,Fe)-2Al exchange equilibria with decreasing temperature. The highest P-T conditions of metamorphism (8–10 kb, 900 °–980 ° C, Ellis, in preparation) were beyond the stability limit of coexisting garnet-cordierite. Secondary cordierite has developed through a large number of mineral reactions in response to cooling of these granulites.A theoretical analysis of the phase relations involving osumilite in the chemical systems K₂O-MgO-Al₂O₃-SiO₂ and K₂O-MgO-FeO-Al₂O₃-SiO₂ is presented. In the pure Mg-system the lower temperature stability limit of Mg-osumilite is inferred to be defined with increasing pressure by the reactions OsCd+En+Kfeld+Qtz, OsSa+En+Kfeld+Qtz, OsSill+En+Kfeld+Qtz. In iron-bearing systems an important reaction involving osumilite is Os+GtCd+Hy+Kfeld+Qtz.At moderate temperatures and pressures, osumilite is limited to rocks which lie on the Mg-rich side of the Cd-Hy stable tie line on an AFM diagram. At higher pressures and temperatures osumilite occurs in a widerrange of rock compositions because of the stability of coexisting garnet and osumilite. Petrographic data, as well as chemographic relations indicate that for many common rock compositions, garnet, cordierite, hypersthene, sapphirine and sillimanite cannot coexist with both osumilite and K-feldspar.Published with the permission of the Director, Bureau of Mineral Resources     

Modeling of deep-seated high-alumina parageneses on the basis of the stability fields of corundum- and spinel-normative assemblages of the system CaO–MgO–Al2O3–SiO2

To elaborate physicochemical models for the origin of crystalline rocks, experimental studies of the field of high-alumina assemblages of the system CaO–MgO–Al₂O₃–SiO₂ were carried out at 10–30 kbar and 1250–1535 °C. We have determined the phase relations between the melt (L) and An, Sp, Cpx, Cor, and Ga, the slope of the rays of the monovariant reactions An + Sp = Cpx + Cor + (Ga) and L = Cpx +Ga + Cor + Sp, the position of the nonvariant point (An, Sp, Cpx, Cor, Ga, L), and the compositions of phases participating in these reactions. Based on a topological analysis of the studied segment of the system CaO–MgO–Al₂O₃–SiO₂, we have substantiated that “eclogitization” must follow the reaction Opx + An + Sp = Cpx + Ga. A fundamental continuous series of eutectic monovariant equilibria was observed: L = Cpx + Opx + Fo + An, L = Cpx + Opx + An + Sp, L = Cpx (+ Ga) + An + Sp, and L = Cpx + Cor (+ Ga) + An. A change in the melt composition in this series of eutectic reactions depending on pressure must reflect the most likely magma genesis trend in nature. Comparision of the composition fields in which the above series of reactions is observed with the composition fields of the rocks of magmatic formations showed that this series is most similar to the alkali-earth series of rocks. The mineralogical compositions of cumulates and phenocrysts found in the effusive and dike varieties of these rocks correspond to unique sets of subsolidus phase associations and individual subsolidus phases crystallizing in this fundamental eutectic series.