Cr-Saturation Arrays in Concentrate Garnet Compositions from Kimberlite and their Use in Mantle Barometry

The spinel–garnet transition in Cr/Al-enriched peridotiticbulk compositions is known from experimental investigationsto occur at 20–70 kbar, within the pressure range sampledby kimberlites. We show that the Cr₂O₃–CaO compositionsof concentrate garnets from kimberlite have maximum Cr/Ca arrayscharacterized by Cr₂O₃/CaO 0·96–0·81, andinterpret the arrays as primary evidence of chromite–garnetcoexistence in Cr-rich harzburgitic or lherzolitic bulk compositionsderived from depth within the lithosphere. Under Cr-saturatedconditions on a known geotherm, each Cr/Ca array implicitlydelineates an isobar inside a garnet Cr₂O₃–CaO diagram.This simplification invites a graphical approach to calibratean empirical Cr/Ca-in-pyrope barometer. Carbonaceous chromite–garnetharzburgite xenoliths from the Roberts Victor kimberlite tightlybracket a graphite–diamond constraint (GDC) located atCr₂O₃ = 0·94CaO + 5·0 (wt %), representing a pivotalcalibration corresponding to 43 kbar on a 38 mW/m² conductivegeotherm. Additional calibration points are established at 14,17·4 and 59·1 kbar by judiciously projecting garnetcompositions from simple-system experiments onto the same geotherm.The garnet Cr/Ca barometer is then simply formulated as follows(in wt %):

if Cr₂O₃ 0·94CaO + 5, then P₃₈ (kbar) = 26·9+ 3·22Cr₂O₃ – 3·03CaO, or

if Cr₂O₃ <0·94CaO + 5, then P₃₈ (kbar) = 9·2+ 36[(Cr₂O₃+ 1·6)/(CaO + 7·02)].

A small correction to P₃₈ values, applicable for 35–48mW/m² conductive geotherms, is derived empirically by requiringconventional thermobarometry results and garnet concentratecompositions to be consistent with the presence of diamondsin the Kyle Lake kimberlite and their absence in the Zero kimberlite.We discuss application of the P₃₈ barometer to estimate (1)real pressures in the special case where chromite–garnetcoexistence is known, (2) minimum pressures in the general casewhere Cr saturation is unknown, and (3) the maximum depth ofdepleted lithospheres, particularly those underlying Archaeancratons. A comparison with the P_Cr barometer of Ryan et al.(1996, Journal of Geophysical Research 101, 5611–5625)shows agreement with P₃₈ at 55 ± 2 kbar, and 6–12%higher P_Cr values at lower P₃₈. Because the P_Cr formulationsystematically overestimates the 43 kbar value of the GDC by2–6 kbar, we conclude that the empirical Cr/Ca-in-garnetbarometer is preferred for all situations where conductive geothermsintersect the graphite–diamond equilibrium. KEY WORDS: Cr-pyrope; chromite; P₃₈ barometer; mantle petrology; lithosphere thickness     

Calibration and Applications of Spinel Equilibria in the System FeO-Al2O3-SiO2

A new thermobarometer, based on the equilibrium: has been calibrated with experiments carried out in the piston-cylinderapparatus. Reversed equilibria were obtained using well-calibrated2.54 cm NaCl furnace assemblies and Ag₈₀Pd₂₀capsules with f_O2bufferedat or near iron-wustite. The equilibrium is located between5.2–5.4, 6.6–6.8, and 8.6–8.8 kb at 880, 940,and 1020?C, respectively, and at 5.2 and 8.8 kb between 865–880and 1020–1030?C, respectively. X-ray refinement data indicate that the hercynite (a = 8.15546?) has approximately 18 per cent inverse character. M?ssbauerspectra reveal that 4 mol per cent of the Fe is ferric (2 percent magnetite component). Broad Mossbauer lines and a Fe²+energy level splitting of 3.7 kJ mol^–1 calculated fromthe Mossbauer spectra are consistent with the X-ray determineddegree of inversion, although no separate octahedral Fe²⁺ spectraldoublet is resolved. Calibration of this equation allows calculation of the equilibrium: Thermobarometers based on the above equilibria are widely applicablein granulite fades rocks and yield pressure/temperature datathat are consistent with other well-calibrated barometers andthermometers.     

The Solubility of Alumina in Orthopyroxene Coexisting with Garnet in FeO-MgO--Al2O3--SiO2 and CaO--FeO--MgO--Al2O3--SiO2

The pressure-temperature-compositional (P-T-X) dependence ofthe solubility of Al₂O₃ in orthopyroxene coexisting with garnethas been experimentally determined in the P-T range 5–30kilobars and 800–1200 ?C in the system FeO—MgO—Al₂O₃—SiO₂(FMAS). These results have been extended into the CaO—FeO—MgO—Al₂O₃—SiO₂(CFMAS) system in a further set of experiments designed to determinethe effect of the calcium content of garnet on the Al₂O₃ contentsof coexisting orthopyroxene at near-constant Mg/(Mg + Fe). Startingmaterials were mainly glasses of differing Mg/(Mg + Fe) or Ca/(Ca+ Mg + Fe) values, seeded with garnet and orthopyroxene of knowncomposition, but mineral mixes were also used to demonstratereversible equilibrium. Experiments were performed in a piston-cylinderapparatus using a talc/pyrex medium. Measured orthopyroxene and corrected garnet compositions werefitted by multiple and stepwise regression techniques to anequilibrium relation in the FMAS system, yielding best-fit,model-dependent parameters G^o_y= –5436 + 2.45T cal mol^–1,and W^M1_FeA1= –920 cal mol^–1. The volume change ofreaction, V^o, the entropy change, S^o₉₇₀ and the enthalpy changeH^o_1,970, were calculated from the MAS system data of Perkinset al. (1981) and available heat capacity data for the phases.Data from CFMAS experiments were fitted to an expanded equilibriumrelation to give an estimate of the term W^ga_CaMg = 1900 ? 400cal/mole cation, using the other parametric values already obtainedin FMAS. The experimental data allow the development of a arnet-orthopyroxenegeobarometer applicable in FMAS and CFMAS: where This geobarometer is applicable to both pelitic and metabasicgranulites containing garnet orthopyroxene, and to garnet peridoditeand garnet pyroxenite assemblages found as xenoliths in diatremesor in peridotite massifs. It is limited, however, by the necessityof an independent temperature estimate, by errors associatedwith analysis of low Al₂O₃ contents in orthopyroxenes in high-pressureor low-temperature parageneses, and by uncertainties in thecomposition of garnet in equilibrium with orthopyroxene. Ananalysis of errors associated with this formulation of the geobarometersuggests that it is subject to great uncertainty at low pressuresand for Fe-rich compositions. The results of application ofthis geobarometer to natural assemblages are presented in acompanion paper.     

Stability and Phase Relations of Trioctahedral Calcium Brittle Micas (Clintonite Group)

On the pseudobinary join CaO:3MgO:Al₂O₃:2SiO₂:_xH2O–CaO:1.25MgO:2.75 Al₂O₃: 0.25SiO₂:_xH₂O clintonite mixed crystals Ca(Mg_{1+ x}Al_{2 – x}) (Al_{4 – x}Si_xO₁₀)(OH)₂ with x rangingfrom 0.6 to 1.4 occur in the temperature range 600–830?C, 2 kb fluid pressure. On the MgSirich side clintonites coexistwith chlorite, forsterite, diopside, and calcite (due to smallamounts of CO₂ in the gas phase) and, at lower temperatures,also with idocrase, hydrogrossularite, and aluminous serpentine.Decomposition of clintonite over a divariant temperature rangeoccurs above 830 ?C, 2 kb; clintonite-free subsolidus assemblagescomprising three or four solid phases are formed in the temperatureranges 890 ?–1120 ?C. The subsolidus assemblages can berepresented in a polyhedron defined by the corners forsterite,diopside, melilite, spinel, anorthite, corundum, and calciumdialuminate. Above 1120 ?C partial melting occurs. The upper thermal stability limits of three selected compositionshave been reversed in the P-T range 0.5–20 kb and 730–1050 ?C, respectively. Below some 4 kb breakdown is dueto the divariant reactions: (1)Ca(Mg_2.25Al_0.75)(Al_2.75)(Si_1.25O₁₀)(OH)₂ spinel+diopside_ss+forsterite+clintonite_ss+vapor, (2)Ca(Mg₂Al)(Al₃SiO₁₀)(OH)₂ spinelx002B;melilite_ss+anorthite+clintonite_ss+vapor, (3)Ca(Mg_1.75Al_1.25)(Al_3.25)(Si_0.75O₁₀)(OH)₂ spinel+melilite_ss+corundum+clintonite_ss+vapor, At the terminations of the divariant temperature ranges (1)melilite_ss, (2) diopside_ss, and (3) anorthite enter those assemblagesand clintonitess disappears completely. The reactions can berepresented by the following equations (1)log,_H2O = 10.2879–8113/T+0.0856(P–1)/T, (2)log = 9.5852–7325/T+0.0794(P–1)/T, (3)log = 7.8358–5250/T+0.077(P–1)/T, with P expressed in bars and Tin ?K. Above 4 kb the upper thermalstability limit of clintonite is defined by incongruent melting,with grossularite participating at pressures above 9 kb. Thesecurves exhibit a very steep, probably even negative slope inthe P-T diagram. There is a close correspondence between natural clintonite-bearingassemblages and thosefound experimentally. The rarity of clintonitein nature is not due to special conditions of pressure and temperaturebut rather due to special bulk compositions of the rocks.     

A Theoretical Study on the Formation of Growth Zoning in Garnet Consuming Chlorite

Chemical zoning of garnet is often used to deduce P–Tpaths of rocks by inverse calculation. To validate the derivedP–T paths, it is desired to establish a method to predictthe chemical compositions of garnet theoretically. This studyproposes a new forward calculation of the formation of Mg–Fe–Mngarnet from chlorite, which solves the non-linear simultaneousequations using nested iterative calculations. Growth of garnetconsuming chlorite and quartz was modelled in a MnO–FeO–MgO–Al₂O₃–SiO₂–H₂Osystem, using the most recent thermodynamic data for the minerals.The prograde P–T history of the Sambagawa metamorphicbelt, SW Japan, was modelled. To reproduce growth zoning, crystallizedgarnet was removed step by step from the system; perfect diffusionwas assumed for chlorite. The proposed model derived the evolutionof molar amounts and chemical compositions of Mg–Fe–Mnchlorite and garnet. It successfully reproduced the shape ofthe observed chemical profile of garnet, although the temperaturecondition was higher than general observations. The Mn contentof the garnet core was generally high, and Mg/Fe ratio alwaysstarted rising rapidly after Mn was depleted. Thermodynamicproperties of minerals, initial chlorite composition, P–Tpath, H₂O partial pressure, and Ca content in garnet were variedto test the behaviour of the system. The properties of Mn phasesinfluenced only the chemical composition of the garnet core.The temperature range in which garnet grew depended on the H₂Opartial pressure or the Ca content in garnet. KEY WORDS: chemical equilibrium; chemical zoning; garnet; forward modelling; Sambagawa metamorphic belt     

Equilibrium Compositions of Coexisting Garnet and Orthopyroxene: Experimental Determinations in the System FeO-MgO-Al2O3-SiO2, and Applications

We have determined the Fe-Mg fractionation between coexistinggarnet and orthopyroxene at 20–45 kb, 975–1400?C,and the effect of iron on alumina solubility in orthopyroxeneat 25 kb, 1200?C, and 20 kb, 975?C in the FMAS system. The equilibriumcompositions were constrained by experiments with crystallinestarting mixtures of garnet and orthopyroxene of known initialcompositions in graphite capsules. All iron was assumed to beFe²⁺. A mixture of PbO with about 55 mol per cent PbF₂ provedvery effective as a flux. The experimental results do not suggest any significant dependenceof K_D on Fe/Mg ratio at T 1000?C. The lnK_D vs. l/T data havebeen treated in terms of both linear and non-linear thermodynamicfunctional forms, and combined with the garnet mixing modelof Ganguly & Saxena (1984) to develop geothermometric expressionsrelating temperature to K_D and Ca and Mn concentrations in garnet. The effect of Fe is similar to that of Ca and Cr³⁺ in reducingthe alumina solubility in orthopyroxene in equilibrium withgarnet relative to that in the MAS system. Thus, the directapplication of the alumina solubility data in the MAS systemto natural assemblages could lead to significant overestimationof pressure, probably by about 5 kb for the relatively commongarnetlherzolites with about 25 mol per cent Ca+Fe²⁺ in garnetand about 1 wt. per cent Al₂O₃ in orthopyroxene.     

Experimental Interaction of Granitic and Basaltic Magmas and Implications for Mafic Enclaves

We have performed time series experiments for periods rangingfrom 3 min to 44 h on the interaction of granite melt and partiallymolten basalt at 920C and 10 kbar, in the presence of 5 wt.%water. With time, the assemblage of the basalt domain changesfrom predominantly amphibole+plagioclase to clinopyroxene+garnet;the melt fraction increases from {small tilde}2•5 to 40%;and between the two domains, the melt compositions progressivelyequilibrate. Initially in each run, melts of the basalt domainhave uniform plateau concentrations for SiO₂, Al₂O₃, CaO, MgO,and FeO because the activities of these components are regulatedby the mineral assemblage, but at advanced stages of reaction,no such control is evident. We have derived analytical expressionsto describe and simulate the diffusion profiles. The concentrationprofiles for SiO₂, Al₂O₃, CaO, and Na₂O in the granite, emanatingfrom the basalt–granite interface, have been used to estimateeffective diffusivities. The values from the shorter runs arecompared with those of the experiment of longest duration forwhich we assumed finite couples in our calculations. In thediffusion calculations for K₂O the difference in melt fractionbetween the two domains is accounted for. The resulting values(in cm²/s) are: D_Na2O=6 10^–7, D_K2O=3 10^–7, D_MgO=9 10^–8, D_CaO=(4–6) 10^–8, and D_SiO2 and D_Al2O3=(3–0•6) 10^–8. They are in reasonable agreement with values fromother studies. On the basis of our experiments we calculatethat mafic enclaves of magmatic origin should equilibrate toa large degree with their host magma in slowly cooling non-convectinggranitic plutons. Enclaves approaching complete re-equilibrationretain distinctly higher modal amounts of mafic minerals. Theydo not compositionally resemble binary magma mixtures, but aremore like host magma with accumulated crystals. We show thatthe modal differences between enclave and host are indicativeof the temperature of homogenization and that, in principle,this temperature can be deduced from equilibrium phase diagrams. ^* Present address: Mineralogisch-Petrologisches Institut, Universitt Gttingen, Goldschmidtstrasse 1, 3400 Gttingen, Germany     

Archean Shoshonitic Lamprophyres of the Abitibi Subprovince, Canada: Petrogenesis, Age, and Tectonic Setting

Archean shoshonitic lamprophyre dikes are prevalent along majortranslithospheric structures that demark tectonostratigraphicterranes in the Abitibi greenstone belt of the Superior Province.The lamprophyres post-date volcanism, tonalitic batholiths,deformation, and metamorphism of the terranes, and are mostprominently developed in trans-tensional graben, where theyare associated with molasse sediments and an alkaline suiteof plutons, stocks, and trachytes. Mineralogically, the dikesare characterized by zoned phiogopite or hornblende phenocrystsand/or diopsidic pyroxene, restriction of feldspar to the groundmass,globular segregations of K-feldspar and calcite, olivine ‘pilite’,and accessory Ti-magnetite, Cr-spinel, apatite, titanite, andSr-rich calcite; crustal xenoliths are sporadically present. Compositionally, weakly altered primititive dikes have contentsof SiO₂ (41–48 wt.%), TiO₂ (06–11 wt.%), P₂O₅(041–076 wt.%), Cr (258–915 ppm), Co (36–84ppm), Ni (159–368 ppm), and Sc (15–32 ppm), mg-numbers(72–79), and K₂O/Na₂O ratios (10–43) similar tothose of Phanerozoic shoshonitic lamprophyres. The primitivedikes are also characterized by extreme enrichments of K, Rb,Ba, Cs, U, and Th, enhanced light rare earth elements (REE),and fractionated REE patterns [La_n=33–274; (La/Yb)_n=16–87].On mid-ocean ridge basalt (MORB) normalized plots the dikesshow coherent patterns, with (1)enrichment of K, Rb, and Barelative to Sr and LREE, (2) variable enrichments of Rb andBa relative to K, (3) troughs at Ta–Nb and Ti, and (4)variable negative P and positive Sm anomalies. Compositionalvariations of lamprophyre suites within restricted areas areinterpreted to reflect melting of compositionally heterogeneoussources, variable degrees of assimilation–fractional crystallization,and mixing of distinct batches of lamprophyric magmas. Primary¹⁸O values of the magmas are close to 63 as given by resistantpyroxene; these are ¹⁸O-relative to MORB, but comparable withPhanerozoic alkali basalts and lamprophyres. Mica, clinopyroxene,hornblende, and feldspar do not retain magmatic equilibriumfractionations for oxygen isotopes. A concordant U–Pbage of 26742 Ma was obtained from titanite, similar to theages of shoshonitic plutons in the same area. The lamprophyredikes possess a total range of _Nd between 041 and 211(1),and define a distinct field in common with other late Archeanshoshonites on an f^(Sm/Nd) vs. _Nd plot. Pyroxenes yield a low⁸⁷Sr/⁸⁶Sr(0701102), whereas whole-rock Rb-Sr isotope systematicsare disturbed. Lamprophyres are not known from pre-27-Ga terranes. Their compositionand inferred geodynamic setting is consistent with an originin a depleted mantle wedge, enriched in large ion lithophileelements (LILE) and LREE during subduction by slab and sediment(low Sr/Nd) dehydration. Partial melting may have been triggeredby rebound and decompression that followed accretional collisionof two allochthonous greenstone terranes at a plate margin.The onset of shoshonitic magmatism at 27 Ga coincides withthe transition from tonalite–trondhjemite–granodiorite(TTG) dominated magmatism with high (La/Yb)_n and low Yb (slabmelting) to mantle-wedge derived granites featuring lower (La/Yb)_nand higher Yb (slab dehydration), owing to decreasing heat flow.Accretion of greenstone belts, and their buoyant harzburgiticroots, consolidated a thick subcontinental mantle lithosphereby 27 Ga, which was subsequently the source of Jurassic kimberlitesthat intruded the persistently reactivated Archean translithosphericstructures.     

Origin of Grandite Garnet in Calc-Silicate Granulites: Mineral-Fluid Equilibria and Petrogenetic Grids

The role of clinopyroxene in producing grandite garnet is evaluatedusing data from an ultrahigh-temperature metamorphosed calc-silicategranulite occurrence in the Eastern Ghats Belt, India. ‘Peak’pressure–temperature conditions of metamorphism were previouslyconstrained from associated high Mg–Al granulites as c.0·9 GPa, >950°C, and the rocks were near-isobaricallycooled to c. 750°C. Grandite garnet of variable compositionwas produced by a number of reactions involving phases suchas clinopyroxene, scapolite, plagioclase, wollastonite and calcite,in closely spaced domains. Compositional heterogeneity is preservedeven on a microscale. This precludes pervasive fluid fluxingduring either the peak or the retrograde stage of metamorphism,and is further corroborated by computation of fluid–rockratios. With the help of detailed textural and mineral compositionalstudies leading to formulation of balanced reactions, and usingan internally consistent thermodynamic dataset and relevantactivity–composition relationships, new petrogenetic gridsare developed involving clinopyroxene in the system CaO–Al₂O₃–FeO–SiO₂–CO₂–O₂in T–aCO₂–fO₂ space to demonstrate the importanceof these factors in the formation of grandite garnet. Two singularcompositions in garnet-producing reactions in this system arededuced, which explain apparently anomalous textural relations.The possible role of an esseneite component in clinopyroxenein the production of grandite garnet is evaluated. It is concludedthat temperature and fO₂ are the most crucial variables controllinggarnet composition in calc-silicate granulites. fO₂, however,behaves as a dependent variable of CO₂ in the fluid phase. Externalfluid fluxing of any composition is not necessary to producechemical heterogeneity of garnet solid solution. KEY WORDS: grandite garnet; role of clinopyroxene; internal buffering; oxidation–decarbonation equilibria     

Reaction Textures in a Suite of Spinel Granulites from the Eastern Ghats Belt, India: Evidence for Polymetamorphism, a Partial Petrogenetic Grid in the System KFMASH and the Roles of ZnO and Fe2O3

Spinel granulites, with or without sapphirine, occur as lensesin garnetiferous quartzofeldspathic gneisses (leptynites) nearGokavaram in the Eastern Ghats Belt, India. Spinel granulitesare mineralogically heterogeneous and six mineral associationsoccur in closely spaced domains. These are (I) spinel–quartz–cordierite,(II) spinel–quartz–cordierite–garnet–orthopyroxene–sillimanite,(III) spinel–cordierite–orthopyroxene–sillimanite,(IV) spinel–quartz–sapphirine–sillimanite–garnet,(V) spinel–quartz-sapphirine–garnet and (IV) rhombohedral(Fe–Ti) oxide–cordierite–orthopyroxene–sillimanite.Common to all the associations are a porphyroblastic garnet(containing an internal schistosify defined by biotite, sillimaniteand quartz), perthite and plagioclase. Spinel contains variableamounts of exsolved magnetite and is distinctly Zn rich in thesapphirine-absent associations. X_Mg in the coexisting phasesdecreases in the order cordierite–biotite–sapphirine–orthopyroxene–spinel–garnet–(Fe–Ti)oxides. Textural criteria and compositional characteristicsof the phases document several retrograde mineral reactionswhich occurred subsequent to prograde dehydration melting reactionsinvolving biotite, sillimanite, quartz, plagioclase and spinel.The following retrograde mineral reactions are deduced: (1)spinel + quartz cordierite, (2) spinel + quartz garnet + sillimanite,(3) garnet + quartz cordierite + orthopyroxene, (4) garnet+ quartz + sillimanite cordierite, (5) spinel + cordierite orthopyroxene + sillimanite, (6) spinel + sillimanite + quartz sapphirine, (7) spinel + sapphirine + quartz garnet + sillimanite,and (8) spinel + quartz sapphirine + garnet. A partial petrogeneticgrid for the system FeO–MgO–Al₂O₃–SiO₂–K₂O–H₂Oat high fo₂, has been constructed and the effects of ZnO andFe₂O₃ on this grid have been explored Combining available experimentaland natural occurrence data, the high fo₂ invariant points inthe partial grid have been located in P–T space. Geothermobarometricdata and consideration of the deduced mineral reactions in thepetrogenetic grid show that the spinel granulites evolved throughan anticlockwise P–T trajectory reaching peak metamorphicconditions >9 kbar and 950C, followed by near-isobaric cooling(dT/dP = 150C/kbar). This was superimposed by an event of near-isothermaldecompression (dT/dP = 15C/kbar). The studied spinel granulites,therefore, preserve relic prograde mineral associations andreaction textures despite being metamorphosed at very high temperatures,and bear evidence of polymetamorphism. KEY WORDS: spinel granulite; Eastern Ghats; India; polymetamorphism; geothermometry; geobarometry Corresponding author     

Mesoproterozoic Reworking of Palaeoproterozoic Ultrahigh-temperature Granulites in the Central Indian Tectonic Zone and its Implications

In the southern periphery of the Sausar Mobile Belt (SMB), thesouthern component of the Central Indian Tectonic Zone (CITZ),a suite of felsic and aluminous granulites, intruded by gabbro,noritic gabbro, norite and orthopyroxenite, records the polymetamorphicevolution of the CITZ. Using sequences of prograde, peak andretrograde reaction textures, mineral chemistry, geothermobarometricresults and petrogenetic grid considerations from the felsicand the aluminous granulites and applying metamorphosed maficdyke markers and geochronological constraints, two temporallyunrelated granulite-facies tectonothermal events of Pre-Grenvillianage have been established. The first event caused ultrahigh-temperature(UHT) metamorphism (M₁) (T 950°C) at relatively deepercrustal levels (P 9 kbar) and a subsequent post-peak near-isobariccooling P–T history (M₂). M₁ caused pervasive biotite-dehydrationmelting, producing garnet–orthopyroxene and garnet–rutileand sapphirine–spinel-bearing incongruent solid assemblagesin felsic and aluminous granulites, respectively. During M₂,garnet–corundum and later spinel–sillimanite–biotiteassemblages were produced by reacting sapphirine–spinel–sillimaniteand rehydration of garnet–corundum assemblages, respectively.Applying electron microprobe (EMP) dating techniques to monazitesincluded in M₁ garnet or occurring in low-strain domains inthe felsic granulites, the UHT metamorphism is dated at 2040–2090Ma. Based on the deep crustal heating–cooling P–Ttrajectory, the authors infer an overall counterclockwise P–Tpath for this UHT event. During the second granulite event,the Palaeoproterozoic granulites experienced crustal attenuationto 6·4 kbar at T 675°C during M₃ and subsequentnear-isothermal loading to 8 kbar during M₄. In the felsic granulites,the former is marked by decomposition of M₁ garnet to orthopyroxene–plagioclasesymplectites. During M₄, there was renewed growth of garnet–quartzsymplectites in the felsic granulites, replacing the M₃ mineralassemblage and also the appearance of coronal garnet–quartz–clinopyroxeneassemblages in metamorphosed mafic dykes. Using monazites frommetamorphic overgrowths and metamorphic recrystallization domainsfrom the felsic granulite, the M₄ metamorphism is dated at 1525–1450Ma. Using geochronological and metamorphic constraints, theauthors interpret the M₃–M₄ stages to be part of the sameMesoproterozoic tectonothermal event. The result provides thefirst documentation of UHT metamorphism and Palaeo- and Mesoproterozoicmetamorphic processes in the CITZ. On a broader scale, the findingsare also consistent with the current prediction that isobaricallycooled granulites require a separate orogeny for their exhumation. KEY WORDS: Central Indian Tectonic Zone; UHT metamorphism; counterclockwise P–T path; monazite chemical dating     

Calculated Phase Relations in High-Pressure Metapelites in the System NKFMASH (Na2O-K2O-FeO-MgO-Al2O3-SiO2-H2O)

Using an internally consistent thermodynamic dataset and updatedmodels of activity–composition relation for solid solutions,petrogenetic grids in the system NKFMASH (Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NKMASH and NKFASH have been calculated withthe software THERMOCALC 3.1 in the P–T range 5–36kbar and 400–810°C, involving garnet, chloritoid,biotite, carpholite, talc, chlorite, kyanite/sillimanite, staurolite,phengite, paragonite, albite, glaucophane, jadeite, with quartz/coesiteand H₂O in excess. These grids, together with calculated AFMcompatibility diagrams and P–T pseudosections, are shownto be powerful tools for delineating the phase equilibria andP–T conditions of Na-bearing pelitic assemblages for avariety of bulk compositions from high-P terranes around theworld. These calculated equilibria are in good agreement withpetrological studies. Moreover, contours of the calculated phengiteSi isopleths in P–T pseudosections for different bulkcompositions confirm that phengite barometry is highly dependenton mineral assemblage. KEY WORDS: phase relations; HP metapelite; NKFMASH; THERMOCALC; phengite geobarometry     

The Role of Volatiles in the Thermal History of Metamorphic Terranes

Analytical and numerical solutions to the differential equationsfor the conduction of heat with heat production or with fluidflow have been used to evaluate the role of volatiles in thethermal history of regional metamorphic terranes. The maximumthermal effect from pervasive, single-pass, regional volatileflow may be predicted from a steady-state solution given byBredehoeft & Papadopoulos (1965). For fluid velocity v_F(m/s) and connected porosity , combinations of volatile fluxv_F (m³ of fluid/m²s) and transport distance L(m) such that vLis greater than 3?6?10^–7 should produce regional temperatureincreases due to fluid flow, if the flow persists for l0⁵–10⁶a (depending on the transport distance L). The absolute valueof the temperature increase due to volatile flow will be greaterin regions with higher ambient geothermal gradients. For L=20km, a volatile flux of 1?8 ? 10^–11 (m³ of fluid/m²s) orgreater is required to achieve a temperature effect. Few geologicprocesses release volatiles at this rate for extended periodsof time, so regional thermal effects from the single-pass, pervasiveflow of volatiles are unlikely. A new analytical solution forthe steady state temperature distribution between idealizedparallel channels of fluid flow is presented along with theresults of two-dimensional numerical models of channelized fluidflow. Both approaches show that little temperature increaseis expected near channels of fluid flow relative to the rocksbetween the channels, unless the channels exceed 100 m in widthor unless the fluid fluxes are very large and transient. A possiblethermal effect of volatile flow in metamorphic terranes is theproduction of metamorphic hot spots due to focusing of volatilesinto widely spaced channels or conduits exceeding 1 km in width.Given a sufficient fluid flux (exceeding 10^–10 m³ of fluid/m²s),thermal gradients of over 100K from center to edge may be producedin such channels during relatively short time intervals (10⁵–10⁶a).     

Element Mobility During Incipient Granulite Formation at Kabbaldurga, Southern India

At Kabbaldurga, infiltration of carbonic fluids along a systemof ductile shears and foliation planes has led to partial transformationof Archaean grey biotite–hornblende gneiss to coarse-grainedmassive charnockite at about 2.5 b.y. ago. The dehydration ofthe gneiss assemblage was induced by a marked metasomatic changeof the reacting system from granodioritic to granitic, and obviouslytook place under conditions of an open system at 700–750?C and 5–7 kb. Extensive replacement of plagioclase (An_16–30)by K-feldspar through Na, Ca–K exchange reactions withthe ascending carbonic fluids led to strong enrichment in K,Rb, Ba, and SiO₂, and to a depletion in Ca. Progressive dissolutionof hornblende, biotite, magnetite, and the accessory mineralsapatite and zircon resulted in a marked depletion in Fe, Mg,Ti, Zn, V, P, and Zr. Most important is the recognition of REEmobility: with advancing charnockitization, the moderately fractionatedREE distribution patterns of the grey gneisses (La_N270; La_N/Yb_N= 5–20; Eu_N27; Eu/Eu^* = 0.6–0.3) give way to stronglyfractionated REE patterns with a positive Eu-anomaly (La_N200;La_N/Yb_N = 20–80; Eu_N22; Eu/Eu^* = 0.6–1.8). The systematicdepletion especially in the HREE is due to the progressive dissolutionof zircon, apatite (and monazite), which strongly concentratethe REE. Stable isotope data (¹⁸O of 6.9–8.0 per mille for gneissesand charnockites; ¹³C of –8.5 and –6.5 per millefor late carbonate) indicate a magmatogenic source for the carbonicfluids. In contrast to the currently favoured derivation ofcarbonic fluids by decarbonation of the upper mantle or degassingof underplated basaltic intrusions, it is discussed here thatabundant fluid inclusions in lower crustal charnockites providedan extensive reservoir of ‘fossil’ carbonic fluids.Shear deformation has tapped this reservoir and generated thechannel-ways for fluid ascent. Charnockitization of the Kabbaldurgatypethus appears to be a metasomatic process which is tectonicallycontrolled and restricted to the crustal level of the amphiboliteto granulite transition.     

The Effect of Reaction Overstep on Garnet Microtextures in Metapelitic Rocks of the Ilesha Schist Belt, SW Nigeria

Garnet-bearing assemblages of K-rich and K-poor metapelitesfrom the Ilesha Schist belt, SW Nigeria, are investigated. K-richsamples contain the assemblages (A) garnet–staurolite–muscovite–chlorite–magnetite,(B) andalusite–garnet–staurolite–muscovite–chlorite–magnetiteand (C) sillimanite–andalusite–garnet–muscovite–chlorite–magnetite.K-poor samples contain the assemblages (D) garnet–staurolite–cordierite–chloriteand (E) garnet–cordierite–chlorite ± staurolite.All assemblages contain quartz, plagioclase, biotite and ilmenite.P–T pseudosections calculated in the system CaO–Na₂O–K₂O–TiO₂–MnO–FeO–MgO–Al₂O₃–SiO₂ –H₂O ± O₂ suggest peak metamorphismat 590 ± 20°C at 5 ± 0·5 kbar, followedby retrogression to 550°C at 3·0 kbar, in agreementwith field evidence, domain assemblages, mineral compositions,modes and geothermobarometry. The absence of compositional zonationshows that garnet in all investigated rocks nucleated and grewat constant P–T–X in equilibrium with associatedminerals on the thin-section scale. However, the garnet-in reactiondid not begin until the establishment of a significant temperatureoverstep of     

Thermodynamic Mixing Properties of Muscovite-Paragonite Crystalline Solutions at High Temperatures and Pressures, and their Geological Applications

Reversed Na-K exchange data between mica and a 2 molal aqueous(Na,K)Cl fluid (Flux & Chatterjee, 1986) have been employedto model the thermodynamic mixing behaviour of muscovite-paragonitecrystalline solutions on the basis of the Redlich-Kister equation.For these binary micas, G^ex_m may be expressed as where A=11222+1.389 T+0.2359 P, B=–1134+6.806 T–0.0840 P, and C=–7305+9.043 T, with T in K, P in b, G^ex_m, A, B, and C in joules/mol. G_m^ex is well constrained between 450 and 620?C, and may be extrapolatedbeyond that range with caution. The calculated solvi are skewedtoward the paragonite end member. In the range up to 15 kb,the critical temperature, T_c and the critical composition, X_cmay be expressed as a function of P by the relations: and with P indicated in bars. Calculated phase relations of muscovite-paragonite crystallinesolutions have been depicted in terms of the system KAlSi₃O₈-NaAlSi₃O₈-Al₂O₃-SiO₂-H₂O.These data may be applied to appropriate assemblages involvingmica, alkali feldspar, an Al₂ polymorph, and quartz to estimateP, T and a_H2O conditions of their equilibration. In principle,the muscovite limb of the solvus may be used to obtain geothermometricdata for coexisting muscovite-paragonite pairs, provided theequilibrium pressure is independently known. However, such applicationmust be restricted for the present to micas on the ideal muscovite-paragonitejoin. Mica-alkali feldspar-Al₂SiO₅-quartz or mica-plagioclase-Al₂SiO₅-quartzassemblages may be used to deduce a_H2O in the coexisting fluid,if P, and T of equilibrium are independently known. Examplesof such geological applications are given.     

Petrogenesis of the Eastern Bushveld Complex: Crystallization of the Middle Critical Zone

The bronzite—chromite-anorthite assemblage of the F—unit(Cameron & Emerson, 1959) from the Critical Zone of theBushveld Igneous Complex, was examined with the aid of an electrolyticcell designed after Sato (1971). The resultant fO₂-T data reveala last equilibration at an fO₂ value of 10^{11·82 ±·40} atm and at a temperature of 1091 ± 35 °C.These fO₂-T data when compared with: (1) a one atmosphere quenching—technique solidus determinationof 1110 ± 5 °C, (2) the Bushveld plagioclase compositional trends (Cameron,1970), (3) Bushveld petrofabric examinations (Cameron, 1969) (4) phase equilibria in the system CaO–MgO–FeO–CaAl₂Si₂O₈–SiO₂(Roeder & Osborn, 1966), (5) phase equilibria in the system CaAl₂Si₂O₈–NaAlSi₃O₈–SiO₂–MgO–Fe–O₂–H₂O–CO₂(Eggler, 1974), all support the idea that the Eastern Bushveld magma was notappreciably differentiating in the middle Critical Zone betweenF and the L Horizons, an accumulation of nearly 220 meters.     

Synthesis and Stability Relations of Mg--Al Pumpellyite, Ca4Al5MgSi6O21(OH)7

Hydrothermal synthesis and investigations of stability relationsof Mg—Al pumpellyite were conducted using high-pressurecold-seal apparatus over the temperature range 250–600°C and 2–8 kb P_fluid. Mg—Al pumpellyite Ca₄Al₅MgSi₆O₂₁(OH)₇was synthesized from partially crystalline gel mixtures of stoichiometriccomposition at 275–410 °C, 6–9 kb P_fluid, andruns of 7–90 days. Pure monomineralic synthetic Mg—Alpumpellyite has refractive index n_ß = 1.624 (2) andcell dimensions = 8.825 (8) Á, b = 5.875 (5) Á,c = 19.10 (1) Á, and ß = 97.39 (7)°. The high temperature assemblage of the equivalent bulk compositionconsists of clinozoisite, hydrogrossular/grossular, aluminousseptechlorite/chlorite, quartz, and H₂O. Hydrogrossular wassynthesized in the presence of quartz at 8 kb from 400–500°C, and hydrogrossular + quartz are unstable with respectto grossular + H₂O at 400 °C and 8 kb P_fluid. At 8 kb P_fluid,aluminous septechlorite forms at temperatures below 500 °Cwhereas aluminous 14 Á chlorite crystallizes at 500–600°C. The equilibrium relations of Mg—Al pumpellyite were determinedusing subequal mixtures of synthetic Mg—Al pumpellyiteand its high temperature assemblage. The reaction 9 Mg—Alpumpellyite = 9 clinozoisite + 6 grossular + 2 chlorite + 4quartz + 19 H₂O occurs at temperatures of 390 °C at 8 kb,368 °C at 5 kb, and near 325 °C at 2 kb P_fluid. Thereversal data yield an approximate value of –3141 joules/mole°K for the standard entropy of formation for the syntheticMg—Al pumpellyite. The Schreinemakers' relations for pumpellyite, prehnite, clinozoisite,tremolite, grossular, and amesite in the presence of excessquartz and fluid were constructed in the pseudo-ternary systemCaO–Al₂O₃–MgO(SiO₂–H₂O). The results, togetherwith reconnaissance experiments on the reaction 4 Mg—Alpumpellyite + 2 quartz = 8 prehnite + aluminous septechlorite+ 2 H₂O, locate the invariant point [TR] at approximately 5.7kb P_fluid and 375 °C. The results of the present study arenot compatible with previous experimental data on the invariantpoint [GR]. The P–T oriented phase relations are used to interpretsome natural parageneses developed in low-grade metabasalticrocks recrystallized under conditions of low _co2. The high-temperaturestability relations of Mg—Al pumpellyite are useful todenote the onset of greenschist facies metamorphism in rocksof basaltic composition.     

Phase Equilibria in the Pyroxene Quadrilateral

Experimental phase equilibrium data on compositions of coexistingpyroxenes in the quadrilateral enstatite-diopside-ferrosilite-hedenbergitehave been used to model pyroxene solid solutions and to formulatepyroxene geothermometers. Each pyroxene is treated as a solidsolution of four quad-components using the Kohler formulation where G_ij^* is the excess free energy of mixing in a binary solutioncalculated with binary mole fractions (e.g. X_i^o = X_i/(X_i+X_j))and X_i is the mole fraction in a multicomponent solution. Thefit to the experimental data is achieved by minimizing the totalGibbs free energy of the assemblage. The following set of thermochemicaldata and simple mixture parameters (W_ij) are found to be bestsuited. Standard (T = 298?15 K) enthalpy and entropy of formationfrom elements for fictive orthohedenbergite are –1416?8kJ and 84?88 J K^–1 mol ^–1 respectively. The heatcapacity is given by 114?67+17?09E-3T–31?40E5T^–2.The W_ij data are: Opx: W₁₂ = W₂₁ = 25 W₁₃ = (13?1–0-015T),W₃₁ = (3?37–0?005T), W₂₃ = 20, W₃₂ = 16, W₂₄ = 5, W₄₂= 7, W₃₄ = 15, W₄₃ = 15; Cpx: W₁₂ = (25?484+0?0812P), W₂₁ =(31?216–0?0061P),W₃₁ = W₁₃ = 0W₁₄ = (93?3–0?045T), W₄₁ = (–20?0+0?028T),W₂₃ = 24, W₃₂ = 15, W₂₄ = 12, W₄₂ = 12, W₃₄ = (16?941+0?00592P),W₄₃ = (20?697–0?00235P). Coexisting pyroxene compositionshave been computed in the temperature range of 700 to 1400?C. Two geothermometers have been constructed, one based on atomicfraction of iron (Fe/(Fe + Mg)) in orthopyroxene and the Fe-Mgdistribution coefficient and the other, based on wollastonitecontent of clinopyroxene. The two scales yield different temperatureswhen applied to the same rock. In igneous pyroxenes, the Catransfer ceased at 150 to 200?C above the closure temperatureof the Fe-Mg ion-exchange. In metamorphic rocks an oppositeeffect seems to have prevailed.     

Volcan Popocatepetl, Mexico. Petrology, Magma Mixing, and Immediate Sources of Volatiles for the 1994-Present Eruption

Volcán Popocatépetl has been the site of voluminousdegassing accompanied by minor eruptive activity from late 1994until the time of writing (August 2002). This contribution presentspetrological investigations of magma erupted in 1997 and 1998,including major-element and volatile (S, Cl, F, and H₂O) datafrom glass inclusions and matrix glasses. Magma erupted fromPopocatépetl is a mixture of dacite (65 wt % SiO₂, two-pyroxenes+ plagioclase + Fe–Ti oxides + apatite, 3 wt % H₂O, P= 1·5 kbar, f_O2 = NNO + 0·5 log units) and basalticandesite (53 wt % SiO₂, olivine + two-pyroxenes, 3 wt % H₂O,P = 1–4 kbar). Magma mixed at 4–6 km depth in proportionsbetween 45:55 and 85:15 wt % silicic:mafic magma. The pre-eruptivevolatile content of the basaltic andesite is 1980 ppm S, 1060ppm Cl, 950 ppm F, and 3·3 wt % H₂O. The pre-eruptivevolatile content of the dacite is 130 ± 50 ppm S, 880± 70 ppm Cl, 570 ± 100 ppm F, and 2·9 ±0·2 wt % H₂O. Degassing from 0·031 km³ of eruptedmagma accounts for only 0·7 wt % of the observed SO₂emission. Circulation of magma in the volcanic conduit in thepresence of a modest bubble phase is a possible mechanism toexplain the high rates of degassing and limited magma productionat Popocatépetl. KEY WORDS: glass inclusions; igneous petrology; Mexico; Popocatépetl; volatiles