The Formation of Chrysoberyl in Metamorphosed Pegmatites

Mineral assemblages in pegmatite samples from Kolsva, Swedenand Marikov, Czechoslovakia show that chrysoberyl is alwaysaccompanied by quartz, and is a breakdown product of primarypegmatitic beryl. Textures and the mineral-forming process forthe Kolsva pegmatite are explained by the reactions beryl +K-feldspar + H+ = chrysoberyl + quartz + SiO_{2, aq} + K⁺ + H₂Oor alternatively beryl —K—feldspar + H₂O = chrysoberyl+ quartz + melt. Mineral assemblages from mica-rich parts ofthe pegmatite include sillimanite—K—feldspar, muscovite—K—feldspar—sillimanite,and annite—magnetite—spinel—sillimanite—garnet.Details about the composition and the textural relationshipsof these minerals are given; they indicate a post-pegmatiticmetamorphic event at P—T conditions near to the anatecticregime. The samples from Marikov show textures, which are explainedby the reactions beryl + albite + H⁺ = chrysoberyl + quartz+ Na⁺ + H₂O or alternatively beryl + albite + H₂O = chrysoberyl+ quartz + melt. Breakdown of muscovite produces sillimaniteaccording to the reactions beryl + albite + muscovite + H⁺ =chrysoberyl + quartz + sillimanite + Na⁺ + K⁺ + H₂O or alternativelyberyl + albite + muscovite + H₂O = chrysoberyl + quartz + sillimanite+ melt. Similar reaction textures and mineral assemblages were foundin other chrysoberyl-bearing pegmatites (Maroankora, Madagascar;Helsinki, Finland; Haddam, Greenfield, Greenwood, U.S.A.). Hydrothermal experiments located the reaction beryl + alkalifeldspar + H₂O = chrysoberyl + phenakite + melt at P—Tconditions between the K—feldspar—quartz—H₂Osolidus and the K—feldspar—albite—quartz-H₂Osolidus. It is concluded that the formation of Al-rich minerals likechrysoberyl and sillimanite in pegmatites is due to a post-pegmatiticevent at high P—T conditions. The question as to whichof the alternative set of reactions is more likely, the ionicequilibria or the anatectic chrysoberyl formation, must be leftopen. The previous hypothesis of a desilification of a pegmatitewhich intruded into SiO₂-poor country rocks, or of the assimilationof Al₂O₃-rich country rocks, cannot explain the mineral assemblagesof the two pegmatites.     

Low-temperature Compatibility Relations of Cordierite in Haplopelites of the System K2O--MgO--Al2O3--SiO2--H2O

The equilibrium temperatures of the reaction muscovite+chlorite+quartz= cordierite+phlogopite+H₂O (1) in the pure system K₂O—MgO—Al₂O₂—SiO₂—H₂Owere found to be 495±10°C at 1 kb P_H2O; 525±10°Cat 2 kb; 610±15°C at 5 kb; 635±10°C at6 kb. From intersection of this curve with the lower temperaturestability limit of cordierite close to 645°C, 6.5 kb P_H2O,a reaction cordieritc+muscovite = phlogopite+aluminum silicate+quartz+H₂O(2) is generated which has a negative slope and passes throughthe points 645°C, 6.5 kb PH₂O and 700°C, 5 kb PH₂O.On the high-pressure side of this reaction curve cordieriteis restricted to K₂O—poor bulk compositions. Application of the experimentally determined phase relationsto more complex natural pelitic rocks suggests that reaction(1) represents maximum temperatures for the disappearance ofchlorite from pelitic assemblages containing muscovite and quartz,whereas reaction (2) gives maximum water pressures for the disappearanceof cordierite from these rocks.     

Thermodynamic data of lawsonite and zoisite in the system CaO–Al2O3–SiO2–H2O based on experimental phase equilibria and calorimetric work

The enthalpy of drop-solution in molten 2PbO·B₂O₃ of synthetic and natural lawsonite, CaAl₂(Si₂O₇)(OH)₂·H₂O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is (_fH^Oxides=-168.7Dž.4 kJ mol^-1, or (_fH⁰₂₉₈=-4,872.5dž.0 kJ mol^-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca₂Al₃(SiO₄)(Si₂O₇)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al₂O₃-SiO₂-H₂O (CASH). The following data for lawsonite and zoisite were obtained: (_fH⁰₂₉₈ (lawsonite)=-4,865.68 kJ mol^-1 , S⁰₂₉₈ (lawsonite)=229.27 J K^-1 mol^-1 , (_fH⁰₂₉₈ (zoisite)=-6,888.99 kJ mol^-1 , S⁰₂₉₈ (zoisite)=297.71 J K^-1 mol^-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.     

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.     

The Stability of Andradite, Hedenbergite, and Related Minerals in the System Ca--Fe--Si--O--H

Phase relations for the bulk compositions 3CaO·2FeO_x·3SiO₂+excessH₂O and CaO·FeO_x·2SiO₂+excess H₂O were determinedusing conventional hydrothermal techniques with solid phaseoxygen buffers to control fO₂. Andradite, Ca₃Fe³⁺₂Si₃O₁₂, synthesized above 550 °C hasan average unit cell edge, a_o, of 12.055±0.001 Å,and an index of refraction, n, of 1.887±0.003. Belowthis temperature, a_o increases whereas n decreases, indicatingthe formation of a member of the andradite-hydroandradite solidsolution. At 2000 bars P_fluid andradite is stable above an f_O2of 10¹⁵ bar at 800 °C and 10-³² bar at 400 °C. At lowerf_O2 andradite+fluid gives way at successively lower temperaturesto the condensed assemblages magnetite+wollastonite, kirschsteinite(CaFe²⁺SiO₄)+ wollastonite and kirschsteinite+xonotlite (Ca₆Si₆O₁₇(OH)₂). Synthetic hedenbergite, CaFe²⁺Si₂O₆, has average unit cell dimensionsof a_o = 9.857± 0.004 Å, b_o = 9.033±0.002Å, c_o = 5.254±0.002 Å and ß = 104.82°±0.03°,and refractive indices of n = 1.731±0.003 and n = 1.755±0.005.At 2000 bars P_fiuid, hedenbergite is stable below an f_O2 of10-¹³ bar at 800 °C and 10-²⁸ bar at 400 °C. Above thesef_O2 values, hedenbergite+O₂ breaks down to andradite+magnetite+quartz. The mineral pair andradite +hedenbergite thus limit the f_O2range possible for their joint formation under equilibrium conditions. The hydration of wollastonite to xonotlite occurs at much lowertemperatures than previous experimental work indicated. A tentativehigh temperature limit for this reaction is set at 185°±15°C and 5000±25 bars and 210°±15 °Cand 2000±20 bars. Inasmuch as the growth of xonotlitefrom wollastonite + H₂O was never accomplished, this high temperaturelimit does not represent an equilibrium univariant curve. Nine phases were encountered in the study of andradite and hedenbergite.They are andradite, hedenbergite, magnetite, wollastonite, kirschsteinite,xonotlite, quartz, ilvaite, and vapor (fluid). An invariantpoint analysis using the method of Schreinemakers shows thetopologic relations of the reactions involved. The resultinggrid can be used to interpret natural occurrences.     

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.     

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     

A Clinopyroxene Paragenesis of Albite--Epidote--Amphibolite Facies in Meta-Syenites from the South-East Tauern Window, Austria

Mineral assemblages and textures are described from clinopyroxene-bearingmeta-syenites and related rocks from a small area in the PenninicBasement Complex of the south-east Tauern Window. Evidence from mineral textures, mineral compositions and geobarometryindicate that the clinopyroxene, a sodic salite, crystallizedas part of an equilibrium albite-epidote-amphibolite faciesparagenesis in the 35–40 Ma meso-Alpine metamorphic event.Phase relations in co-facial quartz + albite + K-feldspar +sphene-bearing meta-syenites and meta-granites are examinedusing a projection from these minerals onto the plane (A1₂O₃+ Fe₂O₃)-CaO-(MgO + FeO + MnO). The projection demonstratesthat salitic clinopyroxene can only be a stable phase in suchrocks if the bulk-rock Al/Na + K ratios are low. This is confirmedby comparing the whole-rock analyses of clinopyroxene-bearingmeta-syenites with those of clinopyroxene-free meta-syenitesand meta-granites. Mineral assemblages in a variety of lithologies from the south-eastTauern Window are used to construct a generalized AKM diagramfor magnesian albite + epidote + quartz-bearing rocks of thealbite-epidote-amphibolite facies. Thermochemical calculations indicate that the meta-syeniteswere metamorphosed at temperatures close to 500 C and at a pressureof 6+2 –4 kb. Fluids in equilibrium with meta-syeniteand meta-granite mineral assemblages had X_H2O values of 0–95,assuming X_H2O + X_CO2O= 1.0.     

Stability of Yoderite in the Absence and in the Presence of Quartz: an Experimental Study in the System MgO-Al2O3-Fe2O3-SiO2-H2O

The water-pressure temperature stability field of yoderite,ideally Mg₂Al_5.6Fe^{3 +} _0.4Si₄O₁₈(OH)₂, was determined at highoxygen fugacities by high-pressure bracketing runs on eightpossible breakdown reactions involving the phases chlorite,kyanite, talc, staurolite, pyrope, enstatite, boron-free kornerupine,cordierite, quartz, and invariably an excess of hematite. Yoderitewas found to be stable over the surprisingly large PT rangefrom 6 to 25 kbar water pressure and 590 to 795 C. It is thusa high-pressure mineral covering the upper amphibolite and portionsof the eclogite facies. In the presence of quartz its upperpressure stability is reduced to some 15 kbar, and its uppertemperature stability to 715 C. Two of the yoderite-producingreactions are anomalous as they show dehydration in the directiontowards lower temperatures. Importantly, this is also true forthe reaction kyanite + talc + hematite+H₂O=yoderite+quartz whichis responsible for the only yoderite occurrence in nature atMautia Hill, Tanzania. Preliminary thermodynamic calculationsindicate that—owing to this unusual dehydration behavior—thestability field for the assemblage yoderite+quartz disappearsfor water activities lower than 0.5. The rarity of yoderitein natural rocks, which is in contrast to its large PT stabilityfield, must be explained on chemical rather than on physicalgrounds. Yoderite can only occur in whiteschist-type bulk compositionsrich in MgO, Al₂O₃, SiO₂, and containing some iron, but poorin alkalis and CaO. Oxygen fugacities must be unusually highto keep Fe trivalent, and—at least for rocks with excessquartz—the water activity must be high as well. In anenvironment of this kind, yoderite formation in the Mautia Hillwhiteschist may have occurred even at constant total pressureand temperature simply by an influx of hydrous fluid duringthe late stages of metamorphism under amphibolite facies conditions.     

Synthesis and Stability Relations of Epidote, Ca2Al2FeSi3O12 (OH)

Hydrothermal investigation of the bulk composition 2CaO·Al₂O₃·l/2Fe₂O₂·3SiO₂+excessH₂O (Ps 33 +excess H₂O) has been conducted using conventionalapparatus and solid oxygen buffer techniques. Coarse-grainedepidotes (over 150 microns in some cases) were readily synthesizedfrom oxide mixtures with a 98 per cent yield as well as fromtheir high temperature equivalents at 600–700 °C and5 kb P_fluid and over a range of oxygen fugacities. Electronmicroprobe analyses show that maximum Fe⁺³ content of syntheticepidotes varies as a function of fo₂. Epidote is most iron-rich(Ps 33 ± 2) at high (HM and CCO) oxygen buffers and becomesprogressively more aluminous (Ps 25 ± 3) with decreasingfo₂ values and temperatures. Such variation is consistent withthe change of refractive indices and cell dimensions. The meanrefractive indices and cell dimensions for synthetic epidote(Ps 33) are N = 1.745 ± 0.005, N = l.786±0.005,a = 8.920±0.005 Å, b = 5.645±0.004 Å,c = 10.190 ű0.006 Å, and ß = 115°31'±4' and for epidote (Ps 25) are N = 1.735±0.005,N = 1.775±0.005, a = 8.891±0.005 Å, b =5.625±0.004 Å, c = 10.177±0.006 Å,and ß = 115° 30'±3'. Mössbauer spectraindicate synthetic epidotes are relatively disordered. Garnets of intermediate composition in the grossular-andraditeseries were synthesized and the cell dimensions and refractiveindices vary linearly with composition. With successive decreasein fo₂, garnet synthesized on the Ps 33 bulk composition movestoward the grossular end member with simultaneously increasingalmandine component; concomitantly the hercynite component ofthe coexistent magnetite increases. The fo₂-T-P_fluid relations were determined by employing mineralmixtures of synthetic epidote and its high temperature equivalentin subequal proportions. Equilibrium was demonstrated for thereactions (1) epidote (Ps 33) = anorthite+grandite+FeO_x+quartz+ fluid, and (2) epidote (Ps 25) (+quartz) = garnet₃₈+anorthite+magnetitc+fluid.With fo₂ defined by the HM buffer, epidote (Ps 33) is stableup to 748 °C, 5 kb, 678 °C, 3 kb, and 635 °C, 2kb P_fluid. With fo₂ defined by the NNO buffer, the epidote (Ps25) high temperature stability limit is reduced about 100 °Cat 5kb P_fluid. At slightly lower fo₂, than defined by the QFMbuffer, epidote is not stable at any temperatures; the assemblagehedenbergite+anorthite+garnet₃₈+fluid replaces epidote in thepresence of excess quartz. Combined with previously determined equilibria for prehnite,andradite, and hedenbergite, isobaric fo,-T relations were furtherinvestigated by chemographic analysis interrelating the phasesprehnite, epidote, grandite, hedenbergite, wollastonite, anorthite,and magnetite in the system CaO-Fe₂O₃-Al₂O₃-SiO₂-H₂0. Such analysisallowed the construction of a semi-quantitative petrogeneticgrid applicable to natural parageneses in low µCO₂ environments,and the delineation of the low temperature stability limit ofepidote as a function of fo₂. Enlargement of the epidote stabilityrange toward both high and low temperatures with increasingfo₂, is consistent with widespread occurrences of epidote inlow- and mediumgrade metamorphic rocks.     

Synthesis of tourmaline solid solutions in the system Na2O–MgO–Al2O3–SiO2–B2O3–H2O–HCl and the distribution of Na between tourmaline and fluid at 300 to 700 °C and 200 MPa

Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃(OH) and Mg-foitite &ding6F;(Mg₂Al)Al₆ (Si₆O₁₈)(BO₃)₃(OH)₃(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO₂-saturated system Na₂O-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg_-1Na_-1 and minor AlMg_-1H_-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Na_fluid/Na_tur)앾.878-14.692 (r²=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Na_fluid/Na_tur)욝.813-6.231 (r²=0.95), where Na_fluid is the concentration of Na⁺ in the final fluid (mol/l) and Na_tur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).     

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     

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.     

Melting Behaviour of Model Lherzolite in the System CaO-MgO-Al2O3-SiO2-FeO at 0{middle dot}7-2{middle dot}8 GPa

Fe–Mg exchange is the most important solid solution involvedin partial melting of spinel lherzolite, and the system CaO–MgO–Al₂O₃–SiO₂–FeO(CMASF) is ideally suited to explore this type of exchange duringmantle melting. Also, if primary mid-ocean ridge basalts arelargely generated in the spinel lherzolite stability field bynear-fractional fusion, then Na and other highly incompatibleelements will early on become depleted in the source, and themelting behaviour of mantle lherzolite should resemble the meltingbehaviour of simplified lherzolite in the CMASF system. We havedetermined the isobarically univariant melting relations ofthe lherzolite phase assemblage in the CMASF system in the 0·7–2·8GPa pressure range. Isobarically, for every 1 wt % increasein the FeO content of the melt in equilibrium with the lherzolitephase assemblage, the equilibrium temperature is lower by about3–5°C. Relative to the solidus of model lherzolitein the CaO–MgO–Al₂O₃–SiO₂ system, melt compositionsin the CMASF system are displaced slightly towards the alkalicside of the basalt tetrahedron. The transition on the solidusfrom spinel to plagioclase lherzolite has a positive Clapeyronslope with the spinel lherzolite assemblage on the high-temperatureside, and has an almost identical position in P–T spaceto the comparable transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O(CMASN) system. When the compositions of all phases are describedmathematically and used to model the generation of primary basalts,temperature and melt composition changes are small as percentmelting increases. More specifically, 10% melting takes placeover 1·5–2°C, melt compositions are relativelyinsensitive to the degree of melting and bulk composition, andequilibrium and near-fractional melting yield similar melt compositions.FeO and MgO are the oxides that exhibit the greatest changein the melt with degree of melting and bulk composition. Theamount of FeO decreases with increasing degree of melting, whereasthe amount of MgO increases. The coefficients for Fe–Mgexchange between the coexisting crystalline phases and melt,K_dFe–Mg^xl–liq, show a relatively simple and predictablebehaviour with pressure and temperature: the coefficients forolivine and spinel do not show significant dependence on temperature,whereas the coefficients for orthopyroxene and clinopyroxeneincrease with pressure and temperature. When melting of lherzoliteis modeled in the CMASF system, a strong linear correlationis observed between the mg-number of the lherzolite and themg-number of the near-solidus melts. Comparison with meltingin the CMASN system indicates that Na₂O has a strong effecton lherzolite melting behaviour only at small degrees of melting. KEY WORDS: CMASF; lherzolite solidus; mantle melting     

Petrology of the Blue Mountain Complex, Marlborough, New Zealand

Blue Mountain is a central-type alkali ultrabasic-gabbro ringcomplex (1?1?5 km) introducing Upper Jurassic sediments, Marlborough,New Zealand. The ultrabasic-gabbroic rocks contain lenses ofkaersutite pegmatite and sodic syenite pegmatite and are intrudedby ring dykes of titanaugite-ilmenite gabbro and lamprophyre.The margin of the intrusion is defined by a ring dyke of alkaligabbro. The plutonic rocks are cut by a swarm of hornblende-biotite-richlamprophyre dykes. Thermal metamorphism has converted the sedimentsto a hornfels ranging in grade from the albite-epidote hornfelsfacies to the upper limit of the hornblende hornfels facies. The rocks are nepheline normative and consist of olivine (Fo_82-74),endiopside (Ca₄₅Mg₄₈Fe₇-Ca₃₆Mg₅₅Fe₉), titanaugite (Ca₄₀Mg₅₀Fe₁₀-Ca₄₄Mg₃₉Fe₁₇),plagioclase (An_73-18), and ilmenitetitaniferous magnetite, withvarious amounts of titaniferous hornblende and titanbiotite.There is a complete gradation between end-iopside and titanaugitewith the coupled substitution R_y^+z+Si(Ti⁺⁴+Fe⁺³)+Al⁺³ and asympathetic increase in CaAl₂SiO₆ (0?2-10?2 percent) and CaTiAl₂O₆(2?1-8?1 per cent) with fractionation. Endiopside shows a small,progressive Mg enrichment along a trend subparallel to the CaMgSi₂O₆-Mg₂Si₂O₆boundary, and titanaugite is enriched in Ca and Fe⁺²+Fe⁺³ withdifferentiation. Oscillatory zoning between endiopside and titanaugiteis common. Exsolved ilmenite needles occur in the most Fe-richtitanaugites. The amphiboles show the trend: titaniferous hornblende(1?0–5?7 per cent TiO₂)kaersutite (6?4 per cent TiO₂)Fe-richhastingsite (18?0–19?1 per cent FeO as total Fe). Biotiteis high in TiO₂ (6?6–7?8 per cent). Ilmenite and titaniferousmagnetite (3?5–10?6 per cent TiO₂) are typically homogeneousgrains; their composition can be expressed in terms of R⁺²RO₃:R⁺²O:R₂⁺³O₄. The intrusion of igneous rocks was probably controlled by subterraneanring fracturing. Subsidence of the country rock within the ringfracture provided space for periodic injections of magma froma lower reservoir up the initial ring fracture to form the BlueMountain rocks at a higher level. Downward movement of the floorof the intrusion during crystallization caused inward slumpingof the cumulates which affected the textural, mineralogical,and chemical evolution of the rocks in different parts of theintrusion. The order of mineral fractionation is reflected by the chemicalvariation in the in situ ultrabasic-gabbroic rocks and the successiveintrusions of titanaugite-ilmenite gabbro and lamprophyre ringdykes, marginal alkali gabbro and lamprophyre dyke swarm. Aninitial decrease, then increase in SiO₂; a steady decrease inMgO, CaO, Ni, and Cr: an initial increase, then decrease inFeO+Fe₂O₃, TiO₂, MnO, and V; almost linear increase in Al₂O₃and late stage increase in alkalis and P₂O₃, implies fractionationof olivine and endiopside, followed by titanaugite and Fe-Tioxides, followed by plagioclase, hornblende, biotite, and apatite.Reversals in the composition of cumulus olivine and endiopsideand Solidification Index, indicate that the ultrabasic-gabbroicsequence is composed of four main injections of magma. The ultrabasic rocks crystallized under conditions of high PH₂Oand fairly high, constant P_O2; P_H2 and P_O2 increased duringthe formation of the gabbroic rocks until fracturing of thechamber roof occurred. The abundance of euhedral amphibole inthe latter injection phases suggests that amphibole accumulatedfrom a hydrous SiO₂ undersaturated magma when an increase inP_O2, stabilized its crystallization. Plutonic complexes similar to Blue Mountain are found withinand beneath the volcanic piles of many oceanic islands, e.g.Canaries, Reunion, and Tahiti, and those intruding thick sedimentarysequences, as at Blue Mountain, e.g. the pipe-like intrusionsof the Monteregian Hills, Quebec.     

Petrology of Biotite-Cordierite-Garnet Gneiss of the McCullough Range, Nevada I. Evidence for Proterozoic Low-Pressure Fluid-Absent Granulite Grade Metamorphism in the Southern Cordillera

Proterozoic migmatitic paragneisses exposed in the McCulloughRange, southern Nevada, consist of cordierite+almanditic garnet+biotite+sillimanite+plagioclase+K-feldspar+quartz+ilmenite+hercynite.This assemblage is indicative of a low-pressure fades seriesat hornblende-granulite grade. Textures record a single metamorphicevent involving crystallization of cordierite at the expenseof biotite and sillimanite. Thermobarometry utilizing cation exchange between garnet, biotite,cordierite, hercynite, and plagioclase yields a preferred temperaturerange of 590–750?C and a pressure range of 3–4 kb.Equilibrium among biotite, sillimanite, quartz, garnet, andK-feldspar records a_H2O between 0?03 and 0?26. The low a_H2Otogetherwith low f_O2 (QFM) and optical properties of cordierite indicatemetamorphism under fluid-absent conditions. Preserved mineralcompositions are not consistent with equilibrium with a meltphase. Earlier limited partial melting was apparently extensiveenough to cause desiccation of the pelitic assemblage. The relatively low pressures attending high-grade metamorphismof the McCullough Range paragneisses allies this terrane withbiotite-cordierite-garnet granulites in other orogenic belts.aosure pressures and temperatures require a transient apparentthermal gradient ofat least 50?C/km during part of this Proterozoicevent in the southern Cordillera. ^*Present address: Institute of Geophysics and Planetary Physics, University of California, Los Angeles, CA 90024-1567     

Phase Relations in Peridotitic and Pyroxenitic Rocks in the Model Systems CMASH and NCMASH

Alpine-type peridotites and associated pyroxenites are foundas lenses in the continental crust in many different orogens.The reconstruction of the pressure–temperature (P–T)evolution of these rocks is, however, difficult or even impossible.With geothermobarometry, usually one point on the overall P–Tpath can be obtained. To use the different mineral assemblagesobserved in ultramafic rocks as P–T indicators, quantitativeP–T phase diagrams are required. This study presents newcalculated phase diagrams for peridotitic and pyroxenitic rocksin the model systems CaO–MgO–Al₂O₃–SiO₂–H₂O(CMASH) and Na₂O–CaO–MgO–Al₂O₃–SiO₂–H₂O(NCMASH), which include the respective solid solutions as continuousexchange vectors. These phase diagrams represent applicablepetrogenetic grids for peridotite and pyroxenite. On the basisof these general petrogenetic grids, phase diagrams for particularperidotite and pyroxenite bulk compositions are constructed.In an example of pyroxenite from the Shackleton Range, Antarctica,the different observed mineral assemblages are reflected bythe phase diagrams. For these rocks, a high-pressure metamorphicstage around 18 kbar and an anticlockwise P–T evolution,not recognized previously, can be inferred. KEY WORDS: Antarctic; high-pressure metamorphism; peridotite; phase diagrams; pyroxenite     

The Origin and Composition of Metasomatic Fluids and Amphiboles beneath Malaita, Solomon Islands

A suite of mantle peridotite xenoliths from the Malaitan alnoitedisplay both trace element enrichment and modal metasomatism.Pargasitic amphibole is present in both garnet- and spinelbearingxenoliths, formed by reaction of a metasomatic fluid (representedby H₂O and Na₂O) with the peridotite assemblage. Two pargasite-formingreactions are postulated, whereby spinel is totally consumed: 6MgAl₂O₄ + 8CaMgSi₂O₆ + 7Mg₂Si₂O₆ + 4H₂O + 2Na₂O = 4NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 6Mg₂SiO₄ or spinel is both a reactant (low Cr) and a product (high Cr): 24MgAlCrO₄ + 16CaMgSi₂O₆ + 14Mg₂Si₂O₆ + 8H₂O + 4Na₂O = 8NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 12MgCr₂O₄ + 12Mg₂SiO₄ Seven garnet—spinel-peridotites display cryptic metasomatismas demonstrated by the LREE enrichment in clinopyroxenes. TheLREE enrichment correlates positively with ¹⁴³ND/¹⁴⁴ND (0?512771–0?513093)which defines a mixing line between a mantle MORB source anda metasomatic fluid. Isotopic evidence (Sr and Nd) from garnet,clinopyroxene, and amphibole demonstrate this fluid has notoriginated in the alnoite sensu stricto. Calculated amphiboleequilibrium liquids show a range in La/Yb and Ce/Yb ratios similarto those calculated for the augite and subcalcic diopside megacrysts.Sr and Nd isotope analyses from amphibole are within error ofthe augite (PHN4074) and subcalcic diopside megacrysts (CRN2I6,PHN4069, and PHN4085). It is concluded that fluids emanatedfrom a proto-alnoite magma throughout megacryst fractionation,and the mixing line was generated during the crystallizationof the subcalcic diopsides. This study demonstrates that metasomatismrepresented in these xenoliths is not a prerequisite for alnoitemagmatism, but is a consequence of it.     

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

Petrogenetic grids in the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NCKMASH and NCKFASH calculated with the softwareTHERMOCALC 3.1 are presented for the P–T range 7–30kbar and 450–680°C, for assemblages involving garnet,chloritoid, biotite, carpholite, talc, chlorite, kyanite, staurolite,paragonite, glaucophane, jadeite, omphacite, diopsidic pyroxene,plagioclase, zoisite and lawsonite, with phengite, quartz/coesiteand H₂O in excess. These grids, together with calculated compatibilitydiagrams and P–T and T–X_Ca and P–X_Ca pseudosectionsfor different bulk-rock compositions, show that incorporationof Ca into the NKFMASH system leads to many of the NKFMASH invariantequilibria moving to lower pressure and/or lower temperature,which results, in most cases, in the stability of jadeite andgarnet being enlarged, but in the reduction of stability ofglaucophane, plagioclase and AFM phases. The effect of Ca onthe stability of paragonite is dependent on mineral assemblageat different P–T conditions. The calculated NCKFMASH diagramsare powerful in delineating the phase equilibria and P–Tconditions of natural pelitic assemblages. Moreover, contoursof the calculated phengite Si isopleths in P–T and P–X_Capseudosections confirm that phengite barometry in NCKFMASH isstrongly dependent on mineral assemblage. KEY WORDS: phase relations; metapelites; NCKFMASH; THERMOCALC; phengite geobarometry     

(Ruby--Sapphire)--Chromian Mica--Tourmaline Rocks from Westland, New Zealand

Boulders of the assemblage ruby—sapphire corundum, chromianmuscovite, margarite, tourmaline (chromian chlorite, Zn—Mnchromite and Mn—Ti magnetite) occur in glacial moraineand rivers of north Westland, South Island of New Zealand. Thelocation, Cr-rich composition of the boulders and the presenceof rare serpentinite rinds indicate that they are derived fromultramafic rocks (Pounamu Ultramafics) that occur within AlpineSchist of the Southern Alps. The largest sample is progressivelyzoned outwards from a corundum—margarite core, throughan intermediate zone of Cr-muscovite, to an outer zone of Cr-chloritethat is in contact with serpentinite. Most finds consist oferosion-resistant corundum-rich cores. In the corundum, Cr₂O₃content ranges from 0.5 to 13%, with red coloration becomingmore intense with increasing Cr. In addition to the dominantCr³⁺ Al³⁺ substitution, those of (Fe, V)³⁺ Cr³⁺ and (Ti⁴⁺+Fe²⁺) 2Cr³⁺ result in spectacular colour zoning from colourlessto deep ruby red-carmine and pale blue to dark blue—violet.Corundum has grown by replacement of the micaceous matrix thatconsists of chromian muscovite (0.10–4.10% Cr₂O₃) andchromian margarite (0.46–1.20% Cr₂O₃). Both micas containa significant paragonite component (up to 21.5% in muscoviteand up to 40.8% in margarite). Late phase muscovite is Ba richwith up to 4.77% BaO, and margarite has up to 0.66% SrO. Tourmalineoccurs as veins, vein outgrowths and larger poikilitic crystalsthat replace the mica matrix. Chromium content ranges between0.82 and 3.6% Cr₂O₃. High bulk rock Al (up to 78% Al₂O₃), K,Ca, Cr and Na, and low Si (14.5–23.1% SiO₂), suggest thatthe corundum—Cr-silicate rocks are the products of extrememetasomatic alteration of quartzofeldspathic schist enclavesin serpentinite. Isocon analysis indicates that conversion ofthe schist to the micaceous matrix of the corundum rocks involvesconservation of Ca, Al, K, volatiles and Sr, a mass loss of59% and a volume reduction of 69% consequent on removal of 70–80%Si and all other elements (most >80%), with enrichment ofbetween 900 and 1800% Cr. The formation of corundum from themica matrix involved a further mass—volume reduction anddecrements in Si, Ca, K, volatiles and Sr from reaction sites.Concentric mineral zonation in single rock samples and zoning—replacementin minerals, e.g. Cr in corundum and chromite, Ti, Fe²⁺ in corundum,Ba in muscovite, Sr in margarite, and Mn and Zn in chromiteand magnetite, imply element redistribution during metasomatism.Experimental reaction between quartzofeldspathic schist andserpentinite at 450C and 2 kbar produced reaction sequencescontaining newly formed Ca-plagioclase—phlogopitic micachloriteand muscovite—chlorite that in terms of composition areanalogous with the observed (corundum—margarite)—muscovite—chloritezonation. The temperature of metamorphism of garnet zone rocks(45020C) that contain the corundum—Cr-silicate rocksis well below that of the breakdown of muscovite and margariteto form corundum and indicates the importance of fluid composition,particularly the cation—hydrogen variables a_Ca²⁺/H⁺, aK⁺/H₊and a_S1O2. Introduction of boron into the schist (from serpentinite),and boron released from the breakdown of original tourmalinein the schist, resulted in tourmaline veining and reaction ofthe mica matrix to form tourmaline that invoved both a massand volume increase and addition of Fe, Mg together with B. KEY WORDS: corundum—Cr-silicate rocks; metasomatism; New Zealand; Southern Alps ^*Corresponding author.