Stability Relations of the Ferruginous Biotite, Annite

Annite, KFe₃AISi₃O₁₀(OH)₂ a member of the iron biotites andthe ferrous analogue of phlogopite, has been synthesized andits phase relations have been determined as functions of temperature,fugacity of oxygen (fo₂), and total pressure (P_totalPH₂O+PH₂).A method for controlling fo₂at high total pressures is described,and data for the ‘oxygen buffers’ used are given.Buffers range from quartz+iron+fayalite assemblages (low fo₂)to magnetite-hematite assemblages (high fo₂). Optical propertiesand unit-cell dimensions of synthetic annites depend on theconditions of synthesis. By recalculating published analyses of natural iron-rich biotitesit can be shown that one cannot assume a constant hydrogen contentfor such biotites. Oxidation may have occurred by drying at115?C. Octahedral occupancy therefore cannot be calculated fromsuch data. Phase relations of annite are presented in 2,070 and 1,035 barsections. Depending on fo₂-T values annite was found to decomposeto one of the following assemblages: hematite+ sanidine, magnetite+sanidine,fayalite+leucite+kalsilite, iron+sanidine. All decompositionsare dehydration and redox reactions and are sensitive to changesin fH₂0 and fo₂ (or fH₂0 and fH₂). At 2, 070 bars total pressureannite+magnetite+sanidine can coexist between 425?C and 825?C, depending upon the magnitude of fo₂. In the presence of quartz the stability field of annite is morerestricted. Phase equilibria in the system KAlSiO₄–SiO₂–Fe–O₂–H₂have been summarized schematically. Wherever possible, thermodynamic extrapolations are made totest the internal consistency of the data. Enthalpies of formationare calculated for both annite and phlogopite. Ranges of fo₂values in nature as well as mechanisms for changes in fo₂ areinvestigated. It is useful to distinguish between assemblageswhich are internally buffered with respect to fo₂changes andthose which are not buffered. The applications of individualreactions involving annite to specific geologic problems arediscussed with respect to igneous, metamorphic, and sedimentaryrocks.     

Petrology of an Andalusite-Type Regional Metamorphic Terrane, Panamint Mountains, California

The terrane in the Panamint Mountains, California, was regionallymetamorphosed under low-pressure conditions and subsequentlyunderwent retrograde metamorphism. Prograde metamorphic isogradsthat mark the stability of tremolite + calcite, diopside, andsillimanite indicate a westward increase in grade. The studywas undertaken to determine the effects of the addition of Caon the types of assemblages that may occur in pelitic schists,to contribute to the understanding of the stability limits inP – T – aH₂O – X_Fe of the pelitic assemblagechlorite + muscovite + quartz, and to estimate the change inenvironment from prograde to retrograde metamorphism. Peliticassemblages are characterized by andalusite + biotite + stauroliteand andalusite + biotite + cordierite. Within a small changein grade, chlorite breaks down over nearly the entire rangein Mg/(Mg + Fe) to biotite + aluminous mineral. Chlorite withMg/(Mg + Fe) = 0.55 is stable to the highest grade, and thegeneralized terminal reaction is chlorite + muscovite + quartz= andalusite + biotite + cordierite + H₂O. Calcic schists arecharacterized by the assemblage epidote + muscovite + quartz+ chlorite + actinolite + biotite + calcite + plagioclase atlow grades and by epidote + muscovite + quartz + garnet + hornblende+ biotite + calcite + plagioclase at high grades. Epidote doesnot coexist with any AFM phase that is more aluminous than garnetor chlorite. Lithostatic pressure ranged from 2.3 kb to 3.0kb. During prograde-metamorphism temperatures ranged from lessthan 400° to nearly 700°C, and X_H2O (assuming P_H2O +P_CO3 = P_total) is estimated to be 0.25 in siliceous dolomite,0.8 in pelitic schist, and 1.0 in calcic schist. Temperatureduring retrograde metamorphism was 450° ± 50°C,and all fluid were H₂O-rich. A flux of H₂O-rich fluid duringfolding is believed to have caused retrograde metamorphism.The petrogenetic grid of Albee (1965b) is modified to positionthe (A, Cd) invariant point relative to the aluminosilicatetriple point, which allows the comparison of facies series thatinvolve different chloritoid-reactions.     

Phase Relations and Crystallization Sequence in a Contact-Metamorphosed Rock from the Gunflint Iron Formation, Minnesota

Portions of the Gunflint Iron Formation, originally a ferruginoussediment, were metamorphosed by the intrusion of the DuluthComplex to assemblages containing: pigeonite (Wo₁₀En₂₄Fs₆₆)+olivine(Fo₁₃Fa₃₇)+Fe-Ti oxide (Mt₆₂Usp₃₄Hc₄)+plagioclase (An₉₄Ab₆)+vapor+augite (Wo₄₀En₂₀Fs₄₀) or cummingtonite Fe/(Fe+Mg) {smalltilde} 0.69; quartz was present but probably was not in equilibriumwith olivine. Comparison with synthetic phase-equilibrium studiesindicate conditions of initial recrystallization of T 800 °C,P_total 2kb, fo₂ slightly below that of the pure fayalite-magnetite-quartzassemblage, and P_H2O < P_total. During the slow cooling process following initial recrystallization,the phases present underwent a complex series of exsolution,inversion, oxidation, and hydration reactions. Pigeonite initiallyexsolved augite along (001), then inverted to orthopyroxene,which then exsolved augite along (100). The augite exsolvedonly pigeonite on (001) during its cooling history. The Fe-Tioxide for the most part oxidized to an intergrowth of magnetiteand ilmenite, although unoxidized portions later exsolved ulvöspinel.Cummingtonite exsolved actinolite, forming irregular patchesof the latter. Olivine, orthopyroxene, and augite reacted withplagioclase to form retrograde amphiboles. Orthopyroxene had difficulty nucleating during this slow coolingprocess, forming only at widely spaced points in mosaics ofprimary pigeonite grains, and never nucleating within primaryaugite grains. The resulting orthopyroxene grains are much largerthan the original pigeonite grains.     

Contact Metamorphosed Ultramafic Rocks in the Western Sierra Nevada Foothills, California

Within the western Sierra Nevada metamorphic belt, linear bodiesof alpine-type ultramafic rock, now composed largely of serpentineminerals, parallel the regional strike and commonly coincidewith major fault zones. Within this metamorphic belt, east ofSacramento, California, ultramafic rocks near a large maficintrusion, the Pine Hill Intrusive Complex, have been emplacedduring at least two separate episodes. Those ultramafic rocks,evidently unaffected by the Pine Hill Intrusive Complex andcomposed largely of serpentine minerals, were emplaced alonga major fault zone after emplacement of the Pine Hill IntrusiveComplex. Those ultramafic rocks, contact metamorphosed by thePine Hill Intrusive Complex, show a zonation of mineral assemblagesas the igneous contact is approached: olivine+antigorite+chlorite+tremolite+Fe-Cr spinel olivine+talc+chlorite+tremolite+Fe-Crspinel olivine+anthophyllite+chlorite+tremolite+Fe-Cr spinel olivine+orthopyroxene+aluminous spinel+hornblende+Fe-Cr spinel.Superimposed on these mineral assemblages are abundant secondaryminerals (serpentine minerals, talc, chlorite, magnetite) whichformed after contact metamorphism. Correlation of observed mineralassemblages with the experimental systems, MgO-SiO₂-H₂O andMgO-Al₂O₃-SiO₂-H₂O suggests an initial contact temperature of775±25 °C for the Pine Hill Intrusive Complex assumingPtotal P_fluid PH₂O. The pressure acting on the metamorphic rockduring emplacement of the intrusion is estimated to be a minimumof 1.5 kb.     

Petrogenesis of Carbonate-orthopyroxenites (Sagvandites) and related rocks from Troms, Northern Norway

Carbonate-orthopyroxenites from Troms consist of enstatite andmagnesite with variable amounts of olivine, talc, serpentine,chlorite, and phlogopite and include the ore minerals chromite,magnetite, pentlandite, pyrite, and in some cases pyrrhotite,heazlewoodite, millerite, and maucherite. Related rocks compriseolivine-magnesite-, talc-magnesite and olivine-orthopyroxene(saxonite)-assemblages. Allochemical replacement reactions,involving mobile CO₂, H₂O, and SiO₂, are shown to comprise themain petrogenetic mechanism. Saxonite, however, may representa possible source material. Discussion of the model system MgO-SiO₂-CO₂-H₂O for P_flukl =2 and 7 kb, respectively, indicates that best agreement withpetrographic evidence is reached assuming elevated pressuresand both gas-excess and gas-deficiency conditions by means oflocal equilibria. The gas-deficient assemblage enstatite+talc+forsterite+magnesiteis presumed to be stable at pressures above 5 kb. Recalculationof whole-rock analyses to a CO₂-free basis by several alternativemethods suggests that rock evolution could have followed thetrend dunite saxonite orthopyroxenite sagvandite+related rocks.A simple geometric method is used to outline possible schemesof rock evolution, involving gas-deficient phase assemblages.     

Prehnite-Pumpellyite to Greenschist Fades Transition in the Karmutsen Metabasites, Vancouver Island, B.C.

Mineral paragenescs in the prehnite-pumpellyite to greenschistfades transition of the Karmutsen metabasites are markedly differentbetween amygdule and matrix, indicating that the size of equilibriumdomain is very small. Characteristic amygdule assemblages (+chlorite + quartz) vary from: (1) prehnite + pumpeUyite + epidote,prehnite + pumpellyite + calcite, and pumpellyite + epidote+ calcite for the prehnite-pumpellyite facies; through (2) calcite+ epidote + prehnite or pumpellyite for the transition zone;to (3) actinolite + epidote + calrite for the greenschist facies.Actinolite first appears in the matrix of the transition zone.Na-rich wairakites containing rare analcime inclusions coexistwith epidote or Al-rich pumpellyite in one prehnite-pumpellyitefacies sample. Phase relations and compositions of these wairakite-bearingassemblages further suggest that pumpellyite may have a compositionalgap between 0.10 and 0.15 X_Fe?. Although the facies boundaries are gradational due to the multi-varianceof the assemblages, several transition equilibria are establishedin the amygdule assemblages. At low X_co2, pumpellyite disappearsprior to prehnite by a discontinuous-type reaction, pumpellyite+ quartz + CO₂ = prehnite + epidote + calcite + chlorite + H₂O,whereas prehnite disappears by a continuous-type reaction, prehnite+ CO₂ = calcite + epidote + quartz-l-H₂O. On the other hand,at higher X_CO2 a prehnite-out reaction, prehnite + chlorite+ H₂O + CO₂ = calcite + pumpellyite + quartz, precedes a pumpellyiteoutreaction, pumpellyite + CO₂ = calcite + epidote + chlorite +quartz + H₂O. The first appearance of the greenschist faciesassemblages is defined at both low and high XCOj by a reaction,calcite + chlorite + quartz = epidote + actinolite+ H₂O + CO₂.Thus, these transition equilibria are highly dependent on bothX_Fe³⁺ + of Ca-Al silicates and X_H20 of the fluid phase. Phaseequilibria together with the compositional data of Ca-Al silicatesindicate that the prehnite-pumpellyite to greenschist faciestransition for the Karmutsen metabasites occurred at approximately1.7 kb and 300?C, and at very low X_co2, probably far less than0.1.     

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.     

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.     

Eclogite and Related High-Pressure Regional Metamorphic Rocks from the Andes of Ecuador

High-pressure, regional metamorphic rocks (the Raspas Formation)constitute an inclusion more than 10 km long and 3 km wide ina protrusion of extensively serpentinized harzburgite in ElOro Province, southwestern Ecuador. The high-pressure rocks,all feldspar-free, consist of a dominant pelitic schist withquartzite layers, eclogite, eclogite amphibolite, garnetite,and retrograde mafic rocks. The pelitic schist is coarse grainedand is composed of quartz + phengite + paragonite + garnet +chloritoid + rutile + graphite ± kyanite ± pyrite.Eclogite is fine to medium grained, massive to strongly foliated(average mode: omphacite (Jd₄₂Ac₆(Di + He)₃₂), 38.2 per cent;garnet (Alm₅₃ Spess₂ Pyr₁₉ Gross₂₆), 26.6; barroisite (4.1 percent Na₂O), 22.6; clinozoisite, 4.1; rutile, 2.1; quartz, 5.7;other minerals, 0.7).Eclogite amphibolite is a medium-grainedand massive to foliated rock composed of amphibole (3.1 percent Na₂O) + garnet + zoisite + kyanite + rutile + pyrite ±omphacite± paragonite ± quartz ± apatite. Retrogrademafic rocks include glaucophane schist, greenschist, and coarse-grained,amphibole-rich rocks. Prograde metamorphism took place in an active Benioff zone.Based on phase relations in the pelitic schist, partitioningof Mg/(Mg + Fe_total + Mn) in garnet-amphibole and in omphacite-amphibolepairs (Dòbretsov et al., 1975), the absence of lawsonite,and other evidence, the conditions of metamorphism are estimatedto have been T = 580 ° ± 20 °C and P _total =13 ± 3 kb (43 ± 10 km depth). P _H2O ranged from P _total in pelitic schist, through P _total in eclogite amphibolitc,to «P _total in eclogite. Retrograde metamorphism accompaniedrapid uplift of the Raspas Formation during which the rockspassed through the stability field of glaucophane-epidote schist,but not the stability field of lawsonite. The inclusion of high-pressure rocks was carried upward intactin a protrusion of extensively serpentinized harzburgite whichrose diapirically through the relatively denser amphiboliteand greenschist which constitute the regional basement of ElOro Province. Serpentinization of harzburgite began at depth,and continued coevally with eclogitization. Protrusive riseoccurred upon abandonment of the Benioff zone. Radiometric K-Arages on the uplift of the Raspas Formation and the youngestlavas of a volcanic are of Jurassic-Early Cretaceous age ineastern Ecuador are synchronous (132 m.y.). Present address: Département de Géologie, Université Laval, Québec, P. Q. G1K 7P4 Canada     

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.     

The Klokken Gabbro-Syenite Complex, South Greenland: Quantitative Interpretation of Mineral Chemistry

The layered syenite series in the Klokken stock formed by continuousin situ fractionation of a trachytic magma in a chamber linedby gabbro with 3000 m of cover rocks. The following mineralsand reactions are assessed as geothermometers and barometers:two feldspars; hypersolvus ternary feldspars; ferrohedenbergite-ß-wollastonite;clinopyroxene-olivine Fe-Mg exchange; Fe-Ti oxides; sanidine-magnetite-annite;ferroedenite stability. Estimates of silica activity are obtainedfrom the silica-magnetite-fayalite assemblage. The gabbros ended magmatic crystallization at > 1000–1050°C.The less fractionated members of the syenite range probablycrystallized with P_H2O < P_total, at T > 870°C and,P_H2O 800 bars. In the more fractionated syenites P_H2O = P_totalduring intercumulus feldspar growth, and all magmatic phasescrystallized within the interval 940–830°C and P_H2O< 1100 bars. Magmatic f_O2 (bars) was 1 log unit below theQFM buffer. a_SIO2 in gabbros was slightly above the albite-nephelinebuffer, but rose suddenly to just <1 in the syenites, a jumpmirrored by minor elements in pyroxenes and opaque oxides. Biotitegrew subsolidus in most rocks, at f_O2 < QFM, except in intermediaterocks when f_O2 > QFM and was defined by the sanidine-magnetite-biotiteassemblage. In these rocks P_H2O of 450 bars at 760°C isobtained using existing experimental data, but application ofthis data to Fe-rich biotites in the layered series (where biotiteis an intercumulus phase) requires P > 10 kb at magmatictemperatures. High TiO₂ or F: OH probably accounts for increasedT stability of natural annites at low P. The syenitic liquid fractionated down a low temperature zonein a multicomponent system precipitating alk fsp + ol + cpx+ mt and the more fractionated members of the layered serieshad a negligible crystallization interval, a prerequisite forthe development of the unique Klokken-type inversely gradedmineral layering.     

Metamorphic History of Sapphirine-bearing and Related Magnesian Gneisses from Namaqualand, South Africa

Sapphirine occurs with cordierite, phlogopite, spinel, sillimanite,corundum, orthopyroxene, and gedrite in granulite facies Mg-and Al-rich paragneisses within the low P, high T NamaqualandMetamorphic Complex. The gneisses reveal a three-stage texturalhistory. Sapphirine appeared during a second stage of progrademineral growth which produced nodular structures and intergrowthsinvolving spinel, corundum, and sillimanite, pseudomorphingan earlier generation of coarse, amphibolite facies minerals.A third generation of coarse, cross-cutting, mainly hydrousminerals (gedrite, kornerupine, phlogopite) is sporadicallydeveloped. The wide variety of cofacial mineral assemblages allows thedelineation of the stable mineral associations of sapphirinein the system K₂O-MgO-FeO-Al₂O₃-SiO₂-H₂O under P-T conditionsindependently estimated at about 5 kb, 750–800 °C.The natural assemblages provide constraints which, taken togetherwith existing thermodynamic and experimental data, allow theestimation of P-T slopes of sapphirine equilibria. The mineraltextures thus indicate sapphirine growth under increasing T,decreasing a(H₂O), and constant or slightly increasing P. The preservation of prograde reaction textures during fine-grainedmineral growth probably results from the reduced importanceand/or more CO₂-rich composition of the metamorphic fluid undergranulite facies conditions in these refractory rocks. Aqueousfluids were locally reintroduced after the metamorphic peak.     

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.     

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.     

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     

Cordierite-Cummingtonite Facies Rocks from the Gold Brick District, Colorado

The unusual association of cordierite and cummingtonite (? gedrite+ chlorite + biotite + ilmenite + plagioclase + quartz) definesa metamorphic facies within aluminous, low-Ca amphibolites fromthe Proterozoic rocks of the Gold Brick District, east of Gunnison,Colorado. More Fe-rich bulk chemistries in the same facies arecharacterized by assemblages consisting of cordierite+-gedrite+ garnet + chlorite + biotite + ilmenite + plagioclase + quartz,whereas more Mg-rich compositions are characterized by cordierite+ anthophyllite + chlorite + biotite + ilmenite ? plagioclase+ quartz. The assemblage gedrite 4- cummingtonite + chlorite+ biotite + ilmenite + plagioclase + quartz was also observed.Coexisting cordierite+ anthophyllite + cummingtonite was notobserved in any rocks, apparently because this assemblage isstable over only a very narrow range of bulk compositions. Metamorphosedpelitic rocks are more iron rich than the assemblage cordierite+ gedrite + garnet + chlorite + biotite + ilmenite + plagioclase+ quartz and consist of garnet ?cordierite ?staurolite ? chlorite? andalusite + biotite + ilmenite + plagioclase + quartz? microclineor muscovite. Mineral rim compositions from cordierite-bearing amphibolitesand metapelites determined by electron microprobe analysis showsystematic Fe/Mg partitioning and define assemblages that occupynon-overlapping regions of the compositional system SiO₂-TiO₂-Al₂O₃-MnO-FeO-MgO-CaO-Na₂O-K₂O-H₂Oas determined by algebraic and statistical methods developedby Braun & Stout (1975) and Fisher (1989). Graphical methods(projections) produced spurious overlaps not confirmed by themore rigorous algebraic tests. The spurious overlaps were generatedbecause standard projective analysis was not able simultaneouslyto account for the important effects of the components Na₂O,CaO, and MnO on the AFM topologies. The results of algebraicand statistical analysis are consistent with an equilibriumorigin at constant values of temperature and pressure. The cordierite-cummingtonite facies encompasses the relativelylow-pressure and moderate-temperature conditions associatedwith the stability field of andalusite. Garnet-biotite geothermo-metry,and garnet, aluminosilicate, silica, plagioclase (GASP) geobarometrysuggest that temperatures and pressures were nearly constantacross the study area at 550( ? 70) ?C and 3 kb, respectively,near the peak of metamorphism. Other geothermometers and geobarometers,and independent pressure and temperature estimates, are compatiblewith garnet-biotite thermometry and GASP geo-barometry. Gradientsin fO₂ or H₂O are not required to explain the compatibilityof these assemblages at constant T and P. Cordierite + cummingtonite-bearingrocks can apparently be derived from anthophyllite +garnet-bearingrocks by increasing temperature or decreasing pressure.     

Phase Equilibria for Calcic Scapolite, and Implications of Variable Al-Si Disorder for P-T, T-XCO2, and a-X Relations

Carbonate scapolite is a potentially powerful mineral for calculatingCO₂ activities in non-calcareous rocks, but an analysis of thethermodynamics and phase equilibria of carbonate scapolite isfirst necessary. This includes an evaluation of Al-Si disorderin meionite, as this has the greatest effect on derived phaserelations. Available experimental data on meionite stability,X-ray diffraction refinements and nuclear magnetic resonancespectra for calcic scapolite do not uniquely constrain the Al-Siordering state of synthetic meionite. However, the data aremost consistent with a high degree of Al-Si disorder and inconsistentwith long-range Al-Si order. An internally consistent thermodynamicdata set was derived and used to calculate P-T and T-X_CO2 equilibriainvolving meionite in the CaO-Al₂O₃-SiO₂-CO₂-H₂O (CASCH) system.The effect of Al-Si disorder is illustrated by calculating thephase equilibria using an ordered, an arbitrary intermediatedisordered, and a completely Al-Si disordered standard statefor meionite. The Gibbs free energy of meionite was calculatedfrom reversals (at 790–815?C, 2–15 kb) on the reaction 3 Anorthite +Calcite =Meionite The _fG?_{m, 298} for each of the standard states is –13 146?6,–13128?8, and –130930kJ/mol, respectively. Becauseof the steep slope of reaction (1) and limited temperature rangeover which it breaks down, meionite used in the experimentsto constrain reaction (1) must possess a limited range of Al-Sidisorder. The P-T slope of reaction (1) increases, and the slopeof meionite decarbonation equilibria changes from positive tonegative in T-X_CO2 and P-T space, as a function of increasingAl-Si disorder. Meionite has a wide stability field at highT in T-X space at 5 and 10 kb (P_Total=P_Fluid), being stableto X_CO2=0?06. Meionite alone breaks down to undersaturated gehleniteand/or corundum-bearing assemblages at 5 kb, and to clinozoisiteat 10 kb. The effect of solid solutions on the T-X stabilityof meionite is similar to that of increasing pressure, stabilizingmeionite to lower temperature. Variable Al-Si disorder doesnot significantly affect the upper limit of meionite stabilityin T-X_CO2 space. Activity-composition relations for meionitein carbonate scapolite were calculated relative to reaction(1) from data on natural scapolite-plagioclase-calcite assemblages.The extent of departure from ideality varies as a function ofAl-Si disorder. Negative deviations from ideality are indicatedfor natural scapolite solid solutions at T<750?C, based ona disordered Al-Si standard state for meionite. This is likelyto reflect a more ordered Al-Si distribution in natural scapolitescompared with the synthetic endmember standard state. Present address: Department of Earth and Space Sciences, State University of New York, Stony Brook, New York 11794-2100     

Dehydration-melting of Biotite Gneiss and Quartz Amphibolite from 3 to 15 kbar

We performed vapor-absent melting and crystallization experimentson two bulk compositions that model metamorphic rocks containinga single hydrous phase: a biotite gneiss [37% bio (mg-number55), 34% qtz, 27% plg (An₃₈), 2% ilm] and a quartz amphibolite[54% hbl (mg-number 60), 24% qtz, 20% plg (An₃₈), 2% ilm]. Experimentswere performed at 3 and 5 kbar in internally heated pressurevessels (IHPV), and at 7, 10, 125 and 15 kbar in piston cylinderapparatus (PC), from the vapor-absent solidi to (at least) thetemperature at which the hydrous mineral disappeared. Dehydration-meltingbegins at similar temperatures in both bulk compositions, rangingfrom T850C at P = 3 kbar T930C at P = 15 kbar. The hydrousmineral disappears 50C above the solidus in both systems, exceptin IHPV experiments at f(O₂) above Ni–NiO, in which biotitestability extends up to atleast 80C above the solidus. At theT at which the hydrous minerals disappear the biotite gneissproduces 2–3 times more melt than the quartz amphibolite(50–60 wt% vs 20–30 wt%). In both systems, variationsin melt productivity with P are controlled by three competingfactors: (1) the positive d P/dT slopes of the solidi, (2) decreasingH₂O activity with increasing P at constant H₂O content, and(3) Na₂O activity, which increases with P concomitantly withbreakdown of plagioclase. Melt productivities at T = 920–950Care maximized at intermediate pressures (7 kbar). The biotitegneiss produces strongly peraluminous granitic melts (SiO₂>70wt%) and residual assemblages of quartz norite (P>125 kbar)or garnet pyroxenite (P>125 kbar). The quartz amphiboliteproduces strongly peraluminous granodioritic melts (SiO₂>70wt%) that coexist with clinopyroxene + orthopyroxene + plagioclase+ quartz at P>10 kbar)garnet. The results of coupled meltingand crystallization experiments on the quartz amphibolite suggestthat strongly peraluminous granitoid rocks (e.g. cordierite-bearingand two-mica granites) can be derived from melting of Al-poorprotoliths. KEY WORDS: dehydration-melting; biotite gneiss; amphibolite; felsic magmas ^*Corresponding author     

Phase Equilibria of Margarite-Bearing Schists and Chloritoid + Hornblende Rocks from Western New Hampshire, USA

A variety of uncommon garnet-grade assemblages have been foundin rocks from three outcrops in the western part of centralNew Hampshire, and include the associations Grt+MrgCld, Grt+Bt+CldMrg,and Mrg+Cld+HblGrt (all rocks contain Ms, Chl, Ilm, and Qtz).These unusual rocks coexist with more typical Grt+Bt+Chl+Plmetapelites and amphibolites. Rim P–T conditions are {smalltilde}49035C and 5•751•25 kbar. Projection of the assemblages from Qtz, H₂O, and Ilm into theCa–Al'–Na–(Fe+Mg) tetrahedron, and from Qtz,Ilm, H₂O, and Chl into the Ca–Al'–Fe'–Mn tetrahedronindicates that Ca/(Ca+Na) and Mn differ among the assemblagesin a systematic fashion. Common Grt+Bt+Chl+Pl assemblages arerestricted to relatively high Mn and low Ca/(Ca+Na) values,whereas Cld+Bt+Mrg and Cld+Hbl+Mrg assemblages are stable atlow Mn and high Ca/(Ca+Na). These data suggest that at thisgrade Cld+Bt is more stable than Grt+Chl in the KFMASH system,whereas in the Ca—KFMASH system, Hbl+Cld assemblages arestable. Composition space analysis using the singular value decompositionmethod indicates that compositions of minerals from individualsamples are consistent with local equilibrium, but that differentoutcrops may not have all equilibrated at the same P–T–a_H2Oconditions. Thermodynamic analysis suggests that a garnet-zoneprograde sequence of ferromagnesian associations for these bulkcompositions would be Hbl+Cld+Grt+ChlBt+Cld+Grt+ChlBt+Grt+Chl. Staurolite-grade rocks from the same stratigraphic units areexposed across strike, and contain the assemblage Grt+StBtPl(all rocks contain Ms, Qtz, Chl, and Ilm). Margarite is commonlypresent as inclusions in the cores of garnets, but is absentas inclusions near garnet rims and from the matrix; conversely,staurolite inclusions are present towards the rims of the garnets,but are absent from the cores. These inclusion relations suggestthat margarite may react to form staurolite and garnet withincreasing grade via a reaction such as chlorite+margarite=staurolite+garnet+H₂O. Biotite is common in the matrix but is not typically abundant,and appears to have been the last phase to join the assemblage.Biotite is inferred to have joined the Grt+St+Chl assemblagesafter margarite breakdown through the reaction Grt+Chl+Ms=St+Bt+H₂O. Thus, uncommon margarite assemblages may evolve into commonGrt+Bt+St+Chl assemblages. ^* Present address: Department of Geology and Geophysics, University of Wisconsin-Madison, Madison, Wisconsin 53706.     

Melting of a Hydrous Mantle: I. Phase Relations of Natural Peridotite at High Pressures and Temperatures with Controlled Activities of Water, Carbon Dioxide, and Hydrogen

Four natural peridotite nodules ranging from chemically depletedto Fe-rich, alkaline and calcic (SiO₂=43?7–45?7 wt. percent, Al₂O3=1?6O–8?21 wt. per cent, CaO=0?70–8?12wt. per cent,alk=0?10–0?90 wt. per cent and Mg/(Mg+Fe²⁺)=0?94–0?85)have been investigated in the hypersolidus region from 800?to 1250?C with variable activities of H₂O, CO₂, and H₂. Thevapor-saturated peridotite solidi are 50–200?C below thosepreviously published. The temperature of the beginning of meltingof peridotite decreases markedly with decreasing Mg/(Mg+Fe)of the starting material at constant CaO/Al₂O₃. Conversely,lowering CaO/Al₂O₃ reduces the temperature at constant Mg/(Mg+Fe)of the starting material. Temperature differences between thesolidi up to 200?C are observed. All solidi display a temperatureminimum reflecting the appearance of garnet. This minimum shiftsto lower pressure with decreasing Mg/(Mg+Fe) of the startingmaterial. The temperature of the beginning of melting decreasesisobarically as approximately a linear function of the mol fractionof H₂O in the vapor (X_H2O). The data also show that some CO₂may dissolve in silicate melts formed by partial melting ofperidotite. Amphibole (pargasitic hornblende) is a hypersolidus mineralin all compositions, although its P/T stability field dependson bulk rock chemistry. The upper pressure stability of amphiboleis marked by the appearance of garnet. The vapor-saturated (H₂O) liquidus curve for one peridotiteis between 1250? and 1300?C between 10 and 30 kb. Olivine, spinel,and orthopyroxene are either liquidus phases or coexist immediatelybelow the temperature of the peridotite liquidus. The data suggest considerable mineralogical heterogeneity inthe oceanic upper mantle because the oceanic geotherm passesthrough the P/T band covering the appearance of garnet in variousperidotites. The variable depth to the low-velocity zone is explained byvariable a_H2O conditions in the upper mantle and possibly alsoby variations in the composition of the peridotite itself. It is suggested that komatiite in Precambrian terrane couldform by direct melting of hydrous peridotite. Such melting requiresabout 1250?C compared with 1600?C which is required for drymelting. The genesis of kimberlite can be related to partial meltingof peridotite under conditions of (). Such activities of H₂Oresult in melting at depths ranging between 125 and 175 km inthe mantle. This range is within the minimum depth generallyaccepted for the formation of kimberlite.