Studies in the System KAlSiO4--Mg2SiO4--SiO2--H2O: I, Inferred Phase Relations and Petrologic Applications

The results of synthesis experiments in the system KAlSiO₄—Mg₂SiO₄—SiO₂—SiO₂H₂Ohave been used to outline the melting and sub-solidus phaserelations at temperatures from 700 to 1200 C and pressuresto 3 kilobars. Studies in this system provide a framework withinwhich petrologic features of the near-surface potassic rocks,some lamprophyres, charnockitic granites, kimberlites, and alliedmica peridotites may be discussed. On the basis of the experimentalstudies the pressure-temperature stability limits of coexistingphases are considered. The bivariant phase relations providea means by which the olivine biotite and pyroxene biotitereaction relations observed in potassic rocks may be accountedfor. The phase relations provide a mechanism for crossing the‘equilibrium thermal divides’ forsterite-potashfeldspar and enstatite-potash feldspar, from the silica-undersaturatedto the silica-oversaturated region. The petrologic importanceof water-undersaturatsed magmas is stressed throughout the discussion.     

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.     

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

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

Melting Relations in Part of the System CaO-MgO-Al2O3-SiO2-Na2O-H2O under 5kb Pressure

In the system CaO-MgO-Al₂O₃-SiO₂-Na₂O-H₂O under 5 kb pressurethe invariant equilibrium forsterite-orthopyroxene-Ca-rich clinopyroxene-amphibole-plagioclase-liquid-vapourhas been identified at 960?12 ?C. A similar invariant assemblagewith spinel replacing Ca-rich clinopyroxene exists at 950?8?C. The liquid in the former equilibrium contains 16.5 per cent(wt.) normative quartz and 3 per cent Na₂O; the plagioclaseis more calcic than An₈₇; the pyroxenes contain about 3 percent Al₂O₃ and the amphibole is hypersthene-normative. Two anhydrousthermal maxima, the olivine-Ca-rich clinopyroxene-plagioclaseand the orthopyroxene-Ca-rich clinopyroxene-plagioclase dividezones are not encountered in this system, and nepheline-normativeliquids may crystallize amphibole?olivine?Ca-rich clinopyroxeneto produce quartz-normative residual liquids of andesite-typecomposition. A thermal maximum involving amphibole-olivine-Ca-richclinopyroxene-liquid-vapour exists for liquids containing approximately11 per cent normative nepheline and liquids more undersaturatedthan this will crystallize these phases to produce extremelynephelinitic liquids. Phase diagrams are presented which facilitate the predictionof crystallization sequences and liquid evolution paths forany basic or intermediate composition under the conditions employedhere.     

The Phase Relations of Aluminous Iron Biotites in the System KAISi3O8-KAISiO4-AI2O3-Fe-O-H

The experimental work on biotites has primarily involved compositionsalong the annite-phlogopite join, but most natural biotitescontain significantly larger amounts of aluminum. At the sametime, the aluminum content of natural biotites varies considerably.The available evidence indicates that these variations in thealuminum content of biotite depend on the conditions of formationand the whole rock chemistry. Experiments on the phase relations of aluminous iron biotitesin the silica deficient system KAlSiO₄-KAlSi₃O₈-Al₂O₃-Fe-O-H(pfluid = 2 kb) indicate that compositions up to Ann₇₅ can besynthesized on the join annite [K₂Fe₆Al₂Si₆O₂₀(OH)₄]-aluminumbiotite [K₂Al₆Al₂Al₆O₂₀(OH)₄]. The aluminous biotites are stableto higher temperatures than annite. An isobaric divariant equilibrium,Bio_ss-Mt_ss-Sa-Lc-V, extends to higher oxygen fugacities fromthe Ann-Mt-Sa-Lc-V curve of Eugster & Wones (1962). Compositioncontours on this surface indicate that both the magnetite andbiotite become more aluminous with increasing temperature and/oroxygen fugacity. The Bio_ss-Mt_ss-Sa-Lc-V reaction surface isterminated by equilibria involving the additional phases muscovite,corundum, and hercynite respectively as the conditions becomemore reducing. At 2 kb fluid pressure; aluminum-rich iron biotiteis stable to 555 °C on the HM buffer, 763 °C on theMt-Hc-Cor buffer, 820 °C on NNO, and about 860 °C onQFM. The data obtained can be applied to a number of biotitesyenites and appears to explain why iron-rich aluminum biotitesoccur in these rocks.     

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     

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     

Calculated Phase Relations in the System Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O with Applications to UHP Eclogites and Whiteschists

Pressure–temperature grids in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O and its subsystems have been calculatedin the range 15–45 kbar and 550–900°C, usingan internally consistent thermodynamic dataset and new thermodynamicmodels for amphibole, white mica, and clinopyroxene, with thesoftware THERMOCALC. Minerals considered for the grids includegarnet, omphacite, diopside, jadeite, hornblende, actinolite,glaucophane, zoisite, lawsonite, kyanite, coesite, quartz, talc,muscovite, paragonite, biotite, chlorite, and plagioclase. Compatibilitydiagrams are used to illustrate the phase relationships in thegrids. Coesite-bearing eclogites and a whiteschist from Chinaare used to demonstrate the ability of pseudosections to modelphase relationships in natural ultrahigh-pressure metamorphicrocks. Under water-saturated conditions, chlorite-bearing assemblagesin Mg- and Al-rich eclogites are stable at lower temperaturesthan in Fe-rich eclogites. The relative temperature stabilityof the three amphiboles is hornblende > actinolite > glaucophane(amphibole names used sensu lato). Talc-bearing assemblagesare stable only at low temperature and high pressure in Mg-and Al-rich eclogites. For most eclogite compositions, talccoexists with lawsonite, but not zoisite, in the stability fieldof coesite. Water content contouring of pressure–temperaturepseudosections, along with appropriate geotherms, provides newconstraints concerning dehydration of such rocks in subductingslabs. Chlorite and lawsonite are two important H₂O-carriersin subducting slabs. Depending on bulk composition and pressure–temperaturepath, amphibole may or may not be a major H₂O-carrier to depth.In most cases, dehydration to make ultrahigh-pressure eclogitestakes place gradually, with H₂O content controlled by divariantor higher variance assemblages. Therefore, fluid fluxes in subductionzones are likely to be continuous, with the rate of dehydrationchanging with changing pressure and temperature. Further, eclogitesof different bulk compositions dehydrate differently. Dehydrationof Fe-rich eclogite is nearly complete at relatively shallowdepth, whereas Mg- and Al-rich eclogites dehydrate continuouslydown to greater depth. KEY WORDS: dehydration; eclogites; phase relations; THERMOCALC; UHP metamorphism; whiteschists     

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

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

The Distribution of H2O between Cordierite and Granitic Melt: H2O Incorporation in Cordierite and its Application to High-grade Metamorphism and Crustal Anatexis

Experiments defining the distribution of H₂O [D_w = wt % H₂O(melt)/wt% H₂O(crd)]) between granitic melt and coexisting cordieriteover a range of melt H₂O contents from saturated (i.e. coexistingcordierite + melt + vapour) to highly undersaturated (cordierite+ melt) have been conducted at 3–7 kbar and 800–1000°C.H₂O contents in cordierites and granitic melts were determinedusing secondary ion mass spectrometry (SIMS). For H₂O vapour-saturatedconditions D_w ranges from 4·3 to 7 and increases withrising temperature. When the system is volatile undersaturatedD_w decreases to minimum values of 2·6–5·0at moderate to low cordierite H₂O contents (0·6–1·1wt %). At very low aH₂O, cordierite contains less than 0·2–0·3wt % H₂O and D_w increases sharply. The D_w results are consistentwith melt H₂O solubility models in which aH₂O is proportionalto X_w² (where X_w is the mole fraction of H₂O in eight-oxygenunit melt) at X_w     

四元体系Na+//Cl-,CO32-,B4O72--H2O273 K介稳相平衡研究

采用等温蒸发法研究简单四元体系Na+//CI-,CO32-,B4O72---H2O 273 K时的介稳相平衡,并测定该体系273 K平衡液相中各组分的溶解度及密度,该体系的介稳相图和密度组成图显示:该四元体系在273 K时的相图由3条溶解度单变量线、3个结晶区及1个共饱和点组成.体系属简单共饱型,无复盐或固溶体形成,3个结晶区分别对应单盐Na2CO3?10H2O,NaCI和Na2B4O7?10H2O.共饱点E处于Na2CO3?10H2O,NaCI及Na2B4O,?10H2O3盐共饱和,所对应的平衡液相组成为ω(Na2CO3)=6.81%,ω(NaCl)=21.69%,ω(Na2B4O7)=0.65%.ω(H20)=70.85%.研究体系在273 K下,Na2CO3?10H2O是碳酸钠盐的唯一析出形式,且硼酸钠对碳酸钠有盐析作用.     

中-低压泥质岩在KFMASH体系中的相平衡关系

利用内部一致热力学数据库、可靠的固溶体活度模型，用有关程序THERMOCALC 3．1计算了KFMASH(K2O-FeO-MgO-Al2O3-SiO2-H2O)体系和亚体系KMASH、KFASH中的岩石成因格子。温压范围为P=0．05～1．2GPa，T=450～900℃．包括黑云母、白云母、钾长石、绿泥石、硬绿泥石、十字石、堇青石、斜方辉石、石榴石、尖晶石、红柱石、蓝晶石、矽线石、石英(过量)、熔体和水(固相线以下水过量、固相线以上水不过量)．．利用这些成因格子以及所计算的AFM图、P-T视剖面图，可以很好地阐明泥质岩石中低压变质作用的相平衡关系及P-T条件。所计算的结果与岩石学研究非常吻合，能解释从绿片岩相至麻粒岩相的一系列变化。尤其是熔体的引入，使我们能够定量计算高角闪岩相以上出现的混合岩化过程。     

Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} K2O at 1{middle dot}1 GPa

The compositions of multiply saturated partial melts are valuablefor the thermodynamic information that they contain, but aredifficult to determine experimentally because they exist onlyover a narrow temperature range at a given pressure. Here wetry a new approach for determining the composition of the partialmelt in equilibrium with olivine, orthopyroxene, clinopyroxeneand spinel (Ol + Opx + Cpx + Sp + Melt) in the system CaO–MgO–Al₂O₃–SiO₂(CMAS) at 1·1 GPa: various amounts of K₂O are added tothe system, and the resulting melt compositions and temperatureare extrapolated to zero K₂O. The ‘sandwich’ experimentalmethod was used to minimize problems caused by quench modification,and Opx and Cpx were previously synthesized at conditions nearthose of the melting experiments to ensure they had appropriatecompositions. Results were then checked by reversal crystallizationexperiments. The results are in good agreement with previouswork, and establish the anhydrous solidus in CMAS to be at 1320± 10°C at 1·1 GPa. The effect of K₂O is todepress the solidus by 5·8°C/wt %, while the meltcomposition becomes increasingly enriched in SiO₂, being quartz-normativeabove 4 wt % K₂O. Compared with Na₂O, K₂O has a stronger effectin depressing the solidus and modifying melt compositions. Theisobaric invariant point in the system CMAS–K₂O at whichOl + Opx + Cpx + Sp + Melt is joined by sanidine (San) is at1240 ± 10°C. During the course of the study severalother isobaric invariant points were identified and their crystaland melt compositions determined in unreversed experiments:Opx + Cpx + Sp + An + Melt in the system CMAS at 1315 ±10°C; in CMAS–K₂O, Opx + Cpx + Sp + An + San + Meltat 1230 ± 10°C and Opx + Sp + An + San + Sapph +Melt at 1230 ± 10°C, where An is anorthite and Sapphis sapphirine. Coexisting San plus An in three experiments helpdefine the An–San solvus at 1230–1250°C. KEY WORDS: feldspar solvus; igneous sapphirine; mantle solidus; partial melting; systems CMAS and CMAS–K₂O     

Li+/Cl-,CO32-,B4O72--H2O四元体系 298 K介稳相平衡的研究

根据对西藏扎布耶盐湖四元子体系L i /C l-,CO32-,B4O72--H2O 298 K介稳平衡实验数据,绘制出的介稳平衡相图及物化性质(密度、pH值、电导率、折光率)组成图的研究结果表明:该四元体系属简单共饱型,无复盐或固溶体形成;其溶解度等温图含有一个共饱点、3条单变量曲线和3个结晶相区;3个结晶相区分别对应为L i2B4O7.3H2O,L i2CO3和L iC lH2O。     

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.     

Liquidus Equilibria in the System K2O-Na2O-Al2O3-SiO2-F2O-1-H2O to 100 MPa: I. Silicate-Fluoride Liquid Immiscibility in Anhydrous Systems

Liquidus relations in the four-component system Na₂O–Al₂O₃–SiO₂–F₂O_–1were studied at 0· 1 and 100 MPa to define the locationof fluoride–silicate liquid immiscibility and outlinedifferentiation paths of fluorine-bearing silicic magmas. Thefluoride–silicate liquid immiscibility spans the silica–albite–cryoliteand silica–topaz–cryolite ternaries and the haplogranite-cryolitebinary at greater than 960°C and 0· 1–100 MPa.With increasing Al₂O₃ in the system and increasing aluminum/alkalication ratio, the two-liquid gap contracts and migrates fromthe silica liquidus to the cryolite liquidus. The gap does notextend to subaluminous and peraluminous melt compositions. Forall alkali feldspar–quartz-bearing systems, the miscibilitygap remains located on the cryolite liquidus and is thus inaccessibleto differentiating granitic and rhyolitic melts. In peralkalinesystems, the magmatic differentiation is terminated at the albite–quartz–cryoliteeutectic at 770°C, 100 MPa, 5 wt % F and cation Al/Na =0· 75. The addition of topaz, however, significantlylowers melting temperatures and allows strong fluorine enrichmentin subaluminous compositions. At 100 MPa, the binary topaz–cryoliteeutectic is located at 770°C, 39 wt % F, cation Al/Na 0·95, and the ternary quartz–topaz–cryolite eutecticis found at 740°C, 32 wt % F, 30 wt % SiO₂ and cation Al/Na 0· 95. Such location of both eutectics enables fractionationpaths of subaluminous quartz-saturated systems to produce fluorine-rich,SiO₂-depleted and nepheline-normative residual liquids. KEY WORDS: silicate melt; granite; rhyolite; fluorine; liquid immiscibility     

Solid-Fluid Equilibria in the System KAlSi3O8-NaAlSi3O8-Al2SiO5-SiO2-H2O-HCl

Activity diagrams in the system KAlSi₃O₈-NaAlSi₃O₈-Al₂SiO₅-SiO₂-H₂O-HClhave been calculated in terms of a_K+/a_H+ and a_N+/a_H+ from existingexperimental data. They show the effect of temperature, pressure,and a_H2O on the stability fields of the alkali feldspars, micas,and aluminium silicate. These activity diagrams are useful in revealing the bufferingcapacity of mineral assemblages and the chemical potential gradientsestablished by changes in T, P, a_H2O, and mineral assemblage.An analysis of mineral paragenesis in terms of these diagramssuggests that mosaic equilibrium, allowing limited metasomatismand internal buffering of chemical potentials, best describemetamorphic systems. Thus the dehydration reaction: muscovite+quartz=K-feldspar+Al₂SiO₅+H₂O which is most important in closed systems, probably fails todescribe in detail the mechanism of natural muscovite decomposition.Rather the decomposition of muscovite is more likely representedby ionic reactions. The replacement of muscovite by feldspar: muscovite+6 SiO₂+2 K⁺=3 K-feldspar+2 H⁺ muscovite+6 SiO₂+3 Na⁺=3 Albite+K⁺+2 H⁺ is favored at high temperature and low pressure, and may accountfor the crystallization of some feldspars in metamorphic rocks.The reaction involving aluminium silicate replacement of muscovite: 2 muscovite+2 H⁺=3 Al₂SiO₅+3 SiO₂+3 H₂O+2 K⁺ is favored at high temperature and pressure and low a_H2O, andcould contribute to the development of the aluminium silicates.It is concluded that both activity diagrams and AKNa projectionsshould be used together to more completely evaluate mineralparagenesis in terms of mosaic equilibria.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O: corrections and additional experimental data

Melting relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been reinvestigated using Schreinemakers analysis and hydrothermal experiments. The reaction sanidine+muscovite+zoisite+quartz+vapor =melt has been bracketed at 10, 15, and 20 kbars and 670–680, 680–690, and 690–700° C, respectively and it marks the lowest solidus temperatures in the system investigated.Below 10 kbars, experimental data on the beginning of melting in zoisite- or muscovite-bearing anorthite+sanidine assemblages have been obtained, which are not showing any differences and therefore point to melt compositions close to the feldspar-quartz join.     

Stability of the assemblage orthopyroxene-sillimanite-quartz in the system MgO-FeO-Fe2O3-Al2O3-SiO2-H2O

The stability of coexisting orthopyroxene, sillimanite and quartz and the composition of orthopyroxene in this assemblage has been determined in the system MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-H₂O as a function of pressure, mainly at 1,000° C, and at oxygen fugacities defined mostly by the hematite-magnetite buffer. The upper stability of the assemblage is terminated at 17 kbars, 1,000° C, by the reaction opx+Al-silicate gar+qz, proceeding toward lower pressures with increasing Fe/(Fe+Mg) ratio in the system. The lower stability is controlled by the reaction opx+sill+qz cord, which occurs at 11 kbars in the iron-free system but is lowered to 9 kbars with increasing Fe/(Fe+Mg). Spinel solid solutions are stabilized, besides quartz, up to 14 kbars in favour of garnet in the iron-rich part of the system (Fe/(Fe+Mg)0.30). Ferric-ferrous ratios in orthopyroxene are increasing with increasing ferro-magnesian ratio. At least part of the generally observed increase in Al content with Fe²⁺ in orthopyroxene is not due to an increased solubility of the MgAlAlSiO₆ component but rather of a MgFe³⁺AlSiO₆ component. The data permit an estimate of oxygen fugacity from the composition of orthopyroxene in coexistence with sillimanite and quartz.