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.     

川西甲基卡花岗伟晶岩型锂矿床中熔体、流体包裹体固相物质研究

川西甲基卡二云母花岗岩和伟晶岩内发育大量原生熔体包裹体和富晶体流体包裹体。为了查明甲基卡成矿熔体、流体性质与演化特征,运用激光拉曼光谱和扫描电镜鉴定了甲基卡花岗伟晶岩型锂矿床中二云母花岗岩及伟晶岩脉不同结构带内的原生熔体、流体包裹体的固相物质。分析结果表明,甲基卡二云母花岗岩石英内熔体包裹体的矿物组合为磷灰石+白云母、白云母+钠长石、白云母+石墨;伟晶岩绿柱石内富晶体流体包裹体的矿物组合主要为刚玉、富铝铁硅酸盐+刚玉+锂辉石、锂辉石+石英+锂绿泥石;伟晶岩锂辉石内富晶体流体包裹体的矿物组合主要为磷灰石、锡石、磁铁矿、石英+钠长石+锂绿泥石、萤石、富钙镁硅酸盐+富铁铝硅酸盐+富铁硅酸盐+石英;花岗岩浆熔体与伟晶岩浆熔体(流体)具有一定的差异,成矿熔体、流体成分总体呈现出碱质元素(Na、Si、Al)、挥发分(F、P、CO_2)含量增高及基性元素(Fe、Mg、Ca)降低的特征;包裹体中子矿物与主矿物的化学成分具有一定的差别,揭示出伟晶岩熔体(流体)存在局部岩浆分异作用,具不混溶性及非均匀性。因此认为,伟晶岩熔浆(流体)为岩浆分异与岩浆不混溶共同作用的产物,挥发分含量的增高(F、P、CO_2)使伟晶岩能够与稀有金属组成各类络合物或化合物,这对于稀有金属成矿起到了至关重要的作用。     

Margarite in kyanite- and corundum-bearing anorthosite,amphibolite, and hornblendite from central Fiordland,New Zealand

Margarite is both abundant and widespread throughout a sequence of interstratified amphibolite, hornblendite, and metamorphosed anorthosite from the upper Lyvia River, central Fiordland. These rock types comprise part of a metamorphosed layered intrusion. Assemblages recorded from these rocks are the product of two distinct phases of metamorphism. First generation assemblages typically comprise plagioclase (An_84–96), hornblende, kyanite, and minor corundum. Clinozoisite and chlorite occur as late stage breakdown products of plagioclase and hornblende. Margarite developed during the second phase of metamorphism.Within the corundum-bearing rocks replacement of corundum or plagioclase by margarite can be observed directly. On the basis of these observations the following reaction is evident: 1 corundum+1 anorthite+1H₂O=1 margarite.In other assemblages the formation of margarite can be attributed to the breakdown of kyanite and clinozoisite according to the reaction: 2 kyanite+2 clinozoisite=1 margarite+3 anorthite.Margarite is found, however, to contain appreciable amounts of paragonite solid-solution (up to 28 mol%) and plagioclase produced (second generation) is not pure anorthite but of intermediate compositions (An_46–62). The reaction therefore involves the introduction of both soda and silica. Margarite also crystallized independently of clinozoisite according to a reaction of the general form: 5 pargasite+17 kyanite+19 H₂O =8 margarite+4 chlorite+7 plagioclase.Application of available experimental data suggests that the margarite formed between 550 and 720 ° C up to a maximum pressure of 9.5 kb. Whereas the involvement of albite component (second generation plagioclase) will tend to lower the temperatures and pressures necessary for the occurrence of margarite, this effect is partially offset by the significant amounts of paragonite end-member held within the margarite. An independent estimate of the metamorphic conditions in metapelites suggests that the introduction of albite lowers equilibration temperatures by about 2 ° C for every 1% albite.     

The upper stability limit of the assemblage paragonite + quartz and its natural occurrences

The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al₂SiO₅.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H₂O has been located experimentally. The reversed P _{H 2 O}-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H₂O runs through the following P _{H 2 O}-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H₂O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G _f,298 ⁰ of the Al₂SiO₅ polymorphs may in fact be due to an error of similar magnitude in G _f,298 ⁰ of corundum.A best estimate of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of paragonite based on these considerations yield: S ₂₉₈ ⁰ : 67.61±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ : –1411.4±2.7 kcal gfw^–1 G _f,298 ⁰ : –1320.9±4.0 kcal gfw^–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.     

喜马拉雅东段库曲岩体锂、铍和铌钽稀有金属矿物研究及指示意义

稀有金属矿物记录了花岗伟晶岩成岩成矿的重要信息。喜马拉雅是全球著名的淡色花岗岩带,库曲岩体位于喜马拉雅东段的特提斯喜马拉雅岩系中。本文调查了库曲岩体的二云母花岗岩、白云母花岗岩、电气石花岗岩和花岗伟晶岩,其中,花岗伟晶岩涉及花岗岩的伟晶岩相和独立伟晶岩脉。库曲岩体产出的稀有金属矿物包括锂辉石、锂绿泥石、绿柱石、铌铁矿-钽铁矿、钇铀钽烧绿石和细晶石,它们主要赋存于似文象伟晶岩、石英-钠长石-白云母伟晶岩、块体长石-钠质细晶岩、块体长石-电气石钠质细晶岩、锂辉石-块体长石-细晶岩、白云母花岗岩的伟晶岩相以及电气石花岗岩内。显微镜观察、电子探针和LA-ICP-MS测试结果显示锂辉石具有四种产状,包括粗粒锂辉石自形-半自形晶、细粒锂辉石-石英镶嵌晶、中细粒锂辉石-钾长石-钠长石-云母镶嵌晶以及发育锂绿泥石的粗粒锂辉石,揭示了其形成时复杂的熔流体动荡结晶环境。绿柱石背散射电子图像（BSE）下呈均一结构和不均一结构（蚀变边、不规则分带和补丁分带）,元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。铌铁矿族矿物包括原生、蚀变边和不规则分带结构,部分被钇铀钽烧绿石和细晶石交代。与原生铌铁矿相比,蚀变边和不规则分带铌铁矿族矿物总体上富钽贫锰,显示了结晶分异、过冷却引起的过饱和以及流体作用。根据稀有金属矿物揭示的成因信息,独立伟晶岩脉（似文象伟晶岩）、白云母花岗岩的伟晶岩相和电气石花岗岩在岩浆分异程度、经历的演化过程、以及流体活动方面存在差异,很可能是不同期次岩浆活动的产物。库曲岩体绿柱石的Rb和Zn含量、以及铌铁矿族矿物的Sc₂O₃、SiO₂和PbO含量,与已有指示标志存在相关性,作为潜在指示标志仍需开展更多的研究工作。综合含锂辉石伟晶岩的产出、岩浆分异演化程度、多期花岗质岩浆活动、复杂的流体作用以及所属锂丰度高值区等因素,库曲岩体是喜马拉雅东段找锂的有利地段。     

An experimental investigation on the P-T stability of Mg-staurolite in the system MgO-Al2O3-SiO2-H2O

The pressure-temperature stability field of Mg-staurolite, ideally Mg₄Al₁₈Si₈O₄₆(OH)₂, was bracketed for six possible breakdown reactions in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). Mg-staurolite is stable at water pressures between 12 and 66 kbar and temperatures of 608–918 °C, requiring linear geotherms between 3 and 18 °C/km. This phase occurs in rocks that were metamorphosed at high-pressure, low-temperature conditions, e.g. in subducted crustal material, provided they are of appropriate chemical composition. Mg-staurolite is formed from the assemblage chlorite + kyanite + corundum at pressures <24 kbar, whereas at pressures up to 27 kbar staurolite becomes stable by the breakdown of the assemblage Mg-chloritoid + kyanite + corundum. Beyond 27 kbar the reaction Mg-chloritoid + kyanite + diaspore = Mg-staurolite + vapour limits the staurolite field on its low-temperature side. The upper pressure limit of Mg-staurolite is marked by alternative assemblages containing pyrope + topaz-OH with either corundum or diaspore. At higher temperatures Mg-staurolite breaks down by complete dehydration to pyrope + kyanite + corundum and at pressures below 14 kbar to enstatite + kyanite + corundum. The reaction curve Mg-staurolite = talc + kyanite + corundum marks the low-pressure stability of staurolite at 12 kbar. Mg-staurolite does not coexist with quartz because alternative assemblages such as chlorite-kyanite, enstatite-kyanite, talc-kyanite, pyrope-kyanite, and MgMgAl-pumpellyite-kyanite are stable over the entire field of Mg-staurolite. Received: 16 April 1997 / Accepted: 24 September 1997     

Rare metal-bearing pegmatites from the Southeastern Desert of Egypt： Geology, geochemical characteristics, and petrogenesis

The pegmatite province of the Southeastern Desert (SED) is part of a pegmatite district that extends from Egypt (extends to 1200 km2). Rare metal pegmatites are divided into (1) unzoned, Sn-mineralized; (2) zoned Li, Nb, Ta and Be-bearing; and (3) pegmatites and pegmatites containing colored, gem-quality tourmaline. The Rb/Sr data reflect a crustal origin for the rare metal pegmatites and indicate that the original SED magma was generated during the peak of regional metamorphism and predates the intrusion of post-tectonic leucogranites. These bodies developed an early border zone consisting of coarse to very coarse muscovite quartz alkali feldspar, followed by an intermediate zone of dominant quartz feldspar muscovite rock. Garnet, tourmaline, beryl, galena, pyrite, amblygonite, apatite and monazite are rare accessories in both zones. Cassiterite tends to concentrate in replacement zones and along fractures in albite quartz muscovite-rich portions. The highest concentrations of cassiterite occur in irregular greisenized zones which consist dominantly of micaceous aggregates of green Li-rich muscovite, quartz, albite and coarse-grained cassiterite. The different metasomatic post-solidification alterations include sodic and potassic metasomatism, greisenization and tourmalinization. Geochemically, the pegmatite-generating granites have a metaluminous composition, showing a differentiation trend from coarse-grained, unfractionated plagioclase-rich granite towards highly fractionated fine- to medium-grained, local albite-rich rock. Economically important ore minerals introduced by volatile-rich, rare metal-bearing fluids, either primarily or during the breakdown of the primary mineral assemblages, are niobium-tantalum oxides, Sn-oxides (cassiterite), Li-silicates (petalite, spodumene, euctyptite, and pollucite), Li-phosphates (amblygonite, montebrasite and lithopilite) and minor REE-minerals (Hf-zircon, monazite, xenotime, thorian, loparite and yttrio-fluorite). The pollucite is typically associated with spodumene, petalite, amblygonite, quartz and feldspar. The primary pollucite has Si/Al (at) ratios of 2.53-2.65 and CRK of 79.5- 82.2. Thorian loparite is essentially a member of the loparite (NaLREETi2O6)-lueshite (NaNbO3)-ThTi2O6-ThNb4O12 quaternary system with low or negligible contents of other end-member compositions. The mineral compositionally evolved from niobian loparite to niobian thorian and thorian loparite gave rise to ceriobetafite and belyankinite with high ThO2 contents. Thorian loparite is metamict or partly metamict and upon heating regains a structure close to that of synthetic loparite NaLaTi2O6.     

Paragenesis and petrogenesis of a corundum-bearing marble at Hunza (Kashmir)

A calcite-marble containing gem-quality ruby is exposed in the Hunza Valley, northwestern part of the Karakoram mountains, Pakistan zone of Kashmir. The marble forms concordant intercalations within sillimanite- and garnet-bearing biotite-plagioclase gneisses and mica schists. The metamorphic sequence is cut by discordant aplite and pegmatite dikes. The following mineral assemblages are recognized in the marble:1) Calcite+corundum+phlogopite±margarite±sheridanite±Al-rich pargasite±anorthite (An 96.7),2) calcite+spinel±corundum+phlogopite+sheridanite.Microprobe analyses are given for the essential minerals including corundum (ruby) and three different colour varieties of spinel. On the basis of recent experimental data, especially in the system CaO - Al₂O₃ - SiO₂ - H₂O -CO₂ (and related subsystems), we assume that, during the regional metamorphism, temperatures of about 600 – 620°C and a water vapour pressure of about 6 kb were realized in part of the Hunza area. The gas phase must have contained roughly 20 mole-% of CO₂. Thus the total fluid pressure may have reached about 7 kb. Presumably, temperatures increased in northwest direction, perhaps up to about 700°C. The estimated P-T conditions are consistent with a geothermal gradient of about 25°C/km.     

Stability of the assemblage cordierite—Corundum in the system MgO-Al2O3-SiO2-H2O

The assemblage Mg-cordierite — corundum is formed stably through the reaction chlorite+Al-silicate=cordierite+corundum+H₂O at 535° C, 2kb; 615°, 5 kb; and 665° C, 7 kb water pressure. In the order of increasing pressure andalusite, sillimanite, and kyanite participate as stable phases in this equilibrium. A spinel-Al-silicate tie-line is only stable at high temperatures not likely to be attained in rocks. The natural assemblage spinel-Al-silicate is, however, to be explained by the additional presence of FeO in these rocks.     

Phase relations in the greenschist-blueschist-amphibolite-eclogite facies in the system Na2O-CaO-FeO-MgO-Al2O3-SiO2-H2O (NCFMASH), with application to metamorphic rocks from Samos, Greece

Calculated phase equilibria among the minerals sodic amphibole, calcic amphibole, garnet, chloritoid, talc, chlorite, paragonite, margarite, omphacite, plagioclase, carpholite, zoisite/clinozoisite, lawsonite, pyrophyllite, kyanite, sillimanite, quartz and H₂O are presented for the model system Na₂O-CaO-FeO-MgO-Al₂O₃-SiO₂-H₂O (NCFMASH), which is relevant for many greenschist, blueschist, amphibolite and eclogite facies rocks. Using the activity-composition relationships for multicomponent amphiboles constrained by Will and Powell (1992), equilibria containing coexisting calcic and sodic amphiboles could be determined. The blueschist–greenschist transition reaction in the NCFMASH system, for example, is defined by the univariant reaction sodic amphibole + zoisite = calcic amphibole + chlorite + paragonite + plagioclase (+ quartz + H₂O) occurring between approximately 420 and 450 °C at 9.5 to 10 kbar. The calculated petrogenetic grid is a valuable tool for reconstructing the PT-evolution of metabasic rocks. This is shown for rocks from the island of Samos, Greece. On the basis of mineral and whole rock analyses, PT-pseudosections were calculated and, together with the observed mineral assemblages and reaction textures, are used to reconstruct PT-paths. For rocks from northern Samos, pseudomorphs after lawsonite preserved in garnet, the assemblage sodic amphibole-garnet-paragonite-chlorite-zoisite-quartz and the retrograde appearance of albitic plagioclase and the formation of calcic amphibole around sodic amphibole constrain a clockwise PT-path that reaches its thermal maximum at some 520 °C and 19 kbar. The derived PT-trajectory indicates cooling during exhumation of the rocks and is similar to paths for rocks from the western part of the Attic-Cycladic crystalline complex. Rocks from eastern Samos indicate lower pressures and are probably related to high-pressure rocks from the Menderes Massif in western Turkey. Received: 8 July 1997 / Accepted: 11 February 1998     

A staurolite-talc assemblage in tourmaline-phlogopite-chlorite schist from northern Victoria Land,Antarctica, and its petrogenetic significance

Staurolite and corundum are found as inclusions in tourmaline in a talc-phlogopite-chlorite-albite chist near Mount Bernstein (71°37S, 163°07E), northern Victoria Land, Antarctica. These inclusions are interpreted as relics of a staurolite-talc-corundum-chlorite assemblage that was stable during an early stage in the metamorphic cycle and subsequently armored by tourmaline, probably during the middle stage. Pressures and temperatures during the middle stage are estimated to be 650–700°C and 5.5–6.4 kbar. The transition from the early to the middle stage represents a roughly isothermal decrease in pressure of 2–3 kbar. During a late retrograde stage (T=300–370°C, P=3–5 kbar), staurolite was partly replaced by a muscovitic aggregate containing clinozoisite, pumpellyite, and margarite.The staurolite is unusually Si-poor (26.77, 25.85 weight % SiO₂ or 7.275, 7.091 Si per formula unit for 46 oxygens anhydrous), Al-rich (58.00, 57.85% Al₂O₃, 18.579, 18.702 Al), low in divalent cations (Fe+Mg+Mn+Zn=3.301, 3.560) and magnesian (atomic Mg/(Mg+Fe)=0.42, 0.40). Ion microprobe analysis of the first grain indicates about 0.2% Li₂O (0.219 Li) is present. The following substitutions are proposed to explain the unusual chemistry of this staurolite (crystallographic site notation of Smith 1968, in bold letters): Al(Si)+Al(Al(3A,B))Si(Si)+Fe(Fe), Li(Fe)+Al(Al(3A,B))2 Fe(Fe), and 2 Al(Al(3A,B)) 3 Fe(Fe).According to a pressure-temperature diagram constructed by the method of Schreinemakers for the model system FeO-MgO-Al₂O₃-SiO₂ (H₂O in excess), the talc-staurolite assemblage should be stable only in quartz-free rocks at temperatures near 700° C and pressures of 8 kbar or more. The rarity of the staurolite-talc assemblage even in Mg-Al-rich rocks metamorphosed at the appropriate pressure-temperature conditions is attributed to the appearance of anthophyllite or, in Na₂O-bearing rocks, gedrite. Orthoamphibole-cordierite and orthoamphibolekyanite assemblages with chlorite or corundum are incompatible with staurolite-talc±albite. In rocks lacking corundum and formed at pressures above the stability limit of cordierite, staurolite-talc may be metastable relative to orthoamphibole-kyanite, while in corundum-bearing rocks, staurolite-talc may appear under certain conditions, possibly at higher water activities than the orthoamphibole-kyanite assemblage.     

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.     

Corundum,Cr-muscovite rocks at O'Briens,Zimbabwe: the conjunction of hydrothermal desilicification and LIL-element enrichment — geochemical and isotopic evidence

Monomineralic domains of chlorite, corundum and Cr muscovite coexist over a kilometer scale within ultramafic schists of the Harare greenstone belt (2.73 Ga). This exotic lithological association includes the conjunction of some of the most aluminous (Al₂O₃88 wt%) and potassic (K₂O10 wt%) rocks known. The paragenetic sequence developed from chloritecorundumcorundum+ diaspore: Cr muscovite variably overprinted both the corundum and chloritite domains. Terminal stages were marked by sporadic production of andalusite+quartz, and finally margarite.Chlorite (Cr₂O₃=0.31–2.65 wt%), corundum (0.79–2.66 wt%), and diaspore are all Cr-rich varieties. The chromian (Cr₂O₃3.86 wt%) paragonitic muscovite incorporates up to 17% of the paragonite molecule, and significant Mg and Fe substitutions.The suite of rocks are characterized by chondritic Ti/Zr ratios (–x=107), systematically enhanced Cr (up to 14000 ppm) and Ni (up to 1200 ppm) abundances, low levels of the alteration-insensitive incompatible elements Th, Ta, Nb. Chlorite, corundum and Cr muscovite represent progressive stages in the incremental metasomatic alteration of a komatiite precursor. Mass balance calculations, constrained by the isochemical behaviour of Ti, Zr and Hf reveal that the komatiite chloritite transformation involved volumetric contractions of 60% by hydrothermal leaching of Si, Fe, Mn, Ca and Na. Reaction of chloritite to corundum involved further volumetric reductions of 50% due to essentially quantitative loss of Si, Fe, Mn, Mg, K and Ca. Conversion of corundum to muscovite required additions of Si, K, Fe, Mn, Mg, Rb and Ba at 50–200% dilation. K, Rb, Ba, Li and Cs are enriched by up to 2×10³ over background abundances in ultramafic rocks, and the suite is also enriched in B, Se, Te, Bi, As, Sb and Au. REE were extensively leached during chloritite-corundum stages, whereas LREE additions accompany development of muscovite. Ti, Zr, Hf and Al were all concentrated by selective leaching of mobile components, but absolute additions of Al accompanied development of the corundum domains due to Al precipitation in response to depressurization.Corundum ( ¹⁸O=3.5–4.8), muscovite ( ¹⁸O=6.7–7.5) and chlorite (4.5–5.6) are isotopically uniform and formed at 380–520° C from a fluid where ¹⁸O=5.6–6.9. The corundum is ¹⁸O depleted relative to either igneous or anatectic counterparts (O_cor=7.6–8.2), or to gibbsitic laterites ( ¹⁸O=12–17).Previous genetic schemes involving metamorphism of exhalites or bauxite, or Si-undersaturation of magmas, can all be ruled out from the data. The chloritite, corundum, Cr-muscovite association represents sequential alteration products of ultramafic rocks by high temperature, low pH hydrothermal solutions carrying LIL-elements, and in which excursions of pH and/or degree of quartz undersaturation account for the mineralogical transitions. A deep level acid epithermal system, or fluid advection across steep inverted thermal gradients in a thrust regime could account for required hydrothermal conditions.     

Experimental studies on the formation of inclusions in plagioclases from metatonalites,Hohe Tauern,Austria (lower temperature stability limit of the paragenesis anorthite plus potash feldspar)

New experimental data are presented at stability conditions of paragenesis in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O. These results are used to estimate the pressure temperature conditions under which minute inclusions, mostly consisting of zoisite/clinozoisite and muscovite, have crystallized in calcic plagioclases from metatonalites and metadiorites (Hohe Tauern, Austria). In the pressure region 1.5–8 kb the following reactions were observed: zoisite+muscovite+quartz=anorthite+potash feldspar+water (1) grossularite+muscovite+quartz=anorthite+potash feldspar+water (2) zoisite+quartz=anorthite+grossularite+water (3) natural plagioclase with its inclusions (zoisite/clinozoisite and muscovite) (4) =more basic plagioclase without inclusions.In order to determine the curves of reaction (1), (2) and (3), runs were made in hydrothermal bombs using synthetic phases crystallized from gels as starting materials. The reaction curves (1), (2) and (3) intersect at an invariant point at 7.25±0.5 kb and 685±20° C. In runs to define the reaction (4), it could be demonstrated that the inclusion minerals zoisite/ clinozoisite and muscovite became instable at slightly lower temperatures than those occurring in reaction (1). These facts illustrate that the reaction curve (1), found in the pure system, gives possible information about the pressure temperature conditions during the formation of the inclusions.     

An example of occurence and breakdown of paragonite

Paragonite occurs in pelitic schists and amphibole schists of the Ötztal Alps (Tyrol); its occurence in amphibole schists is controlled by the Na₂O/K₂O, in pelitic schists by the local fabric. Some analysis of the bulk chemistry of the paragonite bearing rocks and one microprobe analysis of paragonite are given. Paragonite is stable together with muscovite, together with quartz it is unstable. Its breakdown can be described by the reaction: paragonite+quartz kyanite+albite+H₂O. The age of this breakdown is discussed by comparison of experimental, field and radiometric data, it is thought to be of Variscian age.     

Synthesis and upper stability of paragonite

The mineral paragonite, NaAl₂[AlSi₃O₁₀ (OH)]₂, has been synthesized on its own composition starting from a variety of different materials. Indexed powder data and refined cell parameters are given for both the 1M and 2M₁ polymorphs obtained. The upper stability limit of paragonite is marked by its breakdown to albite + corundum + vapour. The univariant equilibria pertaining to this reaction have been established by reversing the reaction at six different pressures, the equilibrium curve running through the following intervals: 1 kb: 530°–550° C 2 kb: 555°–575° C 3 kb: 580°–600° C 5kb: 625°–640° C 6 kb: 620°–650° C 7 kb: 650°–670° C.Comparison with the upper stability limit of muscovite (Velde, 1966) shows that paragonite has a notably lower thermal stability thus explaining the field observation that paragonite is absent in many higher grade metamorphic rocks in which muscovite is still stable.The enthalpy and entropy of the paragonite breakdown reaction have been estimated. Since intermediate albites of varying structural states are in equilibrium with paragonite, corundum and H₂O along the univariant equilibrium curve, two sets of data pertaining to the entropy of paragonite (S ₂₉₈ ⁰ ) as well as the enthalpy ( H _f,298 ⁰ ) and Gibbs free energy ( G _f,298 ⁰ ) of its formation were computed, assuming (1) high albite and (2) low albite as the equilibrium phase. The values are: (1) (2) S ₂₉₈ ⁰ 67.8±3.9 cal deg^–1 gfw^–1 63.7±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ –1417.9±2.7 kcal gfw^–1 –1420.2±2.6 kcal gfw^–1 G _f,298 ⁰ –1327.4±4.0 kcal gfw^–1 –1328.5±4.0 kcal gfw^–1.Adapted from a part of the author's Habilitationsschrift accepted by the Ruhr University, Bochum (Chatterjee, 1968).     

Crystal chemistry and OH defect concentrations in spodumene from different granitic pegmatites

Thirty spodumene samples of distinct paragenetic types (primary magmatic, secondary after petalite and hydrothermal) from variety of granitic pegmatites were characterized by electron microprobe, polarized FTIR spectroscopy and Mössbauer spectroscopy. The FTIR spectra of OH (weak sharp pleochroic bands at 3,425, 3,410, 3,395 cm⁻¹ and in the 3,500–3,470 spectral region) are strongly polarized with maximum absorption parallel to n_γ. The majority of OH dipoles are presumably generated by a partial replacement of O2 oxygen atoms with an orientation pointing above the Li vacancy site. The separation of the bands probably resulted from a replacement of the coordinating Al by Fe and Si by Al. Homogeneous spodumene mostly close to its ideal formula LiAlSi₂O₆ shows Fe (0.00–0.10 apfu as Fe³⁺; Fe³⁺ >> Fe²⁺) and Na (0.00–0.04 apfu) as the only minor cations and Fe³⁺Al₋₁ substitution up to 10 mol% of the LiFe³⁺Si₂O₆ component. Hydrogen concentrations (from 0.1 up to <5 ppm H₂O by weight) vary as a function of genetic type with the highest amounts in high-temperature magmatic spodumene. Differences among particular genetic types of spodumene are related to maximum solubility of OH in spodumene structure at given P–T conditions and at actual chemical composition of spodumene. OH defect concentrations in spodumene follow a trend, LT/LP pyroxenes containing lower hydrogen contents compared to HT/HP ones. The hydrogen contents in particular genetic types of spodumene and their decrease with decreasing T and P are consistent with petrologic models of the pegmatite (sub)types formations.     

Geology,Fluid Inclusion Characteristics and H–O–C Isotopes of Large Lijiagou Pegmatite Spodumene Deposit in Songpan–Garze Fold Belt,Eastern Tibet: Implications for ore Genesis

The large, newly discovered Lijiagou pegmatite spodumene deposit, is located southeast of the Ke'eryin pegmatite ore field, in the central Songpan–Garze Fold Belt (SGFB), Eastern Tibet. The Lijiagou albite spodumene pegmatites are unzoned, granite‐pegmatites of the subtype LCT (Lithium, Cesium, and Tantalum) and consist of medium‐ to coarse‐grained spodumene, lepidolite, microcline, albite, quartz, muscovite, and accessory amounts of beryl, cassiterite, columbite–tantalite and zircon. Secondary fluid inclusions in quartz and spodumene include two‐phase aqueous inclusions (V + L), mono‐phase vapor inclusions (V); three‐phase CO₂‐rich CO₂–H₂O inclusions (CO₂ + V + L) and less abundant liquid inclusions (L). The homogenization temperature of the fluid inclusions are low (257.3 to 204.3°C in early stage, 250.3 to 199.6°C in middle stage, 218.7 to 200.6°C in late stage). Fluid inclusions were formed during the long cooling period from the temperature of the pegmatite emplacement. Liquid–vapor–gas boiling was extensive during the middle and late stages. The salinity of the corresponding stages are 15.4 to 13.0 wt.% NaCl equiv., 12.5 to 9.1 wt.% NaCl equiv. and 9.8 to 7.8 wt.% NaCl equiv., respectively. δ¹⁸O values of fluid are 7.2 to 5.2‰, 5.6 to 3.9‰ and 2.7 to −0.2‰ from early to late stages; and δD range from −75.1 to −76.8‰, −59.0 to −73.5‰ and −61.6 to −85.5‰ respectively. The δ¹³C of CO₂ values are −5.6 to −6.6‰, −8.5 to −19.9‰, −11.8 to −18.7‰ from early to late stages, suggesting that CO₂ in the fluids were probably sourced from a magmatic system, possibly with some mixing of CO₂ dissolved in groundwater. δD and δ¹⁸O values of fluid indicate that the fluids were originally magmatic water and mixed with some meteoric water in late stage. The magma evolution sequence in the Ke'eryin orefield, from the central two‐mica granite through the Lijiagou deposit out to the distal pegmatites, with the ages gradually decreasing, indicates that the Ke'eryin complex rocks are the product of multistage magmatic activity. The large Lijiagou spodumene deposit is a typical magmatic, fractional crystallization related pegmatite deposit.     

Effects of H2O on the Disequilibrium Breakdown of Muscovite+Quartz

We have examined in detail the effect of H₂O on the texturesand mechanisms produced during the breakdown of muscovite+quartzunder experimental disequilibrium conditions using low-porosityrock samples. Under H₂O conditions (1 wt.% H₂O added) muscovitereacts completely in <5 months at 757?C to a metastable assemblageof peraluminous meltmullite+biotite, a reaction which delaysthe formation of the stable equilibrium assemblage. In contrast,muscovite in the H₂O undersaturated experiments breaks downby both the stable dehydration reaction producing K feldspar+sillimanite+biotiteand by metastable melting reactions in the same sample. Thecom position of the metastable melt is controlled by a numberof kinetic factors which change as a function of time and reactionprogress. Early melts are highly siliceous and sodic due tothe rapid dissolution of quartz relative to muscovite, coupledwith the incongruent melting of the paragonite component ofmuscovite and crystallization of biotite. The delayed nucleationof mullite results in Al supersaturation of the melt, whichinhibits the rate of the melting reaction. Once mullite nucleatesthe degree of Al melt supersaturation is decreased and the rateof muscovite dissolution increases. After complete reactionof muscovite the melt chemistry continues to change as Si diffusesinto the pseudomorphs from adjacent quartz. Even after 5 monthsat 757?C large compositional gradients in Si and Al still persistwithin the melt. In the H₂O experiments metastable melting occursinitially, catalysed by traces of grain boundary fluid or byfluid released from the dehydration of muscovite. However, oncemelting starts any fluid is strongly fractionated into the meltphase, reducing µH₂O Under these conditions further meltingis inhibited and the stable dehydration reaction will continue.Examination of examples of natural muscovite reacted under disequilibriumconditions in xenolithic and contact metamorphic rocks at lowpressures suggests that metastable melting is an important processunder certain geological conditions. It is possible that itis widespread in contact metamorphic rocks, but the texturesindicative of metastable melting reactions are obscured duringthe extended cooling histories of such rocks.     

Origin of the pyrophyllite-diaspore deposits of the Bundelkhand Complex,Central India

Twenty three samples from the pyrophyllite-diaspore deposits have been investigated by x-ray diffraction and geochemical methods. The mineral assemblages belong to the K₂O-Al₂O₃-SiO₂-H₂O system. Higher concentrations of Ti, Cr and Zr in the deposits as compared with the associated granites and gneisses suggest their laterite type parentage. Existing mineral assemblages are a result of low grade metamorphism (up to about 350°C) of the primary residual deposits containing a kaolinite - diaspore - quartz assemblage.