Phase relations in silicic systems at one-atmosphere pressure

An important control on magma rheology is the extent to which the magma crystallizes during ascent as a result of the effective undercooling created by volatile exsolution. To assess this undercooling, we need to know the final (anhydrous) one-atmosphere phase relations of silicic magmas. For this reason, we have performed one-atmosphere controlled-fO₂ crystallization experiments on dacitic to rhyolitic melt compositions (67–78 wt% SiO₂) and determined equilibrium phase assemblages, melt fractions, and some phase compositions over a range of temperatures. Experiments were run at oxygen fugacities between NNO+1 and NNO+2 and temperatures of 1,000 to 1,250°C. Constant phase compositions and sample crystallinities in runs longer than 3.5 days suggest that these runs closely approached compositional equilibrium. Additionally, melting experiments with similar compositions yielded results closely resembling those obtained in crystallization experiments. All samples have liquidus temperatures between 1,250 and 1,200 °C, with plagioclase the liquidus phase for the two most mafic samples and quartz for the most silicic sample. When associated glass compositions are projected into the Qz-Ab-Or system they define a revised one-atmosphere quartz-feldspar cotectic 5–10% less quartz normative than previously estimated. Glass compositions from each sample plot along this cotectic between 1,100 and 1,000 °C, consistent with the plagioclase-quartz co-crystallization textures found in runs at these temperatures. This cotectic constrains glass compositions to a maximum silica content of 76±1 wt% SiO₂. Reported glass compositions in excess of 77 wt% SiO₂ in volcanic samples suggest non-equilibrium crystallization, perhaps a consequence of large melt undercoolings.Editorial responsibility: I. Carmichael     

Geochemistry and zircon U–Pb chronology of charnockites in the Yinshan Block,North China Craton: tectonic evolution involving Neoarchaean ridge subduction

The Yinshan Block, part of the Neoarchaean basement of the Western Block of the North China Craton, is composed of granite–greenstone and granulite–charnockite complexes. We report research on a suite of charnockites from the granulite–charnockite complex and characterize their geochemistry, zircon U–Pb geochronology, and Hf isotopic composition. The charnockites can be divided into intermediate (SiO₂ = 59–63 wt.%) and silicic (SiO₂ = 69–71 wt.%) groups. U–Pb zircon data yield protolith formation ages of 2524 ± 4 Ma, 2533 ± 15 Ma, followed by metamorphism at 2498 ± 3 Ma, 2490 ± 11 Ma, respectively, for these groups. Although the intermediate charnockites are characterized by higher Al₂O₃, TiO₂, Fe₂O₃^T, MnO, MgO, CaO, P₂O₅, K₂O, Sr, and ΣREE content than the silicic charnockites, the ages and Hf isotopic composition of zircons and REE patterns of both intermediate and silicic charnockites are remarkably consistent, which indicates that they are genetically related. These charnockites are predominantly metaluminous to slightly peraluminous, calc-alkalic to calcic, and magnesian – characteristics generally related to a subduction setting. High-Sr + Ba granites with low K₂O/Na₂O characteristics, shown by these charnockites, imply a mixture of mafic and felsic magmas generated from an enriched mantle + lower crust. High MgO, Ni, Cr and Mg#, low K₂O/Na₂O, and metaluminous to slightly peraluminous natures imply that the source rocks most likely were amphibolites. Coeval calc-alkaline magmatism and high-T granulite-facies metamorphism under low-H₂O activity in the area lead us to propose a model involving mid-ocean ridge subduction within a Neoarchaean convergent margin. The arc-related rocks accreted along the continent margin, and became a barrier when the lithospheric mantle ascended through the slab window. Melt derived from the decompressing mantle mixed with melt derived from the overlying, juvenile lower crust melt, which was warmed and metamorphosed by the ascending lithospheric mantle.     

Evidence for extreme fractionation of peralkaline silicic magmas, the Boseti volcanic complex, Main Ethiopian Rift

Matrix glass and melt inclusions in phenocrysts from pantellerite lavas of the Boseti volcanic complex, Ethiopia, record extreme fractionation of peralkaline silicic magma, with Al₂O₃ contents as low as 2.3?wt.%, FeO* contents up to 17?wt.% and SiO₂ contents ~65?wt.%. The new data, and published data for natural and experimental glasses, suggest that the effective minimum composition for peralkaline silicic magmas has ~5?wt.% Al₂O₃, 13?wt.% FeO* and 66?±?2?wt.% SiO₂. The dominant fractionating assemblage is alkali feldspar?+?fayalite?+?hedenbergite?+?oxides?±?quartz. Feldspar – melt relationships indicate that the feldspar is close to the minimum on the albite-orthoclase solid solution loop through the entire crystallization history. There is petrographic, mineralogical and geochemical evidence that magma mixing may have been a common process in the Boseti rhyolites.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

Peralkaline silicic melts of island arcs, active continental margins, and intraplate continental settings: Evidence from the investigation of melt inclusions in minerals and quenched glasses of rocks

Based on the analysis of data on the composition of melt inclusions in minerals and quenched glasses of igneous rocks, we considered the problems of the formation of peralkaline silicic magmas (i.e., whose agpaitic index, the molar ratio AI = (Na₂O + K₂O)/Al₂O₃, is higher than one). The mean compositions of peralkaline silicic melts are reported for island arcs and active continental margins and compared with the compositions of melts from other settings, primarily, intraplate continental areas. Peralkaline silicic rocks are rather common in the latter. Such rocks are rare in island arcs and active continental margins, but agpaitic melts were observed in inclusions in phenocrysts of plagioclase, quartz, pyroxene, and other minerals. Plagioclase fractionation from an alkali-rich melt with AI < 1 is considered as a possible mechanism for the formation of peralkaline silicic melts (Bowen’s plagioclase effect). However, the analysis of available experimental data on plagioclase-melt equilibria showed that natural peralkaline melts are almost never in equilibrium with plagioclase. For the same reason, the melting of the majority of crustal rocks, which usually contain plagioclase, does not produce peralkaline melts. The existence of peralkaline silicic melt inclusions in plagioclase phenocrysts suggests that plagioclase can crystallize from peralkaline melts, and the plagioclase effect may play a certain role. Another mechanism for the formation of peralkaline silicic magmas is the melting of alkali-rich basic and intermediate rocks, including the spilitized varieties of subalkali basalts.     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

Genesis and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif,Mongolia: Evidence from melt inclusions

Melt inclusions were studied by various methods, including electron and ion microprobe analysis, to determine the compositions of melts and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif in Mongolia. Primary crystalline and coexisting melt inclusions were found in quartz from the rare-metal granites of intrusive phase V. Among the crystalline inclusions, we identified potassium feldspar, albite, tuhualite, titanite, fluorite, and diverse rare-metal phases, including minerals of zirconium (zircon and gittinsite), niobium (pyrochlore), and rare earth elements (parisite). The observed crystalline inclusions reproduce almost the whole suite of major and accessory minerals of the rare-metal granites, which supports the possibility of their crystallization from a magmatic melt. Melt inclusions in quartz from these rocks are completely crystallized. Their daughter mineral assemblage includes quartz, microcline, aegirine, arfvedsonite, polylithionite, a zirconosilicate, pyrochlore, and a rare-earth fluorocarbonate. The melt inclusions were homogenized in an internally heated gas vessel at a temperature of 850°C and a pressure of 3 kbar. After the experiments, many inclusions were homogeneous and consisted of silicate glass. In addition to silicate glass, some inclusions contained tiny quench zircon crystals confined to the boundary of inclusions, which indicates that the melts were saturated in zircon. In a few inclusions, glass coexisted with a CO₂ phase. This allowed us to estimate the content of CO₂ in the inclusion as 1.5 wt %. The composition of glasses from the homogeneous melt inclusions is similar to the composition of the rare-metal granites, in particular, with respect to SiO₂ (68–74 wt %), TiO₂ (0.5–0.9 wt %), FeO (2.2–4.6 wt %), MgO (0.02 wt %), and Na₂O + K₂O (up to 8.5 wt %). On the other hand, the glasses of melt inclusions appeared to be strongly depleted compared with the rocks in CaO (0.22 and 4 wt %, respectively) and Al₂O₃ (5.5–7.0 and 9.6 wt %, respectively). The agpaitic index is 1.1–1.7. The melts contain up to 3 wt % H₂O and 2–4 wt % F. The trace element analysis of glasses from homogenized melt inclusions in quartz showed that the rare-metal granites were formed from extensively evolved rare-metal alkaline melts with high contents of Zr, Nb, Th, U, Ta, Hf, Rb, Pb, Y, and REE, which reflects the metallogenic signature of the Khaldzan Buregtey deposit. The development of unique rare metal Zr–Nb–REE mineralization in these rocks is related to the prolonged crystallization differentiation of melts and assimilation of enclosing carbonate rocks.     

Transition from I‐type to A‐type magmatism in the Sanandaj–Sirjan Zone,NW Iran: an extensional intra‐continental arc

The South Dehgolan pluton, in NW Iran was emplaced into the Sanandaj–Sirjan magmatic–metamorphic zone. This composite intrusion comprises three main groups: (1) monzogabbro–monzodiorite rocks, (2) quartz monzonite–syenite rocks, and (3) a granite suite which crops out in most of the area. The granites generally show high SiO₂ content from 72.1%–77.6 wt.% with diagnostic mineralogy consisting of biotite and amphibole along the boundaries of feldspar–quartz crystals which implies anhydrous primary magma compositions. The granite suite is metaluminous and distinguished by high FeOt/MgO ratios (av. 9.6 wt.%), typical of ferroan compositions with a pronounced A‐type affinity with high Na₂O + K₂O contents, high Ga/Al ratios, enrichment in Zr, Nb, REE, and depletion in Eu. The quartz monzonite–syenites show intermediate SiO₂ levels (59.8%–64.5 wt.%) with metaluminous, magnesian to ferroan characteristics, intermediate Na₂O + K₂O contents, enrichment in Zr, Nb, REE, Ga/Al, and depletion in Eu. The monzogabbro–monzodiorites show overall lower SiO₂ content (48.5%–55.9 wt.%) with metaluminous and calc‐alkaline compositions, relatively lower Na₂O + K₂O contents, low Ga/Al ratios, and FeOt/MgO (av. 1.6 wt.%) ratios, low abundances of Zr, Nb, and lower REE element concentrations relative to the granites and quartz monzonite–syenites. These geochemical differences among the three different rocks suites are likely to indicate different melt origins. We suggest that the South Dehgolan pluton resulted from a change in the geodynamic regime, from compression to extension in the Sanandaj–Sirjan zone during Mesozoic subduction of the Neo‐Tethys oceanic crust beneath the Central Iranian microcontinent. Copyright © 2015 John Wiley & Sons, Ltd.     

Subsolidus segregation of quartz in metamorphic differentiation of metasedimentary rocks

Thermodynamic modeling of the SiO₂–TiO₂–Al₂O₃–Fe₂O₃–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅–H₂O (STAFMMCNKPOH) system at 600°C, 5 kbar has been applied to investigate dissolution and re-precipitation of quartz. Comparing silica molality in the STAFMMCNKPOH and SiO₂–H₂O systems, there is seen to be no effect of mineral assemblage on quartz solubility. From quantitatively estimated water/rock ratio required to dissolve quartz completely, one can deduce that the segregation of quartz appears to be due to diffusive transport of silica in inner pore fluid rather than to advective transport (in fluid flow).     

Effect of Silicate Matter on Pyrochlore Solubility in Fluoride Solutions at <Emphasis Type="Italic">Т</Emphasis> = 550–850°C, <Emphasis Type="Italic">Р</Emphasis> = 50–100 MPa (Experimental Studies)

The experimental results of natural pyrochlore behavior in KF solutions in the presence of quartz at 550–850°C and 50–100 MPa are presented. It is shown that silicate matter (quartz) exerts a significant effect on pyrochlore solubility in aqueous solutions of fluorides of alkaline metals under hydrothermal conditions. This study of the fluid inclusions has revealed the occurrence of reactions of high-temperature hydrolysis of KF under the experimental conditions: KF + H₂O = KOH + HF; in which case, the interaction with quartz SiO₂ + 2KOH = K₂SiO₃ + H₂O is followed by the formation of a silicate glass phase (an aqueous solution–melt). This phase of alkaline glass is a Nb concentrator (Nb₂O₅ up to 16 wt %). The coefficient of Nb distribution between the glass and the fluid is ≈500 (in favor of the glass). It is determined that the phase of the silicate solution–melt can serve as an effective concentrator of the ore component (Nb) at the last lowtemperature stages of crystallization of rare-metal granites.     

Low‐P and high‐T metamorphism of basalts: Insights from the Sudbury impact melt sheet aureole and thermodynamic modelling

Low‐pressure and high‐temperature (LP–HT) metamorphism of basaltic rocks, which occurs globally and throughout geological time, is rarely constrained by forward phase equilibrium modelling, yet such calculations provide valuable supplementary thermometric information and constraints on anatexis that are not possible to obtain from conventional thermometry. Metabasalts along the southern margin of the Sudbury Igneous Complex (SIC) record evidence of high‐grade contact metamorphism involving partial melting and melt segregation. Peak metamorphic temperatures reached at least ~925°C at ~1–3 kbar near the SIC contact. Preservation of the peak mineral assemblage indicates that most of the generated melt escaped from these rocks leaving a residuum characterized by a plagioclase–orthopyroxene–clinopyroxene–ilmenite‐magnetite±melt assemblage. Peak temperatures reached ~875°C up to 500 m from the SIC lower contact, which marks the transition to metabasalts that only experienced incipient partial melting without melt loss. Metabasalts ~500 to 750 m from the SIC contact are characterized by a similar two‐pyroxene mineral assemblage, but typically contain abundant hornblende that overgrew clino‐ and orthopyroxene along an isobaric cooling path. Metabasalts ~750 to 1,000 m from the SIC contact are characterized by a hornblende–plagioclase–quartz–ilmenite assemblage indicating temperatures up to ~680°C. Mass balance and phase equilibria calculations indicate that anatexis resulted in 10–20% melt generation in the inner ~500 m of the aureole, with even higher degrees of melting towards the contact. Comparison of multiple models, experiments, and natural samples indicates that modelling in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCFMASHTO) system results in the most reliable predictions for the temperature of the solidus. Incorporation of K₂O in the most recent amphibole solution model now successfully predicts dehydration melting by the coexistence of high‐Ca amphibole and silicate melt at relatively low pressures (~1.5 kbar). However, inclusion of K₂O as a system component results in prediction of the solidus at too low a temperature. Although there are discrepancies between modelling predictions and experimental results, this study demonstrates that the pseudosection approach to mafic rocks is an invaluable tool to constrain metamorphic processes at LP–HT conditions.     

Melting of plagioclase-quartz assemblages at 2 kbar water pressure

The melting of plagioclase and quartz has been investigated at P _H2O =2kb. A single crystal of plagioclase was surrounded by quartz powder and water. A reaction rim consisting of glass and of An-rich plagioclase developed around unchanged starting plagioclase. Microprobe determinations of melt and coexisting plagioclase compositions reveal a strong fractionation of plagioclase components between melt and new plagioclase. For example at 850° C the approximate X _An of melt is 0.3 and that of plagioclase is 0.8. The temperature interval between beginning of melting and complete melting of cotectic compositions is 100° C or more for quartz-plagioclase mixtures with plagioclases between An 40 and An 75. In comparison to the system Ab-An-H₂O the plagioclase melting loop is somewhat wider in the investigated system Qz-Ab-An-H₂O but the temperature interval is much smaller (100° C) than in the system Ab-An-H₂O (200° C). The solidus data indicated by the new plagioclase compositions are practically identical with those observed in beginning of melting experiments. The results show that fractionation of plagioclase components between partial melts and restite plagioclase can be more pronounced in multi-component rocks than in the pure plagioclase system. This finding is important for the development of albite rich rocks from more basic compositions.     

Chemical composition,volatile components,and trace elements in the magmatic melt of the Kurama mining district,Middle Tien Shan: Evidence from the investigation of inclusions in quartz

Melt and fluid inclusions were investigated in six quartz phenocryst samples from the igneous rocks of the extrusive (ignimbrites and rhyolites) and subvolcanic (granite porphyries) facies of the Lashkerek Depression in the Kurama mining district, Middle Tien Shan. The method of inclusion homogenization was used, and glasses from more than 40 inclusions were analyzed on electron and ion microprobes. The chemical characteristics of these inclusions are typical of silicic magmatic melts. The average composition is the following (wt %): 72.4 SiO₂, 0.06 TiO₂, 13.3 Al₂O₃, 0.95 FeO, 0.03 MnO, 0.01 MgO, 0.46 CaO, 3.33 Na₂O, 5.16K₂O, 0.32 F, and 0.21 Cl. Potassium strongly prevails over sodium in all of the inclusions (K₂O/Na₂O averages 1.60). The average total of components in melt inclusions from five samples is 95.3 wt %, which indicates a possible average water content in the melt of no less than 3–4 wt %. Water contents of 2.0 wt % and 6.6 wt % were determined in melt inclusions from two samples using an ion microprobe. The analyses of ore elements in the melt inclusions revealed high contents of Sn (up to 970 ppm), Th (19–62 ppm, 47 ppm on average), and U (9–26 ppm, 18 ppm on average), but very low Eu contents (0.01 ppm). Melt inclusions of two different compositions were detected in quartz from a granite porphyry sample: silicate and chloride, the latter being more abundant. In addition to Na and K chlorides, the salt inclusions usually contain one or several anisotropic crystals and an opaque phase. The homogenization temperatures of the salt inclusions are rather high, from 680 to 820°C. In addition to silicate inclusions with homogenization temperatures of 820–850°C, a primary fluid inclusion of aqueous solution with a concentration of 3.7 wt % NaCl eq. and a very high density of 0.93 g/cm³ was found in quartz from the ignimbrite. High fluid pressure values of 6.5–8.3 kbar were calculated for the temperature of quartz formation. These estimates are comparable with values obtained by us previously for other regions of the world: 2.6–4.3 kbar for Italy, 3.7 kbar for Mongolia, 3.3–8.7 kbar for central Slovakia, and 3.3–9.6 kbar for eastern Slovakia. Unusual melt inclusions were investigated in quartz from another ignimbrite sample. In addition to a gas phase and transparent glass, they contain spherical Feoxide globules (81.2 wt % FeO) with high content of SiO₂ (9.9 wt %). The globules were dissolved in the silicate melt within a narrow temperature range of 1050–1100°C, and the complete homogenization of the inclusions was observed at temperatures of 1140°C or higher. The combined analysis of the results of the investigation of these inclusions allowed us to conclude that immiscible liquids were formed in the high-temperature silicic magma with the separation of iron oxide-dominated droplets.     

Petrogenesis of andalusite–kyanite–sillimanite veins and host rocks, Sanandaj-Sirjan metamorphic belt, Hamadan, Iran

Quartz‐rich veins in metapelitic schists of the Sanandaj‐Sirjan belt, Hamadan region, Iran, commonly contain two Al₂SiO₅ polymorphs, and, more rarely, three coexisting Al₂SiO₅ polymorphs. In most andalusite and sillimanite schists, the types of polymorphs in veins correlate with Al₂SiO₅ polymorph(s) in the host rocks, although vein polymorphs are texturally and compositionally distinct from those in adjacent host rocks; e.g. vein andalusite is enriched in Fe₂O₃ relative to host rock andalusite. Low‐grade rocks contain andalusite + quartz veins, medium‐grade rocks contain andalusite + sillimanite + quartz ± plagioclase veins, and high‐grade rocks contain sillimanite + quartz + plagioclase veins/leucosomes. Although most andalusite and sillimanite‐bearing veins occur in host rocks that also contain Al₂SiO₅, kyanite‐quartz veins crosscut rocks that lack Al₂SiO₅ (e.g. staurolite schist, granite). A quartz vein containing andalusite + kyanite + sillimanite + staurolite + muscovite occurs in andalusite–sillimanite host rocks. Textural relationships in this vein indicate the crystallization sequence andalusite to kyanite to sillimanite. This crystallization sequence conflicts with the observation that kyanite‐quartz veins post‐date andalusite–sillimanite veins and at least one intrusive phase of a granite that produced a low‐pressure–high‐temperature contact aureole; these relationships imply a sequence of andalusite to sillimanite to kyanite. Varying crystallization sequences for rocks in a largely coherent metamorphic belt can be explained by P–T paths of different rocks passing near (slightly above, slightly below) the Al₂SiO₅ triple point, and by overprinting of multiple metamorphic events in a terrane that evolved from a continental arc to a collisional orogen.     

Evolution of the trachydacite and pantellerite magmas of the bimodal volcanic association of Dzarta-Khuduk, Central Mongolia: Investigation of inclusions in minerals

Using various methods of melt inclusion investigation, including electron and ion microprobe techniques, we estimated the composition, evolution, and formation conditions of melts producing the trachydacites and pantellerites of the Late Paleozoic bimodal volcanic association of Dzarta-Khuduk, Central Mongolia. Primary crystalline and melt inclusions were detected in anorthoclase from trachydacites and quartz from pantellerites and pantelleritic tuffs. Among the crystalline inclusions, we identified hedenbergite, fluorapatite, and pyrrhotite in the trachydacites and F-arfvedsonite, fluorite, ilmenite, and the rare REE diorthosilicate chevkinite in the pantellerites. Melt inclusions in anorthoclase from the trachydacites are composed of glass, a gas phase, and daughter minerals (F-arfvedsonite, fluorite, villiaumite, and anorthoclase rim on the inclusion wall). Melt inclusions in quartz from the pantellerites are composed of glass, a gas phase, and a fine-grained salt aggregate consisting of Li, Na, and Ca fluorides (griceite, villiaumite, and fluorite). Melt inclusions in quartz crystalloclasts from the pantelleritic tuffs are composed of homogeneous silicate glasses. The phenocrysts of the trachydacites and pantellerites crystallized at temperatures of 1060–1000°C. During thermometric experiments with quartz-hosted melt inclusions from the pantellerites, the formation of immiscible silicate and salt (fluoride) melts was observed at a temperature of 800°C. Homogeneous melt inclusions in anorthoclase from the trachydacites have both trachydacite and rhyolite compositions (wt %): 68–70 SiO₂, 12–13 Al₂O₃, 0.34–0.74 TiO₂, 5–7 FeO, 0.4–0.9 CaO, and 9–12 Na₂O + K₂O. The agpaitic index ranges from 0.92 to 1.24. The glasses of homogenized melt inclusions in quartz from the pantellerites and pantelleritic tuffs have rhyolitic compositions. Compared with the homogeneous glasses trapped in anorthoclase of the trachydacites, quartz-hosted inclusions from the pantellerites show higher SiO₂ (72–78 wt %) and lower Al₂O₃ contents (7.8–10.0 wt %). They also contain 0.14–0.26 wt % TiO₂, 2.5–4.9 wt % FeO, 9–11 wt % Na₂O + K₂O, and 0.9–0.15 wt % CaO and show an agpaitic index of 1.2–2.05. Homogeneous melt inclusions in quartz from the pantelleritic tuffs contain 69–72 wt % SiO₂. The contents of other major components, including TiO₂, Al₂O₃, FeO, and CaO, are close to those in the homogeneous glasses of quartzhosted melt inclusions in the pantellerites. The contents of Na₂O + K₂O are 4–10 wt %, and the agpaitic index is 1.0–1.6. The glasses of melt inclusions from each rock group show distinctive volatile compositions. The H₂O content is up to 0.08 wt % in anorthoclase of the trachydacites, 0.4–1.4 wt % in quartz of the pantellerites, and up to 5 wt % in quartz of the pantelleritic tuffs. The content of F in the glasses of melt inclusions in the phenocrysts of the trachydacites is no higher than 0.67 wt %, and up to 1.4–2.8 wt % in quartz from the pantellerites. The Cl content is up to 0.2 wt % in the glasses of melt inclusions in the minerals of the trachydacites and up to 0.5 wt % in the glasses of quartz-hosted melt inclusions from the pantellerites. The investigation of trace elements in the homogenized glasses of melt inclusions in minerals showed that the trachydacites and pantellerites were formed from strongly evolved rare-metal alkaline silicate melts with high contents of Li, Zr, Rb, Y, Hf, Th, U, and REE. The analysis of the composition of homogeneous melt inclusions in the minerals of the above rocks allowed us to distinguish magmatic processes resulting in the enrichment of these rocks in trace and rare earth elements. The most important processes are the crystallization differentiation and immiscible separation of silicate and fluoride salt melts. It was also shown that all the melts studied evolved in spatially separated magma chambers. This caused the differences in the character of melt evolution between the trachydacites and pantellerites. During the final stages of differentiation, when the magmatic system was saturated with respect to ore elements, Na-Ca fluoride melts were separated and extracted considerable amounts of Li.     

Partial melting of metagreywacke: a calculated mineral equilibria study

Greywacke occurs in most regionally metamorphosed orogenic terranes, with depositional ages from Archean to recent. It is commonly the dominant siliciclastic rock type, many times more abundant than pelite. Using calculated pseudosections in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O system, the partial melting of metagreywacke is investigated using several natural protolith compositions that reflect the main observed compositional variations. At conditions appropriate for regional metamorphism at mid‐crustal depths (6–8 kbar), high‐T subsolidus assemblages are dominated by quartz, plagioclase and biotite with minor garnet, orthoamphibole, sillimanite, muscovite and/or K‐feldspar (±Fe–Ti oxides). Modelled solidus temperatures are dependent on bulk composition and vary from 640 to 690 °C. Assuming minimal melting at the H₂O‐saturated solidus, initial prograde anatexis at temperatures up to ～800 °C is characterized by very low melt productivity. Significant melt production in commonly occurring (intermediate) metagreywacke compositions is controlled by the breakdown of biotite and production of orthopyroxene (±K‐feldspar) across multivariant fields until biotite is exhausted at 850–900 °C. Assuming some melt is retained in the source, then at temperatures beyond that of biotite stability, melt production occurs via the consumption of plagioclase, quartz and any remaining K‐feldspar as the melt becomes progressively more Ca‐rich and H₂O‐undersaturated. Melt productivity with increasing temperature across the melting interval in metagreywacke is generally gradational when compared to metapelite, which is characterized by more step‐like melt production. Comparison of the calculated phase relations with experimental data shows good consistency once the latter are considered in terms of the variance of the equilibria involved. Calculations on the presumed protolith compositions of residual granulite facies metagreywacke from the Archean Ashuanipi subprovince (Quebec) show good agreement with observed phase relations. The degree of melt production and subsequent melt loss is consistent with the previously inferred petrogenesis based on geochemical mass balance. The results show that, for temperatures above 850 °C, metagreywacke is sufficiently fertile to produce large volumes of melt, the separation from source and ascent of which may result in large‐scale crustal differentiation if metagreywacke is abundant.     

Phase equilibria and melt productivity in the pelitic system: implications for the origin of peraluminous granitoids and aluminous granulites

Peraluminous granitoid magmas are a characteristic product of ultrametamorphism leading to anatexis of aluminous metasedimentary rocks in the continental crust. The mechanisms and characteristic length-scales over which these magmas can be mobilized depend strongly on their melt fraction, because of their high viscosities. Thus, it is of fundamental importance to understand the controls exerted by pressure, temperature and bulk composition of the source material on melt productivity. We have studied experimentally the vapour-absent melting behaviour of a natural metapelitic rock and our results differ greatly from those of previous experimental and theoretical investigations of melt productivity from metamorphic rocks. Under H₂O-undersaturated conditions, bulk composition of the source material is the overriding factor controlling melt fraction at temperatures on the order of 850–900° C. Granitoid melts formed in this temperature interval by the peritectic dehydration-melting reaction: $$\begin{gathered} Biotite + plagioclase + aluminosilicate + quartz \hfill \\ = melt + garnet \hfill \\ \end{gathered} $$ have a restricted compositional range. As a consequence, melt fractions will be maximized from protoliths whose modes coincide with the stoichiometry of the melting reaction. This “optimum mode” (approximately 38% biotite, 32% quartz, 22% plagioclase and 8% aluminosilicate) reflects the fact that generation of low-temperature granitoid liquids requires both fusible quartzo-feldspathic components and H₂O (from hydrous minerals). Metapelitic rocks rich in mica and aluminosilicate and poor in plagioclase contain an excess of refractory material (Al₂O₃, FeO, MgO) with low solubility in low-temperature silicic melts, and will therefore be poor magma sources. Melt fraction varies inversely with pressure in the range 7–13 kbar, but the effect is not strong: the decrease (at constant temperature) over this pressure range is of at most 15 vol% (absolute). The liquids produced in our experiments are silicarich (68–73 wt% SiO₂), strongly peraluminous (2–5 wt% normative corundum) and very felsic (MgO+FeO^* +TiO₂ less than 3 wt%, even at temperatures above 1000° C). The last observation suggests that peraluminous granitoids with more than 10% mafic minerals (biotite, cordierite, garnet) contain some entrained restite. Furthermore, because liquids are also remarkably constant in composition, we believe that restite separation is more important than fractional crystallization in controlling the variability within and among peraluminous granitoids. We present liquidus phase diagrams that allow us to follow the phase relationships of melting of silica-and alumina-saturated rocks at pressures corresponding to the mid- to deep-continental crust. Garnet, aluminosilicate, quartz and ilmenite are the predominant restitic phases at temperatures of about 900° C, but Ti-rich biotite or calcic plagioclase can also be present, depending on the bulk composition of the protolith. At temperatures above 950–1050° C (depending on the pressure) the restitic assemblage is: hercynitic spinel+ilmenite+quartz±aluminosilicate. Our results therefore support the concept that aluminous granulites (garnet-spinel-plagioclase-aluminosilicate-quartz) can be the refractory residuum of anatectic events.     

Oxygen isotope study of quartz-Al2SiO5 pairs from the Mica Creek area, British Columbia: implications for the recovery of peak metamorphic temperatures

Oxygen isotope analyses of quartz-Al₂SiO₅ pairs have been made for samples from the Mica Creek area, British Columbia. We have analysed quartz–kyanite nodules and quartz–kyanite and quartz–sillimanite in multiphase pelitic rocks from the staurolite–kyanite, kyanite, and sillimanite zones. Apparent temperatures calculated from oxygen isotopic fractionation range from 555 °C (staurolite–kyanite zone) to 695 °C (sillimanite zone). Temperatures from the quartz–kyanite nodules range from 630 to 675 °C. Some of the nodules show isotopic disequilibrium. Most of the results confirm predictions that bimineralic rocks will yield an estimate of peak metamorphic temperatures, when the less abundant mineral (an aluminium silicate) is the slower oxygen diffuser. Using cooling rates of 10–100 °C Ma^?1 for the multiphase rocks, measured crystal sizes and modes, the Fast Grain Boundary diffusion model with ‘wet’ diffusion data (P_H2O?1.0 kbar) yields predicted apparent temperatures which are generally lower than the measured apparent temperatures. The agreement is improved if slower diffusion coefficients are used. This suggests that f (H₂O) during cooling was lower than that of the hydrothermal experiments and thus that there was little interaction with aqueous fluids of internal or external origin to modify the isotopic compositions. The measured apparent isotopic temperatures and apparent garnet–biotite Fe–Mg exchange temperatures show very poor agreement for the sillimanite zone samples, with the garnet–biotite Fe–Mg exchange temperatures generally higher than the oxygen isotope temperatures. Compared with the other calibrations that we tested the measured apparent temperatures using the Sharp calibration show the best agreeement with recently published P–T grids, although some variability in agreement is expected due to variable f (H₂O) during cooling.     

Experimental investigation of K and Na partitioning between miscible liquids

Model silicate melts with variable Al₂O₃ and SiO₂ contents were experimentally saturated with alkalis at a total pressure of 1 atm and temperatures of 1300–1470°C, using the crucible supported loop technique. It was shown that Al₂O₃ content has little influence on the degree of silicate melt saturation with K and Na. In contrast, SiO₂ content strongly affects the solubility of alkalis in silicate melts. Model calculations were performed to evaluate the behavior of alkalis during the contamination/mixing of basic and silicic magmas.     

Sapphirine parageneses from the Caraiba complex, Bahia, Brazil: the influence of Fe2+–Fe3+ distribution on the stability of sapphirine in natural assemblages

Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe₂O₃ in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al₂O₃–Fe₂O₃–SiO₂–H₂O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe³⁺ content and a high X_Mg= (Mg/ (Mg+Fe²⁺)) under these P–T conditions.