Compositional relations among hornblende and pyroxenes in basic granulites and an application to the origin of garnets

Three new sets of mineral and rock chemical data on basic granulites confirm the trends in compositional relationships, with respect to magnesium and iron, among hornblende, orthopyroxene and calcic pyroxene advanced by Sen (1970) and Ray and Sen (1970). Analysing the interrelationships among magnesium-iron distribution coefficients between hornblende-orthopyroxene and hornblende-calcic pyroxene, tetrahedral aluminium contents of hornblendes, and temperature of equilibration, it can be shown that equilibrium temperatures are higher with the Mg/(Mg+Fe) ratios of hornblendes increasing. An application of these relations to ferromagnesian phases of some garnet-bearing basic granulites points to formation of garnets in response to decreasing temperature.     

Feldspathic hornblende and garnet granulites and associated anorthosite pegmatites from Doubtful Sound,Fiordland, New Zealand

Feldspathic hornblende granulites from Doubtful Sound, New Zealand with the assemblage plagioclase+hornblende+clinopyroxene+orthopy-roxene +oxide+apatite are criss-crossed by a network of garnetiferous anorthosite veins and pegmatites. The feldspathic gneiss in contact with anorthosite has a reaction zone containing the assemblage plagioclase +garnet+clinopyroxene+quartz+rutile+apatite. The garnet forms distinctive coronas around clinopyroxene. The origin of these rocks is discussed in the light of mineral and whole rock chemical analyses and published experimental work.It is thought that under conditions leading up to 750 °C, 8 kb load pressure and 5 kb H₂O pressure, partial melting occured in feldspathic hornblende granulites. The melt migrated into extensional fractures and eventually crystallised as anorthosite pegmatites and veins. The gneisses adjacent to the pegmatites from which the melt was extracted changed composition slightly, by the loss of H₂O and Na₂O, so that plagioclase reacted simultaneously with hornblende, orthopyroxene, and oxide to form garnet, clinopyroxene, quartz and rutile.     

The crystallization of pyroxenes and amphiboles in some alkaline rocks and the presence of a pyroxene compositional gap

Ca- and Na-rich pyroxene-amphibole compositions and textures from a range of felsic alkaline rocks have been studied in detail. The data indicate that in a single sample, when amphibole crystallizes, a gap is observed between Ca- and Na-rich pyroxene compositions. This break in composition is analogous to Aoki's (1964) immiscibility gap between Ca-and Na-rich pyroxenes and can be overlooked when considering pyroxene compositions from a suite of rocks. The role of volatiles in governing the stability and composition of amphiboles is discussed. The presence of late crystallizing Na-rich pyroxene is related to the development of peralkinity in the late-stage melts.On extrusion, many alkaline rocks lose their volatiles and amphibole is absent. In these rocks complete zoning from Ca-rich to Na-rich pyroxene compositions are observed within the one sample.     

Sm–Nd geochronology and petrography of garnet pyroxene granulites in the northern Sulu region of China and their geotectonic implication

Abundant garnet-bearing granulite lenses are widely distributed in the northern part of the Sulu region and adjacent areas. They are possibly re-metamorphosed high-pressure metamorphic rocks. On the basis of detailed petrographic study, samples WD01, WD04 and ML06 from Laixi and Wendeng were identified as high-pressure granulites, and WH1 from Weihai as an original coesite-bearing eclogite. Three high-pressure granulite samples give mineral-WR isochron ages of 1846±76, 1743±79 and 1752±30 Ma. TDM ages are 3.3, 3.0 and 2.8 Ga. The Sm–Nd mineral-WR isochron ages are interpreted to date as the metamorphic resetting within the medium-pressure granulite facies, representing an isotopic re-homogeneity during uplifting of the high-pressure granulites from deep continent crust. It is important that Sm–Nd chronological characteristics are the same as Archaean high-pressure granulites in the North China craton. However, sample WH1 from Weihai demonstrates abnormal Sm–Nd characteristics. Its whole rock _Nd (0) value is +129. TDM age is 1.3 Ga, and constrains the minimum age of re-metamorphosed eclogite protolith formation to the mid-Proterozoic. This result is identical to those reported by Jahn (1994), showing complicated processes of metamorphism and metasomatism. The data in this paper provide further evidence to define the boundary between the North China craton and UHPM belt in eastern Shandong and to understand the geotectonic nature of the boundary.     

Intergrowth of pyroxene and pyroxenoid; chain periodicity faults in pyroxene

Intergrowth of clinopyroxenes (augite, A) and pyroxenoids (Fe-rhodonite and pyroxferroite, Pxo) was observed by transmission electron microscopy. The following orientation relationship was found: (001)_Pxo is parallel to \((1\mathop {\bar 1}\limits^ + \bar 1)_{\text{A}}\) and \([1\bar 10]_{Pxo}\) is parallel to [011]_A. This relationship can be explained by similarities of the structures of clinopyroxenes and pyroxenoids. It contradicts a suggestion based on structural arguments of Koto et al. (1976). Chain periodicity faults parallel to \((1\mathop {\bar 1}\limits^ + \bar 1)\) are also observed in pure clinopyroxenes.     

A pyroxene geotherm

Phase equilibria determined in high-pressure studies of the systems Mg₂Si₂O₆-CaMgSi₂O₆ and MgSiO₃-Mg₃Al₂Si₃O₁₂ can be used to estimate equilibration conditions of ultramafic rocks containing the assemblage enstatite + diopside + garnet. Garnet lherzolite nodules from kimberlites in northern Lesotho appear to have equilibrated in the upper mantle at depths ranging from 100 to 200 km and at temperatures in the range 900–1400°C. Temperature-depth points for these lherzolites form a trend that is interpreted as a segment of a fossil geotherm. The trend is inflected to higher temperatures at its deep end. Lherzolites that plot on the shallow limb of the geotherm have a granular texture whereas those that plot on the deep limb are intensely sheared. It is suggested that the shearing took place in response to plate movements during the break-up of Gondwanaland and that the sheared lherzolites were stress-heated as much as 300°C above their ambient, preshearing temperatures. The point of inflection of the geotherm may mark the top of the low-velocity zone beneath Lesotho in Late Cretaceous time.     

Diffusion of 40Ar in hornblende

Measured radiogenic ⁴⁰Ar loss from two compositionally contrasting hornblendes following isothermal-hydrothermal treatment have provided model diffusion coefficients in the temperature range of 750° C to 900° C. Eight experiments using a hornblende (77–600) with a Mg/(Mg +Fe) ratio of 0.72 yield a linear array on an Arrhenius plot with a slope corresponding to an activation energy of 66.1 kcal-mol^–1 and a frequency factor of 0.061 cm²-sec^–1, assuming spherical geometry for the mineral aggregate. Five experiments undertaken on a hornblende (M Mhb-1) with a Mg/(Mg+Fe) ratio of 0.36 show similar behavior to the Mgrich sample, suggesting that the diffusivity of Ar in hornblendes is not sensitive to the Mg/Fe ratio.These data are consistent with kinetic information obtained from a geological experiment using the thermal effect of a granitoid intrusion. Together these data yield an activation energy of 64.1±1.7 kcal-mol^–1 and a frequency factor of 0.024± _0.011 ^0.053 cm²-sec^–1. For a hornblende with an effective diffusion radius of 80 m, these diffusion parameters predict closure temperatures between 578° C and 490° C for cooling rates in the range 500 to 5° C-Ma^–1.     

Microdenticles on naturally weathered hornblende

Microdenticles (with lengths in the micron-submicron range rather than tens of microns) are developed on the lateral surfaces of larger “classic” denticles on naturally weathered hornblende from weathered amphibolite of the Carroll Knob Complex in western North Carolina. Microdenticles share the shape and orientation of the larger more typical denticles, producing arrays of microdenticles that give the larger host denticle the appearance of a surface covered with imbricate pointed or rounded scales. The arrays of imbricate microdenticles are formed by low-temperature aqueous alteration during weathering of the Carroll Knob Complex hornblende; they are later-stage corrosion forms on already-corroded surfaces of hornblende that show larger-scale evidence of typical weathering. In the Carroll Knob occurrence, hornblende microdenticles are associated with dilute weathering solutions, suggesting possible control by extreme undersaturation of solutions with respect to hornblende.     

Hydrogen defect saturation in natural pyroxene

Dehydration via the redox reaction: OH^? + Fe²⁺ ? O^2? + Fe³⁺ + ½H₂ is believed to be a commonly occurring process in pyroxenes and other nominally anhydrous minerals (NAMs) from the upper mantle and appears to be fast enough to allow significant dehydration during magma ascent. Nevertheless, the mobility of hydrogen incorporating defects is controlled by cation diffusion with approximately two orders of magnitude slower reaction kinetics than the iron redox reaction, and host defects have a much higher likelihood to be preserved than the hydrogen itself. Therefore, restoring hydrogen into the structure would be possible by driving the redox reaction backwards, as long as temperature and time are limited so as not to change the defect state of the crystal structure. Here we investigate the re-hydration capacity of megacryst and xenocryst ortho- and clinopyroxene by stepwise thermal annealing of crystallographically oriented samples in 1 atm H₂. H concentration was measured by FTIR spectroscopy after each annealing step. Most samples show only a small increase in water content up to a presumed saturation level, after which further heat treatments in H₂ resulted in a slight decrease in water contents. However, two of the studied samples, both fairly Fe rich megacrysts, are significantly rehydrated. Some samples or crystal sections exhibit a practically inert behavior, with minor fluctuations around initial water concentrations. Present results indicate that most mantle pyroxenes have not been substantially dehydrated during late stage magma processes, and that restoring water is possible in samples which have lost considerable amounts of water.     

Diffusion of 40Ar in metamorphic hornblende

Isothermal, hydrothermal experiments were performed on two compositionally contrasting hornblendes from amphibolites in order to examine Ar diffusion behavior in metamorphic hornblendes. Ten experiments on sample RF were performed at temperatures of 750°C, 800°C, and 850°C and pressures of 1 kbar using measured grain radii of 158, 101, and 34 m. Eight experiments on sample 118576 were performed under the same conditions using measured grain radii of 145, 77, and 25 m. Minor (<5%) alteration was observed in high temperature runs. Diffusion coefficients were calculated from measured radiogenic ⁴⁰Ar loss following treatment assuming a spherical geometry for the mineral aggregate. Diffusivities calculated for different grain sizes vary by up to an order of magnitude for a given temperature indicating that the effective diffusion radius was less than the measured grain radius. Diffusivities for RF and 118576 calculated for grain radii of 101 and 145 m, respectively, form a linear array on an Arrhenius diagram with slopes indicating activation energies of 60 kcal/mol. No correlation between Mg number (100 Mg/(Mg+Fe)) and activation energy was observed. Diffusivities calculated for these experiments are higher than previously reported results from similar experiments performed on hornblendes. A comparison of results for 34 m splits from these two studies indicates higher apparent diffusivities (by a factor of 5), which probably result from observed phyllosilicate inter-growths (chlorite) and/or exsolution lamellae that partition the metamorphic hornblendes into smaller subdomains. Diffusivities calculated for experiments performed on 65 m and 34 m splits of ⁴⁰Ar/³⁹Ar standard MMhb-1 at 800°C and 1 kbar are consistent with a previously reported activation energy of 65 kcal/mol. Arrhenius parameters which emerge from the empirical model of Fortier and Giletti (1989) agree with experimental results to within analytical uncertainty. Although results of these experiments support previously reported estimates of the activation energy of ⁴⁰Ar in hornblende (60 kcal/mol), phyllosilicate intergrowths and/or microstructures such as exsolution lamellae within the two metamorphic hornblendes result in extremely small diffusion domains, which may lead to lower Ar retentivities and lower closure temperatures. The effective diffusion dimension for ⁴⁰Ar in hornblende is not likely to be defined by dislocations but rather by some larger structure within the crystal. TEM and SEM studies may provide some insight into the effective diffusion dimension for ⁴⁰Ar in amphiboles, thereby enabling better estimates of closure temperatures and more precise temperature-time reconstructions.     

Garnet and pyroxene compositions in some diamondiferous eclogites

Analyses are reported for garnet and pyroxene from 17 eclogites that contain diamond. The garnets contain small but significant contents of Na, Ti and P and the pyroxenes contain traces of K. The diamond-bearing eclogites do not constitute a unique compositional group but show a range of mineral compositions consistent with a very high P-T environment.     

Andalusite in granulites of the bohemian massif

Summary In granulites of South-Bohemia not only the usually occurring Al₂SiO₅ polymorphs, kyanite and sillimanite, were found but also andalusite. Its presence indicates that the metamorphic development of these granulites is characterized by a high PT-gradient. The granulitic rocks of the Bohemian Massif can be regarded as a facies series ranging from the granulite facies through the amphibolite facies to the hornblende-hornfels facies. The lower limit of the PT-conditions of this series should be placed below the position of the triple point of Al₂SiO₅.

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Andalusit in Granuliten der Böhmischen Masse

Zusammenfassung In den Mineralparagenesen der südböhmischen Granulite wurde neben den üblicherweise auftretenden Al₂SiO₅-Modifikationen, Disthen und Sillimanit, auch Andalusit gefunden. Seine Anwesenheit weist darauf hin, daß die metamorphe Entwicklung der erwähnten Granulite durch einen ausgeprägten PT-Gradienten gekennzeichnet wurde. Die Granulitgesteine der Böhmischen Masse kann man als eine Faziesserie ansehen, die von der Granulitfazies über die Amphibolitfazies bis in die Hornblende-Hornfelsfazies reicht. Die untere Grenze der PT-Bedingungen dieser Serie ist unter die Lage des Tripelpunktes von Al₂SiO₅ zu setzen.

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With 5 Figures     

An evaluation of garnet-clinopyroxene geothermometry in granulites

Four new formulations of the garnet-clinopyroxene geothermometer (Ellis and Green 1979; Ganguly 1979; Saxena 1979; Dahl 1980) have been evaluated in the Adirondacks and five other granulite terranes using results from 94 mineral pairs. The Saxena and Ganguly formulations give temperatures that are generally 100–150° C above those constrained by phase equilibria and other independent thermometry while the empirical calibration of Dahl gives widely scattered, erratic results. Despite some scatter in the data, the Ellis and Green calibration appears to be more accurate and precise than the others and is the most useful garnet-clinopyroxene thermometer currently available for quantitative thermometry in granulites. All four formulations are sensitive to large variations (>70–80° C) in temperature suggesting that problems with accuracy and precision can be improved with further refinement of model-based aspects of the thermometers.     

Development of quartz ribbons in quartzofeldspathic granulites

In high-grade (granulite facies) quartzofeldspathic rocks the progressive development of a fabric records contrasting deformation behaviour of quartz and feldspar. Feldspar has undergone deformation mainly by recrystallization-accommodated dislocation creep and produced smaller recrystallized grains progressively in the course of deformation. Quartz has not deformed solely by dislocation creep but also by a diffusion-controlled mechanism. Dislocation climb is important in the dislocation creep of quartz. In contrast to feldspar, quartz grains have not recrystallized into smaller grains at any stage of deformation. Rather, they have transformed initially to short monocrystalline ribbons and ultimately to long polycrystalline ribbons. This textural change of quartz is a continuous process and has taken place in the course of bulk textural change of the rocks during the deformation.     

Retrograde processes in migmatites and granulites revisited

Many migmatites and granulites preserve evidence of a clockwise P–T evolution involving decompression (decrease in P) while close to the thermal peak. The extent of post‐thermal peak reaction is influenced by several factors, including: (1) the P–T path in relation to invariants in the system and the Clapeyron slopes of the equilibria; (2) the rate of cooling; and (3) the availability of fluid (H₂O‐rich volatile phase or melt) for fluid‐consuming reactions. Reaction may occur between products of a prograde (increasing T) fluid‐generating reaction as the same equilibrium is re‐crossed in the retrograde (decreasing T) sense. In general, reaction reversal or ‘back reaction’ requires the P–T path to approximate isobaric heating and cooling, without significant decompression, and evolved fluid to remain within the equilibration volume. The larger the decompression segment in the P–T evolution, the more chance there is of crossing different reactions along the retrograde segment from those crossed along the prograde segment. For common pelite compositions, we may generalize by considering three pressure regimes separated by the [Spl, Ms, H₂O] invariant in KFMASH (approximately 9 kbar) and the intersection of muscovite breakdown with the H₂O‐rich volatile phase‐saturated solidus (approximately 4 kbar). Reaction reversal cannot occur along P–T paths that traverse around one of these points, but may occur along P–T paths confined to one of the three regimes in between. Additionally, above the solidus, melt segregation and loss potentially change the composition of the equilibration volume; and, the size of the equilibration volume shrinks with decreasing T. Since the proportion of melt to residue in the equilibration volume may change with decreasing size, the composition of the equilibration volume may change throughout the supra‐solidus part of the retrograde segment of the P–T evolution. If melt has been lost from the equilibration volume, reaction reversal may not be possible or may be only partial; indeed, the common preservation of close‐to‐peak mineral assemblages in migmatite and granulite demonstrates that extensive reaction with melt is uncommon, which implies melt isolation or loss prior to crossing potential melt‐consuming reactions. Water dissolved in melt is transported through the crust to be exsolved on crystallization at the solidus appropriate to the intrinsic a(H₂O). This recycled water causes retrogression at subsolidus conditions. Consideration of the evidence for supra‐solidus decompression‐dehydration reactions, and review of microstructures that have proven controversial, such as corona and related microstructures, selvage microstructures and ‘late’ muscovite, leads to the conclusion that there is more than one way for these microstructures to form and reminds us that we should always consider multiple working hypotheses!     

The stability of osumilite in metapelitic granulites

Abstract A petrogenetic grid and related diagrams derived from KFMASH-system experiments demonstrate that osumilite is stable in relatively magnesian bulk rock compositions ( X _Mg > 0.6) at temperatures in excess of 875° C and pressures less than 11 kbar. The experiments, involving the dehydration melting of biotite in synthetic metapelites, were conducted in the range 850–1000° C. Both the mineral assemblages and phase compositions reported from well-documented natural examples of osumilite-bearing rocks are reproduced by the experiments at P-T conditions similar to those previously estimated for these occurrences. Peak metamorphic P-T conditions can be reliably inferred from distinctive osumilite-bearing assemblages identified in the phase diagrams, thereby avoiding the problems of diffusional re-equilibration that often prohibits conventional geothermobarometry from recovering peak conditions. Integration of the experimental data with recent independent experiments, after correcting the latter for an underestimated friction correction, allows extension of the petrogenetic grid to higher temperatures. The extended grid is applied to assess and refine the metamorphic history of the Napier Complex, East Antarctica: the high- P stability limit for osumilite in the Napier Complex is 9–10 kbar, the prograde P-T-t path is not necessarily anticlockwise and isobaric cooling in the Scott and Tula mountains occurred, respectively, at pressures greater and less than reactions in the range 8–9 kbar. The stability range for osumilite predicted by the KFMASH-system petrogenetic grid overlaps many more metamorphic terranes than osumilite is found in. Whilst osumilite is not distinctive in thin section and is prone to retrogression, it is possible that carbon dioxide present in the natural system stabilizes cordierite at the expense of osumilite.     

On the formation of granulites

The tectonic settings for the formation and evolution of regional granulite terranes and the lowermost continental crust can be deduced from pressure–temperature–time (P–T–time) paths and constrained by petrological and geophysical considerations. P–T conditions deduced for regional granulites require transient, average geothermal gradients of greater than 35°C km^?1, implying minimum heat flow in excess of 100 mWm^?2. Such high heat flow is probably caused by magmatic heating. Tectonic settings wherein such conditions are found include convergent plate margins, continental rifts, hot spots and at the margins of large, deep-seated batholiths. However, particular P–T–time paths do not allow specific tectonic settings to be distinguished at this time. Under different conditions, both clockwise, CW (P_max attained before T_max), and anticlockwise, ACW (P_max attained slightly after T_max), paths are possible in the same tectonic setting. Both CW and ACW end-member paths can yield nearly isobaric cooling, IBC, paths. Such cooling paths are clearly not an artefact of thermobarometry, but can be constrained by solid–solid and devolatilization equilibria and geophysical modelling. In terms of understanding the evolution of the deep crust, a potentially significant group of regional granulite terranes are those that show evidence for ACW-IBC paths. Such paths are the likely result of: (i) episodic igneous activity resulting in intrusions within all levels of the crust, (ii) thickening of the crust by magmatic underplating, (iii) slow uplift as a result of the formation of a deep, garnet-rich crustal root and (iv) excavation resulting from a later tectonic event unrelated to that resulting in the formation of the granulites. The later event might be triggered by the delamination of the garnet-rich, lowermost crust.     

Perpotassic granulites from southern Bohemia

Garnetiferous, perpotassic granulites associated with voluminous, felsic calc-alkaline garnet-kyanite granulites in the Blanský les massif are described as a new rock type. A K₂O content near 13 wt%, Zr content ranging from 17 to 5877 ppm, primary Ca-Mg-Fe garnet (pyrope up to 33 mol %), and the absence of primary plagioclase and quartz characterize the new type of granulite. Calcium is incorporated only in garnet and apatite. Owing to the content of garnet the bulk syenitic compositions are metaaluminous to peraluminous. The perpotassic granulites are accompanied by subordinated melanocratic perpotassic granulite and alkali-feldspar melanocratic granulite containing up to 20 vol % quartz. These rock types also contain highly variable amounts of zircon. High-pressure, noneutectic partial melting of crustal rocks and crystallization under upper mantle conditions is suggested as the main process in generation of perpotassic granulites. A polyphase, ductile to brittle deformation and recrystallization in pyroxene granulite and later in amphibolite facies accompanied obduction of the granulite massif which carries numerous enclaves of pyrope peridotite. Euhedral equant zircon crystals up to 4 mm long enclosed in large garnet crystals and in the alkali feldspar matrix of perpotassic granulite represent a uniform, high-temperature population with a nearly concordant U-Pb system (Aftalion et al. 1989). The Hercynian age of this zircon indicates the role of the Hercynian anatexis of crustal rocks under upper mantle conditions in generation of granulites in the Moldanubian zone of the Bohemian massif.     

张宣隆起核部的转枝莲辉石闪长岩

位于冀西北张家口-宣化地区的转枝莲辉石闪长岩侵入水泉沟正长岩杂岩体中。该岩石由紫苏辉石、次透辉石、黑云母、中长石、正长石以及磷灰石、钛铁矿等副矿物组成。全岩分析结果SiO253％～59％。本文根据上述两点将其命名为辉石闪长岩。通过岩石成因、稀土元素分布模式和岩石的Sr-Nd同位素组成研究,认为岩体是上地幔和下地壳物质部分熔融的产物。辉石闪长岩的Rh-Sr等时线年龄为143Ma。     

Measurement error in compositional data

Compositional data, consisting of vectors of proportions summing to unity such as the geochemical compositions of rocks, have proved difficult to analyze. Recently, the introduction of logistic and logratio transformations between the d-dimensional simplex and Euclidean space has allowed the use of familiar multivariate methods. The problem of how to model and analyze measurement errors in such data is approached through the concept of a perturbation of a composition. Such modeling allows investigation of the role of rescaling, quantification of measurement error, analysis of observor error, and assessment of the effect of measurement error on inferences.