Kinetic control of staurolite–Al2SiO5 mineral assemblages: Implications for Barrovian and Buchan metamorphism

The distribution and textural features of staurolite–Al₂SiO₅ mineral assemblages do not agree with predictions of current equilibrium phase diagrams. In contrast to abundant examples of Barrovian staurolite–kyanite–sillimanite sequences and Buchan‐type staurolite–andalusite–sillimanite sequences, there are few examples of staurolite–sillimanite sequences with neither kyanite nor andalusite anywhere in the sequence, despite the wide (~2.5 kbar) pressure interval in which they are predicted. Textural features of staurolite–kyanite or staurolite–andalusite mineral assemblages commonly imply no reaction relationship between the two minerals, at odds with the predicted first development (in a prograde sense) of kyanite or andalusite at the expense of staurolite in current phase diagrams. In a number of prograde sequences, the incoming of staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is coincident or nearly so, rather than kyanite or andalusite developing upgrade of a significant staurolite zone as predicted. The width of zones of coexisting staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is much wider than predicted in equilibrium phase diagrams, and staurolite commonly persists upgrade until its demise in the sillimanite zone. We argue that disequilibrium processes provide the best explanation for these mismatches. We suggest that kyanite (or andalusite) may develop independently and approximately contemporaneously with staurolite by metastable chlorite‐consuming reactions that occur at lower P–T conditions than the thermodynamically predicted staurolite‐to‐kyanite/andalusite reaction, a process that involves only modest overstepping (<15°C) of the stable chlorite‐to‐staurolite reaction and which is favoured, in the case of kyanite, by advantageous nucleation kinetics. If so, the pressure difference between Barrovian kyanite‐bearing sequences and Buchan andalusite‐bearing sequences could be ~1 kbar or less, in better agreement with the natural record. The unusual width of coexistence of staurolite and Al₂SiO₅ minerals, in particular kyanite and andalusite, can be accounted for by a combination of lack of thermodynamic driving force for conversion of staurolite to kyanite or andalusite, sluggish dissolution of staurolite, and possibly the absence of a fluid phase to catalyse reaction. This study represents an example of how kinetic controls on metamorphic mineral assemblage development have to be considered in regional as well as contact metamorphism.     

Resolving the Routine Presence of Kyanite,Andalusite and Sillimanite across a Region using Foliation Intersection/Inflection Axes Preserved in Porphyroblasts,Petrographic Observations and Thermobarometry

Constraints from P-T pseudosections (MnNCKFMASH system), foliation intersection/inflection axes preserved in porphyroblasts (FIAs), mineral assemblages and textural relationships for rocks containing all three Al2SiO5 polymorphs indicate a kyanite→ andalusite→ sillimanite sequential formation at different times rather than stable coexistence at the Al2SiO5 triple point. All three Al2SiO5 polymorphs grew in the Chl, Bt, Ms, Grt, St, Pl and Crd bearing Ordovician Clayhole Schist in Balcooma, northeastern Australia separately along a looped P-T-t-D path that swaps from clockwise to anticlockwise in the tectono-metamorphic history of the region. Kyanite grew during crustal thickening in an Early Silurian Orogenic event followed by decompression/heating, andalusite and fibrolitic sillimanite growth during Early Devonian exhumation.     

Interpreting prograde-growth histories of Al2SiO5 triple-point rocks using oxygen-isotope thermometry: an example from the Truchas Mountains, USA

Oxygen‐isotope compositions of kyanite, andalusite, prismatic sillimanite and fibrolite from the Proterozoic terrane in the Truchas Mountains, New Mexico differ from one another, suggesting that these minerals did not grow in equilibrium at the Al₂SiO₅ (AS) polymorph‐invariant point as previously suggested. Instead, oxygen‐isotope temperature estimates indicate that growth of kyanite, andalusite and prismatic sillimanite occurred at c. 575, 615 and 640 °C respectively. Temperature estimates reported in this paper are interpreted as those of growth for the different AS polymorphs, which are not necessarily the same as peak metamorphic temperatures for this terrane. Two distinct temperature estimates of c. 580 °C and c. 700 °C are calculated for most fibrolite samples, with two samples yielding clear evidence of quartz‐fibrolite oxygen‐isotope disequilibrium. These data indicate that locally, and potentially regionally, oxygen‐isotope disequilibrium between quartz and fibrolite may have resulted from rapid fibrolite nucleation. Pressures of mineral growth that were extrapolated from oxygen‐isotope thermometry results and calculated using petrological constraints suggest that kyanite and one generation of fibrolite grew during M1 at 5 kbar, and that andalusite, prismatic sillimanite and a second generation of fibrolite grew during M2 at 3.5 kbar. M1 and M2 therefore represent two distinct metamorphic events that occurred at different crustal levels. The ability of the AS polymorphs to retain δ¹⁸O values of crystallization make these minerals ideal to model prograde‐growth histories of mineral assemblages in metamorphic terranes and to understand more clearly the pressure–temperature histories of multiple metamorphic events.     

Composition and conditions of formation of andalusite-kyanite-sillimanite pegmatoid segregations in metamorphic rocks of the Tsel block (Mongolian Altay)

Pegmatoid segregations containing three polymorphous Al₂SiO₅ modifications have been revealed in metamorphic rocks of the Tsel block localized in the Hercynian belt on the southern flank of Mongolian Altay. Petrographic study showed a successive substitution of polymorphs in the sequence: andalusite–kyanite–fibrolite–sillimanite. Estimated parameters of the host-rock metamorphism indicate that the mineral assemblage of pegmatoid veins formed at two successive stages of metamorphism: andalusite-sillimanite and kyanite-sillimanite. It is suggested that the transformation of Al₂SiO₅ from one to another polymorphous modification occurs by the ion exchange mechanism with the participation of muscovite.     

Raman spectra from the Al2SiO5 polymorphs at high pressures and room temperature

Raman spectra of the three Al₂SiO₅ polymorphs; andalusite, sillimanite and kyanite were recorded as a function of pressure at room temperature. All the Raman active bands which could be observed from the high-pressure cell showed a linear pressure dependence for each of the three Al₂SiO₅ polymorphs and no phase changes were observed over the pressure ranges used in this study. In andalusite and to a lesser extent in sillimanite, vibrations which could be correlated with internal motions of the SiO₄ tetrahedra were generally well separated from the lattice modes and showed a greater pressure dependence than that observed for other modes. The distinct pressure dependence of the internal SiO₄ modes is less evident in kyanite, probably due to the lack of continuous tetrahedral chains and the fact that the rigid SiO₄ tetrahedra now form an integral part of the structural network. At ambient pressure, kyanite also exhibits two fluorescence bands at 705 and 706.2 nm which are due to small amounts of Cr³⁺ in the kyanite crystals. These fluorescence bands showed a non-linear frequency shift as pressure was increased.     

Metasomatic albitites and related biotite-rich schists from a low-pressure polymetamorphic terrane, Snake Creek Anticline, Mount Isa Inlier, north-eastern Australia: microstructures and P–T–d paths

Rocks of the Snake Creek Anticline are mainly pelitic schists, psammitic schists and quartzites that were metamorphosed during multiple high‐T/low‐P events extending from D1 to D5, with the metamorphic peak occurring late to post‐D3. Albitites are widespread, but are concentrated in five areas. They are typically fine‐ to medium‐grained, and consist of albite, with or without combinations of quartz, biotite, staurolite, cordierite, garnet, andalusite, sillimanite, kyanite, gedrite and tourmaline. From the presence or absence of albite inclusions in porphyroblasts, the albitites are interpreted as forming early in the D3 event as a result of infiltration of external fluids. Psammitic schists and quartzites were preferentially altered, but pelitic schists were also albitized in localities where the alteration was more extreme, with the replacement of muscovite total and the replacement of quartz and biotite variable. Structural controls on albitization include fracturing and syn‐D3 shear zones in fold hinges. Biotite schists with abundant porphyroblasts (combinations of staurolite, garnet, andalusite and cordierite) occur adjacent to albitites, and it is argued that they formed by the addition of Fe and Mg sourced from the albitites. In several albitite‐rich areas, cordierite grew early in D3 and was partly or entirely replaced during or after D3 by combinations of biotite, andalusite, tourmaline, staurolite and sillimanite. A postulated P–T–d path involved an increase in pressure (with or without a decrease in temperature) subsequent to early D3 albitization, followed by an increase in temperature up to the metamorphic peak (late D3 to early D4. The metamorphism was contemporary in part with the emplacement of the Williams Batholith (c. 1550–1500 Ma), which probably supplied the Na‐rich fluids.     

Hercynite as the product of staurolite decomposition in the contact aureole of Vedrette di Ries,eastern Alps,Italy

Metapelitic hornfelses in the contact aureole of the Vedrette di Ries pluton exhibit the terminal decomposition of Zn-poor Fe-staurolite in a muscovite-quartz-free domain. The reaction takes place only within coarsegrained sillimanite that has replaced andalusite porphyroblasts during prograde metamorphism. The product is a gahnite-poor hercynitic spinel, which occurs as very small grains closely associated in space with resorbed staurolite. Microstructural observations indicate that bereynite growth postdates the pseudomorphs of sillimanite after andalusite. The textural evidence for a genetic relationship between hercynite and staurolite is confirmed by the identical Fe/Mg/Zn ratios of the two minerals, which causes the collinearity of hercynite, staurolite and Al₂SiO₅ in FeO–MgO–ZnO–Al₂O₃–SiO₂–H₂O composition space (FMZASH), and indicates hercynite formed by the reaction: Fe-staurolite = 3.85hercynite + 5.1sillimanite + 2.55quartz + 2H₂O Staurolite inclusions within andalusite did not break down to form hercynite, indicating a kinetic control, as well as little overstepping of the equilibrium conditions, of the reaction forming hercynite. Assuming overstepping did not occur, modelling of the reaction with existing thermodynamic data in the simplified FASH system suggests that the terminal breakdown of staurolite to form hercynite occurred at 2.5–3.75kbar and 585–655°C.     

Stable isotope constraints on the Al2SiO5'triple-point' rocks from the Proterozoic Priest pluton contact aureole, New Mexico, USA

The Priest pluton contact aureole in the Manzano Mountains, central New Mexico preserves evidence for upper amphibolite contact metamorphism and localized retrograde hydrothermal alteration associated with intrusion of the 1.42 Ga Priest pluton. Quartz–garnet and quartz–sillimanite oxygen isotope fractionations in pelitic schist document an increase in the temperatures of metamorphism from 540 °C, at a distance of 1 km from the pluton, to 690 °C at the contact with the pluton. Comparison of calculated temperature estimates with one‐dimensional thermal modelling suggests that background temperatures between 300 and 350 °C existed at the time of intrusion of the Priest pluton. Fibrolite is found within 300 m of the Priest pluton in pelitic and aluminous schist metamorphosed at temperatures >580 °C. Coexisting fibrolite and garnet in pelitic schist are in oxygen isotope equilibrium, suggesting these minerals were stable reaction products during peak metamorphism. The fibrolite‐in isograd is coincident with the staurolite‐out isograd in pelitic schist, and K‐feldspar is not observed with the first occurrence of fibrolite. This suggests that the breakdown of staurolite and not the second sillimanite reaction controls fibrolite growth in staurolite‐bearing pelitic schist. Muscovite‐rich aluminous schist locally preserves the Al₂SiO₅ polymorph triple‐point assemblage – kyanite, andalusite and fibrolite. Andalusite and fibrolite, but not kyanite, are in isotopic equilibrium in the aluminous schist. Co‐nucleation of fibrolite and andalusite at 580 °C in the presence of muscovite and absence of K‐feldspar suggests that univariant growth of andalusite and fibrolite occurred. Kyanite growth occurred during an earlier regional metamorphic event at a temperature nearly 80 °C lower than andalusite and fibrolite growth. Quartz–muscovite fractionations in hydrothermally altered pelitic schist and quartzite are small or negative, suggesting that late isotopic exchange between externally derived fluids and muscovite, but not quartz, occurred after peak contact metamorphism and that hydrothermal alteration in pelitic schist and quartzite occurred below the closure temperature of oxygen self diffusion in quartz (<500 °C).     

Borosilicate- and phengite-bearing veins from the Grenville Province of Labrador: evidence for rapid uplift

Quartzo‐feldspathic veins emplaced within a migmatite terrane near Wilson Lake in the Grenville Province of central Labrador record a metamorphic event not evident in the host rocks. The discordant veins are undeformed and have undisturbed primary igneous/hydrothermal textures. Most of the veins contain euhedral kyanite, as well as aggregates of kyanite, K‐feldspar, phlogopite and minor dumortierite which are likely pseudomorphs after primary phengite. The reconstructed phengite compositions range from 3.1 to 3.2 Si per 11 oxygen formula unit. The pseudomorph assemblage is interpreted as the product of phengite + quartz melting under H₂O‐undersaturated conditions, which brackets P–T conditions of formation to about 9–16 kbar and 775–875 °C. A parallel vein that is likely of the same generation contains the borosilicate phases, dumortierite, prismatine and grandidierite, but no kyanite. The borosilicate assemblages constrain the P–T conditions of vein crystallization to ≥10 kbar and c. 750–850 °C. Vein emplacement is constrained to T ≤ 875 °C at the same pressures, which is well within the kyanite zone. Because the host rocks and veins must have experienced the same P–T history following vein emplacement, the presence of unreacted sillimanite in the host migmatites implies insufficient time for host rock equilibration. Slow reaction rates because of anhydrous conditions are not a likely explanation given the abundance of biotite and hornblende in the host rocks. The ductility implied by the breakdown of a hydrous phase (phengite) and the production of an H₂O‐undersaturated melt in the veins contrasts with the apparently brittle behaviour of the host rocks. The absence of deformation since the time of vein emplacement, even at temperatures above 750 °C, suggests that the deep crust in this part of Labrador had a very short residence time under conditions of the kyanite zone. Rapid decompression from those conditions is consistent with quartz + phengite melting and accounts for the relatively brittle behaviour of the terrane as it was uplifted.     

Deformation-induced polymorphic transformation: experimental deformation of kyanite, andalusite, and sillimanite

Torsion experiments were performed on the Al₂SiO₅ polymorphs in the sillimanite stability field to determine basic rheological characteristics and the effect of deformation on polymorphic transformation. The experiments resulted in extensive transformation of andalusite and kyanite to sillimanite. No transformation occurred during the hot-press (no deformation) stage of sample preparation, which was carried out at similar P–T conditions and duration as the torsion experiments. Experiments were conducted on fine-grained (< 15 µm) aggregates of natural andalusite, kyanite and sillimanite at 1250 °C, 300 MPa, and a constant shear strain rate of 2 × 10^− 4/s to a maximum shear strain of 400%. Electron back-scattered diffraction (EBSD) analysis of the experiments revealed development of lattice-preferred orientations, with alignment of sillimanite and andalusite [001] slightly oblique to the shear plane. The kyanite experiment could not be analyzed using EBSD because of near complete transformation to sillimanite. Very little strain ( 30%) is required to produce widespread transformation in kyanite and andalusite. Polymorphic transformation in andalusite and kyanite experiments occurred primarily along 500 µm wide shear bands oriented slightly oblique and antithetic to the shear plane and dominated by sub-µm (100–150 nm) fibrolitic sillimanite. Shear bands are observed across the entire strain field preserved in the torsion samples. Scanning transmission electron microscope imaging shows evidence for transformation away from shear bands; e.g. fibrolitic rims on relict andalusite or kyanite. Relict grains typically have an asymmetry that is consistent with shear direction. These experimental results show that sillimanite is by far the weakest of the polymorphs, but no distinction can yet be made on the relative strengths of kyanite and andalusite. These observations also suggest that attaining high bulk strain energy in strong materials such as the Al₂SiO₅ polymorphs is not necessary for triggering transformation. Strain energy is concentrated along grain boundaries, and transformation occurs by a dynamic recrystallization type process. These experiments also illustrate the importance of grain-size sensitive creep at high strains in a system with simultaneous reaction and deformation.     

The selective replacement of the aluminium silicates by white mica: A comment

Characteristic patterns in the preferential replacement of Al₂SiO₅ polymorphs by white mica have been interpreted by Kwak (1971) as indicating that, for alkali equilibria, the fields in order of decreasing stability are: kyanite + soln < andalusite + soln < sillimanite + soln Alternatively, preferential replacement patterns may be interpreted as reflecting the repetition of certain types of Pressure-Temperature-time paths in various metamorphic episodes.I am grateful to J. S. Fox for commenting on this comment.     

Synmetamorphic veining: origin of andalusite-bearing veins in the Vedrette di Ries contact aureole, Eastern Alps, Italy

Discordant andalusite-biotite-quartz-bearing veins occur in the contact aureole of the Vedrette di Ries pluton (Italian Eastern Alps), never outside the area of contact metamorphic andalusite development. Andalusite veins are found only within andalusite-bearing hornfelses, and vein biotite occurs wherever host-rock garnet is partially replaced by biotite. Veins formed during contact metamorphism, synchronously with the crystallization of andalusite and biotite within host rocks. Their pegmatitic structure and their orientation suggest that vein parageneses crystallized within fluid-filled cavities that opened by hydraulic fracturing. A mechanism of synmetamorphic veining is proposed to explain rock failure and subsequent mineral deposition within veins. During hydrofracturing induced by dehydration reactions in response to heating in the aureole, fissures were immediately filled with locally derived fluids. The lack of large-scale flux, together with high fluid pressures required by hydrofracturing, suggest fluid in the cavities was a virtually stagnant, passive medium, and that mass-transport toward fractures was driven by intergranular diffusion. Because temperature and P_f values within veins are similar to those in the host rock, vein assemblages are interpreted as the stable, high-T side of reactions taking place within pelitic schists, at the time when fractures opened. Once nucleation of product phases occurred, chemical components released by dissolution of reactant minerals were driven to precipitation sites by chemical potential gradients. Since nucleation was favoured at the strained grains of vein walls, andalusite and biotite simultaneously grew in vein and host rock. The proposed genetic model contrasts with generally adopted metasomatic mechanisms for the genesis of Al₂SiO₅-bearing veins, in not requiring large fluid/rock ratios or a highly ‘aggressive’ fluid composition. The mechanism of synmetamorphic veining may be particularly useful in the interpretation of vein occurrences in medium- and deep-crustal rocks which have undergone extensive devolatilization.     

The effect of whole-rock MnO content on the stability of garnet in pelitic schists during metamorphism

Garnet-bearing mineral assemblages are commonly observed in pelitic schists regionally metamorphosed to upper greenschist and amphibolite facies conditions. Modelling of thermodynamic data for minerals in the system Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O, however, predicts that garnet should be observed only in rocks of a narrow range of very high Fe/Mg bulk compositions. Traditionally, the nearly ubiquitous presence of garnet in medium- to high-grade pelitic schists is attributed qualitatively to the stabilizing effect of MnO, based on the observed strong partitioning of MnO into garnet relative to other minerals. In order to quantify the dependence of garnet stability on whole-rock MnO content, we have calculated mineral stabilities for pelitic rocks in the system MnO–Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O for a moderate range of MnO contents from a set of non-linear equations that specify mass balance and chemical equilibrium among minerals and fluid. The model pelitic system includes quartz, muscovite. albite, pyrophyllite, chlorite, chloritoid, biotite, garnet, staurolite, cordierite, andalusite, kyanite. sillimanite, K-feldspar and H₂O fluid. In the MnO-free system, garnet is restricted to high Fe/Mg bulk compositions, and commonly observed mineral assemblages such as garnet–chlorite and garnet–kyanite are not predicted at any pressure and temperature. In bulk compositions with X_Mn= Mn/(Fe + Mg + Mn) > 0.01, however, the predicted garnet-bearing mineral assemblages are the same as the sequence of prograde mineral assemblages typically observed in regional metamorphic terranes. Temperatures predicted for the first appearance of garnet in model pelitic schist are also strongly dependent on whole-rock MnO content. The small MnO contents of normal pelitic schists (X_Mn= 0.01–0.04) are both sufficient and necessary to account for the observed stability of garnet.     

Amphibolites with staurolite and other aluminous minerals: calculated mineral equilibria in NCFMASH

Amphibolite facies mafic rocks that consist mainly of hornblende, plagioclase and quartz may also contain combinations of chlorite, garnet, epidote, and, more unusually, staurolite, kyanite, sillimanite, cordierite and orthoamphiboles. Such assemblages can provide tighter constraints on the pressure and temperature evolution of metamorphic terranes than is usually possible from metabasites. Because of the high variance of most of the assemblages, the phase relationships in amphibolites depend on rock composition, in addition to pressure, temperature and fluid composition. The mineral equilibria in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) model system demonstrate that aluminium content is critical in controlling the occurrence of assemblages involving hornblende with aluminous minerals such as sillimanite, kyanite, staurolite and cordierite. Except in aluminous compositions, these assemblages are restricted to higher pressures. The iron to magnesium ratio (X_Fe), and to a lesser extent, sodium to calcium ratio, have important roles in determining which (if any) of the aluminous minerals occur under particular pressure–temperature conditions. Where aluminous minerals occur in amphibolites, the P–T–X dependence of their phase relationships is remarkably similar to that in metapelitic rocks. The mineral assemblages of Fe‐rich amphibolites are typically dominated by garnet‐ and staurolite‐bearing assemblages, whereas their more Mg‐rich counterparts contain chlorite and cordierite. Assemblages involving staurolite–hornblende can occur over a wide range of pressures (4–10 kbar) at temperatures of 560–650 °C; however, except in the more aluminous, iron‐rich compositions, they occupy a narrow pressure–temperature window. Thus, although their occurrence in ‘typical’ amphibolites may be indicative of relatively high pressure metamorphism, in more aluminous compositions their interpretation is less straightforward.     

Crustal growth during back‐arc closure: Cretaceous exhumation history of Cordillera Darwin,southern Patagonia

The Cordillera Darwin metamorphic complex is unique in the Andes in exposing kyanite–staurolite schist north of the Beagle Channel in southern Patagonia. Garnet in amphibolite facies pelitic schists from Bahía Pia has patchy textures whereby some grains consist of clear, grossular‐rich garnet with fine‐grained S1 inclusion trails truncated by regions of turbid spessartine–pyrope‐rich garnet with biotite, muscovite, plagioclase and quartz inclusions. Micron‐scale aqueous inclusions in turbid garnet are consistent with recrystallization facilitated by fluid ingress; S2 inclusion trails indicate this was broadly contemporary with the growth of kyanite and staurolite in the matrix. Pseudosection modelling in Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) is used to infer a P–T path dominated by decompression from 12 to 9 kbar at T ≈ 620 °C, coupled with garnet mode decreasing from ～5% to <1%. U–Th–Pb in situ dating of S2 monazite indicates that staurolite and kyanite growth and thus exhumation was underway before 72.6 ± 1.1 Ma. Contact aureoles developed adjacent to late granite intrusions include sillimanite‐bearing migmatites formed at P ≈ 6 kbar after 72 Ma. Metamorphism of southern Cordillera Darwin induced by continental underthrusting beneath the arc, related to closure of the Rocas Verdes back‐arc basin, was terminated by thrusting‐controlled exhumation, with the rocks at P ≈ 9 kbar by c. 73 Ma and 6 kbar by c. 70 Ma.     

The selective replacement of the aluminum silicates by white mica

From considerations of relativeG-T surfaces inferred from publishedP-T data and the occurrence of replacement textures of Al₂SiO₅ polymorphs in rocks, the relative positions of curves representing the following equation in _K+ —T — pH ispace on substituting Al₂SiO₅ different polymorphs are derived.3 Al₂SiO₅ + 3 SiO₂ (quartz) + 2 K⁺ + 3 H₂O 2 KAl₂[AlSi₃O₁₀](OH)₂ (muscovite)+ 2 H⁺. The curves are different because of the differentG-T values for the polymorphs which, in the field, is borne out by the observation that in a rock containing two or three Al₂SiO₅ polymorphs, in nearly all instances only one polymorph is replaced by white mica. Instances of textural relations showing the interpreted selective replacement of one Al₂SiO₅ polymorph by a white mica in the presence of one (or two) other Al₂SiO₅ polymorph(s) are cited both from the literature and various field examples. The selective replacement of kyanite if sillimanite and/or andalusite is/are present, and of andalusite if only sillimanite is present are interpreted to show that generally during the muscovitization reaction, the field of sillimanite in the above reaction (left hand side) at a particular pH (H⁺ concentration) and is larger in _K+ —T space than that of andalusite which in turn is larger than that of kyanite. Theoretically it is shown that variations to this can exist but the field evidence suggests these only occur under rare geological conditions. Although this is not totally conclusive, the selectiveness of the replacement is interpreted to show that the fluid was buffered with respect to K⁺ and H⁺ on or near the curve of the polymorph showing the lowest stability field until that polymorph is totally consumed, after which the fluid composition moves to the next lowest curve for the remaining polymorph(s) present in the rock. The alteration of more than one polymorph by an apparently simultaneous process of alteration is rare and usually occurs at a low grade of metamorphism. This is interpreted to show that the buffering reaction could not keep pace with the influx of fluid and change the composition of this fluid (in most cases).     

The Effects of Fe3? and Mn3? on Aluminum Silicate Phase Relations in North-Central New Mexico, U.S.A.

Aluminum silicate triple-point occurrences are common in metamorphicrocks of northern New Mexico. The three polymorphs show extensivesolid solution, with Fe and Mn substituting for Al. Mineraltextures, the spatial distribution of phases, and the systematicpartitioning of Fe and Mn indicate that the kyanite-andalusite-sillimaniteassemblages crystallized in equilibrium. The compositions ofminerals in the three-phase assemblage vary across the studyarea, recording regional variations in the pressures and temperaturesof metamorphism. The highest-pressure rocks, exposed at RioMora, contain kyanite at higher elevations and sillimanite atlower elevations. A sub-horizontal isograd separates the twominerals. Kyanite and sillimanite have nearly identical Fe contentwhich varies systematically with X_Fe2O3 in hematite or ilmenite.Andalusite occurs only along a single manganiferous layer, incrystals rich in MnAlSiO₅ and saturated in FeAlSiO₅. Triple-pointassemblages can be found wherever the folded manganiferous layercrosses the unfolded kyanite-sillimanite isograd. The TruchasRange, preserving slightly lower pressures of metamorphism,shows kyanite-andalusite-sillimanite in rocks with titaniferoushematite. Andalusite is enriched in Fe relative to kyanite andsillimanite, but no polymorphs contain Mn. Rocks with lowerX_Fe2O3 in hematite have kyanite and sillimanite without andalusite,whereas rocks with pure hematite contain only andalusite. Theshallowest erosional levels are preserved in the western PicurisRange where the three polymorphs occur as pure minerals in ilmenite-bearingrocks. Hematitic samples contain only andalusite which showsextensive solid solution of both Fe and Mn. The assemblage kyanite-andalusite-sillimanite is not invariant.Iron and manganese both add degrees of freedom. These transitionmetals have stabilized the three-phase assemblage, in apparentchemical equilibrium, across a P-T interval of 500-540 ?C, 3?8-4?6kb in rocks from New Mexico. The saturation level of FeAlSiO5in andalusite does not vary with Mn content but does vary withpressure and temperature. Calculations indicate that a 2-3 kbdecrease in pressure or a 25-50 ?C increase in temperature resultsin a 1 mole per cent increase in X_FeAlSiO5 in iron-saturatedandalusite.     

Phase relationships in Buchan facies series pelitic assemblages: calculations with application to andalusite-staurolite parageneses in the Mount Lofty Ranges,South Australia

Low-pressure, medium- to high-temperature (Buchan-type) regional metamorphism of pelitic rocks in the Mount Lofty Ranges, South Australia, is defined by the development of biotite, staurolite-andalusite, fibrolite, prismatic sillimanite and migmatite zones. K-feldspar makes its first appearance in the prismatic sillimanite zone and here we restrict our discussion to lower grade assemblages containing prograde muscovite, concentrating particularly on well-developed andalusitestaurolite parageneses. In general, the spatial distribution and mineral chemical variation of these assemblages accord with the predictions of petrogenetic grids and P-T and T-X _Fe pseudo-sections constructed from the internally consistent data set of Holland and Powell (1990) in the system KFMASH, assuming a(H₂O) 1, although analysed white mica compositions are systematically more aluminous than predicted. Importantly, the stability ranges of most critical assemblages predicted by these grids and pseudo-sections coincide closely with P-T estimates calculated using the data set of Holland and Powell (1990) from the Mount Lofty Ranges assemblages. With the exception of Mn in garnet and Zn in one staurolite-cordierite-muscovite assemblage non-KFMASH components do not significantly appear to have affected the stability ranges of the observed assemblages. An apparent local reversal in isograd zonation in which andalusite first appears down-grade of staurolite suggests a metamorphic field gradient concave towards the temperature axis and, together with evidence for essentially isobaric heating of individual rocks, is consistent with the exposures representing an oblique profile through a terrain in which heat was dissipated from intrusive bodies at discrete structural levels.Mineral abbreviations used in figures als Al₂SiO₅ phase - bi biotite - chl chlorite - ky kyanite - ph phengite - sill sillimanite - and andalusite - cd cordieritc - gt garnet - mu muscovite - q quartz - st staurolite     

Thermobarometry, Geochronology and the Interpretation of P-T-t Data in the Britt Domain, Ontario Grenville Orogen, Canada

Textural evidence, thermobarometry, and geochronology were usedto constrain the pressure-temperature-time (P—T—t)history of the southern portion of the Britt domain in the CentralGneiss Belt, Ontario Grenville Province. Typical metapeliticassemblages are quartz+plagioclase+ biotite + garnet + kyanite alkali feldspar sillimanite rutile ilmenite staurolite gahnite muscovite. Metatonalitic assemblages have quartz+ plagioclase + garnet biotite + hornblende + rutile + ilmenite.Metagabbroic rocks contain plagioclase + garnet + clinopyroxene+ biotite + ilmenite hornblende rutile quartz. Notabletextural features include overgrowths of sillimanite on kyaniteand of spinel on staurolite. The spinel overgrowths can be modeledby the breakdown of staurolite via the reaction Fe-staurolite= hercynite +kyanite + quartz + H₂O. The decomposition of stauroliteto her-cynite has a steep dP/dT slope and constrains the lateprograde path of a staurolite metapelite. Garnet—Al₂SiO₅—plagioclase—quartz(GASP) barometry applied to metapelitic garnets that preservecalcium zoning reveals a pressure decrease from 11 to 6 kbat an assumed temperature of 700 C. Garnet—plagioclase—ilmenite—rutile—quartzand garnet—clinopyroxene—plagioclase—quartzbarometry is in good agreement with pressures obtained withthe GASP barometer. Geochronologic data from garnet, allanite,and monazite in metapelitic rocks give ages that fall into twogroups, 1–4 Ga and 1.1 Ga, suggesting the presence ofat least two metamorphic events in the area. It is most reasonableto assign the 1.4 Ga age to the high-pressure data and the 1.1Ga age to the lower-pressure data. Collectively the P—T—tdata indicate a complex and protracted history rather than asingle cycle of burial and uplift for this part of the GrenvilleProvince.     

Petrology of thermally metamorphosed pelitic rocks in the Champawat Area,Kumaun Himalaya

In the Champawat area, Kumaun Himalaya, greenschist facies regionally metamorphosed rocksviz chlorite-phyllite and schist have been subjected to thermal metamorphism due to emplacement of batholithic granite/granodiorite body. As a consequence, biotite, garnet, andalusite, fibrolite, sillimanite and perthite minerals have formed in the contact rocks. The conspicuous absence of cordierite and staurolite reported from such aureole rocks is due to higher FeO/MgO ratio of the bulk rock composition in the former while the absence of staurolite is due to low Al₂O₃/FeO+MgO ratio in the schists. AFM diagram demonstrates that in muscovite-bearing schist, the bulk composition of chlorite- and cordierite-bearing rocks are restricted to low FeO/MgO side and thus the restricted occurrence of former and the absence of latter in the contact rocks of the area. This is further evident from the common occurrence of almandine-rich garnet in the rocks.