K2O FeO MgO Al2O3 SiO2 H2O Research Articles

Preservation of evidence for prograde metamorphism in ultrahigh‐temperature, high‐pressure kyanite‐bearing granulites, South Harris, Scotland

AbstractMineralogical and mineral chemical evidence for prograde metamorphism is rarely preserved in rocks that have reached ultrahigh‐temperature (UHT) conditions (>900 °C) because high diffusion and reaction rates erase evidence for earlier assemblages. The UHT, high‐pressure (HP) metasedimentary rocks of the Leverburgh belt of South Harris, Scotland, are unusual in that evidence for the prograde history is preserved, despite having reached temperatures of ∼955 °C or more. Two lithologies from the belt are investigated here and quantitatively modelled in the system NaO–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O: a garnet‐kyanite‐K‐feldspar‐quartz gneiss (XMg = 37, A/AFM = 0.41), and an orthopyroxene‐garnet‐kyanite‐K‐feldspar quartzite (XMg = 89 A/AFM = 0.68). The garnet‐kyanite gneiss contains garnet porphyroblasts that grew on the prograde path, and captured inclusion assemblages of biotite, sillimanite, plagioclase and quartz (<790 °C, <9.5 kbar). These porphyroblasts preserve spectacular calcium zonation features with an early growth pattern overgrown by high‐Ca rims formed during high‐P metamorphism in the kyanite stability field. In contrast, Fe‐Mg zonation in the same garnet porphyroblasts reflects retrograde re‐equilibration, as a result of the relatively faster diffusivity of these ions. Peak P–T are constrained by the occurrence of coexisting orthopyroxene and aluminosilicate in the quartzite. Orthopyroxene porphyroblasts [y(opx) = 0.17–0.22] contain sillimanite inclusions, indicative of maximum conditions of 955 ± 45 °C at 10.0 ± 1.5 kbar. Subsequently, orthopyroxene, kyanite, K‐feldspar and quartz developed in equilibrated textures, constraining the maximum pressure conditions to 12.5 ± 0.8 kbar at 905 ± 25 °C. P–T–X modelling reveals that the mineral assemblage orthopyroxene‐kyanite‐quartz is compositionally restricted to rocks of XMg > 84, consistent with its very rare occurrence in nature. The preservation of unusual high P–T mineral assemblages and chemical disequilibrium features in these UHT HP rocks is attributed to a rapid tectonometamorphic cycle involving arc subduction and terminating in exhumation.

Calculated Phase Relations in the System NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O) for High-Pressure Metapelites

Petrogenetic grids in the system NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O) and the subsystems NCKMASH and NCKFASH calculated with the software THERMOCALC 3.1 are presented for the P–T range 7–30 kbar and 450–680°C, for assemblages involving garnet, chloritoid, biotite, carpholite, talc, chlorite, kyanite, staurolite, paragonite, glaucophane, jadeite, omphacite, diopsidic pyroxene, plagioclase, zoisite and lawsonite, with phengite, quartz/coesite and H2O in excess. These grids, together with calculated compatibility diagrams and P–T and T–XCa and P–XCa pseudosections for different bulk-rock compositions, show that incorporation of Ca into the NKFMASH system leads to many of the NKFMASH invariant equilibria moving to lower pressure and/or lower temperature, which results, in most cases, in the stability of jadeite and garnet being enlarged, but in the reduction of stability of glaucophane, plagioclase and AFM phases. The effect of Ca on the stability of paragonite is dependent on mineral assemblage at different P–T conditions. The calculated NCKFMASH diagrams are powerful in delineating the phase equilibria and P–T conditions of natural pelitic assemblages. Moreover, contours of the calculated phengite Si isopleths in P–T and P–XCa pseudosections confirm that phengite barometry in NCKFMASH is strongly dependent on mineral assemblage.

Calculated phase equilibria in K2O‐FeO‐MgO‐Al2O3‐SiO2‐H2O for sapphirine‐quartz‐bearing mineral assemblages

AbstractSapphirine, coexisting with quartz, is an indicator mineral for ultrahigh‐temperature metamorphism in aluminous rock compositions. Here a new activity‐composition model for sapphirine is combined with the internally consistent thermodynamic dataset used by THERMOCALC, for calculations primarily in K2O‐FeO‐MgO‐Al2O3‐SiO2‐H2O (KFMASH). A discrepancy between published experimentally derived FMAS grids and our calculations is understood with reference to H2O. Published FMAS grids effectively represent constant aH2O sections, thereby limiting their detailed use for the interpretation of mineral reaction textures in compositions with differing H2O.For the calculated KFMASH univariant reaction grid, sapphirine + quartz assemblages occur at P–T in excess of 6–7 kbar and 1005 °C. Sapphirine compositions and composition ranges are consistent with natural examples. However, as many univariant equilibria are typically not ‘seen’ by a specific bulk composition, the univariant reaction grid may reveal little about the detailed topology of multi‐variant equilibria, and therefore is of limited use for interpreting the P–T evolution of mineral assemblages and reaction sequences. Calculated pseudosections, which quantify bulk composition and multi‐variant equilibria, predict experimentally determined KFMASH mineral assemblages with consistent topology, and also indicate that sapphirine stabilizes at increasingly higher pressure and temperature as XMg increases. Although coexisting sapphirine and quartz can occur in relatively iron‐rich rocks if the bulk chemistry is sufficiently aluminous, the P–T window of stability shrinks with decreasing XMg. An array of mineral assemblages and mineral reaction sequences from natural sapphirine + quartz and other rocks from Enderby Land, Antarctica, are reproducible with calculated pseudosections. That consistent phase diagram calculations involving sapphirine can be performed allows for a more thorough assessment of the metamorphic evolution of high‐temperature granulite facies terranes than was previously possible. The establishment of a a‐x model for sapphirine provides the basis for expansion to larger, more geologically realistic chemical systems (e.g. involving Fe3+).

Metamorphic evolution of the Georgetown Inlier, northeast Queensland, Australia; evidence for an accreted Palaeoproterozoic terrane?

AbstractMineral textures, coupled with thermodynamic modelling in the MnO–Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (MnNCKFMASH) model system, of mid‐amphibolite facies metapelites from the Georgetown Inlier, northeast Australia, point to the recording of two separate and unrelated metamorphic events. The first occurred contemporaneously with Palaeo‐ to Mesoproterozoic orogenesis and involved heating and burial to temperatures and pressures of approximately 600–650 °C and 6.0–7.0 kbar. Textural evidence for the up‐temperature (and pressure) prograde part of this path is inferred from the inclusion of garnet in biotite and staurolite. The second metamorphic event resulted in a low‐pressure thermal overprint that is equated with the advective addition of heat to the terrane via the emplacement of the Forsayth Batholith (c. 1550 Ma). This event is inferred from subsequent growth of andalusite and randomly orientated fibrolitic sillimanite after garnet, biotite and staurolite. This two stage metamorphic evolution, when coupled with a number of other distinct geological characteristics, suggests that the Georgetown Inlier is dissimilar to the other Australian Palaeoproterozoic terranes with which it is commonly correlated.

A mineral equilibria study of the hydrothermal alteration in mafic greenschist facies rocks at Kalgoorlie, Western Australia

AbstractThe influx of a H2O–CO2‐dominated fluid into actinolite‐bearing metabasic rocks during greenschist facies metamorphism in the Kalgoorlie area of Western Australia resulted in a zoned alteration halo around inferred fluid conduits that contain gold mineralisation. The alteration halo is divided into two outer zones, the chlorite zone and the carbonate zone, and an inner pyrite zone adjacent to the inferred fluid conduits. Reaction between the fluid and the protolith resulted in the breakdown of actinolite and the development of chlorite, dolomite, calcite and siderite. In addition, rocks in the pyrite zone developed muscovite‐bearing assemblages as a consequence of the introduction of potassium by the fluid. Mineral equilibria calculations undertaken using the computer software thermocalc in the model system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–CO2 show that mineral assemblages in the outer zones of the alteration halo are consistent with equilibrium of the protoliths with a fluid of composition XCO2 = CO2/(CO2 + H2O) = 0.1–0.25 for temperatures of 315–320 °C. The inner zone of the alteration halo reflect equilibrium with a fluid of composition XCO2≈ 0.25. Fluid‐rock buffering calculations show that the alteration halo is consistent with interaction with a single fluid composition and that the zoned structure of the halo reflects the volume of this fluid with which the rocks reacted. This fluid is likely to have also been the one responsible for the gold mineralisation at Kalgoorlie.

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Discerning the history of burial, residence at depth and exhumation of high grade metamorphic rocks from an orogen is essential to understanding crustal differentiation and orogenesis. Such high grade rocks are inferred to exist beneath the Yinchuan Basin, which is overlain by a thick covering of younger sediments, and is located at the inferred southwest boundary of the Paleoproterozoic Khondalite Belt in the northwestern North China Craton. The metamorphic basement sampled from a recently completed deep borehole in the Yinchuan Basin is migmatitic and contains an assemblage of garnet, biotite, sillimanite, plagioclase, quartz, minor K-feldspar and local occurrences of muscovite. Phase equilibrium modelling in the Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O system constrains the peak P–T conditions of anatexis to 6–10 kbar at 760–810 °C, followed by final crystallization at 4.5–5.5 kbar and 690–710 °C. Ti-in-zircon thermometry for the narrow metamorphic zircon rims provides a temperature range of 687–753 °C, demonstrating formation during retrogression to the solidus. NanoSIMS U–Pb analyses on the metamorphic overgrowths of zircon grains yields an upper intercept age of 1895 ± 36 Ma. Chronological and chemical analyses of monazite indicate irregular bright gray domains with relatively high Th and low Y and HREE contents developed during prograde metamorphism (1962 ± 8 Ma). Conversely, dark domains with low Th and high Y and HREE overgrew during retrograde cooling (1892 ± 14 Ma) that was synchronous with the development of metamorphic zircon rims. LA-ICP-MS U–Pb analyses of detrital zircons reveal that the metamorphic basement beneath the Yinchuan Basin has a sedimentary protolith of Paleoproterozoic age. The results directly confirm the existence of Paleoproterozoic basement beneath the Yinchuan Basin, and the well-constrained P–T–t path supports the involvement of the basement (as part of the western Khondalite Belt) in burial and exhumation processes during the 1.96–1.89 Ga period, during which anatexis occurred for ∼70 Ma.

Phase relations in high-pressure metapelites in the system KFMASH (K2O?FeO?MgO?Al2O3?SiO2?H2O) with application to natural rocks

Using a previously published, internally consistent thermodynamic dataset and updated models of activity–composition relations for solid solutions, petrogenetic grids in the model system KFMASH (K2O–FeO–MgO–Al2O3–SiO2–H2O) and the subsystems KMASH and KFASH have been calculated with the software THERMOCALC 3.1 in the P–T range 5–36 kbar and 400–810 °C, involving garnet, chloritoid, biotite, carpholite, talc, chlorite, staurolite and kyanite/sillimanite with phengite, quartz/coesite and H2O in excess. These grids, together with calculated AFM compatibility diagrams and pseudosections, are shown to be powerful tools for delineating the phase equilibria and P–T conditions of pelitic high-P assemblages for a variety of bulk compositions. The calculated equilibria and mineral compositions are in good agreement with petrological observation. The calculation indicates that the typical whiteschist assemblage kyanite–talc is restricted to the rocks with extremely high XMg values, decreasing XMg in a bulk composition favoring the stability of chloritoid and garnet. Also, the chloritoid–talc paragenesis is stable over 19–20 kbar in a temperature range of ca. 520–620 °C, being more petrologically important than the previously highlighted assemblage talc–phengite. Moreover, contours of the calculated Si isopleths in phengite in P–T and P–X pseudosections for different bulk compositions extend the experimentally derived phengite geobarometers to various KFMASH assemblages.

The metamorphic evolution of metapelitic granulites from Radok Lake, northern Prince Charles Mountains, east Antarctica; evidence for an anticlockwise P–T path

AbstractMineral textures in metapelitic granulites from the northern Prince Charles Mountains, coupled with thermodynamic modelling in the K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3 (KFMASHTO) model system, point to pressure increasing with increasing temperature on the prograde metamorphic path, followed by retrograde cooling (i.e. an anticlockwise P–T path). Textural evidence for the increasing temperature part of the path is given by the breakdown of garnet and biotite to form orthopyroxene and cordierite in sillimanite‐absent rocks, and through the break‐down of biotite and sillimanite to form spinel, cordierite and garnet in more aluminous assemblages. This is equated to the advective addition of heat from the regional emplacement of granitic and charnockitic magmas dated at c. 980 Ma. A subsequent increase in pressure, inferred from the break‐down of spinel and quartz to sillimanite, cordierite and garnet in aluminous rocks, is attributed to crustal thickening related to upright folding dated at 940–910 Ma. The terrane attained peak metamorphic temperatures of c. 880 °C at pressures of c. 6.0–6.5 kbar during this event. Subsequent cooling is inferred from the localised breakdown of cordierite and garnet to form biotite and sillimanite that developed in the latter stages of the same event. The textural observations described are interpreted via the application of P–T and P–T–X pseudosections. The latter show that most rock compositions preserve only fragments of the overall P–T path; a result of different rock compositions undergoing mineral assemblage changes, or changes in mineral modal abundance, on different sections of the P–T path. The results also suggest that partial melting during granulite facies metamorphism, coupled with melt loss and dehydration, initiated a switch from pervasive ductile, to discrete ductile/brittle deformation, during retrograde cooling.

The interpretation of reaction textures in Fe‐rich metapelitic granulites of the Musgrave Block, central Australia: constraints from mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

AbstractFe‐rich metapelitic granulites of the Musgrave Block, central Australia, contain several symplectic and coronal reaction textures that post‐date a peak S2 metamorphic assemblage involving garnet, sillimanite, spinel, ilmenite, K‐feldspar and quartz. The earliest reaction textures involve spinel‐ and quartz‐bearing symplectites that enclose garnet and to a lesser extent sillimanite. The symplectic spinel and quartz are in places separated by later garnet and/or sillimanite coronas. The metamorphic effects of a later, D3, event are restricted to zones of moderate to high strain where a metamorphic assemblage of garnet, sillimanite, K‐feldspar, magnetite, ilmenite, quartz and biotite is preserved. Quantitative mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3 (KFMASHTO) using Thermocalc 3.0 and the accompanying internally consistent dataset provide important constraints on the influence of TiO2 and Fe2O3 on biotite‐bearing and spinel‐bearing equilibria, respectively. Biotite‐bearing equilibria are shifted to higher temperatures and spinel‐bearing equilibria to higher pressures and lower temperatures in comparison to the equivalent equilibria in K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH). The sequence of reaction textures involving spinel is consistent with a D2 P–T path that involved a small amount of decompression followed predominantly by cooling within a single mineral assemblage stability field. Thus, the reaction textures reflect changes in modal proportions within an equilibrium assemblage rather than the crossing of a univariant reaction. The D3 metamorphic assemblage is consistent with lower temperatures than those inferred for D2.

Thermodynamic modelling of the reaction muscovite+cordierite→Al2SiO5+biotite+quartz+ H2O: constraints from natural assemblages and implications for the metapelitic petrogenetic grid

AbstractThe reaction muscovite+cordierite→biotite+Al2SiO5 +quartz+H2O is of considerable importance in the low pressure metamorphism of pelitic rocks: (1) its operation is implied in the widespread assemblage Ms + Crd +And± Sil + Bt + Qtz, a common mineral assemblage in contact aureoles and low pressure regional terranes; (2) it is potentially an important equilibrium for pressure estimation in low pressure assemblages lacking garnet; and (3) it has been used to distinguish between clockwise and anticlockwise P–T paths in low pressure metamorphic settings. Experiments and thermodynamic databases provide conflicting constraints on the slope and position of the reaction, with most thermodynamic databases predicting a positive slope for the reaction. Evidence from mineral assemblages and microtextures from a large number of natural prograde sequences, in particular contact aureoles, is most consistent with a negative slope (andalusite and/or sillimanite occurs upgrade of, and may show evidence for replacement of, cordierite). Mineral compositional trends as a function of grade are variable but taken as a whole are more consistent with a negative slope than a positive slope. Thermodynamic modelling of reaction 1 and associated equilibria results in a low pressure metapelitic petrogenetic grid in the system K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH) which satisfies most of the natural and experimental constraints. Contouring of the Fe–Mg divariant interval represented by reaction 1 allows for pressure estimation in garnet‐absent andalusite+cordierite‐bearing schists and hornfelses. The revised topology of reaction 1 allows for improved analysis of P–T paths from mineral assemblage sequences and microtextures in the same rocks.

A counterclockwise P–T path for anatectic pelites, south-central Massachusetts

Pelitic gneisses, cordierite ± garnet-bearing pegmatites and leucocratic garnetiferous melt segregations (garnet leucosomes) from within the Acadian (360 Ma) granulite-facies of south-central Massachusetts were investigated to further understand the counterclockwise P–T evolution of the Merrimack synclinorium. The rocks were investigated with specific reference to phase equilibria in the system Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O (NaKFMASH) in the context of the petrogenetic grid proposed by Spear et al. (1999). An early low pressure history is suggested by the widespread occurrence of sillimanite pseudomorphs after andalusite as well as abundant matrix K-feldspar in both gneisses and partial melts. Biotite-consuming, fluid-absent melting of pelitic gneisses produced cordierite ± garnet-bearing pegmatites and garnet ± cordierite leucosomes at conditions of 700–750 °C and 4–5 kbar. The major reaction is Qtz + Sil + Bt = Kfs + Crd + Grt + Melt (KFMASH). Magnesian gneisses melted to form cordierite ± garnet-bearing pegmatites and iron-richer gneisses melted to form garnet ± cordierite-bearing leucosomes. Previous studies of the quartz ± plagioclase–K-feldspar–sillimanite–biotite ± garnet ± cordierite assemblages in the gneisses suggest peak metamorphism at 700–750 °C and 6–7 kbar. Retrograde reactions are essentially the reverse of prograde reactions and produced intergrowths of pale green biotite + sillimanite + quartz on cordierite and/or garnet grain boundaries within the melt products as well as late muscovite. Water dissolved in the melt during prograde metamorphism was available for retrogression as the melts cooled. The rocks investigated record part of a counterclockwise P–T path.

Inference of a detailed P–T path from P–T pseudosections using metapelitic rocks of variable composition from a single outcrop, Shackleton Range, Antarctica

AbstractGenerally, P–T pseudosections for reduced compositional systems, such as K2O–FeO–MgO–Al2O3–SiO2–H2O, Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O and MnO–K2O–FeO–MgO–Al2O3–SiO2–H2O, are well suited for inferring detailed P–T paths, comparing mineral assemblages observed in natural rocks with those calculated. Examples are provided by P–T paths inferred for four metapelitic samples from a 1 m2 wide outcrop of the Herbert Mountains in the Shackleton Range, Antarctica. The method works well if the bulk composition used is reconstituted from average mineral modes and mineral compositions (AMC) or when X‐ray fluorescence (XRF) data are corrected for Al2O3 and FeO. A plagioclase correction is suitable for Al2O3. Correction for FeO is dependent on additional microscopic observations, e.g. the kind and amount of opaque minerals. In some cases, all iron can be treated as FeOtot, whereas in others a magnetite or hematite correction yields much better results. Comparison between calculated and observed mineral modes and mineral compositions shows that the AMC bulk composition is best suited to the interpretation of rock textures using P–T pseudosections, whereas corrected XRF data yield good results only when the investigated sample has few opaque minerals. The results indicate that metapelitic rocks from the Herbert Mountains of the Northern Shackleton Range underwent a prograde P–T evolution from about 600 °C/5.5 kbar to 660 °C/7 kbar, followed by nearly adiabatic cooling to about 600 °C at 4.5 kbar.

Cretaceous evolution of a metamorphic core complex, the Veporic unit, Western Carpathians (Slovakia): P–T conditions and in situ40Ar/39Ar UV laser probe dating of metapelites

AbstractAlpine metamorphism, related to the development of a metamorphic core complex during Cretaceous orogenic events, has been recognized in the Veporic unit, Western Carpathians (Slovakia). Three metamorphic zones have been distinguished in the metapelites: 1, chloritoid + chlorite + garnet; 2, garnet + staurolite + chlorite; 3, staurolite + biotite + kyanite. The isograds separating the metamorphic zones have been modelled by discontinuous reactions in the system K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH). The isograds are roughly parallel to the north‐east‐dipping foliation related to extensional updoming along low‐angle normal faults. Thermobarometric data document increasing P–T conditions from c. 500 °C and 7–8 kbar to c. 620 °C and 9–10 kbar, reflecting a coherent metamorphic field gradient from greenschist to middle amphibolite facies. 40Ar/39Ar data obtained by high spatial resolution in situ ultraviolet (UV) laser ablation of white micas from the rock slabs constrain the timing of cooling and exhumation in the Late Cretaceous. Mean dates are between 77 and 72 Ma; however, individual white mica grains record a range of apparent 40Ar/39Ar ages indicating that cooling below the blocking temperature for argon diffusion was not instantaneous. The reconstructed metamorphic P–T–t path is ‘clockwise’, reflecting post‐burial decompression and cooling during a single Alpine orogenic cycle. The presented data suggest that the Veporic unit evolved as a metamorphic core complex during the Cretaceous growth of the Western Carpathian orogenic wedge. Metamorphism was related to collisional crustal shortening and stacking, following closure of the Meliata Ocean. Exhumation was accomplished by synorogenic (orogen‐parallel) extension and unroofing in an overall compressive regime.

A petrogenetic grid for aluminous granulite facies metapelites in the KFMASH system

AbstractDue to the retrograde cation exchange problems experienced by conventional geothermobarometers above their closure temperatures, petrogenetic grids are a potentially powerful alternative to unravelling the P–T evolution of ultrahigh‐T granulite terranes. A new qualitative KFMASH (K2O–FeO–MgO–Al2O3–SiO2–H2O) petrogenetic grid for Mg–Al rich metapelites containing K‐feldspar, sillimanite and quartzofeldspathic melt that successfully accounts for the majority of assemblages composed of variations of sapphirine, spinel, garnet, orthopyroxene, cordierite, biotite and quartz is developed. Univariant reactions are predicted utilizing a newly derived ‘melt projection’ and these reactions are entirely consistent with algebraically calculated reaction coefficients obtained using a set of standard phase compositions. Based upon observations of commonly associated mineral assemblages in natural lithologies the [Spr, Spl], [Qtz, Spl], [Bt, Spl], [Opx, Spr], [Opx, Qtz] and [Bt, Opx] invariant points are assumed to be stable, whilst the [Grt, Spr], [Grt, Qtz], [Spr, Qtz] and [Crd, Qtz] are assumed to be metastable. Biotite‐bearing assemblages are confined to the lowest temperatures, and sapphirine + quartz to the highest temperatures. Orthopyroxene + sillimanite ± quartz assemblages are confined to the highest pressures, whilst spinel‐bearing assemblages are stabilized by lower pressures. The alternative choice of invariant point stability leads to significant differences between this grid and previously proposed topologies. Spinel cannot be stable along with the orthopyroxene and sillimanite assemblage as previously proposed. Further, more subtle differences in topology result from the treatment of H2O in the chemographic projection used to deduce univariant reactions, and projecting from a water‐bearing quartzofeldspathic melt does not yield the same reaction coefficients as projection from H2O. The new grid allows reinterpretation of previously proposed evolutionary P–T paths for Mg–Al rich granulites from the Napier Complex and Rauer Group, East Antarctica, and In Ouzzal, Algeria.

Partial melting in the Inzie Head gneisses: the role of water and a petrogenetic grid in KFMASH applicable to anatectic pelitic migmatites

AbstractA sequence of prograde isograds is recognized within the Dalradian Inzie Head gneisses where pelitic compositions have undergone variable degrees of partial melting via incongruent melting reactions consuming biotite. Three leucosome types are identified. At the lowest grades, granitic leucosomes containing porphyroblasts of cordierite (CRD‐melt) are abundant. At intermediate grades, CRD‐melt mingles with garnetiferous leucosomes (GT‐melt). At the highest grades, CRD‐melt coexists with orthopyroxene‐bearing leucosomes (OPX‐melt), while garnet is conspicuously absent. The prograde metamorphic field gradient is constrained to pressures of 2–3 kbar below the CRD‐melt isograd, and no greater than 4.5 kbar at the highest grade around Inzie Head.A petrogenetic grid, calculated using thermocalc, is presented for the K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH) system for the phases orthopyroxene, garnet, cordierite, biotite, sillimanite, H2O and melt with quartz and K‐feldspar in excess. For the implied field gradient, the reaction sequence predicted by the grid is consistent with the successive prograde development of each leucosome type. Compatibility diagrams suggest that, as anatexis proceeded, bulk compositions may have been displaced towards higher MgO content by the removal of (relatively) ferroan granitic leucosome. An isobaric (P = 4 kbar) T–aH2O diagram shows that premigmatization fluids must have been water‐rich (aH2O > 0.85) and suggests that, following the formation of small volumes of CRD‐melt, the system became fluid‐absent and melting reactions buffered aH2O to lower values as temperatures rose. GT‐ and OPX‐melt formed by fluid‐absent melting reactions, but a maximum of 7–11% CRD‐melt fraction can be generated under fluid‐absent conditions, much less than the large volumes observed in the field. There is strong evidence that the CRD‐melt leucosomes could not have been derived by buoyantly aided upwards migration from levels beneath the migmatites. Their formation therefore required a significant influx of H2O‐rich fluid, but in a quantity insufficient to have exhausted the buffering capacity of the solid assemblage plus melt. Fluid : rock ratios cannot have exceeded 1 : 30. The fluid was channelled through a regionally extensive shear zone network following melt‐induced failure. Such an influx of fluid at such depths has obvious consequences for localized crustal magma production and possibly for cordierite‐bearing granitoids in general.

The effect of TiO2 and Fe2O3 on metapelitic assemblages at greenschist and amphibolite facies conditions: mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

Mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3 (KFMASHTO) using thermocalc and its internally consistent thermodynamic dataset constrain the effect of TiO2 and Fe2O3 on greenschist and amphibolite facies mineral equilibria in metapelites. The end‐member data and activity–composition relationships for biotite and chloritoid, calibrated with natural rock data, and activity–composition data for garnet, calibrated using experimental data, provide new constraints on the effects of TiO2 and Fe2O3 on the stability of these minerals. Thermodynamic models for ilmenite–hematite and magnetite–ulvospinel solid solutions accounting for order–disorder in these phases allow the distribution of TiO2 and Fe2O3 between oxide minerals and silicate minerals to be calculated. The calculations indicate that small to moderate amounts of TiO2 and Fe2O3 in typical metapelitic bulk compositions have little effect on silicate mineral equilibria in metapelites at greenschist to amphibolite facies, compared with those calculated in KFMASH. The addition of large amounts of TiO2 to typical pelitic bulk compositions has little effect on the stability of silicate assemblages; in contrast, rocks rich in Fe2O3 develop a markedly different metamorphic succession from that of common Barrovian sequences. In particular, Fe2O3‐rich metapelites show a marked reduction in the stability fields of staurolite and garnet to higher pressures, in comparison to those predicted by KFMASH grids.

Experimental Aspects of UHP Metamorphism in Pelitic Systems

Recent experimental studies have addressed mineral phases that can be expected to occur in metasedimentary rocks at ultrahigh-pressure conditions. These studies are based mainly on the P-T location of reaction curves using reversals and the determination of compressibility data as well as the compositional change of solid solution phases with P and T in fixed mineral assemblages. In the system SiO2, the reactions bounding the coesite stability field as well as the rheology of coesitites and the kinetics of the coesite-quartz transformation are discussed. In the system Al2O3-SiO2-H2O, the stability relations of kyanite, piezotite, OH-topaz, and diaspore are reviewed. In MgO-Al2O3-SiO2-H2O, investigations on the enstatite polymorphs, talc, the 10 Å phase, MgMgAl-pumpellyite, and pyrope, which can coexist with coesite, are reported. Experimental studies on Mg-chloritoid, Mg-staurolite, and chlorite also are reviewed. In FeO-Al2O3-SiO2-H2O, chloritoid, staurolite, and ferrosilite are addressed. In K2O-Al2O3-SiO2-H2O, K-feldspar, hollandite-type KAlSi3O8, K-cymrite, kalsilite, wadeite-type K2Si4O9, and the KAlSi2O6 component in clinopyroxenes are considered. In K2O-FeO-MgO-Al2O3-SiO2-H2O (KFMASH), studies on various white and dark micas are mainly reported, but also information on stilpnomelane and zussmanite is given. Subsequently, various borates, borosilicates, and phosphates—most of them are rich in Al and therefore have the possibility of occurring in UHP metapelites—are addressed. Finally, aragonite, dolomite, and magnesite are considered as well. At the end of the paper a summary is presented that points to the necessity of continuing with various kinds of studies related to the determination of thermodynamic properties of end-member phases and solid solution series. Such studies will enable us to elucidate the stable topology of phase relations in KFMASH and related systems. In addition, such thermodynamic data are needed for more reliable geothermobarometry.

Phase relations and P–T conditions of the Ryoke pelitic and psammitic metamorphic rocks in the Ina district, Central Japan

The Ina district of the Ryoke Belt is divided into two mineral zones, based on the mineral parageneses of the pelitic and psammitic rocks at the peak metamorphism. A biotite–muscovite zone (quartz + plagioclase + biotite + muscovite with or without K‐feldspar) constitutes the northwestern part, and a biotite–cordierite–K‐feldspar zone (quartz + plagioclase + biotite + cordierite + K‐feldspar) comprises the central to southern and eastern parts. The isograd reaction between two mineral zones is defined by a divariant reaction: Mg‐rich biotite + muscovite + quartz = Fe‐rich biotite + cordierite + K‐feldspar + H2O (1), which, in the K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH) system, occurs at ∼ 590 °C at 0.2 GPa and 660 °C at 0.4 GPa. Fibrolite accompanied by andalusite porphyroblasts in aluminous pelitic rocks of the biotite–muscovite zone and the low‐grade part of the biotite–cordierite–K‐feldspar zone, suggests that sillimanite was the stable aluminosilicate at the peak metamorphic condition throughout the area. In the high‐grade part of the biotite–cordierite–K‐feldspar zone, fibrolite mostly occurs as inclusions in cordierite or in plagioclase. The phase relations and the compositional zoning of plagioclase in relation to fibrolite inclusions suggest that fibrolite was formed under relatively high‐pressure conditions, and that partial melting took place.

Phase equilibria and the pressure-temperature path of the highest-grade Ryoke metamorphic rocks in the Yanai district, SW Japan

The garnet-cordierite zone, the highest-grade zone of the Ryoke metamorphic rocks in the Yanai district, SW Japan, is defined by the coexistence of garnet and cordierite in pelitic rocks. Three assemblages in this zone are studied in detail, i.e. spinel + cordierite + biotite, garnet + cordierite + biotite and garnet + biotite, all of which contain quartz, K-feldspar and plagioclase. The Mg/(Fe + Mg) in the coexisting minerals decreases in the following order: cordierite, biotite, garnet and spinel. Two facts described below are inconsistent with the paragenetic relation in the K2OFeOMgOAl2O3SiO2H2O (KFMASH) system in terms of an isophysical variation. First, garnet and biotite in the last assemblage have Mg/(Fe + Mg) higher than those in the second. Second, the first two assemblages are described by the reaction, $$$$

Singularities in NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O)

A new petrogenetic grid is presented for the system NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O), in which Ca is incorporated in garnet, and CaAlNa−1Si−1 solid solution is considered for both the plagioclase and white‐mica structures. A compatibility diagram for plagioclase‐bearing metapelitic assemblages within the NCKFMASH system also has been derived. A dominant feature of the NCKFMASH grid is the singularities and associated singular reactions which occur along plagioclase+margarite‐ and plagioclase+paragonite‐bearing univariant equilibria. The singularities represent compositional coplanarities which occur in response to the CaAlNa−1Si−1 substitution occurring at different rates in plagioclase and white‐mica. This is controlled by a fundamental difference in the mixing within the two mineral structures. The singularities give rise to a number of intriguing phase diagram features, including azeotropes. From the results presented here, it is predicted that the occurrence of margarite and paragonite in pelitic rocks is controlled by equilibria related to the singularities. The presence of these white‐micas is strongly dependent upon bulk composition, and plagioclase‐bearing, margarite/paragonite‐free assemblages, typical of Barrovian‐type terranes, are predicted for bulk compositions of Mg/(Mg+Fe)≈0.4 and Ca/(Ca+Na)≈0.4 at for example 5.5 kbar.