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.     

Metamorphism of pelites in NKFMASH – a new petrogenetic grid with implications for the preservation of high-pressure mineral assemblages during exhumation

A petrogenetic grid for metapelites in the system NKFMASH is presented. The P–T range is investigated in three sections: (1) The high‐ and ultrahigh‐pressure range is discussed in the system NFMASH because phengite is the only stable potassic phase. (2) The transition region is characterised by four NKFMASH‐invariant points that separate high‐pressure glaucophane‐bearing from medium‐pressure biotite‐bearing metapelites. (3) The medium‐pressure range contains the fifth NKFMASH‐invariant point. The univariant reactions of this point terminate the stability range of paragonite, which breaks down to form staurolite or kyanite and plagioclase during decompression and/or heating. As the growth of albitic plagioclase by decomposition of paragonite via continuous reactions may be conspicuous already before these staurolite‐ or kyanite‐producing reactions are reached, such albite porphyroblast schists are typical indicators of a former high‐pressure metamorphic history. Considering the preservation of high‐pressure metapelitic assemblages, those crossing the NKFMASH‐transition region during exhumation commonly dehydrate and preservation is unlikely. Three types of metapelites have a fairly good survival potential: (1) low‐temperature metapelites (up to c. 540 °C) with an exhumation path back into the chlorite + albite stability field, (2) assemblages with chloritoid + glaucophane, and (3) the relatively high‐temperature glaucophane + kyanite and jadeite + kyanite bearing parageneses, that are relatively dry at the onset of exhumation. A comparison with data from the literature shows that these rock types are the most abundant in nature.     

Experimental study of metamorphic reactions and dehydration processes at the blueschist–eclogite transition during warm subduction

The transition between blueschist and eclogite plays an important role in subduction zones via dehydration and densification processes in descending oceanic slabs. There are a number of previous petrological studies describing potential mineral reactions taking place at the transition. An experimental determination of such reactions could help constrain the pressure–temperature conditions of the transition as well as the processes of dehydration. However, previous experimental contributions have focused on the stability of spontaneously formed hydrous minerals in basaltic compositions rather than on reactions among already formed blueschist facies minerals. Therefore, this study conducted three groups of experiments to explore the metamorphic reactions among blueschist facies minerals at conditions corresponding to warm subduction, where faster reaction rates are possible on the time scale of laboratory experiments. The first group of experiments was to establish experimental reversals of the reaction glaucophane+paragonite to jadeite+pyrope+quartz+H₂O over the range of 2.2–3.5 GPa and 650–820°C. This reaction has long been treated as key to the blueschist–eclogite transition. However, only the growth of glaucophane+paragonite was observed at the intersectional stability field of both paragonite and jadeite+quartz, confirming thermodynamic calculations that the reaction is not stable in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O. The second set of experiments involved unreversed experiments using glaucophane+zoisite ±quartz in low‐Fe and Ca‐rich systems and were run at 1.8–2.4 GPa and 600–780°C. These produced omphacite+paragonite/kyanite+H₂O accompanied by compositional shifts in the sodium amphibole, glaucophane, towards sodium–calcium amphiboles such as winchite (?(CaNa)(Mg₄Al)Si₈O₂₂(OH)₂) and barroisite (?(CaNa)(Mg₃Al₂)(AlSi₇)O₂₂(OH)₂). This suggests that a two‐step dehydration occurs, first involving the breakdown of glaucophane+zoisite towards a paragonite‐bearing assemblage, then the breakdown of paragonite to release H₂O. It also indicates that sodium–calcium amphibole can coexist with eclogite phases, thereby extending the thermal stability of amphibole to greater subduction zone depths. The third set of experiments was an experimental investigation at 2.0–2.4 GPa and 630–850°C involving a high‐Fe (Fe#=Fe_total/(Fe_total+Mg)≈0.36) natural glaucophane, synthetic paragonite and their eclogite‐forming reaction products. The results indicated that garnet and omphacite grew over most of these pressure–temperature conditions, which demonstrates the importance of Fe‐rich glaucophane in forming the key eclogite assemblage of garnet+omphacite, even under warm subduction zone conditions. Based on the experiments of this study, reaction between glaucophane+zoisite is instrumental in controlling dehydration processes at the blueschist–eclogite transition during warm subduction.     

Dehydration of metapelites during high‐P metamorphism: The coupling between fluid sources and fluid sinks

Polymetamorphic metapelites and embedded eclogites share a complex, episodic interplay of dehydration and fluid infiltration at the eclogite type‐locality (Saualpe–Koralpe, Eastern Alps, Austria). The metapelites inherited a fluid content (i.e. mineral‐bound OH expressed in terms of mol.% H₂O) of ～6–7 mol.% H₂O from high‐T–low‐P metamorphism experienced during the Permian. At or near P_max of the subsequent Eoalpine event (～20 kbar and 680^°C), the breakdown of paragonite to Na‐rich clinopyroxene and kyanite in metapelites released a discrete pulse of hydrous fluid. Prior to the dehydration event, the rocks were largely fluid absent, allowing only limited re‐equilibration during the prograde Eoalpine evolution. Similarly, Permian‐aged gabbros have persisted metastably due to the absence of a catalyst prior to fluid‐induced re‐equilibration. The fluid triggered partial to complete eclogitization along a fluid infiltration front partially preserved in metagabbro. Near‐isothermal decompression to ～7.5–10 kbar and 670–690°C took place under fluid‐absent conditions. After decompression, a second breakdown of phengitic white mica and garnet produced muscovite, biotite, plagioclase and ～0.1–0.7 mol.% H₂O that enhanced extensive fluid‐aided re‐equilibration of the metapelites. Potential relicts of high‐P assemblages were largely obliterated and replaced by the recurrent amphibolite facies assemblage garnet+biotite+staurolite+kyanite+muscovite+plagioclase+ilmenite+quartz. The hydrous fluid originating from the metapelites infiltrated the embedded eclogites at these P–T conditions and induced the local breakdown of the peak assemblage omphacite and garnet to fine‐grained symplectites of diopside and plagioclase. Further fluid infiltration led to the formation of hornblende–quartz poikiloblasts at the expense of the symplectites. The metapelites re‐equilibrated until the growth of retrograde staurolite consumed any remaining free fluid, thereby terminating the process. Further re‐equilibration is inhibited by both the lack of a catalytic fluid and H₂O as a reactant essential for rehydration reactions. The interplay between fluid sources and fluid sinks describes a closed cycle for the rocks at the eclogite type‐locality. Final, near‐isobaric cooling is indicated by a slight increase of X_Fe in garnet rims. Post‐decompression dehydration and fluid‐aided re‐equilibration arrested by the introduction of staurolite might explain the apparently homogeneous retrogression conditions as well as the notorious absence of diagnostic high‐P assemblages in metapelites at the eclogite type‐locality.     

Phase relations in andalusite-sillimanite type Fe-rich metapelites: Tono contact metamorphic aureole, northeast Japan

Mineral assemblages in metapelites of the contact aureole of the Tono granodiorite mass, northeast Japan, change systematically during progressive metamorphism along an isobaric path at 2-3 kbar. The bulk rock compositions of metapelites are aluminous with A' values on an AFM projection larger than that of the chlorite join. The metapelites commonly contain paragonite in the low-grade zone. With increasing temperatures, andalusite is formed by the breakdown of paragonite. The importance of pyrophyllite as a source of Al₂SiO₅ polymorphs is limited in typical pelitic rocks.
The most common type of metapelite in the study area has FeO/(FeO + MgO) = 0.5–0.6, and develops assemblages involving chlorite, andalusite, biotite, cordierite, K-feldspar, sillimanite and almandine, with paragenetic changes similar to other andalusite-sillimanite type aureoles. Rocks with FeO/(FeO + MgO) > 0.8 progressively develop chloritoid-bearing assemblages from Bt-Chl-Cld, And-Bt-Cld, to And-Bt at temperatures between the breakdown of paragonite and the appearance of cordierite in the more common pelitic rocks in the aureole. The paragenetic relations are explained by a KFMASH univariant reaction of Chl + Cld = And + Bt located to the low-temperature side of the formation of cordierite by the terminal equilibrium of chlorite. A P-T model depicting the relative stability of chloritoid and staurolite at low- and medium-pressure conditions, respectively, is proposed, based on the derived location of the Chl + Cld = And + Bt reaction combined with the theoretical phase relations among biotite, chlorite, chloritoid, garnet and staurolite.     

Metamorphic evolution of kyanite–staurolite-bearing epidote–amphibolite from the Early Palaeozoic Oeyama belt, SW Japan

Early Palaeozoic kyanite–staurolite‐bearing epidote–amphibolites including foliated epidote–amphibolite (FEA), and nonfoliated leucocratic or melanocratic metagabbros (LMG, MMG), occur in the Fuko Pass metacumulate unit (FPM) of the Oeyama belt, SW Japan. Microtextural relationships and mineral chemistry define three metamorphic stages: relict granulite facies metamorphism (M1), high‐P (HP) epidote–amphibolite facies metamorphism (M2), and retrogression (M3). M1 is preserved as relict Al‐rich diopside (up to 8.5 wt.% Al₂O₃) and pseudomorphs after spinel and plagioclase in the MMG, suggesting a medium‐P granulite facies condition (0.8–1.3 GPa at > 850 °C). An unusually low‐variance M2 assemblage, Hbl + Czo + Ky ± St + Pg + Rt ± Ab ± Crn, occurs in the matrix of all rock types. The presence of relict plagioclase inclusions in M2 kyanite associated with clinozoisite indicates a hydration reaction to form the kyanite‐bearing M2 assemblage during cooling. The corundum‐bearing phase equilibria constrain a qualitative metamorphic P–T condition of 1.1–1.9 GPa at 550–800 °C for M2. The M2 minerals were locally replaced by M3 margarite, paragonite, plagioclase and/or chlorite. The breakdown of M2 kyanite to produce the M3 assemblage at < 0.5 GPa and 450–500 °C suggests a greenschist facies overprint during decompression. The P–T evolution of the FPM may represent subduction of an oceanic plateau with a granulite facies lower crust and subsequent exhumation in a Pacific‐type orogen.     

Calculated stabilities of sodic phases in the Sambagawa metapelites and their implications

Pressure (P)–temperature (T) pseudosection analyses were carried out on metapelites from Sambagawa belt by using Perple_X 07 so as to determine mineral equilibria and the stability of sodic phases, in the model system MnO–Na₂O–K₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–(CO₂) under high‐pressure (HP) conditions (0.5–2.5 GPa/400–600 °C). A pressure–X_NA [=Na/(Na+Al–2K–1.5Ca)] pseudosection at 500 °C is also calculated to examine the effect of Na/Al value of the bulk‐rock composition on the stabilities of sodic minerals. The bulk‐rock compositions of Sambagawa metapelite are variable in X_NA values. The calculation results of stable assemblages in metapelites under the blueschist and eclogite facies conditions indicate that: (i) paragonite and glaucophane are stable throughout the wide X_NA range of bulk‐rock compositions of host rocks; (ii) stable P–T conditions of sodic pyroxene enlarge with increasing X_NA value; and (iii) the stability field of paragonite enlarges with the presence of CO₂ in the metamorphic fluid. The suggested wide stability of paragonite in metapelites and the relationships between the stability of sodic pyroxene and the bulk‐rock compositions explain the reasons why (i) the occurrence of omphacite in metapelites from several subduction‐related terranes is rare; and (ii) paragonite commonly occurs as inclusions in garnet of metapelites from the Besshi region of the Sambagawa belt. Paragonite is an important sodic phase of HP metapelites, and a combination of paragonite and quartz with high residual pressure included in garnet may be a useful indicator to verify the evidence for the eclogite facies metamorphism recorded in metapelites.     

Deformation, mass transfer and mineral reactions in an eclogite facies shear zone in a polymetamorphic metapelite (Monte Rosa nappe, western Alps)

This study analyses the mineralogical and chemical transformations associated with an Alpine shear zone in polymetamorphic metapelites from the Monte Rosa nappe in the upper Val Loranco (N‐Italy). In the shear zone, the pre‐Alpine assemblage plagioclase + biotite + kyanite is replaced by the assemblage garnet + phengite + paragonite at eclogite facies conditions of about 650 °C at 12.5 kbar. Outside the shear zone, only minute progress of the same metamorphic reaction was attained during the Alpine metamorphic overprint and the pre‐Alpine mineral assemblage is largely preserved. Textures of incomplete reaction, such as garnet rims at former grain contacts between pre‐existing plagioclase and biotite, are preserved in the country rocks of the shear zone. Reaction textures and phase relations indicate that the Alpine metamorphic overprint occurred under largely anhydrous conditions in low strain domains. In contrast, the mineralogical changes and phase equilibrium diagrams indicate water saturation within the Alpine shear zones. Shear zone formation occurred at approximately constant volume but was associated with substantial gains in silica and losses in aluminium and potassium. Changes in mineral modes associated with chemical alteration and progressive deformation indicate that plagioclase, biotite and kyanite were not only consumed in the course of the garnet‐and phengite‐producing reactions, but were also dissolved ‘congruently’ during shear zone formation. A large fraction of the silica liberated by plagioclase, biotite and kyanite dissolution was immediately re‐precipitated to form quartz, but the dissolved aluminium‐ and potassium‐bearing species appear to have been stable in solution and were removed via the pore fluid. The reaction causes the localization of deformation by producing fine‐grained white mica, which forms a mechanically weak aggregate.     

Separate or shared metamorphic histories of eclogites and surrounding rocks? An example from the Bohemian Massif

Eclogite boudins occur within an orthogneiss sheet enclosed in a Barrovian metapelite‐dominated volcano‐sedimentary sequence within the Velké Vrbno unit, NE Bohemian Massif. A metamorphic and lithological break defines the base of the eclogite‐bearing orthogneiss nappe, with a structurally lower sequence without eclogite exposed in a tectonic window. The typical assemblage of the structurally upper metapelites is garnet–staurolite–kyanite–biotite–plagioclase–muscovite–quartz–ilmenite ± rutile ± silli‐manite and prograde‐zoned garnet includes chloritoid–chlorite–paragonite–margarite, staurolite–chlorite–paragonite–margarite and kyanite–chlorite–rutile. In pseudosection modelling in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) using THERMOCALC, the prograde path crosses the discontinuous reaction chloritoid + margarite = chlorite + garnet + staurolite + paragonite (with muscovite + quartz + H₂O) at 9.5 kbar and 570 °C and the metamorphic peak is reached at 11 kbar and 640 °C. Decompression through about 7 kbar is indicated by sillimanite and biotite growing at the expense of garnet. In the tectonic window, the structurally lower metapelites (garnet–staurolite–biotite–muscovite–quartz ± plagioclase ± sillimanite ± kyanite) and amphibolites (garnet–amphibole–plagioclase ± epidote) indicate a metamorphic peak of 10 kbar at 620 °C and 11 kbar and 610–660 °C, respectively, that is consistent with the other metapelites. The eclogites are composed of garnet, omphacite relicts (jadeite = 33%) within plagioclase–clinopyroxene symplectites, epidote and late amphibole–plagioclase domains. Garnet commonly includes rutile–quartz–epidote ± clinopyroxene (jadeite = 43%) ± magnetite ± amphibole and its growth zoning is compatible in the pseudosection with burial under H₂O‐undersaturated conditions to 18 kbar and 680 °C. Plagioclase + amphibole replaces garnet within foliated boudin margins and results in the assemblage epidote–amphibole–plagioclase indicating that decompression occurred under decreasing temperature into garnet‐free epidote–amphibolite facies conditions. The prograde path of eclogites and metapelites up to the metamorphic peak cannot be shared, being along different geothermal gradients, of about 11 and 17 °C km^?1, respectively, to metamorphic pressure peaks that are 6–7 kbar apart. The eclogite–orthogneiss sheet docked with metapelites at about 11 kbar and 650 °C, and from this depth the exhumation of the pile is shared.     

Bulk chemical control on metamorphic monazite growth in pelitic schists and implications for U–Pb age data

Several petrographic studies have linked accessory monazite growth in pelitic schist to metamorphic reactions involving major rock‐forming minerals, but little attention has been paid to the control that bulk composition might have on these reactions. In this study we use chemographic projections and pseudosections to argue that discrepant monazite ages from the Mount Barren Group of the Albany–Fraser Orogen, Western Australia, reflect differing bulk compositions. A new Sensitive High‐mass Resolution Ion Microprobe (SHRIMP) U–Pb monazite age of 1027 ± 8 Ma for pelitic schist from the Mount Barren Group contrasts markedly with previously published SHRIMP U–Pb monazite and xenotime ages of c. 1200 Ma for the same area. All dated samples experienced identical metamorphic conditions, but preserve different mineral assemblages due to variable bulk composition. Monazite grains dated at c. 1200 Ma are from relatively magnesian rocks dominated by biotite, kyanite and/or staurolite, whilst c. 1027 Ma grains are from a ferroan rock dominated by garnet and staurolite. The latter monazite population is likely to have grown when staurolite was produced at the expense of garnet and chlorite, but this reaction was not intersected by more magnesian compositions, which are instead dominated by monazite that grew during an earlier, greenschist facies metamorphic event. These results imply that monazite ages from pelitic schist can vary depending on the bulk composition of the host rock. Samples containing both garnet and staurolite are the most likely to yield monazite ages that approximate the timing of peak metamorphism in amphibolite facies terranes. Samples too magnesian to ever grow garnet, or too iron‐rich to undergo garnet breakdown, are likely to yield older monazite, and the age difference can be significant in terranes with a polymetamorphic history.     

Fluid flow and Al transport during quartz-kyanite vein formation, Unst, Shetland Islands, Scotland

Quartz‐kyanite veins, adjacent alteration selvages and surrounding ‘precursor’ wall rocks in the Dalradian Saxa Vord Pelite of Unst in the Shetland Islands (Scotland) were investigated to constrain the geochemical alteration and mobility of Al associated with channelized metamorphic fluid infiltration during the Caledonian Orogeny. Thirty‐eight samples of veins, selvages and precursors were collected, examined using the petrographic microscope and electron microprobe, and geochemically analysed. With increasing grade, typical precursor mineral assemblages include, but are not limited to, chlorite+chloritoid, chlorite+chloritoid+kyanite, chlorite+chloritoid+staurolite and garnet+staurolite+kyanite+chloritoid. These assemblages coexist with quartz, white mica (muscovite, paragonite, margarite), and Fe‐Ti oxides. The mineral assemblage of the selvages does not change noticeably with metamorphic grade, and consists of chloritoid, kyanite, chlorite, quartz, white mica and Fe‐Ti oxides. Pseudosections for selvage and precursor bulk compositions indicate that the observed mineral assemblages were stable at regional metamorphic conditions of 550–600 °C and 0.8–1.1 GPa. A mass balance analysis was performed to assess the nature and magnitude of geochemical alteration that produced the selvages adjacent to the veins. On average, selvages lost about −26% mass relative to precursors. Mass losses of Na, K, Ca, Rb, Sr, Cs, Ba and volatiles were −30 to −60% and resulted from the destruction of white mica. Si was depleted from most selvages and transported locally to adjacent veins; average selvage Si losses were about −50%. Y and rare earth elements were added due to the growth of monazite in cracks cutting apatite. The mass balance analysis also suggests some addition of Ti occurred, consistent with the presence of rutile and hematite‐ilmenite solid solutions in veins. No major losses of Al from selvages were observed, but Al was added in some cases. Consequently, the Al needed to precipitate vein kyanite was not derived locally from the selvages. Veins more than an order of magnitude thicker than those typically observed in the field would be necessary to accommodate the Na and K lost from the selvages during alteration. Therefore, regional transport of Na and K out of the local rock system is inferred. In addition, to account for the observed abundances of kyanite in the veins, large fluid‐rock ratios (10²–10³ m³_fluid m⁻³_rock) and time‐integrated fluid fluxes in excess of ∼10⁴ m³_fluid m⁻²_rock are required owing to the small concentrations of Al in aqueous fluids. It is concluded that the quartz‐kyanite veins and their selvages were produced by regional‐scale advective mass transfer by means of focused fluid flow along a thrust fault zone. The results of this study provide field evidence for considerable Al mass transport at greenschist to amphibolite facies metamorphic conditions, possibly as a result of elevated concentrations of Al in metamorphic fluids due to alkali‐Al silicate complexing at high pressures.     

Petrogenesis and implications of jadeite‐bearing kyanite eclogite from the Sanbagawa belt (SW Japan)

Jadeite‐bearing kyanite eclogite has been discovered in the Iratsu body of the Sanbagawa belt, SW Japan. The jadeite + kyanite assemblage is stable at higher pressure–temperature (P–T) conditions or lower H₂O activity [a(H₂O)] than paragonite, although paragonite‐bearing eclogite is common in the Sanbagawa belt. The newly discovered eclogite is a massive metagabbro with the peak‐P assemblage garnet + omphacite + jadeite + kyanite + phengite + quartz + rutile. Impure jadeite is exclusively present as inclusions in garnet. The compositional gap between the coexisting omphacite (P2/n) and impure jadeite (C2/c) suggests relatively low metamorphic temperatures of 510–620 °C. Multi‐equilibrium thermobarometry for the assemblage garnet + omphacite + kyanite + phengite + quartz gives peak‐P conditions of ~2.5 GPa, 570 °C. Crystallization of jadeite in the metagabbro is attributed to Na‐ and Al‐rich effective bulk composition due to the persistence of relict Ca‐rich clinopyroxene at the peak‐P stage. By subtracting relict clinopyroxene from the whole‐rock composition, pseudosection modelling satisfactorily reproduces the observed jadeite‐bearing assemblage and mineral compositions at ~2.4–2.5 GPa, 570–610 °C and a(H₂O) >0.6. The relatively high pressure conditions derived from the jadeite‐bearing kyanite eclogite are further supported by high residual pressures of quartz inclusions in garnet. The maximum depth of exhumation in the Sanbagawa belt (~80 km) suggests decoupling of the slab–mantle wedge interface at this depth.     

Garnet and staurolite producing reactions in a chlorite-chloritoid schist

During prograde metamorphism garnet and, in some higher grade samples, staurolite were produced in a chlorite-chloritoid schist, part of the Precambrian Z to Cambrian Hoosac Formation near Jamaica, VT. Garnet grew during two prograde events separated by a retrogression. This sequence resulted in distinctive inclusion textures and zoning anomalies in garnet produced by diffusive alteration. Textures, reaction space analysis, and mineral compositional variations constrain the possible sequence of reactions in these rocks. Below the staurolite isograd, and to some unknown extent above it, garnet grew by the reaction chloritoid+chlorite+quartz→garnet+H₂O. With increasing grade the mineral compositions are displaced towards lower Mn/Fe and higher Mg/Fe ratios. The data are compatible with equilibrium with respect to exchange reactions for the matrix assemblages on a thin section scale and with minerals having closely followed equilibrium paths during reaction. The staurolite isograd coincides with the reaction chloritoid+quartz→garnet+staurolite+chlorite+H₂O. This reaction is continuous and trivariant with ZnO becoming an additional component concentrated in staurolite. During this reaction both the Mn/Fe and Mg/Fe ratios of the phases appear to have decreased. This new chemical trend is recorded by garnet zoning profiles and is compatible with trends predicted from phase diagrams. Thus there are two distinct types of garnet zoning reversals in these samples. One is near the textural unconformity and is best explained by diffusive alteration during partial resorption of first stage garnet. The other occurs near the outer rim of garnet in staurolite zone samples and marks the onset of a new prograde garnet producing reaction.     

Staurolite-forming reactions in the eastern Dalradian rocks of Scotland

Data on mineral and rock compositions along with textural relations are used to deduce the staurolite-forming reactions in eastern Dalradian rocks in Scotland. Initially staurolite is formed as a product of the breakdown of the assemblage chloritoid +quartz in iron-rich metapelites. With increase in grade the iron-rich rocks are succeeded by more magnesium-rich ones and staurolite is formed as a product of the breakdown of the assemblage chloritoid +chlorite+muscovite.     

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.     

On the “late” formation of paragonite and its breakdown in pelitic rocks of the southern Damara Orogen (Namibia)

The formation of paragonite at the transition from the low-grade to the medium-grade matamorphism and its breakdown in the presence of quartz in the upper medium grade in common metapelites is investigated.The microprobe work on the white micas from the low and medium-grade rocks yields compositional differences in respect to the celadonite substitutions and the paragonite content. The low-grade white micas are phengites having Si^[4] 6.25 to 6.44 and Al_tot 4.89 to 5.20. The paragonite component in solid solution in the phengites ranges from 11 to 17 mole %. In the transition from the low-grade to the medium-grade metamorphism, concomitant with the breakdown of chlorite, the phengites change to muscovites having Si^[4] 6.07 to 6.16 and Al_tot 5.36 to 5.56. At the same time, the amount of paragonite in solid solution increases up to 22±2 mole % and paragonite makes its first appearance as a separate mineral. The increase of the percentage of paragonite in solid solution in the muscovites is due to the drastical modal decrease of muscovite in the course of the breakdown of chlorite. The formation of paragonite is readily explained by the muscovite-paragonite solvus. Paragonite forms thin lamellae (1–20 m) interlayered with muscovite lamellae (1–40 m). The average composition is Pg_88.5Ms₇Mar_4.5. Paragonite occurs together with staurolite+biotite, kyanite+biotite, cordierite +biotite, and andalusite+biotite. In the presence of quartz, it breaks down in the lower part of the andalusite zone to andalusite and albite-rich plagioclase. At the same time, the amount of paragonite in solid solution in the muscovites decrease to 11–15 mole %. The basal spacings d(002) of the phengites and muscovites investigated show a clear dependence on the Na⁺ content and the celadonite substitutions.     

Retrograde replacement of andalusite by Ca–Na mica in chloritoid-bearing metapelites. PTX modelling of rocks with different Al content in the MnNCKFMASH system

Andalusite porphyroblasts are totally pseudomorphosed by margarite–paragonite aggregates in aluminous pelites containing the peak mineral assemblage andalusite, chlorite, chloritoid, margarite, paragonite, quartz ± garnet, in a NW Iberia contact area. Equilibria at low P–T are investigated using new KFMASH and (mainly) MnCNKFMASH grids constructed with Thermocalc 3.21. P–T and T–X pseudosections with phase modal volume isopleths are constructed for compositions relatively richer and poorer in andalusite to model the assemblages in an andalusite‐bearing rock that contains a thin andalusite‐rich band (ARB) during retrogression. Their compositions, prior to retrogression, are used in the modelling, and have been retrieved by restoring the pseudomorph‐forming elements into the current‐depleted matrix, except for Al₂O₃ which is assumed to be immobile. Compositional differences between the thin band and the rest of the rock have not resulted in differences in andalusite porphyroblast retrogression. The absence of chloritoid resorbtion implies either a pressure increase at constant reacting‐system composition, or that its composition changed during retrogression at constant pressure, by becoming enriched in the progressively replaced andalusite porphyroblasts. T–X pseudosections at 1 kbar model this latter process using as end‐members in X, first, the restored original rock and ARB compositions, and, then the same process, taking into account the change in composition of both as retrogression proceeded. The MnNCKFMASH pseudosections of rocks with different Al contents facilitate making further deductions on the rock‐composition control of the resulting assemblages upon retrogression. Andalusite eventually disappears in relatively Al‐poor rocks, resulting, as in this study, in a rock formed by chloritoid–chlorite as the only FM minerals, plus margarite–paragonite pseudomorphs of andalusite. In rocks richer in Al, chlorite would progressively disappear and a kyanite/andalusite–chloritoid assemblage would eventually be stable at retrograde conditions. The Al‐silicate, stable during retrogression in Al‐rich rocks, indicates pressure conditions and hence the tectonic context under which retrogression took place.     

The initial garnet‐in reaction involving siderite–rhodochrosite,garnet re‐equilibration and P–T–t paths of graphitic schists in the Black Hills orogen,South Dakota,USA

It is generally thought that garnet in metapelites is produced by continuous reactions involving chlorite or chloritoid. Recent publications have suggested that the equilibrium temperatures of garnet‐in reactions may be significantly overstepped in regionally metamorphosed terranes. The growth of small spessartine–almandine garnet crystals on Mn‐siderite at the garnet isograd in graphitic metapelites in the Proterozoic Black Hills orogen, South Dakota, demonstrates that Mn‐siderite was the principal reactant that produced the initial garnet in the schists. Moreover, the positions of garnet compositions in isobaric, T–(C/H) pseudosections for the schists show that the temperature of the garnet‐in reaction from Mn‐siderite was overstepped minimally at the most. In the Black Hills, garnet was initially produced during regional metamorphism beginning at c. 1755 Ma due to the collision of Wyoming and Superior cratons, and was subsequently partially or fully re‐equilibrated at more elevated temperatures and pressures during intrusion of the Harney Peak Granite (HPG) at c. 1715 Ma. Garnet occurs in graphitic schists in garnet, staurolite and sillimanite zones, the latter being a product of contact metamorphism by HPG. During metamorphism, coexisting fluid contained both CO₂ and CH₄. In the garnet zone, garnet crystals contain petrographically distinct cores with inclusions of quartz, graphite and other minerals. Centres of the cores have distinctly elevated Y concentrations that mark the positions of garnet nucleation. The elevated Y is thought to have come from the Mn‐siderite onto which Y was probably absorbed during precipitation in an ocean. In the upper garnet and staurolite zones, the cores were overgrown by inclusion‐poor mantles. Mantles are highly zoned and have more elevated Fe and Mg and lower Mn and Ca than cores. The growth of mantles is attributed to late‐orogenic heating by leucogranite magmas and attendant influx of H₂O that caused consumption of graphite in rock matrices. A portion of the Proterozoic terrane that includes the HPG is surrounded by four large faults. In this ‘HPG block’, garnet is inclusion‐poor and its composition does not preserve its early growth history. This garnet appears to have re‐equilibrated by internal diffusion of its major components and/or recrystallization of an earlier inclusion‐rich garnet. It has equilibrated within the kyanite stability range, and together with remnant kyanite in the high‐strain aureole of the HPG, indicates that the HPG block had a ≥6 kbar history. The HPG block has undergone decompression during emplacement of the HPG. The decompression is evident in occurrences of retrograde andalusite and cordierite in the thermal aureole of the HPG. The data support a polybaric metamorphic history of the Black Hills orogen with different segments of the orogen having their own clockwise P–T–t paths.     

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.     

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

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