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

Alpine 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.     

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.     

Chemographic analysis of assemblages involving pyrophyllite, chloritoid, chlorite, kaolinite, kyanite, quartz: application to metapelites in the Witwatersrand goldfields, South Africa

The Witwatersrand goldfields contain abundant assemblages that include pyrophyllite, chloritoid, chlorite, kaolinite and/or kyanite, with quartz. A chemographic analysis of the system Fe(Mg)-Al-Si-O-H involving these minerals yields 22 potential phase diagrams. Using orientation criteria and thermodynamic calculations as further constraints, this list has been reduced to three possible diagrams. New thermodynamic data favour one of these in particular.
This chemographic analysis demonstrates that formation of chloritoid is not restricted to the breakdown reaction of kaolinite plus chlorite in the F(M)ASH system, as stated by previous studies, but could be from pyrophyllite + chlorite → chloritoid + quartz + H₂O.
The metamorphic temperature variation between Witwatersrand goldfields exceeded 65 C, based on chlorite and chloritoid compositions. The lower and upper pressure limits are constrained by the andalusite to kyanite, and the sudoite/chlorite to carpholite boundaries, i.e. 1.5–2.8, and 7 kbar, respectively. The widespread pyrophyllite, chlorite and Fe-chloritoid in all the Witwatersrand goldfields, and the local occurrence of sudoite indicate a consistent low-pressure environment in which Mg-chloritoid would not be stable.     

Staurolite-quartzite bands in kyanite quartzite at big rock,Rio Arriba County,New Mexico

Concordant igneous-looking bands of ferruginous bulk composition occur in a highly aluminous Precambrian metasedimentary series composed predominantly of kyanite quartzite. The bands consist of quartz, staurolite, and magnetite (partially martitized) with accessory amounts of muscovite, chlorite (pseudomorphous after biotite), chloritoid, apatite, and monazite. Quartz is found in three types (I–III) differing in appearance as well as in origin. Staurolite, in combination with quartz-II, shows peculiar radial sieve textures caused by mimetic crystallization after preexisting chloritoid rosettes. The chloritoid has been largely consumed, either by a reaction with hypothetical former kyanite to produce staurolite+ quartz with rock composition unchanged, or, possibly, by metasomatic introduction of oxygen (oxidation) to yield staurolite+quartz+magnetite; the remaining chloritoid, however, persisted in stable equilibrium with the other minerals of the rock. The staurolite quartzites are thus considered to represent original sedimentary bands which have undergone several stages of recrystallisation and (possibly) metasomatic modification during their metamorphic history. Their igneous aspect results from annealing crystallisation during a late static, i.e. postdeformational, thermal event of regional metamorphism.Chemical analysis of the staurolite shows no unusual features. For all staurolites plotted there is a positive relationship of the excess H⁺ over 2.0 and the Si⁺⁴-deficiency in the unit cell. This suggests partial substitution of 4 H⁺ for Si⁺⁴.The formation of staurolite in regional metamorphic rocks with excess silica, low alkali contents, and (FeO+MgO)/Al₂O₃ ratios < 1 showing chloritoid at lower grades appears to be governed, in many cases, by the reaction chloritoid+Al-silicate=staurolite+quartz+H₂O.The assemblage chloritoid-staurolite may be stable in regional metamorphism over a limited pressure-temperature range.     

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

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

Mass transfer and porosity evolution during low temperature water–rock interaction in gneisses of the simano nappe: Arvigo,Val Calanca,Swiss Alps

Late Alpine fissures and fractures in amphibolite-facies basement gneisses at Arvigo (Val Calanca, Swiss Alps) show distinct cm-sized reaction selvages parallel to the fracture walls that composed of subgreenschist facies assemblages produced by the interaction of water present in the fracture porosity with the old high-grade gneiss assemblages. The process of selvage or reaction-vein formation occurred in the brittle deformation regime and at temperatures characteristic of, first the prehnite-pumpellyite facies and then later of the zeolite facies. The vein formation occurred during uplift and cooling at very late stages of the Alpine orogeny. The reaction veins are composed of a selvage of altered gneiss on both sides of the central fracture and a central zone with fissure minerals that have been growing in the open fracture pore space. The central zone of the Arvigo veins contains an early assemblage with epidote, prehnite and chlorite and a late succession sequence of various species of zeolite. The veins of the Arvigo quarry are convincing evidence that fracture fluids in gneiss and granite have the potential to precipitate Ca–zeolite. This is an important find because many fluids recovered from deep continental drill holes and from geothermal energy exploration are found to be oversaturated in respect to a number of Ca–zeolite species. Vein formation during late uplift and cooling of the Alps occurred at continuously decreasing T and at hydrostatic pressure: (1) coexisting prehnite/epidote records temperatures of 330–380°C, (2) chlorite formation at temperature of 333 ± 32°C and (3) formation of zeolites <250°C. In the selvages the prime reaction is the replacement of plagioclase by albite along a sharp reaction front that separates the selvage from unaltered gneiss. In addition to albitisation, chloritisation of biotite is the second important reaction in the alteration process. The reactions release components for the formation of Ca–Al silicates. The water–rock interaction is associated with a depletion of Al, Si, Ca, Fe and K in the altered wall rock. The overall reaction is associated with an increase in porosity of up to 14.2 ± 2.2% in the selvage zone (altered wall rock), caused by the volume decrease during albitisation and the removal of biotite. The propagation of the sharp reaction front through the gneiss matrix occurred via a dissolution-reprecipitation mechanism. Zeolite formation is tied to the plagioclase alteration reaction in the rock matrix, which releases components for zeolite formation to a CO₂-poor aqueous liquid.     

P–T modelling of the andalusite–kyanite–andalusite sequence and related assemblages in high-Al graphitic pelites. Prograde and retrograde paths in a late kyanite belt in the Variscan Iberia

The exceptional andalusite–kyanite–andalusite sequence occurs in Al‐rich graphitic slates in a narrow pelite belt on the hangingwall of a ductile normal fault in NW Variscan Iberia. Early chiastolite is replaced by Ky–Ms–Pg aggregates, which are overgrown by pleochroic andalusite near granites intruded along the fault. Slates plot in AKFM above the chloritoid‐chlorite tie‐line. Their P–T grids are modelled with Thermocalc v2.7 and the 1998 databases in the NaKFMASH and KFMASH systems. The univariant reaction Ctd + And/Ky = St + Chl + Qtz + H₂O ends at progressively lower pressure as F/FM increases and A/AFM decreases, shrinking the assemblage Cld–Ky–Chl, and opening a chlorite‐free Cld–Ky trivariant field on the low temperature reaction side. This modelling matches the observed absence of chlorite in high F/FM rocks, which is restricted to low pressure in the andalusite stability field. The P–T path deduced from modelling shows a first prograde event in the andalusite field followed by retrogression into the kyanite field, most likely coupled with a slight pressure increase. The final prograde evolution into the andalusite field can be explained by two different prograde paths. Granite intrusion caused the first prograde part of the path with andalusite growth. The subsequent thermal relaxation, together with a_H2O decrease, generated the retrograde andalusite–kyanite transformation, plus chlorite consumption and chloritoid growth. This transformation could have been related to folding in the beginning, and aided later by downthrowing due to normal faulting. Heat supplied by syntectonic granite intrusion explains the isobaric part of the path in the late stages of evolution, causing the prograde andalusite growth after the assemblage St–Ky–Chl. Near postectonic granites, a prograde path with pressure decrease originated the assemblage St–And–Chl.     

Chemical Features of White Micas from the Piemonte Calc-schists, Western Alps and Implications for K–Ar Ages of Metamorphism

Anomalously large chemical ranges in muscovite-paragonite and muscovite-celadonite systems are observed in white micas from the Piemonte calcschists in the Chisone valley area, internal western Alps. The petrographical and chemical observations on white mica strongly suggest that most mica crystals with high Na/K ratios in the chlorite zone are of detrital origin, and were derived from the pre-Alpine high-temperature metamorphic sequence such the Caledonian and/or Variscan. Submicroscopic muscovite (Ms) - paragonite (Pg) composite aggregates occur in the chlorite zone and their EPMA analyses give an apparent chemical composition range from Ms_0.6Pg_0.4 to Ms_0.2Pg_0.8. In the rutile zone, the paragonite content of the white micas is less than 20%, suggesting that the white micas have been homogenized during the Alpine metamorphism even if detrital white micas existed.Metamorphic mica is also very heterogeneous. The total range in Si content becomes wider with increasing of metamorphic grade: 3.22–3.39 pfu for the chlorite zone, 3.07–3.45 pfu for the chloritoid zone and 3.06–3.59 pfu for the rutile zone. This clearly indicates that the micas have experienced significant retrogressive chemical reactions during cooling and exhumations of the host schists.The detrital white mica in the chlorite zone has not reset well in its K-Ar system during the Alpine subduction-related metamorphism. The wide range of the white mica K-Ar ages from 115 to 41 Ma must be due to a mixture of various amounts of detrital white mica in the separates. This feature is also observed in the chloritoid zone though the age variation is not so large as that in the chlorite zone. In contrast, the mica in the rutile zone, which was higher than 450°C, has been reset completely during Alpine HP metamorphism.     

Application of lithogeochemistry to exploration for deep VMS deposits in high grade metamorphic rocks, Snow Lake, Manitoba

Volcanic-associated massive sulphide deposits in the Snow Lake area of Manitoba are related to mineralogically and chemically distinct alteration zones. It is generally accepted that these zones represent crosscutting, subconformable or conformable synvolcanic alteration zones, which were coeval with and have been metamorphosed with the massive sulphides. Metamorphism ranges from upper greenschist facies to middle amphibolite facies. Surface lithogeochemical anomalies led to the discovery of small massive sulphide lenses at a vertical depth of 250 m in the Raindrop Lake area, southwest of Snow Lake, Manitoba. Variations in mineral assemblages of middle amphibolite facies alteration zones and analysis of variations in major and trace element chemistry were used to guide deep drilling at Raindrop Lake. The massive sulphide lenses are stratigraphically underlain by a low angle crosscutting “pipe” and a conformable footwall “apron” alteration.The alteration zones are composed of assemblages of garnet, staurolite and chlorite, and, less significantly, biotite, muscovite and kyanite. They are characterized by loss of Na and Ca, and addition of Fe, Mg, Cu and Zn. Mapping the alteration is aided by the application of the metamorphic AFM phase diagram for the appropriate metamorphic facies. Increasing intensity of alteration can be identified by the first appearance of new mineral phases, which are represented on the AFM diagram. These mineral trends coincide with loss of Na and Ca relative to Al, and increased Mg and Fe. Chemical alteration indices ACNK (molecular proportion Al₂O₃/(CaO + Na₂O + K₂O) and AI = 100 × [(MgO + K₂O)/(MgO + K₂O + CaO + Na₂O)] combined with Cu and Zn variation helped to quantify the intensity of alteration, despite being insensitive to Fe.The crosscutting pipe is dominantly Fe enriched, with a Cu-enriched core, Zn enriched margins and widespread Na and Ca depletion. Mineralogically it is identified by garnet, staurolite and chlorite and follows an iron and aluminum enrichment trend on the AFM diagram. The conformable alteration zone is characterized by local strong Mg enrichment, extensive Na and Ca depletion and variable Cu and Zn. Mineralogically it is characterized by the presence of chlorite and kyanite and follows a magnesium and aluminum enrichment trend on the AFM diagram.     

Widespread fluid infiltration during metamorphism of the Witwatersrand goldfields: generation of chloritoid and pyrophyllite

Abstract Chloritoid and pyrophyllite occur together in all major goldfields of the Witwatersrand Basin and are widespread in virtually all rock types of the upper Witwatersrand Supergroup, including metaconglomeratic reefs and altered mafic rocks. Both minerals are particularly characteristic of the pelitic horizons intimately associated with reef packages, but they are also developed locally in the regionally persistent metapelites that have basin-wide extent. Pyrophyllite is particularly common in foliated zones, adjacent to quartz veins, and near unconformably overlying auriferous conglomerates. The wide distribution of chloritoid and pyrophyllite in metapelites of the Witwatersrand Basin is attributed to alteration of chlorite-rich shales, rather than to unusual premetamorphic starting materials. This alteration event involved the redistribution of many elements, with up to 40% volume loss, mainly due to removal of silica. Removal of most of the Mg and some Fe accounts for the stabilization of chloritoid and pyrophyllite. Relatively immobile elements included Al, Ti, Nb, Cr, V, P, La and Ce, whereas Si, Fe, Mn, Zn, Co, Ni, Cu, Mg and Ca were lost, and K, Rb and Ba were introduced by an infiltrating fluid. The alteration event is inferred to have been within the chloritoid and pyrophyllite stability field (and thus syn-metamorphic) as bulk chemical changes in metapelites are from chlorite directly towards chloritoid and then pyrophyllite, rather than to lower grade minerals such as kaolinite. Muscovite–chlorite–chloritoid and muscovite–chloritoid–pyrophyllite assemblages are attributed to fluid buffering along appropriate curves, as their production by metamorphism of lower grade mineral mixes is considered unlikely, based on the present bulk rock compositional data. A metamorphic timing for the alteration accounts for the correlation of strongly foliated areas with greater degrees of inferred alteration. The transitions from chlorite to chloritoid to pyrophyllite define zones of increasing alteration. Widespread infiltration as part of peak metamorphism is suggested by the distribution of chloritoid and pyrophyllite, quartz veining and textures. Fluid:rock ratios calculated from a silica budget in one metapelitic horizon exceed 100:1 over many square kilometres. These values need not imply multi-pass fluid flow, as much of the silica migration may be redistribution on a scale of a few metres, from source rocks into veins. Although infiltration during metamorphism may have affected much of the upper Witwatersrand succession, channelized fluid flow within reef packages, along faults and unconformities and in certain metaconglomerates and metapelites is inferred.     

Characteristic Features of REE and Pb–Zn–Ag Mineralizations in the Na Son Deposit,Northeastern Vietnam

The Na Son deposit is a small‐scale Pb–ZnPb–Zn–Ag deposit in northeast Vietnam and consists of biotite–chlorite schist, reddish altered rocks, quartz veins and syenite. The biotite–chlorite schist is intruded by syenite. Reddish altered rocks occur as an alteration halo between the biotite–allanite‐bearing quartz veins and the biotite–chlorite schist. Allanite occurs in the biotite–allanite‐bearing quartz veins and in the proximal reddish altered rocks. Rare earth element (REE) fluorocarbonate minerals occur along fractures or at rim of allanite crystals. The later horizontal aggregates of sulfide veins and veinlets cut the earlier reddish altered rocks. The earlier Pb–Zn veins consist of a large amount of galena and lesser amounts of sphalerite, pyrite and molybdenite. The later Cu veins cutting the Pb–Zn veins include chalcopyrite and lesser amounts of tetrahedrite and pyrite. The occurrences of two‐phase H₂O–CO₂ fluid inclusions in quartz from biotite–allanite‐bearing quartz veins and REE‐bearing fluorocarbonate minerals in allanite suggest the presence of CO₂ and F in the hydrothermal fluid. The oxygen isotopic ratios of the reddish altered rocks, biotite–chlorite schist, and syenite range from +13.9 to +14.9 ‰, +11.5 to +13.3 ‰, and +10.1 to +11.6 ‰, respectively. Assuming an isotopic equilibrium between quartz (+14.6 to +15.8 ‰) and biotite (+8.6 ‰) in the biotite–allanite‐bearing quartz vein, formation temperature was estimated to be 400°C. At 400°C, δ¹⁸O values of the hydrothermal fluid in equilibrium with quartz and biotite range from +10.5 to +11.7 ‰. These δ¹⁸O values are consistent with fluid that is derived from metamorphism. Assuming an isotopic equilibrium between galena (+1.5 to +1.7 ‰) and chalcopyrite (+3.4 ‰), the formation temperature was estimated to be approximately 300°C. The formation temperature of the Na Son deposit decreased with the progress of mineralization. Based on the geological data, occurrence of REE‐bearing minerals and oxygen isotopic ratios, the REE mineralization is thought to result from interaction between biotite–chlorite schist and REE‐, CO₂‐ and F‐bearing metamorphic fluid at 400°C under a rock‐dominant condition.     

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.     

'Forbidden zone' subduction of sediments to 150 km depth— the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, China

The solid‐state reaction magnesite (MgCO₃) + calcite (aragonite) (CaCO₃) = dolomite (CaMg(CO₃)₂) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km^?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO₂ to the overlying mantle wedge.     

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.     

A petrogenetic grid for pelitic schists in the system SiO2-Al2O3-FeO-MgO-K2O-H2O

A quantitative petrogenetic grid for pelitic schists in the system KFMASH that includes the phases garnet, chlorite, biotite, chloritoid, cordierite, staurolite, talc, kyanite, andalusite, sillimanite, and pyrophyllite (with quartz, H₂O and muscovite or K-feldspar in excess) is presented. The grid is based on thermodynamic data of Berman et al. (1985) and Berman (1988) for endmember KFASH and KMASH equilibria and natural Fe-Mg partitioning for the KFMASH system. Calculation of P-T slopes and the change in Fe/(Fe+Mg) along reactions in the KFMASH system were made using the Gibbs method. In addition, the effect on the grid of MnO and CaO is evaluated quantitatively. The resulting grid is consistent with typical Buchan and Barrovian parageneses at medium to high grades. At low grades, the grid predicts an extensive stability field for the paragenesis chloritoid+biotite which arises because of the unusual facing of the reaction chloritoid+biotite + quartz+H₂O = garnet+chlorite+muscovite, which proceeds to the right with increasing T in the KFMASH system. However, the reaction proceeds to the left with increasing T in the MnKFASH system so the assemblage chloritoid + biotite is restricted to bulk compositions with high Fe/(Fe+Mg+Mn). Typical metapelites will therefore contain garnet+chlorite at low grades rather than chloritoid + biotite.     

P-T evolution of metasediments from the Eclogite Zone, south-central Tauern Window, Austria

Petrologic data on the paragenesis of (I) kyanite-zoisite marbles and (II) garnet-chloritoid quartz-mica schists are presented with the goal of providing constraints on the pressure-temperature evolution of the Eclogite Zone, Tauern Window, Austria. The peak metamorphic assemblages in the two rock types are: (I) kyanite + zoisite + dolomite + quartz; zoisite + muscovite + dolomite + calcite + quartz; and (II) garnet + chloritoid + kyanite + muscovite + quartz + epidote ± dolomite ± Zn-staurolite. The estimated peak metamorphic conditions are 19 ± 2 kbar, 590 ± 20°C.

Secondary alteration of the kyanite-zoisite marbles was accomplished in two stages. The early stage resulted in the production of margarite, paragonite, secondary muscovite and chlorite and the later stage resulted in the formation of sudoite (a di/trioctahedral Mg---Al layer silicate) and kaolinite. The early alteration is bracketed at conditions between 3 and 10 kbar, 450–550°C and the later alteration between 200 and 350°C, P 3 kbar.

The P-T path is characterized by maximum burial to approximately 19 kbar (60–70 km) (at≈590°C), followed by nearly isothermal decompression to approximately 10 kbar (30 km), and then more gradual decompression with cooling to approximately 3 kbar (10 km). Alteration was apparently accomplished by the influx of H₂O-rich fluids, with the composition of the fluid locally buffered by the mineral assemblage.     

The upper thermal stability of chlorite + quartz: an experimental study in the system MgO-Al2O3-SiO2-H2O

Experiments up to water pressures of 21 kbar have been undertaken to bracket the reactions chlorite + quartz = talc + kyanite + H₂O, chlorite + quartz = talc + cordierite + H₂O, and talc + kyanite + quartz = cordierite ± H₂O by reversed runs in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). These reaction curves intersect at an invariant point (IP1) at PH₂O = 6.4 ± 0.2 kbar and a temperature of 624 ± 4°C. The curve of the chlorite + quartz breakdown to talc + kyanite + H₂O at water pressures above 6.4 kbar shows a negative dP/dT, with the slope decreasing with rising pressure, whereas the slope of the breakdown curve to talc + cordierite + H₂O at water pressures is clearly positive. The composition of the chlorite solid solution reacting with quartz has been estimated to be approximately Mg_4.85Al_1.15[Al_1.15Si_2.85O₁₀](OH)₈ over the entire pressure range investigated. The composition of the talc solid solution forming by the breakdown of chlorite + quartz appears to be Mg_2.94Al_0.06[Al_0.06Si_3.94O₁₀](OH)₂ at PH₂O = 2kbar. With increasing pressure, the Al content of talc decreases, reaching a value of about 0.06 atoms per formula unit at P,H₂O = 21 kbar. As a consequence of the new experimental data, the existing phase topologies of the MASH-system and K₂O-MASH-system have been revised. For example, the invariant point IP1 and the univariant reaction curve kyanite + talc + H₂O = chlorite + cordierite are stable. For this reason, the development of medium- to high-temperature metamorphic rocks compositionally approximating the MASH-system must be reconsidered. The whiteschists from Sar e Sang, Afghanistan, are treated as an example. The application of the present experimental data to metamorphic rocks of more normal composition requires the examination of the influence of further components. This leads to the conclusion that the introduction of Fe²⁺ into magnesian chlorite extends its stability field in the presence of quartz by 10°-15°C in comparison with pure Mg-chlorite.     

Chloritoid, and the Isochemical Character of Barrow's Zones

It is argued that despite poverty of outcrop the apparent restrictionof chloritoid to a wedge-shaped area at the north-eastern extremityof Barrow's zones is real. Two possible interpretations of thisrestriction are considered: (a) That the chloritoid producingreaction (as yet unidentified) was characterized by a lowerP/T than that of the reaction muscovite+ chlorite+chloritoid+quartz staurolite+biotite+H²O, whereby, with increasing grade, chloritoidgives way to staurolite. A pressure gradient increasing fromnorth-east to south-west (postulated on separate grounds, Chinner,1966) would then result in the convergence of the chloritoidand staurolite isograds towards the south-west, and the eventualsuppression of the chloritoid isograd to give the wedge-shapedoutcrop actually found, (b) The lack of low-grade hydrous assemblagesaluminous enough to give chloritoid or staurolite with increasinggrade suggests that the low-grade limit of chloritoid (and,to the south-west, of staurolite) may not be an isograd, buta chemical boundary. Such a boundary could either be metasedimentary,or metasomatic, representing an alkali gradient of the typestudied by Orville, in which, essentially, potassium and waterreleased within the high-grade metamorphic zones have migratedto low-grade zones to form more micaceous assemblages. The widespreadexistence of ‘shimmer aggregate‘ muscovite alterationof aluminous minerals in thesillimanite, kyanite, and staurolitezones provides evidence of potassium transfer during the waneof metamorphic temperatures on a scale comparable to that which,during the main metamorphic imprint, would have been requiredto mask the development of peraluminous assemblages in the chlorite,biotite, and garnet zones.     

Mineralogy and Isotope Geochemistry of Active Submarine Hydrothermal Field at Suiyo Seamount, Izu–Bonin Arc, West Pacific Ocean

This report presents mineralogical, geochemical and isotopic data on samples obtained using the Benthic Multi‐coring System (BMS) to drill a submarine hydrothermal deposit developed in a caldera on the summit of the Suiyo Seamount in the Izu–Bonin Island Arc, south of Japan. This deposit is regarded as the first example of Kuroko‐type sulfide mineralization on a volcano at the volcanic front of an island arc. The mineralization and hydrothermal alteration below the 300 × 150‐m area of active venting was investigated to depths of 2–9 m below the sea floor. Drilling beneath the area of active venting recovered a sequence of altered volcanic rocks (dacite lavas, pyroclastic rocks of dacite–rhyolite compositions and pumice) associated with sulfide veining and patches/veins of anhydrite. No massive sulfide was found, however, and the subsea‐floor mineralization to 10 m depth is dominated by anhydrite and clay minerals with some sulfides. Sulfide‐bearing samples contained high Au (up to 42 ppm), Ag (up to 263 ppm), As (up to 1550 ppm), Hg (up to 55 ppm), Sb (up to 772 ppm), and Se (up to 24 ppm). Electron probe microanalyzer indicated that realgar, orpiment, and mimetite were major As‐bearing minerals. The sulfides were also characterized by high Zn (>10%) compared to Cu (<6.3%) and Pb (<0.6%). The δ²⁰²Hg/¹⁹⁸Hg, δ²⁰²Hg/¹⁹⁹Hg and δ²⁰²Hg/²⁰⁰Hg of the sulfide‐bearing dacite samples and a sulfide chimney decreased with increasing Hg/Zn concentration ratio. The variation of the δ²⁰²Hg/¹⁹⁸Hg ranged from ?2.8 to +0.5‰ to relative to S‐HG02027. The large range of these δ²⁰²Hg/¹⁹⁸Hg was greater than might be expected for such a heavy element and may be due to a predominance of kinetic effects. The variation of δ²⁰²Hg/¹⁹⁸Hg of sulfide‐bearing dacite samples suggested that light Hg isotope in the vapor mixed with oxygenated seawater near sea floor during mineralization. Lead isotope ratios of the sulfide were very similar to those of the dacite lava, suggesting that lead is of magmatic origin. The ⁸⁷Sr/⁸⁶Sr ratio (0.70872) of anhydrite was different from that of the dacite lava, and suggests an Sr derivation predominantly from seawater. Hydrothermal alteration of the dacite in the Suiyo hydrothermal field was characterized by Fe‐sulfides, anhydrite, barite, montmorillonite, chlorite/montmorillonite mixed‐layer minerals, mica, and chlorite with little or no feldspar or cristobalite. Hydrothermal clay minerals changed with depth from montmorillonite to chlorite/montmorillonite mixed‐layer minerals to chlorite and mica. Hydrogen isotope ratios of chlorite/montmorillonite and mixed‐layer, mica‐chlorite composites obtained below the active venting sites ranged from ?49 to ?24‰, suggesting seawater as the dominant fluid causing alteration. Oxygen isotope ratios of anhydrite ranged from 9.2 to 10.4‰ and anhydrite formation temperatures were calculated to be 188–207°C. Oxygen isotope ratios ranged from +5.2 to +9.2‰ for montmorillonite, +3.2 to +4.5‰ for chlorite/montmorillonite mixed‐layer minerals, and +2.8 to +3.8‰ in mixtures of chlorite and mica. The formation temperatures of montmorillonite and of the chlorite–mica mixture were 160–250°C and 230–270°C, respectively. The isotope temperatures for clay minerals (220–270°C) and anhydrite (188°C) were significantly lower than the borehole temperature (308.3°C) measured just after the drilling, suggesting that temperature at this site is now higher than when clay minerals and anhydrite were formed.     

The origin of chloritoid – 3‐mica pseudomorph growth in staurolite–muscovite schist,Bangriposi (Eastern India)

At Bangriposi, variable stages in replacement of staurolite by chloritoid – Na–K–Ca mica shimmer aggregates in muscovite schists provides insight into the complex interplay between fluid flow, mass transfer, and dissolution–precipitation during pseudomorph growth. Idioblastic chloritoid growing into mica caps without causing visible deformation, and monomineralic chloritoid veins (up to 300 μm wide) within shimmer aggregates replacing staurolite attest to chloritoid nucleation in fluid‐filled conduits along staurolite grain boundaries and crystallographic planes. The growth of shimmer aggregates initiated along staurolite margins, and advanced inwards into decomposing staurolite along networks of crystallographically controlled fluid‐filled conduits. Coalescence among alteration zones adjacent to channel fills led to dismemberment and the eventual demise of staurolite. Mass balance calculation within a volume‐fixed, silica‐conserved reference frame indicate the shimmer aggregates grew via precipitation from fluids in response to mass transport that led to the addition of H₂O, K₂O, Na₂O and CaO in the reaction zone, and Al₂O₃ was transported outward from the inward‐retreating margin of decomposing staurolite. This aided precipitation of chloritoid in veins and in the outer collars, and as disseminated grains in the shimmer aggregates at mid‐crustal condition (~520 ± 20 °C, 5.5 ± 2.0 kbar). Computation using one‐dimensional transport equation suggests that staurolite decomposition involved advection dominating over diffusive transport; the permeation of externally derived H₂O caused flattening of chemical potential gradients in H₂O and aqueous species, for example, and , computed using the Gibbs method. This suggests that staurolite decomposition was promoted by the infiltration of a large volume of H₂O that flattened existing chemical potential gradients. In the initial stages of replacement, chloritoid super‐saturation in fluid caused preferential nucleation and growth of chloritoid at staurolite grain boundaries and in crystallographic planes. As reaction progressed, further chloritoid nucleation was halted, but chloritoid continued to grow as the 3‐mica aggregates continued to replace the remaining staurolite in situ, while the chloritoid‐compatible elements were transported in the water‐rich phase facilitating continued growth of the existing chloritoid grains.