Contrasting mineral parageneses in high-temperature calc-silicate granulites: examples from the Eastern Ghats, India

Abstract Three types of mineral associations are described from calc-silicate granulites from the Eastern Ghats, India, where geothermobarometry in associated rocks suggests extremely high P–T conditions of metamorphism ( c . 9 ± 1 kbar, 950° C). These mineral associations are: (i) calcite + quartz + scapolite + plagioclase, (ii) calcite + scapolite + wollastonite + porphyroblastic garnet + coronal garnet and (iii) calcite + quartz + wollastonite + scapolite + porphyroblastic garnet + coronal garnet, all coexisting with K-feldspar, titanite and clinopyroxene. The first two associations evolved through nearly isobaric cooling retrograde paths, whereas the third evolved through a nearly isothermal decompression path followed by an isobaric cooling retrograde path. Textural and compositional characteristics suggest the following mineral reactions in the calc-silicate granulites: calcite + quartz = wollastonite + CO₂, calcite + plagioclase = scapolite, calcite + scapolite + wollastonite = porphyroblastic garnet ± quartz + CO₂, CaTs + wollastonite = coronal garnet (association ii) and wollastonite + scapolite = coronal garnet (association iii) + quartz + CO₂. Andradite content in garnet was buffered by the redox equilibria wollastonite + hedenbergite + O₂= andradite + quartz (association iii) and wollastonite + andradite + CaTs + scapolite = hedenbergite + calcite + grossular + O₂ (association ii). The contrasting mineral parageneses have been ascribed to interplay of variables such as X _CO2, f _O2, f _HCl in the fluid, bulk Na content and the nature of the retrograde P–T–X _CO2 paths through which the rocks evolved.     

Wollastonite at Nuliyam,Kerala, southern India: a reassessment of CO2-infiltration and charnockite formation at a classic locality

The occurrence of a charnockitised felsic gneiss adjacent to a marble/calc-silicate horizon at Nuliyam, southern India, has been cited in recent literature as a classic example of the dehydration of crustal rocks resulting from the advective infiltration of CO₂-rich fluids generated from a local carbonate source. Petrographic study of the Nuliyam calc-silicate, however, reveals it to consist of abundant wollastonite and scapolite and contain locally discordant veins rich in wollastonite. At the pressure—temperature conditions proposed for charnockite formation in recent studies, 5 kbar and 725°C, this wollastonite-bearing mineral assemblage was stable in the presence of a fluid phase only if X _CO2 was near 0.25 and could not have coexisted with the fluid causing biotite breakdown and charnockite development in adjacent rocks (X _CO2>0.85). The stable coexistence of wollastonite and scapolite prohibits the calc-silicate from being a source for fluid driving charnockitisation at the required P-T conditions. Textural observations such as the limited replacement of wollastonite by calcite+quartz symplectites and mosaics, are consistent with late fluid infiltration into the calc-silicate. The extensive isotopic, chemical and mineral abundance data of Jackson and Santosh (1992) are re-interpreted and integrated with these observations to develop a model involving the infiltration of an externally derived CO₂-rich fluid during high-temperature decompression. Increased charnockite development next to the calc-silicate has arisen because the calc-silicate acted as a relatively unreactive and impermeable barrier to fluid transport and caused fluid ponding beneath antiformal closures. The Nuliyam charnockite/calc-silicate locality is an example of a structural trap in a metamorphic setting rather than a site where charnockite formation can be attributed to local fluid sources.     

Wollastonite and scapolite in Precambrian calc-silicate granulites from Australia and Antarctica

Abstract Scapolite, wollastonite, calcite, diopside, grossular-andradite garnet and sphene occur in calc-silicate rocks in the granulite terrain of the Arunta Block, central Australia. This assemblage buffers the CO₂ activity at a low value, so that any coexisting fluid phase must be H₂O rich and CO₂ poor ( X _co2 = 0.2-0.3). In contrast, the H₂O activity in the surrounding felsic and mafic granulites was low. Thus fluid activities during granulite facies metamorphism were locally buffered in various rock units and fluid flow appears to have been restricted or fluid may have been absent. Late retrograde rims of garnet and garnet-quartz separate phases formed in the high-grade stage. Formation of these rims would have required either an influx of water-rich fluid or a decrease in pressure. Evidence from the surrounding granulites shows that in one locality, the calc-silicate rocks had undergone late isobaric hydration; in another locality, minor uplift had occurred soon after peak P-T conditions. In both, scapolite had partly broken down to plagioclase-calite. A calc silicate rock from the granulite terrain of Enderby Land, Antarctica, contains scapolite, wollastonite, calcite, diopside, quartz and sphene; this assemblage also indicates low CO₂ activities. In this rock, wollastonite has broken down to calcite-quartz, to indicate isobaric cooling without influx of hydrous fluid.     

Reaction textures in scapolite–wollastonite–grossular calc-silicate rock from the Kerala Khondalite Belt, Southern India: evidence for high-temperature metamorphism and initial cooling

Scapolite–wollastonite–grossular bearing calc-silicate rocks from the Vellanad area in the Kerala Khondalite Belt (KKB) of Southern India preserve a number of reaction textures which help to deduce their P–T–fluid history. Textures include calcite+plagioclase±quartz symplectites after scapolite, grossular+quartz coronas between wollastonite and plagioclase, grossular coronas between wollastonite and plagioclase+calcite that replace former scapolite, and grossular blebs replacing anorthite+calcite+quartz pseudomorphs of scapolite. Garnet coronas are also observed between clinopyroxene and wollastonite or scapolite or plagioclase. The reactions, apart from those involving clinopyroxene, can be modelled in the simple CaO–Al₂O₃–SiO₂–CO₂ system and interpreted using partial reaction grids constructed for the activities of end-members in the analysed phases. The reaction topologies produced are good approximations for the peak as well as retrograde mineral assemblages and reaction textures. For the compositions of the phases present in this study, the medium pressure calc-silicate assemblages are defined by the stable pseudo-invariant points [Qtz], [Mei] and [Grs]. The textural features interpreted using these activity-corrected grids indicate a phase of isobaric cooling from about 835°C to 750°C at 6 kbar in the Vellanad area. This is inconsistent with earlier studies on other lithologies from the KKB, most of which imply a post-peak P–T path involving near-isothermal decompression. However, as the temperatures obtained for the KKB from the calc-silicates are higher than those previously deduced from metapelites and garnet–orthopyroxene assemblages, the phase of near-isobaric cooling reported here is inferred to have proceeded prior to the onset of the decompression documented from studies of other rock types.     

Fluid-rock history of granulite facies humite-marbles from Ambasamudram, southern India.

An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest X_CO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest X_CO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at X_CO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high X_CO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO₂ fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low X_H2O.     

The Blosseville Coast basalts of East Greenland: Their occurrence,composition and temporal variations

In the system CaO-MgO-A1₂O₃-SiO₂ the tie lines connecting anorthite with other phases are sequentially broken down with increasing pressure according to the following univariant reactions: anorthite+ enstatite_ss+sillimanite pyrope-grossular_ss+quartz (3), anorthite+enstatite_ss pyrope-grossular_ss+diopside_ss+quartz (2), anorthite+pyrope-grossular_ss+ quartz diopside_ss+kyanite (4) and anorthite+diopside_ss grossular-pyrope_ss +kyanite+quartz (8). At 1,200 ° C these reactions occur at 14.5± 0.5, 15.5±0.5, 19.5±0.5 and 26.4±1 kilobar and have positive slopes (dP/dT) of 1±0.5, 2.8±0.5, 13.3±0.5 and 24±2bars/°C respectively. An invariant point involving kyanite rather than sillimanite, occurs at 850 °C±25 °C and 14.5±0.5kbar at the intersection of reactions (3), (2) and (4). Reaction(4) exhibits significant curvature with an increase in dP/dT from 13.3±0.5 to 18.5± 0.5 bars/°C between 1,050° and 850° C. The pressure at which the complete grossular-pyrope join is stable with quartz is estimated at 41 ± 1 kbar at 1,200 ° C. The pressure at which garnet appears according to reaction (2) is lowered by 5 kbar for a composition with anorthite and orthopyroxene (En_0.5Fs_0.5). Enstatite and plagioclase (An_0.5Ab_0.5) first produce garnet at 2 kbar higher pressure than enstatite and pure anorthite (reaction (2)). The calcium content of garnet in various divariant assemblages is relatively insensitive to temperature but very sensitive to pressure, it is therefore a useful geobarometer. At metamorphic temperatures of 700–850 °C pressures of 8–10 kbar are required for the formation of quartz-bearing garnet granulites containing calcic plagioclase and with (Mg/Mg+Fe) bulk = 0.5.     

Contact metamorphic mineral assemblages,late Triassic Newark group,New Jersey

Essentially isochemical thermal metamorphism of soda-rich Stockton, Lockatong and Brunswick formations of the Newark Group by diabase sills produced unusually varied and unique mineral assemblages, most of which are predominantly Na. feldspar and biotite. Within a meter of a sill Stockton arkose was altered to quartzo-feldspathic hornfels with common diopside and sphene. Within 50 m of a sill Lockatong calcitic and dolomitic mudstone formed calc-silicate hornfels with differing combinations of diopside-hedenbergite, andradite and grossular, prehnite, datolite, idocrase and wollastonite. Within a meter of a sill metamorphosed Lockatong calcareous feldspathic argillite contains sanidine-anorthoclase, aegirine, aegirine-augite, riebeckite and scapolite. Lockatong analcime-dolomite argillite was altered to unique feldspathoidal assemblages containing cancrinite, natrolite-thomsonite and rarely sodalite within 134 m, and nepheline within 30 m of the Byram Sill. Reddish-brown Brunswick mudstone produced spotted pelitic hornfels within a few 10's of meters of a sill.Response to thermal metamorphism varied directly with diminishing grain size. In both sandstone and mudstone Na. feldspar increases and K. feldspar decreases toward intrusions; quartz is rare or absent in highest-grade hornfels. Development of biotite was retarded by detrital clay minerals and hematite pigment, as well as by low temperature. Minor differences in composition among carbonate-rich and analcime-rich Lockatong deposits led to a diversity of closely associated assemblages. Aqueous solutions and relatively low temperature, probably in part during retrogressive metamorphism, produced hydrous minerals. Datolite, tourmaline, scapolite and fluorite suggest minor additions of volatiles, but the widespread feldspathoids were made from soda-rich sedimentary rocks without significant additions from an igneous source.     

Humite- and scapolite-bearing assemblages in marbles and calcsilicates of Dronning Maud Land, Antarctica: new data for Gondwana reconstructions

This study investigates marbles and calcsilicates in Central Dronning Maud Land (CDML), East Antarctica. The paleogeographic positioning of CDML as part of Gondwana is still unclear; however, rock types, mineral assemblages, textures and P–T conditions observed in this study are remarkably similar to the Kerala Khondalite Belt in India. The CDML marbles and calcsilicates experienced a Pan-African granulite facies metamorphism at c. 570 Ma and an amphibolite facies retrogression at c. 520 Ma. The highest grade assemblage in marbles is forsterite+spinel+calcite+dolomite, in calcsilicates the assemblages are diopside+spinel, diopside+garnet, scapolite+wollastonite+clinopyroxene±quartz, scapolite±anorthite±calcite+clinopyroxene+wollastonite. These assemblages constrain the peak metamorphic conditions to 830±20 °C, 6.8±0.5 kbar and X _CO2>0.46. During retrogression, highly fluoric humite-group minerals (humite, clinohumite, chondrodite) replaced forsterite, and garnet rims formed at the expense of scapolite during reactions with wollastonite, calcite or clinopyroxene but without involvement of anorthite. Metamorphic conditions were about 650 °C, 4.5±0.7 kbar, 0.2< X _CO2^fluid<0.36, and the co-existence of garnet, clinopyroxene, wollastonite and quartz constrains f_O2 to FMQ-1.5 log units. Mineral textures indicate a very limited influx of H₂O-rich fluid during amphibolite facies retrogression and point to significant variations of fluid composition in mm-sized areas of the rock. Gypsum was observed in two samples; it probably replaced metamorphic anhydrite which appears to have formed under amphibolite facies conditions. The observed extensive anorogenic magmatism (anorthosites, A-type granitoids) and the character of metamorphism between 610 and 510 Ma suggest that the crustal thermal structure was characterized by a long-lived (50–100 Ma) rise of the crustal geotherm probably caused by magmatic underplating.     

Vesuvianite-wollastonite-grossular-bearing calc-silicate rock near Tatapani,Surguja district,Chhattisgarh

This paper reports the occurrence of vesvianite + wollastonite + grossular + diopside + microcline + quartz assemblage in an enclave of calc-silicate rocks occurring within quartzofeldspathic gneiss near Tatapani in the western part of Chhotanagpur Gneissic Complex. The enclave contains phlogopite-absent and phlogopite-bearing calc-silicate rocks, the latter being much more abundant than the former. The above assemblage occurs in the phlogopite-absent rock. Phlogopite-bearing rock contains the assemblage phlogopite + salite + microcline + plagioclase + quartz. A strong schistosity is developed in both the calc-silicate rocks and the minerals are syntectonic with the major foliation-forming event in the area. The vesuvianite-bearing assemblage is formed by amphibolite facies regional metamorphism of a calcareous protolith at pressure < 4 kbar and X_{CO 2} (fluid) < 0.15.     

Wollastonite--Scapolite Assemblages as Indicators of Granulite Pressure-Temperature-Fluid Histories: The Rauer Group, East Antarctica

Mid-Proterozoic ( 1000 Ma) granulite facies calc-silicates fromthe Rauer Group, East Antarctica, contain grossular-wollastonite-scapolite-dinopyroxene( + quartz or calcite) assemblages which preserve symplectiteand corona textures typically involving the growth of secondarywollastonite. The textures include (1) wollastonite rims betweenquartz and calcite; (2) wollastonite-plagioclase rims and intergrowthsbetween quartz and scapolite; (3) wollastonite-scapolite-clinopyroxeneinter-growths replacing grossular; and (4) wollastonite-plagioclasesymplectites replacing grossular or earlier symplectites (3). Reactions between grossular, scapolite, wollastonite, calcite,quartz, anorthite, and vapour, have been modelled in the CaO-Al₂O₃SiO₂-H₂O-CO₂and more complex systems using the internally consistent data-setof Holland & Powell (1990). Reactions producing scapoliteand wollastonite consume vapour as temperature increases (i.e., carbonation), in agreement with the results of Moecher &Essene (1990). These calc-silicates can therefore behave asfluid sinks under high-grade conditions. Conversely, they maybe important fluid sources on cooling and contribute to theformation of post-metamorphic CO₂rich fluid inclusions in isobaricallycooled granulites. P-T-_CO2 diagrams calculated for typical phase compositions (e.g., garnet, scapolite) demonstrate that the observed texturesare a record of near-isothermal decompression at 800–850 C, consistent with P—rpath determinations based on otherrock types from the Rauer Group. For example, texture (2) resultsfrom crossing the reaction Scapolite + Quartz = Wollastonite + Plagioclase + V on decompression, at 6. 5–7 kb, 820 C, and a_CO2 of0–4–0–5. Furthermore, correlations betweenmodes of product phases (e. g., wollastonitexlinopyroxene) andreactant garnet composition preclude open-system behaviour inthe formation of these textures, consistent with post-peak vapour-absentreactions such as Grossular + Calcite + Quartz = Wollastonite + Scapolite occurring on decomposition at high temperatures (>800C). Reaction textures developed in calc-silicates from other granuliteterranes often involve the formation of grossular ( + quartz calcite) as rims on wollastonite-scapolite, or replacementof wollastonite by calcite-quartz. These textures have developedprincipally in response to cooling below 780–810 C andmay be signatures of near-isobaric cooling. Infiltration ofhydrous fluid is not a necessary condition for the productionof garnet coronas in wollastonite-scapolite granulites. ^*Present address: Department of Earth Sciences, University ofMelbourne, Parkville, Victoria 3052, Australia     

Wollastonite at the Sterling Hill Fe–Zn–Mn ore body, Ogdensburg, New Jersey

Summary Wollastonite occurs abundantly at the Sterling Hill Fe–Zn–Mn ore deposit, Ogdensburg, New Jersey, one of the few occurrences of wollastonite in regionally metamorphosed rocks; it is absent from the surrounding Franklin marble. Wollastonite occurs in two distinct bands along the inner margins of the synclinal ore deposit. Minerals associated with wollastonite include calcite, grossular-andradite, diopsidic pyroxene, alkali feldspar, and rarely vesuvianite, quartz or bustamite. Assuming the generally accepted values of 750°C at 5kbar at Sterling Hill during metamorphism in the Grenville Orogeny, thermodynamic modeling of reactions involving garnet and wollastonite suggest XCO₂ 0.35 in the wollastonite-bearing rocks. Infiltrating metamorphic fluid rich in H₂O was necessary for the formation of wollastonite; at XCO₂ of 0.35, the calculated minimum volumetric water:rock ratio is 0.51. The source of the water is believed to be the dehydration of water-rich phases in adjacent ores or mafic rocks. The chemical compositions, textures, stratigraphy, and calculated metamorphic conditions show that wollastonite formed from calcite and quartz at the peak of the Grenville Orogeny.Present address: Maryland State Highway AdministrationReceived August 18, 2002; revised version accepted February 5, 2003     

Melting and subsolidus reactions in the system K2O−CaO−MgO−Al2O3−SiO2−H2O: experiments and petrologic application

Experiments with synthetic starting materials of muscovite, phlogopite, zoisite, kyanite and quartz were performed in the pressure temperature range 10–25 kbar, 640–780° C under water excess conditions. The reaction muscovite+zoisite+quartz+vapor=liquid+kyanite was bracketed at 10.5 kbar/689–700° C, 15.5 kbar/709–731° C and 20 kbar/734–745° C. The equivalent reaction in the Mg-bearing system muscovite_ss +zoisite+quartz+vapor=liquid+kyanite+phlogopite_ss lies at the same temperature around 10 kbar and approximately 10° C higher around 20 kbar, compared with the Mg-free reaction. At slightly higher temperatures formation of melt and tremolite_ss was reversibly observed from the assemblage phlogopite_ss+zoisite +kyanite+quartz around 10.5 kbar/690–710° C, 15.5 kbar/720–750° C and 20.5 kbar/745–760° C. In the subsolidus region, the reaction muscovite_ss+talc_ss+ tremolite_ss=phlogopite_ss+zoisite+quartz+vapor were located in the range 700° C/16.7–19.0 kbar and 740° C/19.7–20.8 kbar. From these data, a wedge shaped stability field of phlogopite_ss+zoisite+quartz appears with a high P, T termination around 21 kbar/755° C. Muscovite+tremolite+talc or kyanite comes in at higher pressures. These phase relations are in qualitative accord with petrographic observations from high pressure metamorphic areas. Formation and crystallization of melts in rocks of a wide compositional range involving zoisite/epidote has been ascribed to relatively high pressures and is consistent with experimentally determined stability fields in the simplified KCMASH system.     

Genesis of wollastonite- and grandite-rich skarns in a suite of marble-calc-silicate rocks from Sittampundi, Tamil Nadu: constraints on the P–T–fluid regime in parts of the Pan-African mobile belt of South India

The Pan-African tectonothermal activities in areas near Sittampundi, south India, are characterized by metamorphic changes in an interlayered sequence of migmatitic metapelites, marble and calc-silicate rocks. This rock sequence underwent multiple episodes of folding, and was intruded by granite batholiths during and subsequent to these folding events. The marble and the calc-silicate rocks develop a variety of skarns, which on the basis of mineralogy; can be divided into the following types: Type I: wollastonite?+?clinopyroxene (mg#?=?71–73)?+?grandite (16–21 mol% Adr)?+?quartz?±?calcite, Type II: grandite (25–29 mol% Adr )?+?clinopyroxene (mg#?=?70)?+?calcite?+?quartz, and Type III: grandite (36–38 mol% Adr)?+?clinopyroxene (mg#?=?55–65)?+?epidote?+?scapolite?+?calcite?+?quartz. Type I skarn is 2–10 cm thick, and is dominated by wollastonite (>70 vol%) and commonly occurs as boudinaged layers parallel to the regional foliation Sn₁ related to the Fn₁ folds. Locally, thin discontinuous lenses and stringers of this skarn develop along the axial planes of Fn₂ folds. The Type II skarn, on the other hand, is devoid of wollastonite, rich in grandite garnet (40–70 vol%) and developed preferentially at the interface of clinopyroxene-rich calc-silicates layers and host marble during the later folding event. Reaction textures and the phase compositional data suggest the following reactions in the skarns: 1. calcite?+?SiO₂?→?wollastonite?+?V, 2. calcite?+?clinopyroxene?+?O₂?→?grandite?+?SiO₂?+?V, 3. scapolite?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V and 4. epidote?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V Textural relations and composition of phases demonstrate that (a) silica metasomatism of the host marble by infiltration of aqueous fluids (X_CO2?<?0.15) led to production of large volumes of wollastonite in the wollastonite-rich skarn whereas mobility of FeO, SiO₂ and CaO across the interface of marble and calc-silicate and infiltration of aqueous fluids (X_CO2?<?0.35) were instrumental for the formation of grandite skarns. Composition of minerals in type II skarn indicates that Al₂O₃ was introduced in the host marble by the infiltrating fluid. Interpretation of mineral assemblages observed in the interlayered metapelites and the calcareous rocks in pseudosections, isothermal P-X_CO2 and isobaric T-X_CO2 diagrams tightly bracket the “peak” metamorphic conditions at c.9?±?1 kbar and 750°?±?30°C. Subsequent to ‘peak’ metamorphic conditions, the rocks were exhumed on a steeply decompressive P–T path. The estimated ‘peak’ P–T estimates are inconsistent with the “extreme” metamorphic conditions (>11 kbar and >950°C) inferred for the Pan-African tectonothermal events from the neighboring areas. Field and petrological attributes of these skarn rocks are consistent with the infiltration of aqueous fluid predominantly during the Fn₁ folding event at or close to the ‘peak’ metamorphic conditions. Petrological features indicate that the buffering capacity of the rocks was lost during the formation of type I and II skarns. However, the host rock could buffer the composition of the permeated fluids during the formation of type III skarn. Aqueous fluids derived from prograde metamorphism of the metapelites seem to be the likely source for the metasomatic fluids that led to the formation of the skarn rocks.     

Reaction textures in calc-silicate granulites from the Bolingen Islands, Prydz Bay, East Antarctica: implications for the retrograde P–T path

Calc-silicate granulites from the Bolingen Islands, Prydz Bay, East Antarctica, exhibit a sequence of reaction textures that have been used to elucidate their retrograde P–T path. The highest temperature recorded in the calc-silicates is represented by the wollastonite- and scapolite-bearing assemblages which yield at least 760°C at 6 kbar based on experimental results. The calc-silicates have partially re-equilibrated at lower temperatures (down to 450°C) as evidenced by the successive reactions: (1) wollastonite + scapolite + calcite = garnet + CO₂, (2) wollastonite + CO₂= calcite + quartz, (3) wollastonite + plagioclase = garnet + quartz, (4) scapolite = plagioclase + calcite + quartz, (5) garnet + CO₂+ H₂O = epidote + calcite + quartz, and (6) clinopyroxene + CO₂+ H₂O = tremolite + calcite + quartz.
The reaction sequence observed indicates that a CO₂ was relatively low in the wollastonite-bearing rocks during peak metamorphic conditions, and may have been further lowered by local infiltration of H₂O from the surrounding migmatitic gneisses on cooling. Fluid activities in the Bolingen calc-silicates were probably locally variable during the granulite facies metamorphism, and large-scale CO₂ advection did not occur.
A retrograde P–T path, from the sillimanite stability field ( c. 760°C at 6 kbar) into the andalusite stability field ( c. 450°C at <3 kbar), is suggested by the occurrence of secondary andalusite in an adjacent cordierite–sillimanite gneiss in which sillimanite occurs as inclusions in cordierite.     

P CO2 in low-grade metamorphism; zeolite,carbonate, clay mineral,prehnite relations in the system CaO-Al2O3-SiO2-CO2-H2O

Equilibria for several reactions in the system CaO-Al₂O₃-SiO₂-CO₂-H₂O have been calculated from the reactions calcite+quartz=wollastonite+CO₂ (5) and calcite+Al₂SiO₅+quartz=anorthite+CO₂ (19) and other published experimental studies of equilibria in the systems Al₂O₃-SiO₂-H₂O and CaO-Al₂O₃-SiO₂-H₂O.The calculations indicate that the reactions laumontite+CO₂=calcite+kaolinite+2 quartz+2H₂O (1) and laumontite+calcite=prehnite+quartz+3H₂O+CO₂ (3) in the system CaO-Al₂O₃-SiO₂-CO₂-H₂O, are in equilibrium with an H₂O-CO₂ fluid phase having -0.0075 for P _fluid=P _total=2000 bars.These calculations limit the stability of zeolite assemblages to low p CO₂.Using the above reactions as model equilibria, several probelms of p CO₂ in low grade metamorphism are discussed. (a) the problem of producing zeolitic minerals from metasedimentary assemblages of carbonate, clay mineral, quartz. (b) the significance of calcite (or aragonite) associated with zeolite (or lawsonite) in low grade metamorphism and hydrothermal alteration. (c) the reaction of zeolites (or lawsonite) with calcite (or aragonite) to produce dense Ca-Al-hydrosilicates (eg. prehnite, zoisite, grossular).     

Experiments on the phase transition calcite+wollastonite+ +epidote=grossular-andraditess+CO2+H2O

The reaction 2 epidote+2 calcite+3 wollastonite3 grossular-andradite_ss+ 2 CO₂+1 H₂O has been explored by hydrothermal experiments at a total fluid pressure of 1000 bars. For a grossular-andradite_ss of andradite ₂₅ composition, the isobaric univariant curve passes through the points 458°C: X_CO2=0.00; 521°C: X_CO2=0.026; 523°C: X_CO2=0.052; 526°C: 0.088; 528°C: X_CO2=0.104. This curve intersects the isobaric univariant curve of the reaction calcite+quartz+[H₂O] wollastonite+CO₂+[H₂O] at the isobaric invariant point around 528°C and X_CO2=0.12. At higher values of X_CO2, this reaction is replaced by another one, namely: 2 epidote+5 calcite+3 quartz3 grossular-andradite_ss+5 CO₂+ 1 H₂O. It is demonstrated that both the reactions do actually take place during the metamorphism of calcareous rocks. The petrologic significance of contrasted sequence of reactions within this system observed by various workers is also discussed.     

Contact metamorphism of pelitic,psammitic and calcareous sediments in the Southern Highlands of New South Wales

Contact metamorphism has been recognized along a 4 km wide belt adjacent to the shallow‐dipping eastern margin of the Arthursleigh Tonalite, an Early Devonian pluton of the Marulan Batholith, eastern New South Wales. In Ordovician psammitic and pelitic rocks three zones of progressive contact metamorphism range from muscovite + biotite + chlorite assemblages in the outer zone to K‐feldspar + cordierite assemblages adjacent to the pluton and in metasedimentary xenoliths. Retrograde phenomena include extensive replacement of metamorphic minerals by ‘sericite’ and chlorite. Calcareous metasediments adjacent to the tonalite typically contain assemblages of quartz + calcic plagioclase + ferrosalite + sphene, or wollastonite + calcite + diopside with minor grossularite and vesuvianite. Thermal effects in volcanic rocks along the western margin of the pluton are confined to recrystallization of the groundmass.

The regional geology indicates confining pressures of approximately 1 kbar at the time of emplacement of the tonalite. Contact metamorphic temperatures were estimated from two‐feldspar geothermometry to attain a maximum of approximately 590°C for rocks in the innermost zone of the aureole and 700°C for the xenoliths. Fluid compositions attending progressive contact metamorphism were water‐rich (Xco₂<0.2) and, during cooling, these fluids probably account for the extensive retrograde hydration observed in the aureole.     

P-T-X conditions of calc-silicate formation: evidence from fluid inclusions and phase equilibria; Llano Uplift, central Texas, USA

Abstract The Llano Uplift in central Texas is a Grenville aged (c. 1.1 Ga) metamorphic terrane consisting predominantly of amphibolite facies mineral assemblages. The formation of these assemblages has been attributed to the emplacement of relatively late granite plutons throughout the area. Two types of granitic intrusion have previously been recognized: (1) Town Mountain Granites, which occur as relatively large, circular-shaped bodies of coarse-grained granite, and (2) Younger Granites which are present as smaller and more irregular bodies of finer-grained granite. In the central part of the uplift, wollastonite-bearing calc-silicate rocks occur within the Valley Spring Gneiss. The development of these calc-silicate rocks has been linked to infiltrating fluids presumably derived from spatially associated Younger Granites. The stability of coexisting quartz, calcite, wollastonite, grossular and anorthite and coexisting quartz, calcite, wollastonite, andradite and hedenbergite shows that the calc-silicate rocks equilibrated under H₂O-rich conditions with χCO₂ <0.10. Fluid inclusions present within the calc-silicate minerals are H₂O-rich with salinities of <17 wt% equivalent NaCl. The absence of any detectable CO₂ in the fluid inclusions may indicate entrapment of the inclusions at lower pressures and more H₂O-rich conditions compared to the stability of the peak metamorphic mineral assemblage. Homogenization temperatures, measured for texturally primary inclusions, range from 360 to 368° C corresponding to a density range from 0.53 to 0.82 g/cm³. Isochores for these fluid inclusions, when combined with the stability of the solid-solid equilibria Grs + Qtz = Wo + An, yield formation conditions of 500–550° C at 1–2 kbar. This indicates that the granitic intrusions involved in the formation of the Blount Mountain calc-silicates were emplaced at a pressure of at least 1–2 kbar.     

Stability of the scapolite meionite (3CaAl2Si2O2 · CaCO3) at high pressures and storage of CO2 in the deep crust

The stability field of the end-member scapolite meionite was determined in piston-cylinder apparatus. Meionite has very high thermal stability at high pressures, exceeding 1500° C at 20 kbar. Below 6 kbar and 1270 ° C scapolite breakdown is subsolidus, to an-orthite + gehlenite + wollastonite + CO₂, with a slope of 20 bars/degree. An extrapolation of existing thermodynamic data for CO₂ permits calculation of ΔG _F ^o =-2384.5 kcal/mol for meionite at 1270 ° C, very close to the value for 3 anorthite + calcite. Above 1270 ° C, scapolite begins to melt to An+Geh+Liq+CO₂, and as pressure increases the melting curve steepens, the Geh and An being progressively replaced by Liq+corundum with Al in 6-coordination. At pressures >25kbar dp/dt becomes negative, corundum is the only crystalline product, and CO₂ bubbles disappear from the quenched glass, indicating a solubility of CO₂ under these conditions of about 5 wt. percent in the liquid. The subsolidus breakdown of meionite at high pressures to grossularite + kyanite + quartz + calcite nearly coincides with the upper pressure limits of anorthite. Thus scapolite is essentially limited to crustal rocks. In view of its great thermal stability, meionite can play a role as a primary mineral in deep-seated basic or intermediate magmatic processes. It is also likely that CO₂ coming from the earth's interior will be captured by reaction with plagioclase and clinopyroxene. Scapolite has been noted in basic granulite inclusions from basaltic pipes in three continents. It seems probable that scapolite acts as a major storage site for CO₂ in the deep crust.     

Beginning of melting in the granite system Qz-Or-Ab-An-H2O

The beginning of melting in the system Qz-Or-Ab-An-H₂ O was experimentally reversed in the pressure range kbar using starting materials made up of mixtures of quartz and synthetic feldspars. With increasing pressure the melting temperature decreases from 690° C at 2 kbar to 630° C at 17 kbar in the An-free alkalifeldspar granite system Qz-Or-Ab-H₂O. In the granite system Qz-Or-Ab-An-H₂O the increase of the solidus temperature with increasing An-content is only very small. In comparison to the alkalifeldspar granite system the solidus temperature increases by 3° C (7° C) if albite is replaced by plagioclase An 20 (An 40). The difference between the solidus temperatures of the alkalifeldspar granite system and of quartz — anorthite — sanidine assemblages (system Qz-Or-An-H₂O) is approximately 50° C. With increasing water pressures plagioclase and plagioclase-alkalifeldspar assemblages become unstable and are replaced by zoisite+kyanite+quartz and zoisite+muscovite-paragonite_ss +quartz, respectively. The pressure stability limits of these assemblages are found to lie between 6 and 16 kbar at 600° C. At high water pressures (10–18 kbar) zoisite — muscovite — quartz assemblages are stable up to 700 and 720° C. The solidus curve of this assemblage is 10–20° C above the beginning of melting of sanidine — zoisite — muscovite — quartz mixtures. The amount of water necessary to produce sufficient amounts of melt to change a metamorphic rock into a magmatic looking one is only small. In case of layered migmatites it is shown that 1 % of water (or even less) is sufficient to transform portions of a gneiss into (magmatic looking) leucosomes. High grade metamorphic rocks were probably relatively dry, and anatectic magmas of granitic or granodioritic composition are usually not saturated with water.