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.     

Fluid flow and mass transport at the Valentine wollastonite deposit, Adirondack Mountains, New York State

The Valentine wollastonite skarn in the north-west Adirondack Mountains, New York, is a seven million ton deposit which resulted from channellized infiltration of H₂O-rich, silica-bearing fluids. The wollastonite formed by reaction of these fluids with non-siliceous calcite marble. The skarn formed at the contact of the syenitic Diana Complex and was subsequently overprinted by Grenville-age granulite facies metamorphism and retrograde hydrothermal alteration during uplift. Calcite marbles adjacent to the deposit have generally high δ¹⁸O values (c. 21‰), typical of Grenville marbles which have not exchanged extensively with externally derived fluids. Carbon isotopic fractiona-tions between coexisting calcite and graphite in the marbles indicate equilibration at 675d? C, consistent with the conditions of regional metamorphism. Oxygen isotopic ratios from wollastonite skarn are lower than in the marbles and show a 14‰ variation (-1‰ to 13‰). Some isotopic heterogeneity is preserved from skarn formation, and some represents localized exchange with low-δ¹⁸O retrograde fluids. Detailed millimetre- to centimetre-scale isotopic profiles taken across skarn/marble contacts reveal steep δ¹⁸O gradients in the skarn, with values increasing towards the marble. The gradients reflect isotopic evolution of the fluid as it reacted with high δ¹⁸O calcite to form wollastonite. Calcite in the marble preserves high δ¹⁸O values to within <5 mm of the skarn contact. The preservation of high δ¹⁸O values in marbles at skarn contacts and the disequilibrium fractionation between wollastonite skarn and calcite marble across these contacts indicate that the marbles were not infiltrated with significant quantities of the fluid. Thus, the marbles were relatively impermeable during both the skarn formation and retrograde alteration. Skarn formation may have been episodic and fluid flow was either chaotic or dominantly parallel to lithological contacts. Although these steep isotope gradients resemble fluid infiltration fronts, they actually represent the sides of the major flow system. Because chromatographic infiltration models of mass transport require the assumption of pervasive fluid flow through a permeable rock, such models are not applicable to this hydrothermal system and, by extension, to many other metamorphic systems where low-permeability rocks restrict fluid migration pathways. Minimum time-integrated fluid fluxes have been calculated at the Valentine deposit using oxygen isotopic mass balance, reaction progress of fluid buffering reactions, and silica mass balance. All three approaches show that large volumes of fluid were necessary to produce the skarn, but silica mass balance calculations yield the largest minimum flux and are hence the most realistic.     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.     

Tectonothermal evolution of the gneiss complex at Salur in the Eastern Ghats Grnaulite Belt of India

Textural relations, thermobarometry and petrogenetic grid considerations in the syn-tectonic granitoid massif and the enveloping metasedimentary gneisses at Salur are consistent with a counter-clockwise P–T –t path for the rocks. The low-P/high-T prograde sector is documented by the pre- to syn-D₁ cordierite±orthopyroxene±garnet±spinel–bearing metatexite leucosomes in metapelites. Heating and loading of the rocks (syn- to post-D₁) resulted in the formation of garnet+orthopyroxene± cordierite-bearing diatexites, and decomposition of cordierite in metatexite leucosomes to orthopyroxene+sillimanite+biotite+quartz symplectites. Near-peak temperature, 850 °C at 8.0 kbar, was reached syn- to post-D₂. Post-peak cooling resulted in the stabilization of coronal grossular and anorthite+calcite symplectites at the expense of scapolite+wollastonite+calcite assemblages in calc-silicate gneisses, and the resetting of cation exchange temperatures at 700–750 °C. Near-isothermal decompression at c. 700–750 °C is manifested by the decomposition of garnet porphyroblasts in the granitoid gneisses to plagioclase+orthopyroxene/ilmenite/biotite two-phase coronas and restabilization of cordierite at garnet margins in metapelites. Subsequent low-P, near-isobaric cooling led to the overprinting of granulite facies assemblages by muscovite+calcite assemblages, and further resetting of cation exchange thermometers to lower temperatures c. 600 °C. The tectonothermal evolution of the Salur gneiss complex vis-a-vis the Eastern Ghats Belt is therefore consistent with high degrees of lower crustal melting, followed by prograde heating of the cover rocks due to magma invasion synchronous with crustal compression, and finally thermal relaxation over a protracted period punctuated by tectonic/erosional denudation of the thickened crust.     

Formation of wollastonite-bearing marbles during late regional metamorphic channelled fluid flow in the Upper Calcsilicate Unit of the Reynolds Range Group,central Australia*

Abstract Granulite facies marbles from the Upper Calcsilicate Unit of the Reynolds Range, central Australia, contain metre-scale wollastonite-bearing layers formed by infiltration of water-rich (X_CO2= 0.1–0.3) fluids close to the peak of regional metamorphism at c. 700° C. Within the wollastonite marbles, zones that contain <10% wollastonite alternate on a millimetre scale with zones containing up to 66% wollastonite. Adjacent wollastonite-free marbles contain up to 11% quartz that is uniformly distributed. This suggests that, although some wollastonite formed by the reaction calcite + quartz = wollastonite + CO₂, the wollastonite-rich zones also underwent silica metasomatism. Time-integrated fluid fluxes required to cause silica metasomatism are one to two orders of magnitude higher than those required to hydrate the rocks, implying that time-integrated fluid fluxes varied markedly on a millimetre scale. Interlayered millimetre -to centimetre-thick marls within the wollastonite marbles contain calcite + quartz without wollastonite. These marls were probably not infiltrated by significant volumes of water-rich fluids, providing further evidence of local fluid channelling. Zones dominated by grandite garnet at the margins of the marl layers and marbles in the wollastonite-bearing rocks probably formed by Fe metasomatism, and may record even higher fluid fluxes. The fluid flow also reset stable isotope ratios. The wollastonite marbles have average calcite (Cc) δ¹⁸O values of 15.4 ± 1.6% that are lower than the average δ¹⁸O(Cc) value of wollastonite-free marbles (c. 17.2 ± 1.2%). δ¹³C(Cc) values for the wollastonite marbles vary from 0.4% to as low as -5.3%, and correlations between δ¹⁸O(Cc) and δ¹³C(Cc) values probably result from the combination of fluid infiltration and devolatilization. Fluids were probably derived from aluminous pegmatites, and the pattern of mineralogical and stable isotope resetting implies that fluid flow was largely parallel to strike.     

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.     

Prograde and retrograde fluid flow during contact metamorphism of siliceous carbonate rocks from the Ballachulish aureole,Scotland

 Siliceous dolomites and limestones contain abundant retrograde minerals produced by hydration-carbonation reactions as the aureole cooled. Marbles that contained periclase at the peak of metamorphism bear secondary brucite, dolomite, and serpentine; forsterite-dolomite marbles have retrograde tremolite and serpentine; wollastonite limestones contain secondary calcite and quartz; and wollastonite-free limestones have retrograde tremolite. Secondary tremolite never appears in marbles where brucite has replaced periclase or in wollastonite-bearing limestones. A model for infiltration of siliceous carbonates by CO₂-H₂O fluid that assumes (a) vertical upwardly-directed flow, (b) fluid flux proportional to cooling rate, and (c) flow and reaction under conditions of local equilibrium between peak temperatures and ≈400 °C, reproduces the modes of altered carbonate rocks, observed reaction textures, and the incompatibility between tremolite and brucite and between tremolite and wollastonite. Except for samples from a dolomite xenolith, retrograde time-integrated flux recorded by reaction progress is on the order of 1000 mol fluid/cm² rock. Local focusing of flow near the contact is indicated by samples from the xenolith that record values an order of magnitude greater. Formation of periclase, forsterite, and wollastonite at the peak of metamorphism also required infiltration with prograde time-integrated flux approximately 100–1000 mol/cm². The comparatively small values of prograde and retrograde time-integrated flux are consistent with lack of stable isotope alteration of the carbonates and with the success of conductive thermal models in reproducing peak metamorphic temperatures recorded by mineral equilibria. Although isobaric univariant assemblages are ubiquitous in the carbonates, most formed during retrograde metamorphism. Isobaric univariant assemblages observed in metacarbonates from contact aureoles may not record physical conditions at the peak of metamorphism as is commonly assumed. Received: 19 September 1995 / Accepted: 14 March 1996     

Calc-silicate reactions and bedding-controlled isotopic exchange in the Notch Peak aureole, Utah: implications for differential fluid fluxes with metamorphic grade

Fluid compositions and bedding‐scale patterns of fluid flow during contact metamorphism of the Weeks Formation in the Notch Peak aureole, Utah, were determined from mineralogy and stable isotope compositions. The Weeks Formation contains calc‐silicate and nearly pure carbonate layers that are interbedded on centimetre to decimetre scales. The prograde metamorphic sequence is characterized by the appearance of phlogopite, diopside, and wollastonite. By accounting for the solution properties of Fe, it is shown that the tremolite stability field was very narrow and perhaps absent in the prograde sequence. Unshifted oxygen and carbon isotopic ratios in calcite and silicate minerals at all grades, except above the wollastonite isograd, show that there was little to no infiltration of disequilibrium fluids. The fluid composition is poorly constrained, but X(CO₂)_fluid must have been >0.1, as indicated by the absence of talc, and has probably increased with progress of decarbonation reactions. The occurrence of scapolite and oxidation of graphite in calc‐silicate beds of the upper diopside zone provide the first evidence for limited infiltration of external aqueous fluids. Significantly larger amounts of aqueous fluid infiltrated the wollastonite zone. The aqueous fluids are recorded by the presence of vesuvianite, large decreases in δ¹⁸O values of silicate minerals from c. 16‰ in the diopside zone to c. 10‰ in the wollastonite zone, and extensive oxidation of graphite. The carbonate beds interacted with the fluids only along margins where graphite was destroyed, calcite coarsened, and isotopic ratios shifted. The wollastonite isograd represents a boundary between a high aqueous fluid‐flux region on its higher‐grade side and a low fluid‐flux region on its lower‐grade side. Preferential flow of aqueous fluids within the wollastonite zone was promoted by permeability created by the wollastonite‐forming reaction and the natural tendency of fluids to flow upward and down‐temperature near the intrusion‐wall rock contact.     

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.     

Stability of fluorite and titanite in a calc-silicate rock from the Vizianagaram area, Eastern Ghats Belt, India

In the Vizianagaram area (E 83°29.442′; N 18°5.418′) of the Eastern Ghats Belt, India, a suite of graphite‐bearing calc‐silicate granulites, veined by syenitic rocks, developed wollastonite‐rich veins at 6–7 kbar and > 850 °C. During subsequent near‐isobaric cooling wollastonite was replaced by calcite + quartz and a graphic intergrowth of fluorite + quartz ± clinopyroxene. Titanite with variable Al and F contents is present throughout the rock. Combining the compositional variation of titanite and recent experimental data, it is demonstrated that the mineral assemblage, the composition of coexisting fluids and the mobility of Al exert a far greater control on the composition of titanite than pressure, temperature or the whole rock composition. Thermodynamically computed isothermal–isobaric logf_O2– logf_CO2 and logf_F2– logf_O2 grids in the systems Ca–Fe–Si–O–F (CISOF; calcite‐free) and Ca–Fe–Si–O–F–C–H (CISOFV; calcite‐present) demonstrate the influence of bulk rock and fluid compositions on the stability of the fluorite‐bearing assemblages in diverse geological environments and resolve the problem of the stability of titanite in fayalite + fluorite‐bearing rocks in the Adirondacks. The mineralogy of the studied rocks and the topological constraints tightly fix the logf_O2, logf_F2 and logf_CO2 at ?15.8, ?30.6 and 4.1, respectively, at 6.5 kbar and c. 730 °C. Because of the similarity in the P–T conditions, the compositions of pore fluids in the fluorite‐bearing assemblages of the Adirondacks and the Eastern Ghats Belt have been compared.     

Allochemical retrograde metamorphism in shear zones: an example in metapelites, Virginia, USA

Abstract Metapelites in the Altavista area, southwest Virginia Piedmont, USA, underwent allochemical hydrothermal retrograde metamorphism in synmetamorphic shear zones. The metapelites of the Evington Group were metamorphosed in a prograde sequence of chlorite, staurolite, and sillimanite zones. Garnet–biotite geothermometry and phase relations support eastward increasing metamorphic grade, ranging from 570° C in the staurolite zone to 650° C in the sillimanite zone at c. 5.8 kbar. Sillimanite-zone rocks later underwent progressive retrogression around shear zones which acted as fluid conduits. Retrograde assemblages are successively zoned around the shear zones with staurolite-, chloritoid- and kyanite-bearing assemblages. The shear zones commonly contain kyanite or tourmaline veins. Applicable phase equilibria indicate that retrogression occurred during isobaric cooling through c. 200–270° C. Rock compositional changes with retrogression occurred in steps: SiO₂ was gained in the early stages of the retrogression but lost in the late stages; Al₂O₃, K₂O, and H₂O were increasingly gained through the sequence; CaO was increasingly lost. Addition of H₂O and decreasing temperatures resulted in new ferromagnesian minerals (staurolite, chloritoid, chlorite) and changes in H₂O, SiO₂, Al₂O₃, K₂O, and CaO contents produced muscovite and sodic plagioclase. Subsequent to prograde metamorphism, deeply derived fluids migrated upwards along shear zones, providing fluid and energy for the retrograde reactions. The sheared rocks underwent fluid infiltration with fluid fluxes of 1.8 × 10⁷–4.3 × 10⁷ cm³/cm² corresponding to minimum estimated fluid-to-rock ratios of 7.5–21 as a function of position within the shear zone. Fluid flow was from high to low temperature early and low to high temperature later in the retrogression.     

P–T–fluid evolution in the Mahalapye Complex, Limpopo high-grade terrane, eastern Botswana

Metapelites, migmatites and granites from the c. 2 Ga Mahalapye Complex have been studied for determining the P–T–fluid influence on mineral assemblages and local equilibrium compositions in the rocks from the extreme southwestern part of the Central Zone of the Limpopo high‐grade terrane in Botswana. It was found that fluid infiltration played a leading role in the formation of the rocks. This conclusion is based on both well‐developed textures inferred to record metasomatic reactions, such as Bt ? And + Qtz + (K₂O) and Bt ± Qtz ? Sil + Kfs + Ms ± Pl, and zonation of Ms | Bt + Qtz | And + Qtz and Grt | Crd | Pl | Kfs + Qtz reflecting a perfect mobility (Korzhinskii terminology) of some chemical components. The conclusion is also supported by the results of a fluid inclusion study. CO₂ and H₂O ( = 0.6) are the major components of the fluid. The fluid has been trapped synchronously along the retrograde P–T path. The P–T path was derived using mineral thermobarometry and a combination of mineral thermometry and fluid inclusion density data. The Mahalapye Complex experienced low‐pressure granulite facies metamorphism with a retrograde evolution from 770 °C and 5.5 kbar to 560 °C and 2 kbar, presumably at c. 2 Ga.     

Evidence for pre-regional metamorphic fluid infiltration of the Lower Calcsilicate Unit, Reynolds Range Group (central Australia)

Grandite garnet-rich calcsilicate rocks from the Lower Calcsilicate Unit of the regionally metamorphosed Reynolds Range Group (central Australia) crop out along a strike-parallel section in which a transition zone from M2₂ amphibolite to granulite facies rocks is exposed. Across this transition the grandite-rich layers do not show systematic changes in mineral assemblages, compositions and modes, or stable isotope compositions. These layers are deformed by F2₂ folds that are associated with the peak of regional low-pressure/high-temperature metamorphism. Therefore, the grandite-rich layers appear to pre-date regional metamorphism and to have acted as closed chemical systems during prograde M2₂ metamorphism. Mineral assemblages in the grandite-rich layers are consistent with their formation through the infiltration of oxidized, water-rich fluids (X_co2 < 0.1–0.3; log f_o2 -16 to -14). The stable isotope values of calcite (Δ¹³C=-4.2 to -0.8%₀ PDB; Δ¹⁸O = 10.5–14.0%⁰ V-SMOW) and bulk-silicate fractions (Δ¹⁸O = 6.1 to 10.8%) of the grandite-rich layers are most consistent with the infiltrating fluid being from a magmatic source. It is most likely that fluid infiltration occurred during the pre-M2₂ contact metamorphism (M2₁) that affected much of the Reynolds Range Group. The preservation of these assemblages is probably due to their high variance and little pervasive fluid-rock interaction having occurred during M2₂. The clinopyroxene- and feldspar-rich calcsilicate rocks that host the grandite-rich layers contain poikiloblastic grandite garnet that formed during prograde M2₂ metamorphism. Thin marbles that locally occur with the grandite-rich layers contain a third garnet generation that is post- or late M2₂. This grossular-rich garnet occurs in coronas around calcite, plagioclase, clinopyroxene, wollastonite and scapolite. These coronas are consistent with cooling and/or compression. However, because the marble assemblages are themselves overprinted by M2₁ grandite-rich layers the development of coronal garnet does not reflect a continuous P-T-t path. Rather, it more probably reflects the partial re-equilibration of M2₁ contact metamorphic assemblages to post-M2₂ conditions.     

Constraints on the timing and conditions of high‐grade metamorphism,charnockite formation and fluid–rock interaction in the Trivandrum Block,southern India

Incipient charnockites have been widely used as evidence for the infiltration of CO₂‐rich fluids driving dehydration of the lower crust. Rocks exposed at Kakkod quarry in the Trivandrum Block of southern India allow for a thorough investigation of the metamorphic evolution by preserving not only orthopyroxene‐bearing charnockite patches in a host garnet–biotite felsic gneiss, but also layers of garnet–sillimanite metapelite gneiss. Thermodynamic phase equilibria modelling of all three bulk compositions indicates consistent peak‐metamorphic conditions of 830–925 °C and 6–9 kbar with retrograde evolution involving suprasolidus decompression at high temperature. These models suggest that orthopyroxene was most likely stabilized close to the metamorphic peak as a result of small compositional heterogeneities in the host garnet–biotite gneiss. There is insufficient evidence to determine whether the heterogeneities were inherited from the protolith or introduced during syn‐metamorphic fluid flow. U–Pb geochronology of monazite and zircon from all three rock types constrains the peak of metamorphism and orthopyroxene growth to have occurred between the onset of high‐grade metamorphism at c. 590 Ma and the onset of melt crystallization at c. 540 Ma. The majority of metamorphic zircon growth occurred during protracted melt crystallization between c. 540 and 510 Ma. Melt crystallization was followed by the influx of aqueous, alkali‐rich fluids likely derived from melts crystallizing at depth. This late fluid flow led to retrogression of orthopyroxene, the observed outcrop pattern and to the textural and isotopic modification of monazite grains at c. 525–490 Ma.     

Effects of cation substitutions in garnet and pyroxene on equilibrium oxygen isotope fractionations

High-grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet, and to investigate the effects on fractionation factors of the cation substitutions Fe³⁺Al_?1 and Ca(Fe,Mg)_?1. Recrystallized, granulite facies (725 °C) wollastonite ores from the northern Adirondack highlands contain essentially only the minerals clinopyroxene (a Di–Hd solid solution)+garnet (a Grs–Adr solid solution)±wollastonite, and exhibit a systematic dependence of measured fractionations on the Fe³⁺ content of calcic garnet: Δ(Cpx–CaGrt)=(0.14±0.12)+(0.78±0.20)X_Adr and Δ(Wo–CaGrt)=(0.15±0.22)+(0.57±0.33)X_Adr. In eclogites formed at T ≤650 °C, measured compositions of Ca-poor garnet and omphacite combined with experimental data indicate that Ca-poor, Fe-rich garnet is enriched in ¹⁸O compared to both diopside and grossular: extrapolating to 1000 K, Δ(Alm–Di)≈c. 0.2 and Δ(Alm–Grs)≈c. 0.5. Orthopyroxene and clinopyroxene from Gore Mountain, New York, show a constant fractionation that is independent of rock type, as expected if they have the same closure temperature. These data imply Δ(Opx-Cpx)≈c. 0.7 at 1000 K. Measured fractionations among Ca-poor garnet, orthopyroxene, clinopyroxene and hornblende in the Gore Mountain rocks further indicate an ¹⁸O enrichment in Ca-poor garnet over Grs (≈c. 0.5 at 1000 K). The new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite, diopside, grossular, wollastonite and feldspar, but consistently indicate a significant isotope effect for the simple octahedral cation substitutions Fe³⁺Al_?1 (Grs vs. Adr) and Ca(Fe,Mg)_?1 (Ca-poor garnet vs. Grs; Opx vs. Cpx). Neither cation substitution has been directly investigated for its effect on ¹⁸O/¹⁶O fractionation with experiments in silicates. Chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends.     

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.     

Active skarn formation beneath Lascar Volcano, northern Chile: a petrographic and geochemical study of xenoliths in eruption products

Calcsilicate xenoliths occur in large numbers in some lavas and pyroclastic flows of Lascar Volcano. Their whole-rock major element and REE compositions indicate that the protolith was the Upper Cretaceous Yacoraite Formation, which crops out extensively in NW Argentina. The whole-rock major element compositions of the xenoliths fall into specific groups suggesting a strong geochemical zonation in the skarn zone. Three geochemical zones have been identified; (1) an outer metamorphic zone rich in wollastonite; (2) a middle zone rich in pyroxene and garnet; (3) an inner zone rich in pyroxene and magnetite. The two innermost zones have developed from the wollastonite zone by infiltration of metasomatic fluids rich in Fe, Mn, Mg, Ti and Al. Whole-rock REE patterns have not changed significantly during prograde metamorphism and metasomatism, indicating REE immobility in the altering fluids. Retrograde alteration by acid-sulphate fluids produced anhydrite skarns and secondary calcite and wilkeite veins in the wollastonite zone. The carbon and oxygen isotopic compositions of this calcite indicate that it formed by Rayleigh crystallization from a low-temperature (<200 °C) fluid containing dissolved H₂CO₃. The calculated δ¹⁸O of the water in this fluid suggests a magmatic origin whereas the calculated δ¹³C of the dissolved carbonate is consistent with derivation from rocks of the Yacoraite Formation at 350 °C. It is suggested that the magmatic acid-sulphate fluid was responsible for leaching carbonate from the surrounding carbonate rocks and redepositing it in the skarn zone. REEs were mobilized during the retrograde acid-sulphate and acid-carbonate alteration. A negative Ce anomaly associated with this carbonate and sulphate indicates high oxygen fugacities in the mineralizing fluids.     

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.     

Textural and isotopic development of marble assemblages during the Barrovian-style M2 metamorphic event,Naxos, Greece

A detailed petrological analysis of the marble assemblages observed within the M2 metamorphic complex on Naxos is presented. Two distinct periods of mineral growth are documented; the first is associated with prograde M2 metamorphism and the second with retrograde M2 metamorphism occurring during ductile extensional thinning of the complex. The textural and miner-alogical characteristics and the carbon and oxygen isotope compositions of each generation are described, and the P-T-X _{CO 2} conditions at which these two mineral generations were stable, and the compositions of the fluids present during metamorphism are characterised. Whereas the low variance and stable isotope compositions of prograde siliceous dolomite assemblages are consistent with internally buffered fluid evolution, the retrograde mineral generation is shown to have grown as a result of the infiltration of a water-rich fluid phase that transported silica, Al₂O₃, Na₂O and FeO into the host rocks. This observation, together with the stable isotope compositions of the retrograde calcite, and the fact that occurrences of veins of this type are limited to marbles in the highest grade areas (T>600° C) of the metamorphic complex, suggests that the fluids responsible for vein formation were generated during the crystallisation of melts as the metamorphic complex cooled from peak temperatures. The existence of this second generation of minerals has significant implications for previous studies of heat transport by fluid flow on Naxos, because many of the unusually low ¹⁸O compositions of pelites at high grades may be ascribable to the effects of interaction with retrograde M2 fluids, rather than with prograde fluids.     

Carboniferous eclogite and garnet–omphacite granulite from northeastern Hainan Island,South China: Implications for the evolution of the eastern Palaeo‐Tethys

High‐P (HP) eclogite and associated garnet–omphacite granulite have recently been discovered in the Mulantou area, northeastern Hainan Island, South China. These rocks consist mainly of garnet, omphacite, hornblende, quartz and rutile/ilmenite, with or without zoisite and plagioclase. Textural relationships, mineral compositions and thermobarometric calculations demonstrate that the eclogite and garnet–omphacite granulite share the same three‐stage metamorphic evolution, with prograde, peak and retrograde P?T conditions of 620–680°C and 8.7–11.1 kbar, 820–860°C and 17.0–18.2 kbar, and 700–730°C and 7.1–8.5 kbar respectively. Sensitive high‐resolution ion microprobe U–Pb zircon dating, coupled with the identification of mineral inclusions in zircon, reveals the formation of mafic protoliths before 355 Ma, prograde metamorphism at c. 340–330 Ma, peak to retrograde metamorphism at c. 310–300 Ma, and subsequent pegmatite intrusion at 295 Ma. Trace element geochemistry shows that most of the rocks have a MORB affinity, with initial ε_Nd values of +2.4 to +6.7. As with similar transitional eclogite–HP granulite facies rocks in the thickened root in the European Variscan orogen, the occurrence of relatively high P?T metamorphic rocks of oceanic origin in northeastern Hainan Island suggests Carboniferous oceanic subduction leading to collision of the Hainan continental block, or at least part of it, with the South China Block in the eastern Palaeo‐Tethyan tectonic domain.