High-temperature metamorphic imprint on calc-silicate granulites of Rayagada,Eastern Ghats,India: implication for the isobaric cooling path

 Calc-silicate granulites from Rayagada, north-central sector of Eastern Ghats granulite belt show a wide range of mineral assemblages and chemical compositions, which can be grouped as Gr. I (grossular- rich garnet-wollastonite-scapolite-calcite-clinopyroxene), Gr. II (andradite-rich garnet-scapolite-calcite-clinopyr- oxene), and Gr. III (scapolite-calcite-clinopyroxene-plagioclase) assemblages. Petrographic features suggest the following several reactions in the CaO–Al₂O₃–SiO₂-vapor system: Mei+4Wo+Cal=3Grs+Qtz +2CO₂, Mei+3Wo+2Cal=3Grs+CO₂, Mei= 3An+Cal, Wo+CO₂=Cal+Qtz, Mei+5Wo =3Grs+2Qtz+CO₂, An+Wo=Grs+Qtz, Mei+ 5Cal+3Qtz=3Grs+6CO₂, and the following reactions in the CaO–FeO–MgO–Al₂O₃–SiO₂-vapor system: Cpx_ss+Scp+Wo=Grt_ss+Qtz+CO₂, 4Hd+ 2Cal+O₂=2Adr+2Qtz+2CO₂, Cpx_ss+Scp= Grt_ss+Cal+Qtz. These reactions have been used to estimate peak T-X _CO2 condition for these granulites. A maximum temperature of ∼920 °C has been calculated at an estimated pressure of 9 kbar. A T-X _CO2 diagram shows an isobaric cooling from ∼920 °C to ∼815 °C. A range of X _CO2 (0.50 at 920 °C to 0.25 at 815 °C) has been observed for Gr. I calc-silicate granulites based on the reaction sequences including coronal garnet-forming reactions. This sequence is suggestive of internal fluid buffering rather than external fluid influx and the differences in X _CO2 conditions has been thought to be due to local buffering of fluid phases. Group II and Gr. III calc-silicate granulites, on the other hand, exhibit relatively lower temperature conditions. Received: 11 September 1995/Accepted: 20 June 1996     

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     

Determination of time-integrated metamorphic fluid fluxes from the reaction progress of multivariant assemblages

An expression is derived for the calculation of time-integrated metamorphic fluid fluxes in two or more dimensions in rocks undergoing multivariant reactions under conditions of varying pressure, temperature and angle of flow. This calcuation requires knowledge of mineral assemblages, modes and compositions, which are obtained from isobaric T-X _CO2 pseudosections constructed using the program THERMOCALC and compared with those observed in east central Vermont. THERMOCALC is capable of reproducing peak mineral assemblages, modes, compositions and the observed reaction sequences within the system KCaNaFMASCH for two kyanite grade pelitic carbonate rocks from a Barrovian style regional metamorphic terrain in east central Vermont, U.S.A. Calculation of fluid fluxes for decarbonation reactions under conditions of horizontal, layer-parallel flow produces time-integrated fluid flux figures of the order of 10⁸ moles m⁻². Allowance for possible cross-layer flow from adjacent dehydrating pelites reduces this figure significantly, with episodic cross-layer fluxes of the order of 10⁵ moles m⁻² being capable of driving the observed decarbonation. Chlorite bearing carbonate protoliths would have initially dehydrated with increasing temperature, a process requiring down-temperature fluid flow to produce the assemblages currently observed. Received: 28 January 1998 / Accepted: 20 September 1998     

Formation and destruction of periclase by fluid flow in two contact aureoles

Periclase formed in steeply dipping marbles from the Beinn an Dubhaich aureole, Scotland, and the Silver Star aureole, Montana, by the reaction dolomite = periclase + calcite + CO₂. Equilibrium between rock and fluids with X _{CO 2} < 1 requires that reaction was infiltration-driven. Brucite pseudomorphs after periclase occur in the Beinn an Dubhaich aureole either as bed-by-bed replacement of dolomite or in a lens along the contact between dolomite and a pre-metamorphic dike. Transport theory predicts that infiltration drove both periclase reaction and ¹⁸O-depletion fronts which moved at significantly different velocities along the flow path. The distributions of brucite and ¹⁸O-depleted rocks are identical in surface exposures, thus indicating upward flow. Time-integrated flux (q) was <500 mol/cm² and the fluid source was magmatic. Because periclase and its hydrated equivalent brucite are unaltered to dolomite by retrograde reactions, the exposure of brucite marbles accurately images the flow paths of peak metamorphic fluids. In the Silver Star aureole brucite pseudomorphs after periclase exclusively occur in tabular bodies that are beds with elevated Mg/Ca. The spatial pattern of ¹⁸O-depletion requires upward vertical fluid flow. Estimated prograde q ≈ 10³–10⁴ mol/cm² and the fluid source was magmatic. Low Mg/Ca, ¹⁸O-depleted, brucite-free rocks pose a dilemma because the periclase reaction front should have traveled ≈18 times further through them than the isotope alteration front. The dilemma is resolved by reaction textures that indicate periclase and brucite were destroyed in low Mg/Ca rocks by infiltration-driven retrograde carbonation reactions. Values of retrograde q were ≈10³–10⁴ mol/cm². Brucite (after periclase) was preserved only in high Mg/Ca layers where periclase developed in greater abundance. The geometry of brucite marbles at Silver Star thus reflects the location of high Mg/Ca beds rather than the geometry of fluid flow. Retrograde reactions must be considered before the mineralogical record of prograde fluid flow can correctly be interpreted. In both aureoles fluid flow, mineral reaction, and isotope depletion were structurally controlled by bedding and lithologic contacts. Received: 30 July 1996 / Accepted: 21 March 1997     

Retrograde fluids in the Archean Shawmere anorthosite, Kapuskasing Structural Zone, Ontario, Canada

The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO₂ < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO₂ < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO₂ > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H₂O-rich to CO₂-rich. The calcite in the retrograde veins has δ¹⁸O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ¹³C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO₂-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO₂ ≈ 1.13 to 1.05 g/cm³). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO₂-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO₂-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO₂-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996     

Kornerupine parageneses in whiteschists and other magnesian rocks: is kornerupine + talc a high-pressure assemblage equivalent to tourmaline + orthoamphibole?

Kornerupine, (□,Fe,Mg)(Mg,Fe,Al)₉(Si,Al,B)₅ (O,OH,F)₂₂, has been reported with talc in rocks from six localities worldwide, but only at Chilapila Hill in the Lufilian Arc, Zambia do textural relationships imply that kornerupine (Krn) equilibrated with talc (Tlc) during a prograde metamorphic event at T≈ 640 °C, P≈ 13 kbar; a prograde Krn + Tlc assemblage has also been reported from Mautia Hill, Tanzania (P ≤ 13 kbar). In order to estimate possible constraints on the stability range for the kornerupine + talc paragenesis in nature, we constructed a P-T diagram in the model system MgO-Al₂O₃-SiO₂-H₂O (MASH) for seven phases quartz (Qtz), B-free kornerupine sensu stricto, anthophyllite (Ath), chlorite (Chl), cordierite (Crd), kyanite (Ky), and talc. The minimum pressure for Krn + Tlc + Ky stability in MASH is close to that for Ky + Tlc stability, i.e., 6–8 kbar, at T≤ 780 °C. However, in the natural system, B₂O₃ and Na₂O are major constituents in Krn and orthoamphibole (Oam), respectively, and dravitic tourmaline (Tur) is widespread. The critical assemblage alternative to Krn + Tlc in nature is Tur + Oam. The upper pressure limit of Tur + Ath is determined by the upper pressure for anthophyllite: 7.7–10.5 kbar at 682–794 °C in the MgO-SiO₂-H₂O system (Chernosky et al. 1985, Am Mineral 70:223–236), and is undoubtedly higher in the presence of Na₂O, CaO, and Al₂O₃. At three of the six localities, talc is a retrograde phase; nonetheless, it possibly equilibrated with kornerupine on the retrograde path or during a later metamorphic event at P-T conditions appropriate for Ky + Tlc. At the sixth locality (Mulvoj, southwestern Pamir Mountains, Tajikistan), Krn is found in the same thin section as talc and kyanite and all three minerals formed during a prograde metamorphic event at T≥ 650 °C, P near 7 kbar. However, Krn is restricted to a lens 4 to 6 mm thick of phlogopite + anthophyllite + Tur and it does not touch either talc or kyanite. A reaction relating the Mulvoj and Chilapila Hill (Krn + Tlc + Ky + Qtz + Tur) parageneses is calculated from compositions in the Mulvoj rock to be 0.40Tur + 2.55Ath + 1.33H₂O + 0.27F = Krn + 2.16Tlc + 0.36B₂O₃ + 0.02Rutile + 0.19Na₂O + 0.17CaO. Given the difference in metamorphic pressures estimated for Mulvoj and Chilapila Hill, Krn + Tlc is inferred to be favored by increasing pressure as well as by low Na₂O and CaO contents. Some FeO, F, Fe₂O₃, and BeO are present in measurable amounts in at least one of the phases in the Mulvoj and Chilapila Hill whiteschists (e.g., Krn contains 0.24–0.67 wt% BeO), but the effect of these constituents is subordinate to that of Na₂O, CaO and B₂O₃. The Krn + Tlc could be a more important assemblage in B-bearing whiteschists than has been reported to date, particularly at pressures where orthoamphibole is no longer stable. Received: 21 April 1997 / Accepted: 13 October 1997     

Fluid infiltration and regional metamorphism of the Waits River Formation, north-east Vermont, USA

Abstract The Siluro-Devonian Waits River Formation of north-east Vermont was deformed, intruded by plutons and regionally metamorphosed during the Devonian Acadian Orogeny. Five metamorphic zones were mapped based on the mineralogy of carbonate rocks. From low to high grade, these are: (1) ankerite-albite, (2) ankerite-oligoclase, (3) biotite, (4) amphibole and (5) diopside zones. Pressure was near 4.5kbar and temperature varied from c. 450° C in the ankerite-albite zone to c. 525° C in the diopside zone. Fluid composition for all metamorphic zones was estimated from mineral equilibria. Average calculated χ_co2[= CO₂/(CO₂+ H₂O)] of fluid in equilibrium with the marls increases with increasing grade from 0.05 in the ankerite-oligoclase zone, to 0.25 in the biotite zone and to 0.44 in the amphibole zone. In the diopside zone, χ_CO2 decreases to 0.06. Model prograde metamorphic reactions were derived from measured modes, mineral chemistry, and whole-rock chemistry. Prograde reactions involved decarbonation with an evolved volatile mixture of χ_CO2 > 0.50. The χ_CO2 of fluid in equilibrium with rocks from all zones, however, was generally <0.40. This difference attests to the infiltration of a reactive H₂O-rich fluid during metamorphism. Metamorphosed carbonate rocks from the formation suggests that both heat flow and pervasive infiltration of a reactive H₂O-rich fluid drove mineral reactions during metamorphism. Average time-integrated volume fluxes (cm³ fluid/cm² rock), calculated from the standard equation for coupled fluid flow and reaction in porous media, are (1) ankerite-oligoclase zone: c. 1 × 10⁴; (2) biotite zone: c. 3 × 10⁴; (3) amphibole zone: c. 10 × 10⁴; and diopside zone: c. 60 × 10⁴. The increase in calculated flux with increasing grade is at least in part the result of internal production of volatiles from prograde reactions in pelitic schists and metacarbonate rocks within the Waits River Formation. The mapped pattern of time-integrated fluxes indicates that the Strafford-Willoughby Arch and the numerous igneous intrusions in the field area focused fluid flow during metamorphism. Many rock specimens in the diopside zone experienced extreme alkali depletion and also record low χ_CO2. Metamorphic fluids in equilibrium with diopside zone rocks may therefore represent a mixture of acid, H₂O-rich fluids given off by the crystallizing magmas, and CO₂-H₂O fluids produced by devolatilization reactions in the host marls. Higher fluxes and different fluid compositions recorded near the plutons suggest that pluton-driven hydrothermal cells were local highs in the larger regional metamorphic hydrothermal system.     

Evolution of metamorphic volatiles during exhumation of microdiamond-bearing granulites in the Western Gneiss Region, Norway

Fluid inclusions in garnet, kyanite and quartz from microdiamond-bearing granulites in the Western Gneiss Region, Norway, document a conspicuous fluid evolution as the rocks were exhumed following Caledonian high- and ultrahigh-pressure (HP–UHP) metamorphism. The most important of the various fluid mixtures and daughter minerals in these rocks are: (N₂ + CO₂ + magnesian calcite), (N₂ + CO₂ + CH₄ + graphite + magnesian calcite), (N₂ + CH₄), (N₂ + CH₄ + H₂O), (CO₂) and (H₂O + NaCl + CaCl₂ + nahcolite). Rutile also occurs in the N₂ + CO₂ inclusions as a product of titanium diffusion from the garnet host into the fluid inclusions. Volatiles composed of N₂ + CO₂ + magnesian calcite characterise the ambient metamorphic environment between HP–UHP (peak) and early retrograde metamorphism. During progressive decompression, the mole fraction of N₂ increased in the fluid mixtures; as amphibolite-facies conditions were reached, CH₄ and later, H₂O, appeared in the fluids, concomitant with the disappearance of CO₂ and magnesian calcite. Graphite is ubiquitous in the host lithologies and fluid inclusions. Thermodynamic modelling of the metamorphic volatiles in a graphite-buffered C-O-H system demonstrates that the observed metamorphic volatile evolution was attainable only if the f _O2 increased from c. −3.5 (±0.3) to −0.8 (±0.3) log units relative to the FMQ oxygen buffer. External introduction of oxidising aqueous solutions along a system of interconnected ductile shear zones adequately explains the dramatic increase in the f _O2. The oxidising fluids introduced during exhumation were likely derived from dehydration of oceanic crust and continental sediments previously subducted during an extended period of continental collision in conjunction with the Caledonian orogeny. Received: 15 December 1997 / Accepted: 25 May 1998     

High CO2 content of fluid inclusions in gold mineralisations in the Ashanti Belt, Ghana: a new category of ore forming fluids?

Fluid inclusions were studied in samples from the Ashanti, Konongo-Southern Cross, Prestea, Abosso/Damang and Ayanfuri gold deposits in the Ashanti Belt, Ghana. Primary fluid inclusions in quartz from mineralised veins of the Ashanti, Prestea, Konongo-Southern Cross, and Abosso/Damang deposits contain almost exclusively volatile species. The primary setting of the gaseous (i.e. the fluid components CO₂, CH₄ and N₂) fluid inclusions in clusters and intragranular trails suggests that they represent the mineralising fluids. Microthermometric and Raman spectroscopic analyses of the inclusions revealed a CO₂ dominated fluid with variable contents of N₂ and traces of CH₄. Water content of most inclusions is below the detection limits of the respective methods used. Aqueous inclusions are rare in all samples with the exception of those from the granite-hosted Ayanfuri mineralisation. Here inclusions associated with the gold mineralisation contain a low salinity (<6 eq.wt.% NaCl) aqueous solution with variable quantities of CO₂. Microthermometric investigations revealed densities of the gaseous inclusions of 0.65 to 1.06 g/cm³ at Ashanti, 0.85 to 0.98 g/cm³ at Prestea, up to 1.02 g/cm³ at Konongo-Southern Cross, and 0.8 to 1.0 g/cm³ at Abosso/Damang. The fluid inclusion data are used to outline the PT ranges of gold mineralisation of the respective gold deposits. The high density gaseous inclusions found in the auriferous quartz at Ashanti and Prestea imply rather high pressure trapping conditions of up to 5.4 kbar. In contrast, mineralisation at Ayanfuri and Abosso/Damang is inferred to have occurred at lower pressures of only up to 2.2 kbar. Mesothermal gold mineralisation is generally regarded to have formed from fluids characterized by H₂O > CO₂ and low salinity ( ±  6 eq.wt.%NaCl). However, fluid inclusions in quartz from the gold mineralisations in the Ashanti belt point to distinctly different fluid compositions. Specifically, the predominance of CO₂ and CO₂ >> H₂O have to be emphasized. Fluid systems with this unique bulk composition were apparently active over more than 200␣km along strike of the Ashanti belt. Fluids rich in CO₂ may present a hitherto unrecognised new category of ore-forming fluids. Received: 30 May 1996 / Accepted: 8 October 1996     

Fluid regime and the behavior of ore, trace, and rare-earth elements during granitization of metagabbro-norites of the Belomorian Group (Gorelyi Island, Kandalaksha Bay)

The study of metagabbro-norites of the Belomorian Group metamorphosed under the amphibolite-lower granulite facies conditions (Gorelyi Island, Kandalaksha Bay) showed that at contact with Bt-Hbl-Kfs-Pl-Qtz gneiss-granites they were affected by silicic-alkaline H₂O-Cl-CO₂ brines, which caused the enrichment in alkalis, silica, Rb, Ba, Pb, Zr, LREE and redistribution of Cu, Zn, Cr, Co, V, and Ni along the filtration pathway. The granitization of metagabbro-norite proceeded simultaneously with increase in fluid oxygen fugacity from one log unit below to four log units above QFM. The microprobe determinations of Cl content in biotites and apatites made it possible to calculate variations in the $ f_{H_2 O} The study of metagabbro-norites of the Belomorian Group metamorphosed under the amphibolite-lower granulite facies conditions (Gorelyi Island, Kandalaksha Bay) showed that at contact with Bt-Hbl-Kfs-Pl-Qtz gneiss-granites they were affected by silicic-alkaline H₂O-Cl-CO₂ brines, which caused the enrichment in alkalis, silica, Rb, Ba, Pb, Zr, LREE and redistribution of Cu, Zn, Cr, Co, V, and Ni along the filtration pathway. The granitization of metagabbro-norite proceeded simultaneously with increase in fluid oxygen fugacity from one log unit below to four log units above QFM. The microprobe determinations of Cl content in biotites and apatites made it possible to calculate variations in the -f _HCl relations in fluid during its percolation through the rock. It was shown that biotite was formed at metamorphic peak in the presence of highly aggressive high-f _HCl fluids (log /f _HCl ≈ 0.8–1.2). Apatite was formed in the presence of less acid and more aqueous residual solutions (log /f _HCl ≈ 2.98−3.91), which presumably lost their salt components at metamorphic peak. The calculations showed that the flux of fluid that percolated through the rock during granitization accounted for q ≈ 4 × 10² to 2 × 10³ cm³/cm². Due to insignificant volume of the fluid, the transformations spanned only marginal part of the metagabbro-norites on Gorelyi Island. Original Russian Text ? L.I. Khodorevskaya, 2009, published in Petrologiya, 2009, Vol. 17, No. 4, pp. 397–414.     

Partial melting of the Appin Quartzite driven by fracture-controlled H2O infiltration in the aureole of the Ballachulish Igneous Complex, Scottish Highlands

The Ballachulish Igneous Complex consists of an outer quartz diorite and an inner granite, emplaced at about 300 MPa, initially at 1000 to 1050 °C. The contact aureole (0.5–2 km wide) occurs in metapelites and metapsammites plus minor graphitic slates, carbonate rocks and metaquartzites. A textural examination of the arkosic Appin Quartzite, which was previously believed to have melted only within a few metres of the intrusion, demonstrates that partial melting occurred up to 500 m away from the vertical eastern contact. Coupling petrographic observations with Qtz-Ab-Or-H₂O phase relations, we determined both the amounts of actual melt and the maximum possible amounts of melt in the samples. Melting efficiency was everywhere less than 100% and decreased with distance from the intrusion. Though perhaps not the only possible source of fluid throughout the aureole, simple models demonstrate that H₂O evolution from the pluton would have been volumetrically sufficient and persisted long enough to account for the observed partial melting. A time-integrated fluid flux of 7000 kg/m² from the pluton is necessary to account for the observed amounts of partial melt in the Appin Quartzite. From its inefficiency, we infer that infiltration of the Appin Quartzite cannot have occurred along interconnected grain-edge channels. Rather, it was controlled by hydraulic fracturing, with fracture density determining melting efficiency. Bulk-rock permeability is calculated to be 10⁻²⁰ m², an order of magnitude lower than that necessary to permit pervasive flow of all the fluid exsolving from the pluton. There is little difference between the calculated time-integrated fluid flux through the Appin Quartzite on the eastern flank and an estimate of the infiltrating flux through the pelitic Leven Schist on the western flank in the time interval during which both rock types were above their solidus temperature, despite differences in their equilibrium quartz-H₂O dihedral angles at temperatures immediately below the solidus, and differences in the attitude of the contact. The rates of H₂O expulsion from the cooling pluton are consistent with highly efficient fracture-dominated flow, allowing insufficient time for textural equilibration. Received: 26 March 1998 / Accepted: 8 March 1999     

The effects of solid solution and diffusion on infiltration-driven metamorphism with application to metaperidotite,Val d’Efra,Central Swiss Alps

The complication introduced by solid solutions in the analysis of infiltration-driven mineral reactions is that the mole fraction of tracer component i in fluid (X _i) changes with reaction progress (ξ). The effect was incorporated into transport models for coupled fluid flow and mineral reaction by parameterizing the relation between X _i and ξ. With specific reference to carbonation and hydration during regional metamorphism of the peridotite body in Val d’Efra, whose constituent minerals are all solid solutions, infiltration of a disequilibrium fluid produces a single sharp reaction front if rock is assumed uniform in composition. The reaction front separates completely unreacted rock downstream from rock upstream with ξ at a steady-state limit (ξ_ss ≤ ξ_max) that depends on input fluid composition (ξ_max is the maximum possible value). Novel phenomena develop, however, if the flow medium, like the metaperidotite body, is composed of many small domains that differ in initial mineral modes and compositions but with X _i homogenized at a spatial scale larger than the size of the domains (e.g., by diffusion). In this case, infiltration of a disequilibrium fluid produces up to as many different reaction fronts along the flow path as there are domains with 0 ≤ ξ < ξ_ss in all domains except upstream from the slowest moving front where ξ = ξ_ss in all domains. Measured values of ξ in the metaperidotite, (all 0 < ξ < ξ_max) are best reproduced by down-temperature infiltration of a disequilibrium fluid with X_\textCO2 =  0. 1 9 6 X_{{{\text{CO}}_{2} }} = \, 0. 1 9 6 into a multi-domain medium with uniform X_\textCO2 X_{{{\text{CO}}_{2} }} at each spatial point along the flow path (homogenized across the domains at the m-scale by diffusion), and time-integrated fluid flux ≥1,836 mol fluid/cm² rock. Results resolve the paradox of the widespread spatial distribution of reactants and products of infiltration-driven decarbonation/dehydration reactions in regional metamorphic terrains (which in the absence of solid solution and compositional domains indicate up-temperature flow) and the prediction of hydrodynamic models that regional metamorphic fluid flow normally is directed vertically upward and down temperature.     

The oxygen isotope fractionation behaviour of kyanite in experiment and nature

The oxygen isotope fractionation between kyanite and calcium carbonate has been investigated experimentally at four temperatures in the range between 625 and 775 °C at 13 kbar. Because of low exchange rates, the isotopic reaction was enhanced by polymorphic transformation of andalusite to kyanite. With this experimental modification a close approach to equilibrium was reached in all runs. The temperature dependence of the equilibrium fractionation is described by the equation 1000 ln _ky-cc=−2.62×10⁶/T ². Application of the experimental results to natural quartz-kyanite-garnet assemblages indicates the preservation of the oxygen isotope composition of kyanite acquired during its formation, reflecting its extremely low oxygen diffusivity. This refractory behaviour restricts the use of kyanite for thermometry but opens the possibility to use its O-isotope composition as an indicator for recognition of polymetamorphic rock histories and reconstruction of the prograde evolution of a metamorphic sequence. Received: 8 June 1998 / Accepted: 24 August 1998     

Metamorphism and phase relations in carbonate rocks from the Nevado-Filábride Complex (Cordilleras Béticas, Spain): application of the Ttn + Rt + Cal + Qtz + Gr buffer

Phase relations and metamorphic conditions have been studied in metacarbonate rocks from the Nevado-Filábride Complex (Cordilleras Béticas) through forward modeling. In many rock samples, the assemblage titanite + rutile + calcite + quartz + graphite buffered the composition of the C-O-H fluid present during metamorphism. Over a wide range of P-T conditions, fluid compositions computed for this buffer are essentially binary H₂O-CO₂ mixtures. This buffer also constrains the chemical potentials of TiO₂, CaO and SiO₂. Consequently it is possible to make a thermodynamic projection through these components to predict the stable phase relations consistent with the buffer. Using this method, phase relations have been analyzed in a rock containing the buffer assemblage and paragonite, albite, phengite, epidote, and chlorite. The equilibrium P-T conditions for this assemblage are constrained, by minimization of the differences between predicted and observed mineral compositions, to be 560 ± 15 °C and 9.5 ± 1 kbar. Conditions obtained compare well with those estimated from other studies in different lithologic units. The inferred metamorphic fluid composition is H₂O-rich (). Received: 11 October 1995 / Accepted 5 August 1996     

Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

Graphite precipitation in C—O—H fluid inclusions: closed system compositional and density changes,and thermobarometric implications

 Equilibrium C–O–H fluid speciation calculations predict that graphite will precipitate from initially graphite saturated fluid inclusions during cooling and exhumation of metamorphic rocks. In the case that no mass is gained or lost by the inclusions, the original X _O ratio [O/(O+H)] of the fluid phase must be maintained. Given this closed system constraint, the down-temperature progress of graphite precipitation can easily be monitored as a function of the varible X _O, and produces some effects that are of significance to fluid inclusion studies: 1. Variation of the H₂O : CO₂ : CH₄ relationship in the graphite-saturated COH fluid, namely increase of X _H2 ^O and decrease of the carbonic fraction; 2. Decrease of fluid density due to precipitation of graphite, which is denser than the residual fluid; 3. Alteration of the CO₂ : CH₄ ratio of the fluid, depending on the initial O : H ratio of the fluid: for X _O>1/3, fluids increase their CO₂ : CH₄ ratio with decreasing temperature, and vice-versa. This implies that the CO₂ : CH₄ ratio measured at room T will not represent the trapping value, which is in any case closer to unity. As a consequence of density reduction, isochores extrapolated from densities observed at room temperature do not pass through the pressure-temperature conditions at which the inclusion was trapped, with pressure underestimates of up to 2 kbar. Actual P-T trapping conditions are located along the equilibrium “bulk isochore” (curve of constant-X _O, constant-volume) of the fluid. Alteration of the CO₂ : CH₄ ratio is a mechanism by which a CO₂-rich or CH₄-rich carbonic phase can be formed from aqueous fluids that are slightly off the neutral X _O=1/3 value. Subsequent segregation of this phase from the aqueous counterpart may account for the formation of pure CO₂ and CH₄ fluids in the upper crust. Received: 15 March 1995 / Accepted: 1 June 1995     

Hydroxyl defects in garnets from mantle xenoliths in kimberlites of the Siberian platform

A suite of more than 200 garnet single crystals, extracted from 150 xenoliths, covering the whole range of types of garnet parageneses in mantle xenoliths so far known from kimberlites of the Siberian platform and collected from nearly all the kimberlite pipes known in that tectonic unit, as well as some garnets found as inclusions in diamonds and olivine megacrysts from such kimberlites, were studied by means of electron microprobe analysis and single-crystal IR absorption spectroscopy in the v _OH vibrational range in search of the occurrence, energy and intensity of the v _OH bands of hydroxyl defects in such garnets and its potential use in an elucidation of the nature of the fluid phase in the mantle beneath the Siberian platform. The v _OH single-crystal spectra show either one or a combination of two or more of the following major v _OH bands, I 3645–3662 cm⁻¹, II 3561–3583 cm⁻¹, III 3515–3527 cm⁻¹, and minor bands, Ia 3623–3631 cm⁻¹, IIa 3593–3607 cm⁻¹. The type of combination of such bands in the spectrum of a specific garnet depends on the type of the rock series of the host xenolith, Mg, Mg-Ca, Ca, Mg-Fe, or alkremite, on the xenolith type as well as on the chemical composition of the respective garnet. Nearly all garnets contain band systems I and II. Band system III occurs in Ti-rich garnets, with wt% TiO₂ > ca. 0.4, from xenoliths of the Mg-Ca and Mg-Fe series, only. The v _OH spectra do not correspond to those of OH⁻ defects in synthetic pyropes or natural ultra-high pressure garnets from diamondiferous metamorphics. There were no indications of v _OH from inclusions of other minerals within the selected 60 × 60 μm measuring areas in the garnets. The v _OH spectra of pyrope-knorringite- and pyrope-knorringite-uvarovite-rich garnets included in diamonds do not show band systems I to III. Instead, they exhibit one weak, broad band (Δv _OH 200–460 cm⁻¹) near 3570 cm⁻¹, a result that was also obtained on pyrope-knorringite-rich garnets extracted from two olivine megacrysts. The quantitative evaluation, on the basis of relevant existing calibrational data (Bell et al. 1995), of the sum of integral intensities of all v _OH bonds of the garnets studied yielded a wide range of “water” concentrations within the set of the different garnets, between values below the detection limit of our single-crystal IR method, near 2 × 10⁻⁴ wt%, up to 163 × 10⁻⁴ wt%. The “water” contents vary in a complex manner in garnets from different xenolith types, obviously depending on a large number of constraints, inherent in the crystal chemistry as well as the formation conditions of the garnets during the crystallization of their mantle host rocks. Secondary alteration effects during uplift of the kimberlite, play, if any, only a minor role. Despite the very complex pattern of the “water” contents of the garnets, preventing an evaluation of a straightforward correlation between “water” contents of the garnets and the composition of the mantle's fluid phase during garnet formation, at least two general conclusions could be drawn: (1) the wide variation of “water” contents in garnets is not indicative of regional or local differences in the composition of the mantle's fluid phase; (2) garnets formed in the high-pressure/high-temperature diamond-pyrope facies invariably contain significantly lower amounts of “water” than garnets formed under the conditions of the graphite-pyrope facies. This latter result (2) may point to significantly lower f _H2O and f _O2 in the former as compared to the latter facies. Received: 25 November 1997 / Accepted: 9 March 1998     

Pressure dependence of hydroxyl solubility in coesite

 The solubility of hydroxyl in coesite was investigated in multianvil experiments performed at 1200 °C over the nominal pressure range 5–10 GPa, at an f _O2 close to the Ni-NiO buffer. The starting material for each experiment was a cylinder of pure silica glass plus talc, which dehydrates at high P and T to provide a source of water and hydrogen (plus enstatite and excess SiO₂). Fourier-transform infrared (FTIR) spectra of the recovered coesite crystals show five sharp bands at 3606, 3573, 3523, 3459, and 3299 cm⁻¹, indicative of structurally bonded hydrogen (hydroxyl). The concentration of hydrogen increases with pressure from 285 H/10⁶ Si (at 5 GPa) to 1415 H/10⁶ Si (at 10 GPa). Assuming a model of incorporation by (4H)_Si defects, the data are fit well by the equation C _OH=Af ² _H2<\INF>Oexp(−PΔV/RT), with A=4.38 H/10⁶ Si/GPa, and ΔV=20.6 × 10⁻⁶ m³ mol⁻¹. An alternative model entailing association of hydrogen with cation substitution can also be used to fit the data. These results show that the solubility of hydroxyl in coesite is approximately an order of magnitude lower than in olivines and pyroxenes, but comparable to that in pyropic garnet. However, FTIR investigations on a variety of ultrahigh pressure metamorphic rocks have failed in all cases to detect the presence of water or hydrogen in coesite, indicating either that it grew in dry environments or lost its hydrogen during partial transformation to quartz. On the other hand, micro-FTIR investigations of quartz crystals replacing coesite show that they contain varying amounts of H₂O. These results support the hypothesis that preservation of coesite is not necessarily linked to fast exhumation rates but is crucially dependent on limited fluid infiltration during exhumation. Received: 23 August 1999 / Accepted: 10 April 2000     

Halogen-bearing minerals in syenites and high-grade marbles of Dronning Maud Land,Antarctica: monitors of fluid compositional changes during late-magmatic fluid-rock interaction processes

Meta-sedimentary rocks including marbles and calcsilicates in Central Dronning Maud Land (CDML) in East Antarctica experienced a Pan-African granulite facies metamorphism with peak metamorphic conditions around 830 ± 20 °C at 6.8 ± 0.5 kbar which was accompanied by the post-kinematic intrusion of huge amounts of syenitic (charnockitic) magmas at 4.5 ± 0.7 kbar. The marbles and calcsilicates may represent meta-evaporites as indicated by the occurrence of metamorphic gypsum/anhydrite and Cl-rich scapolite that formed in the presence of saline fluids with X _NaCl in the range 0.15–0.27. The marbles and calcsilicates bear biotite, tremolite and/or hornblende and humite group minerals (clinohumite, chondrodite and humite) which are inferred to have crystallized at about 650 °C and 4.5 kbar. The syenitic intrusives contain late-magmatic biotite and amphibole (formed between 750 and 800 °C) as well as relictic magmatic fayalite, orthopyroxene and clinopyroxene. Two syenite and two calcsilicate samples contain fluorite. Corona textures in the marbles and calcsilicates suggest very low fluid-rock ratios during the formation of the retrograde (650 °C) assemblages. Biotite in all but two syenite samples crystallized at log(f _{H 2 O}/f _HF) ratios of 2.9 ± 0.4, while in the calcsilicates, both biotite and humite group minerals indicate generally higher log(f _{H 2 O}/f _HF) values of up to 5.2. A few samples, though, overlap with the syenite values. Log(f _{H 2 O}/f _HCl) derived from biotite covers the range 0.5–2.6 in all rock types. Within a single sample, the calculated values for both parameters vary typically by 0.1 to 0.8 log units. Water and halogen acid fugacities calculated from biotite-olivine/orthopyroxene-feldspar-quartz equilibria and the above fugacity ratios are 1510–2790 bars for H₂O, 1.3–5.3 bars for HF and 7–600 bars for HCl. The results are interpreted to reflect the reaction of relatively homogeneous magmatic fluids [in terms of log(f _{H 2 O} /f _HF)] derived from the late-magmatic stages of the syenites with both earlier crystallized, still hotter parts of the syenites and with adjacent country rocks during down-temperature fluid flow. Fluorine is successively removed from the fluid and incorporated into F-bearing minerals (close to the syenite into metamorphic fluorite). In the course of this process log(f _{H 2 O} /f _HF) increases significantly. Chlorine preferably partitions into the fluid and hence log(f _{H 2 O} /f _HCl) does not change markedly during fluid-rock interaction. Received: 28 November 1997 / Accepted: 27 April 1998     

Himalayan inverted metamorphism constrained by oxygen isotope thermometry

Inverted metamorphic field gradients are preserved in two amphibolite facies metapelitic sequences forming the crystalline core zone of the Himalayan orogen in the Sutlej valley (NW India). In the High Himalayan Crystalline Sequence (HHCS), metamorphic conditions increase upwards from the staurolite zone at the base, through the kyanite-in and sillimanite-in isograds, finally to reach partial melting conditions at the top. The structurally lower Lesser Himalayan Crystalline Sequence (LHCS) shows a gradual superposition of garnet-in, staurolite-in and kyanite + sillimanite-in isograds. Although phase equilibria constraints imply inverted temperature field gradients in both units, garnet-biotite (GARB) rim thermometry indicates final equilibration at a nearly uniform temperature around T ≈ 600 °C across these sequences. The P-T path and garnet zoning data show that this apparent lack of thermal field gradient is mainly the consequence of a resetting of the GARB equilibria during cooling. In order to constrain peak temperature conditions, 20 samples along the studied section have been analysed for oxygen isotope thermometry. The isotopic fractionations recorded by quartz-garnet and quartz-aluminosilicate mineral pairs indicate temperatures consistent with phase equilibria and P-T path constraints for metamorphic peak conditions. Together with barometry results, based on net transfer continuous reactions, the oxygen isotope thermometry indicates peak conditions characterized by: (1) a temperature increase from T ≈ 570 to 750 °C at a nearly constant pressure around P ≈ 800 MPa, from the base to the top of the HHCS unit; (2) a temperature increase from T ≈ 610 to 700 °C and a pressure decrease from P ≈ 900 to 700 MPa, from the base to the top of the LHCS metapelites. Oxygen isotope thermometry thus provides the first quantitative data demonstrating that the Himalayan inverted metamorphism can be associated with a complete inversion of the thermal field gradient across the crystalline core zone of this orogen. Received: 1 April 1999 / Accepted: 12 July 1999