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

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

Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO–SiO2–H2O±Al2O3

The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H₂O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al₂O₃ in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.     

Solubility of water in the α, β and γ phases of (Mg,Fe)2SiO4

 The solubility of hydroxyl in the α, β and γ phases of (Mg,Fe)₂SiO₄ was investigated by hydrothermally annealing single crystals of San Carlos olivine. Experiments were performed at a temperature of 1000° or 1100 °C under a confining pressure of 2.5 to 19.5 GPa in a multianvil apparatus with the oxygen fugacity buffered by the Ni:NiO solid-state reaction. Hydroxyl solubilities were determined from infrared spectra obtained of polished thin sections in crack-free regions ≤100 μm in diameter. In the α-stability field, hydroxyl solubility increases systematically with increasing confining pressure, reaching a value of ∼20,000 H/10⁶Si (1200 wt ppm H₂O) at the α-β phase boundary near 13 GPa and 1100 °C. In the β field, the hydroxyl content is ∼400,000 H/10⁶Si (24,000 wt ppm H₂O) at 14–15 GPa and 1100 °C. In the γ field, the solubility is ∼450,000 H/10⁶Si (27,000 wt ppm H₂O) at 19.5 GPa and 1100 °C. The observed dependence of hydroxyl solubility with increasing confining pressure in the α phase reflects an increase in water fugacity with increasing pressure moderated by a molar volume term associated with the incorporation of hydroxyl ions into the olivine structure. Combined with published results on the dependence of hydroxyl solubility on water fugacity, the present results for the α phase can be summarized by the relation C _OH = A(T)f nH₂Oexp(−PΔV/RT), where A(T) = 1.1 H/10⁶Si/MPa at 1100 °C, n = 1, and ΔV = 10.6×10^–6 m³/mol. These data demonstrate that the entire present-day water content of the upper mantle could be incorporated in the mineral olivine alone; therefore, a free hydrous fluid phase cannot be stable in those regions of the upper mantle with a normal concentration of hydrogen. Free hydrous fluids are restricted to special tectonic environments, such as the mantle wedge above a subduction zone. Received: 10 February 1995 / Accepted: 23 October 1995     

Diffusion and solubility of hydrogen and water in periclase

Cylinders of synthetic periclase single crystals were annealed at 0.15–0.5 GPa and 900–1200 °C under water-saturated conditions for 45 min to 72 h. Infrared spectra measured on the quenched products show bands at 3,297 and 3,312 cm^?1 indicating V _OH ^? centers (OH-defect stretching vibrations in a half-compensated cation vacancy) in the MgO structure as a result of proton diffusion into the crystal. For completely equilibrated specimens, the OH-defect concentration, expressed as H₂O equivalent, was calculated to 3.5 wt ppm H₂O at 1,200 °C and 0.5 GPa based on the calibration method of Libowitzky and Rossmann (Am Min 82:1111–1115, 1997). This value was confirmed via Raman spectroscopy, which shows OH-defect-related bands at identical wavenumbers and yields an H₂O equivalent concentration of about 9 wt ppm using the quantification scheme of Thomas et al. (Am Min 93:1550–1557, 2008), revised by Mrosko et al. (Am Mineral 96:1748–1759, 2011). Results of both independent methods give an overall OH-defect concentration range of 3.5–9 (+4.5/?2.6) ppm H₂O. Proton diffusion follows an Arrhenius law with an activation energy E _a = 280 ± 64 kJ mol^?1 and the logarithm of the pre-exponential factor logD_o (m² s^?1) = ?2.4 ± 1.9. IR spectra taken close to the rims of MgO crystals that were exposed to water-saturated conditions at 1,200 °C and 0.5 GPa for 24 h show an additional band at 3,697 cm^?1, which is related to brucite precipitates. This may be explained by diffusion of molecular water into the periclase, and its reaction with the host crystal during quenching. Diffusion of molecular water may be described by logD_H2O (m² s^?1) = ?14.1 ± 0.4 (2σ) at 1,200 °C and 0.5 GPa, which is ~ 2 orders of magnitude slower than proton diffusion at identical P-T conditions.     

The temperature dependence of water solubility in enstatite

The solubility of water in pure enstatite was measured on samples synthesized under water-saturated conditions at 15 kbar and temperatures ranging from 700 to 1,100°C. Polarized FTIR measurements on millimetre-sized, clear crystals showed that water solubility increases strongly with temperature, from 101 ppm by weight at 700°C to 269 ppm by weight at 1,100°C. The position and shape of the infrared bands hardly changes with temperature, with one notable exception: a band close to 3,380 cm^–1 is present in samples synthesized between 700 and 1,000°C, while this band is absent from samples synthesized at 1,100°C. This effect appears to be very reproducible and points towards a slight change in the crystal structure of enstatite between 1,000 and 1,100°C at 15 kbar. The water solubility data of this study as well as those of Rauch and Keppler (Contrib Mineral Petrol 143:525–536, 2002) can be reproduced by the equation where K is water solubility, is water fugacity, A is 0.01354 ppm/bar, V^solid=12.1 cm³/mol is the volume change of enstatite during incorporation of water, and H^{1 bar}=-4,563 J/mol is the reaction enthalpy at 1 bar. This equation predicts the following behaviour of water solubility in enstatite as a function of pressure and temperature: (1) water solubility increases with pressure up to a maximum around 80 kbar; (2) water solubility decreases with temperature at 1 bar; and (3) water solubility increases with temperature between 10 and 100 kbar. If the observed temperature dependence for enstatite were representative for other upper mantle minerals as well, it would have the following implications: (1) Lateral temperature gradients in the upper mantle could cause major variations in water contents at the same depth; in particular, hot mantle plumes may scavenge water from the surrounding shallow upper mantle. (2) The scavenging of water by hot plumes could be a major factor in increasing the mobility of plumes. (3) The predicted temperature dependence of water solubility at the base of the upper mantle may allow plumes to bypass the transition zone water filter postulated by Bercovici and Karato (Nature 425:39–44, 2003).     

Water solubility in pyrope to 100 kbar

The solubility and incorporation mechanism of water in natural, almost pure pyrope from Dora Maira, Western Alps was investigated. The infrared spectrum of the natural, untreated sample (58 ppm water) shows several exceptionally sharp bands in the OH-stretching region, including a single band at 3601.9 cm⁻¹ and a band system with main components at 3640.5, 3650.8 and 3660.6 cm⁻¹. High-temperature and high-pressure infrared spectra suggest that the two absorption features arise from almost free OH groups in sites with different compressibility and thermal expansivity, with the site causing the 3601.9 cm⁻¹ band being much stiffer. Pyrope samples were annealed in a piston-cylinder or multi-anvil apparatus for several days in the presence of excess water, excess SiO₂ and excess Al₂SiO₅ to determine the equilibrium solubility of water in pyrope to 100 kbar. Total solubility increases with pressure, however, this is exclusively due to the high-frequency band system, while the intensity of the low-frequency band decreases with pressure. At 1000 °C and the oxygen fugacity of the Ni-NiO buffer, the bulk solubility can be described by the equation c _OH =Af _H2O ^0.5exp(−PΔV/RT) with A = 0.679 ppm/bar^0.5 and ΔV = 5.71 cm³/mol. This equation implies the incorporation of water in the crystal as isolated OH groups. With increasing temperature, solubility appears to decrease with ΔH = − 14 kJ/mol. At Fe-FeO buffer conditions, solubility is 30 to 50% lower than with the Ni-NiO buffer, suggesting that the incorporation of OH is not coupled to the reduction of Fe³⁺. Possibly, the 3601.9 cm⁻¹ band is associated with the tetrahedral OH B defect and the high-frequency system with the dodecahedral OH Li defect. Based on the experimentally established solubility model, it is estimated that garnet in a hot subducted slab will transport 170 ppm of water into the mantle beyond the breakdown limit of amphibole. In a cold slab, 470 ppm of water can be incorporated into garnet at the breakdown limit of phengite. These numbers imply that a significant fraction of the total water in the hydrosphere has been recycled into the mantle since the Proterozoic. Received: 6 January 1997 / Accepted: 27 March 1997     

The solubility of water in NaAlSi3O8 melts: a re-examination of Ab−H2O phase relationships and critical behaviour at high pressures

The solubility of water in melts in the NaAlSi₃O₈–H₂O system at high P and T was deduced from the appearance of quenched products and from water concentrations in the quenched glasses measured by ion probe, calibrated by hydrogen manometry. Starting materials were gels with sufficient water added to ensure saturation of the melts under the run conditions. Experiments were carried out for 10–30 h in an internally heated argon pressure vessel (eight at 1400° C and 0.2–0.73 GPa and three at 0.5 GPa and 900–1200° C) and for 1 h in a piston-cylinder apparatus (three at 1200° C, 1–1.3 GPa). No bubbles were observed in the glasses quenched at P<0.5 GPa or from T<1300° C at 0.5 GPa. Bubble concentration in glasses quenched from 1400° C was low at 0.5, moderate at 0.55 GPa and very high at 0.73 GPa and still higher in glasses quenched in the piston cylinder. Water concentration was measured in all glasses, except for the one at 0.55 GPa, for which it was only estimated, and for those at 0.73 GPa because bubble concentration was too high. Inferred water solubilities in the melt increase strongly with increasing P at 1400° C (from 6.0 wt% at 0.2 GPa to 15 at 0.55 GPa) and also with increasing T at 0.5 GPa (from 9.0 wt% at 900° C to 12.9 at 1400° C). The T variation of water solubility is fundamental for understanding the behaviour of melts on quenching. If the solubility decreases with T at constant P (retrograde solubility), bubbles cannot form by exsolution on isobaric quenching, whereas if the solubility is prograde they may do so if the cooling rate is not too fast. It is inferred from observed bubble concentrations and from our and previous solubility data that water solubility is retrograde at low P and prograde at and above 0.45 GPa; it probably changes with T from retrograde below to prograde above 900° C at 0.5 GPa. Moreover, the solubility is very large at higher pressures (possibly>30 wt% at 1.3 GPa and 1200° C) and critical behaviour is approached at 1.3 GPa and 1200° C. The critical curve rises to slightly higher P at lower T and intersects the three-phase or melting curve at a critical end point near 670° C and 1.5 GPa, above which albite coexists only with a supercritical fluid.     

Paragonite stability at 700°C in the presence of H<Subscript>2</Subscript>O–NaCl fluids: constraints on H<Subscript>2</Subscript>O activity and implications for high pressure metamorphism

We carried out reversed piston-cylinder experiments on the equilibrium paragonite = jadeite + kyanite + H₂O at 700°C, 1.5–2.5 GPa, in the presence of H₂O-NaCl fluids. Synthetic paragonite and jadeite and natural kyanite were used as starting materials. The experiments were performed on four different nominal starting compositions: X(H₂O)=1.0, 0.90, 0.75 and 0.62. Reaction direction and extent were determined from the weight change in H₂O in the capsule, as well as by optical and scanning electron microscopy (SEM). At X(H₂O)=1.0, the equilibrium lies between 2.25 and 2.30 GPa, in good agreement with the 2.30–2.45 GPa reversal of Holland (Contrib Miner Petrol 68:293–301, 1979). Lowering X(H₂O) decreases the pressure of paragonite breakdown to 2.10–2.20 GPa at X(H₂O)=0.90 and 1.85–1.90 GPa at X(H₂O)=0.75. The experiments at X(H₂O) = 0.62 yielded the assemblage albite + corundum at 1.60 GPa, and jadeite + kyanite at 1.70 GPa. This constrains the position of the isothermal paragonite–jadeite–kyanite–albite–corundum–H₂O invariant point in the system Na₂O–Al₂O₃–SiO₂–H₂O to be at 1.6–1.7 GPa and X(H₂O)~0.65±0.05. The data indicate that H₂O activity, a(H₂O), is 0.75–0.86, 0.55–0.58, and <0.42 at X(H₂O)=0.90, 0.75, and 0.62, respectively. These values approach X(H₂O)², and agree well with the a(H₂O) model of Aranovich and Newton (Contrib Miner Petrol 125:200–212, 1996). Our results demonstrate that the presence or absence of paragonite can be used to place limits on a(H₂O) in high-pressure metamorphic environments. For example, nearly pure jadeite and kyanite from a metapelite from the Sesia Lanzo Zone formed during the Eo-Alpine metamorphic event at 1.7–2.0 GPa, 550–650°C. The absence of paragonite requires a fluid with low a(H₂O) of 0.3–0.6, which could be due to the presence of saline brines.     

High-pressure single-crystal X-ray diffraction study of jadeite and kosmochlor

The crystal structures of natural jadeite, NaAlSi₂O₆, and synthetic kosmochlor, NaCrSi₂O₆, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure–volume data have been fit to a third-order Birch–Murnaghan equation of state yielding V ₀ = 402.5 (4) Å³, K ₀ = 136 (3) GPa, and K ₀ ^′  = 3.3 (2) for jadeite and V ₀ = 420.0 (3) Å³, K ₀ = 123 (2) GPa and K ₀ ^′  = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025–1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO₄ tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3–O3–O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges.     

Submicron-sized fluid inclusions and distribution of hydrous components in jadeite,quartz and symplectite-forming minerals from UHP jadeite–quartzite in the Dabie Mountains,China: TEM and FTIR investigation

Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO₂-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH⁻) and free water (H₂O) in the form of clusters of water molecules. The H₂O transformed from OH⁻ during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H₂O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.     

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

Evolution of a tourmaline-bearing lawsonite eclogite from the Elekdağ area (Central Pontides,N Turkey): evidence for infiltration of slab-derived B-rich fluids during exhumation

An undated high-pressure low-temperature tectonic mélange in the Elekda area (central Pontides, N Turkey) comprises blocks of MORB-derived lawsonite eclogite within a sheared serpentinite matrix. In their outer shells, some of the eclogite blocks contain large (up to 6 cm) tourmaline crystals. Prograde inclusions in poikiloblastic garnet from a well-preserved eclogite block are lawsonite, epidote/clinozoisite, omphacite, rutile, glaucophane, chlorite, Ba-bearing phengite, minor actinolite, winchite and quartz. In addition, glaucophane, lawsonite and rutile occur as inclusions in omphacite. These inclusion assemblages document the transition from a garnet-lawsonite-epidote-bearing blueschist to a lawsonite eclogite with the peak assemblage garnet + omphacite I + lawsonite + rutile. Peak metamorphic conditions are not well-constrained but are estimated approximately 400–430°C and >1.35 GPa, based on Fe–Mg exchange between garnet and omphacite and the coexistence of lawsonite + omphacite + rutile. During exhumation of the eclogite–serpentinite mélange in the hanging wall of a subduction system, infiltration of B-rich aqueous fluids into the rims of eclogite blocks caused retrogressive formation of abundant chlorite, titanite and albite, followed by growth of tourmaline at the expense of chlorite. At the same time, omphacite I (X_Jd=0.24–0.44) became unstable and partially replaced by omphacite II characterized by higher X_Jd (0.35–0.48), suggesting a relatively low silica activity in the infiltrating fluid. Apart from Fe-rich rims developed at the contact to chlorite, tourmaline crystals are nearly homogeneous. Their compositions correspond to Na-rich dravite, perhaps with a small amount of excess (tetrahedral) boron (~5.90 Si and 3.10 B cations per 31 anions). ¹¹ B values range from –2.2 to +1.7. The infiltrating fluids were most probably derived from subducting altered oceanic crust and sediments.     

Compressional behavior of omphacite to 47 GPa

Omphacite is an important mineral component of eclogite. Single-crystal synchrotron X-ray diffraction data on natural (Ca, Na) (Mg, Fe, Al)Si₂O₆ omphacite have been collected at the Advanced Photon Source beamlines 13-BM-C and 13-ID-D up to 47 GPa at ambient temperature. Unit cell parameter and crystal structure refinements were carried out to constrain the isothermal equation of state and compression mechanism. The third-order Birch–Murnaghan equation of state (BM3) fit of all data gives V ₀ = 423.9(3) Å³, K _T0 = 116(2) GPa and K _T0′ = 4.3(2). These elastic parameters are consistent with the general trend of the diopside–jadeite join. The eight-coordinated polyhedra (M2 and M21) are the most compressible and contribute to majority of the unit cell compression, while the SiO₄ tetrahedra (Si1 and Si2) behave as rigid structural units and are the most incompressible. Axial compressibilities are determined by fitting linearized BM3 equation of state to pressure dependences of unit cell parameters. Throughout the investigated pressure range, the b-axis is more compressible than the c-axis. The axial compressibility of the a-axis is the largest among the three axes at 0 GPa, yet it quickly drops to the smallest at pressures above 5 GPa, which is explained by the rotation of the stiffest major compression axis toward the a-axis with the increase in pressure.     

Constraining peak P–T conditions in UHP eclogites: calculated phase equilibria in kyanite‐ and phengite‐bearing eclogite of the Tromsø Nappe,Norway

Kyanite‐ and phengite‐bearing eclogites have better potential to constrain the peak metamorphic P–T conditions from phase equilibria between garnet + omphacite + kyanite + phengite + quartz/coesite than common, mostly bimineralic (garnet + omphacite) eclogites, as exemplified by this study. Textural relationships, conventional geothermobarometry and thermodynamic modelling have been used to constrain the metamorphic evolution of the Tromsdalstind eclogite from the Tromsø Nappe, one of the biggest exposures of eclogite in the Scandinavian Caledonides. The phase relationships demonstrate that the rock progressively dehydrated, resulting in breakdown of amphibole and zoisite at increasing pressure. The peak‐pressure mineral assemblage was garnet + omphacite + kyanite + phengite + coesite, inferred from polycrystalline quartz included in radially fractured omphacite. This omphacite, with up to 37 mol.% of jadeite and 3% of the Ca‐Eskola component, contains oriented rods of silica composition. Garnet shows higher grossular (X_Grs = 0.25–0.29), but lower pyrope‐content (X_Prp = 0. 37–0.39) in the core than the rim, while phengite contains up to 3.5 Si pfu. The compositional isopleths for garnet core, phengite and omphacite constrain the P–T conditions to 3.2–3.5 GPa and 720–800 °C, in good agreement with the results obtained from conventional geothermobarometry (3.2–3.5 GPa & 730–780 °C). Peak‐pressure assemblage is variably overprinted by symplectites of diopside + plagioclase after omphacite, biotite and plagioclase after phengite, and sapphirine + spinel + corundum + plagioclase after kyanite. Exhumation from ultrahigh‐pressure (UHP) conditions to 1.3–1.5 GPa at 740–770 °C is constrained by the garnet rim (X_Ca^Grt = 0.18–0.21) and symplectite clinopyroxene (X_Na^Cpx = 0.13–0.21), and to 0.5–0.7 GPa at 700–800 °C by sapphirine (X_Mg = 0.86–0.87) and spinel (X_Mg = 0.60–0.62) compositional isopleths. UHP metamorphism in the Tromsø Nappe is more widespread than previously known. Available data suggest that UHP eclogites were uplifted to lower crustal levels rapidly, within a short time interval (452–449 Ma) prior to the Scandian collision between Laurentia and Baltica. The Tromsø Nappe as the highest tectonic unit of the North Norwegian Caledonides is considered to be of Laurentian origin and UHP metamorphism could have resulted from subduction along the Laurentian continental margin. An alternative is that the Tromsø Nappe belonged to a continental margin of Baltica, which had already been subducted before the terminal Scandian collision, and was emplaced as an out‐of‐sequence thrust during the Scandian lateral transport of nappes.     

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     

Solubility of CO2 in a Ca-rich leucitite: effects of pressure,temperature, and oxygen fugacity

The solubility of carbon dioxide in a Ca-rich leucitite has been investigated as a function of pressure (0.1–2.0 GPa), temperature (1200–1600°C), and oxygen fugacity. The experiments were done in a rapid-quench internally-heated pressure vessel (0.1 GPa) and a piston cylinder (0.5–2.0 GPa). The leucitite glass, previously equilibrated at NNO, and silver oxalate were loaded in Fe-doped Pt capsules (oxidized conditions) and graphitelined Pt capsules (reduced conditions). Secondary Ion Mass Spectrometry and bulk carbon analyses were used to determine the amount of dissolved carbon. Speciation of carbon was characterized by Fourier transform microinfrared spectroscopy. At oxidized conditions, only CO₃ ^2- is observed as a dissolved species. The solubility is high with CO₂ contents in the melt attaining 6.2 wt% at 2.0 GPa and 1350°C. The solubility increases with pressure and shows a significant negative temperature dependence. An excellent correlation is obtained when the data are fit to a model, based on the simplified solubility reaction CO₂ ^(vapor)+O^2-(melt)CO₃ ^2-(melt), which describes the solubility of CO₂ as a function of pressure, temperature and fCO₂. At reduced conditions, the amount of carbon dissolved is significantly lower, and CO₃ ^2- is still the only species present in the melt. If the solubility model established at oxidized conditions is applied, the carbon dissolved appears to be essentially a function of fCO₂ alone although divergence increases in a consistent manner with pressure and temperature. This could suggest a low but significant solubility of CO with a positive temperature dependence or a departure of the calculated fluid compositions determined by the equation of state from the actual ones. The strong preferential solubility of carbon in its oxidized C⁴⁺ form, even at reduced conditions, implies that ascending melts with high CO₂ solubility can experience significant oxidation through degassing. This could reconcile the oxidized nature of some Ca-rich alkaline magmas with more reduced mantle source regions.     

The influence of Al2O3 on the H2O content in periclase and ferropericlase at 25 GPa

In this paper I present results of IR spectroscopic measurements of water solubility in Al-bearing periclase and ferropericlase (Mg# = 88) synthesized at 25 GPa and 1400–2000 °C. The IR spectra of their crystals show narrow absorption peaks at 3299, 3308, and 3474 cm^?1. The calculated H₂O contents are 11–25 ppm in periclase (Al₂O₃ = 0.9–1.2 wt.%) and 14–79 ppm in ferropericlase (Al₂O₃ = 0.9–2.9 wt.%). Ferropericlase contains more H₂O and Al₂O₃ than periclase at 1800–2000 °C. I suggest that addition of Al₂O₃ does not influence the solubility of water in ferropericlase but can favor the additional incorporation of Fe₂O₃ into the structure. The incorporation of Fe³⁺ into ferropericlase increases water solubility as a result of iron reduction to Fe²⁺. It is shown that water has limited solubility in ferropericlase from mantle peridotite; therefore, ferropericlase cannot be considered an important hydrogen-bearing mineral in the lower mantle.     

Origin of retrograde fluid in ultrahigh-pressure metamorphic rocks: Constraints from mineral hydrogen isotope and water content changes in eclogite-gneiss transitions in the Sulu orogen

By taking advantage of having depth profiles between contrasting lithologies from core samples of the Chinese Continental Scientific Drilling (CCSD) project, a combined study was carried out to examine changes in mineral H isotope, total water and hydroxyl contents in garnet and omphacite across the contacts between ultrahigh-pressure (UHP) eclogite and gneiss in the Sulu orogen, east-central China. The samples of interest were from two continuous core segments from the CCSD main hole at depths of 734.21-737.16 and 929.67-932.86 m, respectively. The results show δD values of −116‰ to  − 64‰ for garnet and −104‰ to −82‰ for omphacite, consistent with incorporation of meteoric water into protoliths of UHP metamorphic rocks by high-T alteration. Both equilibrium and disequilibrium H isotope fractionations were observed between garnet and omphacite, suggesting fluid-assisted H isotope exchange at local scales during amphibolite-facies retrogression. While bulk water analysis gave total H₂O concentrations of 522-1584 ppm for garnet and 1170-20745 ppm for omphacite, structural hydroxyl analysis yielded H₂O contents of 80-413 ppm for garnet and 228-412 ppm for omphacite. It appears that significant amounts of molecular H₂O are present in the minerals, pointing to enhanced capacity of water storage in the UHP eclogite minerals. Hydrogen isotope variations in the transition between eclogite and gneiss show correlations with variations in their water contents. Petrographically, the degree of retrograde metamorphism generally increases with decreasing distance from the eclogite-gneiss boundary. Thus, retrograde metamorphism results in mineral reactions and H isotope variation. Because hydroxyl solubility in nominally anhydrous minerals decreases with dropping pressure, significant amounts of water are expected to be released from the minerals during decompression exhumation. Decompression exsolution of structural hydroxyl from 1 m³ volume of eclogite composed of only garnet and omphacite results in release of a quantitative estimate of 3.07-3.44 kg water that can form 140-156 kg amphibole during exhumation. Therefore, it is concluded that fluid for retrogression of the eclogites away from the eclogite-gneiss boundary was derived from the decompression exsolution of structural hydroxyl and molecular H₂O in nominally anhydrous minerals. For the eclogites adjacent to gneiss, in contrast, the retrograde metamorphism was principally caused by aqueous fluid from the gneiss which is relatively rich in water. Consequently, both the origin and availability of metamorphic fluid during exhumation of deeply subducted continental crust are deciphered by this combined study focusing on the transitions and the retrograde processes between the felsic and mafic UHP rocks.     

Relics of eclogite facies metamorphism in the Austroalpine basement,Hochgrössen (Speik complex), Austria

Summary Retrograde eclogites and serpentinites from the Hochgr?ssen massif, Styria, are parts of the Speik complex in the Austroalpine basement nappes of the Eastern Alps. They are in tectonic contact with pre-Alpine gneisses, amphibolites, and Permo-Triassic quartz phyllites (Rannach Series). The eclogites are derived from ocean-floor basalts with affinities to mid-ocean ridge and back-arc basin basalts. Fresh eclogites are rare and contain omphacite with a maximum of 39 mol% jadeite content, garnet (Py_15–19) and amphibole. Retrograde eclogites consist of amphibole and symplectites of Na-poor clinopyroxene (5–8 mol% Jd) + albite ± amphibole. Amphiboles are classified as edenite, pargasite, tschermakite, magnesiohornblende and actinolite. In relatively fresh eclogite, edenite is a common amphibole and texturally coexists with omphacite and garnet. An average temperature of 700 °C was obtained for eclogite facies metamorphism using garnet-pyroxene thermometry. A minimum pressure of 1.5 GPa is indicated by the maximum jadeite content in omphacite. Thermobarometric calculations using the TWEEQ program for amphibole in textural equilibrium with omphacite and garnet give pressures of 1.8–2.2 GPa at 700 °C. The equilibrium assemblage of Na-poor clinopyroxene, albite, amphibole and zoisite in the symplectites gives a pressure of about 0.6–0.8 GPa at 590–640 °C. ⁴⁰Ar/³⁹Ar radiometric dating of edenitic amphibole in textural equilibrium with omphacite gave a plateau age of 397.3 ± 7.8 Ma, and probably indicates retrograde cooling through the closure temperature for amphibole (∼500 °C). The age of the high-pressure metamorphism thus must be pre-Variscan and points to one of the earliest metamorphic events in the Austroalpine nappes known to date. Received June 11, 2000; revised version accepted January 2, 2001     

Implications to garnet-clinopyroxene geothermometry of non-ideal solid solution in jadeitic pyroxenes

Garnet-clinopyroxene geothermometry has been applied to numerous rock types from the blueschist and eclogite terrain of the Sesia zone in the Western Alps. Discrepancies in apparent temperatures of up to 600° C have been found suggesting substantial deviation from ideal behaviour of the garnet-clinopyroxene equilibria in certain assemblages. Assemblages containing jadeitic pyroxenes rather than omphacitic or diopsidic pyroxenes yield very low K _D (2.0) values and correspondingly high apparent temperatures (> 1,000° C). The garnets coexisting with high-Na pyroxenes have compositions similar to those coexisting with omphacitic pyroxenes. Departure from ideal behaviour of these garnets is likely to be minor and is accomodated in the formulation of the geothermometer. Numerous examples of coexisting garnet-clinopyroxene pairs indicate that there is no obvious relationship of K _D with jadeite content in pyroxenes with jadeite content less than 70%, but at higher values, K _D varies inversely with the jadeite content. The dependence of K _D upon the jadeite content in the high-Na pyroxenes is believed to be due to the preference of M2 sites for Fe²⁺ in the enstatite-jadeite substitution (Fe²⁺MgNa_–1Al_–1). This substitution is usually very limited and has no demonstrable effect upon X _Fe ^Cpx when the M1 (Fe²⁺+Mg) content of the pyroxenes is high as in omphacitic and diopsidic pyroxenes. However, when the M1 (Fe²⁺+Mg) content is low, as in jadeitic pyroxenes, the non-ideality of the enstatite type exchange has a marked effect on X _Fe ^Cpx and consequently on garnet-clinopyroxene calculations.