Pyrope-rich Garnet Research Articles

Multicomponent diffusion in garnets I: general theoretical considerations and experimental data for Fe–Mg systems

We have carried out a combined theoretical and experimental study of multicomponent diffusion in garnets to address some unresolved issues and to better constrain the diffusion behavior of Fe and Mg in almandine–pyrope-rich garnets. We have (1) improved the convolution correction of concentration profiles measured using electron microprobes, (2) studied the effect of thermodynamic non-ideality on diffusion and (3) explored the use of a mathematical error minimization routine (the Nelder-Mead downhill simplex method) compared to the visual fitting of concentration profiles used in earlier studies. We conclude that incorporation of thermodynamic non-ideality alters the shapes of calculated profiles, resulting in better fits to measured shapes, but retrieved diffusion coefficients do not differ from those retrieved using ideal models by more than a factor of 1.2 for most natural garnet compositions. Diffusion coefficients retrieved using the two kinds of models differ only significantly for some unusual Mg–Mn–Ca-rich garnets. We found that when one of the diffusion coefficients becomes much faster or slower than the rest, or when the diffusion couple has a composition that is dominated by one component (>75 %), then profile shapes become insensitive to one or more tracer diffusion coefficients. Visual fitting and numerical fitting using the Nelder-Mead algorithm give identical results for idealized profile shapes, but for data with strong analytical noise or asymmetric profile shapes, visual fitting returns values closer to the known inputs. Finally, we have carried out four additional diffusion couple experiments (25–35 kbar, 1,260–1,400 °C) in a piston-cylinder apparatus using natural pyrope- and almandine-rich garnets. We have combined our results with a reanalysis of the profiles from Ganguly et al. (1998) using the tools developed in this work to obtain the following Arrhenius parameters in D = D0 exp{–[Q1bar + (P–1)ΔV+]/RT} for DMg* and DFe*: Mg: Q1bar = 228.3 ± 20.3 kJ/mol, D0 = 2.72 (±4.52) × 10−10 m2/s, Fe: Q1bar = 226.9 ± 18.6 kJ/mol, D0 = 1.64 (±2.54) × 10−10 m2/s. ΔV+ values were assumed to be the same as those obtained by Chakraborty and Ganguly (1992).

Phase relations during peak metamorphism and decompression of the UHP kyanite eclogites, Pohorje Mountains (Eastern Alps, Slovenia)

Phase relations among the mineral assemblages of UHP kyanite eclogite were investigated in the Pohorje Mountains of the Eastern Alps. Ultrahigh-pressure metamorphism resulted from intracontinental subduction during the Cretaceous (ca. 92Ma). Kyanite-bearing eclogites are associated with meta-ultramafic rocks including UHP garnet peridotites and are embedded in metapelitic gneisses and micaschists. The kyanite eclogites contain a peak metamorphic assemblage of garnet, omphacite, kyanite and phengite. Pyrope-rich garnet is unzoned and almost free of inclusions. The non-stoichiometric supersilicic omphacite contains up to 5mol% of Ca-Eskola molecule. Breakdown of omphacite during decompression resulted in exsolution of oriented rods of silica. Phengite contains up to 3.5 Si a.p.f.u. Polycrystalline quartz inclusions in peak-pressure minerals – garnet, omphacite and kyanite – are surrounded by radial fractures diagnostic of the former presence of coesite. Peak-pressure minerals are replaced by symplectites of diopside+plagioclase+amphibole after omphacite, plagioclase+biotite after phengite and sapphirine+corundum+spinel+anorthite after kyanite. Sapphirine has composition close to (Mg, Fe)12.4 Al38.9 Si4.5 O80 in average, which is amongst the most aluminous yet reported. Peak metamorphic conditions were constrained from calculated phase equilibria in the NKCFMASH system with the fixed bulk-rock composition, and conventional geothermobarometry. This approach led to consistent results, the calculated peak P–T conditions of 3.0–3.7GPa and 710–940°C, in the stability field of coesite and the same range as metamorphic conditions recorded by the associated garnet peridotites. This implies that eclogites and their host rocks were subducted to depths of about 100km. The relatively high temperature at peak pressure, compared to UHP rocks of Tertiary age in the Western Alps where mostly oceanic crust was subducted, probably resulted from radiogenic heat production by subducting continental crust, in the intra-continental setting of the Cretaceous subduction zone in the Eastern Alps.

An Experimental Study of Carbonated Eclogite at 3{middle dot}5-5{middle dot}5 GPa--Implications for Silicate and Carbonate Metasomatism in the Cratonic Mantle

We have experimentally investigated a K-bearing altered mid-ocean ridge basalt (MORB) composition to which 10% CaCO3 was added (GA1+10%cc), at temperatures of 1050-1400oC and pressures of 3•5-5•5 GPa. Experiments were conducted in piston-cylinder apparatus in Pt-Gr (Pt with inner graphite) and Au-Pd capsules. Sub-solidus assemblages for both sets of experiments contain clinopyroxene, garnet, carbonate, rutile, coesite and K-feldspar. Apatite was observed only in the Pt-Gr experiments. Melting behaviour in experiments using different capsule materials contrasted markedly. Experiments in Pt-Gr capsules showed the silicate solidus to be at temperatures less than 1100oC at 3•5GPa and less than 1050oC at 4•5-5•0 GPa.These are similar (3•5GPa) or lower (4•5-5•0 GPa) temperatures compared with the carbonate solidus (1075-1125oC at 3•5-5•0 GPa). Melts in the Pt-Gr runs evolve with increasing degree of melting from K-rich silicate melts at the lowest degree of melting to carbonate-silicate immiscible liquids and silicate-carbonate melts at intermediate degrees of melting, and finally to silicate melts at the highest degrees of melting. Experiments in Au-Pd capsules were performed only at 5•0GPa. The carbonate solidus is between 1200 and 1225oC (at least 100oC higher than in the experiments in Pt-Gr capsules at the same pressure-temperature conditions).The first melts to be produced are carbonatitic and exhibit increasing SiO2 content with increasing temperature.This contrast in melting behaviour is explained by the relatively rapid diffusion of H through the Pt-Gr capsules, resulting in formation of H2O, and thus dramatically depressing both the silicate and the carbonate solidi in the Pt-Gr experiments compared with those in the Au-Pd experiments. This presumably reflects the lower permeability of Au-Pd to H, resulting in a much lower H2O/CO2 ratio in the Au-Pd encapsulated experiments. The presence of water in the melt was demonstrated by Fourier transform infrared (FTIR) spectroscopic analysis of one Pt-Gr experiment, indicating ~0•5wt % H2O in the bulk composition. Further confirmation that H2O plays such a role in the Pt-Gr experiments was provided by an additional experiment performed in a Au-Pd capsule with ~10 wt % H2Ospecifically added. In this experiment immiscible carbonate and silicate melts were observed. Carbonate- silicate liquid immiscibility is considered to occur as a result of the H2O present in the system. These results can be applied to natural systems in several ways. First, the presence of a small amount of either silicate melt or H2O-fluid in the system will act as a ‘flux’, depressing the carbonate solidus to much lower temperatures than inanhydrous systems. Second, the full trend in melt evolution from silicate-rich to carbonate-rich melts, which is also observed in inclusions in diamonds, can be explained by melting of K- and CO2-bearing, water-undersaturated MORB compositions. In cratonic environments low-degree silicate and immiscible silicate and carbonate melts will metasomatize the overlying mantle in different ways, producing, in the first instance, Si enrichment and crystallization of additional orthopyroxene, phlogopite, pyrope-rich garnet and consuming olivine, and, in the second case, carbonate metasomatism, with additional magnesite-dolomite, clinopyroxene and apatite. Both metasomatic styles have been described in natural peridotite xenoliths from the cratonic lithosphere.

Crustal growth during back-arc closure: Cretaceous exhumation history of Cordillera Darwin, southern Patagonia

The Cordillera Darwin metamorphic complex is unique in the Andes in exposing kyanite–staurolite schist north of the Beagle Channel in southern Patagonia. Garnet in amphibolite facies pelitic schists from Bahia Pia has patchy textures whereby some grains consist of clear, grossular-rich garnet with fine-grained S1 inclusion trails truncated by regions of turbid spessartine–pyrope-rich garnet with biotite, muscovite, plagioclase and quartz inclusions. Micron-scale aqueous inclusions in turbid garnet are consistent with recrystallization facilitated by fluid ingress; S2 inclusion trails indicate this was broadly contemporary with the growth of kyanite and staurolite in the matrix. Pseudosection modelling in Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3 (NCKFMASHTO) is used to infer a P–T path dominated by decompression from 12 to 9 kbar at T ≈ 620 °C, coupled with garnet mode decreasing from ∼5% to <1%. U–Th–Pb in situ dating of S2 monazite indicates that staurolite and kyanite growth and thus exhumation was underway before 72.6 ± 1.1 Ma. Contact aureoles developed adjacent to late granite intrusions include sillimanite-bearing migmatites formed at P ≈ 6 kbar after 72 Ma. Metamorphism of southern Cordillera Darwin induced by continental underthrusting beneath the arc, related to closure of the Rocas Verdes back-arc basin, was terminated by thrusting-controlled exhumation, with the rocks at P ≈ 9 kbar by c. 73 Ma and 6 kbar by c. 70 Ma.

Direct evidence for upper mantle structure in the NW Pacific Plate: Microstructural analysis of a petit-spot peridotite xenolith

Petit-spots, the late Miocene alkali basaltic volcanoes on the Early Cretaceous NW Pacific Plate, originate at the base of the lithosphere. The petit-spot volcanic rocks enclose fragments of tholeiitic basalt, dolerite, gabbro, and mantle peridotite, providing a unique window into the entire section of subducting oceanic lithosphere. We provide here the first direct observations on the deep structure of the Pacific lithosphere using microstructural analyses of a petit-spot peridotite xenolith. The xenolith is a lherzolite that consists mainly of coarse- and medium-grained olivine, orthopyroxene, and clinopyroxene, as well as fine-grained aggregates of spinel and orthopyroxene that probably represent replaced pyrope-rich garnet. A strong deformational fabric is marked by a parallel alignment of millimeter-sized elongate minerals and their crystallographic preferred orientation. The olivine displays a [010] fiber pattern with a girdle of [100] axes and a maximum of [010] perpendicular to the foliation, a pattern which is consistent with a transpressional deformation in high temperature conditions at the base of oceanic lithosphere. Our microstructural observations and seismic data indicate that the lower part of the NW Pacific lithosphere possess an early stage structure of mantle flow at the asthenosphere. This interpretation is compatible with a conventional model in which oceanic lithosphere is thickened during cooling and plate convection. A discrepancy between the weak anisotropy in the petit-spot peridotite and the strong azimuthal anisotropy from the seismic data in the NW Pacific plate implies the existence of a highly anisotropic component in the deep oceanic lithosphere.

Thermoelastic properties of minerals at high temperature

The knowledge of elasticity of the minerals is useful for interpreting the structure and composition of the lower mantle and also in seismic studies. The purpose of the present study is to discuss a simple and straightforward method for evaluating thermoelastic properties of minerals at high temperatures. We have extended the Kumar’s formulation by taking into the account the concept of anharmonicity in minerals above the Debye temperature (θ D). In our present study, we have investigated the thermophysical properties of two minerals (pyrope-rich garnet and MgAl2O4) under high temperatures and calculated the second-order elastic constant (C ij ) and bulk modulus (K T) of the above minerals, in two cases first by taking Anderson–Gruneisen parameter (δ T) as temperature-independent and then by treating δ T as temperature-dependent parameter. The results obtained when δ T is temperature-dependent are in close agreement with experimental data.

Analysis of temperature dependence of thermal pressure of solids

Various models for determination of the temperature dependence of thermal pressure are critically examined in the light of experimental data. We have considered Mg2SiO4, Olivine, MgAl2O4, Pyrope rich garnet, Fe2SiO4, Grossular garnet, MnO, NaCl and KCl. The superiority of one model over others is discussed. The model is extended to study the compression behaviour at different temperatures, and the combined effect of pressure and temperature on thermal pressure of San Carlo Olivine. A good agreement obtained between theory and experiment demonstrates the validity of the present approach.

The Oxidation State of Metasomatized Mantle Wedge: Insights from C-O-H-bearing Garnet Peridotite

Oxygen fugacity (fO2) is an important parameter in determining the relative stabilities of phase assemblages. Whereas a number of studies have been devoted to determining the redox state of low-pressure assemblages in the mantle system, the fO2 of the supra-subduction mantle wedge is still poorly known. An essential input for fO2 estimates is the determination of the ferric–ferrous iron content of key mantle minerals such as garnet, which can be measured using the ‘flank method’ technique on an electron microprobe. We selected samples of orogenic peridotites from the ultrahigh-pressure Sulu belt (Eastern China) and from the Ulten Zone (Italian Alps) for detailed case studies; these correspond to slices of metasomatized mantle wedge sampled at different depths. They are characterized by the assemblage phlogopite + magnesite +amphibole in equilibrium with olivine, orthopyroxene and Fe3+-bearing garnet. The ‘flank method’ measurements indicate that these pyrope-rich garnets contain Fe3+/ΣFe up to 0·12–0·14. For peridotite mineral assemblages fO2 can be evaluated from equilibria involving the Fe3+-garnet component skiagite (Fe2+3Fe3+2Si3O12) on the basis of Fe3+–Al substitution on the octahedral site, which is sensitive to the garnet oxidation state. We modelled non-ideal mixing of Al and Fe3+ on the octahedral site and non-ideal mixing on the dodecahedral site, with a symmetric regular solution model for reciprocal solid solutions of Ca–Fe2+–Mg–Al–Fe3+-garnet. This allowed us to calculate garnet-peridotite fO2, given the presence of Fe3+ in garnet. Our results indicate that the Sulu and Ulten peridotites record high oxygen fugacities (FMQ to FMQ + 2) compared with garnet peridotite xenoliths from the sub-cratonic mantle equilibrated at similar pressures. The determination of the oxygen fugacity of these hydrate–carbonate-bearing garnet peridotites allowed us to estimate the speciation of C–O–H metasomatic fluids derived from the subducting slab, which are enriched in CO2. The fO2 evaluation of the metasomatized mantle-wedge peridotites, representing the oxygen chemical potential μO2, provides a first step in unravelling the relationship between μO2 and the metasomatic phase assemblage.

Electrical conductivity of pyrope-rich garnet at high temperature and high pressure

Garnet is one of the important constituent minerals in the upper mantle and the transition zone of the Earth's mantle. However, there were very few previous works on its electrical conductivity. We have measured the electrical conductivity of single crystal of pyrope-rich garnet (∼Py 73-Alm 14-Grs 13) under the conditions of 4–16 GPa, 873–1473 K and frequency range from 10 −2 to 10 6 Hz, with a range of water content (from less than 10 to 7000 H/10 6 Si). A KAWAI-type multi-anvil apparatus and a Solarton-1260 Impedance/Gain Phase analyzer were used in this study. The impedance spectra showed two circles correspondent to the intrinsic resistivity of the crystal and to the effects of charge accumulation at the electrodes. The DC electrical conductivity was determined by the impedance spectroscopy. Molybdenum and molybdenum oxide solid buffer was used to control the oxygen fugacity. Results on hydrous and anhydrous samples were compared to determine the influence of water content on the electrical conductivity of single crystal garnet. Under anhydrous conditions, the electrical conductivity of garnet increases with temperature and decreases with pressure. When we used a thermal activation parameterization, we obtain the following relationship: σ = A exp(−( E * + PV *)/ RT), A = 1036(±236) (1 − 0.044(±0.007) P(GPa)) S/m or A = exp[7.16(±0.37) (1 − 0.012(±0.009) P(GPa))] S/m, E * = 128 ± 6 kJ/mol and V * = 2.50 ± 0.48 cm 3/mol. Hydrous garnet crystals have significantly higher electrical conductivity with different temperature and pressure sensitivity, and the conductivity in these samples increases with the water content. The results can be summarized as σ = A ⋅ C w r exp [ − ( E * + P V * ) / R T ] with A = 1950 (+870, −600) S/m, r = 0.63 ± 0.19, E * = 70 ± 5 kJ/mol and V * = −0.57 ± 0.05 cm 3/mol. These results are similar to those obtained by Wang et al. [Wang, D.J., Mookherjee, M., Xu, Y.S., Karato. S., 2006. The effect of water on the electrical conductivity of olivine. Nature 443, 977–980] for olivine, Huang et al. [Huang, X.G., Xu, Y.S., Karato, S., 2005. Water content in the transition zone from electrical conductivity of wadsleyite and ringwoodite. Nature 434, 746–749] for wadsleyite and ringwoodite and we suggest that the mechanism of hydrogen conduction is likely common to these minerals. We conclude that hydrogen enhances the electrical conductivity of pyrope-rich garnet and its effect increases with pressure but decreases with temperature. At a typical pressure and temperature in the upper mantle, the influence of water is substantial.

Metamorphic history and geodynamic significance of high-grade metabasites from the ophiolitic mélange beneath the Yarlung Zangbo ophiolites, Xigaze area, Tibet

Blocks of highly foliated amphibolite are locally embedded within a serpentinite mélange underlying the Yarlung Zangbo ophiolites in the Xigaze area of southern Tibet. The ophiolites are remnants of an Early Cretaceous back-arc basin within the Permo-Cretaceous Tethys Ocean, which are exposed along in the Yarlung Zangbo Suture Zone (YZSZ). These amphibolites are interpreted as fragments of a dismembered dynamothermal sole. Three types of amphibolite are present: (1) common amphibolite with assemblages of Hbl + Pl ± Ep ± Ap ± Ttn, (2) clinopyroxene-bearing amphibolite with Hbl ± Pl ± Cpx ± Ep ± Ttn ± Qtz ± Ap and (3) garnet–clinopyroxene-bearing amphibolite characterized by the assemblages Hbl + Cpx + Grt + Pl ± Rt and Grt + Hbl + Pl (corona assemblage). In all three types, plagioclase is pseudomorphed by late albite–prehnite. Retrograde cataclastic veins containing assemblages of Prh + Ab + Ep ± Chl are also present. P–T estimates indicate that the amphibolites reached peak metamorphic conditions of 13–15 kbar and 750–875 °C. Partial replacement of pyrope-rich (up to 35 mole%) garnet by Al-tschermakite (Al 2O 3 up to 21 wt%) reflects a high pressure (≈18 kbar, 600 °C) metamorphic event followed by rapid exhumation. Soon after exhumation, the amphibolites were intruded by very fine-grained diabase dykes that were then hydrothermally altered. The field relationships and metamorphic history of the amphibolites indicate formation during inception of subduction within a back-arc basin prior to obduction of the ophiolites onto the Indian passive margin.

THERMAL EXPANSION STUDY OF A UVAROVITE RICH GARNET

Thermal expansion measurements have been performed on a uvarovite rich garnet sample for the first time and compared with the expansion data on grossular and pyrope-rich garnets reported in the literature. A semiclassical model has been used to analyze the data and to obtain various thermodynamic parameters. Using these parameters, the lattice specific heat and the corresponding entropy have also been calculated.

Rare earth element fractionation in magmatic Ca-rich garnets

Igneous garnets have the potential to strongly fractionate rare earth elements (REE). Yet informations on partition coefficients are very scant, and criteria for distinguishing between hydrothermal and magmatic garnets are ambiguous. To fill this gap, we present trace element and isotopic data for two types of Ca-rich garnets from phonolites (Mt. Somma-Vesuvius). Both Ca-garnet populations are different in their style and dynamics of fractionation: one population is progressively strongly depleted in HREE from core to rim, reflecting REE fractionation in the host phonolite via earlier-crystallized garnets. Such examples for extreme changes in HREE in garnets are only known for hydrothermal grandites by REE-bearing fluids. The second garnet population is homogeneous and formed in a closed system. Near-flat patterns between Sm and Lu confirm experimental data indicating lower D(Sm)/D(Lu) for Ca-rich garnets than for e.g. pyrope-rich garnets. It follows: D Grt/PhMelt for La = 0.5, Sm = 48 and Yb = 110.

Electrical conductivities of pyrope-almandine garnets up to 19 GPa and 1700 C

Electrical conductivities of polycrystalline garnets ranging in chemical composition from almandine (Fe 3 Al 2 Si 3 O 12 ) to pyrope (Mg 3 Al 2 Si 3 O 12 ) were measured at 10 GPa and 19 GPa at temperatures ranging from 300 to 1700 °C using complex impedance spectroscopy in a multianvil device. Mössbauer spectroscopy of each sample was carried out both before and after the electrical measurements to characterize the oxidation state of Fe in the almandine bearing garnets. Similar to the behavior of other ferromagnesian silicates, the substitution of Fe for Mg along this compositional join dramatically increases electrical conductivity, but this compositional effect is reduced with increasing temperature. Conductivities increase with increasing total Fe content, as the average Fe 2+ -Fe 3+ distance decreases. At 10 GPa, activation energies for conductivity vary smoothly with composition and increase rapidly toward the pyrope end-member composition, where it reaches a value of 2.5 eV. The results are consistent with an electrical conductivity mechanism involving small polaron mobility in the Fe-bearing garnets at 10 GPa. At 19 GPa, however, there is virtually no change in the activation energy as a function of Fe-Mg substitution for the pyrope-rich garnets. These higher pressure measurements reflect a mechanism involving oxygen related point defects, as conductivities increase with pressure at constant T for each garnet, and the effect of pressure is greater for the more Mg-rich garnets. The data also allow for a more quantitative evaluation of the effect of chemical composition, specifically Fe-Mg substitution, on the electrical conductivity profile of the mantle, using a recently developed laboratory- derived model. We apply the model using these data to a portion of the transition zone between 520 and 660 km, in which we vary the garnet composition from Py 100 to Py 85 Alm 15 . Although only a minor effect on bulk mantle conductivity results, we conclude that the overall garnet composition may, however, be important in characterizing the magnitude of any EC discontinuity with respect to the above-lying mantle.

Exhumation History of a Garnet Pyroxenite-bearing Mantle Section from a Continent-Ocean Transition (Northern Apennine Ophiolites, Italy)

Garnet clinopyroxenite and garnet websterite layers occur locally within mantle peridotite bodies from the External Liguride Jurassic ophiolites (Northern Apennines, Italy). These ophiolites were derived from an ocean–continent transition similar to the presentday western Iberian margin. The garnet clinopyroxenites are mafic rocks with a primary mineral assemblage of pyrope-rich garnet þ sodic Al-augite (Na2O 2.5 wt %, Al2O3 12.5 wt %), with accessory graphite, Fe–Ni sulphides and rutile. Decompression caused Na-rich plagioclase (An50–45) exsolution in clinopyroxene porphyroclasts and extensive development of symplectites composed of secondary orthopyroxene þ plagioclase (An85–72) þ Al-spinel ± clinopyroxene ± ilmenite at the interface between garnet and primary clinopyroxene. Further decompression is recorded by the development of an olivine þ plagioclase-bearing assemblage, locally under syn-kinematic conditions, at the expense of two-pyroxenes þ Al-spinel. Mg-rich garnet has been also found in the websterite layers, which are commonly characterized by the occurrence of symplectites made of orthopyroxene þ Al-spinel ± clinopyroxene. The enclosing peridotites are Ti-amphibole-bearing lherzolites with a fertile geochemical signature and a widespread plagioclase-facies mylonitic foliation, which preserve in places a spinel tectonite fabric. Lu–Hf and Sm–Nd mineral isochrons (220 ± 13 Ma and 186.0 ± 1.8 Ma, respectively) have been obtained from a garnet clinopyroxenite layer and interpreted as cooling ages. Geothermobarometric estimates for the high-pressure equilibration have yielded T 1100 C and P 2.8 GPa. The early decompression was associated with moderate cooling, corresponding to T 950 , and development of a spinel tectonite fabric in the lherzolites. Further decompression associated with plagioclase–olivine growth in both peridotites and pyroxenites was nearly isothermal. The shallow evolution occurred under a brittle regime and led to the superposition of hornblende to serpentine veining stages. The garnet pyroxenitebearing mantle from the External Liguride ophiolites represents a rare tectonic sampling of deep levels of subcontinental lithosphere exhumed in an oceanic setting. The exhumation was probably accomplished through a two-step process that started during Late Palaeozoic continental extension. The low-pressure portion of the exhumation path, probably including also the plagioclase mylonitic shear zones, was related to the Mesozoic (Triassic to Jurassic) rifting that led to continental break-up. In Jurassic times, the studied mantle sequence became involved in an extensional detachment process that resulted in sea-floor denudation.

INSIGHTS INTO THE ORIGIN OF MANTLE GRAPHITE FROM A NEW OCCURENCE IN GARNET PYROXENITES FROM THE EXTERNAL LIGURIDE PERIDOTITES (NORTHERN APENNINE, ITALY)

The occurrence of elemental carbon in the mantle, either as diamond or, more rarely as graphite, is almost uniquely restricted to peridotite and eclogite xenoliths derived from cratonic lithospheric mantle. In non-cratonic areas, the occurrence of graphite-bearing garnet pyroxenites has been only reported for mantle bodies exhumed in orogenic settings, namely the Ronda (Davies et al., 1993) and Beni Bousera (Pearson et al., 1993) massifs, where the graphite may occur as diamond pseudomorphs and was interpreted as originated from crustally-derived, biogenic carbon recycled into mantle through subduction on the basis of 13C-depleted isotopic composition. Mantle peridotites of the External Liguride units represent slices of subcontinental lithospheric mantle exhumed during the rifting phases leading to the Jurassic Ligurian Tethys formation. These mantle rocks locally enclose up to meter-sized layers of graphite-bearing garnet pyroxenites. The high-pressure protoliths were characterised by coarsegrained isotropic texture and anhydrous bimineralic assemblage, consisting of pyrope-rich garnet (Prp53-45Alm29- 38Grs11-20) + sodic Al-augite (Na2O ~2.5 wt%, Al2O3 ~ 12.5 wt%), with accessory amounts of Fe-Ni sulphides and rutile. Geothermobarometric estimates for the high-pressure equilibration have yielded T = 1150-1200 °C and P = 2.6-3.0 GPa. Graphite (up to 3 vol%) occurs as flakes and stacks of flakes with grain size up to 2-3 mm. No pseudomorphs with octahedral or cubic simmetry suggesting the former ocurrence of diamond have been observed, in agreement with pressure estimates. The enclosing peridotites do not contain any vein or disseminated graphite. Sulphides (mainly pyrrhotine and pentlandite derived from high-T monosulphide solid solutions) occur as tiny rounded blebs into garnet and clinopyroxene or as interstitial crystals; their abundance may locally reach up to ~ 5 vol % . Graphite crystals were analysed by microRaman spectrometry on fresh fracture surfaces. Well defined first (O-) and second order (S-) peaks, and the absence of first order D-peaks indicate a highly ordered structure similar to that of graphite crystallised at high temperature in peridotite and eclogite xenoliths (Pearson et al., 1994). C isotope composition (d13C= - 4.5) reflects a typical mantle signature. Whole-rock and mineral trace element evidence indicate that the graphite-bearing garnet pyroxenites have suffered some partial melting (Tribuzio et al., this meeting). The observed sulphides may have originated from trapped (immiscible) sulphide melt. We propose that graphite precipitation was possibly related to carbon saturation reached in these sulphide liquids or to carbon nucleation on a sulphide medium, in agreement with experimental evidence and common diamond-sulphide association in higher pressure peridotite and eclogite xenoliths (Bulanova, 2002; Bulanova et al., 1998; Haggerty, 1986; Jacob et al., 2004; Litvin et al., 2002).

EXHUMATION HISTORY OF SUBCONTINENTAL GARNET PYROXENITE-BEARING MANTLE FROM THE EXTERNAL LIGURIDE OPHIOLITES (NORTHERN APENNINE, ITALY): IMPLICATIONS FOR RIFTING AND MANTLE EXHUMATION PROCESSES AT OCEAN-CONTINENT TRANSITION

The External Liguride Jurassic ophiolites derive from an ocean-continent transition similar to the West Iberian margin. The mantle sequence consists of spinel and spinel-plagioclase lherzolites recording a lithospheric thinning history culminated into mantle exhumation at the ocean-floor. They represent unroofed subcontinental litosphere of the former Adria-Europe system largely affected by thermochemical erosion, heating and refertilization by asthenospheric melts during the Ligurian Tethys formation (Rampone et al., 1995; Piccardo et al., 2004). Peridotite bodies which escaped melt contamination and intrusion preserve relics of a deep-seated litospheric origin, i.e. occurrence of graphitebearing garnet clinopyroxenite and websterite layers. The garnet pyroxenite-bearing mantle from the External Liguride ophiolites therefore represents a unique tectonic sampling of deep levels of subcontinental lithosphere exhumed in an oceanic setting. Garnet clinopyroxenites are mafic rocks with a primary assemblage of pyrope-rich garnet + sodic Al-augite (Na2O ~2.5 wt%, Al2O3 ~12.5 wt%), with minor amounts of orthopyroxene, graphite, Fe-Ni sulphides and rutile. Decompression yielded Na-rich plagioclase (An50-45) exsolutions in clinopyroxene porphyroclasts and extensive development of symplectites composed of secondary orthopyroxene + plagioclase (An85-72) + Al-spinel ± clinopyroxene ± ilmenite at the interface between garnet and primary clinopyroxene. Further decompression is recorded by the development of an olivine+ plagioclase-bearing assemblage, locally under synkinematic conditions, at the expenses of two-pyroxene + Alspinel. Mg-rich garnet has been also found in websterite layers, which are commonly characterised by the occurrence of symplectites made of orthopyroxene + Al-spinel ± clinopyroxene. The enclosing peridotites are Ti-amphibole-bearing lherzolites with a fertile geochemical signature and a widespread plagioclase-facies mylonitic foliation, which preserve in places a spinel tectonite fabric. Lu-Hf and Sm-Nd mineral isochrons (220 ± 13 Ma and 186 ± 1.8 Ma, respectively) have been obtained from a garnet clinopyroxenite layer and interpreted as cooling ages. Geothermobarometric estimates for the high-pressure equilibration have yielded T = 1150-1200 °C and P = 2.6-3.0 GPa. The early decompression was associated with significant cooling, corresponding to T = 900-1050°C, and development of the spinel tectonite fabric in the lherzolites. Further decompression associated with plagioclase-olivine growth in both peridotites and pyroxenites was nearly isothermal. The shallow evolution was characterized by a widespread polyphase brittle deformation under decreasing temperature conditions, coupled with hydration. In particular, the brittle evolution includes an early amphibolite-facies veining stage, followed by low-temperature hydrothermal alteration and serpentinisation associated with polyphase cataclasis. The exhumation was likely accomplished as a two-step process starting during Late Palaeozoic continental extension. The low-pressure portion of the exhumation path, possibly including also the plagioclase mylonitic shear zones, was related to the Mesozoic (Triassic to Jurassic) rifting that led to continental break-up. In Jurassic times, the studied mantle sequence was involved into an extensional detachment structure up to sea-floor exhumation, which was associated with development of serpentinisation-related hydrothermal activity. Integrated values of cooling and uplift rates for the Jurassic rifting evolution are ~35°C/Ma and 0.6-1.4 mm yr-1.

SIMS analyses on trace and rare earth elements in coexisting clinopyroxene and mica from minette mafic enclaves in potassic syenites crystallized under high pressures

Trace and rare earth element contents were determined by SIMS technique in clinopyroxene and mica crystals from minette lamprophyric enclaves in a potassic syenite host. This co-mingled system was crystallized at high pressures, which varied about 3–5 GPa, as indicated by the presence of K-clinopyroxenes and pyrope-rich garnet with measurable amounts of K2O and Na2O, among the near-liquidus phases. Major and trace element composition of these lamprophyric enclaves is quite similar to those observed in silica-rich lamproites, suggesting that similar sources were involved in their origin. In a general view, the concentrations of most trace and rare earth elements in clinopyroxene of the studied enclaves are higher than those referred to by other authors. Clinopyroxene/melt partition coefficient for most trace elements are close to determinations in alkali-basalts and lamproites from Leucite Hills, with considerable differences relative to Gaussberg lamproites. Furthermore, these partition data are completely different from those determined for potassic lavas crystallized under crustal pressures. Spidergrams for clinopyroxenes exhibit negative-Sr anomalies relative to LREE, which have been associated by most authors to crystallization under low-pressures, out of garnet stability field. The presence of pyrope together with K-clinopyroxene excludes such hypotheses for the studied enclaves. Y and HREE are concentrated in clinopyroxene, whilst the other trace elements have Kd 3) determined in the studied phlogopite is unusual in lamproites, lamprophyres, and basalts, but frequently observed in phlogopite from metasomatic mantle samples, as well as in acid magmas. This partition value may indicate the lack of other mineral phase with high partition for this element during crystallization, and may be enhanced by the liquid composition progressively closer to alkali feldspar, an unsuitable structure for six-coordinated cations. Ce/Yb, Rb/Sr, and Zr/Hf ratios in clinopyroxene and mica suggest that the minettic magma could produce the host Piquiri potassic syenite by fractional crystallization. This hypothesis is not consistent with Ba concentrations in clinopyroxene and mica, which suggest that a Ba-bearing phase (e.g. alkali feldspar) should be among the fractionated phases in order to produce the potassic syenites.

High-pressure minerals in mafic microgranular enclaves: evidences for co-mingling between lamprophyric and syenitic magmas at mantle conditions

Mafic microgranular enclaves, composed of diopside and rare magnesium biotite phenocrysts in a groundmass of diopside, biotite, apatite, Fe-Ti-oxides, and alkali feldspar, are associated with Neoproterozoic Piquiri potassic syenite in southern Brazil. Co-genetic mica and clinopyroxene cumulates present inclusions of pyrope-rich garnet in diopside phenocrysts. Textural evidence, as well as the chemical and mineralogical composition, suggest that enclaves crystallized from a lamprophyric magma and co-mingled with the host syenitic magma. The contrasting temperature between both magmas and the consequent chilling was important for the preservation of some early-crystallized minerals in the mafic magma. Diopside groundmass grains contain micro-inclusions of K-rich augite and phlogopite, and some clinopyroxene phenocrysts and elongate groundmass crystals have potassium-rich cores. The pyrope-rich garnet have high #mg number (67–68), with appreciable amounts of Na2O and K2O comparable to pyrope synthesized at 5 GPa. The extremely high K2O contents of K-rich augite micro-inclusions suggest non-equilibrium with the parental magma, whereas the other K-rich clinopyroxenes are similar to K-clinopyroxenes produced at 5–6 GPa. K-clinopyroxene and garnet in mafic microgranular enclaves suggest that lamprophyric magma started its crystallization at upper mantle conditions, and chilled clinopyroxenes with measurable amounts of K2O are taken as evidence that co-mingling began still at mantle pressures.

Chromian dissakisite-(Ce) in a garnet lherzolite from the Chinese Su-Lu UHP metamorphic terrane: Implications for Cr incorporation in epidote-group minerals and recycling of REE into the Earth’s mantle

Chromian dissakisite-(Ce), a Cr-enriched Mg analogue of allanite-(Ce), is found in a garnet lherzolite from the Su-Lu ultrahigh-pressure (UHP) metamorphic terrane, eastern China. Major minerals of the lherzolite are olivine [ X Mg = Mg/(Mg + Fe) = 0.92], pyrope-rich garnet (Prp70.1–73.2Alm11.3–13.4Grs6.9–8.3Uvr3.6–5.1Anr0–0.4Sps0.7–1.7), orthopyroxene ( X Mg = 0.92–0.93), and clinopyroxene (XMg = 0.92–0.95). The chromian dissakisite-(Ce) occurs as a single-crystal inclusion in a clinopyroxene neoblast that also contains several irregularly shaped olivine grains. It is partly metamict, and there is intensive radial cracking in the surrounding clinopyroxene. Its composition is represented by the averaged formula: (Ca0.86Na0.03)0.89(REE0.86Th0.04)0.90(Mg0.98Fe2+0.20Fe3+0.21Cr0.36Al1.39Ti0.04)Si3.03O12(OH), with Ce2O3, MgO and Cr2O3 contents up to 13.1, 7.3, and 5.4 wt%, respectively. Because the M3 site in the chromian dissakisite-(Ce) is fully occupied by Mg and Fe2+, Fe3+ and Cr can only occupy the smaller M1 site. Similar site occupancy is noted for a chromian allanite from the Sanbagawa metamorphic belt, Japan, which contains up to 0.547 Cr atoms per formula unit (apfu). Such compositional characteristics of the chromian dissakisite/allanite and existing polarized absorption data on Cr-bearing epidote suggest the existence of possible end-members, “CeCa(Mg,Fe)CrAlSi3O12(OH),” for the epidote-group minerals, which may form solid solution with Ca2Al3Si3O12(OH) through coupled substitutions of REEMgCa−1Al−1, REEFeCa−1Al−1, and CrAl−1. The rare earth elements (REE), Ca, and Na total 1.79 apfu, implying that Mn and Fe2+ are also present on the nine-coordinated A1 site. The high REE abundance, the presence of minor Na, and the Mg and Cr-enriched characteristics of the mineral suggest that it was formed as a result of reaction between the host lherzolite and crust-derived melt/fluid at UHP conditions. Textural relations suggest that the chromian dissakisite-(Ce) was unstable in the garnet lherzolite and reacted with olivine to form clinopyroxene. Dissakisite-(REE) in subducted ultramafic rocks can transport rare earth elements into the Earth’s mantle.

Evolution of spinel–pyroxene symplectite in spinel–lherzolites from the Horoman Complex, Japan

We examined the textural and geochemical characteristics of spinel–pyroxene symplectites in spinel–lherzolites collected from the lowest, middle, and upper parts (LZ1, MZ, and UZ1, respectively) of the Horoman Peridotite Complex, Japan. The modal proportion of the minerals within symplectite is almost the same, i.e., orthopyroxene:clinopyroxene:spinel = 2:1:1. The size of the symplectite minerals increases from the lowest through to the middle to the upper parts in the complex. The reconstructed major element composition of the bulk symplectites is intermediate between pyrope-rich garnet and olivine. The model garnet compositions of the LZ1satisfies garnet stoichiometry and those of the MZ and UZ1 are not consistent with garnet stoichiometry. The primitive mantle-normalized pattern in trace elements for the LZ1 symplectite is similar to that of pyrope-rich garnet from fertile peridotites, particularly in its enrichment of HREE and a positive Zr anomaly. Thus, the LZ1 symplectite has inherited both major and trace element signatures from pre-existing garnet whereas the compositions of the MZ and UZ1 symplectites were modified during and/or after breakdown of pre-existing garnet. Geochemical and textural variations of symplectites might basically correspond to temperature differences within the complex during upwelling of the Horoman Complex. The basal part of the complex (LZ1) experienced the lowest temperature decompression path in the complex, which resulted in less textural and chemical modification. On the other hand, the higher part of the complex (UZ1) experienced a relatively higher temperature decompression path than other parts of the complex, resulting in chemical equilibration among the constituent minerals and coarsening of the symplectite minerals. Selective enrichment of Sr and LREE in the symplectite may indicate that the metasomatism by a Sr- and LREE-rich melt/fluid occurred during and/or after the formation of symplectite.