Trace-element partitioning between garnet,clinopyroxene and Fe-rich picritic melts at 3 to 7 GPa

We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py₆₃Al₂₅Gr₁₂) and clinopyroxene (∼Ca_0.2Mg_0.6Fe_0.2Si₂O₆) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D ^cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca_0.3–0.5Mg_0.3–0.6Fe_0.07–0.2Si₂O₆) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca_0.2Mg_0.7Fe_0.1Si₂O₆). D ^grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py_70–88Al_l7–20Gr_8–14). 97SB68 D _LREE^grt/liq values are higher and D _HREE^grt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py_20–70Al_10–50Gr_10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.     

Melt- versus fluid-induced metasomatism in spinel to garnet wedge peridotites (Ulten Zone, Eastern Italian Alps): clues from trace element and Li abundances

The peridotite bodies of the Ulten Zone (Upper Austroalpine, Italian Eastern Alps) are enclosed in Variscan migmatites and derive from a mantle wedge environment. They display the progressive transformation of porphyroclastic spinel peridotites (T=1,200°C; P=1.5 GPa) into fine-grained garnet–amphibole peridotites (T=850°C; P=3 GPa). Detailed bulk-rock and mineral trace element analyses of a sample suite documenting the entire metamorphic evolution of the peridotites revealed several stages of metasomatism. The spinel peridotites derive from a depleted mantle that became enriched in some large ion lithophile element (LILE) and light rare earth elements (LREE). The same signature pertains to clinopyroxene and orthopyroxene, indicating that this metasomatic signature was acquired at the recorded temperature of 1,200°C. Such a temperature is considerably above the wet peridotite solidus and hence the metasomatic agent must have been a hydrous melt. Moreover, the Li-enrichment of the spinel-facies pyroxenes (up to 24 ppm Li) reflects disequilibrium distribution after exchange with a presumably mafic melt. ^cpx/opx D _Li=3–7 and ^cpx/ol D _Li=2.7–8 indicate that the spinel-facies clinopyroxene hosts higher Li amounts than the coexisting minerals. LREE fractionation, variable LREE enrichment, LILE enrichment with respect to HFSE (average clinopyroxene Pb _N /Nb _N =16–90) in spinel lherzolites can be related to chromatographic effects of porous melt flow. The significant enrichment of pyroxenes from the spinel lherzolites in Pb, U and Li indicates that the metasomatic melt was subduction-related. All these features suggest that the spinel lherzolites formed a mantle wedge layer percolated by melts carrying recycled crustal components and rising from a deeper source of subduction magmas. The garnet + amphibole peridotites equilibrated at temperatures well below the wet solidus in the presence of an aqueous fluid. Bulk-rock trace element patterns display pronounced positive anomalies in Cs, Ba, Pb and U and moderate enrichment in Li, indicating addition of a crustal component to the mantle rocks. Amphibole hosts most of these trace elements. Clinopyroxene displays high LILE/HFSE (Pb _N /Nb _N =300–600), low Ce/Pb (1.4–2.7 in garnet-facies clinopyroxene compared with 2.6–24.5 in the spinel-facies one) and variable LILE and LREE enrichments. The coupled increase of modal amphibole, Sr and Pb, together with positive Pb–Sr and Pb–U correlations, further indicate that incompatible element influx in these samples was fluid-mediated. In the garnet-facies samples, amphibole and, interestingly, olivine have similarly high Li concentrations as clinopyroxene, leading to ^cpx/amph D _Li=0.7 and ^cpx/ol D _Li=0.7–0.8, the latter being up to ten times lower than in the spinel-facies rocks. Due to its high modal abundance, olivine is the main host of Li in the garnet–amphibole peridotites. The observed metasomatic features provide evidence for the infiltration of an aqueous fluid in the mantle wedge above a subducting slab. This fluid most likely derived from subducted crustal rocks that underwent partial melting. Successive retrograde re-equilibration during exhumation of the garnet peridotite is accompanied by garnet and clinopyroxene breakdown and amphibole formation. This process produced minor changes, such as an increase of HREE and Li in amphibole, and an increase of Li in olivine. The general trace element signature remains essentially unchanged during retrogression and further hydration, indicating that fluids with a similar composition to the one present at the garnet–amphibole peridotite formation, were responsible for increased amphibole formation. The combined evidence from the metamorphic and metasomatic evolution indicates that the peridotites experienced first corner flow in a mantle wedge, followed by subduction and finally entrapment and exhumation within a crustal slab. During their entire history the Ulten peridotites were percolated first by melts and then by aqueous fluids, which added recycled crustal components to the mantle wedge.     

Hydrogen partitioning between melt,clinopyroxene, and garnet at 3 GPa in a hydrous MORB with 6 wt.% H<Subscript>2</Subscript>O

To understand partitioning of hydrogen between hydrous basaltic and andesitic liquids and coexisting clinopyroxene and garnet, experiments using a mid-ocean ridge basalt (MORB) + 6 wt.% H₂O were conducted at 3 GPa and 1,150–1,325°C. These included both isothermal and controlled cooling rate crystallization experiments, as crystals from the former were too small for ion microprobe (SIMS) analyses. Three runs at lower bulk water content are also reported. H₂O was measured in minerals by SIMS and in glasses by SIMS, Fourier Transform infrared spectroscopy (FTIR), and from oxide totals of electron microprobe (EMP) analyses. At 3 GPa, the liquidus for MORB with 6 wt.% H₂O is between 1,300 and 1,325°C. In the temperature interval investigated, the melt proportion varies from 100 to 45% and the modes of garnet and clinopyroxene are nearly equal. Liquid composition varies from basaltic to andesitic. The crystallization experiments starting from above the liquidus failed to nucleate garnets, but those starting from below the liquidus crystallized both garnet and clinopyroxene. SIMS analyses of glasses with >7 wt.% H₂O yield spuriously low concentrations, perhaps owing to hydrogen degassing in the ultra-high vacuum of the ion microprobe sample chamber. FTIR and EMP analyses show that the glasses have 3.4 to 11.9 wt.% water, whilst SIMS analyses indicate that clinopyroxenes have 1,340–2,330 ppm and garnets have 98–209 ppm H₂O. D _H ^cpx−gt is 11 ± 3, D _H ^cpx−melt is 0.023 ± 0.005 and D _H ^gt−melt is 0.0018 ± 0.0006. Most garnet/melt pairs have low values of D _H ^gt−melt, but D _H ^gt−melt increases with TiO₂ in the garnet. As also found by previous studies, values of D _H ^cpx−melt increase with Al₂O₃ of the crystal. For garnet pyroxenite, estimated values of D _H ^{pyroxenite−melt} decrease from 0.015 at 2.5 GPa to 0.0089 at 5 GPa. Hydration will increase the depth interval between pyroxenite and peridotite solidi for mantle upwelling beneath ridges or oceanic islands. This is partly because the greater pyroxene/olivine ratio in pyroxenite will tend to enhance the H₂O concentration of pyroxenite, assuming that neighboring pyroxenite and peridotite bodies have similar H₂O in their pyroxenes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Single clinopyroxene thermobarometry for garnet peridotites. Part I. Calibration and testing of a Cr-in-Cpx barometer and an enstatite-in-Cpx thermometer

Experimental clinopyroxenes synthesized at 850–1500 °C and 0–60 kbar in the CMS and CMAS-Cr systems and in more complex lherzolitic systems have been used to calibrate a Cr-in-Cpx barometer and an enstatite-in-Cpx thermometer for Cr-diopsides derived from garnet peridotites. The experiments cover a wide range of possible natural peridotitic compositions, from fertile pyrolite to refractory, high-Cr lherzolite. The barometer is based on the Cr exchange between clinopyroxene and garnet. Pressure is formulated as a function of temperature and clinopyroxene composition:

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Tourmaline breakdown in a pelitic system: implications for boron cycling through subduction zones

Pressure–temperature conditions of tourmaline breakdown in a metapelite were determined by high-pressure experiments at 700–900°C and 4–6 GPa. These experiments produced an eclogite–facies assemblage of garnet, clinopyroxene, phengite, coesite, kyanite and rare rutile. The modal proportions of tourmaline clearly decreased between 4.5 and 5 GPa at 700°C, between 4 and 4.5 GPa at 800°C, and between 800 and 850°C at 4 GPa, with tourmaline that survived the higher temperature conditions appearing corroded and thus metastable. Decreases in the modal abundance of tourmaline are accompanied by decreasing modal abundance of coesite, and increasing that of clinopyroxene, garnet and kyanite; the boron content of phengite increases significantly. These changes suggest that, with increasing pressure and temperature, tourmaline reacts with coesite to produce clinopyroxene, garnet, kyanite, and boron-bearing phengite and fluid. Our results suggest that: (1) tourmaline breakdown occurs at lower pressures and temperatures in SiO₂-saturated systems than in SiO₂-undersaturated systems. (2) In even cold subduction zones, subducting sediments should release boron-rich fluids by tourmaline breakdown before reaching depths of 150 km, and (3) even after tourmaline breakdown, a significant amount of boron partitioned into phengite could be stored in deeply subducted sediments.     

Melting experiments on the enstatite-diopside join at 70–224 kbar,including the melting of diopside

 Melting relations on the enstatite−diopside (En, Mg₂Si₂O₆−Di, CaMgSi₂O₆) join, including the compositions of crystalline phases and melts coexisting along the solidi, were experimentally determined in the pressure range 70–224 kbar with a split-sphere anvil apparatus (USSA-2000). Melting is peritectic in enstatite-rich compositions at 70–124 kbar (1840–2100° C) and eutectic at higher pressures, while the diopside-rich clinopyroxene melts azeotropically at 70–165 kbar and up to 300° C lower temperatures than the eutectic. Orthopyroxene is replaced with enstatite-rich clinopyroxene at 120 kbar and 2090°C. First garnet with 17 mol% Di forms on the solidus at 158 kbar and 2100° C. Two garnets coexist on the solidus at 165–183 kbar and 2100° C, garnet coexists with CaSiO₃ perovskite at 183–224 kbar (2100–2230° C) and two coexisting perovskites are stable at higher pressures. The melting curve of diopside was determined at 80–170 kbar; the slope becomes negative at 140 kbar and 2155° C. At 170 kbar and 2100° C, diopside with 96% Di breaks down to garnet with 89% Di and CaSiO₃ perovskite. The new data were used to calculate an improved temperature-pressure phase diagram for the CMAS system, which can be useful for estimating the mineralogy of the Earth's upper mantle. Received: 15 October 1994 / Accepted: 15 October 1995     

Melting of carbonated pelites at 8–13 GPa: generating K-rich carbonatites for mantle metasomatism

The melting behaviour of three carbonated pelites containing 0–1 wt% water was studied at 8 and 13 GPa, 900–1,850°C to define conditions of melting, melt compositions and melting reactions. At 8 GPa, the fluid-absent and dry carbonated pelite solidi locate at 950 and 1,075°C, respectively; >100°C lower than in carbonated basalts and 150–300°C lower than the mantle adiabat. From 8 to 13 GPa, the fluid-present and dry solidi temperatures then increase to 1,150 and 1,325°C for the 1.1 wt% H₂O and the dry composition, respectively. The melting behaviour in the 1.1 wt% H₂O composition changes from fluid-absent at 8 GPa to fluid-present at 13 GPa with the pressure breakdown of phengite and the absence of other hydrous minerals. Melting reactions are controlled by carbonates, and the potassium and hydrous phases present in the subsolidus. The first melts, which composition has been determined by reverse sandwich experiments, are potassium-rich Ca–Fe–Mg-carbonatites, with extreme K₂O/Na₂O wt ratios of up to 42 at 8 GPa. Na is compatible in clinopyroxene with D_\textNa^{\textcpx/\textcarbonatite} = 10-18 D_{\text{Na}}^{{{\text{cpx}}/{\text{carbonatite}}}} = 10{-}18 at the solidus at 8 GPa. The melt K₂O/Na₂O slightly decreases with increasing temperature and degree of melting but strongly decreases from 8 to 13 GPa when K-hollandite extends its stability field to 200°C above the solidus. The compositional array of the sediment-derived carbonatites is congruent with alkali- and CO₂-rich melt or fluid inclusions found in diamonds. The fluid-absent melting of carbonated pelites at 8 GPa contrasts that at ≤5 GPa where silicate melts form at lower temperatures than carbonatites. Comparison of our melting temperatures with typical subduction and mantle geotherms shows that melting of carbonated pelites to 400-km depth is only feasible for extremely hot subduction. Nevertheless, melting may occur when subduction slows down or stops and thermal relaxation sets in. Our experiments show that CO₂-metasomatism originating from subducted crust is intimately linked with K-metasomatism at depth of >200 km. As long as the mantle remains adiabatic, low-viscosity carbonatites will rise into the mantle and percolate upwards. In cold subcontinental lithospheric mantle keels, the potassic Ca–Fe–Mg-carbonatites may freeze when reacting with the surrounding mantle leading to potassium-, carbonate/diamond- and incompatible element enriched metasomatized zones, which are most likely at the origin of ultrapotassic magmas such as group II kimberlites.     

Geochemical syntheses among the cratonic,off-cratonic and orogenic garnet peridotites and their tectonic implications

Garnet-bearing mantle peridotites, occurring as either xenoliths in volcanic rocks or lenses/massifs in high-pressure and ultrahigh-pressure terrenes within orogens, preserve a record of deep lithospheric mantle processes. The garnet peridotite xenoliths record chemical equilibrium conditions of garnet-bearing mineral assemblage at temperatures (T) ranging from ~700 to 1,400°C and pressures (P) > 1.6–8.9 GPa, corresponding to depths of ~52–270 km. A characteristic mineral paragenesis includes Cr-bearing pyropic garnet (64–86 mol% pyrope; 0–10 wt% Cr₂O₃), Cr-rich diopside (0.5–3.5 wt% Cr₂O₃), Al-poor orthopyroxene (0–5 wt% Al₂O₃), high-Cr spinel (Cr/(Cr + Al) × 100 atomic ratio = 2–86) and olivine (88–94 mol% forsterite). In some cases, partial melting, re-equilibration involving garnet-breakdown, deformation, and mantle metasomatism by kimberlitic and/or carbonatitic melt percolations are documented. Isotope model ages of Archean and Proterozoic are ubiquitous, but Phanerozoic model ages are less common. In contrast, the orogenic peridotites were subjected to ultrahigh-pressure (UHP) metamorphism at temperature ranging from ~700 to 950°C and pressure >3.5–5.0 GPa, corresponding to depths of >110–150 km. The petrologic comparisons between 231 garnet peridotite xenoliths and 198 orogenic garnet peridotites revealed that (1) bulk-rock REE (rare earth element) concentrations in xenoliths are relatively high, (2) clinopyroxene and garnet in orogenic garnet peridotites show a highly fractionated REE pattern and Ce-negative anomaly, respectively, (3) Fo contents of olivines for off-cratonic xenolith are in turn lower than those of orogenic garnet and cratonic xenolith but mg-number of garnet for orogenic is less than that of off-cratonic and on-cratonic xenolith, (4) Al₂O₃, Cr₂O₃, CaO and Cr# of pyroxenes and chemical compositions of whole rocks are very different between these garnet peridotites, (5) orogenic garnet peridotites are characterized by low T and high P, off-cratonic by high T and low P, and cratonic by medium T and high P and (6) garnet peridotite xenoliths are of Archean or Proterozoic origin, whereas most of orogenic garnet peridotites are of Phanerozoic origin. Taking account of tectonic settings, a new orogenic garnet peridotite exhumation model, crust-mantle material mixing process, is proposed. The composition of lithospheric mantle is additionally constrained by comparisons and compiling of the off-cratonic, on-cratonic and orogenic garnet peridotite.     

Experimental phase and melting relations of metapelite in the upper mantle: implications for the petrogenesis of intraplate magmas

We performed a series of piston-cylinder experiments on a synthetic pelite starting material over a pressure and temperature range of 3.0–5.0 GPa and 1,100–1,600°C, respectively, to examine the melting behaviour and phase relations of sedimentary rocks at upper mantle conditions. The anhydrous pelite solidus is between 1,150 and 1,200°C at 3.0 GPa and close to 1,250°C at 5.0 GPa, whereas the liquidus is likely to be at 1,600°C or higher at all investigated pressures, giving a large melting interval of over 400°C. The subsolidus paragenesis consists of quartz/coesite, feldspar, garnet, kyanite, rutile, ±clinopyroxene ±apatite. Feldspar, rutile and apatite are rapidly melted out above the solidus, whereas garnet and kyanite are stable to high melt fractions (>70%). Clinopyroxene stability increases with increasing pressure, and quartz/coesite is the sole liquidus phase at all pressures. Feldspars are relatively Na-rich [K/(K + Na) = 0.4–0.5] at 3.0 GPa, but are nearly pure K-feldspar at 5.0 GPa. Clinopyroxenes are jadeite and Ca-eskolaite rich, with jadeite contents increasing with pressure. All supersolidus experiments produced alkaline dacitic melts with relatively constant SiO₂ and Al₂O₃ contents. At 3.0 GPa, initial melting is controlled almost exclusively by feldspar and quartz, giving melts with K₂O/Na₂O ~1. At 4.0 and 5.0 GPa, low-fraction melting is controlled by jadeite-rich clinopyroxene and K-rich feldspar, which leads to compatible behaviour of Na and melts with K₂O/Na₂O ≫ 1. Our results indicate that sedimentary protoliths entrained in upwelling heterogeneous mantle domains may undergo melting at greater depths than mafic lithologies to produce ultrapotassic dacitic melts. Such melts are expected to react with and metasomatise the surrounding peridotite, which may subsequently undergo melting at shallower levels to produce compositionally distinct magma types. This scenario may account for many of the distinctive geochemical characteristics of EM-type ocean island magma suites. Moreover, unmelted or partially melted sedimentary rocks in the mantle may contribute to some seismic discontinuities that have been observed beneath intraplate and island-arc volcanic regions.     

Fluid-assisted retrogression of garnet and P–T history of metapelites from HP/UHP metamorphic terrane (Pohorje Mountains, Eastern Alps)

Fluid inclusions in garnet combined with element X-ray mapping, phase equilibrium modelling and conventional thermobarometry have been used to constrain the metamorphic evolution of metapelitic gneiss from the HP/UHP metamorphic terrane of Pohorje Mountains in the Eastern Alps, Slovenia. Retrograde P–T trajectory from ~2.75 GPa and 780°C is constrained by the composition of matrix phengite (6.66 apfu Si) coexisting with garnet cores, kyanite and quartz. The intersection of the X _Prp = 0.25 isopleth for the garnet with the upper stability boundary for K-feldspar in the matrix indicates near-isothermal decompression to ~0.9 GPa at 720°C. Temperatures over 650°C during this stage are corroborated by the high degree of ordering of graphite inclusions associated with Zn, Mg-rich staurolite and phlogopite in the Mg-rich (X _Prp = 0.22–0.25) garnet cores. Majority of garnet porphyroblasts are depleted in Mg (down to X _Prp = 0.09) and enriched in Mn (up to X _Sps = 0.12) along cracks and at their margins. The associated retrograde mineral assemblage comprises Zn, Mg-poor staurolite, muscovite, biotite–siderophyllite, sillimanite and quartz. The onset of the retrogression and the compositional modification of the garnet porphyroblasts were accompanied by the addition of fluid-deposited graphite around older graphite inclusions, probably due to removal of water from a graphite-buffered COH fluid by dissolution in partial silicic melt. Instantaneous expulsion of water near the melt solidus (640°C, max. 0.45 GPa) caused dissolution of the graphite at redox conditions corresponding to 0.25–1.25 logfO₂ units below the QFM buffer, giving rise to a H₂O–CO₂–CH₄ fluid trapped in primary inclusions in Mn-rich, Mg-poor, almandine garnet that reprecipitated within the retrogressed domains. The absence of re-equilibration textures and consistent densities of the fluid inclusions reflect a near-isochoric cooling postdating the near-isothermal decompression. Bulk water content in the metapelite attained 2 wt% during this stage. The low-degree partial melting and extensive hydration due to the release of the internally derived, low-pressure aqueous fluids led to the reset of peak-pressure mineral assemblage.     

Water partitioning between mantle minerals from peridotite xenoliths

The speciation and amount of water dissolved in nominally anhydrous silicates comprising eight different mantle xenoliths has been quantified using synchrotron micro-FTIR spectroscopy. Samples studied are from six geographic localities and represent a cross-section of the major upper mantle lithologies from a variety of tectonic settings. Clinopyroxene contains between 342 and 413 ppm H₂O. Orthopyroxene, olivine and garnet contain 169–201, 3–54 and 0 to <3 ppm H₂O, respectively. Pyroxenes water contents and the distribution of water between ortho- and clinopyroxene is identical regardless of sample mineralogy (D _water^cpx/opx = 2.1 ± 0.1). The total water contents of each xenolith are remarkably similar (113 ± 14 ppm H₂O). High-resolution spectroscopic traverses show that the concentration and speciation of hydrous defects dissolved in each phase are spatially homogeneous within individual crystals and identical in different crystals interspersed throughout the xenolith. These results suggest that the amount of water dissolved in the silicate phases is in partial equilibrium with the transporting melt. Other features indicate that xenoliths have also preserved OH signatures of equilibrium with the mantle source region: Hydroxyl stretching modes in clinopyroxene show that garnet lherzolites re-equilibrated under more reducing conditions than spinel lherzolites. The distribution of water between pyroxenes and olivine differs according to xenolith mineralogy. The distribution of water between clinopyroxene and olivine from garnet peridotites (D _water^cpx/oliv(gnt) = 22.2 ± 24.1) is a factor of four greater than mineral pairs from spinel-bearing xenoliths (D _water^cpx/oliv(sp) = 88.1 ± 47.8). Such an increase in olivine water contents at the spinel to garnet transition is likely a global phenomenon and this discontinuity could lead to a reduction of the upper mantle viscosity by 0.2–0.7 log units and a reduction of its electrical resistivity by a factor of 0.5–0.8 log units.     

Phase relations and chemistry of Ti-rich K-richterite-bearing mantle assemblages: an experimental study to 8.0 GPa in a Ti-KNCMASH system

Experiments have been conducted in a peralkaline Ti-KNCMASH system representative of MARID-type bulk compositions to delimit the stability field of K-richterite in a Ti-rich hydrous mantle assemblage, to assess the compositional variation of amphibole and coexisting phases as a function of P and T, and to characterise the composition of partial melts derived from the hydrous assemblage. K-richterite is stable in experiments from 0.5 to 8.0 GPa coexisting with phlogopite, clinopyroxene and a Ti-phase (titanite, rutile or rutile + perovskite). At 8.0 GPa, garnet appears as an additional phase. The upper T stability limit of K-richterite is 1200–1250 °C at 4.0 GPa and 1300–1400 °C at 8.0 GPa. In the presence of phlogopite, K-richterite shows a systematic increase in K with increasing P to 1.03 pfu (per formula unit) at 8.0 GPa/1100 °C. In the absence of phlogopite, K-richterite attains a maximum of 1.14 K pfu at 8.0 GPa/1200 °C. Titanium in both amphibole and mica decreases continuously towards high P with a nearly constant partitioning while Ti in clinopyroxene remains more or less constant. In all experiments below 6.0 GPa ΣSi + Al in K-richterite is less than 8.0 when normalised to 23 oxygens+stoichiometric OH. Rutiles in the Ti-KNCMASH system are characterised by minor Al and Mg contents that show a systematic variation in concentration with P(T) and the coexisting assemblage. Partial melts produced in the Ti-KNCMASH system are extremely peralkaline [(K₂O+Na₂O)/Al₂O₃ = 1.7–3.7], Si-poor (40–45 wt% SiO₂), and Ti-rich (5.6–9.2 wt% TiO₂) and are very similar to certain Ti-rich lamproite glasses. At 4.0 GPa, the solidus is thought to coincide with the K-richterite-out reaction, the first melt is saturated in a phlogopite-rutile-lherzolite assemblage. Both phlogopite and rutile disappear ca. 150 °C above the solidus. At 8.0 GPa, the solidus must be located at T≤1400 ^°C. At this temperature, a melt is in equilibrium with a garnet- rutile-lherzolite assemblage. As opposed to 4.0 GPa, phlogopite does not buffer the melt composition at 8.0 GPa. The experimental results suggest that partial melting of MARID-type assemblages at pressures ≥4.0 GPa can generate Si-poor and partly ultrapotassic melts similar in composition to that of olivine lamproites. Received: 23 December 1996 / Accepted: 20 March 1997     

Phase relations and formation of sodium-rich majoritic garnet in the system Mg3Al2Si3O12–Na2MgSi5O12 at 7.0 and 8.5 GPa

The pseudo-binary system Mg₃Al₂Si₃O₁₂–Na₂MgSi₅O₁₂ modelling the sodium-bearing garnet solid solutions has been studied at 7 and 8.5 GPa and 1,500–1,950°C. The Na-bearing garnet is a liquidus phase of the system up to 60 mol% Na₂MgSi₅O₁₂ (NaGrt). At higher content of NaGrt in the system, enstatite (up to ∼80 mol%) and then coesite are observed as liquidus phases. Our experiments provided evidence for a stable sodium incorporation in garnet (0.3–0.6 wt% Na₂O) and its control by temperature and pressure. The highest sodium contents were obtained in experiments at P = 8.5 GPa. Near the liquidus (T = 1,840°C), the equilibrium concentration of Na₂O in garnet is 0.7–0.8 wt% (∼6 mol% Na₂MgSi₅O₁₂). With the temperature decrease, Na concentration in Grt increases, and the maximal Na₂MgSi₅O₁₂ content of ∼12 mol% (1.52 wt% Na₂O) is gained at the solidus of the system (T = 1,760°С). The data obtained show that most of natural diamonds, with inclusions of Na-bearing garnets usually containing <0.4 wt% Na₂O, could be formed from sodium-rich melts at pressures lower than 7 GPa. Majoritic garnets with higher sodium concentrations (>1 wt% Na₂O) may crystallize at a pressure range of 7.0–8.5 GPa. However the upper pressure limit for the formation of naturally occurring Na-bearing garnets is restricted by the eclogite/garnetite bulk composition.     

The high PT stability of apatite and Cl partitioning between apatite and hydrous potassic phases in peridotite: an experimental study to 19 GPa with implications for the transport of P,Cl and K in the upper mantle

High PT experiments were performed in the range 2.5–19 GPa and 800–1,500°C using a synthetic peridotite doped with trace elements and OH-apatite or with Cl-apatite + phlogopite. The aim of the study was (1) to investigate the stability and phase relations of apatite and its high PT breakdown products, (2) to study the compositional evolution with P and T of phosphate and coexisting silicate phases and (3) to measure the Cl-OH partitioning between apatite and coexisting calcic amphibole, phlogopite and K-richterite. Apatite is stable in a garnet-lherzolite assemblage in the range 2.5–8.7 GPa and 800–1,100°C. The high-P breakdown product of apatite is tuite γ-Ca₃ (PO₄)₂, which is stable in the range 8–15 GPa and 1,100–1,300°C. Coexisting apatite and tuite were observed at 8 GPa/1,050°C and 8.7 GPa/1,000°C. MgO in apatite increases with P from 0.8 wt% at 2.5 GPa to 3.2 wt% at 8.7 GPa. Both apatite and tuite may contain significant Na, Sr and REE with a correlation indicating 2 Ca²⁺=Na⁺ + REE³⁺. Tuite has always higher Sr and REE and lower Fe and Mg than apatite. Phosphorus in the peridotite phases decreases in the order P_melt ≫ P_grt ≫ P_Mg2SiO4 > P_cpx > P_opx. The phosphate-saturated P₂O₅ content of garnet increases from 0.07 wt% at 2.5 GPa to 1.5 wt% at 12.8 GPa. Due to the low bulk Na content of the peridotite, ^[8]Na^[4]P^[8]M²⁺ ₋₁ ^[4]Si₋₁ only plays a minor role in controlling the phosphorus content of garnet. Instead, element correlations indicate a major contribution of ^[6]M^2+[4]P^[6]M³⁺ ₋₁ ^[4]Si₋₁. Pyroxenes contain ~200–500 ppm P and olivine has 0.14–0.23 wt% P₂O₅ in the P range 4–8.7 GPa without correlation with P, T or X_Mg. At ≥12.7 GPa, all Mg₂SiO₄ polymorphs have <200 ppm P. Coexisting olivine and wadsleyite show an equal preference for phosphorus. In case of coexisting wadsleyite and ringwoodite, the latter fractionates phosphorus. Although garnet shows by far the highest phosphorus concentrations of any peridotite silicate phase, olivine is no less important as phosphorus carrier and could store the entire bulk phosphorus budget of primitive mantle. In the Cl-apatite + phlogopite-doped peridotite, apatite contains 0.65–1.35 wt% Cl in the PT range 2.5–8.7 GPa/800–1,000°C. Apatite coexists with calcic amphibole at 2.5 GPa, phlogopite at 2.5–5 GPa and K-richterite at 7 GPa, and all silicates contain between 0.2 and 0.6 wt% Cl. No solid potassic phase is stable between 5 and 8.7 GPa. Cl strongly increases the solubility of K in hydrous fluids. This may lead to the breakdown of phlogopite and give rise to the local presence in the mantle of fluids strongly enriched in K, Cl, P and incompatible trace elements. Such fluids may get trapped as micro-inclusions in diamonds and provide bulk compositions suitable for the formation of unusual phases such as KCl or hypersilicic Cl-rich mica.     

Geobarometry for Peridotites: Experiments in Simple and Natural Systems from 6 to 10 GPa

Experiments with peridotite minerals in simple (MgO–Al₂O₃–SiO₂,CaO–MgO–SiO₂ and CaO–MgO–Al₂O₃–SiO₂)and natural systems were conducted at 1300–1500°Cand 6–10 GPa using a multi-anvil apparatus. The experimentsin simple systems demonstrated consistency with previous lowerpressure experiments in belt and piston–cylinder set-ups.The analysis of spatial variations in pyroxene compositionswithin experimental samples was used to demonstrate that pressureand temperature variations within the samples were less than0·4 GPa and 50°C. Olivine capsules were used in natural-systemexperiments with two mineral mixtures: SC1 (olivine + high-Alorthopyroxene + high-Al clinopyroxene + spinel) and J4 (olivine+ low-Al orthopyroxene + low-Al clinopyroxene + garnet). Theexperiments produced olivine + orthopyroxene + garnet ±clinopyroxene assemblages, occasionally with magnesite and carbonate-richmelt. Equilibrium compositions were derived by the analysisof grain rims and evaluation of mineral zoning. They were comparedwith our previous experiments with the same starting mixturesat 2·8–6·0 GPa and the results from simplesystems. The compositions of minerals from experiments withnatural mixtures show smooth pressure and temperature dependencesup to a pressure of 8 GPa. The experiments at 9 and 10 GPa producedandradite-rich garnets and pyroxene compositions deviating fromthe trends defined by the lower pressure experiments (e.g. higherAl in orthopyroxene and Ca in clinopyroxene). This discrepancyis attributed to a higher degree of oxidation in the high-pressureexperiments and an orthopyroxene–high-P clinopyroxenephase transition at 9 GPa. Based on new and previous resultsin simple and natural systems, a new version of the Al-in-orthopyroxenebarometer is presented. The new barometer adequately reproducesexperimental pressures up to 8 GPa. KEY WORDS: garnet; mineral equilibrium; multi-anvil apparatus; orthopyroxene; geobarometry     

Tectonic implications of garnet-bearing mantle xenoliths exhumed by Quaternary magmatism in the Hangay dome, central Mongolia

Garnet-bearing mantle xenoliths have been recovered from Quaternary alkali basalts, both within and peripheral to the Hangay dome of central Mongolia. Microfabric analysis and thermobaromery, combining empirical thermobarometers and the self-consistent dataset of THERMOCALC, indicate that garnet websterites from the Shavaryn-Tsaram volcanic centre at the dome core were formed in the spinel-lherzolite upper mantle at pressures of 17–18 kbars and temperatures of 1,070–1,090°C, whereas garnet lherzolites were derived from greater depths (18–20 kbars). Garnet lherzolites from the Baga Togo Uul vents near the dome edge were formed at 18–22 kbars under significantly cooler conditions (960–1,000°C). These xenoliths reveal reaction coronas of (1) orthopyroxene, clinopyroxene, plagioclase and spinel mantling garnets; (2) spongy rims of olivine replacing orthopyroxene and (3) low-Na, low-Al clinopyroxene replacing primary clinopyroxene. Trace-element abundances indicate that clinopyroxene from these coronas is in chemical equilibrium with the host magma. The thermobarometric and textural data suggest that lherzolite xenoliths from both sites were derived from depths of 60–70 km and entrained in magma at 1,200–1,300°C. The average rate of ascent, as determined by olivine zoning, lies in the range 0.2–0.3 m s⁻¹. The contrast in thermal profiles of the upper mantle between the two sites is consistent with a mantle plume beneath the Hangay dome with elevated thermal conditions beneath the core of the dome being comparable to estimates of the Pleistocene geotherm beneath the Baikal rift.     

H<Subscript>2</Subscript>O storage capacity of MgSiO<Subscript>3</Subscript> clinoenstatite at 8–13 GPa, 1,100–1,400°C

We present H₂O analyses of MgSiO₃ pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C. Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals were high clinoenstatite (C2/c) during conditions of synthesis. H₂O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy on randomly oriented crystals. Measured H₂O concentrations increase with pressure and range from 0.08 wt.% H₂O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H₂O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend, which we attribute to diminishing activity of H₂O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure. We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H₂O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H₂O partitioning between olivine and clinoenstatite gives values of D ^ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D ^wd/CEn, gives a value of 2.8 ± 0.4.     

Archean to Middle Proterozoic evolution of Baltica subcontinental lithosphere: evidence from combined Sm–Nd and Lu–Hf isotope analyses of the Sandvik ultramafic body,Norway

Combined Sm–Nd and Lu–Hf age and isotope data indicate that Mg- and Cr-rich ultramafic rocks at Sandvik, Western Gneiss Region (WGR), Norway, originated from depleted Archean lithospheric mantle that was chemically and physically modified in Middle Proterozoic time. The Sandvik outcrop consists of garnet peridotite and garnet-olivine pyroxenite and thin garnet pyroxenite layers. These contain two principal mineral assemblages: an earlier porphyroclastic assemblage of grt + opx + cpx ± ol (1,200–1,000°C, 40–50 kbar) and a later kelyphitic assemblage of grt + spl + am ± opx ± ol (700–750°C; 12–18 kbar). A CHUR Hf model age indicates a period of melt extraction at ca. 3.3 Ga for garnet peridotite, reflecting extremely high Lu/Hf ratios and very radiogenic present-day ¹⁷⁶Hf/¹⁷⁷Hf (ε_Hf=+2,165). Lu–Hf garnet-cpx-whole rock ages of two olivine-bearing samples (garnet peridotite and garnet-olivine pyroxenite) from the outcrop are ca. 1,255 Ma, whereas two olivine-free garnet pyroxenites yield Lu–Hf ages of ca. 1,185 Ma. All Sm–Nd garnet-cpx-whole rock ages of these samples are significantly younger (ca. 1,150 Ma for garnet peridotite and ca. 1,120 Ma for garnet pyroxenite). The isotope systematics indicate that the Lu–Hf ages represent cooling from an earlier period of formation/recrystallization for garnet peridotite whereas they probably reflect formation/recrystallization ages of the garnet pyroxenite. The Sm–Nd ages and isotope systematics of the garnet peridotite samples are consistent with an episode of LREE metasomatism, perhaps facilitated by a fluid of carbonatitic composition that strongly decoupled Sm–Nd and Lu–Hf. The Sm–Nd ages of the garnet pyroxenite may represent either LREE metasomatism or cooling, and, like the peridotites, Lu–Hf ages are older than Sm–Nd ages. The age data, as well as the inferred Nd isotope composition of the fluid that affected the olivine-bearing samples, suggest that these rocks were not in contact during the LREE metasomatic event. Moreover, the pyroxenite layers cannot have been emplaced as magmas into the host peridotite. The pyroxenite layers are interpreted to be tectonically juxtaposed with the host olivine-bearing samples sometime after 1,150 Ma but before development of kelyphite.     

Temperature-dependent isotopic fractionation of lithium between clinopyroxene and high-pressure hydrous fluids

The fractionation of lithium isotopes between synthetic spodumene as representative of Li-bearing clinopyroxene and Cl- and OH-bearing aqueous fluids was experimentally determined between 500 and 900°C at 2.0 GPa. In all the experiments, ⁷Li was preferentially partitioned into the fluid. The fractionation is temperature dependent and approximated by the equation Δ⁷Li_{(clinopyroxene–fluid)}=−4.61×(1,000/T [K]) + 2.48; R ²=0.86. Significant Li isotopic fractionation of about 1.0‰ exists even at high temperatures of 900°C. Using neutral and weakly basic fluids revealed that the amount of fractionation is not different. The Li isotopic fractionation between altered basalt and hot spring water (350°C) in natural samples is in good agreement with our experimentally determined fractionation curve. The data confirm earlier speculations drawn from the Li isotopic record of dehydrated metamorphic rocks that fluids expelled from a dehydrating slab carry heavier Li into the mantle wedge, and that a light Li component is introduced into the deeper mantle. Li and Li isotopes are redistributed among wedge minerals as fluids travel across the wedge into hotter regions of arc magma production. This modifies the Li isotopic characteristics of slab-derived fluids erasing their source memory, and explains the absence of cross-arc variations of Li isotopes in arc basalts.