Cr-rich magnesiochloritoid eclogites from the Monviso ophiolites (Western Alps, Italy)

Cr-rich magnesiochloritoid in the eclogitized ophiolites of the Monviso massif occurs in the least differentiated rocks of the gabbroic sequence (troctolites to melatroctolites). Chloritoid ( X _Mg=0.63–0.85; Cr≤0.55, atoms) co-exists with omphacite, talc and garnet. Minor, syn-eclogitic minerals are chromite, rutile and sometimes magnesite and Cr–Ti oxides.
Coronitic textures, indicative of a static recrystallization, characterize the analysed samples. Layers of variable mineral composition develop among igneous plagioclase, olivine, clinopyroxene and spinel. The minerals in the coronitic layers display sharp compositional zonings. The igneous minerals are commonly not preserved; their presence in the original assemblage is inferred from the mineralogical composition of the pseudomorphs.
Syn-eclogitic volatile components are indicated by the development of OH-bearing minerals (e.g. chloritoid & talc) and carbonates (e.g. magnesite), and supported by the presence of coarse-grained and fibrous mineral growths. The complex pseudomorphic replacements of igneous minerals suggest that these rocks changed their mineralogical composition prior to the eclogite facies recrystallization, most likely during ocean-floor metamorphism. It is suggested that syn-eclogitic fluids formed by breakdown reactions of pre-eclogitic volatile-bearing minerals.
Geothermobarometry indicates that the investigated rocks recrystallized at a depth corresponding to 2.4  GPa and temperatures of 620±50  °C. The attainment of high-pressure conditions is supported by the presence of magnesiochloritoid, magnesite and garnet with high pyrope content (up to 58  mol%). P–T  estimates point to a very low thermal gradient (about 9  °C km⁻¹), comparable to that deduced in the adjacent Dora-Maira ultra-high pressure unit.     

Eclogitization of the Monviso ophiolite (W. Alps) and implications on subduction dynamics

To constrain deep (40–100 km) subduction dynamics, extensive P–T data are provided on the eclogitic Monviso ophiolite derived from the subducted Liguro‐Piemontese oceanic lithosphere (which was exhumed, together with associated continental units, before the Alpine collision). The Monviso ophiolite has so far been interpreted either as a fossilized subduction channel, with tectonic blocks detached from the slab at different depths and gathered in a weak serpentinized matrix, or as a more or less continuous portion of oceanic lithosphere. To evaluate potential heterogeneities within and between the various subunits, extensive sampling was undertaken on metasedimentary rocks and Fe–Ti metagabbros. The results indicate that the Monviso ophiolite comprises two main coherent tectonic subunits (the Monviso and Lago Superiore Units) detached during subduction at different depths and later juxtaposed at epidote–blueschist facies during exhumation along the subduction interface. Raman spectroscopy of carbonaceous material suggests (i) a difference in peak temperature of ～50 °C between these two subunits and (ii) a good temperature homogeneity within each subunit. Pseudosections and average P–T estimates using thermocalc in the Lago Superiore Unit suggest for the first time homogeneous HP to UHP conditions (～550 °C, 26–27 kbar). Parageneses, peak conditions and tectonic setting are very similar to those of the Zermatt‐Saas ophiolite, 200 km northwards, thus suggesting a common detachment mechanism for the whole Western Alpine belt.     

Fluid composition and evolution in coesite-bearing rocks (Dora-Maira massif,Western Alps): implications for element recycling during subduction

Fluid inclusions and F, Cl concentration of hydrous minerals were analysed in the coesite-pyrope quartzite, the interlayered jadeite quartzite and their country-rock gneiss from the Dora-Maira massif using a combination of microthermometry, Raman spectrometry, synchrotron X-ray microfiuorescence and electron microprobe analysis. Three populations of fluid inclusions were recognized texturally and can be related to distinct metamorphic stages. A low-salinity aqueous fluid occurs in the retrogressed country gneiss and as late secondary inclusions in jadeite quartzite and chloritized pyrope. An earlier secondary population is found in matrix quartz of the jadeite- and pyro-pe-quartzites. This population can be related to the early decompression and so to incipient breakdown of garnet into phlogopite-bearing assemblages. The inclusion fluid is highly saline (up to 84 wt% equivalent NaCl) and contains Na, Ca, Fe, Cu and Zn as major cations. In pyrope quartzite, additional K was found in these brines, which locally coexist with CO₂-rich inclusions. The oldest fluid inclusions are preserved in kyanite grains included in fresh pyrope and in pyrope itself. In pyrope, all inclusions have decrepitated and contain magnesite, an Mg-phosphate, sheet-silicate(s), a chloride and an opaque phase, with no fluid preser ved. In contrast, the kyanite inclusions in pyrope preserve primary H₂O-CO₂ low-salinity fluid inclusions, probably owing to the low compressibility of the kyanite inclusions and host garnet. In spite of in-situ re-equilibration, these inclusions can be interpreted as relics of the dehydration fluid that attended pyrope growth. These correlations between textural and chemical fluid inclusion data and metamorphic stages are consistent with the fluid composition calculated from the halogen content of different generations of phlogopite and biotite. The preservation of different fluid compositions, both in time and space, is evidence for local control and possibly origin of the fluids, in agreement with isotopic data. These results, in particular the absence of CO₂ in the jadeite quartzite, are best interpreted in terms of a fluid-melt system evolution. With increasing metamorphism, partitioning of H₂O, Na, Ca, Fe and heavy metals into melt (jadeite quartzite) and Mg, Na/K, F, CO₂ and P(?) into a residual aqueous fluid can account for depletion in Na, Ca and Fe of the pyrope quartzite. During the retrograde path, a _{H 2 O} rose as melt crystallized, generating the two populations of hypersaline and water-rich fluids that were highly reactive to pyrope. The process of fluid-melt interaction envisioned here coupled with models of melt extraction in subduction zones provides an attractive opportunity for the instantaneous ( < 1 Ma) and selective transport of elements between a downgoing slab and the overlying mantle wedge.     

Exhumation of oceanic blueschists and eclogites in subduction zones: Timing and mechanisms

High-pressure low-temperature (HP–LT) metamorphic rocks provide invaluable constraints on the evolution of convergent zones. Based on a worldwide compilation of key information pertaining to fossil subduction zones (shape of exhumation P–T–t paths, exhumation velocities, timing of exhumation with respect to the convergence process, convergence velocities, volume of exhumed rocks,…), this contribution reappraises the burial and exhumation of oceanic blueschists and eclogites, which have received much less attention than continental ones during the last two decades.Whereas the buoyancy-driven exhumation of continental rocks proceeds at relatively fast rates at mantle depths (≥ cm/yr), oceanic exhumation velocities for HP–LT oceanic rocks, whether sedimentary or crustal, are usually on the order of the mm/yr. For the sediments, characterized by the continuity of the P–T conditions and the importance of accretionary processes, the driving exhumation mechanisms are underthrusting, detachment faulting and erosion. In contrast, blueschist and eclogite mafic bodies are systematically associated with serpentinites and/or a mechanically weak matrix and crop out in an internal position in the orogen.Oceanic crust rarely records P conditions > 2.0–2.3 GPa, which suggests the existence of maximum depths for the sampling of slab-derived oceanic crust. On the basis of natural observations and calculations of the net buoyancy of the oceanic crust, we conclude that beyond depths around 70 km there are either not enough serpentinites and/or they are not light enough to compensate the negative buoyancy of the crust.Most importantly, this survey demonstrates that short-lived (< ～ 15 My), discontinuous exhumation is the rule for the oceanic crust and associated mantle rocks: exhumation takes place either early (group 1: Franciscan, Chile), late (group 2: New Caledonia, W. Alps) or incidentally (group 3: SE Zagros, Himalayas, Andes, N. Cuba) during the subduction history. This discontinuous exhumation is likely permitted by the specific thermal regime following the onset of a young, warm subduction (group 1), by continental subduction (group 2) or by a major, geodynamic modification of convergence across the subduction zone (group 3; change of kinematics, subduction of asperities, etc).Understanding what controls this short-lived exhumation and the detachment and migration of oceanic crustal slices along the subduction channel will provide useful insights into the interplate mechanical coupling in subduction zones.     

Retrograde P-T-t path for the Voltri Massif eclogites (Ligurian Alps, Italy): some tectonic implications

The retrograde P-T trajectory of the eclogitic Fe-Ti-gabbros from the Ligurian Alps is constrained by the appearance of mineral parageneses post-dating the Na-clinopyroxene + garnet eclogitic assemblage and indicating the following sequence of metamorphic events: (1) amphibolitic stage— edenite/katophorite + plagioclase (An_33–43) + oxides in symplectitic aggregates; (2) glaucophanic stage— a porphyroblastic glaucophanic amphibole has overgrown the symplectite, winchite also occurs as thin rims around glaucophane and both amphiboles are, sometimes, armoured by atoll garnets; (3) albite-amphibolite stage—barroisite/katophorite + albite + epidote + oxides ± chlorite overprint the glaucophanic stage minerals; (4) greenschist stage—represented by actinolite + albite + epidote + oxide paragenesis.
The metamorphic evolution is complex and the decompression path, on a P–T diagram, is significantly different from those defined in the literature for the Voltri eclogites. The main features inferred from the P–T path are the following: (1) the pressure climax does not match the thermal climax, the maximum temperature conditions are in fact achieved during the early stage of uplift; (2) a decrease in temperature, suggested by the appearance of glaucophane after the amphibolitic symplectite; (3) successive uplift, probably accompanied by an increase in temperature. The complexity of the P-T path drawn for the Voltri eclogites can be explained with a mechanism of successive underthrusts propagating from the innermost to the outermost sector of the Ligurian Alps.     

HFSE systematics of rutile-bearing eclogites: New insights into subduction zone processes and implications for the earth’s HFSE budget

The depleted mantle and the continental crust are generally thought to balance the budget of refractory and lithophile elements of the Bulk Silicate Earth (BSE), resulting in complementary trace element patterns. However, the two high field strength elements (HFSE) niobium and tantalum appear to contradict this mass balance. All reservoirs of the silicate Earth exhibit subchondritic Nb/Ta ratios, possibly as a result of Nb depletion.In this study a series of nineteen orogenic MORB-type eclogites from different localities was analyzed to determine their HFSE concentrations and to contribute to the question of whether subducted oceanic crust could form a hidden reservoir to account for the mass imbalance of Nb/Ta between BSE and the chondritic reservoir. Concentrations of HFSE were analyzed with isotope dilution (ID) techniques. Additionally, LA-ICPMS analyses of clinopyroxene, garnet and rutile have been performed. Rutile is by far the major host for Nb and Ta in all analyzed eclogites. However, many rutiles revealed zoning in Nb/Ta ratios, with cores being higher than rims. Accordingly, in situ analyses of rutiles have to be evaluated carefully and rutile cores do not necessarily reflect a bulk rock Nb and Ta composition, although over 90% of these elements reside in rutile.The HFSE concentration data in bulk rocks show that the orogenic eclogites have subchondritic Nb/Ta ratios and near chondritic Zr/Hf ratios. The investigated eclogites show neither enrichment of Nb compared to similarly incompatible elements (e.g. La), nor fractionation of Nb/Ta ratios relative to MOR-basalts, the likely precursor of these rocks. This indicates that during the conversion of the oceanic crust to eclogites in most cases, (1) HFSE and REE have similar mobility on average, possibly because both element groups remain in the down going slab, and (2) no significant fractionation of Nb/Ta occurs in subducted oceanic crust. With an average Nb/Ta ratio of 14.2 ± 1.4 (2s.e.), the investigated eclogites cannot balance the differences between BSE and chondrite. Additionally, as their average Nb/Ta is indistinguishable from the Nb/Ta of MORB, they are also an unlikely candidate to balance the potentially small differences in Nb/Ta between the continental crust and the mantle.     

Trace-element-rich brines in eclogitic veins: implications for fluid composition and transport during subduction

Primary and pseudosecondary fluid inclusions occur in oscillatory-and sector-zoned omphacite in eclogitic veins from the Monviso ophiolitic complex in the Western Alps. The inclusions contain aqueous brines and daughter crystals of halite, sylvite, calcite, dolomite, albite, anhydrite and/or gypsum, barite, baddeleyite, rutile, sphene, Fe oxides, pyrite and monazite. This daughter mineral suite indicates high solubilites of Na, K, Ca, Mg, Fe, Zr, Ti, P, Ba, Ce, La, Th, and S species and provides direct evidence for transport of high-fieldstrenght, large-ion-lithophile, and light-rare-earth elements as dissolved species during subduction. Fluid-inclusion heterogeneities preserved within and between adjacent grains in the veins, however, suggest that the scale of fluid equilibration was small. A crack-seal geometry in some of the veins implies that fluid release in pulses rather than steady flow controlled mineral deposition and growth in the veins. From these observations, we develop a model of fluid release and entrapment in which pulses of fluid are associated in time with increments of shear and tensile failure; the rate of fluid release and the reduction in porosity both depend on the rate of plastic flow. Vein fluids may initially be derived from decreptitation of early fluid inclusions in the host eclogites, Small-scale fluid heterogeneities implied by the fluid inclusions in the veins are best interpreted in terms of limited fluid flow, and hence limited metasomatism. We conclude that element recycling into the mantle wedge during subduction will depend at least as strongly on fluid transport mechanisms as on element solubilities in the fluid phase. At Monviso, despite evidence for high trace element solubilities in saline brines, the elements were not removed from the downgoing slab prior to teaching depths of 40 km.     

U-Pb dating of magmatic zircon and metamorphic baddeleyite in the Ligurian eclogites (Voltri Massif,Western Alps)

U-Pb geochronology with ion microprobe (SHRIMP) analysis has been carried out on eclogite-facies rocks of the Beigua Unit, an ophiolitic slice of the Voltri Massif, Western Alps. The investigated samples are eclogites and high-pressure metasomatic rocks (metarodingites and centimetre-sized Ti-clinohumite-bearing dykes). Zircon contained in an eclogitic metagabbro and a metarodingite preserves magmatic zoning patterns and trace element compositions. The zircon ages of 160±1 and 161±3 Ma are interpreted to date the crystallization of the gabbroic protoliths. Ti-clinohumite dykes in the same unit contain baddeleyite crystals in textural equilibrium with Ti-clinohumite, diopside, chlorite and magnetite, which form the eclogite-facies assemblage in these rocks. Baddeleyite also contains inclusions of such minerals, indicating its formation at high pressure. The baddeleyite has cathodoluminescence intensity and chaotic patterns similar to metamorphic zircon. It contains a significant amount of Hf (1.3–1.7 wt%), traces of Ti, Y, Nb, Ta, REE, U and Th. Its chondrite-normalised trace element pattern has strong enrichment in middle REE, positive Ce-anomaly and small negative Eu-anomaly. This represents the first report of baddeleyite formed during regional metamorphism, and suggests that this mineral could (re)crystallize easier than zircon under low-temperature, high-pressure conditions. The age of the baddeleyite is interpreted as likely dating the eclogite-facies metamorphism in the Beigua Unit at 33.6±1.0 Ma. This age is very close to the Early Oligocene age of the overlying Tertiary continental breccias and conglomerates, which contains clasts of high-pressure rocks. This sedimentary record, which is unique for Alpine high-pressure units, is direct evidence of fast exhumation of the Beigua eclogites. The young age for the HP metamorphism of the Beigua ophiolite makes a revision of either the palaeogeography prior to collision, or of the subduction setting in the entire region, necessary.Editorial responsibility: J. Hoefs     

Ban-1 Zircon: A New Natural Zircon Reference Material for LA-MC-ICP-MS Zr and Hf Isotopic Determinations

New zircon reference materials for in situ zircon radiogenic Hf isotope and stable Zr isotopic determinations made by laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) are required due to high data productivity and consequently high reference material consumption rate. This study examines a new natural zircon for Zr isotope ratios by double spike thermal ionisation mass spectrometry (TIMS), and for Hf isotopes by bulk solution nebuliser (SN)-MC-ICP-MS with both Zr and Hf determined by LA-MC-ICP-MS. A total of five zirconium isotope measurements from drilled zircons, determined by TIMS, yield a mean δ^94/90Zr_IPGP-Zr value of -0.09 ± 0.06‰ (2s). Five and eight hafnium isotope measurements for powders from the drilled zircons and Ban-1-4 by SN-MC-ICP-MS, yield mean ¹⁷⁶Hf/¹⁷⁷Hf ratios of 0.282985 ± 0.000011 (2s) and 0.282982 ± 0.000007 (2s), respectively. The mean δ^94/90Zr_IPGP-Zr value and ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by LA-MC-ICP-MS analyses are -0.06 ± 0.09‰ (2s, n = 504) and 0.282985 ± 0.000035 (2s, n = 327), respectively. The isotopic homogeneities suggest that the Ban-1 zircon is a suitable reference material for microbeam Zr and Hf isotopic measurements.     

Distinguishing between seafloor alteration and fluid flow during subduction using stable isotope geochemistry: examples from Tethyan ophiolites in the Western Alps

Large amounts of fluid, bound up in the hydrated upper layers of the ocean crust, are consumed at convergent margins and released in subduction zones through devolatilization. The liberated fluids may play an integral role in subduction zone processes, including the generation of arc-magmas. However, exhumed subduction zone rocks often record little evidence of large-scale fluid flow, especially at deeper levels within the subduction zone. Basaltic pillows from the high-pressure Corsican and Zermatt-Saas ophiolites show a range of δ¹⁸O values that overall reflect seafloor alteration prior to subduction. However, comparison between the δ¹⁸O values of the cores and rims of the pillows suggests that the δ¹⁸O values of the pillow rims at least have been modified during subduction and high-pressure metamorphism. Pillows that have not undergone high-pressure metamorphism generally have rims with higher δ¹⁸O values than their cores, whereas the converse is the case in pillows that have undergone high-pressure metamorphism. This reversal in the core to rim oxygen isotope relationship between unmetamorphosed and metamorphosed pillows is strong evidence for fluid–rock interaction occurring during subduction and high-pressure metamorphism. However, the preservation of different δ¹⁸O values in the cores and rims of individual pillows and within and between different pillows suggests that fluid flow within the subduction zone was strongly channelled. Resetting of the δ¹⁸O values in the pillow rims was probably due to fluid-hosted diffusion that occurred over relatively short time-scales (<1 Myr).     

Metasomatism of continental crust during subduction: the UHP whiteschists from the Southern Dora-Maira Massif (Italian Western Alps)

The ultrahigh‐pressure pyrope whiteschists from the Brossasco‐Isasca Unit of the Southern Dora‐Maira Massif represent metasomatic rocks originated at the expense of post‐Variscan granitoids by the influx of fluids along shear zones. In this study, geochemical, petrological and fluid‐inclusion data, correlated with different generations of pyrope‐rich garnet (from medium, to very‐coarse‐grained in size) allow constraints to be placed on the relative timing of metasomatism and sources of the metasomatic fluid. Geochemical investigations reveal that whiteschists are strongly enriched in Mg and depleted in Na, K, Ca and LILE (Cs, Pb, Rb, Sr, Ba) with respect to the metagranite. Three generations of pyrope, with different composition and mineral inclusions, have been distinguished: (i) the prograde Prp I, which constitutes the large core of megablasts and the small core of porphyroblasts; (ii) the peak Prp II, which constitutes the inner rim of megablasts and porphyroblasts and the core of small neoblasts; and (iii) the early retrograde Prp III, which locally constitutes an outer rim. Two generations of fluid inclusions have been recognized: (i) primary fluid inclusions in prograde kyanite that represent a NaCl‐MgCl₂‐rich brine (6–28 wt% NaCl_eq with Si and Al as other dissolved cations) trapped during growth of Prp I (type‐I fluid); (ii) primary multiphase‐solid inclusions in Prp II that are remnants of an alumino‐silicate aqueous solution, containing Mg, Fe, alkalies, Ca and subordinate P, Cl, S, CO₃^2‐, LILE (Pb, Cs, Sr, Rb, K, LREE, Ba), U and Th (type‐II fluid), at the peak pressure stage. We propose a model that illustrates the prograde metasomatic and metamorphic evolution of the whiteschists and that could also explain the genesis of other Mg‐rich, alkali‐poor schists of the Alps. During Alpine metamorphism, the post‐Variscan metagranite of the Brossasco‐Isasca Unit experienced a prograde metamorphism at HP conditions (stage A: ～1.6 GPa and ≤ 600 °C), as indicated by the growth of an almandine‐rich garnet in some xenoliths. At stage B (1.7–2.1 GPa and 560–590 °C), the influx of external fluids, originated from antigorite breakdown in subducting oceanic serpentinites, promoted the increase in Mg and the decrease of alkalies and Ca in the orthogneiss toward a whiteschist composition. During stage C (2.1 < P < 2.8 GPa and 590 < T < 650 °C), the metasomatic fluid influx coupled with internal dehydration reactions involving Mg‐chlorite promoted the growth of Prp I in the presence of the type‐I MgCl₂‐brine. At the metamorphic peak (stage D: 4.0–4.3 GPa and 730 °C), Prp II growth occurred in the presence of a type–II alumino‐silicate aqueous solution, mostly generated by internal dehydration reactions involving phlogopite and talc. The contribution of metasomatic external brines at the metamorphic climax appears negligible. This fluid, showing enrichment in LILE and depletion in HFSE, could represent a metasomatic agent for the supra‐subduction mantle wedge.     

Lu-Hf garnet geochronology of eclogites from the Balma Unit (Pennine Alps): implications for Alpine paleotectonic reconstructions

Three samples of eclogite from the Balma Unit, an ophiolite sheet on top of the Monte Rosa Nappe in the Pennine Alps, were investigated in terms of their P-T evolution, geochemistry, and Lu-Hf geochronology. The paleogeographic origin of this unit is controversial (North Penninic vs. South Penninic). It has been interpreted as a piece of Late Cretaceous oceanic crust, on the basis of ca. 93 Ma U-Pb SHRIMP ages of synmagmatic zircon cores in an eclogite. Trace element and isotope data suggest a mid ocean ridge (MOR) rather than an intraplate or OIB setting for the protoliths of the eclogites. Electron microprobe analyses of representative garnets show typical prograde zoning profiles. Estimated peak metamorphic temperatures of 550–600 Cº most likely did not exceed the closure temperature of the Lu-Hf system. Hence, Lu-Hf ages most likely reflect garnet growth in the studied samples. To minimize inclusion effects on age determinations, a selective digestion procedure for garnet was applied, in which zircon and rutile inclusions are not dissolved. The ages obtained for three samples, 42.3 ± 0.6 Ma (MSWD: 0.47), 42 ± 1 Ma (MSWD: 3.0) and 45.5 ± 0.3 Ma (MSWD: 0.33), are younger than all Lu-Hf ages reported so far for South Penninic Units. Metamorphic zircon domains of the 42.3 Ma sample (PIS1) were previously dated by U-Pb SHRIMP at 40.4 ± 0.7 Ma, indicating that the growth of metamorphic zircon post-dated the onset of garnet growth.These new data put important constraints on the paleogeographic reconstruction of the Alps. The MORB character of the rocks, together with their previously published protolith age, imply that oceanic spreading was still taking place in the Late Cretaceous. This supports a North Penninic origin for our samples because plate tectonic models predict Cretaceous spreading in the North Penninic but not in the South Penninic Ocean. If the Balma Unit is indeed North Penninic, the new Lu-Hf data, in combination with published geochronological data, require that two independent subduction zones consumed the South and North Penninic oceans.     

Partitioning of halogens between mantle minerals and aqueous fluids: implications for the fluid flow regime in subduction zones

We have performed phase equilibrium experiments in the system forsterite–enstatite–pyrope-H₂O with MgCl₂ or MgF₂ at 1,100 °C and 2.6 GPa to constrain the solubility of halogens in the peridotite mineral assemblage and the fluid–mineral partition coefficients. The chlorine solubility in forsterite, enstatite and in pyrope is very low, 2.1–3.9 and 4.0–11.4 ppm, respectively, and it is independent of the fluid salinity (0.3–30 wt% Cl), suggesting that some intrinsic saturation limit in the crystal is reached already at very low chlorine concentrations. Chlorine is therefore exceedingly incompatible in upper-mantle minerals. The fluorine solubility is 170–336 ppm in enstatite and 510–1,110 ppm in pyrope, again independent of fluid salinity. Forsterite dissolves 1,750–1,900 ppm up to a fluid salinity of 1.6 wt% F. At higher fluorine contents in the system, forsterite is replaced by the minerals of the humite group. The lower solubility of chlorine by three orders of magnitude when compared to fluorine is consistent with increasing lattice strain. Fluid–mineral partition coefficients are 10⁰–10² for fluorine and 10³–10⁵ for chlorine. Since the latter values are orders of magnitude higher than those for hydroxyl partitioning, fluid flow from the subducting slab through the mantle wedge will lead to an efficient sequestration of H₂O into the nominally anhydrous minerals in the wedge, whereas chlorine becomes enriched in the residual fluid. Simple mass balance calculations reveal that rock–fluid ratios of up to >3,000 are required to produce the elevated Cl/H₂O ratios observed in some primitive arc magmas. Accordingly, fluid flow from the subducted slab into the zone of melting in the mantle wedge does not only occur rapidly in narrow channels, but at least in some subduction zones, fluid pervasively infiltrates the mantle peridotite and interacts with a large volume of the mantle wedge. Together with the Cl/H₂O ratios of primitive arc magmas, our data therefore constrain the fluid flow regime below volcanic arcs.     

F,Cl and S input via serpentinite in subduction zones: implications for the nature of the fluid released at depth

The abundances of F, Cl and S in arc magmas are systematically higher than in other mantle‐derived magmas, suggesting that these elements are added from the slab along with H₂O. We present ion probe microanalyses of F, Cl and S in serpentine minerals that represent the P–T evolution of the oceanic lithosphere, from its serpentinization at the ridge, to its dehydration at around 100 km depth during subduction. F, Cl and S are incorporated early into serpentine during its formation at mid‐ocean ridges, and serpentinized lithosphere then carries these elements to subduction zones. More than 50% of the F, Cl and S are removed from serpentine during the prograde metamorphic lizardite/antigorite transition. Due to the low solubility of F in water, and to the low amount of water released during this phase transition, the fluids mobilizing these elements must be dominated by SO_X rather than H₂O.     

Ordering in double carbonates and implications for processes at subduction zones

We have studied cation ordering in dolomite in situ as a function of pressure, temperature, and experimental time using the multi-anvil apparatus and synchrotron radiation. Starting with ordered dolomite, we observe the onset of disordering taking place at 950°C, while complete disordering is achieved at 1,070 (±20)°C, for pressures ranging between 3.37 and 4.05 GPa. Pressure does not appear to have significant effect on the order/disorder transition over the investigated range. We find that dolomite can reach its equilibrium ordering state above 900°C within duration of laboratory experiment (few hours), both from disordered state and from ordered state. In addition, we have reversed the dolomite breakdown reaction [magnesite + aragonite = dolomite] between 4.5 and 5.5 GPa, by monitoring diffraction peak intensity. We also have determined that dolomite is stable up to 7.4 GPa at 1,100°C. We confirm some earlier studies where a change in slope (dP/dT) has been observed, but we find a non-zero slope in the low pressure range. Combining the values of entropy obtained from dolomite degree of ordering with enthalpy values deduced from our bracketing of [magnesite + aragonite = dolomite] equilibrium, we model the location of dolomite breakdown in the P–T space as a function of cation ordering. By comparing previous conflicting studies, we show that, although kinetics of order/disorder is fast, disequilibrium dolomite breakdown is possible. Our modeling shows that subducted disordered dolomite present in carbonated sediments could be decomposed to [magnesite + aragonite] at lower pressure (3.5 GPa) than usually considered (>5 GPa). This 2-GPa (60 km) difference is valid on a fast subduction path and is possible if disorder inherited from sedimentation is preserved. On a slow subduction path, however, dolomite breakdown is encountered at about 250 km depth, which is 100 km deeper than currently considered.     

Sub-solidus Oligocene zircon formation in garnet peridotite during fast decompression and fluid infiltration (Duria, Central Alps)

Summary A garnet peridotite lens from Monte Duria (Adula nappe, Central Alps, Northern Italy) contains porphyroblastic garnet and pargasitic amphibole and reached peak metamorphic conditions of ∼830 C, ∼2.8 GPa. A first stage of near isothermal decompression to pressures <2.0 GPa is characterised by domains where fine grained spinel, clinopyroxene, orthopyroxene and amphibole form. The newly formed amphibole contains elevated levels of fluid mobile elements such as Rb, Ba and Pb indicating that recrystallization was assisted by infiltration of a crustal-derived fluid. Further decompression and cooling to ∼720 °C, 0.7–1.0 GPa associated with limited fluid influx is documented by the formation of orthopyroxene-spinel-amphibole symplectites around garnet. Zircon separated from this garnet peridotite exhibits two distinct zones. Domain 1 displays polygonal oscillatory zoning and high trace element contents. It contains clinopyroxene and amphibole inclusions with the same composition as the same minerals formed during the spinel peridotite equilibration, indicating that this domain formed under sub-solidus conditions during decompression and influx of crustal fluids. Domain 2 has no zoning and much lower trace element contents. It replaces domain 1 and is likely related to zircon recrystallization during the formation of the symplectites. SHRIMP dating of the two domains yielded ages of 34.2 ± 0.2 and 32.9 ± 0.3 Ma, respectively, indicating fast exhumation of the peridotite within the spinel stability field. We suggest that the Duria garnet peridotite originates from the mantle wedge above the tertiary subduction of the European continental margin and that it was assembled to the country rock gneisses between 34 and 33 Ma. Third author was Deceased     

西大别浒湾变质带洋壳和陆壳耦合俯冲的锆石U-Pb年龄记录及其动力学意义

西大别浒湾高压变质带是研究秦岭-大别-苏鲁造山带演化的关键区域.本文对该变质带熊店和学河两地的两个榴辉岩样品进行了LA-(MC)-ICPMS锆石U-Pb定年、微量元素分析及Hf同位素测定.熊店榴辉岩岩浆锆石得到的年龄为406±14Ma,具有高的εHf(t)值(εHf(t)=11.3±1.3),年轻的亏损地幔模式年龄(tDM=578±52Ma),其来源可能为亏损地幔,进而说明它们的原岩可能为古特提斯洋壳物质;学河榴辉岩岩浆锆石的年龄为703±8Ma,具有略低的εHf(t)值(εHf(t)=4.11±0.94),较老的亏损地幔模式年龄(tDM=1105±37Ma),其原岩可能为扬子克拉通新元古代裂谷岩浆作用产生的新生陆壳物质.这些结果表明浒湾地区存在原岩形成于新元古代和志留纪两个时期的榴辉岩.熊店榴辉岩中变质锆石的微量元素特征与岩浆锆石类似,可能为完全重结晶成因锆石,其206Ph/238U加权平均年龄为316±1Ma,代表了洋壳榴辉岩榴辉岩相峰期变质的最早时间.学河榴辉岩变质锆石以低Th/U、Nb/Ta比值为特征,其REE组成模式为不明显的Eu负异常,HREE呈平坦型.这些特征反映了这些锆石形成时出现了较大数量的石榴子石与金红石,而缺乏长石.根据锆石Ti温度计计算学河榴辉岩变质锆石形成的温度范围是704～741℃,与榴辉岩相变质温度一致.它们对应的206Pb/238U加权平均年龄为312±3Ma,可作为浒湾变质带榴辉岩相峰期变质年龄,这一结果表明浒湾变质带陆壳成因榴辉岩存在石炭纪榴辉岩相变质事件.空间上相近的古生代洋壳和新元古代陆壳具有相同的榴辉岩相变质年龄表明,浒湾变质带的洋壳和陆壳榴辉岩可能存在石炭纪的耦合俯冲作用.     

Glaucophanites and eclogites from Val Chiusella,Sesia-Lanzo zone (Italian Alps)

In the metabasites of Val Chiusella, metamorphic assemblages are present, corresponding to the glaucophane schist facies, i.e. garnet glaucophanites to omphacite-garnet glaucophanites, as well as to the eclogite facies, i.e., glaucophane eclogites, eclogites, and omphacite felses. Both groups of assemblages are divided by the critical reaction 1 zoisite +1 glaucophane 1.2 omphacite+0.8 garnet+0.7 paragonite +1.4 quartz+0.8 H₂O. From textural evidence it is clear that in the investigated area this reaction proceeded to the right according to a prograde metamorphism. Correspondingly, K ^garn-cpx _D(Fe/Mg) values of coexisting garnet-omphacite pairs in the glaucophane schist facies assemblages are higher than in the eclogite facies assemblages and reflect a temperature increase from about 450 ° C to about 550 ° C at minimum water vapour pressures of 12 to 16 kb.