Melting of metasomatized peridotite at 4–6 GPa and up to 1200 °C: an experimental approach

The phase assemblages and compositions in a K-bearing lherzolite + H2O system are determined between 4 and 6 GPa and 850–1200 °C, and the melting reactions occurring at subarc depth in subduction zones are constrained. Experiments were performed on a rocking multi-anvil apparatus. The experiments had around 16 wt% water content, and hydrous melt or aqueous fluid was segregated and trapped in a diamond aggregate layer. The compositions of the aqueous fluid and hydrous melt phases were measured using the cryogenic LA-ICP-MS technique. The residual lherzolite consists of olivine, orthopyroxene, clinopyroxene, and garnet, while diamond (C) is assumed to be inert. Hydrous and alkali-rich minerals were absent from the run products due to preferred dissolution of K2O (and Na2O) to the aqueous fluid/hydrous melt phases. The role of phlogopite in melting relations is, thus, controlled by the water content in the system: at the water content of around 16 wt% used here, phlogopite is unstable and thus does not participate in melting reactions. The water-saturated solidus, i.e., the first appearance of hydrous melt in the K–lherzolite composition, is located between 900 and 1000 °C at 4 GPa and between 1000 and 1100 °C at 5 and 6 GPa. Compositional jumps between hydrous melt and aqueous fluid at the solidus include a significant increase in the total dissolved solids load. All melts/fluids are peralkaline and calcium-rich. The melting reactions at the solidus are peritectic, as olivine, clinopyroxene, garnet, and H2O are consumed to generate hydrous melt plus orthopyroxene. Our fluid/melt compositional data demonstrate that the water-saturated hybrid peridotite solidus lies above 1000 °C at depths greater than 150 km and that the second critical endpoint is not reached at 6 GPa for a K2O–Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–Cr2O3(–TiO2) peridotite composition.

The behaviour of incompatible elements during hydrous melting of metasomatized peridotite at 4–6 GPa and 1000 °C–1200 °C

Trace element behavior during hydrous melting of a metasomatized garnet–peridotite was examined at pressures of 4–6 GPa and temperatures of 1000 °C–1200 °C, conditions appropriate for fluid penetrating the mantle wedge atop the subducting slab. Experiments were performed in a rocking multi-anvil apparatus using a diamond-trap setup. The compositions of the fluid and melt phases were measured using the cryogenic LA-ICP-MS technique. The water-saturated solidus of the K-lherzolite composition is located between 900 °C and 1000 °C at 4 GPa and between 1000 °C and 1100 °C at 5 and 6 GPa. The partition coefficients between fluid or melt and clinopyroxene reveal an asymmetric MREE trough with a minimum at Dy. The clinopyroxene in equilibrium with aqueous fluids is characterized by DUfluid–cpx > DThfluid–cpx while DUmelt–cpx tends to be similar to DThmelt–cpx. The partition coefficients between fluid or melt and garnet reveal very strong light to heavy REE fractionation, DLa/DLu from 95 (hydrous melt) to 1600 (aqueous fluid). The LILE are highly incompatible with partition coefficients > 50. The behavior of HFSE are decoupled, with DZr,Hf close to 1 while DNb,Ta > 10. Garnet is characterized by DUmelt/fluid–garnet < DThmelt/fluid–garnet. A comparison of our experimental partitioning results for trivalent cations as well as the results from the literature and the calculations carried out using the lattice strain model adapted to the presence of water in the bulk system indicates that H2O in the fluid or melt phase has a prominent effect on trace element partitioning. Garnet in mantle rocks in equilibrium with an aqueous fluid is characterized by significantly higher Do(3 +) for REE in the X site of the garnet compared with the partitioning values of the optimal cation in garnet in equilibrium with hydrous melts. Our data show for the first time that the change in the nature of the mobile phase (fluid vs. melt) does affect the affinities of trace elements into the garnet crystal at conditions below the second critical endpoint of the system. The same also applies for clinopyroxene, although this is less clear. Consequently, our new data allow for refinements in predictive modeling of element transfer from the slab to the mantle wedge and of possible compositions of metasomatized mantle that sources OIB magmatism.

Fluid-related inclusions in Alpine high-pressure peridotite reveal trace element recycling during subduction-zone dehydration of serpentinized mantle (Cima di Gagnone, Swiss Alps).

Serpentinites release at sub-arc depths volatiles and several fluid-mobile trace elements found in arc magmas. Constraining element uptake in these rocks and defining the trace element composition of fluids released upon serpentinite dehydration can improve our understanding of mass transfer across subduction zones and to volcanic arcs. The eclogite-facies garnet metaperidotite and chlorite harzburgite bodies embedded in paragneiss of the subduction melange from Cima di Gagnone derive from serpentinized peridotite protoliths and are unique examples of ultramafic rocks that experienced subduction metasomatism and devolatilization. In these rocks, metamorphic olivine and garnet trap polyphase inclusions representing the fluid released during high-pressure breakdown of antigorite and chlorite. Combining major element mapping and laser-ablation ICP-MS bulk inclusion analysis, we characterize the mineral content of polyphase inclusions and quantify the fluid composition. Silicates, Cl-bearing phases, sulphides, carbonates, and oxides document post-entrapment mineral growth in the inclusions starting immediately after fluid entrapment. Compositional data reveal the presence of two different fluid types. The first (type A) records a fluid prominently enriched in fluid-mobile elements, with Cl, Cs, Pb, As, Sb concentrations up to 10(3) PM (primitive mantle), similar to 10(2) PM Tit Ba, while Rb, B, Sr, Li, U concentrations are of the order of 10(1) PM, and alkalis are similar to 2 PM. The second fluid (type B) has considerably lower fluid-mobile element enrichments, but its enrichment patterns are comparable to type A fluid. Our data reveal multistage fluid uptake in these peridotite bodies, including selective element enrichment during seafloor alteration, followed by fluid-rock interaction along with subduction metamorphism in the plate interface melange. Here, infiltration of sediment-equilibrated fluid produced significant enrichment of the serpentinites in As, Sb, B, Pb, an enriched trace element pattern that was then transferred to the fluid released at greater depth upon serpentine dehydration (type A fluid). The type B fluid hosted by garnet may record the composition of the chlorite breakdown fluid released at even greater depth. The Gagnone study-case demonstrates that serpentinized peridotites acquire water and fluid-mobile elements during ocean floor hydration and through exchange with sediment-equilibrated fluids in the early subduction stages. Subsequent antigorite devolatilization at subarc depths delivers aqueous fluids to the mantle wedge that can be prominently enriched in sediment-derived components, potentially triggering arc magmatism without the need of concomitant dehydration/melting of metasediments or altered oceanic crust.

Variations of clinopyroxene/melt element partitioning during assimilation of olivine/peridotite by low-Mg diorite magma

The effects of crystal chemistry and melt composition on the control of clinopyroxene/melt element partitioning (D) during the assimilation of olivine/peridotite by felsic magma have been investigated in Mesozoic high-Mg diorites from North China. The assimilation resulted in significant increase of Mg, Cr and Ni and only slight (< 30%) decrease of incompatible elements of the magma, and the compositional variations have been mirrored by the normally and reversely zoned clinopyroxene microphenocrysts formed at the early stage of the magma evolution. The Mg# [100 × Mg / (Mg + Fe)] values of the reversely zoned clinopyroxenes increase from 65 to 75 in the core to 85–90 in the high-Mg midsection, and reduce back to 73–79 at the rim. Trace element profiles across all these clinopyroxene domains have been measured by LA-ICP-MS. The melt trace element composition has been constrained from bulk rock analyses of the fine-grained low- and high-Mg diorites. Clinopyroxene/melt partition coefficients for rare earth elements (REE) and Y in the high-Mg group zonings (Mg# > 73–79, DDy < 1.2) are positively correlated with tetrahedral IVAl and increase by a factor of 3–4 as tetrahedral IVAl increases from 0.01 to 0.1 per formula unit (pfu). These systematic variations are interpreted to be controlled by the clinopyroxene composition. In contrast, partition coefficients for low-Mg group zonings (Mg# < 75–79, DDy > 1.2) are elevated by up to an order of magnitude (for REE and Y) or more (for Zr and Hf) at similar IVAl, indicating dominant control of melt composition/structure. DZr and DHf show a larger sensitivity to the compositional change of crystal and melt than DREE. DTi values for the low- and high-Mg zonings show a uniform dependence on IVAl. DSr and DLi are insensitive to the compositional change of clinopyroxene and melt, resulting in Sr depletions in the clinopyroxene zonings with elevated REE without crystallization of plagioclase. Our observations show that crystal chemistry and melt composition/structure may alternatively control clinopyroxene/melt partitioning during the assimilation of peridotite by felsic magma, and may be useful for deciphering clinopyroxene compositions and related crust–mantle processes.

Continuous eclogite melting and variable refertilisation in upwelling heterogeneous mantle

Large-scale tectonic processes introduce a range of crustal lithologies into the Earth's mantle. These lithologies have been implicated as sources of compositional heterogeneity in mantle-derived magmas. The model being explored here assumes the presence of widely dispersed fragments of residual eclogite (derived from recycled oceanic crust), stretched and stirred by convection in the mantle. Here we show with an experimental study that these residual eclogites continuously melt during upwelling of such heterogeneous mantle and we characterize the melting reactions and compositional changes in the residue minerals. The chemical exchange between these partial melts and more refractory peridotite leads to a variably metasomatised mantle. Re-melting of these metasomatised peridotite lithologies at given pressures and temperatures results in diverse melt compositions, which may contribute to the observed heterogeneity of oceanic basalt suites. We also show that heterogeneous upwelling mantle is subject to diverse local freezing, hybridization and carbonate-carbon-silicate redox reactions along a mantle adiabat.

Valle d’Aosta section of the Sesia Zone: multi-stage HP metamorphism and assembly of a rifted continental margin

The spectrum characteristic of the EMC ranges from eclogites (containing omphacite and/or jadeite, garnet, phengite, glaucophane, zoisite, chloritoid, rutile) to phengite schists, calcschists, and marbles, as well as a variety of orthogneisses. Despite the intense polyphase deformation and HP-metamorphic recrystallization, it is possible in some locations to recognize pre-Alpine characteristics in some of the protoliths. For instance, two types of felsic orthogneiss can be distinguished in the Aosta Valley, one derived from Permian granitoids (with local preservation of intrusive contacts, magmatic inclusions, leucocratic veins and other magmatic structures; Stop 3), the other derived from pre-Variscan leuco-monzogranite, such as the building stone mined at the “Argentera” quarry near Settimo Vittone / Montestrutto (Stop 2; so-called “Verde Argento” contains jadeite, phengite, K-feldspar, quartz). Polycyclic and more rarely monocyclic metasediments contain evidence of a complex Alpine PTDt-evolution, locally including relics of their prograde history from blueschist, one or more stages at eclogite facies. Recent petrochronological studies have dated this HP-evolution of the Sesia Zone in some detail. In the area visited, clear evidence of HP-cycling has been identified in one km-size tectonic slice (Stop 1), but not in adjacent parts of the EMC, indicating “yo-yo tectonics”. Partial retrogression and attendant ductile to brittle deformation of the HP-rocks is evident in one of the outcrops (Stop 4). Apart from the four localities in the Sesia Zone, a final outcrop introduces HP-rocks of the adjacent Piemonte oceanic unit, specifically calc-schists and ophiolite members of the “Zermatt-Saas” zone. The hilltop outcrop (Stop 5) displays foliated antigorite schist with peridotite relics (clinopyroxene, spinel) containing lenses derived from doleritic dykes. These fine-grained metarodingites and the folded veins containing Mg-chlorite and titanoclinohumite within serpentinite once again indicate equilibration under low-temperature eclogite facies conditions. However, these units reached that HP stage more than 20 Ma after the youngest eclogite facies imprint recognized in the Sesia Zone. Despite nearly half a century of intense study in the Sesia Zone, the complex assembly of its HP-terranes and their relation to more external parts of the Western Alps remains incompletely understood. This field guide merely introduces a few of the classic outcrops and discusses some of the critical evidence they contain, but it could not incorporate details on each stage of the evolution recognized so far.

UHP Metamorphism Documented in Ti-chondrodite- and Ti-clinohumite-bearing Serpentinized Ultramafic Rocks from Chinese Southwestern Tianshan

The southwestern Tianshan (China) metamorphic belt records high-pressure (HP) to ultrahigh-pressure (UHP) conditions corresponding to a cold oceanic subduction-zone setting. Serpentinites enclosing retrogressed eclogite and rodingite occur as lenses within metapelites in the UHP unit, which also hosts coesite-bearing eclogites. Based on the petrology and petrography of these serpentinites, five events are recognized: (1) formation of a wehrlite–harzburgite–dunite association in the mantle; (2) retrograde metamorphism and partial hydration during exhumation of the mantle rocks close to the seafloor; (3) oceanic metamorphism leading to the first serpentinization and rodingitization; (4) UHP metamorphism during subduction; (5) retrograde metamorphism during exhumation together with a second serpentinization. The peak metamorphic mineral assemblage of the serpentinized wehrlite comprises Ti-chondrodite + olivine + antigorite + chlorite + magnetite + brucite. A computed pseudosection for this serpentinized wehrlite shows that the Al content in antigorite is mostly sensititive to temperature but can also be used to constrain pressure. The average XAl = 0·204 ± 0·026 of antigorite (XAl = Al (a.p.f.u.)/8, where Al is in atoms per formula unit for a structural formula M48T34O85(OH)62, and M and T are octahedral and tetrahedral sites, respectively) included in Ti-chondrodite and average XAl = 0·203 ± 0·019 of antigorite in the matrix result in a well-constrained peak metamorphic temperature of 510–530°C. Peak pressures are less precisely constrained at 37 ± 7 kbar. The Tianshan serpentinites thus record UHP metamorphic conditions and represent the deepest subducted serpentinites discovered so far. The retrograde evolution occurs within the stability field of brucite + antigorite + olivine + chlorite and formation of Ti-clinohumite at the expense of Ti-chondrodite has been observed, suggesting isothermal decompression. The resulting P–T path is in excellent agreement with the metamorphic evolution of country rocks, indicating that the UHP unit in Tianshan was subducted and exhumed as a coherent block. To refine the metamorphic path of the ultramafic rocks, we have investigated the stability fields of Ti-chondrodite and Ti-clinohumite using piston-cylinder experiments. A total of 11 experiments were conducted at 25–55 kbar and 600–750°C in a F-free natural system. Combined with previous experiments and information from natural rocks we constructed a petrogenetic grid for the stability of Ti-chondrodite and Ti-clinohumite in F-free peridotite compositions. The formation of Ti-chondrodite in serpentinites requires a minimum pressure of about 26 kbar, whereas in Ti-rich systems it can form at considerably lower pressures. A key finding is that at UHP conditions, F-free Ti-chondrodite or Ti-clinohumite breaks down in the presence of orthopyroxene between 700 and 750°C, at temperatures that are significantly lower than those of the terminal breakdown reactions of these humite minerals. These breakdown reactions are an additional source of fluid during prograde subduction of serpentinites.