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

Petrologic and geochemical role of serpentinite in subduction zones and plate interface domains

We discuss geochemical tracers in serpentinite for assessing the fluidrock interactions and the element exchange processes experienced by these rocks during subduction. This enables to define the timing of serpentinite accretion to plate interface domains and the evolution of such tectonically active settings. Uptake of As, Sb, Be and reset of B, Sr and Pb isotopes are due to interaction with sediment-derived fluids during prograde subduction metamorphism. This implies the early slicing and accretion of serpentinite (of slab and/or mantle wedge origin) to plateinterface domains, where they uptake crust- and sediment-derived fluids. Serpentinite metasomatism by sediment-derived fluids enable transfer of these elements to subarc depths and their release to de-serpentinization fluids affecting the mantle sources of arc magmas

Linking serpentinite geochemistry with tectonic evolution at the subduction plate-interface: The Voltri Massif case study (Ligurian Western Alps, Italy)

International audienceRecent geochemical work shows that subduction-zone serpentinites are repositories for fluid-mobile elements absorbed during interaction with sediment-derived fluids. Unraveling the geochemical fingerprint of these rocks helps to define timing of tectonic accretion of sediments along the subduction interface and the role of serpentinite in element recycling to volcanic arcs. Here we present the trace element and isotopic composition (B–O–H, Sr, Pb) of high-pressure serpentinites from the Voltri Massif (Ligurian Western Alps, Italy), to discuss their role as incompatible element carriers and their contribution to recycling of sediment-derived components in subduction zones.The serpentinites presented here record metamorphic olivine growth during eclogite-facies metamorphism and show undeformed and mylonitic textures. Field relations show that undeformed rocks are enclosed in deformed ones and that no metasedimentary rocks are present nearby. Undeformed serpentinite has very high δ11BSRM951 (from +26‰ to +30‰), low Sr and Pb isotope ratios (87Sr/86Sr = 0.7053–0.7069; 206Pb/204Pb = 18.131–18.205) and low As and Sb contents (0.1 and 0.01 μg/g, respectively). Oxygen and hydrogen isotope compositions are +4.5‰ and −67‰, respectively. In contrast, mylonitic serpentinite shows lower δ11B (from +22‰ to +17‰), significant enrichment in radiogenic Sr and Pb isotopes (87Sr/86Sr up to 0.7105; 206Pb/204Pb up to 18.725), and enrichment in As and Sb (1.3 and 0.39 μg/g, respectively). δ18O of the mylonitic serpentinites reaches values of +5.9‰, whereas δD is comparable with that of undeformed rocks (approximately −70‰). In mylonitic serpentinites, the B and Sr isotopic values and the fluid-mobile element (FME) concentrations are near those for the Voltri metasedimentary rocks (calc- and mica-schists). Pb systematics also reveal influx of a crust-derived component.Our dataset shows that undeformed serpentinite still preserves an oceanic geochemical fingerprint, whereas mylonitic serpentinite is reset in its concentrations of FME and its B, Sr and Pb isotope compositions, due to interaction with sediment- and crust-derived fluids. The environment of this interaction is either compatible with (i) an outer-rise zone setting, with percolation of seawater-derived fluids enriched in sedimentary components into bending-related fault structures, or with (ii) subduction channel domains, where ascending sediment-derived slab fluids infiltrate slices of former oceanic serpentinite accreted to the plate interface domain. Influx of sediment-derived subduction fluids along major deformation zones in serpentinite modifies the element budget of the rocks, with important implications for element recycling and the tectonic history of serpentinite. The B, Sr and Pb isotopic systematics, coupled with FME concentration in serpentinites are particularly helpful geochemical tracers of interaction between different reservoirs in subduction-interface environments, and are more sensitive than the traditionally applied stable oxygen and hydrogen isotope compositions

Ophicarbonate evolution from seafloor to subduction and implications for deep-Earth C cycling

The chemical and physical processes operating during subduction-zone metamorphism can profoundly influence the cycling of elements on Earth. Deep-Earth carbon (C) cycling and mobility in subduction zones has been of particular recent interest to the scientific community. Here, we present textural and geochemical data (CeO, Sr isotopes and bulk and in-situ trace element concentrations) for a suite of ophicarbonate rocks (carbonate-bearing serpentinites) metamorphosed over a range of peak pressure-temperature (P-T) conditions together representing a prograde subduction zone P-T path. These rocks, in order of increasing peak P-T conditions, are the Internal Liguride ophicarbonates (from the Bracco unit, N. Apennines), pumpellyite- and blueschist-facies ophicarbonates from the Sestri-Voltaggio zone (W. Ligurian Alps) and the Queyras (W. Alps), respectively, and eclogite-facies ophicarbonates from the Voltri Massif. The Bracco oceanic ophicarbonates retain breccia-like textures associated with their seafloor hydrothermal and sedimentary origins. Their trace element concentrations and δ18OVSMOW (+15.6 to +18.2‰), δ13CVPDB (+1.1 to +2.5‰) and their 87Sr/86Sr (0.7058 to 0.7068), appear to reflect equilibration during Jurassic seawater-rock interactions. Intense shear deformation characterizes the more deeply subducted ophicarbonates, in which prominent calcite recrystallization and carbonation of serpentinite clasts occurred. The isotopic compositions of the pumpellyitefacies ophicarbonates overlap those of their oceanic equivalents whereas the most deformed blueschist-facies sample shows enrichments in radiogenic Sr (87Sr/86Sr=0.7075) and depletion in 13C (with δ13C as low as −2.0‰). These differing textural and geochemical features for the two suites reflect interaction with fluids in closed and open systems, respectively. The higher-P-metamorphosed ophicarbonates show strong shear textures, with coexisting antigorite and dolomite, carbonate veins crosscutting prograde antigorite foliation and, in some cases, relics of magnesite-nodules enclosed in the foliation. These rocks are characterized by lower δ18O (+10.3 to 13.0‰), enrichment in radiogenic Sr (87Sr/86Sr up to 0.7096) and enrichment in incompatible and fluid-mobile element (FME; e.g., As, Sb, Pb). These data seemingly reflect interaction with externally-derived metamorphic fluids and the infiltrating fluids likely were derived from dehydrating serpentinites with hybrid serpentinite-sediment compositions. The interaction between these two lithologies could have occurred prior to or after dehydration of the serpentinites elsewhere. We suggest that decarbonation and dissolution/precipitation processes operating in ancient subduction zones, and resulting in the mobilization of C, are best traced by a combination of detailed field and petrographic observations, C, O and Sr isotope systematics (i.e., 3D isotopes), and FME inventories. Demonstration of such processes is key to advancing our understanding of the influence of subduction zone metamorphism on the mobilization of C in subducting reservoirs and the efficiency of delivery of this C to depths beneath volcanic arcs and into the deeper mantle