Volatile (Li, B, F and Cl) mobility during amphibole breakdown in subduction zones

• We track the fate of F, Cl, Li and B in the subducted oceanic crust.
• Halogen budget of metagabbros is mostly stored in amphibole and titanite.
• Li acts as a tracer of sediment/metagabbros interactions during prograde metamorphism.
• 90% to 50% of metagabbro halogen budget is lost to fluid during subduction.

Amphiboles are ubiquitous minerals in the altered oceanic crust. During subduction, their breakdown is governed by continuous reactions up to eclogitic facies conditions. Amphiboles thus contribute to slab-derived fluid throughout prograde metamorphism and continuously record information about volatile exchanges occurring between the slab and the mantle wedge. However, the fate of volatile elements and especially halogens, such as F and Cl, in amphibole during subduction is poorly constrained. We studied metagabbros from three different localities in the Western Alps: the Chenaillet ophiolite, the Queyras Schistes Lustrés and the Monviso meta-ophiolitic complexes. These samples record different metamorphic conditions, from greenschist to eclogite facies, and have interacted with different lithologies (e.g. sedimentary rocks, serpentinites) from their formation at mid-oceanic ridge, up to their devolatilization during subduction. In the oceanic crust, the initial halogen budget is mostly stored in magmatic amphibole (F = 300–7000 ppm; Cl = 20–1200 ppm) or in amphibole corona (F = 100–7000 ppm; Cl = 80–2000 ppm) and titanite (F = 200–1500 ppm; Cl < 200 ppm) formed during hydrothermal seafloor alteration. It is thus the fate of these phases that govern the halogen fluxes between the crust and the overlying mantle and/or the plate interface in subduction zones. Li and B are poorly stored in the oceanic crust (< 5 ppm). In subduction zones, prograde metamorphism of metagabbros is first marked by the crystallization of glaucophane at the expense of magmatic and amphibole coronas. This episode is accompanied with a decrease of halogen concentrations in amphiboles (< 200 ppm of F and Cl) suggesting that these elements can be transferred to the mantle wedge by fluids. In the Queyras Schistes Lustrés complex, the intense deformation and the abundant devolatilization of metasedimentary rocks produce large fluid flows that promote rock chemical hybridization (metasomatic mixing with hybrid composition between metasedimentary rock and metagabbro) at the metasedimentary rock/metagabbro contacts. Such fluid/rock interactions result in a strong addition of Li in glaucophane (up to 600 ppm) whereas halogen concentrations are unaffected. At eclogite facies conditions, metagabbros display low halogens concentrations (< 20 ppm of F and < 100 ppm of Cl) relative to altered oceanic crust (F = 40–650 ppm; Cl = 40–1400 ppm) suggesting that these elements are continuously released by fluids during the first 30–80 km of subduction whatever the tectonic environment (e.g. slab, plate interface) and the considered fluid/rock interactions.