Tracking Fe mobility and Fe speciation in subduction zone fluids at the slab-mantle interface in a subduction channel: A tale of whiteschist from the Western Alps

Fluids released by subducting slabs are important to the geochemical evolution of Earth’s crust-mantle system. However, it is still not well constrained for the mobility of redox sensitive elements (like Fe, C or S) in subduction zone fluids, and its effect on the redox property of the overlying mantle wedge and its derived arc magmas. Iron isotope fractionation is sensitive to the redox state and speciation of Fe in fluids, which can potentially provide clues on the oxygen fugacity (fO2) of slab-derived fluids. Whiteschists at the Dora-Maira Massif in the Western Alps have experienced ultrahigh-pressure metamorphism at subarc depths. They are rich in both SiO2 (mostly >65 wt.%) and MgO (4–10 wt.%), and mainly composed of pyrope, quartz/coesite, talc, phengite and kyanite. They were demonstrated to have a granite protolith, but metasomatized by serpentinite-derived Mg-rich fluids at the slab-mantle interface in a subduction channel. Thus these rocks provide an excellent target to explore the fluid-rock interaction by Fe isotopes. The whiteschists show extremely high δ56Fe values of +0.32 to +1.22‰, being much higher than those of +0.10 to +0.38‰ for the surrounding metagranites. The Fe isotope composition of whiteschists significantly deviates from the igneous differentiation trend defined by rocks with basaltic to rhyolitic compositions. The heavy Fe isotope compositions must be produced by a metasomatic process. The much lower Fe2O3 and FeOt contents and Fe3+/∑Fe ratios but higher δ56Fe values for the whiteschists relative to their protolith suggest the reduction of Fe3+ to Fe2+ and the loss of isotopically light Fe, probably in the form of Fe(II)-Cl and/or Fe(II)-(HS) complexes, through saline fluids and/or HS- bearing fluids. The reduction of Fe3+ to Fe2+ and the possible presence of HS- suggests the occurrence of relatively reduced fluids. Such reduced fluids were probably derived from serpentinite dehydration at the slab-mantle interface in the subduction channel. Therefore, the Fe isotope results demonstrate that the fO2 at the slab-mantle interface can be locally highly heterogeneous, leading to various oxidation states in the mantle wedge and arc magmas.