Subducting serpentinites release reduced, not oxidized, aqueous fluids.

The observation that primitive arc magmas are more oxidized than mid-ocean-ridge basalts has led to the paradigm that slab-derived fluids carry SO2 and CO2 that metasomatize and oxidize the sub-arc mantle wedge. We combine petrography and thermodynamic modelling to quantify the oxygen fugacity (fO2) and speciation of the fluids generated by serpentinite dehydration during subduction. Silicate-magnetite assemblages maintain fO2 conditions similar to the quartz-fayalite-magnetite (QFM) buffer at fore-arc conditions. Sulphides are stable under such conditions and aqueous fluids contain minor S. At sub-arc depth, dehydration occurs under more reducing conditions producing aqueous fluids carrying H2S. This finding brings into question current models in which serpentinite-derived fluids are the cause of oxidized arc magmatism and has major implications for the global volatile cycle, as well as for redox processes controlling subduction zone geodynamics.

Silicate dissolution boosts the CO2 concentrations in subduction fluids.

Estimates of dissolved CO2 in subduction-zone fluids are based on thermodynamic models, relying on a very sparse experimental data base. Here, we present experimental data at 1-3 GPa, 800 °C, and ∆FMQ ≈ -0.5 for the volatiles and solute contents of graphite-saturated fluids in the systems COH, SiO2-COH ( + quartz/coesite) and MgO-SiO2-COH ( + forsterite and enstatite). The CO2 content of fluids interacting with silicates exceeds the amounts measured in the pure COH system by up to 30 mol%, as a consequence of a decrease in water activity probably associated with the formation of organic complexes containing Si-O-C and Si-O-Mg bonds. The interaction of deep aqueous fluids with silicates is a novel mechanism for controlling the composition of subduction COH fluids, promoting the deep CO2 transfer from the slab-mantle interface to the overlying mantle wedge, in particular where fluids are stable over melts.Current estimates of dissolved CO2 in subduction-zone fluids based on thermodynamic models rely on a very sparse experimental data base. Here, the authors show that experimental graphite-saturated COH fluids interacting with silicates at 1-3 GPa and 800 °C display unpredictably high CO2 contents.