Aqueous fluids are effective oxidizing agents of the mantle in subduction zones

Aqueous fluids produced by dehydration of the downgoing slab facilitate chemical exchange in subduction zones, but the efficiency of fluid-mediated redox transfer as a mechanism to deliver oxidized material from the slab to the sub-arc mantle remains hotly debated. Here we report the first direct measurements of the oxidation state of experimentally produced slab fluids using in situ redox sensors. Our experiments show that the dehydration of natural antigorite serpentinite at shallow subduction zone conditions (1 GPa, 800 °C) produces moderately oxidizing fluids (QFM + 2) with elevated concentrations of Na, K, Ca, and Mg. The composition and redox of the experimental fluids are then used to parameterize a thermodynamic reactive transport model to investigate the interaction of slab fluid with the sub-arc mantle from 1–4 GPa and 700–900 °C. Recently determined equation of state parameters for aqueous fluids at high pressures now enables thermodynamic modeling of aqueous fluid–rock interactions at conditions relevant to deep subduction zones for the first time. Our thermodynamic modeling demonstrates that aqueous fluid can efficiently oxidize Fe in mantle minerals via the reduction of H⁺ to H₂ in the fluid. We estimate that < 1–3 kg of serpentinite-derived fluid at 850–900 °C is required to increase the Fe³⁺/ΣFe in 1 kg of sub-arc mantle from MORB-like values (0.15) to those of primitive arc basalts (0.2–0.3). We calculate that a slab fluid flux of 1.4 × 10⁹–1.4 × 10¹⁴ kg year⁻¹ is required to oxidize sufficient sub-arc mantle to produce the average annual flux of magmas at arcs, which overlaps with the estimated range of H₂O flux in subduction zones.