Effects of geodynamic setting on the redox state of fluids released by subducted mantle lithosphere

Abstract

Magnetite breakdown during subduction of serpentinised ultramafic rocks may produce oxidised fluids that oxidise the deep Earth and/or the sub-arc mantle, either via direct transport of ferric iron, or via redox reactions between ferric iron and other elements, such as sulfur. However, so far, there is no consensus on the oxidation state of fluids released during subduction of ultramafic rocks, or the factors that control this oxidation state. Subducted samples from a magma-poor rifted margin and a supra-subduction zone geodynamic setting were compared to examine evidence of changes in opaque phase assemblage and ferric iron content as a consequence of subduction, and as a function of geodynamic setting. Thermodynamic calculations in the system Fe–Ni–O–H–S and Fe–Ni–O–S at the pressures and temperatures of interest were used to constrain oxygen activities and fluid compositions. Samples from New Caledonia, which exemplify supra-subduction zone mantle, contain awaruite (FeNi3) and equilibrated with hydrogen-bearing fluids at oxygen activity less than the FMQ (fayalite–magnetite–quartz) buffer. In contrast, samples from the Zermatt Saas Zone ophiolite, Western Alps, which are thought to represent mantle from a subducted magma-poor rifted margin, contain magnetite plus sulfur-rich phases such as pyrite (FeS2), and are inferred to have equilibrated with hydrogen-poor fluids at oxygen activity greater than FMQ. This major difference is independent of differences in subduction pressure–temperature conditions, variation in peridotite protolith composition, or the nature of adjacent units. We propose that the Zermatt Saas Zone samples would have undergone more complete serpentinisation prior to subduction than the supra-subduction zone (SSZ) New Caledonian samples. This difference explains the different fluid compositions, because incompletely serpentinised rocks containing olivine and brucite retain or evolve awaruite-bearing assemblages that buffer fluid compositions to high hydrogen activity (aH2). Ultramafic rocks are associated with two distinctly different fluid compositions during pre-subduction and subduction serpentinisation. Initially, while olivine is in equilibrium with infiltrating fluid, mineral assemblages that include awaruite in the rocks buffer fluids to H2-bearing, low aO2 compositions. Deserpentinisation of incompletely serpentinised rocks in which awaruite is present also produces H2-bearing fluids. Once awaruite is exhausted, H2-poor, high aO2 fluids co-exist with awaruite-absent assemblages, and deserpentinisation of such rocks would produce H2O-rich fluids. Thus, deserpentinisation of ultramafic rocks could produce either hydrogen-bearing fluids that could infiltrate and reduce the sub-arc mantle, or more oxidised fluids, which could transfer redox budget to other geochemical reservoirs such as the sub-arc mantle. Therefore, the redox contribution of subducted ultramafic rocks to the deep Earth and sub-arc mantle depends on the extent of protolith serpentinisation. Pre-subduction settings that promote extensive serpentinisation by oxidised fluids at high fluid:rock ratios in open systems, such as slow and ultraslow spreading ridges, transform faults, oceanic core complexes, and exhumed mantle at rifted continental margins, may produce more oxidised fluids than those associated with less pervasive serpentinisation and fluids that may be rock-buffered to a reduced state.