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Mantle wedge oxidation from deserpentinization modulated by sediment-derived fluids

Nature Geoscience volume 16, pages 268–275 (2023)Cite this article

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Abstract

High-pressure dehydration of serpentinite during subduction generates fluids that flux and melt the overlying mantle wedge, forming primary arc basalts. These basalts are substantially more oxidized than their mid-ocean ridge counterparts. At the slab surface of current subduction zones, these deserpentinization fluids are intrinsically oxidized, but, owing to the low sulfur content of subducted serpentinite, they only result in a low mantle wedge oxidation rate, which cannot account for the oxidized source of arc basalts. Here we show that infiltration of sediment-derived fluids modulates and can drastically change the oxidation capacity of deserpentinization slab fluids. The modulation of the deserpentinization oxidation capacity mostly depends on the stability and abundance of dissolved oxidized aqueous species of redox-sensitive elements—notably sulfate—and not solely on the oxidation state of the sediment. Infiltration of CH4-bearing fluids derived from graphite-bearing sediment reduces the intrinsically high oxidant capacity of deserpentinization fluids, explaining the relatively low fO2 observed in natural metaperidotite. Infiltration of sulfate-CO2-bearing, sediment-derived fluids—prevalent in modern subduction zones—generates deserpentinization fluids with a high oxidation capacity in cold and hot subduction zones, resulting in a global mantle wedge oxidation rate of 3.5 km3 yr−1. Such slab fluids will oxidize the mantle wedge at a rate similar to that of arc-basalt generation and thus account for the oxidized nature of arc volcanism.

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Fig. 1: Reversible and irreversible cycles of hydration–oxidation of mantle peridotite.
Fig. 2: Conceptual model of the intrinsic and modulated deserpentinization.
Fig. 3: Intrinsic deserpentinization and deserpentinization modulated by sediment-derived fluids.
Fig. 4: Mantle wedge oxidation capacity of deserpentinization fluids modulated by GLOSS-derived fluids.
Fig. 5: Global mantle wedge oxidation rate for intrinsic and sediment-fluid modulated deserpentinization.

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Data availability

A spreadsheet file (xlsx) is provided containing all chemical analyses used to construct Fig. 1 and Extended Data Fig. 4, including the duplicate and new analyses from CdA from this work, and also a Supplementary file (csv). The worldwide subduction zone database83 was used to compute the pressure and temperature conditions for the slab surface deserpentinization84. These pressure and temperature conditions were used to compute the intrinsic fluid chemistry and the fluid composition for high- and low-reducing capacity sediments (graphite and GLOSS, respectively) that were used for infiltration at the same serpentinite dehydration pressure and temperature conditions. The main species are given for three cases: intrinsic (_intr), and for infiltration of 12 mol kg−1 for the cases of graphite-bearing and GLOSS sediment-derived fluids (_graph and _gloss). Fluid bulk compositions are given in mol per formula unit of fluid, and species concentrations are given in units of mol kg−1. This database can be generated for other degrees of infiltration using the Jupyter notebook available at https://github.com/bertopadron/Redox.git. Source data are provided with this paper.

Code availability

All computations were produced using Perple_X v6.9.0 version (Methods).

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Acknowledgements

This work is part of the DESTINE grant PID2019-105192GB-I00, funded by MICIN/AEI/10.13039/501100011033, and ‘EFRD a way making Europe’. J.A.P.-N. acknowledges Ramón y Cajal fellowship RYC2018-024363-I, funded by MICIN/AEI/10.13039/501100011033 and the ESF program ‘FSE invierte en tu futuro’. M.D.M. acknowledges a postdoctoral fellowship (Postdoc_21_00791) funded by the Junta de Andalucía (Consejeria de Conocimiento y Universidades), and co-funded by EFRD and ESF. This research is part of the Junta de Andalucía research groups RNM-131 and RNM-374.

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Authors and Affiliations

  1. Instituto Andaluz de Ciencias de la Tierra (IACT), CSIC–UGR, Granada, Spain

    José Alberto Padrón-Navarta, Manuel D. Menzel, María Teresa Gómez-Pugnaire & Carlos J. Garrido

  2. Géosciences Montpellier, Université de Montpellier & CNRS, Montpellier, France

    José Alberto Padrón-Navarta

  3. Departamento de Geología (Unidad Asociada al IACT, CSIC–UGR), Universidad de Jaén, Escuela Politécnica Superior, Linares, Jaén, Spain

    Vicente López Sánchez-Vizcaíno

  4. Departamento de Mineralogía y Petrología, Universidad de Granada, Granada, Spain

    María Teresa Gómez-Pugnaire

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  1. José Alberto Padrón-Navarta
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Contributions

J.A.P.-N. conceived the project, processed the data, acquired funding and wrote the original manuscript. V.L.S.-V. contributed to the conceptualization, performed the computations, organized the raw data and contributed to the writing of the manuscript. M.D.M. computed the global deserpentinization conditions and assisted with computations. M.T.G.-P. contributed to the writing of the manuscript. C.J.G. contributed to the conceptualization, funding and writing of the manuscript.

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Correspondence to José Alberto Padrón-Navarta or Vicente López Sánchez-Vizcaíno.

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Nature Geoscience thanks Antoine Benard and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Rebecca Neely, in collaboration with the Nature Geoscience team.

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Extended data

Extended Data Fig. 1 The stable mineral assemblage for a high-pressure serpentinite.

X(O2)-P/T (along a thermal gradient, see Methods) pseudosection7 for a representative Ca-poor high-pressure serpentinite from CdA (sample Al98-05a35) with sulphur and carbon content from ref. 27 (these values were confirmed by new, duplicate analyses) and ferric iron from this work (see Supplementary Table 1). The vertical line represents the intrinsic deserpentinization for a fixed O2 content of the system (Path I), corresponding to the bulk O2 for sample Al98-05a (15.602 mol/kg is used instead of the measured 15.672 mol/kg for better agreement with the observed sequence of mineral assemblages at CdA; it likely reflects the amount of ferric iron in antigorite, not accounted for in the available solid solution models89). The horizontal path (IIa) shows schematically the evolution if the system is externally infiltrated by fluids equilibrated with metasedimentary rocks with a high reducing capacity (graphite-bearing metapelite). The quantitative evolution along path IIa is shown in Fig. 3b in the main text (see also Supplementary Figure 6 for the evolution of the speciation in the fluid). Path IIb corresponds to the prograde evolution after the graphite metapelite-infiltrated deserpentinization potentially followed by CdG.

Extended Data Fig. 2 Redox-sensitive elements in the solid phases for a high-pressure serpentinite.

The absolute concentration of redox-sensitive components in the solids (expressed as mol/kg of rock Al98-05a) for the pseudosection shown in Supplementary Figure 1 (see also Fig. 3a in the main text for the contouring of oxygen fugacity relative to the buffer FMQ). All panels were computed from the absolute amounts of mineral phases containing oxygen-sensitive components and their concentration in pure and solid solution endmembers from WERAMI outputs. Computations used the back-calculated method for fluid speciation in PerpleX, except for panel S6+ which was computed using the lagged speciation method that allows mass balance constraints in the region below the complete serpentinite dehydration. The last panel shows the redox budget of the rock referred to the whole mantle reference redox state (Methods).

Extended Data Fig. 3 Prograde evolution for the intrinsic deserpentinization model.

Evolution of key parameters along intrinsic deserpentinization (intrinsic path I in Fig. 3, red vertical line). (a) XMg in antigorite and their dehydrated product olivine and orthopyroxene; (b) H2O content hosted in the solid phases; (c) and (d) bulk sulphur and carbon contents retained in the solid phases; (e) evolution of the oxygen fugacity relative to the FMQ buffer. The blue region corresponds to the temperature conditions of dehydration in Cerro del Almirez (CdA). Note that none of the observables (XMg, S and C content, see Fig. 3b-e in the main text) agrees with the model predictions along with the intrinsic deserpentinization model.

Extended Data Fig. 4 Magnetite content as a function of the state of hydration.

Global compilation of magnetite content in serpentinite and metaperidotite (Chl-harzburgite) against the water content (measured for CdA, this work and ref. 27) or loss of ignition (L.O.I.) as a proxy for water content for samples from the literature (see Methods). The observed decrease in magnetite content relative to common magnetite-bearing serpentinite is reproduced by deserpentinization infiltrated with highly reducing fluids equilibrated with graphite-bearing metapelite. The decrease in magnetite for the intrinsic deserpentinization model is coeval with the precipitation of haematite (dashed red line) which is not observed in natural samples.

Source data

Extended Data Fig. 5 Variation in oxygen fugacity for the intrinsic model.

Intrinsic deserpentinization oxygen fugacity conditions (a) relative to the FMQ buffer, Δlog10fO2[FMQ] and in absolute values (b) for a representative metaserpentinite (sample Al98-05a, see Supplementary Table 1) in a pressure-temperature space. Yellow dots are pressure-temperature deserpentinization conditions at the slab surface for a worldwide compilation of subduction zones83,84, geographically located in (c). (d) Difference between the slab surface intrinsic deserpentinization and the mantle wedge oxygen fugacity (expressed as Δlog10fO2[FMQ]) along the 1000 °C isotherm for the DMM (solid line) and ultradepleted mantle (red dashed line), see also Extended Data Fig. 7, right panels.

Extended Data Fig. 6 Changes in the fluid composition during the infiltration of an external fluid with high reducing potential into a reacting serpentinite.

a. Fluid speciation evolution during the infiltration of a partially dehydrated serpentinite with a fluid equilibrated with a graphite-bearing metapelite at 650 °C and 1.7 GPa. The solvent species H2S and CO2 are expressed as mole fraction, whereas the solute species are expressed as molality (mol/kg). The main oxidizing species (HSO4−) is represented on a linear scale whereas other less abundant species are on a logarithmic scale. b. Modal (vol.%) pyrite abundance in the metaperidotite induced by graphite metapelite fluid infiltration.

Extended Data Fig. 7 Oxygen fugacity conditions of the mantle wedge prior to its interaction with deserpentinization fluids.

Effect of peridotite mantle wedge depletion on the Δlog10fO2[FMQ] evolution during fluxing by different types of deserpentinization slab fluids. The left panel shows the results for (a) a depleted MORB mantle wedge source85 (DMM) and (b) an ultradepleted mantle wedge source86, both for a hot (Central Cascadia) and a cold (Tonga) subduction zone. The mantle wedge Δlog10fO2[FMQ] evolution of the mantle wedge fluxed by fluids sourced from intrinsic deserpentinization and sediment-infiltrated deserpentinization fluids produced by the infiltration of 12 mol/kg of fluids equilibrated with GLOSS and graphite-bearing metapelite. Right panels are the contours of the initial Δlog10fO2[FMQ] of the mantle wedge for a DMM (upper panel) and ultradepleted source (lower panel) before fluxing with slab fluids; shown as yellow dots are the initial Δlog10fO2[FMQ] conditions at the 1000 °C of the mantle wedge for a worldwide compilation of dehydration conditions in hot to cold subduction zones. Central Cascadia (hot subduction) and Tonga (cold subduction) correspond, respectively, to a minimum (2.4 GPa) and maximum pressure (3.3 GPa) for the dehydration of serpentinization at the slab surface. Note that the initial Δlog10fO2[FMQ] conditions depend on the thermal regime of the subduction zone and the depletion of the mantle wedge source, but have a subsidiary effect on the Δlog10fO2[FMQ] evolution of the mantle wedge during fluxing of different types of deserpentinization fluids.

Extended Data Fig. 8 Mantle wedge oxidation capacity of deserpentinization fluids modulated by graphite-bearing metasediments derived fluids.

(a) Modification at the slab surface of the Δlog10fO2[FMQ] and the concentration of HSO4− —relative to the intrinsic deserpentinization fluid (ID)— during infiltration of fluids equilibrated with metasedimentary rocks with a high reducing capacity (graphite-bearing metapelite) for a worldwide compilation of subduction zones83,84 (colour-coded for the pressure at which the serpentinite dehydrates at the slab surface, Source Data). (b) The capacity of these modified, serpentinite-derived fluids (empty dots in a) to oxidize the mantle wedge on top of the slab at near wet-solidus conditions is computed for the hottest (Central Cascadia) and coldest (Tonga) subduction zones. A minimum value range of Δlog10fO2[FMQ] inferred for oxidized IAB source and recorded by high-pressure metasomatized mantle atop of the slab47,90 is given as a horizontal blue-shaded range. Sediment (graphite-bearing)-serpentinite derived fluids have a variable capacity to oxidize the mantle wedge for hot and cold subduction zones, a variable potential that is directly related to the contrasting solubility of HSO4− for the two extreme thermal cases. The metasomatized mantle wedge has an initially depleted composition85. Squares and stars on the red and blue lines indicate the condition range limits at which pyrrhotite (Po), or anhydrite (anh) are the stable minerals hosting S in the rocks. For an ultradepleted MORB mantle, see Extended Data Fig. 7. For interaction with sediments with low reducing capacity (GLOSS), see Fig. 4 in the main text.

Supplementary information

Supplementary Information

Supplementary discussion including two figures.

Supplementary Tables

Bulk rock composition used for modelling and fluid composition and speciation and after interaction with a sediment with high reducing capacity.

Supplementary Data

Composition of deserpentinization fluids for all subduction segments for the intrinsic and modulated models.

Supplementary Code

Jupyter notebook and associated data.

Source data

Source Data Fig. 1

Data used to construct Fig. 1.

Source Data Extended Data Fig. 4

Data used to construct Extended Data Fig. 4.

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Padrón-Navarta, J.A., López Sánchez-Vizcaíno, V., Menzel, M.D. et al. Mantle wedge oxidation from deserpentinization modulated by sediment-derived fluids. Nat. Geosci. 16, 268–275 (2023). https://doi.org/10.1038/s41561-023-01127-0

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