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Redox state of iron during high-pressure serpentinite dehydration

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Abstract

The Cerro del Almirez massif (Spain) represents a unique fragment of serpentinized oceanic lithosphere that has been first equilibrated in the antigorite stability field (Atg-serpentinites) and then dehydrated into chlorite–olivine–orthopyroxene (Chl-harzburgites) at eclogite facies conditions during subduction. The massif preserves a dehydration front between Atg-serpentinites and Chl-harzburgites. It constitutes a suitable place to study redox changes in serpentinites and the nature of the released fluids during their dehydration. Relative to abyssal serpentinites, Atg-serpentinites display a low Fe3+/FeTotal(BR) (=0.55) and magnetite modal content (=2.8–4.3 wt%). Micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy measurements of serpentines at the Fe–K edge show that antigorite has a lower Fe3+/FeTotal ratio (=0.48) than oceanic lizardite/chrysotile assemblages. The onset of Atg-serpentinites dehydration is marked by the crystallization of a Fe3+-rich antigorite (Fe3+/FeTotal = 0.6–0.75) in equilibrium with secondary olivine and by a decrease in magnetite amount (=1.6–2.2 wt%). This suggests a preferential partitioning of Fe3+ into serpentine rather than into olivine. The Atg-breakdown is marked by a decrease in Fe3+/FeTotal(BR) (=0.34–0.41), the crystallization of Fe2+-rich phases and the quasi-disappearance of magnetite (=0.6–1.4 wt.%). The observation of Fe3+-rich hematite and ilmenite intergrowths suggests that the O2 released by the crystallization of Fe2+-rich phases could promote hematite crystallization and a subsequent increase in fo2 inside the portion of the subducted mantle. Serpentinite dehydration could thus produce highly oxidized fluids in subduction zones and contribute to the oxidization of the sub-arc mantle wedge.

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Acknowledgments

We acknowledge SOLEIL for provision of synchrotron radiation facilities on LUCIA beamline (Project No. 20121036). We thank J.-L. Devidal (LMV, Clermont-Ferrand) for his assistance during microprobe analyses, P. Boulhiol (Durham University) for instructive discussions, and MR Reyes-González for sample preparation. We thank N. Malaspina and K. Evans for critical comments on an earlier version of this article, and O. Müntener for his careful editorial handling. The Raman spectroscopy facility at the ENS Lyon is supported by CNRS INSU. This work was supported by ANR11JS5601501 HYDEEP, grant to Nathalie Bolfan-Casanova. The first author is supported by the ERC HabitablePlanet (306655), grant attributed to Helen Williams (Durham University, UK). JAPN has been supported by a EU-FP7-funded Marie Curie postdoctoral grant under contract agreement PIOF-GA-2010-273017. JAPN, VLSV, MTGP, and CJG are supported by “Ministerio de Economía y Competitividad” Grants CGL2012-32067 and CGL2013-42349-Pand Junta de Andalucía Grants RNM-145, RNM-131, and P09-RNM-4495, funded by the European Regional Development Fund. The authors further acknowledge support by the Marie Curie ITN-ZIP funded under Grant agreement PITN-GA-2013-604713.

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Authors and Affiliations

  1. Department of Earth Sciences, Durham University, Durham, DH1 3LE, UK

    Baptiste Debret

  2. Laboratoire Magmas et Volcans, Clermont Université, Université Blaise Pascal, Clermont-Ferrand, France

    Baptiste Debret & Nathalie Bolfan-Casanova

  3. UMR6524 - IRD, R163, LMV, CNRS, Clermont-Ferrand, France

    Baptiste Debret & Nathalie Bolfan-Casanova

  4. Géosciences Montpellier, Université Montpellier 2, Montpellier, France

    José Alberto Padrón-Navarta

  5. Departamento de Física de la Tierra, Astronomía y Astrofísica I, Fac. Physics, Universidad Complutense de Madrid, Madrid, Spain

    Fatima Martin-Hernandez

  6. Dpto. de Física de la Tierra, Instituto de Geociencias (UCM,CSIC), Madrid, España, Spain

    Fatima Martin-Hernandez

  7. Laboratoire de Géologie de Lyon, UMR5276, ENS — Université Lyon 1, Villeurbanne, France

    Muriel Andreani

  8. Instituto Andaluz de Ciencias de la Tierra (IACT), CSIC-UGR, Avenida de las Palmeras 4, 18100, Armilla, Granada, Spain

    Carlos J. Garrido

  9. Departamento de Geología, Escuela Politécnica Superior, Universidad de Jaén (Unidad Asociada al CSIC-IACT Granada), Alfonso X el Sabio 28, 23700, Linares, Spain

    Vicente López Sánchez-Vizcaíno

  10. Departamento de Mineralogía y Petrología, Facultad de Ciencias, Universidad de Granada, Campus Fuentenueva, s/n, 18002, Granada, Spain

    María Teresa Gómez-Pugnaire

  11. Institut des Sciences de la Terre, Université Grenoble I, Grenoble, France

    Manuel Muñoz

  12. Synchrotron SOLEIL, Paris, France

    Nicolas Trcera

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Debret, B., Bolfan-Casanova, N., Padrón-Navarta, J.A. et al. Redox state of iron during high-pressure serpentinite dehydration. Contrib Mineral Petrol 169, 36 (2015). https://doi.org/10.1007/s00410-015-1130-y

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