Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Release of oxidizing fluids in subduction zones recorded by iron isotope zonation in garnet

Abstract

Subduction zones are key regions of chemical and mass transfer between the Earth’s surface and mantle. During subduction, oxidized material is carried into the mantle and large amounts of water are released due to the breakdown of hydrous minerals such as lawsonite. Dehydration accompanied by the release of oxidizing species may play a key role in controlling redox changes in the subducting slab and overlying mantle wedge. Here we present measurements of oxygen fugacity, using garnet–epidote oxybarometry, together with analyses of the stable iron isotope composition of zoned garnets from Sifnos, Greece. We find that the garnet interiors grew under relatively oxidized conditions whereas garnet rims record more reduced conditions. Garnet δ56Fe increases from core to rim as the system becomes more reduced. Thermodynamic analysis shows that this change from relatively oxidized to more reduced conditions occurred during lawsonite dehydration. We conclude that the garnets maintain a record of progressive dehydration and that the residual mineral assemblages within the slab became more reduced during progressive subduction-zone dehydration. This is consistent with the hypothesis that lawsonite dehydration accompanied by the release of oxidizing species, such as sulfate, plays an important and measurable role in the global redox budget and contributes to sub-arc mantle oxidation in subduction zones.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Backscattered electron imagery, and Fe isotope and oxybarometry data, for an analysed garnet from sample 09DSF-23E.
Fig. 2: Fe isotope data, presented as δ56Fe values, plotted against the Δ log FMQ values for each zone (core, intermediate zones, rim).
Fig. 3: Pressure–temperature and mineralogical evolution of the Sifnos samples and model for the release of oxidizing fluids during subduction.

Similar content being viewed by others

Data availability

The data generated or analysed during this study are included in this published article and its Supplementary Information files.

References

  1. Frost, B. R. in Oxide Minerals: Petrologic and Magnetic Significance. Reviews in Mineralogy Vol. 25 (ed. Lindsley, D. H.) 1–9 (Mineralogical Society of America, 1991).

  2. Schmidt, M. W. & Poli, S. Experimentally based water budgets for dehydrating slabs and consequences for arc magma generation. Earth Planet. Sci. Lett. 163, 361–379 (1998).

    Google Scholar 

  3. Magni, V., Bouilhol, P. & van Hunen, J. Deep water recycling through time. Geochem. Geophys. Geosyst. 15, 4203–4216 (2014).

    Google Scholar 

  4. Poli, S. & Schmidt, M. W. H2O transport and release in subduction zones: experimental constraints on basaltic and andesitic systems. J. Geophys. Res. Solid Earth 100, 22299–22314 (1995).

    Google Scholar 

  5. Tatsumi, Y. Formation of the volcanic front in subduction zones. Geophys. Res. Lett. 13, 717–720 (1986).

    Google Scholar 

  6. Marschall, H. R. & Schumacher, J. C. Arc magmas sourced from mélange diapirs in subduction zones. Nat. Geosci. 5, 862–867 (2012).

    Google Scholar 

  7. Breeding, C. M., Ague, J. J. & Bröcker, M. Fluid-metasedimentary rock interactions in subduction-zone mélange: implications for the chemical composition of arc magmas. Geology 32, 1041–1044 (2004).

    Google Scholar 

  8. Kelley, K. A. & Cottrell, E. Water and the oxidation state of subduction zone magmas. Science 325, 605–607 (2009).

    Google Scholar 

  9. Parkinson, I. J. & Arculus, R. J. The redox state of subduction zones: insights from arc-peridotites. Chem. Geol. 160, 409–423 (1999).

    Google Scholar 

  10. Evans, K. A., Elburg, M. A. & Kamenetsky, V. S. Oxidation state of subarc mantle. Geology 40, 783–786 (2012).

    Google Scholar 

  11. Debret, B. & Sverjensky, D. A. Highly oxidising fluids generated during serpentinite breakdown in subduction zones. Sci. Rep. 7, 10351 (2017).

    Google Scholar 

  12. Lee, C. T. A. et al. The redox state of arc mantle using Zn/Fe systematics. Nature 468, 681–685 (2010).

    Google Scholar 

  13. Pons, M.-L., Debret, B., Bouilhol, P., Delacour, A. & Williams, H. Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones. Nat. Commun. 7, 13794 (2016).

    Google Scholar 

  14. Tomkins, A. G. & Evans, K. A. Separate zones of sulfate and sulfide release from subducted mafic oceanic crust. Earth Planet. Sci. Lett. 428, 73–83 (2015).

    Google Scholar 

  15. Evans, K. A. The redox budget of subduction zones. Earth-Sci. Rev. 113, 11–32 (2012).

    Google Scholar 

  16. Debret, B. et al. Isotopic evidence for iron mobility during subduction. Geology 44, 215–218 (2016).

    Google Scholar 

  17. Walters, J. B., Cruz-Uribe, A. M. & Marschall, H. R. Isotopic compositions of sulfides in exhumed high‐pressure terranes: implications for sulfur cycling in subduction zones. Geochem. Geophys. Geosyst. 20, 3347–3374 (2019).

    Google Scholar 

  18. Bénard, A. et al. Oxidising agents in sub-arc mantle melts link slab devolatilisation and arc magmas. Nat. Commun. 9, 3500 (2018).

    Google Scholar 

  19. Canil, D. & Fellows, S. A. Sulphide–sulphate stability and melting in subducted sediment and its role in arc mantle redox and chalcophile cycling in space and time. Earth Planet. Sci. Lett. 470, 73–86 (2017).

    Google Scholar 

  20. Ague, J. J., Baxter, E. F. & Eckert, J. O.Jr. High fO2 during sillimanite zone metamorphism of part of the Barrovian type locality, Glen Clova, Scotland. J. Petrol. 42, 1301–1320 (2001).

    Google Scholar 

  21. Baxter, E. F. & Caddick, M. J. Garnet growth as a proxy for progressive subduction zone dehydration. Geology 41, 643–646 (2013).

    Google Scholar 

  22. Dragovic, B., Baxter, E. F. & Caddick, M. J. Pulsed dehydration and garnet growth during subduction revealed by zoned garnet geochronology and thermodynamic modeling, Sifnos, Greece. Earth Planet. Sci. Lett. 413, 111–122 (2015).

    Google Scholar 

  23. Dragovic, B., Samanta, L. M., Baxter, E. F. & Selverstone, J. Using garnet to constrain the duration and rate of water-releasing metamorphic reactions during subduction: an example from Sifnos, Greece. Chem. Geol. 314–317, 9–22 (2012).

    Google Scholar 

  24. Polyakov, V. B. & Mineev, S. D. The use of Mossbauer spectroscopy in stable isotope geochemistry. Geochim. Cosmochim. Acta 64, 849–865 (2000).

    Google Scholar 

  25. Schauble, E. A., Rossman, G. R. & Taylor, H. P. Theoretical estimates of equilibrium Fe isotope fractionations from vibrational spectroscopy. Geochim. Cosmochim. Acta 65, 2487–2497 (2001).

    Google Scholar 

  26. Inglis, E. C. et al. The behavior of iron and zinc stable isotopes accompanying the subduction of mafic oceanic crust: a case study from Western Alpine ophiolites. Geochem. Geophys. Geosyst. 18, 2562–2579 (2017).

    Google Scholar 

  27. Donohue, C. L. & Essene, E. J. An oxygen barometer with the assemblage garnet–epidote. Earth Planet. Sci. Lett. 181, 459–472 (2000).

    Google Scholar 

  28. Boundy, T. M., Donohue, C. L., Essene, E. J., Mezger, K. & Austrheim, H. Discovery of eclogite facies carbonate rocks from the Lindås Nappe, Caledonides, Western Norway. J. Metamorph. Geol. 20, 649–667 (2002).

    Google Scholar 

  29. Cao, Y., Song, S. G., Niu, Y. L., Jung, H. & Jin, Z. M. Variation of mineral composition, fabric and oxygen fugacity from massive to foliated eclogites during exhumation of subducted ocean crust in the North Qilian suture zone, NW China. J. Metamorph. Geol. 29, 699–720 (2011).

    Google Scholar 

  30. Mattinson, C. G., Zhang, R. Y., Tsujimori, T. & Liou, J. G. Epidote-rich talc-kyanite-phengite eclogites, Sulu terrane, eastern China: P-T-fo2 estimates and the significance of the epidote-talc assemblage in eclogite. Am. Mineral. 89, 1772–1783 (2004).

    Google Scholar 

  31. Groppo, C., Forster, M., Lister, G. & Compagnoni, R. Glaucophane schists and associated rocksfrom Sifnos (Cyclades, Greece): new constraints on the P-T evolution from oxidized systems. Lithos 109, 254–273 (2009).

    Google Scholar 

  32. Hill, P. S., Schauble, E. A. & Young, E. D. Effects of changing solution chemistry on Fe3+/Fe2+ isotope fractionation in aqueous Fe–Cl solutions. Geochim. Cosmochim. Acta 74, 6669–6689 (2010).

    Google Scholar 

  33. Holland, T. J. B. & Powell, R. An internally consistent thermodynamic data set for phases of petrological interest. J. Metamorph. Geol. 16, 309–343 (1998).

    Google Scholar 

  34. Powell, R. & Holland, T. J. B. An internally consistent dataset with uncertainties and correlations: 3. Applications to geobarometry, worked examples and a computer program. J. Metamorph. Geol. 6, 173–204 (1988).

    Google Scholar 

  35. Powell, R. & Holland, T. Optimal geothermometry and geobarometry. Am. Mineral. 79, 120–133 (1994).

    Google Scholar 

  36. Quinn, R. J., Valley, J. W., Page, F. Z. & Fournelle, J. H. Accurate determination of ferric iron in garnets. Am. Mineral. 101, 1704–1707 (2016).

    Google Scholar 

  37. Barr, H. Preliminary fluid inclusion studies in a high-grade blueschist terrain, Syros, Greece. Mineral. Mag. 54, 159–168 (1990).

    Google Scholar 

  38. Palin, R. M., Weller, O. M., Waters, D. J. & Dyck, B. Quantifying geological uncertainty in metamorphic phase equilibria modelling; a Monte Carlo assessment and implications for tectonic interpretations. Geosci. Front. 7, 591–607 (2016).

    Google Scholar 

  39. Pollington, A. D. & Baxter, E. F. High precision microsampling and preparation of zoned garnet porphyroblasts for Sm–Nd geochronology. Chem. Geol. 281, 270–282 (2011).

    Google Scholar 

  40. Dauphas, N. et al. Chromatographic separation and multicollection-ICPMS analysis of iron. Investigating mass-dependent and-independent isotope effects. Anal. Chem. 76, 5855–5863 (2004).

    Google Scholar 

  41. Weyer, S. & Schwieters, J. B. High precision Fe isotope measurements with high mass resolution MC-ICPMS. Int. J. Mass Spectrom. 226, 355–368 (2003).

    Google Scholar 

  42. Millet, M. A., Baker, J. A. & Payne, C. E. Ultra-precise stable Fe isotope measurements by high resolution multiple-collector inductively coupled plasma mass spectrometry with a 57Fe–58Fe double spike. Chem. Geol. 304, 18–25 (2012).

    Google Scholar 

  43. Hibbert, K. E. J., Williams, H. M., Kerr, A. C. & Puchtel, I. S. Iron isotopes in ancient and modern komatiites: evidence in support of an oxidised mantle from Archean to present. Earth Planet. Sci. Lett. 321, 198–207 (2012).

    Google Scholar 

  44. Sossi, P. A., Halverson, G. P., Nebel, O. & Eggins, S. M. Combined separation of Cu, Fe and Zn from rock matrices and improved analytical protocols for stable isotope determination. Geostand. Geoanal. Res. 39, 129–149 (2015).

    Google Scholar 

  45. Connolly, J. A. D. The geodynamic equation of state: what and how. Geochem. Geophys. Geosyst. 10, 10 (2009).

    Google Scholar 

  46. Diener, J. F. A. & Powell, R. Revised activity–composition models for clinopyroxene and amphibole. J. Metamorph. Geol. 30, 131–142 (2012).

    Google Scholar 

  47. White, R. W., Powell, R. & Holland, T. J. B. Progress relating to calculation of partial melting equilibria for metapelites. J. Metamorph. Geol. 25, 511–527 (2007).

    Google Scholar 

  48. Auzanneau, E., Schmidt, M. W., Vielzeuf, D. & Connolly, J. D. Titanium in phengite: a geobarometer for high temperature eclogites. Contrib. Mineral. Petrol. 159, 1 (2010).

    Google Scholar 

  49. Coggan, R. & Holland, T. J. B. Mixing properties of phengitic micas and revised garnet–phengite thermometers. J. Metamorph. Geol. 20, 683–696 (2002).

    Google Scholar 

  50. Powell, R., Holland, T. J. B. H. & Worley, B. Calculating phase diagrams involving solid solutions via non‐linear equations, with examples using THERMOCALC. J. Metamorph. Geol. 16, 577–588 (1998).

    Google Scholar 

  51. Fuhrman, M. L. & Lindsley, D. H. Ternary-feldspar modeling and thermometry. Am. Mineral. 73, 201–215 (1988).

    Google Scholar 

  52. White, R. W., Powell, R. & Clarke, G. L. The interpretation of reaction textures in Fe-rich metapelitic granulites of the Musgrave Block, central Australia: constraints from mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3. J. Metamorph. Geol. 20, 41–55 (2002).

    Google Scholar 

  53. White, R. W., Powell, R., Holland, T. J. B. & Worley, B. A. The effect of TiO2 and Fe2O3 on metapelitic assemblages at greenschist and amphibolite facies conditions: mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3. J. Metamorph. Geol. 18, 497–512 (2002).

    Google Scholar 

  54. Holland, T. & Powell, R. Activity–composition relations for phases in petrological calculations: an asymmetric multicomponent formulation. Contrib. Mineral. Petrol. 145, 492–501 (2003).

    Google Scholar 

  55. Marmo, B. A., Clarke, G. L. & Powell, R. Fractionation of bulk rock composition due to porphyroblast growth: effects on eclogite facies mineral equilibria, Pam Peninsula, New Caledonia. J. Metamorph. Geol. 20, 151–165 (2002).

    Google Scholar 

  56. Brooks, H. L., Dragovic, B., Lamadrid, H. M., Caddick, M. J. & Bodnar, R. Fluid capture during exhumation of subducted lithologies: a fluid inclusion study from Sifnos, Greece. Lithos 332-333, 120–134 (2019).

    Google Scholar 

Download references

Acknowledgements

E.F.B. acknowledges support from NSF grants EAR-0547999 for sample collection and OIA-1545903 for support during this project. A.R.G., B.D. and P.G.S. also acknowledge support from OIA-1545903. E.C.I. was supported as a postdoctoral research assistant on ERC starting grant PRISTINE: 637503 awarded to F. Moynier (IPG Paris).

Author information

Authors and Affiliations

Authors

Contributions

A.R.G. was responsible for the oxybarometry calculations, clean-lab preparation and analysis of Fe isotope compositions and wrote the manuscript. E.C.I. performed Fe isotope compositional analysis and contributed to method development. B.D. was responsible for PT modelling. P.G.S. performed clean-lab preparation, oxybarometry calculations and method development. E.F.B. and K.W.B. contributed by designing the project. All authors contributed to analysis and interpretation of data and editing of the manuscript.

Corresponding author

Correspondence to Ethan F. Baxter.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Primary Handling Editor(s): Melissa Plail; Heike Langenberg.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary figures and tables.

Supplementary Data

Supplementary Tables 1–7.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gerrits, A.R., Inglis, E.C., Dragovic, B. et al. Release of oxidizing fluids in subduction zones recorded by iron isotope zonation in garnet. Nat. Geosci. 12, 1029–1033 (2019). https://doi.org/10.1038/s41561-019-0471-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41561-019-0471-y

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing