Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

  • Paolo A. Sossi
  • Julie Prytulak
  • Hugh St. C. O’Neill
Original Paper

Abstract

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities (\({f_{{{\text{O}}_{\text{2}}}}}\)), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V3+ and V4+ in magnetite, and a mixture of IV- and VI-fold V5+ and V4+ in the melt. The magnitude of the fractionation factor systematically increases with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\) relative to the Fayalite–Magnetite–Quartz buffer (FMQ), from ∆51Vmag-gl = − 0.63 ± 0.09‰ at FMQ − 1 to − 0.92 ± 0.11‰ (SD) at ≈ FMQ + 5, reflecting constant V3+/V4+ in magnetite but increasing V5+/V4+ in the melt with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\). These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.

Keywords

Redox Magnetite Magma Vanadium Stable isotope fractionation Equilibrium 

Notes

Acknowledgements

PAS was funded by an Australian Postgraduate Award and an ANU Vice-Chancellor’s Scholarship. Analytical costs and JPs visit to ANU were funded by Australian Research Council Discovery Grant DP130101355 to H. St. C. O’Neill and J. Prytulak. Many thanks to Jeremy Wykes, Dave Clark and Dean Scott for discussions regarding the piston cylinder experiments, Graham Mortimer for facilitating the set-up of V isotopes at the RSES clean lab, and Les Kinsley for assistance and feedback on running V isotopes on the Neptune Plus. We greatly appreciate two thoughtful and comprehensive reviews by Alan Woodland and Dante Canil that helped improve many aspects of this study, and acknowledge perceptive comments from Adrian Fiege on an earlier version of this work. We are grateful to Othmar Müntener for his exemplary editorial handling.

Supplementary material

410_2018_1451_MOESM1_ESM.pdf (647 kb)
Supplementary material 1 (PDF 647 KB)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Paolo A. Sossi
    • 1
    • 3
  • Julie Prytulak
    • 2
  • Hugh St. C. O’Neill
    • 1
  1. 1.Research School of Earth SciencesAustralian National UniversityCanberraAustralia
  2. 2.Department of Earth Science and EngineeringImperial College LondonLondonUK
  3. 3.Institut de Physique du Globe de Paris, Sorbonne Paris CitéUniversité Paris Diderot, CNRSParisFrance

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