We document for the first time the role played by natural solidification paths on the partitioning of rare earth elements (REE) between clinopyroxene and melt. To do this, we investigated the compositional variation of clinopyroxenes formed under increasing cooling rate conditions from core to rim of a dike at Mt. Etna volcano. As the rate of cooling increases, clinopyroxenes are progressively depleted in Si + Ca + Mg counter-balanced by enrichments in Al + Na + Ti. Consequently, the concentration of REE in clinopyroxene increases due to an increased ease of locally balancing the excess charge at the M2 site as the number of surrounding tetrahedral aluminium atoms increases. Since Aliv in clinopyroxene is a charge-balancing cation for REE, the partition coefficients (DREE) measured at the dike chilled margin are distinctly higher than those from the dike interior. We conclude that, in naturally solidifying magmas, kinetically controlled cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations. This finding is corroborated by the near-parabolic dependence of DREE on cation radius due to charge-balance mechanisms described by the lattice strain model.
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We are grateful to the two anonymous reviewers for their constructive comments on the original manuscript. The associate editor M. Manga and the executive editor J. D. L. White are also acknowledged for their useful suggestions. A. Cavallo is acknowledged for assistance during electron microprobe analysis. S. Mollo was supported by the ERC Starting Grant 259256 GLASS project. The research activities of the HP-HT laboratory of the INGV were supported by the European Observing System Infrastructure Project (EPOS). This study was funded by the “Fondi Ateneo of the University G. d’Annunzio” and the PRIN project “Experimental determination of the glass-forming ability (GFA), nucleation and crystallization of natural silicate melts” awarded to G. Iezzi. J. Blundy acknowledges support from a Wolfson Research Merit Award from the Royal Society and ERC Advanced Grant “CRITMAG”.
Editorial responsibility: M. Manga
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Scarlato, P., Mollo, S., Blundy, J.D. et al. The role of natural solidification paths on REE partitioning between clinopyroxene and melt. Bull Volcanol 76, 810 (2014). https://doi.org/10.1007/s00445-014-0810-1
- Partition coefficient
- Natural solidification path
- Mt. Etna