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The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth

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Abstract

We present the variation in trace element partition coefficients measured at the interface between rapidly cooled clinopyroxene crystals and co-existing melts. Results indicate that, as the cooling rate is increased, clinopyroxene crystals are progressively depleted in Si, Ca and Mg counterbalanced by enrichments in Al (mainly tetrahedral Aliv), Na and Ti. Partition coefficients (Ds) for rare earth elements (REE), high field strength elements (HFSE) and transition elements (TE) increase with increasing cooling rate, in response to clinopyroxene compositional variations. The entry of REE into the M2 site is facilitated by a coupled substitution where either Na substitutes for Ca on the M2 site or Aliv substitutes for Si in the tetrahedral site. The latter substitution reflects an increased ease of locally balancing the excess charge at M2 as the number of surrounding Aliv atoms increases. Due to the lower concentration of Ca in rapidly cooled clinopyroxenes, divalent large ion lithophile elements (LILE) on M2 decrease at the expense of monovalent cations. Conversely, higher concentrations of HFSE and TE on the M1 site are facilitated as the average charge on this site increases with the replacement of divalent-charged cations by Alvi. Although crystallization kinetics modify clinopyroxene composition, deviations from equilibrium partitioning are insufficient to change the tendency of a trace element to be compatible or incompatible. Consequently, there are regular relationships between ionic radius, valence of the trace element and D. At both equilibrium and cooling rate conditions, Ds for isovalent cations define parabola-like curves when plotted against ionic radius, consistent with the lattice strain model, demonstrating that the partitioning of trace elements is driven by charge balance mechanisms; cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations.

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Acknowledgments

We are very grateful to the reviewers, J. E. Hammer and G. A. Gaetani, for their helpful suggestions. T. L. Grove is warmly acknowledged for the editorial handling. A. Cavallo is thanked for assistance during electron microprobe analysis. The research activities of the HP-HT laboratory of the INGV were supported by the European Observing System Infrastructure Project (EPOS). S. Mollo was supported by the ERC Starting grant 259256 GLASS project. 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.”

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Authors and Affiliations

  1. Istituto Nazionale di Geofisica e Vulcanologia, Via di Vigna Murata 605, 00143, Rome, Italy

    S. Mollo & P. Scarlato

  2. School of Earth Sciences, University of Bristol, Wills Memorial Building, Bristol, BS8 1RJ, UK

    J. D. Blundy

  3. Dipartimento INGEO, Università G. d’Annunzio, Via Dei Vestini 30, 66013, Chieti, Italy

    G. Iezzi

  4. C.N.R.-Istituto di Geoscienze e Georisorse, UOS Pavia, Via Ferrata 1, 27100, Pavia, Italy

    A. Langone

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Mollo, S., Blundy, J.D., Iezzi, G. et al. The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth. Contrib Mineral Petrol 166, 1633–1654 (2013). https://doi.org/10.1007/s00410-013-0946-6

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