Trace element partitioning between clinopyroxene and trachy-phonolitic melts : A case study from the Campanian Ignimbrite (Campi Flegrei, Italy)

The partitioning of trace elements between crystals and melts provides an important petrogenetic tool for understanding magmatic processes. We present trace element partition coefficients measured between clinopyroxene phenocrysts and trachy-phonolitic magmas at the Campi Flegrei (Italy), whose late Quaternary volcanism has been characterized by two major caldera-forming events (Campanian Ignimbrite at ~39 ka, and Neapolitan Yellow Tuff at ~15 ka). Our data indicate that the increase of trivalent rare earth elements and yttrium into the crystal lattice M2 site is facilitated by the charge-balancing substitution of Si4+ with Al3+ on the tetrahedral site. Higher concentrations of tetravalent and pentavalent high field strength elements on the M1 site are also measured when the average charge on this site is increased by the substitution of divalent cations by Alvi. In contrast, due to these charge balance requirements, divalent transitional elements become less compatible within the crystal lattice. On the basis of the lattice strain theory, we document that the incorporation of rare earth elements and yttrium in clinopyroxene is influenced by both compositional and physical parameters. Data from this study allow to update existing partitioning equations for rare earth elements in order to construct a self-consistent model for trachy-phonolitic magmas based on the lattice strain theory. The application of this model to natural products from the Campanian Ignimbrite, the largest caldera-forming eruption at the Campi Flegrei, reveals that the complex rare earth element pattern recorded by the eruptive products can be successfully described by the stepwise fractional crystallization of clinopyroxene and feldspar where the clinopyroxene-melt partition coefficient changes progressively as a function of the physicochemical conditions of the system.