Trace element partitioning between clinopyroxene and alkaline magmas: parametrization and role of M1 site on HREE enrichment in clinopyroxenes

Abstract

Trace element partitioning between minerals and liquids provides crucial constraints on igneous processes. We quantified trace element concentrations in clinopyroxene (Cpx) phenocrysts and their phonolite melt inclusions from the 2007–08 eruption of Oldoinyo Lengai (Tanzania), and report Cpx-melt partition coefficients (D) and corresponding partitioning equations for rare earth elements (REE) and high field strength elements (HFSE) in alkaline magmas. Heavy REE (HREE: Er, Tm, Yb, Lu) are enriched relative to middle REE in alkaline Cpx and display a specific partitioning behavior that is characteristic of alkaline systems. HFSE (Ti, Zr, Hf) and HREE have similar D values (DHf = 0.25; DLu = 0.4) that are significantly higher than MREE (DSm = 0.06). High DHREE/DMREE are strongly correlated with the high values of DZr and DHf relative to the low DMREE values. In this study, REE partitioning between phonolite melt and Cpx is not consistent with standard models assuming incorporation of all REE in the Cpx M2 site, but rather highlights HREE substitution in both the M1 and M2 sites. Here we highlight the preferential incorporation of HREE in the VI-coordinated M1 site, whereas light REE and MREE remain mostly distributed in the VIII-coordinated M2 site. REE partitioning is strongly dependent on Cpx chemistry: the ideal ionic radius and HREE incorporation in the M1 site increase with increasing Fe3+ content and decrease with increasing Mg2+ and AlVI content. In our study, we focus on alkaline evolved magmas, and update existing models to obtain adequate DHREE for alkaline evolved melts. We provide equations to quantify REE and HFSE partitioning, and HREE enrichment in Cpx that are based on Cpx major element composition and temperature. We propose a new model based on the lattice strain approach that predicts HREE partitioning between Cpx and alkaline magmas. The knowledge of the melt composition or of the trace element contents is not required to obtain DREE from the new model. An improved parameterization of HFSE partitioning between Cpx and phonolite and trachy–phonolite melts is also provided herein. We discuss the potential implications of the new data on our understanding of REE deposits that are commonly associated with igneous alkaline complexes.