Partitioning of REE, Y, Sr, Zr and Ti between clinopyroxene and silicate melts in the mantle under La Palma (Canary Islands): implications for the nature of the metasomatic agents

Abstract

Ion microprobe analyses of clinopyroxenes in equilibrium with glasses (SiO 2 from 42 to 69 wt%) formed as the result of AFC-type reactions between infiltrating basaltic melt and peridotite wall-rock in the upper mantle under La Palma (Canary Islands) reveal trace element signatures usually ascribed to carbonatite metasomatism (i.e. strong REE-enrichment and Zr,Ti-depletion). Cpx/glass partition coefficients for REE, Y and Sr progressively increase with increasing SiO 2 in response to liquid composition/structure effects, approaching unity for La, Ce and Sr, and exceeding unity for the other REE in the most silicic glasses. Partition coefficients for Zr and Ti remain constant or decrease, probably as the combined effect of melt composition/structure and difficulty of charge-balancing 4 + cations in the crystal. Incorporation of the higher-charged HFSE in the cpx lattice requires complex coupled substitutions (e.g. M1Zr +1 TAl +2 M1R 2+ −1 TSi −2 or M2Na +1 M1Zr +1 TAl +1 M2Ca −1 M1R 2+ −1 TSi −1). Our results demonstrate that REE-enrichment and REE/HFSE fractionation of clinopyroxene do not necessarily reflect these characteristics in the metasomatic agent and that cpx/basalt D cannot confidently be used to infer the geochemical nature of equilibrium melts under upper mantle conditions. Moreover, we provide evidence that the strong REE-enrichment and Zr,Ti-depletion of some clinopyroxene from La Palma xenoliths is a feature commonly observed in clinopyroxenes from various mantle occurrences often interpreted as reflecting chemical interaction with metasomatic fluids and melts of different composition (either alkaline or carbonatitic) and provenance (from either the enriched asthenospheric mantle or the subducted slab). Therefore, claims of carbonatite metasomatism as opposed to silicate melt infiltration based on trace element signatures of investigated clinopyroxene should be regarded with caution unless the role of liquid composition/structure and of crystal chemical control is investigated.