Polybaric/polythermal magma transport and trace element partitioning recorded in single crystals: A case study of a zoned clinopyroxene from Mt. Etna

We present elemental maps and intra-crystal compositional profiles conducted on a representative clinopyroxene phenocryst from the 1974 eccentric lava flows at Mt. Etna volcano (Sicily, Italy). The eruption was fed by deep-seated and primitive magmas ascending through pathways bypassing the central volcanic conduits. These magmas show MgO and Cr contents higher (and REE + Y lower) than those characterizing younger and more evolved eruptions, albeit the bulk rock compositions of both primitive and more evolved products are invariably classified as trachybasalts in the TAS (total alkali vs. silica) diagram. Mafic recharge episodes are recorded by the complex textural features of the clinopyroxene, with a subrounded core enclosed within a concentrically zoned mantle. The core is enriched in Mg + Fe2++Na and depleted in Fe3++Ca relative to the mantle. The jadeite (Jd) component decreases from core to mantle and is counterbalanced by higher Ca-Tschermak (CaTs) contents, as the number of TAl cations in tetrahedral coordination increases. The Jd-rich core incorporates high proportions of rare earth elements and Y (REE + Y) and low concentrations of high field strength elements (HFSE) and transition elements (TE, such as Ni, Cr and Sc), whereas the opposite occurs for the CaTs-rich mantle. The decoupling of REE + Y and HFSE argues against simple changes in melt composition and indicates an additional mechanism driving trace element zonations. Thermobarometric calculations indicate that the early-formed Jd-rich core equilibrated with the host magma at mantle depths (750–950 MPa and 1190–1210 °C), whereas the later CaTs-rich mantle formed at shallower crustal levels (400–700 MPa and 1150–1180 °C) after magma recharge. Quantitative modeling of apparent cation partitioning between clinopyroxene and melt (Di) indicates that DHFSE increase from the Jd-rich core to the CaTs-rich mantle. In contrast, DREE+Y increase up to one order of magnitude at the Jd-rich core due to the enhanced stability of an Na0.5REE + Y0.5MgSiO6 end-member. We infer that compositional changes in clinopyroxene due to the different P-T conditions of the plumbing system may control the concentrations of REE + Y in residual melts derived after partial crystallization and differentiation of primitive magmas, such as those feeding the 1974 eccentric eruption. On this basis, we use DREE+Y measured across the core-mantle interface to constrain the geochemical evolution of recent 2000–2013 magmas at Mt. Etna volcano by Rayleigh fractional crystallization. Results indicate that magma dynamics proceed via a stepwise polybaric-polythermal process accounting for 1) crystallization of Jd-rich clinopyroxenes at high-P, high-T conditions, 2) upward migration of crystal-bearing magmas due to replenishment phenomena with input of fresh magmas and 3) crystallization of CaTs-rich clinopyroxene in low-P, low-T reservoirs. The resulting total amount (~40 vol%) of clinopyroxene fractionated agrees with geophysical data suggesting the presence of highly crystalline magmatic bodies at shallow to intermediate crustal levels below Mt. Etna.