Zr-rich accessory minerals (titanite, perrierite, zirconolite, baddeleyite) record strong oxidation associated with magma mixing in the south Peruvian potassic province

The Oroscocha Quaternary volcano, in the Inner Arc Domain of the Andean Cordillera (southern Peru), emitted peraluminous rhyolites and trachydacites that entrained decimetric to millimetric lamprophyric blobs. These latter show kersantite modal compositions (equal proportion of groundmass plagioclase and K-feldspar) and potassic bulk-rock compositions (1<K₂O/Na₂O<2; 6.7–7.2 wt.% CaO). Kersantite blobs have shapes and microstructures consistent with an origin from a mixing process between mafic potassic melts and rhyolitic melts. Both melts did exchange their phenocrysts during the mixing process. In addition to index minerals of lamprophyres (Ba–Ti–phlogopite, F-rich apatite, andesine and Ca-rich sanidine), the groundmass of kersantite blobs displays essenite-rich diopside (up to 22 mol%), Ti-poor magnetite microlites, Ti-poor hematite microlites and a series of Ca–Ti–Zr- and REE-rich accessory minerals that have never been reported from lamprophyres. Titanite up to 5.3 wt.% ZrO₂ and 5.2 wt.% (Y₂O₃ + REE₂O₃)] and Zr- and Ca-rich perrierite (up to 7.2 wt.% ZrO₂ and 10.8 wt.% CaO) predate LREE- and iron-rich zirconolite and Fe-, Ti-, Hf-, Nb- and Ce-rich baddeleyite (up to 5.3 wt.% Fe₂O₃, 3.2 wt.% TiO₂, 1.5 wt.% HfO₂, 1.2 wt.% Nb₂O₅, 0.25 wt.% CeO₂) in the crystallization order of the groundmass. Isomorphic substitutions suggest iron to occur as Fe³⁺ in all the accessory phases. This feature, the essenitic substitution in the clinopyroxene and the occurrence of hematite microlites, all indicate a drastic increase of the oxygen fugacity (from FMQ − 1 to FMQ + 5 log units) well above the HM synthetic buffer within a narrow temperature range (1100–1000 °C). Such a late-magmatic oxidation is ascribed to assimilation of water from the felsic melts during magma mixing, followed by rapid degassing and water dissociation during eruption of host felsic lavas. Thus, magma mixing involving felsic melt end-members provides a mechanism for mafic potassic melts to be oxidized beyond the HM synthetic buffer curve.