Trace element heterogeneity and crystallization history of the Plesovice zircon: Implications for its use as a U–Pb LA-ICP-MS reference material

Abstract

Zircon crystals from Plešovice hyperpotassic granulite (HPG) have been widely used as a reference material for LA-ICP-MS dating. Detailed cathodoluminescence (CL) imaging and trace element analysis reveal a complex internal structure of Plešovice zircon linked to extreme chemical heterogeneity, which allows us to distinguish different zircon domains formed during its crystallization: (i) rare low-CL cores enriched in U, Nb, HREE and Y; (ii) dominant sector-zoned to oscillatory-zoned domains, and (iii) CL-bright rims poor in trace elements. Relic fine oscillatory zoned areas are chemically homogeneous, whereas coarsened and blurred areas, and CL-dark replacement domains, are heterogeneous. Based on these data we suggest a complex and protracted zircon evolution: (i) crystallization of metamorphic zircon in anatectic calc-alkaline granulite; (ii) magmatic zircon crystallization at high temperature and pressure in a dry ultrapotassic melt at presence of peritectic garnet; (iii) coupled zircon dissolution-precipitation processes triggered by percolating hydrous residual melt; and (iv) coarsening and replacement of the pre-existing zircon due to prolonged exposure to a reactive fluid/hydrous melt. New CA-ID-TIMS U Pb dates between 337.167 ± 0.080 and 337.840 ± 0.080 Ma confirm crystallization age for HPG zircon at around 337.4 Ma and suggest that previously published dates of 336.37 Ma were biased by non-mitigated lead loss. We thus confirm the U/Pb homogeneity of Plešovice reference zircon despite its chemical heterogeneity. We further discuss the implications of using the chemically extremely heterogeneous Plešovice reference zircon as primary or secondary standard for in-situ LA-ICP-MS geochronology, in particular for quantification of the chemical matrix-dependence of the relative sensitivity factor ( β ) of laser ablation.