Alteration and chemical U-Th-total Pb dating of heterogeneous high-uranium zircon from a pegmatite from the Aduiskii massif, middle Urals, Russia

Abstract

The U-Th-Pb isotope system in the accessory mineral zircon may be disturbed, as for instance by the secondary loss of radiogenic lead. The recognition of such alteration is crucial for the sound interpretation of geochronology results, in particular for chemical dating by means of an electron probe micro-analyser (EPMA). Here we present the example of high-U zircon samples from a granite pegmatite from the Aduiskii Massif, Middle Urals, Russia. The structural and chemical heterogeneity of samples was characterised by EPMA, including joint probability distribution (JPD) analysis of back-scattered electrons (BSE), cathodoluminescence (CL) and U M β images, and by Raman and photoluminescence (PL) spectroscopy. We found a high-U interior region (U up to 11.4 wt%) without any obvious indication of alteration. This domain has stoichiometric composition, and its Raman spectrum is similar to that of amorphous ZrSiO4. In addition, altered lower-U regions are present that are non-stoichiometric and contain non-formula elements such as Ca, Al, Fe, and water up to several wt%. Their Raman spectra yielded a band near 760–810 cm−1 which is not related to any ZrSiO4 vibration; we assign it tentatively to the symmetric stretching of (UO2)2+ groups. This assignment is supported by the observation of a fairly intense PL phenomenon whose spectral position and vibrational-coupling structure strongly indicates a uranyl-related emission. Altered zones were formed by both fluid-driven diffusion reaction and coupled dissolution-reprecipitation processes. The variation of BSE and CL intensities in amorphous high-U zircon is controlled by its chemical composition and the presence of water and uranyl groups. We have determined a weighted mean EPMA age of 246 ± 2 Ma, which agrees reasonably well with previous dating results for the Aduiskii Massif.