On the valency state of radiogenic lead in zircon and its consequences

In zircon U–Pb systematics, extreme robustness up to the temperatures of granulite facies and anatexis contrasts with apparently easy loss of radiogenic Pb at low temperatures, often without any metamorphic event being in evidence. Here we propose that this paradoxical behaviour can be understood with the hypothesis that radiogenic Pb in zircon is tetravalent. We review data and arguments in favour of this hypothesis. Diffusion profiles calculated for Pb2+ in a 25 μm radius zircon xenocryst in a melt at 1000 °C, combined with the incompatibility of Pb2+, or for a zircon core inside a younger zircon rim at this temperature, show age effects that should have been observed in SIMS dating. Further, in zircon evaporation as well as in leaching experiments, common Pb is generally released preferentially to radiogenic Pb. After removal of less radiogenic Pb, the evaporation record generally shows pure radiogenic Pb during the final evaporation steps. The distribution of residual Pb in a leached titanite, revealed by PIXE, is similar to that of Ti. Lastly, XANES spectra of a 1 Ga old titanite (predominantly radiogenic Pb) and an Alpine one (predominantly common Pb) are significantly different, although the former does not resemble that of PbO2. The arguments why radiogenic Pb should be tetravalent are based on analogies with studies relating to the tetravalent state of 234Th and the hexavalent state of 234U, which show that α-recoil in silicates generates a strongly oxidizing environment at the site where the recoiling nucleus comes to rest. Further, a zircon grain, being small, should remain highly oxidizing in its interior by the constant loss of β-particles, maintaining the 4+ state of radiogenic Pb.