Characterizing the U-Pb systematics of baddeleyite through chemical abrasion: Application of multi-step digestion methods to baddeleyite geochronology

U–Pb baddeleyite geochronology has become a major tool for dating mafic rocks, especially dikes associated with Large Igneous Provinces. However, in many cases, post-crystallization Pb-loss and intergrowth of baddeleyite and zircon limit the precision and/or accuracy of crystallization ages. We present results from multi-step digestion experiments designed to understand and reduce these effects. Experiments were carried out on Neoproterozoic baddeleyites with zircon inter- and over-growths from the Gannakouriep dike swarm, Namibia, and on fragments of a large Paleoproterozoic baddeleyite from the Phalaborwa carbonatite, South Africa. Multi-step digestion experiments on annealed Phalaborwa baddeleyite were designed to test whether the recently developed chemical abrasion technique for U–Pb zircon geochronology can be applied to baddeleyite. The experiments generated complex results—individual digestion steps were both normally and reversely discordant suggesting that U and Pb were decoupled in the multi-step digestions—and indicate that the current form of multi-step chemical abrasion is not an effective method for reducing the impact of Pb-loss in baddeleyite. A separate set of experiments on the Gannakouriep baddeleyite focused on isolating the zircon and baddeleyite components in composite grains. Conventional single-step digestion experiments for this sample resulted in a discordant suite of analyses with significant scatter attributed to inter- and over-grown zircon and highlight the difficulty of obtaining precise and accurate ages from composite grains. To isolate the baddeleyite and zircon in these grains, a two-step HCl–HF chemical abrasion procedure for annealed grains was developed. This technique was successful at selectively dissolving the baddeleyite and zircon components. Secondary zircon inter- and over-growths of baddeleyite can occur in samples affected by low-temperature alteration to granulite facies metamorphism, and the new HCl–HF chemical abrasion procedure provides a method for resolving both the igneous and metamorphic history of these composite grains.