Thallium isotopes track fluctuations in global manganese oxide burial during the Ediacaran Period

Complex marine ecosystems appear in the geologic record for the first time during the Ediacaran (635 - 541 Ma), after the Marinoan Glaciation but before the Cambrian Explosion. Much debate surrounds the redox-state of global oceans during this diversification, with some arguing for pervasive anoxic conditions and others for increased oxygenation, including the possibility of episodic oxygen increases. Here, we use thallium (Tl) isotopes preserved in organic-rich shales from a deep-water section at Wuhe, South China, to track large-scale perturbations in Mn oxide burial during the Ediacaran. Changes to the Tl isotope composition of seawater over geologic timescales are driven dominantly by fluctuations in global Mn oxide burial, which require persistent O2 at the sediment-water interface. Importantly, the suite of sedimentary rocks analyzed is thought to have been deposited beneath persistent localized euxinia, which is an environment shown to effectively capture the Tl isotope composition of seawater. Within samples previously suggested to host oceanic oxygenation episodes (OOEs) because of high redox-sensitive element (RSE) enrichments (Sahoo et al. 2016, Geobiology), we find Tl isotope values as light as -5 epsilon units, which are indicative of removal of heavy Tl by Mn oxides elsewhere in the Ediacaran ocean and in-line with the presence of deep-marine O2. Intriguingly, between these events, during periods previously viewed as dominantly anoxic, we find Tl isotope excursions to values that are even lighter than during the OOEs (less than -10 epsilon units). To first order, these results imply that an even larger Mn oxide sink was present between the OOEs, which would require pervasive oceanic oxygenation. This interpretation is in direct conflict with interpretations of low RSE enrichments in these same samples, which invoke reservoir drawdown due to widespread anoxia—as well as many other data that suggest dominantly anoxic deep marine conditions through the Ediacaran (e.g. Sperling et al. 2015, Nature). Further work is needed to interpret this paradox.