Timescales and mechanisms of REE and Hf uptake in fossil bones

Rare earth element (REE) patterns of fossil bones and teeth are widely used as proxies for provenance, taphonomy, and palaeoenvironment. In order to investigate if fossil bones behave as closed systems over geologic time, REE profiles were analysed by LA-ICPMS along cross sections of 54 bones from various well-characterised and well-dated settings. These include terrestrial and marine diagenetic environments, covering Early Triassic to Holocene ages. In general, all fossil bones exhibit the highest REE concentrations at the outer rim, gradually decreasing by up to four orders of magnitude toward the inner bone cortex. Intra-bone REE concentration gradients decrease significantly from Quaternary via Tertiary to Mesozoic specimens, suggesting long term REE uptake and open system behaviour of fossil bone. This view is further corroborated by 176Lu–176Hf dating of selected samples, all yielding significantly younger ages than the known chronostratigraphic ages. Hence, there is clear evidence for long term open system behaviour of fossil bones with respect to REE, which is in marked contrast to currently accepted models suggesting that REE uptake is only early diagenetic. Although unexpected, statistically significant four to seven point isochrons are observed for four fossil dinosaur bone samples and one Upper Triassic Mastodonsaurus tooth with MSWDs ranging from 0.083 to 4.5. Notably, mobility of Lu alone cannot account for the observed age patterns. Assuming constant Lu uptake rates over time, the radiometric ages should only be as low as half of the chronostratigraphic age. However, a six-point isochron defined by subsamples of a single Upper Triassic Mastodonsaurus tooth yields an age of 65.2 ± 1.1 Ma (MSWD = 0.68), much younger than half of the stratigraphic age (ca. 234 Ma). Hence, Hf must also undergo late diagenetic exchange. Likely mechanisms to account for the presence of statistically meaningful isochrons as well as for the late diagenetic exchange of both REE and Hf are diffusion, adsorption, and dissolution–reprecipitation processes.