Uptake time and enrichment mechanism of rare earth elements in deep-sea bioapatite

Abstract

Bioapatite is widely recognized as the primary carrier for rare earth elements and yttrium (REY) in deep-sea REY-rich muds. The incorporation of REY into bioapatite occurs at the water-sediment interface, which has the potential to serve as a proxy for reconstructing paleoenvironmental conditions. The timing of REY uptake and the fractionation of rare earth elements (REEs) within bioapatite are crucial factors to understanding the application of these proxies. In this study, we present in-situ geochemical data for bioapatite obtained from surface sediments in the high sedimentation rate Somali Basin of the northwestern Indian Ocean (NWIO), as well as fish teeth within nodules from the low sedimentation rate in the northwestern Pacific Ocean (NWPO). Our findings indicate that the uptake time of REY occurred rapidly, with the ΣREY content reaching 7265 μg/g in bioapatite from the surface sediments in the NWIO within several thousand years. The bone fragments exhibited a high ΣREY content, which was primarily attributed to substitution processes. This led to a notably elevated proportion of middle rare earth elements (MREE) compared to fish teeth. In contrast, the adsorption and substitution mechanisms responsible for REY incorporation decreased from the root to the tip in fish teeth, resulting in a pronounced decline in ΣREY content. The adsorption mechanism was identified as the primary process responsible for REY uptake in the fish teeth within the studied nodules from the NWPO. The fractionation pattern of REEs in these teeth exhibited similarities to that of fish teeth from the NWIO. Therefore, we inferred that the fish teeth within the studied nodules may preserve the original information during late diagenesis. The variation of REY contents in the nodules was influenced by the redox environment, and there is no evidence to support the migration of REY from the nodules into the fish teeth.