Rare earth element and yttrium behaviour during metabolic transfer and biomineralisation in the marine bivalve Mytilus edulis: Evidence for a (partially) biological origin of REY anomalies in mussel shells.

Rare Earth Elements and Yttrium (REY) are widely used as proxies for environmental conditions and biogeochemical processes, but have also become (micro)contaminants of surface waters worldwide. Soft tissues and shells of mussels are increasingly used in environmental science and geology as bioarchives for REY, but REY fractionation by and in these organisms is still not well understood. We report on the distribution of REY in different compartments of marine M. edulis mussels from Norway, and in their ambient water and food (plankton). The shale-normalised REY patterns of all compartments studied decrease from light to heavy REY (LREY and HREY, respectively), while the LREY depletion occasionally reported in the literature cannot be observed. The bivalves show REY concentrations up to five orders of magnitude higher than those in ambient water (with preferential uptake of Ce and of LREY over HREY) but lower than those in their potential plankton food (with minor REY fractionation, except for preferential uptake of La and Y). While metabolic REY fractionation within the bivalves is minor, vital effects affect the REY distribution in the shells of M. edulis mussels. Rejection and decoupling of Ce during shell formation occurs due to Ce oxidation and formation of Ce(IV) solution-complexes in the extrapallial fluid (EPF). While discrimination against HREY incorporation results from strong solution-complexation of the HREY, preferential uptake of La, Gd and Y during shell formation is due to the less stable solution-complexes of these ions. These observations are compatible with the presence of siderophores in the EPF, suggesting that in contrast to freshwater mussel A. anatina, vital effects can to some extent affect the size of anomalies in the REY patterns of marine M. edulis shells. This implies that these anomalies are (partially) of biological origin, which limits their use as paleo-redox proxies.