Vital effects and the fractionation of rare earth elements and yttrium during uptake by and transfer within freshwater bivalves and their shells

Mussels are commonly used as bioarchives in environmental monitoring, yet the impact of vital effects on the trace element or isotope ratios used as biogeochemical proxies is often only ill constrained. A prime example of such trace elements are the Rare Earth elements and Yttrium (REY) which have become (micro)contaminants in freshwater systems worldwide. We here report on the distribution of REY in different soft tissues and in the shells of freshwater bivalve A. anatina, commonly known as "duck mussel", from the Danube River in Hungary and the Vistula River in Poland. Both rivers are contaminated with anthropogenic Gd from contrast agents used in magnetic resonance imaging (MRI). Regardless of the mussels' origin, all of their compartments show very similar shale-normalised REY patterns. None of the samples show any anthropogenic Gd anomaly, implying that in freshwater anthropogenic Gd from MRI contrast agents is either not bioavailable or that REY from ambient river water are insignificant for the REY budget of freshwater mussels. Compared to ambient water, the bivalves bioaccumulate the REY with preferential uptake of Ce and of light REY over heavy REY. However, REY concentrations in mussels are similar to or lower than those in their potential food source, with minor fractionation along the REY series besides slight preferential uptake of La and Y. Comparison of shells and tissues reveals the systematic oxidative decoupling of Ce from its REY neighbours, probably due to the presence of Ce(IV) solution-complexes in the mussels' extrapallial fluid. Despite possible REY fractionation during their initial uptake, vital effects do not impose any major control on REY fractionation during REY transfer within the mussels or during formation of their shells. Mussel shells may, therefore, conveniently be used for environmental monitoring of REY without major disturbance from vital effects.