Naturally grown duckweeds as quasi-hyperaccumulators of rare earth elements and yttrium in aquatic systems and the biounavailability of gadolinium-based MRI contrast agents

Abstract

The use of rare earths and yttrium (REY) in high-technology products is accompanied by their increasing release into the environment. Concerns regarding the (eco-)toxicity and bioaccumulation of these emerging contaminants highlight the need for research on REY uptake by (aquatic) plants.Duckweeds are widespread macrophytes in lentic waters and receive increasing attention as a potential protein-rich food additive. We here provide a baseline dataset for the complete set of REY in naturally grown duckweed assemblages and ambient freshwater and coastal brackish seawater. Our results show that duckweeds strongly bioaccumulate REY and incorporate them at the μg/kg level (dry matter basis). Their shale-normalised (SN) REY patterns are mildly fractionated relative to upper continental crust, regardless of sampling location and season. In contrast, the patterns of ambient waters increase from light to heavy REY (LREY and HREY, resp.) and may show prominent positive anthropogenic GdSN anomalies due to the presence of Gd-based contrast agents (Gd-CAs) applied for magnetic resonance imaging (MRI). The lack of GdSN anomalies in the duckweed assemblages reveals discrimination against the uptake of Gd-CAs by the macrophytes, providing further evidence for the conservative behaviour of these xenobiotics in the environment. High REY concentrations and apparent bulk distribution coefficients between duckweeds and ambient waters of up to 105 show that duckweeds are quasi-hyperaccumulators of REY. Uptake of LREY is up to two orders of magnitude higher than of HREY, possibly due to stronger complexation of HREY with dissolved ligands. The REY closely correlate with Mn but not with Ca, suggesting that uptake of REY and Mn occurs via the same pathway and revealing the negligible role of calcium oxalates. Our study demonstrates that while duckweeds are quasi-hyperaccumulators of REY, there is currently no risk that anthropogenic Gd from MRI contrast agents may enter the food chain via consumption of duckweeds.