Understanding Rare Earth Elements concentrations, anomalies and fluxes at the river basin scale: The Moselle River (France) as a case study.

Anthropogenic activities linked to various new technologies are increasingly disrupting REEs biogeochemical cycles. A catchment-based perspective is therefore necessary to distinguish between natural (i.e., changes in lithology) and human-related sources of REEs variability. In the present study, REEs patterns, anomalies and fluxes were investigated in the French part of the Moselle River basin (Moselle River itself and some of its headstreams and tributaries). The REEs patterns in the headstream waters were highly variable and mostly related to the complex underlying lithology (granite, sandstone, tuff and graywacke). Along the Moselle River, the presence of positive Gd anomalies and a regular LREEs depletion/HREEs enrichment pattern on sandstone/limestone substrates were the most distinctive features. The Gd anomaly varied from 1.8 to 8.7, with anthropogenic Gd representing 45 to 88% of the total Gd. A linear relationship was obtained between the anthropogenic Gd flux and the cumulative population along the watershed. However, the magnitude of the Gd anomalies was shown to depend on the methodological approach chosen for their calculation. The use of a threshold value to identify the presence of an anthropogenic Gd anomaly may therefore be basin (and lithology) dependent, and care has to be taken in comparing results from different rivers or lithologies. Concentration of anthropogenic Gd in the Moselle River and its tributaries were close to, or above, the value of 20 ng/L reported in literature to elicit adverse biological effects in laboratory cell cultures. The ecotoxicological significance of Gd anomalies deserves further investigation because concentrations of anthropogenic Gd may also vary depending on the methodological approach used for calculating Gd anomalies.