Rare earth elements (REEs) behavior in a large river across a geological and anthropogenic gradient

Abstract

To meet the strong demand for green and digital technologies, the production of rare earth elements (REEs) has increased significantly, yet the fate of REEs (Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) in large rivers with multiple hydrological, geochemical, and anthropogenic gradients in their catchments remains poorly documented. Here we evaluated the spatial and temporal evolution of the concentrations, patterns, and speciation of REEs in surface waters along a 550 km transect of the St. Lawrence River (SLR) (Canada) and its tributaries from 2017 to 2020. Particulate and filtered (<0.45 µm) REEs concentrations increased downstream, suggesting that REEs found in the SLR predominantly originate from nearby tributaries, especially those draining the REE-rich Canadian Shield geological formation. Moreover, filtered concentrations were significantly higher in years that experienced intense spring freshets, indicating greater influence of runoff and surface soil processes on water chemistry of the SLR. Correlations with terrestrial-DOM, WHAM speciation modelling, and standardized patterns showed REEs speciation dominated by organic colloids, even in alkaline sites with low DOC and low terrestrial inputs. Strong positive correlations with Fe and Al suggested co-transport on organic matter and adsorption on oxyhydroxides. Compared to the influence of water chemistry and geology, the overall influence of anthropogenic inputs was generally low, although we observed an influence of increased erosion on particulate REEs and we measured anthropogenic gadolinium (Gd) at the Montréal wastewater outlet. Our results provide an integrative understanding of the fate of REEs through a geochemical and landscape perspective in one of the largest rivers in North America.