Rare earth element patterns in sediments from the Great Lakes basin

This study presents a comprehensive analysis of rare earth element (REE) concentrations in >100 sediment samples from Lakes Erie and Huron, two of the North American Great Lakes. Significant intra- and inter-lake variability in REE concentrations is observed for both lakes Erie and Huron (<10 μg/g < versus <6 mg/g ƩREE, respectively). Light (L) REE were enriched over heavy (H) REE in surface sediment samples across both lakes, particularly in the North Channel of Lake Huron. Sediment cores from both lakes contained REE concentrations that are equally variable over time and correlated with major elements and other trace metals, reflective of the strong control of sediment accumulation rates on REE concentrations. Sequential extractions show that REE are predominantly associated with the residual (silicate) fraction (>50%) and likely originated from geogenic sources (basin weathering). However, considerable REE fractions (up to 16%) were also associated with oxide, phosphate minerals and organic/reducible material, particularly for the LREE. We attribute this apportionment and LREE enrichment to aqueous complexation and export from the water column. Finally, REE normalization and pattern-fitting reveal positive Ce anomalies (up to 16.2) in specific locations that could be indicative of hypolimnic redox gradients, whereas minor Gd and Eu anomalies (0.9 for Eu, and 1.02 for Gd, on average) likely relate to the parent rock signature. Our findings contribute valuable baseline data and insights into the complex interplay of geological, hydrodynamic, and environmental factors influencing REE distribution patterns in these lake sediments.