Abundance, distribution, and ecological/environmental risks of critical rare earth elements (REE) in phosphate ore, soil, tailings, and sediments: application of spectroscopic fingerprinting

Purposes: This research focuses on the characterization of phosphate ore, its solid effluents, and nearby contaminated soils in the southwest Tunisia (Gafsa-Metlaoui Basin). It aims also at evaluating the vertical distribution and abundance of critical rare earth elements (REE) in the different materials and their ecological and environmental risks. Materials and methods: The sampled materials went through physical, chemical, and mineralogical characterization which involved XRF, XPS, XRD, and ICP-MS analyses. The REE anomalies and the environmental and ecological indices were calculated. Results and discussions: Results show relatively high concentrations of nine rare REEs, following the sequence La > Ce > Nd > Y > Gd > Eu > Sm > Yb > Tb and trace metal elements (TME) such as Cd, Cr, Mn, Zn, Co, Fe, Sr, Cu, Ni, Pb, Ba that surpass, in some cases, international standards. The vertical distribution of the studied elements within a sediment, tailings, and soil profiles (beyond 20 cm of depth) indicates their likely in-depth migration. TME- and REE-bearing phosphate samples reflect mostly oxic conditions in the southern area with high positive Eu anomalies signifying possible mixing of sources. The environmental assessment indicate no contamination and a moderate enrichment of REEs, except for Eu, which displays significant contamination and extreme enrichment. Whereas, a deficiency of Y has been detected in most of the studied samples except for sludge sample which was also found significantly enriched with REE. Conclusions: There are fundamental similarities between the different studied samples with high carbonate mineral concentrations. Statistical analysis confirmed the spectroscopic fingerprints demonstrating that the different materials share a similar composition. All of these similarities are most likely linked to the impact of mining activities on sediments and soils. Overall, our findings highlight the global effect of ore processing in determining the geochemical and the mineralogical characteristics of the surrounding environments of mines.