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.

Critical raw materials (CRMs) supply is a challenge that EU countries have to face, with many thinking about domestic procurement from natural ore deposits and anthropogenic deposits (landfills and extractive waste facilities). The present research focuses on the possibilities linked to the supply of CRMs and the potential for exploiting rare earth elements (REEs), investigating a large variety of extractive waste and siliceous rocks in the Piedmont region (Northern Italy). Indeed, the recovery of REEs from the extractive waste (EW) of siliceous quarries and other siliceous ore deposits can be a valuable way to reduce supply chain risks. Starting with a review of the literature on mining activities in Piedmont and continuing with the sampling and geochemical, mineralogical, petrographic, and environmental characterization of EW facilities connected to siliceous dimension stones, of kaolinitic gneiss ore deposits, and of soils present near the investigated areas, this study shows that the degree of REEs enrichment differs depending on the sampling area (soil or EW) and lithology. The concentration of REEs in the EW at some sampling sites fulfils the indicators of industrial-grade and industrial recovery; the high cumulative production and potential market values of EW and the positive recovery effects through proven methodologies indicate a viable prospect of REE recovery from EW. However, REE recovery industrialization faces challenges such as the difficulty in achieving efficient large-scale recovery due to large regional differences in REE abundance, the mismatch between potential market value and waste annual production, etc. Nonetheless, in the future, EW from dimension stone quarries could be differentially studied and reused based on the enrichment and distribution characteristics of trace elements. The present paper shows investigation procedures undertaken to determine both CRMs potentialities and environmental issues (on the basis of literature data employed to select the more-promising areas and on sampling and characterization activities in the selected areas), together with procedures to determine the waste quantities and tentative economic values of REEs present in the investigated areas. This approach, tested on a large area (Piedmont region), is replicable and applicable to other similar case studies (at EU and non-EU levels) and offers decision makers the possibility to acquire a general overview of the potential available resources in order to decide whether and where to concentrate efforts (including economic ones) in a more detailed study to evaluate the exploitable anthropogenic deposits.