Mineral Weathering and Metal Leaching under Meteoric Conditions in F-(Ba-Pb-Zn) Mining Waste of Hammam Zriba (NE Tunisia).

Mining waste is an obvious source of environmental pollution due to the presence of heavy metals, which can contaminate soils, water resources, sediments, air, and people living nearby. The F-(Ba-Pb-Zn) deposit of Hammam Zriba located in northeast Tunisia, 8 km southeast of Zaghouan was intensively exploited from 1970 to 1992. More than 250,000 m3 of flotation tailings were produced and stored in the open air in three dumps without any measure of environmental protection. Thus, in this paper, mineralogical and chemical characterization, especially the sulfide and carbonate phases, were carried out to evaluate the potential for acid mining drainage (AMD) and metal leaching (ML). Conventional analytical methods (XRD, XRF, SEM) have revealed that this mining waste contains on average 34.8% barite-celestine series, 26.6% calcite, 23% quartz, 6.3% anglesite, 4.8% fluorite, 2.1% pyrite, and 0.4% sphalerite. The content of sulfides is less important. The tailing leaching tests (AFNOR NFX 31-210 standard) did not generate acidic leachate (pH: 8.3). The acidity produced by sulfide oxidation was neutralized by calcite present in abundance. Furthermore, the leaching tests yielded leachates with high concentrations of heavy metals, above the authorized thresholds. This high mobilization rate in potential toxic elements (PTE) represents a contamination risk for the environment.

Phosphoric acid purification sludge: Potential in heavy metals and rare earth elements.

The present study was carried out to show the potential in heavy metals (HM) and the rare earth elements (REE) which presents the residues of phosphoric-acid(PA) purification. Three different cadmiferous solid residues (according to the nature of the purification process of the PA: BG, BC and BS) were collected from an industrial site located in the south of Tunisia. The mineralogical study showed the predominance of anhydrite, accompanied by quartz, malladrite; calcium sulfate hemihydrate and fluorapophyllite. The microanalysis showed (i) the association of cadmium and zinc, (ii) as well as the presence of associated REEs. The chemical analysis showed that (i) the calcium sulfate concentrations are majority in samples BS, BG and BC (44, 34 and 44%, respectively), (ii) significant concentrations of phosphoric acid (28, 18 and 21% P2O5, respectively), (iii) the HM: Cd, Zn, Cr, Ni, V, Cu, Pb, Co, Mo, Mn and U have proportion in the order of 0.1%. The concentrations of Cd, Zn and Cr are respectively in the order of: 230, 149 and 189 mg/kg for BS, 346, 243 and 153 mg/kg for BG and 183, 129 and 440 mg/kg for BC and (iv) the REEs: La, Ce, Nd, Eu, Y et Yb present considerable mass percentages able to reach 0.2%. A series of extraction tests was led on the cadmiferous sludges to evaluate the rates of HM (Cd, Zn) and REE dissolution, using two solvents (deionized water (DW) and aqueous sodium based alkaline metal solution). The results showed that the dissolution rates of Cd and Zn are respectively in the order of (12-29% and 41-45% for DW; 67-86% and 83-93% for Na2SO4 solution). The extractability of HM and REE is strongly influenced by pH, solvent nature and mineral load in the cadmiferous sludges. The water-soluble metals represent a significant mobile fraction, making the toxic elements more sensitive to mobilization processes, such as leaching and erosion. Whereas, the metals extractable by the Na2SO4 solution represent a very important exchangeable and "co-crystallization" fraction, which reflects the bioavailability of these metals.

Assessment of metal pollution in a former mining area in the NW Tunisia: spatial distribution and fraction of Cd, Pb and Zn in soil.

This study aims to evaluate the impact of the former mining Touiref district (NW Tunisia) on the spatial distribution of metal contamination. In order to characterize the metal content of the tailings and to assess how far the soils from the district could be impacted by metals, a sampling campaign was conducted. According to the spatial distribution concentration maps of potential toxic elements (PTE), the highest concentrations occur near the flotation tailings and in mining facilities and decrease abruptly with distance. These results confirm that wind is the main agent capable of dispersing metals in a W-E direction, with concentrations exceeding the standards of soil quality for Cd, Pb and Zn over several hundred metres away from the source, facilitated by the small-size fraction and low cohesion of tailings particles. Chemical fractionation showed that Pb and Cd were mainly associated with the acid-soluble fraction (carbonates) and Fe-(oxy) hydroxides, while Zn was mainly associated with Fe-(oxy) hydroxides but also with sulphides. Thus, the immobilization of metals in solution may be favoured by the alkaline conditions, promoted by carbonates dissolution. However, being carbonate important-bearing phases of Cd and Pb (but also for Zn), the dissolution facility of these minerals may enhance the release of metals, particularly far away from the mine where the physicochemical conditions can be different. Also, the metal uptake by plants in these alkaline conditions may be favoured, especially if secondary phases with high sorption ability are reduced at this site. A remediation plan to this area is needed, with particularly attention in the confinement of the tailings.

The flotation tailings of the former Pb-Zn mine of Touiref (NW Tunisia): mineralogy, mine drainage prediction, base-metal speciation assessment and geochemical modeling.

The underground extraction of Pb-Zn mineralization in the Touiref area stopped in 1958. A large volume of flotation tailings (more than 500 Mt) containing sulfides were deposited in a tailings impoundment. The goals of this study are to evaluate the neutralization capacity of the unoxidized and oxidized tailings, to assess the speciation of metals between the different components of the tailings material, and to assess the mobility of metals and the secondary minerals' precipitation in pore waters using geochemical modeling. To accomplish these objectives, representative samples from both fresh and oxidized zones were collected along a vertical profile through the tailings pile. Physical, chemical (ICP-MS), and mineralogical characterization (X-ray diffraction (XRD), reflected light microscopy, scanning electron microscope (SEM)) of these samples was performed. Grain size analysis shows that the tailings are dominated by silt- to sand-sized fractions. The microscopic observation highlights the presence of pyrite, marcasite, galena, and sphalerite as primary minerals in a carbonated matrix. The study reveals also the presence of secondary minerals represented by cerussite, smithsonite, anglesite, and Fe oxi-hydroxides as important scavengers for trace elements. The static tests show that the presence of calcite in the tailing samples ensures acid-neutralizing capacity (ANC), which is significantly greater than the acidity potential (PA). The geochemical characterization of the unoxidized samples shows higher Cd, Pb, and Zn concentrations than the oxidized samples containing the highest values for Fe and SO4. Sequential extraction tests show that significant percentages of metals are distributed between the acid-soluble fractions (Cd, Pb, and Zn) and the reducible one (Zn). Pore water analysis indicates that Ca is the dominant cation (8,170 and 6,200 mg L(-1), respectively), whereas sulfate is the principal anion (6,900 and 5,100 mg L(-1), respectively). Saturation index (SI) calculations of minerals in pore water extracted from both the oxidized and unoxidized samples are indicative of gypsum (SI >0) and Fe(III) oxides (SI ≫0) precipitation. The latter controls the Fe concentration in solution.