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Erosion and leaching of metal(loid)s from contaminated sites can spread pollution to adjacent ecosystems and be a source of toxicity for living organisms. Phytostabilization consists of selecting plant species accumulating little or no metal(loid)s in aerial parts to establish a vegetation cover and thus to stabilize the contaminants in the soil. Seeds of white lupin, common vetch, and buckwheat were sown in greenhouse on soils from former French mines (Pontgibaud and Vaulry) contaminated with metal(loid)s including high concentrations of As and Pb (772 to 1064 and 121 to 12,340 mg kg -1 , respectively). After 3 weeks of exposure, the growth of white lupin was less affected than that of the 2 other species probably because metal(loid) concentrations in roots and aerial parts of lupins were lower (5-20 times less Pb in lupin leaves on Pontgibaud soil and 5-10 times less As in lupin leaves on Vaulry soil than in vetch and buckwheat). To limit oxidation and/or scavenge metal(loid)s, white lupin increased the content of proline and total phenolic compounds (TPC) in leaves and roots by a factor 2 whereas buckwheat stimulated the production of TPC by a factor 1.5-2, and non-protein thiols (NPT) by factors around 1.75 in leaves and 6-12 in roots. Vetch accumulated more proline than white lupin but less NPT than buckwheat and less TPC than the 2 other plant species. The level of oxidation was however higher than in control plants for the 3 species indicating that defense mechanisms were not completely effective. Overall, our results showed that white lupin was the best species for phytostabilization but amendments should be tested to improve its tolerance to metal(loid)s., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Anglesite (PbSO 4 ) is a lead sulfate that belongs to the barite group and is naturally ubiquitous in the environment. This work describes a simple way to synthesize crystalline lead sulfate by using a straightforward hydrothermal procedure. Typically, Pb(NO 3 ) 2 and Fe 2 (SO 4 ) 3 precursors were mixed and heated at 94 °C for 24 h. The synthesized samples have been characterized by coupling X-Ray diffraction (XRD) to spectroscopic methods (FTIR and micro-Raman), X-ray absorption spectroscopy (XAS), and electronic microscopy (SEM and TEM). In fine, the results about this new well crystalline synthetic anglesite confirm the efficiency and the importance of this cheap protocol and the synthesized phases obtained. Moreover, the environmental stability and bioaccessibility of anglesite have been done to evaluate environmental stability of anglesite under various physico-chemical conditions and sanitary risks. Finally, the paper allows to obtain precise data on a pure phase in order to be able to more easily evaluate and understand the role of anglesite in as-polluted sites and soils., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Anthropogenic activities such as industrial, mining, or agricultural are the main sources of environmental contamination. One of the most problematic contaminations concerns metals and metalloids from mining activities. This contamination raises the question of the environmental risk induced and the spread of this pollution (geographical and trophic) and the associated health risk. The integrated, multi-analytical approach of this study conducted on the mining district of Cartagena-La Union (Murcia, Spain) as part of the Interreg SUDOE European project "Soil Take Care" aims to (i) precisely define the speciation of contaminants of interest (Zn, Pb, Cd, As), (ii) predict the environmental risk related to storage stability, and (iii) establish the link between the speciation of the bearing phases and the associated health risk. To do this, a representative zone in the Cartagena-La Union mining district close to the populations was chosen. A physic-chemical characterization of the samples was performed (pH, electrical conductivity, CEC, and total metal(loid) concentrations), and the mineralogy was determined using XRD and SEM-EDS. The environmental risk was highlighted from sequential BCR-type extractions and EN-12457 leaching tests. Finally, the health risk was defined using the PSF inhalation bioaccessibility test and UBM bioaccessibility protocol (based on an operational chemical methodology mimicking soil ingestion and its residence in the gastrointestinal tract of the human body). These analyses revealed 2 groups of samples with distinct behavior. The first group of samples presents relatively stable bearing phases, mainly found in the residual fraction (As and Pb), presenting only a low health risk (very low bioaccessible). The second group consists of Cd and/or Zn-bearing phases, mainly labile (resulting from dissolution/precipitation phenomena), while gastric bioaccessibility reaches more than 85%. Note that Pb, Cd, and Zn have the potential to cause non-carcinogenic risks to children and As and Pb present a carcinogenic risk for children and adults even if only the bioaccessible fraction is considered. It has therefore been shown that the meteoric alteration of the tailing induces a change in speciation leads to an increase in environmental and health risks. These results are essential because they highlight the need for an integrated approach in order to clearly highlight the presence of risks but also that this approach will allow a better understanding of the potential rehabilitation path of this site.

A large amount of contaminated sites is shown around the world which may induce a health risk due to the presence of contaminants such as metal (loïd)s bearing phases. Health risk assessment is based on contaminant bioaccessibility. However, it is needed to understand every contaminant behavior in physiological matrix to be a realistic way to assess and interpret these sanitary risks. Due to the complexity of contaminated soil matrix, the use of synthetic minerals seems to be the better tool to understand their behavior in physiological matrix. Then, this study aims to highlight the environmental stability and the behavior during bioaccessibility ingestion (UBM) of selected synthetic lead-bearing phases. For this purpose, three Pb phases (galena, beudantite, and anglesite) commonly found in contaminated environments (particularly mining sites) were synthesized and characterized (structurally and morphologically). The sequential BCR extractions have shown that most of the lead is in a stable and non-mobilizable form (up to 93%). The lead present in these phases represents very few risks of migrating into the environment during physicochemical condition changes. The results of the bioaccessibility revealed a relatively high stability of the pure bearing phases in the physiological matrix. Lead is stable for 97.0% to 99.2% during the gastric phase and 97.0% to 99.9% during the gastro-intestinal phase. Moreover, the synthetic mixtures of galena/beudantite and anglesite/beudantite have been realized considering the proportions commonly found in the mining contexts. This has shown a similar behavior compared to pure phases except in the case of the anglesite mixture inducing a clear cocktail effect (drastic increase of Pb amount from gastro-intestinal phases). At last, this study is a first and interesting step to assess the behavior of these bearing phases in heterogeneous and complex medium such as soil.

The aims of this study correspond to (i) determine the feasibility of synthesize geomaterial from two main Pb-contaminated mining sediments (Sed1 and Sed2) without prior activation in substitution to metakaolin (MK), (ii) understand the mechanisms involved toward two types of silicate solution (Na and K one), and (iii) to evaluate the change in the Pb metallic element speciation and leaching after alkali treatment. The raw material as well as consolidated material were characterized by X-ray diffraction, infrared spectroscopy, and electron microscopy. The mechanical properties were evaluated, and the leaching behavior realized according to EN12457-2. The results evidence the limit of mining sediment incorporation by substitution near 50% whatever the sediments and the alkaline solution used. There is no difference in the mechanical properties up to 10% substitution then decrease with the increase of sediment content. The Pb-bearing phases are dissolved during alkaline treatment and redistributed in the geomaterial matrix. Finally, the leaching experiments clearly evidenced the possibility to stabilize Pb into MK-based geomaterial matrix up to 25-30% weight of mine waste.

Phytoremediation of metal(loid)s by conifers is not widely studied, although conifers may be interesting, particularly in temperate-cold areas and/or on acidic soils. In this study, seeds of Douglas fir were sown in greenhouse and cultivated for 3 months on two Technosols highly contaminated with different concentrations of Pb, As and Sb and collected in two French old former mines located in massif Central or close to it: a mine of gold at La Petite Faye and a mine of lead and silver at Pontgibaud. Two amendments, a nutrient solution (NS) and composted sewage sludge (CSS), were tested in order to stimulate Douglas fir growth and to reduce the metal(loid)s mobility and phytoavailability. The speciation determined by sequential extractions as well as mineralogy highlight different geochemical behaviours of Pb, As and Sb as a function of the Technosol. In all cases, CSS amendments significantly reduced Pb phytoavailability as well as the uptake and translocation of Pb and As. Moreover, CSS stimulated the growth of Douglas firs highlighting that this amendment could be a good strategy for a better phytostabilisation of these metal(loid)s.

The phytoavailabilities and potential remobilization of potentially toxic elements (PTEs) such as Zn, Pb, Cd, As, and Sb were assessed in contaminated technosols from former mining and smelting sites. The PTE concentrations in soil pore water (SPW) and diffusive gradients in thin films (DGT)-measured concentration (C DGT) methods were used to assess the bioavailabilities of PTE and their remobilization in this study. Together with classical Chelex-100 DGT probes to measure Zn, Cd, and Pb, novel ferrihydrite-backed DGT were used for As and Sb measurements alongside with Rhizon soil moisture sampler method for SPW sampling. To assess the phytoavailabilities of PTE, a germination test with dwarf beans as a plant indicator was used for this purpose. Dwarf bean primary leaves showed high Zn concentrations in contrast to Pb and Cd which showed low phytoavailabilities. Despite As and Sb are present in high concentrations in the mine tailings, their phytoavailabilities indicate very low bioavailabilities. The amounts of Zn, Pb, Cd, As, and Sb extracted with DGT devices correlated well with the total dissolved PTE concentrations in the SPW. The highest R values were observed for Zn, followed by Cd and Pb, indicating the ability of the soil to sustain SPW concentrations, which decreased in that order. Good correlations were also observed between each of dissolved PTE concentrations in SPW, DGT-measured PTE concentrations (C DGT), and the accumulation of PTE in dwarf bean primary leaves. It could be concluded that the use of Rhizon soil moisture samplers and DGT methods may be considered to be a good methods to predict the PTE bioavailabilities in contaminated technosols.

This study reports the chemical bioavailability of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated Technosols from two former smelting and mining areas. Though these elements have long been recognized as potentially harmful elements, understanding of their toxicity and environmental behavior in Technosols developed on former mining and smelting sites are more limited, particularly for As and Sb. Surface soils were sampled from metallophyte grassland contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (North France) and from a former mining settling basin contaminated with As, Pb, and Sb located at la Petite Faye (Limoges, France). Various selective single extraction procedures (CaCl2, NaNO3, NH4NO3, DTPA, and EDTA) were used together with germination tests with dwarf beans whose shoots were analyzed for their potentially toxic element concentrations after 21 days of growth. The extraction capacity of the potentially toxic elements followed the order EDTA > DTPA > NH4NO3 > CaCl2 > NaNO3 for both studied areas. Pearson's correlation coefficient analysis between the concentrations of potentially toxic elements accumulated in bean primary leaves or their mineral mass with their extractable concentrations showed a positive significant correlation with dilute CaCl2 and nitrate solutions extraction procedures. In contrast, for all studied elements, except Pb, the complexing and chelating extractants (EDTA and DTPA) exhibited poor correlation with the dwarf bean leaves concentrations. Moreover, results showed that the 0.01 M CaCl2 extraction procedure was the most suitable and provided the most useful indications of metal phytoavailability for studied elements.

Areas polluted by the persistent presence of metal(loid)s induce health problems, especially when recreational activities (on land or water) promote human exposure to the pollutants. This study focuses on one of the most encountered worldwide mining waste, i.e. those from the extraction of Pb-Zn-Ag. The representative Pb-Zn-rich tailing (about 64,100 m(3)) sampled is located near a soccer field and a famous river for fishing. The scientific interests is relative to: (1) mobility and bioaccessibility of metal(oid)s, (2) human risk assessments and (3) relationship between human risks and solid-bearing phases in the environment. Soccer field soils, tailings and sediments from the nearby river were sampled; moreover, metal(loid) speciation (from BCR experiments) and bioaccessibility were measured and solid speciation performed by X-ray diffraction and electron microscopy in order to highlight metal(loid) dispersion and impact. Results demonstrate that the soccer field is highly contaminated by Pb, Zn, As and Sb due primarily to waste runoff. In terms of risk assessment, Pb and As human bioaccessibility highlights the major health risk (48 and 22.5 % of human bioaccessibility, respectively). Since local populations are regularly in close contact with metal(loid)s, the health risk due to pollutant exposure needs to be reduced through sustainable waste disposal and the rehabilitation of polluted sites.

Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pKa1 (4-5) corresponding to the carboxyl groups; pKa2 (6-7) corresponding to the phosphoric groups; pKa3 (8-10) and pKa4 (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.