Relation between solid phase speciation and oral/lung bioaccessibility of metal(loid)s polluted soils in inhabited area: Contribution of synchrotron-based experiment.

The presence of contaminated sites/soils in or near cities can pose significant risks to public health. The city of Viviez (France) was taken in reference site bears significant industrial responsibility, particularly in zinc metallurgy, with the presence of a now rehabilitated smelter. This has led to soil contamination by zinc (Zn), lead (Pb), arsenic (As), and cadmium (Cd), with concentrations reaching up to 4856 mg kg-1, 1739 mg kg-1, 195 mg kg-1, and 110 mg kg-1, respectively. The aim of this study is to comprehend the contamination patterns of the site post-rehabilitation, the geochemical behavior of each element, and their speciation (analyzed through BCR, XRD, and XANES) in relation to associated health risks due to metals accessibility for oral ingestion and inhalation by the local population. The findings revealed that elements inducing health risks were not necessarily those with the highest metal contents. All results are discussed in terms of the relationship between element speciation, stability of bearing phases, and their behavior in different media. XANES is an important tool to determine and estimate the Pb-bearing phases in garden soils, as well as the As speciation, which consist of Pb-goethite, anglesite, and Pb-humate, with variations in proportions (the main phases being 66 %, 12 % and 22 % for Pb-goethite, anglesite, and Pb-humate, respectively) whereas As-bearing phase are As(V)-rich ferrihydrite-like. A new aspect lies in the detailed characterization of solid phases before and after bioaccessibility tests, to qualify and quantify the bearing phases involved in the mobility of metallic elements to understand the bioaccessibility behavior. Ultimately, the health risk associated with exposure to inhabitants, in terms of particle ingestion and inhalation, was assessed. Only ingestion-related risk was deemed unacceptable due to the levels of As and Pb.

Effect of liming on polycyclic aromatic hydrocarbons leaching from hydrocarbon-contaminated tectogenic industriosol.

Soil stabilization/solidification is commonly employed remediation method for contaminated soils. Until now, limited attention has been given to the application of quicklime in polycyclic aromatic hydrocarbons (PAHs) contaminated soil. We treated a tectogenic industriosol spiked with 50 mg kg-1 of four PAHs (12.5 mg kg-1 each of fluorene (FLU), phenanthrene (PHE), fluoranthene (FLT) and pyrene (PYR)) using three different liming agents at 1% (w:w): quicklime (CaO), hydrated lime (Ca(OH)2) and carbonate calcium (CaCO3). All treated samples were leached in water at a solid-liquid ratio of 10, with subsequent analysis of leached soil and leachates for PAHs content. Results revealed that the addition of liming agents led to a reduction in FLU and PHE concentrations in treated soil by 6.81 ± 2.47% and 28.88 ± 4.18%, respectively, compared to a not-treated sol. However, no significant impact was observed on the 4-cycles PAHs (FLT and PYR). The addition of liming agents also significantly decreased the amount of PAHs in the leachate, by 100% for FLU and PHE, and by 74.9 ± 17.5% and 72.3 ± 34.8%, for FLT and PYR, respectively, compared to not limed soil. Among the liming agents, quicklime was the most effective in reducing the amount of 4 cycles PAHs in the leachate. Various mechanisms, such as encapsulation, volatilization and oxidation could contribute to this observed reduction. Quicklime treatment at a concentration of 1% w:w in PAHs-contaminated soil emerges as a promising technique to effectively reduce PAHs concentration in soils and mitigate PAHs mobility through leaching. This study also sheds light on the possibility to limit CO2 emissions and resources exploitation to assure the remediation process, thereby enhancing its overall environmental sustainability.

A fast one-pot synthesize of crystalline anglesite by hydrothermal synthesis for environmental assessment on pure phase.

Anglesite (PbSO4) 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(NO3)2 and Fe2(SO4)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.

Investigating the relationship between speciation and oral/lung bioaccessibility of a highly contaminated tailing: contribution in health risk assessment.

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.

Environmental stability and oral bioaccessibility of synthetic Pb-bearing phases to better evaluate soil health risks.

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.

Immobilization of Pb from mine sediments in metakaolin-based geomaterials.

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.

Assisted phytostabilisation of As, Pb and Sb-contaminated Technosols with mineral and organic amendments using Douglas fir (Pseudotsuga menziesii (Mirb.) Franco).

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.

Diffusive gradients in thin films, Rhizon soil moisture samplers, and indicator plants to predict the bioavailabilities of potentially toxic elements in contaminated technosols.

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.

Douglas fir (pseudotsuga menziesii) plantlets responses to as, PB, and sb-contaminated soils from former mines.

Phytoremediation of metalloids by conifers is not widely studied although they may be relevant for several contaminated sites, especially those located in cold areas and sometimes under dry climates. Here, seeds of Douglas fir were sown in greenhouse on three soils collected in two French former mines: a gold mine (soils L1 and L2) and a lead and silver mine (soil P). These soils are highly contaminated by Pb, As, and Sb at different concentrations. Plants were harvested after ten weeks. Growth parameters, primary metabolite content, and shoot and root ionomes were determined. Douglas firs grown on the soils L1 and P had a lower biomass than controls and a higher oxidation status whereas those grown on the soil L2 exhibited a more developed root system and only slight modifications of carbon and nitrogen nutrition. Based on trace element (TE) concentrations in shoots and roots and their translocation factor (TF), Douglas fir could be a relevant candidate for As phytoextraction (0.8 g. kg(-1) dry weight in shoots and a TF of 1.1) and may be used to phytostabilize Pb and Sb (8.8 g and 127 mg. kg(-1) in roots for Pb and Sb, respectively, and TF lower than 0.1).

Potentially toxic element phytoavailability assessment in Technosols from former smelting and mining areas.

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.

Evaluating the potential of three Fe- and Mn-(nano)oxides for the stabilization of Cd, Cu and Pb in contaminated soils.

The potential of three Fe- and Mn-(nano)oxides for stabilizing Cd, Cu and Pb in contaminated soils was investigated using batch and column experiments, adsorption tests and tests of soil microbial activity. A novel synthetic amorphous Mn oxide (AMO), which was recently proposed as a stabilizing amendment, proved to be the most efficient in decreasing the mobility of the studied metals compared to nano-maghemite and nano-magnetite. Its application resulted in significant decreases of exchangeable metal fractions (92%, 92% and 93% decreases of Cd, Cu and Pb concentrations, respectively). The adsorption capacity of the AMO was an order of magnitude higher than those recorded for the other amendments. It was also the most efficient treatment for reducing Cu concentrations in the soil solution. No negative effects on soil microorganisms were recorded. On the other hand, the AMO was able to dissolve soil organic matter to some extent.

DGT-labile As, Cd, Cu and Ni monitoring in freshwater: toward a framework for interpretation of in situ deployment.

The use of the Diffusive Gradient in Thin Film sampler (DGT) as a monitoring tool for regulatory programs is currently evaluated. In this context, the impact of commonly followed procedures on the accuracy of DGT-labile As, Cd, Cu, and Ni quantification was studied. Initial sampler contamination yields to define quantification limits instead of using blank subtraction, thus avoiding artifact concentrations. Not considering the alteration of element diffusion by the filter membrane leads to significant underestimation. However, diffusion coefficients determined on a non-fouled membrane were found to be suitable for the studied site, making it possible to use data from the literature. When diffusive boundary layer formation is neglected, no loss of accuracy is recorded provided the layer is thinner than 0.5 mm. Finally, exploration of potential biases allowed initiating a framework that might help limit inaccuracies in DGT-labile concentration estimation and interpretation, especially in a low contamination context.

Arsenic (As), antimony (Sb), and lead (Pb) availability from Au-mine Technosols: a case study of transfer to natural vegetation cover in temperate climates.

Soils from old Au-mine tailings (La Petite Faye, France) were investigated in relation to the natural vegetation cover to evaluate the risk of metals and metalloids (Pb, As, Sb) mobilizing and their potential transfer to native plants (Graminea, Betula pendula, Pteridium aquilinum, Equisetum telmateia). The soils are classified as Technosols with high contamination levels of As, Pb, and Sb. The single selective extractions tested to evaluate available fraction (CaCl2, acetic acid, A-Rhizo, and DTPA) showed low labile fractions (<5 % of bulk soil contents), but still significant levels were observed (up to 342.6 and 391.9 mg/kg for As and Pb, respectively) due to the high contamination levels of soils. Even at high soil contaminations (considered as phytotoxic levels for plants), translocation factors for native plants studied are very low resulting in low concentrations of As, Sb, and Pb in their aerial part tissues. This study demonstrates the important role of (1) native plant cover in terms of "stabilization" of these contaminants, and (2) the poor effectiveness of extraction procedures used for this type of soil assemblages, i.e., rich in specific mineral phases.

Environmental and health risk assessment of Pb, Zn, As and Sb in soccer field soils and sediments from mine tailings: solid speciation and bioaccessibility.

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.

Adsorption of copper, cadmium, lead and zinc onto a synthetic manganese oxide.

Due to its simple and inexpensive synthesis, a new amorphous hydrous manganese oxide (AMO) has been studied as a possible chemical stabilizing agent for soils contaminated with metals. Preliminary experiments evaluating the stability of AMO in pure water have reported only minor dissolution (5.70% and 0.24% depending on the w/v ratio). Sorption kinetics have shown fast metal adsorption, especially for Pb. The sorption capacities of AMO for Cu, Cd, Pb, and Zn have been described and compared with synthetic birnessite for pH 4 and 5.5. Both oxides show similar sorption capacities at pH 4 despite the fact that birnessite characteristics (pH of zero point charge, specific surface area and cation exchange capacity) are more favorable for metal sorption. Moreover, the pH adsorption-edges show that the AMO is more pH-dependent than birnessite.

Metal binding properties of extracellular polymeric substances extracted from anaerobic granular sludges.

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.

Abundance and diversity of ammonia-oxidizing prokaryotes in the root-rhizosphere complex of Miscanthus × giganteus grown in heavy metal-contaminated soils.

Mine wastes have been considered as a source of heavy metal (HM) contamination in the environment and negatively impact many important ecosystem services provided by soils. Plants like Miscanthus, which tolerate high HM concentrations in soil, are often used for phytoremediation and provide the possibility to use these soils at least for the production of energy crops. However, it is not clear if plant growth at these sites is limited by the availability of nutrients, mainly nitrogen, as microbes in soil might be affected by the contaminant. Therefore, in this study, we investigated in a greenhouse experiment the response of ammonia-oxidizing microbes in the root-rhizosphere complex of Miscanthus × giganteus grown in soils with different levels of long-term arsenic (As) and lead (Pb) contamination. Quantitative PCR of the ammonia monooxigenease gene (amoA) was performed to assess the abundance of ammonia-oxidizing bacteria (AOB) and archaea (AOA) at two different points of plant growth. Furthermore, bulk soil samples before planting were analyzed. In addition, terminal restriction fragment length polymorphism (T-RFLP) analysis was used to investigate the diversity of archaeal amoA amplicons. Whereas high concentrations of As and Pb in soil (83 and 15 g/kg, respectively) resulted independent from plant growth in a clear reduction of AOA and AOB compared to the control soils with lower HM contents, in soils with contamination levels of 10 g/kg As and 0.2 g/kg Pb, only AOB were negatively affected in bulk soil samples. Diversity analysis of archaeal amoA genes revealed clear differences in T-RFLP patterns in response to the degree of HM contamination. Therefore, our results could clearly prove the different response patterns of AOA and AOB in HM-contaminated soils and the development of archaeal amoA phylotypes which are more tolerant towards HMs in soil samples from the areas that were impacted the most by mining waste, which could contribute to functional redundancy of ammonia-oxidizing microbes in soils and stability of nitrification pattern.

Characterisation of the mineral fraction in extracellular polymeric substances (EPS) from activated sludges extracted by eight different methods.

This work characterises the mineral fraction of EPS extracts obtained using eight different methods from two activated sludges by total mineral content determination, Fourier Transformed Infrared spectrometry and with scanning electron microscopy coupled with an EDX probe. Despite EPS dialysis, the EPS extracts displayed a mineral fraction between 2% and 40% of the EPS dry weight depending on the extraction method used. The main mineral elements found in the EPS extract were Ca, Mg, Na, K, Al, Fe, Mn, P, Si and S, but their contents were strongly affected by the extraction method used. Some of the minerals are associated with the organic molecules within the EPS. The presence of mineral particles of various compositions and structures (clays, quartz or carbonate) in the EPS extract with a wide range in size was clearly demonstrated. Moreover, the association of metallic elements with the mineral particles in the EPS extract was highlighted.

The influence of reducing conditions on the dissolution of a Mn-rich slag from pyrometallurgical recycling of alkaline batteries.

The redox potential (Eh) is a key parameter for controlling the release of elements from solid materials. Nevertheless, this parameter is seldom taken into account during risk assessment studies within any regulatory framework. We studied the incidence of redox changes to the solid materials using two batch procedures: i) a gradient of redox conditions obtained using sodium ascorbate solutions at various concentrations; ii) N(2) bubbling in water. These experiments were performed on two Mn-rich slag samples coming from a pyrometallurgical plant that recycles alkaline batteries. Both samples differed slightly in their chemical composition and solid characterization (i.e. presence of Mn oxide) and presented different behaviours. The present study focused on the release of the main slag elements (i.e. Mn and Si) chosen as indicators of the dissolution of primary silicate phases. Solid phase analyses (SEM-EDS and XRD) were coupled with the monitoring of elements in leachates in order to understand their behaviour and the mechanisms involved. The results indicated that the solid composition plays an important role in the release mechanisms. The presence of Mn oxide enhanced the mobilization of Mn in the greatest reducing conditions (-320 ± 5 mV/SHE), to the extent that 42% of the total Mn was leached. This demonstrated the significance in studying the solid phases (using SEM-EDS and XRD) before and after any leaching experiment. From a laboratory practice point of view, it was easier to use sodium ascorbate and allowed, in our case, greater reducing conditions to be reached.

Alteration of a Mn-rich slag in contact with soil: in-situ experiment during one year.

A Mn-rich slag sample coming from a pyrometallurgical plant recycling alkaline batteries was submitted to environmental conditions during one year. After crushing, the slag was buried in topsoil and the leachate was periodically collected in order to monitor the leached amounts of metallic elements (ME). Results evidenced a low release of the slag constituents (Mn: < 0.01%). The SEM/EDS investigations did not show alteration features supposing a weak dissolution of the primary phases (tephroite, bustamite and leucite). The modification of the pH induced by the slag enhanced the mobility of soil components and of the organic matter, particularly in the vicinity of the soil/slag contact zone. This suggested that the slag indirectly influenced the ME mobility through the organic matter and colloidal transports. The comparison with a classical laboratory column test evidenced the underestimation of the leached amounts due to the differences of operational conditions.