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.

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).

Impact of sludge stabilization processes and sludge origin (urban or hospital) on the mobility of pharmaceutical compounds following sludge landspreading in laboratory soil-column experiments.

This study aimed to determine the effect of sludge stabilization treatments (liming and anaerobic digestion) on the mobility of different pharmaceutical compounds in soil amended by landspreading of treated sludge from different sources (urban and hospital). The sorption and desorption potential of the following pharmaceutical compounds: carbamazepine (CBZ), ciprofloxacin (CIP), sulfamethoxazole (SMX), salicylic acid (SAL), ibuprofen (IBU), paracetamol (PAR), diclofenac (DIC), ketoprofen (KTP), econazole (ECZ), atenolol (ATN), and their solid-liquid distribution during sludge treatment (from thickening to stabilization) were investigated in the course of batch testing. The different sludge samples were then landspread at laboratory scale and leached with an artificial rain simulating 1 year of precipitation adapted to the surface area of the soil column used. The quality of the resulting leachate was investigated. Results showed that ibuprofen had the highest desorption potential for limed and digested urban and hospital sludge. Ibuprofen, salicylic acid, diclofenac, and paracetamol were the only compounds found in amended soil leachates. Moreover, the leaching potential of these compounds and therefore the risk of groundwater contamination depend mainly on the origin of the sludge because ibuprofen and diclofenac were present in the leachates of soils amended with urban sludge, whereas paracetamol and salicylic acid were found only in the leachates of soils amended with hospital sludge. Although carbamazepine, ciprofloxacin, sulfamethoxazole, ketoprofen, econazole, and atenolol were detected in some sludge, they were not present in any leachate. This reflects either an accumulation and/or (bio)degradation of these compounds (CBZ, CIP, SMX, KTP, ECZ, and ATN ), thus resulting in very low mobility in soil. Ecotoxicological risk assessment, evaluated by calculating the risk quotients for each studied pharmaceutical compound, revealed no high risk due to the application on the soil of sludge stabilized by liming or anaerobic digestion.

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.

Interfacial reactions between humic-like substances and lateritic clay: application to the preparation of "geomimetic" materials.

The aim of this study was to understand the mechanisms responsible for the strengthening of "geomimetic" materials, especially the chemical bonding between clay and humic substances. The mineral matter is lateritic clay which mainly consists in kaolinite, goethite, hematite and quartz. The other starting products are fulvic acid (FA) and lime. The preparation of these geomimetic materials is inspired from the natural stabilization of soils by humic substances occurring over thousands of years. The present process involves acidic and alkaline reactions followed by a curing period of 18days at 60°C under a water saturated atmosphere. The acceleration of the strengthening process usually observed in soils makes this an original process for treatment of soils. The consolidation of the "geomimetic" materials could result from two major phenomena: (i) chemical bonding at the interface between the clay particles and iron compounds and the functional groups of the fulvic acid, (ii) a partial dissolution of the clay grains followed by the precipitation of the cementitious phases, namely calcium silicate hydrates, calcium aluminate hydrates and mixed calcium silicum and aluminum hydrates. Indeed, the decrease of the BET specific area of the lateritic clay after 24 h of reaction with FA added to the structural reorganization observed between 900 and 1000°C in the "geomimetic" material, and to the results of adsorption measurements, confirm the formation of organo-ferric complexes. The presence of iron oxides in clay, in the form of goethite, appears to be another parameter in favor of a ligand exchange process and the creation of binding bridges between FA and the mineral matter. Indeed all faces of goethite are likely to be involved in complexation reactions whereas in lateritic clay only lateral faces could be involved. The results of the adsorption experiments realized at a local scale will improve our understandings about the process of adsorption of FA on lateritic clays and its involvement in the strengthening process of materials.

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.