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Heavy metal (HM) pollution in agricultural fields reduces crop productivity and quality, and poses a risk for human health. On these areas, the cultivation of crops devoted to biomaterial and bioenergy production thus constitutes an attractive alternative to food crop production. To maintain the soil productivity and to obtain a biomass compatible with the requirements of industry, the use of the beneficial metalloid silicon, applied on leaves during plant growth, has been considered. A field study using Cannabis sativa L. (cv. Futura 75) was performed during 2 consecutive years on two sites (one soil parcel contaminated with Cd, Zn and Pb, and one taken as uncontaminated control) in the North of France. One half of the plants received weekly foliar spray of Si (2 mM). Photosynthesis-related parameters were analysed in situ, while mineral concentration and fibre properties were determined after 4 months of culture. Our results suggest that Si application improves and preserves the mechanical properties of fibres when plants are exposed to HM stress. Si was also shown to increase by 27% the Cd concentration in leaves and by 30% the Zn concentration in stems. Contaminated fibres and shives containing immobilized HM could be used for specific purposes such as inclusion in cement aglomerates.

ACL; Lolium perenne L., a common plant perennial ryegrass from Europe, northern Africa and Asia, was selected to produce biomass under field conditions. The biomass of this nonfood crop was from a highly contaminated agricultural soil by potentially toxic metals (Cd, Pb and Zn) with the aim of maintaining the agricultural vocation of these soils. In this perspective and in view of the metal concentration (Cd, Pb, Zn, macro- and micro-nutrients), the biomass of ryegrass was considered as a bio ’ore’ resource and was used as the starting material for the preparation of contemporary biosourced catalysts. The heterogeneous catalyst from the current work was successfully used in the synthesis of Moclobemide, used to treat anxiety and major depressive episodes. Through this original approach, Moclobemide was synthesized in one step, in 80% yield under solvent-free conditions.

The conception of two biosourced catalysts (biocatalysts) using stems of miscanthus from the first part of this study are described herein. The temperature and the process used to extract metals from plant as mixture of Lewis acids were investigated in detail and proved to be essential in the design of the biosourced catalysts and their catalytic efficiency. One part of the crude mixture of Lewis acids extracted from the aerial parts of miscanthus plants was used without further treatment as a homogeneous biocatalyst (M1), and the other part was supported on montmorillonite K10 to provide a heterogeneous biocatalyst (MM1). M1 and MM1 were next tested in the synthesis of moclobemide (main ingredient of a drug used to treat depression) and led to excellent yield. Additional comparative experiments with different commercial metallic salts (NaCl, KCl, CaCl2, MgCl2, CuCl2, ZnCl2, FeCl2, FeCl3, MnCl2, and AlCl3) and their mixtures were carried out and underlined the importance of the multimetallic synergy on catalytic activity. Finally, a comparison of this new synthetic method assisted by the biosourced catalyst with the previously described procedures to access moclobemide was realized by calculating their green chemistry metrics. This study revealed that the use of the biosourced catalyst led to one of the greenest synthetic methods described today to produce moclobemide.

Phytomanagement is proposed as a cost-effective and environmentally-friendly suggestion for sustainable use of large metal-contaminated areas. In the current work, the energy crop miscanthus (Miscanthus × giganteus) was grown in ex situ conditions on agricultural soils presenting a Cd, Pb and Zn contamination gradient. After 93 days of culture, shoot and root growth parameters were measured. Soils and plants were sampled as well to study the TE accumulation in miscanthus and the effects of this plant on TE mobility in soils. Results demonstrated that miscanthus growth depended more on the soils silt content rather than TE-contamination level. Moreover, soil organic carbon at T93 increased in the soils after miscanthus cultivation by 25.5–45.3%, whereas CaCl2-extractible TEs decreased due to complex rhizosphere processes driving plant mineral uptake, and organic carbon inputs into the rhizosphere. In the contaminated soils, miscanthus accumulated Cd, Pb and Zn mainly in roots (BCF in roots: Cd '' Zn > Pb), while strongly reducing the transfer of these elements from soil to all organs and from roots to rhizomes, stems and leaves (average TFs: 0.01–0.06, 0.11–1.15 and 0.09–0.79 corresponding to Cd, Pb and Zn respectively). Therefore, miscanthus could be considered a TE-excluder, hence a potential candidate crop for coupling phytostabilization and biomass production on the studied Metaleurop TE-contaminated soils.

International audience; Incidental ingestion of polluted soil particles exposes the population to toxic metal(loid)s. To refine the methods of exposure and risk assessment, it is relevant to use bioaccessible concentrations of metal(loid)s determined via in vitro digestion methods. However, some validated methods are complex and costly, involving high technical skills and numerous reagents. The objective of the present study was to evaluate the suitability of four simple chemical extractions to mimic the bioaccessible fraction of As, Cd, and Pb in the gastric (G) and gastrointestinal (GI) phases obtained using the validated UBM (unified bioaccessibility method) test. Acetic acid (0.11 M), citric acid (0.11 M), EDTA (0.16 M), and hydrochloric acid (HCl, 0.65%) were separately tested in 201 soil samples with a wide range of physicochemical parameters and metal(loid)s concentrations. Significant linear relationships were observed with HCl, EDTA, and to a lesser extent with citric acid. For the cheaper HCl method, correlations with the UBM ranged from 0.91 to 0.99 for the G phase and from 0.72 to 0.97 for the GI phase. This test can be used at least as a first-tier screening to assess the oral bioaccessibility of As, Cd, and Pb.

Miscanthus x giganteus is suggested as a good candidate for phytostabilization of metal-polluted soils. Its late harvest in winter generates large amounts of leaf litter on the soil surface. However, little is known about the mobility and the bioavailability of metals following leaf decomposition and the consequences on the succeeding culture. Ex situ artificial aging for 1, 3, and 6 months was conducted with miscanthus leaf fragments incorporated into three agricultural soils displaying a gradient concentration in Cd (0.6, 3.1 and 7.9 mg kg−1), Pb (32.0, 194.6 and 468.6 mg kg−1), and Zn (48.4, 276.3 and 490.2 mg kg−1) to simulate the leaf litter input over 20 years of miscanthus culture. We investigated the impacts on physicochemical and biological soil parameters, CaCl2-extractable metal, and their subsequent ryegrass shoot concentrations, and hence on ryegrass health. The results showed that the amended soils possessed higher pH along with greater available phosphorous and soil organic carbon values. The respiratory activity and microbial biomass carbon in the amended soils increased mainly after 1 month of aging, and decreased afterwards. Despite the higher Pb- and Zn–CaCl2 extractability in the amended soils, the phytoavailability slightly increased only in the most contaminated soils. Moreover, leaf incorporation did not affect the ryegrass biomass, photosynthetic pigment contents, nor the antioxidative enzyme activities. Conclusively, leaf incorporation induced slight variations in soil physicochemical and biological parameters, as well as metal extractability, but not to an extent that might cause a considerable threat to the subsequent culture. Nevertheless, these results are preliminary data that require confirmation by long-term in-situ experimentations as they reflect the modelization of long-term impact of leaf decomposition on soil-plant system.

The effects of P-fertilizers (mono- and di-calcium phosphates) on the bioavailability of metals and nutrients in leaves and stems of Miscanthus &times, giganteus were studied in mesocosm and field experiments in order to propose a new way for the valorization of miscanthus biomass. The concentration of potentially toxic elements was generally higher in stems than in leaves. Although P-fertilizers were added to contaminated soils under sustainable conditions (from 0.022% to 0.026% w/w), the average of leaf and stem biomass generally increased in the presence of P-fertilizers due to the changes in the speciation of phosphorus. Leaves of the investigated miscanthus may be of great interest as a catalyst in organic chemistry, since the Ca concentration was up to 9000 mg kg&minus, 1 DW. Stems represent a potential biomass that can be used as renewable resource of Lewis acids, currently used in organic syntheses (the sum of Zn, Cu, Mn, Fe, Mg, Si and Al was near 1000 mg kg&minus, 1 DW). The percentage of Cd and Pb in leaves and stems of miscanthus did not significantly change with P-fertilizers. Depending on the mesocosm and field experiments, it ranged from 0.004% to 0.016% and from 0.009% and 0.034% for Cd in leaves and stems, respectively, and from 0.004% to 0.015% and from 0.009% and 0.033% for Pb in leaves and stems, respectively.

This study is focused on the evaluation of the accumulation of Cd, Pb and Zn in five cultivars of Cichorium intybus L. (chicory) which were produced on contaminated agricultural soil. Over a growth period of 211 days, the roots and leaves were collected in four stages and then analyzed by flame atomic absorption spectrometry to measure the concentration and distribution of the target metals in these two chicory organs considering the weather and the nature of the cultivar. For all cultivars, sharp decreases of Pb (from 165 mg kg−1 to 3 mg kg−1), Cd (from 11 mg kg−1 to 5 mg kg−1) and Zn concentrations (from 157 mg kg−1 to 40 mg kg−1) in the roots were highlighted over time. The data collected enabled the calculation of the variation of the bioconcentration factor, the biological absorption coefficient and the translocation factor for Cd, Pb and Zn. These parameters were then correlated with the distribution of the fresh biomass of leaves and roots and several indicators such as chlorophyll content, flavonols, anthocyanin and nitrogen balance index were measured. The study concludes with the discussion on the ability of chicory to clean up contaminated agricultural soil. The current investigation has shown: i) a translocation of Cd (and Zn to a lesser extent) from the roots to the leaves; ii) an increase in the level of anthocyanins with the increase of the metal trace elements concentration in the leaf, while the content of chlorophyll and the nitrogen balance index decrease, which could be linked to the phenomenon of senescence; iii) an ability of the chicory to reduce the bioavailable pool of the three metal trace elements studied, in particular for Cd.

A restoration of highly contaminated garden soil is proposed as a greener alternative to the production of vegetables. Depending on potentially toxic elements and their concentration, ryegrass shoots accumulate these elements in sufficient quantity to be used as a catalyst in organic synthesis. The analysis of Cd, Pb, Zn, Cu, Fe, Mn, and Al in ashes issued from the calcination of ryegrass shoots revealed that the concentration of Zn was highest (&gt, 7000 mg kg&ndash, 1). The ratios between potential Lewis acids (Zn, Cu, Fe, Mn, and Al) to carcinogenic metals (Cd or Pb) were 191 &plusmn, 7 for LA/Cd and 235 &plusmn, 13 for LA/Pb, making the shoots of ryegrass suitable for the production of Zn-rich polymetallic biosourced catalysts. This material was used in the synthesis of idrocilamide under free-solvent condition, providing the drug in a good yield (69.9%). Data show that a limitation of waste, a maximization of the material incorporation in the process, a minimization of the steps, and an optimization of the stoichiometric factor are the main innovative factors in the current process in comparison with those previously reported.

International audience; Two kitchen garden soils (A and B) sampled in contaminated areas were amended using phosphates in sustainable quantities in order to reduce the environmental availability of potentially toxic inorganic elements (PTEs) and to favour the availability of alkali, alkali earth and micronutrients. The environmental availability of PTEs was evaluated using a potential plant for revegetation of contaminated soils (ryegrass) and a mixture of low molecular weight organic acids. Despite the highest contamination level of B, the concentration of metals was highest in the ryegrass shoots grown on A for the two harvests. These results correlated well with those obtained using low molecular weight organic acids for Cd, Zn and Cu, whereas this mixture failed to represent the transfer of nutrients due to the presence of biological and physiological mechanisms. The statistical differences between the biomass of ryegrass obtained at the first and the second harvests were attributed to the decrease of available potassium, implicated in the growth and development of plants. Phosphates increased the ratios Zn/Cd, Zn/Pb and Zn/Cu up to 176 ± 48, 38 ± 6 and 80 ± 12, respectively, and made possible the reduction of the concentration of Cd and Pb in the shoots of ryegrass by 22% and 25%, respectively. The concentration of Zn in the shoots of ryegrass from the first and the second harvests grown on soil A were in the range 1050–2000 mg kg−1, making this plant a potential biomass to (i) produce biosourced catalysts for organic chemistry applications in a circular economy concept and (ii) limit human exposure to commercial Lewis acids. A preliminary application was identified. © 2019, Springer Nature Switzerland AG.

Effects of three phosphorus fertilizers on the shoot biomass and on the accumulation of alkali, alkaline earth, and transition metals in the shoots and roots of ryegrass were studied with two contaminated garden soils. Phosphates were added in sustainable quantities in order to reduce the environmental availability of carcinogenic metals (e.g., Cd and Pb) and to enhance the bioavailability of alkali and alkaline earth metals as well as micronutrients needed by plants. Addition of Ca(H2PO4)2 was the most convenient way to (i) limit the concentration of Cd and Pb, (ii) keep constant the transfer of macro- and micronutrient from the soil to the ryegrass shoots, (iii) decrease the availability of metals, and (iv) increase the ratio values between potential Lewis acids and Cd or Pb in order to produce biosourced catalysis. For instance, the real phytoavailability was reduced by 27%&ndash, 57% and 64.2%&ndash, 94.8% for Cd and Pb, respectively. Interestingly, the real phytoavailability of Zn was the highest in the least contaminated soils. Even if soils were highly contaminated, no visual toxicity symptoms were recorded in the growing ryegrasses. This indicates that ryegrass is suitable for the revegetation of contaminated gardens. To promote the sustainable ryegrass production on contaminated soils for production of new organic fragrance and drugs in green processes according to REACH (Registration, Evaluation, Authorisation, and Restriction of Chemicals) regulation, two processes should be recommended: assisted phytostabilization of the elements, and then assisted phytoextraction by using chelators.

ACL; Three plant biomasses (miscanthus, ryegrass and wheat) have been considered for the preparation of five different sorbents evaluated for their potential to sorb cadmium and lead and four emergent organic compounds (diclofenac, sulfamethoxazole, 17α-ethynylestradiol and triclosan) from artificially contaminated water. Labcreated cartridges were filled with each sorbent and all experiments were systematically compared to activated charcoal Norit®. Results from activated charcoal, wheat straw and acidified wheat straw were supported by the Langmuir and Freundlich models. Wheat straw ashes were an excellent metal extractor that exceeded the potential of well-known activated charcoal. Acidified sorbents (wheat and ryegrass) were very effective in eliminating the selected emerging organic contaminants displaying equipotent or superior activity compared to activated charcoal. These results open the way for further in natura studies by proposing new biosource materials as new effective tools in the fight against water pollution.

Biochars are products that are rich in carbon obtained by pyrolysis processes that consist in introducing a biomass (such as wood or manure) in a closed container and heating it with little or no available air. This paper reports the impacts of pyrolysis parameters on biochar characteristics. A preliminary examination of the scientific literature revealed that the type of feedstock, the temperature, the heating rate and the gas flow were the major parameters influencing the biochar characteristics. This review highlights the multitude of biochars that can be made and shows the importance of characterizing them before their use in soils. Then we assess how the input of biochars in soils can affect soil parameters. A review of the literature showed modifications on: i) the physical properties of soils (i.e. the modification in soil structure and water retention), ii) the chemical properties of soils (i.e. the modification of pH, cation exchange capacity, nutrient availability, the organic matter content) and iii) the biological properties (i.e. the changes in microbial and faunal communities). All these modifications can lead to an increase in crop productivity, which confirms the value of biochars as a soil amendment. Moreover, biochars can also provide an advantage for soil remediation. Indeed, biochars efficiently reduce the bioavailability of organic and inorganic pollutants. In addition, this review focuses on a specific plant that can be used to produce biochars: Miscanthus, a non-wood rhizomatous C4 perennial grass. Miscanthus presents advantages for biochar production due to: i) its lignocellulosic content, ii) its silicon content, which can mitigate environmental stresses (notably for plants grown on contaminated sites) and iii) the greater surface area of the Miscanthus biochars compared to the biochars produced with other feedstock.

An ultrafast liquid chromatography method with fluorescence detection has been optimized for the determination of 15 polycyclic aromatic hydrocarbons (PAHs) using a recent Kinetex-C18 column (250 mm × 4.6 mm). This column has been recently packed with a new brand of porous shell particles with an average particle size of 5 μm to separate various compounds by liquid chromatography, operating at very low pressure. After optimization of the analytical procedure, the separation of the 15 PAHs in spiked tap water samples was achieved without coeluted products in 21.5 min at 16 °C using an aqueous/acetonitrile mobile phase under gradient concentrations with a very low flow rate (0.7–1.0 mL min−1) and low pressure values (870–1590 psi = 60–110 bar), all of these conditions being interesting from an economic point of view. The synchronization of wavelength time changing and the elution time of each compound was performed to avoid baseline deviation. The validation of the whole of the experimental procedure was conducted taking into consideration the following parameters: calibration curve, linearity, limits of detection and quantification, accuracy, sensitivity, precision, and repeatability of the retention time for each PAH. The proposed analytical procedure presented adequate linearity over a concentration range from 0.025 to 10 μg L−1 with a correlation coefficient better than 0.9980. The repeatability (relative standard deviation in percentage, n = 5) of the retention time for the different PAHs investigated ranged from 0.03% to 0.34% and the limit of detection was under 0.6 μg L−1 for most PAHs (excepted for indeno[1,2,3-c,d]pyrene, limit of detection = 1.71 μg L−1). The intraday and interday precisions were below 4%. The recovery of PAH in spiked tap water samples was variable, ranging from 96% to 109%, with relative standard deviation between 0.2% and 4.8%, depending on PAHs and their concentration levels.

International audience; This field study aimed at determining the effect of metal-polluted environments on fluctuating asymmetry (FA) level of Porcellio scaber as a measure of developmental stability (DS). For this, woodlice and litter were collected on 8 sites of northern France located either away from metal pollution source or near metallurgical smelters. Physico-chemical parameters such as pH, C/N ratio and CaCO(3) were measured in litter since they could have potential effects on woodlouse population. Moreover, Cd, Pb, and Zn concentrations in litter were determined to evaluate the contamination degree of each site. The metal body burdens were determined in woodlice to evaluate their impregnation degree. Fluctuating asymmetry levels on males and gravid females were performed on 9 traits (the 2nd and the 3rd articles of antennae, the 1st flagellum segment of the antennae, and the merus, carpus and propodus of the 6th and the 7th pereiopods) according (1) to each site and (2) to two habitat types (cf. metal-contaminated and uncontaminated habitats). Results showed close correlations between litter metal concentrations and metal body burdens in woodlice. However, contrary to the initial hypothesis that metal pollution would induce an increase of the FA level, this seemed to be lower for individuals from metal-contaminated habitats than for those from uncontaminated habitats, and particularly for males. The role of antennae and pereiopods on the foraging behavior and reproduction processes on woodlice were discussed and could explain these observations. (C) 2012 Elsevier Ltd. All rights reserved.

International audience; Aided phytostabilisation using trees and fly ashes is a promising technique which has shown its effectiveness in the management of highly metal-contaminated soils. However, this success is generally established based on topsoil physicochemical analysis and short-term experiments. This paper focuses on the long-term effects of the afforestation and two fly ashes (silico-aluminous and sulfo-calcic called FA1 and FA2, respectively) by assessing the integrity of fly ashes 10 years after their incorporation into the soil as well as the vertical distribution of the physicochemical parameters and trace elements (TEs) in the amended soils (F1 and F2) in comparison with a non-amended soil (R). Ten years after the soil treatment, the particle size distribution analysis between fly ashes and their corresponding masses (fly ash + soil particles) showed a loss or an agglomeration of finer particles. This evolution matches with the appearance of gypsum (CaSO4 2H(2)O) in FA2m instead of anhydrite (CaSO4), which is the major compound of FA2. This finding corresponds well with the dissolution and the lixiviation of Ca, S and P included in FA2 along the F2 soil profile, generating an accumulation of these elements at 30 cm depth. However, no variation of TE contamination was found between 0 and 25 cm depth in F2 soil except for Cd. Conversely, Cd, Pb, Zn and Hg enrichment was observed at 25 cm depth in the F1 soil, whereas no enrichment was observed for As. The fly ashes studied, and notably FA2, were able to reduce Cd, Pb and Zn availability in soil and this capacity persists over the time despite their structural and chemical changes. (C) 2016 Elsevier Ltd. All rights reserved.

International audience; This study aimed at determining, in the laboratory, the effects of poplar litter collected in woody habitats contaminated by heavy metals on growth and metal accumulation in the terrestrial isopod Porcellio scaber. Cd, Pb, and Zn pseudototal and CaCl(2)-extractable concentrations in litter types were determined using AAS. Juveniles were fed ad libitum, individually, for 28 days with four litter types presenting an increasing gradient of metal contamination. Individuals were weighed every week and metal body burdens were determined at the end of the experiment. From the first week until the end of the experiment, a decrease in P. scaber growth related to the increase of metal concentration in litter types was recorded. Significant correlations were observed between metal body burdens and metal concentrations in litter types. However, Cd accumulation in woodlice appeared to be related to the Cd/Zn concentration ratio in litter types. All these results showed the potential of weight gain in P. scaber as a suitable indicator for litter quality assessment with ecological relevance.

An investigation was undertaken to evaluate the empirical model developed by Pelfrene et al. (2012), predicting the human bioaccessibility of Cd and Pb in smelter-contaminated agricultural topsoils, by including other soil uses: 50 urban and 65 woody habitat topsoils collected in the same area. The results showed that land use significantly affected the pseudototal metal concentrations and their oral bioaccessibility. However, whatever the soil's physicochemical parameters and degree of contamination, the ‘agricultural’ model can be used to simulate metal gastric bioaccessibility in urban and woody habitat soils. To simulate gastrointestinal bioaccessibility, this model can be used directly if the pseudototal metal concentrations are on the same order of magnitude as those usually recorded in the agricultural soils studied or after the use of a correction factor if these concentrations are greater. These results showed that the oral bioaccessibility predictions could be applicable for further environmental risk evaluation.

Cadmium concentrations in CaCl2 extracting solutions at various concentrations were determined by graphite furnace atomic absorption using two background correctors: the deuterium and the high-speed self-reversal background correction systems. Under- and overestimation of the Cd absorbance signals in CaCl2 solutions were observed for concentrations greater than 0.005 M using the deuterium lamp while no important effect was observed using the other background correction system. The analytical performance of the spectrometer for the determination of Cd was studied in 0.01 M CaCl2 solution and single extractions were performed using reference materials and contaminated soil samples. Cadmium was determined using the two background correction systems and a third method, which consists of the use of the deuterium lamp without any chemical modifier, was added to the study. The results showed that the third method was unable to determine Cd concentrations in the CaCl2 solution due to the presence of extractable arsenic and iron. For solutions without any dilution or diluted with a very low dilution factor, the CaCl2-extractable Cd concentrations measured using the deuterium lamp were systematically below those found using the high-speed self-reversal method. These differences were explained by the presence of chloride ions in the atomization step.

Environ Pollut 859TF Times Cited:2 Cited References Count:50; International audience; An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using : a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P2O5, free Fe-Mn oxide, and pseudo total Aland trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.

Zinc was bound on montmorillonite K10 by cation exchange to obtain a catalyst named clayzic. In the Friedel-Crafts benzylation of 1,4-dimethoxybenzene, this catalyst was used for the synthesis of substituted diphenylmethanes using 4-chlorobenzyl chloride and 4-bromobenzyl bromide. During the reaction, sub-products from a second benzylation reaction process were observed. For a better understanding of their formation, reactions were carried out at different times to obtain data on the progress of benzylation and the relative ratio of each product was calculated using two different analytical methods. It was shown that the selectivity and reactivity of both aryl halides were reversed under these experimental conditions contrary to those obtained using the more conventional catalyst, zinc dichloride. These results were explained by geometrical and electronic considerations. It was found that the formation of transition states and Wheland intermediates from aryl bromide and chloride in the presence of clayzic can be explained in terms of preferential absorption. Moreover, the high percentage of 4-chlorobenzyl chloride conversion was attributed to its covalent radius, which is smaller than that of Br. At the same time it was shown that the presence of a Brönsted acid, due to the liberation of HCl during the benzylation, is responsible for the poisoning of the clayzic catalyst. Moreover, poisoning effect of the bromine anion could not be excluded.

Ecol Eng Sp. Iss. SI 787XM Times Cited:7 Cited References Count:140; International audience; Studies on two lead and zinc smelters in Northern France (Metaleurop Nord and Umicore) showed that the level of metallic contamination of kitchen garden soils is higher than the agricultural soils located in the same environment. This results most particularly from cropping practices and the addition of various products. Due to the physical and chemical parameters of these soils, the behaviour and transfer of pollutants towards various plants (grass, trees, and vegetables) may be perceptibly different than what is observed on agricultural soils. For a better understanding of pollutant behaviour in kitchen garden topsoils, the Cd, Pb and Zn was fractionated using the SM&T protocol and various extracting solutions (CaCl(2), acetic acid, and citric acid) to evaluate their mobility in two highly contaminated soils chosen in the area affected by the past atmospheric emissions of the two smelters. In addition, agricultural topsoil was sampled in a non-massively contaminated area and was therefore chosen as the control soil. The three soils were amended with a mixture of hydroxyapatite (HA) and diammonium phosphate (DAP). At 6 months, extracting procedures were carried out to evaluate the effects of the amendment on the mobility of Cd, Pb and Zn. This step was then supplemented by an evaluation of the impact of the amendment on the phytoavailability of pollutants, which was determined in plant uptake studies with ryegrass (Lolium perenne L) by considering only the pollutant concentrations in their shoots. Two experiments were carried out. In the first one, unamended and amended soils and ryegrass were watered with distilled water (pH = 7). In the second one, osmosed water (pH = 5.5) was used to evaluate the effects of the acid water-phosphate amendment system on the mobility and phytoavailability of Cd, Pb and Zn. Six months after the start of the experiments, the selective extractions showed that the effectiveness of the amendment studied depended on the element, the soil and the water's pH. Reductions of metal eluted from the contaminated soils were 1.5-37.9% for Cd, and 9.1-80.9% for Pb. Application of P amendment to the combination of osmosed water was generally the most effective for immobilising Cd and Pb elution. In contrast, the mixture of HA and DAP was ineffective for reducing Zn elution. The plant-fresh biomass yield was significantly (p < 0.05) increased by the combination of P amendment and distilled water, whereas a reduction of biomass was recorded with the combined amendment and osmosed water. Addition of P amendment generally reduced Pb uptake in ryegrass shoots (1-47%), while both Cd and Zn were increased by 17.9-79% and 0.45-100%, respectively.

Due to anthropogenic activities, large extends of soils are highly contaminated by Metal Trace Element (MTE). Aided phytostabilisation aims to establish a vegetation cover in order to promote in situ immobilisation of trace elements by combining the use of metal-tolerant plants and inexpensive mineral or organic soil amendments. Eight years after Coal Fly Ash (CFA) soil amendment, MTE bioavailability and uptake by two plants, Lolium perenne and Trifolium repens, were evaluated, as some biological markers reflecting physiological stress. Results showed that the two plant species under study were suitable to reduce the mobility and the availability of these elements. Moreover, the plant growth was better on CFA amended MTE-contaminated soils, and the plant sensitivity to MTE-induced physiological stress, as studied through photosynthetic pigment contents and oxidative damage was lower or similar. In conclusion, these results supported the usefulness of aided phytostabilisation of MTE-highly contaminated soils.

International audience; The spatial distribution of total and CaCl(2)-extracted Cd, Pb and Zn concentrations in smelter-impacted soils was investigated over a polluted site (40km(2)) in Northern France. The study was conducted on 262 soils sampled in woody habitats. Total and extracted concentrations of trace metals (TMs) rose up to 2402 and 59.5mgkg(-1) for Cd, 41 960 and 13.7mgkg(-1) for Pb, 38 760 and 143.0mgkg(-1) for Zn, respectively. The spatial dependence of both total and extracted concentrations showed a high spatial auto-correlation and ordinary kriging was used to predict soil concentrations. Investigating which variables influenced metal concentrations and their spatial distribution, we found that total concentrations mostly depended on the distance from the smelter, the wind and the organic carbon, while extracted concentrations were mainly modulated by the pH. Conditionally to those variables, other soil properties and landscape characteristics influenced both total and extracted concentrations. We conclude that total and extracted TM concentrations are governed by different processes which act at various spatial ranges: total concentrations are mainly related to input and retention of metals (large scale) whereas extracted concentrations were mainly explained by factors controlling metal solubility in soils (local scale). Spatial distributions of total and extracted TMs differed over the area, which should be considered for risk assessment. Maps of risk based on the US EPA's Eco-SSLs (for plants, invertebrates and vertebrates) were realized, showing that wildlife may be at risk but that the relevance of Eco-SSL values is questionable.

The contamination of soils by heavy metals engenders important environmental and sanitary problems in Northern France where a smelter has been located for more than one hundred of years. It has been one of the most important Pb production sites in Europe until its closedown in March 2003. Ore smelting process generated considerable atmospheric emissions of dust. Despite an active environmental strategy, these emissions were still significant in 2002 with up to 17 tonnes of Pb, 32 tonnes of Zn and 1 tonne of Cd. Over the years, the generated deposits have led to an important contamination of the surrounding soils. Previous studies have shown pollutant transfers to plants, which can induce a risk for human and animal health. The objective of this study was to evaluate the consequences of the smelter closedown on the Cd and Pb contents of wheat (grain and straw) cultivated in the area. Paired topsoil and vegetable samples were taken at harvest time at various distances to the smelter. The sample sites were chosen in order to represent a large range of soil metal contamination. Sampling was realised on several wheat harvests between 1997 and 2003. 25 samples were collected before the smelter closedown and 15 after. All ears of about 1 m long of two rows were manually picked and threshed in the lab. Similarly, straw was harvested at the same time. Total metal contents in soil and wheat samples were quantified. A negative correlation between metal concentrations in soil and the distance to the smelter was shown. The wheat grain and straw showed significant Cd and Pb contents. The straw had higher metal contents than the grain. During the smelter activity, the grain contents were up to 0.8 mg kg−1 DM of Cd and 8 mg kg−1 DM of Pb. For the straw, maximum contents were 5 mg kg−1 DM of Cd and 114 mg kg−1 DM of Pb. After the smelter closedown, we observed a very large decrease of Pb in the grain (82%) and in the straw (91%). A smaller decrease was observed for Cd in grain. Despite this improvement, 80% of the studied samples remained non-acceptable for human consumption, according to the European legislation values, due to a high Cd content. Results highlighted a difference in metal accumulation in the plant organs as well as a difference in metal uptake. The approach pointed out the importance of atmospheric fallout in the wheat contamination pathways for Pb. The smelter closedown has lead to a decrease of the Pb content in wheat. It is interesting to relate this finding with the lead blood levels in children living close to the smelter. Those results have confirmed the importance of dust fallout in the plant contamination pathways. Before the closedown, Pb measured in the plant was principally originating from the smelter dust emissions. It raised the question of the sanitary risks for humans and animals living in the surrounding area of the smelter. In the literature, very few articles take the dust deposit as contamination pathways for crops into consideration. However, in highly contaminated sites, this pathway can be very important. Thus, it would be worthy studying the uptake of metal contaminants by plants through the foliar system.