Christophe Waterlot

Cd, Pb and Zn Oral Bioaccessibility of Urban Soils Contaminated in the Past by Atmospheric Emissions from Two Lead and Zinc Smelters

Ingestion of dust or soil particles could pose a potential health risk due to long-term metal trace element (MTE) exposure. Twenty-seven urban topsoil samples (kitchen garden and lawn) were collected and analyzed for Cd, Pb and Zn using the unified Bioaccessibility Research Group of Europe (BARGE) method (UBM) test to estimate the human bioaccessibility of these elements. The quantities of Cd, Pb and Zn extracted from soils indicated, on average, 68, 62 and 47% bioaccessibility, respectively, in the gastric phase and 31, 32 and 23% bioaccessibility, respectively, in the gastro-intestinal phase. Significant positive correlations were observed between concentrations extracted with UBM and total MTE contents. Stepwise multiple regression analysis showed that human bioaccessibility was also affected by some physico-chemical soil parameters (i.e. total nitrogen, carbonates, clay contents and pH). The unified test presents some valuable data for risk assessment. Indeed, the incorporation of oral bioaccessible concentrations into risk estimations could give more realistic information for health risk assessment.

Spatial distribution of metals in smelter-impacted soils of woody habitats: Influence of landscape and soil properties, and risk for wildlife

The spatial distribution of total and CaCl(2)-extracted Cd, Pb and Zn concentrations in smelter-impacted soils was investigated over a polluted site (40 km(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 59.5 mg kg(-1) for Cd, 41 960 and 13.7 mg kg(-1) for Pb, 38 760 and 143.0 mg kg(-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 EPAs 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.

Contamination, Fractionation and Availability of Metals in Urban Soils in the Vicinity of Former Lead and Zinc Smelters, France

Abstract Soil contamination by metals from anthropogenic activities (e.g., mining and smelting) is a major concern for the environment and human health. Environmental availability of cadmium (Cd), lead (Pb), zinc (Zn), copper (Cu), and indium (In) in 27 urban soils located around two former Pb and Zn smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry (FAAS or ETAAS), depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical procedure. Metal partitioning was conducted using a four-step sequential extraction procedure. The results showed that Cd and Zn were mainly in the acid-extractable and reducible forms in the urban soils studied. In contrast, Pb and In were largely in the reducible fraction. However, in some samples, the amount of In extracted in the residual or exchangeable fraction was higher than that in the reducible fraction. Copper was mainly found in the reducible and residual fractions. A pot experiment was conducted in a glasshouse with seven soils (six contaminated and one uncontaminated) and two plant species, ryegrass and lettuce. The results showed transfer of metals from the contaminated soils to the shoots of ryegrass and the edible part of lettuce. The metal bioconcentration factor was in the order of Cd ≫ Cu > In > Zn ≫ Pb for lettuce leaves, whereas for ryegrass shoots, three orders were found, Cd > Zn > Cu ≫ In > Pb, Cd ≥ In > Zn > Cu ≫ Pb, and Zn > Cd > Cu > In > Pb, depending on the physico-chemical properties of the soils, such as pH, cation exchange capacity, carbonates, and organic matter. It was established that the metal toxicity was related to the contamination levels and the physico-chemical properties, including pH, organic matter, and in a lesser extent, Ca, Mg, and phosphorus contents, of the soils. However, it was shown that lettuce could grow on soils having high Cd and CaCO3 contents. Cadmium was one of the most available metals while Pb was always the least available in the soils studied.

Bioaccessibility of trace elements as affected by soil parameters in smelter-contaminated agricultural soils : a statistical modeling approach

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: (i) 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 (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and 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.

Influence of fly ash aided phytostabilisation of Pb, Cd and Zn highly contaminated soils on Lolium perenne and Trifolium repens metal transfer and physiological stress

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.

Assessment of fly ash-aided phytostabilisation of highly contaminated soils after an 8-year field trial Part 2. Influence on plants

Aided phytostabilisation is a cost-efficient technique to manage metal-contaminated areas, particularly in the presence of extensive pollution. Plant establishment and survival in highly metal-contaminated soils are crucial for phytostabilisation success, as metal toxicity for plants is widely reported. A relevant phytostabilisation solution must limit metal transfer through the food chain. Therefore, this study aimed at evaluating the long-term efficiency of aided phytostabilisation on former agricultural soils highly contaminated by cadmium, lead, and zinc. The influence of afforestation and fly ash amendments on reducing metal phytoavailability was investigated as were their effects on plant development. Before being planted with a tree mix, the site was divided into three plots: a reference plot with no amendment, a plot amended with silico-aluminous fly ash and one with sulfo-calcic fly ash. Unlike Salix alba and Quercus robur, Alnus glutinosa, Acer pseudoplatanus and Robinia pseudoacacia grew well on the site and accumulated, overall, quite low concentrations of metals in their leaves and young twigs. This suggests that these three species have an excluder phenotype for Cd, Zn and Pb. After 8 years, metal availability to A. glutinosa, A. pseudoplatanus and R. pseudoacacia, and translocation to their above-ground parts, strongly decreased in fly ash-amended soils. Such decreases fit well together with the depletion of CaCl(2)-extractable metals in amended soils. Although both fly ashes were effective to decrease Cd, Pb and Zn concentrations in above-ground parts of trees, the sulfo-calcic ash was more efficient.

Assessment of fly ash-aided phytostabilisation of highly contaminated soils after an 8-year field trial: part 1. Influence on soil parameters and metal extractability.

Sustainable management of large surface areas contaminated with trace elements is a real challenge, since currently applied remediation techniques are too expensive for these areas. Aided phytostabilisation appears to be a cost efficient technique to reduce metal mobility in contaminated soils and contaminated particle spread. In this context, this study aimed at evaluating the long-term efficiency of aided phytostabilisation on former agricultural soils highly contaminated with trace elements. The influence of afforestation and fly ash amendments to reduce metal mobility was investigated. Before being planted with a tree mix, the study site was divided into three plots: a reference plot with no amendment, the second amended with silico-aluminous fly ash and the third with sulfo-calcic fly ash. After eight years, some soil physico-chemical parameters, including cadmium (Cd), lead (Pb) and zinc (Zn) extractability were modified. In particular, pH decreased on the whole site while organic carbon content increased. The alteration of these parameters influencing trace element mobility is explained by afforestation. Over time, concentrations of CaCl(2)-extractable metals increased and were correlated with the soil pH decrease. In the amended soils, extractable Cd, Pb and Zn concentrations were lower than in the reference soil. The results indicated that the two fly ashes buffered natural soil acidification due to vegetation development and limited trace element mobility and thus could limit their bioavailability. For long-term phytostabilisation, special attention should be focused on the soil pH, metal mobility and phytoavailability analysis.

Growth and metal accumulation in Porcellio scaber exposed to poplar litter from Cd-, Pb-, and Zn-contaminated sites

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.

Gene expression analysis of 4 biomarker candidates in Eisenia fetida exposed to an environmental metallic trace elements gradient: A microcosm study

Past activities of 2 smelters (Metaleurop Nord and Nyrstar) led to the accumulation of high amounts of Metal Trace Elements (TEs) in top soils of the Noyelles-Godault/Auby area, Northern France. Earthworms were exposed to polluted soils collected in this area to study and better understand the physiological changes, the mechanisms of acclimation, and detoxification resulting from TE exposure. Previously we have cloned and transcriptionally characterized potential biomarkers from immune cells of the ecotoxicologically important earthworm species Eisenia fetida exposed in vivo to TE-spiked standard soils. In the present study, analysis of expression kinetics of four candidate indicator genes (Cadmium-metallothionein, coactosin like protein, phytochelatin synthase and lysenin) was performed in E. fetida after microcosm exposures to natural soils exhibiting an environmental cadmium (Cd) gradient in a kinetic manner. TE body burdens were also measured. This microcosm study provided insights into: (1) the ability of the 4 tested genes to serve as expression biomarkers, (2) detoxification processes through the expression analysis of selected genes, and (3) influence of land uses on the response of potential biomarkers (gene expression or TE uptake).

Elaboration, characteristics and advantages of biochars for the management of contaminated soils with a specific overview on Miscanthus biochars

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.