Géraldine Bidar

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.

Effects of grinding and shaking on Cd, Pb and Zn distribution in anthropogenically impacted soils.

The effects of grinding size and shaking process on the results of Cd (cadmium), Pb (lead) and Zn (zinc) distribution measurements three agricultural and three kitchen garden soils highly contaminated by past atmospheric fallout of two lead and zinc smelters in northern France were studied. The physico-chemical parameters and pseudo-total concentration of metals within these soils were determined. The fractionation of metals was performed in triplicate, using the procedure recommended by the Standards, Measurements and Testing program (SM&T), on each air-dried soil sample, ground to pass through 2-mm, 0.315-mm and 0.250-mm sieves and using a reciprocating or rotary shaker. The samples were analysed by flame or electrothermal absorption atomic spectrometry using a self-reversal background system. For both shaking processes, the grinding size had no effect on the fractionation of metals in contaminated agricultural soils. In contrast, using a reciprocating shaker, the fractionation of metals in the kitchen garden samples sieved at <2mm was so different that in the samples prepared to pass through the 0.315-mm and 0.250-mm sieves. Therefore changes (use of a 50 mL graduated polypropylene centrifuge tube, evaporation of the solution to a fixed volume in step 3 and the use of an automatic shaking heating bath) were made to the initial procedure and a rotary shaker was used to improve the suspension of the soil samples during extraction. For all grinding sizes, the fractionation of the three metals contained in the contaminated kitchen garden soil samples was successfully achieved. Nevertheless, some discrepancies from samples sieved at <2mm were obtained. On the other hand, it is worth noting that the effect of the type of shaker on the distribution of metal depended on the soil and the grinding size. From an analytical point of view, precision and trueness were improved after optimisation of the procedure for all sequential extraction procedure steps. The best results were obtained for samples sieved at <0.250 mm. Similar trends were obtained using the CRM BCR(®)-701 certified material. All the results showed that optimisation of the sequential extraction procedure could be adopted for the Cd-, Pb- and Zn-partitioning in contaminated kitchen garden soils with high-level anthropogenic sources.

Sustainability of an in situ aided phytostabilisation on highly contaminated soils using fly ashes: Effects on the vertical distribution of physicochemical parameters and trace elements

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 2H2O) 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.

Prediction of Extractable Cd,Pb and Zn in Contaminated Woody Habitat Soils Using a Change Point Detection Method

Accumulation of heavy metals in soils poses a potential risk to plant production, which is related to availability of the metals in soil. The phytoavailability of metals is usually evaluated using extracting solutions such as salts, acids or chelates. The purpose of this study was to identify the most significant soil parameters that can be used to predict the concentrations of acetic and citric acid-extractable cadmium (Cd), lead (Pb) and zinc (Zn) in contaminated woody habitat topsoils. Multiple linear regression models were established using two analysis strategies and three sets of variables based on a dataset of 260 soil samples. The performance of these models was evaluated using statistical parameters. Cation exchange capacity, CaCO3, organic matter, assimilated P, free Al oxide, sand and the total metal concentrations appeared to be the main soil parameters governing the solubility of Cd, Pb and Zn in acetic and citric acid solutions. The results strongly suggest that the metal solubility in extracting solutions is extractable concentration-dependent since models were overall improved by incorporating a change point. This change point detection method was a powerful tool for predicting extractable Cd, Pb and Zn. Suitable predictions of extractable Cd, Pb and Zn concentrations were obtained, with correlation coefficient (adjusted r) ranging from 0.80 to 0.99, given the high complexity of the woody habitat soils studied. Therefore, the predictive models can constitute a decision-making support tool for managing phytoremediation of contaminated soils, making recommendations to control the potential bioavailability of metals. The relationships between acetic and/or citric acid-extractable concentrations and the concentrations of metals into the aboveground parts of plants need to be predicted, in order to make their temporal monitoring easier.