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.

Effect of nitrate and ammonium fertilization on Zn, Pb, and Cd phytostabilization by Populus euramericana Dorskamp in contaminated technosol.

This study aimed at assessing the effect of nitrogen addition under two forms, nitrate and ammonium, on the stabilization of Zn, Pb, and Cd by Populus euramericana Dorskamp grown in contaminated soils for 35 days under controlled conditions. Temporal changes in the soil pore water (SPW) were monitored for pH, dissolved organic carbon (DOC), and total dissolved concentrations of metals in the soils rhizosphere. Rhizospheric SPW pH decreased gradually with NH4(+) addition and increased with NO3(-) addition up to one unit, while it slightly decreased initially then increased for the untreated control soil DOC increased with time up to six times, the highest increase occurring with NH4(+) fertilization. An increase in the metal concentrations in the rhizospheric SPW was observed for NH4(+) addition associated with the lowest rhizospheric SPW pH, whereas the opposite was observed for the control soil and NO3(-) fertilization. Fertilization did not affect plant shoots or roots biomass development compared to the untreated control (without N addition). Metals were mostly accumulated in the rhizosphere and N fertilization increased the accumulation for Zn and Pb while Cd accumulation was enhanced for NH4(+) addition. Collectively, our results suggest metal stabilization by P. euramericana Dorskamp rhizosphere with nitrogen fertilization and are potential for phytostabilization of contaminated technosol.

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.

Potentially toxic element fractionation in technosoils using two sequential extraction schemes.

This study reports the chemical fractionation of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated technosoils of two former smelting and mining areas using two sequential extraction schemes. The extraction schemes used in this study were the Tessier's scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidizable, and residual to compare the results obtained from two sequential extraction schemes. Surface soils were samples from a waste landfill contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (MDN; North France) and from a settling basin contaminated with PTE such as As, Pb, and Sb located at La Petite Faye (LPF; Limoges, France). The study of the Zn, Pb, Cd, As, and Sb partitioning in the acid soluble, reducible, oxidizable, and residual fractions of the technosoils revealed that Zn, Cd, and Pb were mainly associated with the acid soluble and reducible fractions for MDN site, while As, Sb, and Pb were associated with residual fraction for LPF site. Fractionation results indicate that the percentages of Zn, Pb, Cd, As, and Sb extracted in Fe-Mn oxide bound fraction of Tessier's scheme were always higher than those extracted by modified BCR scheme. This may be attributed to the stronger Tessier's scheme conditions used to extract this fraction. In contrast the percentages of Zn, Pb, Cd, As, and Sb extracted in the organic fraction of the modified BCR scheme were always higher than those of the Tessier's scheme. The order of mobility of PTE was as follows: Cd > Zn > Pb in MDN site and As > Sb > Pb in LPF site. PTE were distributed in all soil fractions, with the most relevant enrichments in extractable and residual fractions. A significant amount of Cd, Pb, and Zn were rather mobile, which suggests that these elements can be readily available to plants and soil organisms.