Valérie Sappin-Didier

Speciation of zinc in contaminated soils.

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100 L kg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.

A kinetic approach to predict soil trace metal bioavailability : preliminary results

The presence of large amounts of trace metals creates a hazard in some soils that is strongly related to the speciation of these metals. The aim of this work was to apply an operationally defined fractionation based on kinetics, which could distinguish “labile” (quickly extracted) and “non-labile” (or slowly labile i.e. slowly extracted) cations by using the extraction kinetics of trace metals by EDTA. This kinetic fractionation was applied to 10 unpolluted soil samples from Burgundy (France) in order to determine their labile concentrations of lead and cadmium. According to this method, cadmium was found to be more mobile than lead, with respect to both labile concentration and the kinetic constants. Moreover, it was also found that the labile concentration of cadmium was related (R2=0.6) to its concentration in wheat shoots; however, no such correlation was found for lead.

Multimetallic contamination from Zn-ore smelter: solid speciation and potential mobility in riverine floodbank soils of the upper Lot River (SW France)

The former Zn-ore smelting activity in Viviez (Aveyron, France) resulted in multimetallic contamination of the upper Lot River system (SW France). This study addresses for the first time the metals/metalloids mobility in impacted riverside fluvial soils due to reducing conditions during long-term flooding events. Six impacted riverside fluvio-soils were sampled along the Riou Mort and Lot rivers. Their levels of contamination decrease with the distance from the contamination source. Higher enrichment factors (EF) relative to French average soil metallic content occur 1 km far from the contamination source and vary from 3 for Sn, to 5 for As, 9 for Sb, 27 for Pb, 40 for Zn and 63 for Cd. At 20 km downstream from the contamination source, EF still reach a value of 3 for Cd and Zn. A micro-physical mineralogical characterisation of contaminated soils revealed a variety of metal-bearing phases: metallic compounds, oxides and sulphides, Fe oxides, glass and silicates as well as coke. Sequential chemical extraction experiments were conducted on the most contaminated soil in order to identify which mineral phases were the best candidates to release metals/metalloids. At the end of experiments more than 70 % of total Cd and As, 55 % of Zn and Sb, and 40 % of Pb and Sn were extracted from the soil. Only Cd appeared as readily mobilised, with 33 % of its total amount being extracted in the first steps of experiments. Under reducing conditions, iron oxyhydroxides, franklinite and multimetallic oxides are the best candidates, in decreasing order of importance, for metals/metalloids release from the soil.

Multielementary (Cd, Cu, Pb, Zn, Ni) Stable Isotopic Exchange Kinetic (SIEK) Method To Characterize Polymetallic Contaminations

A new method is proposed to precisely and simultaneously quantify the exchangeable pool of metals in soils and to describe its reactivity at short- and long-term. It is based on multielementary Stable Isotopic Exchange Kinetics (multi-SIEK), first validated by a comparison between two monoelementary radioactive ((109)Cd*, (65)Zn*) IEK experiments, a mono- ((106)Cd) and multi- ((62)Ni, (65)Cu, (67)Zn, (106)Cd, (204)Pb) SIEK. These experiments were performed on a polluted soil located near the Zn smelter plant of Viviez (Lot watershed, France). The IEK results obtained for Cd and Zn were consistent across the experiments. (109)Cd*, (65)Zn* IEK, and multi-SIEK were then applied on 3 non- and moderate impacted soils that also provided consistent results for Cd and Zn. Within these experimental conditions, it can be concluded that no competition occurs between Cd, Zn, and the other metals during SIEK. Multi-SIEK results indicate that the isotopically exchangeable pool of Ni, Zn, and Cu are small (E(Ni), E(Zn), and E(Cu) values up to 17%) whatever the pollution degree of the soils considered in this study and whatever the duration of the interaction. On the contrary, Cd displays the highest E values (from 35% to 61% after 1 week), and E(Pb) displays a maximum value of 26% after 1 week. The multi-SIEK provides useful information on metal sources and reactivity relationship. Ni would be located in stable pedogenic phases according to its very low enrichment factor. The low E(Zn) and E(Cu) are consistent with location of Zn and Cu in stable phases coming from tailings erosion. Though Pb enrichments in soils may also be attributed to tailings particles, its larger exchangeable pool suggests that the Pb-bearing phases are more labile than those containing Zn and Cu. The high mobility of Cd in upstream soils indicates that it has been mostly emitted as reactive atmospheric particles during high temperature ore-treatment.

Biomarker responses of Eisenia andrei to a polymetallic gradient near a lead mining site in North Tunisia

Eisenia andrei earthworms were exposed for 7 and 14 days to six samples of soil taken from around an abandoned lead (Pb) mine and characterized by different levels of metal contamination (S6-S1, this latter being the most contaminated soil). The organisms were analyzed for metal bioaccumulation and for biological parameters as biomarkers of stress (lysosomal membrane stability; lipofuscin lysosomal content; lysosomal/cytoplasmic volume ratio) and genotoxicity (Micronucleus frequency). Chemical analysis showed the loads of Pb, Cd, Zn, and Cu in the worms following exposure. Among the stress biomarkers, lysosomal membrane stability was significantly affected in the coelomocytes of the earthworms exposed already 7 days to different contaminated soils. Organisms exposed for 14 days to S1 showed in the cells of the chloragogenous tissue, a particularly relevant increase in lipofuscin, a biomarker of oxidative stress, and an increase in the lysosome/cytoplasm volume ratio, indicating stressful condition at the tissue level. Moreover, in the same conditions, a decrease in total body weight was observed. At the longer exposure time, the coelomocytes of worms exposed to S1, S2, and S3 (soils with higher metal concentrations) showed a significant increase in micronuclei (MNi) frequency. Expressions of the P21 and topoisomerase genes, which are involved in DNA repair, showed significant up-regulation in the cells of worms exposed to S1, S2, S3, S4 and to a less extend S6. This may indicate that the worms were only able to successfully reduce the level of DNA damage in S4 and S5 if considering MN frequency data. The biomarker data was integrated by the Earthworm Expert System, allowing an objective interpretation of the complex biological data and clearly defining the areas in which the presence of chemicals is toxic for the edaphic organisms.

Polymetallic pollution from abandoned mines in Mediterranean regions: a multidisciplinary approach to environmental risks

Abandoned mines are a recurrent problem for nearby communities in Mediterranean regions because mine tailings represent a major source of polymetallic contamination. Metal contaminants are emitted in mining areas and dispersed by wind and water erosion in the surroundings. The goal of this literature review was to identify the specific features of polymetallic contamination arising from abandoned mines in the Mediterranean regions. Mediterranean climate conditions and local geochemical context are the most important factors that control the metal-bearing particle dispersion toward the different compartments of ecosystems. Acid mine drainage, as an important source of damage to the environment, is limited to a certain extent by the predominance of carbonate rocks in the Mediterranean regions. In opposite, aeolian contamination is specific to the semiarid conditions of the Mediterranean climate. In this context, impacts on different compartments such as agricultural soils and edible plants or human populations were underlined. The analysis of environmental laws and regulations of North and South Mediterranean countries shows that one of the main differences is the lack of identification and definition of mining waste as a public concern in the latter countries. In order to limit the transfer of contaminants from mining waste to the different components of the environment, phytostabilization of mine tailings was considered as the more adapted green technology even in the Mediterranean region where water access is limited. Finally, this review of polymetallic pollution from abandoned mines in Mediterranean regions enabled to identify priority actions for future research.