Béatrice Marin

Factors affecting distribution and mobility of trace elements (Cu, Pb, Zn) in a perennial grapevine (Vitis vinifera L.) in the Champagne region of France.

Soil and Vitis vinifera L. (coarse and fine roots, leaves, berries) concentration and geochemical partitioning of Cu, Pb and Zn were determined in a contaminated calcareous Champagne plot to assess their mobility and transfer. Accumulation ratios in roots remained low (0.1-0.4 for Cu and Zn, <0.05 for Pb). Differences between elements resulted from vegetation uptake strategy and soil partitioning. Copper, significantly associated with the oxidisable fraction (27.8%), and Zn with the acid soluble fraction (33.3%), could be mobilised by rhizosphere acidification and oxidisation, unlike Pb, essentially contained in the reducible fraction (72.4%). Roots should not be considered as a whole since the more reactive fine roots showed higher accumulation ratios than coarse ones. More sensitive response of fine roots, lack of correlation between chemical extraction results and vegetation concentrations, and very limited translocation to aerial parts showed that fine root concentrations should be used when assessing bioavailability.

Comparison of microwave-assisted digestion procedures for total trace element content determination in calcareous soils

The aim of the study was to determine total trace (Cd, Co, Cr, Cu, Mn, Pb and Zn) and major (Al and Fe) element concentrations in calcareous soils using microwave-assisted digestion procedures. The literature showing lack of consensus regarding digestion procedures and unsatisfying recoveries for calcareous materials, four procedures using various acid combinations (HCl, HNO(3), H(2)O(2), HF) and volumes were tested using a certified reference material (CRM 141R) and natural calcareous soil samples. Digests were analysed by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Repeatability (R.S.D. <5%) and recoveries (82-116%) showed that the procedures were precise and accurate for most elements. Five calcareous soil samples from a Champagne vineyard plot were, then, subjected to these procedures. In calcareous materials, the presence of HF resulted in Al being severely underestimated (recovery <5%) and Co overestimated (recovery >124%) due to complex formation or spectrochemical interferences, respectively. As digestion was not significantly influenced by the addition of H(2)O(2), the procedure corresponding to Aqua regia (HCl-HNO(3)) appeared as the best compromise and was selected for further multielemental environmental studies on calcareous materials, even if the absence of HF could lead to incomplete digestion of accessory silicate minerals. Results for a vineyard plot showed that the soils were contaminated (3.65 mg kg(-1) Cd, 67 mg kg(-1) Cr, 278 mg kg(-1) Cu, 143 mg kg(-1) Pb and 400 mg kg(-1) Zn) as a consequence of urban waste and copper-treatment applications.

Lead distribution in soils impacted by a secondary lead smelter: Experimental and modelling approaches

Smelting activities are one of the most common sources of trace elements in the environment. The aim of this study was to determine the lead distribution in upper horizons (0-5 and 5-10cm) of acidic soils in the vicinity of a lead-acid battery recycling plant in northern France. The combination of chemical methods (sequential extractions), physical methods (Raman microspectroscopy and scanning electron microscopy with an energy dispersive spectrometer) and multi-surface complexation modelling enabled an assessment of the behaviour of Pb. Regardless of the studied soil, none of the Pb-bearing phases commonly identified in similarly polluted environments (e.g., anglesite) were observed. Lead was mainly associated with organic matter and manganese oxides. The association of Pb with these soil constituents can be interpreted as evidence of Pb redistribution in the studied soils following smelter particle deposition.

Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies.

Response of bacterial communities to Pb smelter pollution in contrasting soils

Anthropogenic inputs of trace elements (TE) into soils constitute a major public and environmental health problem. Bioavailability of TE is strongly related to the soil physicochemical parameters and thus to the ecosystem type. In order to test whether soil parameters influence the response of the bacterial community to TE pollution, we collected soil samples across contrasting ecosystems (hardwood, coniferous and hydromorphic soils), which have been contaminated in TE and especially lead (Pb) over several decades due to nearby industrial smelting activities. Bacterial community composition was analysed using high throughput amplicon sequencing and compared to the soil physicochemical parameters. Multivariate analyses of the pedological and biological data revealed that the bacterial community composition was affected by ecosystem type in the first place. An influence of the contamination level was also evidenced within each ecosystem. Despite the important variability in bacterial community structure, we found that specific bacterial groups such as γ-Proteobacteria, Verrucomicrobia and Chlamydiae showed a consistent response to Pb content across contrasting ecosystems. Verrucomicrobia were less abundant at high contamination level whereas Chlamydiae and γ-Proteobacteria were more abundant. We conclude that such groups and ratios thereof can be considered as relevant bioindicators of Pb contamination.

New dendritic ionic liquids (DILs) for extraction of metallic species from water

Four dendritic ionic liquids (DILs) have been easily synthesized from 3rd generation PAMAM and PPI: PAMAM G3 NH3+ Tf2N− (1), PPI G3 NH3+ Tf2N− (2), PPI G3 NH2 Me+ BF4− (3) and PAMAM G3 NH2 Me+ BF4− (4). These DILs are fully characterized by spectroscopic methods (1H, 13C and 19F NMR) and elemental analysis. Compound 1 is hydrophobic while compounds 2–4 are hydrophilic. In order to apply these DILs for the extraction of aqueous metallic cations (Cu2+, Ni2+, Pb2+, Cd2+, and Ag+), liquid–liquid extraction and dialysis were performed. ICP technology has been used to reveal the amount of metallic cation that has been extracted. Compound 1 shows the best results especially for the extraction of Cu2+, Pb2+ and Ag+ cations (up to 98%). Two processes have been employed: liquid–liquid extraction and dialysis.