Emmanuel Joussein

Sorption of Cd(II) and Pb(II) by exopolymeric substances (EPS) extracted from activated sludges and pure bacterial strains: modeling of the metal/ligand ratio effect and role of the mineral fraction.

The present study deals with the sorption of Cd(II) and Pb(II) by exopolymeric substances (EPS) extracted from activated sludges or pure bacterial strains. The percentage of sorbed metal increases with the concentration of the EPS-water solution. Pb(II) always presents a higher affinity than Cd(II) for EPS. For the EPS extracted from pure bacterial strains, only one global binding constant from a simple equilibrium sorption model, may be used to assess the effect of microbial products such as EPS on Cd(II) and Pb(II) speciation or mobility in the environment. However, for EPS extracted from activated sludges, the wide variation of the global binding constants determined for Cd(II) and Pb(II) do not permit such a simple approach. The differences in sorption to metals between the two types of EPS (bacterial, activated sludges) could be explained by the differences in EPS composition: organic macromolecules, as well as the nature of the mineral fraction.

Adsorption of copper, cadmium, lead and zinc onto a synthetic manganese oxide

Due to its simple and inexpensive synthesis, a new amorphous hydrous manganese oxide (AMO) has been studied as a possible chemical stabilizing agent for soils contaminated with metals. Preliminary experiments evaluating the stability of AMO in pure water have reported only minor dissolution (5.70% and 0.24% depending on the w/v ratio). Sorption kinetics have shown fast metal adsorption, especially for Pb. The sorption capacities of AMO for Cu, Cd, Pb, and Zn have been described and compared with synthetic birnessite for pH 4 and 5.5. Both oxides show similar sorption capacities at pH 4 despite the fact that birnessite characteristics (pH of zero point charge, specific surface area and cation exchange capacity) are more favorable for metal sorption. Moreover, the pH adsorption-edges show that the AMO is more pH-dependent than birnessite.

Influence of metakaolin purities on potassium geopolymer formulation: The existence of several networks

Geopolymer materials are obtained by the alkaline activation of aluminosilicate sources, the best of which is metakaolin. However, every raw material is different, and very few comparative studies have been done on different metakaolin sources. The aim of this work is to develop methods for the prediction of the working properties of geopolymer materials based on the reactivity of the metakaolin employed. Infrared spectroscopy showed direct relationships between the wettability, the Si/Al ratio and the kinetics of conversion of Si-O-Si bonds to Si-O-Al bonds. Moreover, it was demonstrated that the presence of impurities and the reactivity of the metakaolin can generate the formation of one or several networks. Finally, a descriptive model of the mechanism of geopolymer formation was proposed that takes into account the quality of metakaolin used.

Characterization of the mineral fraction associated to extracellular polymeric substances (EPS) in anaerobic granular sludges

The extracellular polymeric substances (EPS) extracted from four anaerobic granular sludges contain an important mineral fraction (20-77% of the EPS dry weight). The composition of the mineral fraction of EPS depends strongly of the extraction method applied and to a lesser extend of the origin of the anaerobic sludge. Centrifugation, sonication, and heating extraction procedures yield a similar mineral composition. However, extraction using a cationic exchange resin (CER) leads to an increase of the Na(+) content in the EPS extract because the CER promotes an exchange of divalent and trivalent inorganic elements in the EPS extracts toward Na(+). Chemical extraction protocols were also shown to contaminate the EPS extracts by impurities or carry over of the extractant itself (e.g., ethanol). A part of the mineral fraction is bound to the EPS organic matter and structures the EPS matrix in the granules. Scanning electron microscopic analysis (SEM-EDX) showed that, in addition, solid particles such as CaCO(3) and Ca(5)OH(PO(4))(3) containing various metallic elements (i.e., Al, Fe, Cu, Mn...) are present in the EPS as well. This inorganic fraction, too often neglected in EPS studies, can influence the physicochemical properties of EPS.

HYDROTHERMAL SYNTHESIS, BETWEEN 75 AND 150°C, OF HIGH-CHARGE, FERRIC NONTRONITES

High-charge nontronites were synthesized at 75, 90, 100, 110, 125, and 150°C from a silicoferrous starting gel with Si2FeNa2O6.nH2O composition. This gel was oxidized in contact with air and then hydrothermally treated, for a period of 4 weeks, under equilibrium water pressure. The synthesized nontronites were similar to each other, regardless of the synthesis temperature. Their structural formula, obtained from chemical analysis, X-ray diffraction (XRD), and Fourier transform infrared (FTIR), Mössbauer, and X-ray absorption fine structure spectroscopies is:

Physiological impacts of soil pollution and arsenic uptake in three plant species: Agrostis capillaris, Solanum nigrum and Vicia faba

\left( {{\rm{S}}{{\rm{i}}_{3.25}}{\rm{Fe}}_{0.75}^{3 + }} \right){\rm{Fe}}_2^{3 + }{{\rm{O}}_{10}}{\left( {{\rm{OH}}} \right)_2}{\rm{N}}{{\rm{a}}_{0.75}}

Metal binding properties of extracellular polymeric substances extracted from anaerobic granular sludges

(Si3.25Fe0.753+)Fe23+O10(OH)2Na0.75. A strictly ferric end-member of the nontronite series was therefore synthesized for the first time. The uncommon chemistry of the synthesized nontronites, notably the high level of Fe-for-Si substitution, induced particular XRD, FTIR, and differential thermal analysis-thermogravimetric analysis data. The ethylene glycol expandability of the synthetic nontronites was linked to their crystallinity and depended on the nature of the interlayer cation, moving from smectite to vermiculite-like behavior. As the synthesis temperature increased, the crystallinity of the synthesized clays increased. The nontronite obtained at 150°C had the ‘best crystallinity’, which cannot be improved by increasing synthesis time or temperature.

Evaluating the potential of three Fe- and Mn-(nano)oxides for the stabilization of Cd, Cu and Pb in contaminated soils.

In order to revegetate an industrial soil polluted by trace metals and metalloids (As, Pb, Cu, Cd, Sb), the impact of pollution on three plant species, Solanum nigrum and Agrostis capillaris, both native species in an industrial site, and Vicia faba, a plant model species, is studied. Following the study of soil pollution from the industrial wasteland of Auzon, it appears that the As is the principal pollutant. Particular attention is given to this metalloid, both in its content and its speciation in the soil that the level of its accumulation in plants. In V. faba and A. capillaris, the trace metals and metalloids inhibit the biomass production and involve a lipid peroxidation in the leaves. Furthermore, these pollutants cause a photosynthesis perturbation by stomatal limitations and a dysfunction of photosystem II. Whatever the plant, the As content is less than 0.1 percent of dry matter, the majority of As absorbed is stored in the roots which play the role of trap organ. In parallel, the culture of S. nigrum decreases significantly the exchangeable and weakly adsorbed fraction of As in rhizospheric soil. This study has highlighted the ability of tolerance to trace metals of S. nigrum and to a lesser extent A. capillaris. Our data indicate that V. faba is not tolerant to soil pollution and is not a metallophyte species.

Synthesis of consolidated materials from alkaline solutions and metakaolin: Existence of domains in the Al-Si-K/O ternary diagram

Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pKa1 (4–5) corresponding to the carboxyl groups; pKa2 (6–7) corresponding to the phosphoric groups; pKa3 (8–10) and pKa4 (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.

Characterisation of the mineral fraction in extracellular polymeric substances (EPS) from activated sludges extracted by eight different methods.

The potential of three Fe- and Mn-(nano)oxides for stabilizing Cd, Cu and Pb in contaminated soils was investigated using batch and column experiments, adsorption tests and tests of soil microbial activity. A novel synthetic amorphous Mn oxide (AMO), which was recently proposed as a stabilizing amendment, proved to be the most efficient in decreasing the mobility of the studied metals compared to nano-maghemite and nano-magnetite. Its application resulted in significant decreases of exchangeable metal fractions (92%, 92% and 93% decreases of Cd, Cu and Pb concentrations, respectively). The adsorption capacity of the AMO was an order of magnitude higher than those recorded for the other amendments. It was also the most efficient treatment for reducing Cu concentrations in the soil solution. No negative effects on soil microorganisms were recorded. On the other hand, the AMO was able to dissolve soil organic matter to some extent.