Synthesis of Ge-imogolite: influence of the hydrolysis ratio on the structure of the nanotubes.

The synthesis protocol for Ge-imogolite (aluminogermanate nanotubes) consists of 3 main steps: base hydrolysis of a solution of aluminum and germanium monomers, stabilization of the suspension and heating at 95 °C. The successful synthesis of these nanotubes was found to be sensitive to the hydrolysis step. The impact of the hydrolysis ratio (from n(OH)/n(Al) = 0.5 to 3) on the final product structure was examined using a combination of characterization tools. Thus, key hydrolysis ratios were identified: n(OH)/n(Al) = 1.5 for the formation of nanotubes with structural defects, n(OH)/n(Al) = 2 for the synthesis of a well crystallized Ge imogolite and n(OH)/n(Al) > 2.5 where nanotube formation is hindered. The capability of controlling the degree of the nanotube's crystallinity opens up interesting opportunities in regard to new potential applications.

Combining size fractionation, scanning electron microscopy, and X-ray absorption spectroscopy to probe zinc speciation in pig slurry.

Zinc occurs in high quantity in pig slurry since it is used as an essential micronutrient at high concentrations in animal feeds despite the low Zn assimilation by pigs. Zinc accumulation was measured in soil surface layers that had been amended with pig slurry, while also determining the phytotoxicity as well as the extent of groundwater quality degradation. To accurately predict the mobility and bioavailability of Zn derived from pig slurry spreading, the speciation of this element has to be assessed since the total concentration is not sufficient. This study involved a combination of techniques to investigate Zn speciation in pig slurry. Size fractionation was first performed to account for the complexity of pig slurry, and 75% of total Zn was detected in the 0.45- to 20-mum particle-size range. Then X-ray diffraction, scanning electron microscopy, coupled with energy dispersive spectrometer, and extended X-ray absorption fine structure analyses were combined to assess Zn speciation. The findings highlighted the presence of 49% Zn bound to organic matter, 37% amorphous Zn hydroxides [Zn(OH)(2)], and 14% sphalerite (ZnS).

Determination of zinc speciation in basic oxygen furnace flying dust by chemical extractions and X-ray spectroscopy.

There is a growing concern regarding the environmental and public health risks associated with airborne particulate matter (PM). The basic oxygen furnace is one of the most important atmospheric dust sources of the steel manufacturing process. It emits dust enriched in heavy metal such as Zn, which is assumed to contribute to the toxic potential of atmospheric PM. Dust collected before and after the filtration system was analyzed to determine Zn speciation. To this end, a variety of analytical tools were used and a sequential extraction protocol has been specifically developed for iron and steel dust. The Zn speciation results obtained by EXAFS and sequential extraction were in excellent agreement. Before filtration, the speciation of Zn in BOF was 43% ZnFe(2)O(4), 23% ZnCO(3) and 16% ZnO. The same species were detected after filtration with different proportions. BOF dust after filtration contains more soluble Zn phases which may play a role in the toxic effects of the emissions.

Combination of 13C/ 113Cd NMR, potentiometry, and voltammetry in characterizing the interactions between Cd and two models of the main components of soil organic matter.

This work allowed the characterization of the Cd-binding sites of two compounds taken as models for exudates, the main components of soil organic matter (SOM). The studied compounds were exopolysaccharides (EPS), specifically exudates of roots (polygalacturonic acid) and of soil bacteria (Phytagel). Potentiometric acid-base titrations were performed and fitting of the obtained results indicated the presence of two main classes of acidic sites, defined by their pKa values, for both EPS but of a different nature when comparing the two compounds. The two studied exopolysaccharides presented different acidic/basic site ratios: 0.15 for Phytagel and 0.76 for polygalacturonic acid. Spectroscopic techniques (13C/113Cd NMR, FTIR) distinguished different Cd surroundings for each of the studied EPS, which is in agreement with the titration results. Furthermore, these analyses indicated the presence of -COOH and -OH groups in various proportions for each exopolysaccharide, which should be linked to their reactivity towards cadmium. Cadmium titrations (voltammetric measurements) also differentiated different binding sites for each compound and allowed the determination of the strength of the Cd-binding site of the EPS. Fitting of the results of such voltammetric measurements was performed using PROSECE (Programme d'Optimisation et de Speciation Chimique dans l'Environnement), a software coupling chemical speciation calculation and binding parameter optimization. The fitting, taking into account the Cd2+/H+ competition towards exopolysaccharides, confirmed the acid-base titrations and spectroscopic analyses by revealing two classes of binding sites: (i) one defined as a strong complexant regarding its Cd2+-EPS association (logK = 9-10.4) and with basic functionality regarding H+-EPS association (pKa = 11.3-11.7), and (ii) one defined as a weak complexant (logK = 7.1-8.2) and with acidic functionality (pKa = 3.7-4.0). Therefore the combination of spectroscopic analyses, voltammetry, and fitting allowed the precise characterization of the binding sites of the studied exopolysaccharides, mimicking the main SOM components. Furthermore, the binding parameters obtained by fitting can be used in biogeochemical models to better define the role of key SOM compounds like exudates of roots and of soil bacteria on trace metal transport or assimilation.

Evolution of iron speciation during hydration of C4AF.

It is now well accepted and demonstrated that calcium silicate, calcium aluminate and calcium sulfo aluminate (ettringite, AFm) phases exhibit a good capability to fix metals and metalloids. Unfortunately the role of minor phases and especially calcium-ferric aluminate phase, shorthand C4AF is not well defined. In other systems like in soils or sediments iron phases play a key role in the fixation of pollutant. In cement sorption isotherms, indicated that various metals can be retained by the C4AF hydrated products. Therefore the capabilities of those phase to retain heavy metal should not be neglected. Previous investigations have shown that the minerals formed during the hydration of C4AF are similar to those formed from C3A (pure tri-calcium aluminate) under comparable conditions. Nevertheless no investigation was conducted at the molecular level and there is still a controversy whether Fe substitutes for Al in the hydrated minerals in whole or in part, or if it forms FeOOH clusters scattered throughout the matrix. In this context we have conducted XAS experiments using synchrotron radiation. It was found that the hydration of C4AF forms C3AH6 (hydrogarnet) in which Fe randomly substitutes for Al as well as an amorphous FeOOH phase. Intermediate products like AFm (i.e., an ill organized lamellar phase) are also formed but rapidly evolve to C3AH6; iron does not seem to be incorporated in the AFm structure.

Removal of nom by coagulation-flocculation: a pyrolysis-GC-MS study

Se realizaron remociones del NOM (Materia orgánica natural) en el Río Sena, usando tres coagulantes: cloruro férrico, sulfato de aluminio y policlorosulfato de aluminio. La eficiencia del proceso dependía del pH. Se obtuvieron menores resultados con un pH de 5,5 con el FC y de 6.0 con los coagulantes a base de aluminio. Se analizó la composición del NOM por medio de pirolisis, cromatografía de gas y espectrometría en masa. Se da los resultados obtenidos en detalle, que fueron confirmados por la PC-GC y MS. Se detallan materiales y métodos, los resultados y los comentarios