The nature of coagulant species formed in the system ferric chloride/municipal sewage was explored with Transmission Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (TEM-EDXS) and Fe K-edge X-ray Absorption spectroscopy. Jar-test data combined with chemical analysis of supernatant (dissolved organic carbon, iron, and phosphorus) and Fourier-Transform-Infrared spectroscopy (FTIR) of freeze-dried sediment, provided a detailed description of sewage clarification. The results showed that the nature of coagulant species evolves with Fe concentration. Up to the optimum turbidity removal, mainly iron dimers linked with one phosphate anion are detected. At higher dosages, polymers of hydrolyzed Fe appear even though PO(4) still participates in the formation of coagulant species. TEM observation of freeze-dried sediments corroborates such an evolution of Fe speciation. EDXS analyses reveal that minute amounts of sulfur, silicon, aluminum, and calcium, are associated with the coagulant species. Even though the coagulant species change with Fe concentration, the destabilization mechanism, inferred from electrophoretic mobility of aggregates and the evolution of floc size under cyclic changes of stirring conditions, is equivalent with a charge neutralization of sewage colloids in the whole range of coagulant concentration.

A model of a humic substance (MHS) obtained from auto-oxidation of catechol and glycine, was aggregated at pH 6 and 8 with Al(13) polycations. The fate of Al(13) coagulant species upon association with MHS functional groups was studied using solid state (27)Al Magic-angle spinning (MAS) NMR and CP-MAS (13)C NMR. Electrophoretic measurements and steady-state fluorescence spectroscopy with pyrene as a fluoroprobe, were combined to investigate structural re-organization of humic material with aluminum concentration. MAS (27)Al NMR revealed that the coagulant species are Al(13) polycations or oligomers of Al(13) units at both pHs. CP MAS (13)C spectra indicated that, at low Al concentration, hydrolyzed aluminum species bind selectively to carboxylic groups at pH 6 and to phenolic moieties at pH 8. At higher coagulant concentrations, the remaining functional groups also interact with hydrolyzed Al to yield similar CP MAS (13)C spectra in the optimum concentration range. Negative values of electrophoretic mobility were obtained at optimum coagulant concentrations even though an overall charge balance was achieved between MHS anionic charge and Al(13) cationic charge at pH 6. The polarity-sensitive fluorescence of pyrene revealed that the interaction of Al(13) coagulant species with MHS functional groups induces the formation of intramolecular hydrophobic microenvironments. Such structural changes were reversed upon further addition of Al(13) polycations.

No abstract

Submerged sediment cores were collected upstream of a dam in the Orne River, northeastern France. This dam was built in the context of steelmaking to constitute a water reservoir for blast furnace cooling and wet cleaning of furnace smokes. The dam also enhanced sediment deposition in the upstream zone. This study was performed to unravel the contamination status of sediments and to evidence possible contribution sources. The sediment layers were analyzed for water content, grain size, chemical composition, crystalline phases at a bulk scale and poorly crystalline and amorphous phases at a sub-micrometer scale. Visual aspect, texture, color, and chemical and mineralogical analyses showed that the settled sediments were mainly composed of fine black matter, certainly comprising steelmaking by-products. Those materials were highly enriched with Fe, Zn, Pb and other trace metals, except for a relatively thin layer of surficial sediments that had settled more recently. Bulk mineralogy revealed crystalline iron minerals, such as magnetite, goethite, wuestite and pyrite, in the deep layers of the sediment cores. Furthermore, microscopic investigations evidenced the presence of ferrospheres, goethite nanoparticles and newly formed Fe-aluminosilicates; all originating from the former steelmaking facilities. The variation of iron mineralogy, combined with specific chemical profiles and other sediment features, demonstrate the different contributions that constitute the sediment deposit. Furthermore, chemical and mineralogical features of goethite and Fe-aluminosilicates could be used as a fingerprint for such contaminated sediments.

Phosphate fertilizers represent a major source of trace metal contaminants in agricultural soils. To predict the inputs and the fate of trace metals in soils of the eastern Mediterranean region, a speciation study was conducted using a total of 44 phosphate fertilizers commercialized in the area. The contents in major anions and potentially toxic metals (Zn, Pb, Cd, and Cu) were determined using atomic absorption spectrometry (AAS) and X‐ray fluorescence spectrometry (XRF). The nature of mineral phases in the fertilizer was characterized using X‐ray diffraction and Fourier transform infrared spectrometry. The results show that sulfates are the main Cd‐bearing phases when present in the P‐fertilizer. The contents in Zn and Pb were linearly related, whereas the levels of Sb, Ag, Pd, Nb, Mo, and P2O5 were strongly correlated to each other. The annual average inputs of Zn, Cu, Pb, and Cd were calculated to be 922, 124, 26, and 6 g/ha per year, respectively. Even though such inputs comply with the maximal metals concentrations authorized in temperate countries, an accumulation of those metals in the typical arid and alkaline soils of the eastern Mediterranean countries is expected.

No abstract

No abstract

No abstract