Releases of phosphate fertilizer industry in the surrounding environment: investigation on heavy metals and polonium-210 in soil.

Distribution of Cu, Zn, Pb, Cr, Ni, Mn concentrations and the activity of polonium-210 in the surrounding area of a phosphate fertilizer industry located on the eastern coast of the Mediterranean Sea has been determined. Nineteen sampling sites were distributed around the industrial zone on a surface area of about 100,000 m2. Atomic absorption spectroscopy and Alpha spectroscopy were used to quantify the heavy elements and polonium-210, respectively. Investigation on a particle scale was conducted by TEM and SEM coupled to EDX and X-ray cartography to determine the nature of heavy elements carriers and their distribution. Heavy elements were mainly concentrated inside the particle size fraction < 50 microm. Their levels decreased with distance increasing from the industry. According to the reference soil, enrichment factors were about 10, 15, 32 and 100 times for Zn, Pb, Cu, and Cr, respectively inside the particle size fraction < 50 microm on the closest sites to the industry. The main contaminant sources were transport and storage of row materials and the free release of phosphogypsum waste. Heavy elements were entrapped inside agglomerates of sulfates, phosphates and iron oxihydroxides in a diffused shape. Polonium-210 with an enrichment factor of about 56, showed the same behavior of the spatial distribution of the trace elements.

Fate of coagulant species and conformational effects during the aggregation of a model of a humic substance with Al13 polycations.

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.

Effect of arsenate As (V) on the biomarkers of Myriophyllum alterniflorum in oligotrophic and eutrophic conditions.

Alternate watermilfoil, Myriophyllum alterniflorum is an aquatic macrophyte found in the Limousin rivers (France) whose potential for biomonitoring of metal pollution has been demonstrated. The objective of the present study carried out in vitro was to identify biomarkers for an early detection of the pollution by a metalloid As (V) in eutrophic and oligotrophic conditions. A synthetic medium of similar composition to the waters of the River Vienne was prepared. The morphological development of watermilfoil was monitored for 30 days, with or without contamination by 100 µg L(-1) As (V). In addition, the mineralization of plants and the analysis of biomarkers (chlorophylls, photosynthetic and respiratory intensities …) were investigated after 21 days. Our results indicated that eutrophic medium, induced a decrease in chlorophyll pigments, in growth and an increase in H2O2 compared to the oligotrophic medium. While, the presence of As (V), led to a decrease in the osmotic potential, pigment content, photosynthesis and respiration rates and an inhibition of shoot branching of plants in both conditions. However, a significant increase in H2O2 content was noted in the eutrophic medium. Finally, As (V) was found to be more accumulated in roots than shoots in both conditions but was more accumulated in oligotrophic one. Therefore, we can conclude that the water trophic level modifies the response of M. alterniflorum in presence of arsenate. Thus, M. alterniflorum shows a great promise in water-quality biomonitoring.

Clarification of municipal sewage with ferric chloride: the nature of coagulant species.

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.