Aggregating ability of ferric chloride in the presence of phosphate ligand.

Complexing anions such as phosphate or silicate play an ambivalent role in the performance of hydrolyzing metal coagulants: On one hand, they significantly interfere with the hydrolytic pathway of conventional iron or aluminum coagulants, the associated destabilization mechanism remaining rather elusive; on the other hand, they have been shown to be key ingredients in the formulation of innovative coagulant solutions exhibiting improved removal efficiency, their action mechanism at the molecular scale being presently poorly understood. In this paper, we explore the effect of small additions of phosphate ligand on the chemical coagulation of silica nanoparticles with ferric chloride. Transmission Electron Microscopy-Energy Dispersed X-ray Spectroscopy (TEM-EDXS) combined with Extended X-ray absorption Fine Structure Spectroscopy (EXAFS) at the Fe K-edge are used to provide an insight into the nature of coagulant species, whereas jar-tests, laser diffraction, Small Angle X-ray Scattering (SAXS), and electrophoretic mobility, are used to investigate the aggregation dynamics of silica particles in the presence of phosphate ligand. We show that, in spite of a slight increase in the consumption of iron coagulant, the addition of phosphate significantly improves the formation of silica aggregates provided that the elemental Fe/P ratio remains above 7. Such effects originate from both a large increase in the overall number of coagulant species, the binding of a phosphate ligand terminating the growth of polymeric chains of edge-sharing Fe octahedra, and a change in the nature of the coagulant species that evolves with the Fe/P ratio, small polycations built-up from Fe-oligomers linked by phosphate tetrahedra being eventually formed. Those non-equilibrium nanosize Fe-P coagulant species assemble the silica nanoparticles to form hetero-aggregates whose structure is consistent with a Diffusion-Limited Cluster Aggregation mechanism.

Amendment of soil by biochars and activated carbons to reduce chlordecone bioavailability in piglets.

Chlordecone (Kepone or CLD) is a highly persistent pesticide formerly used in French West Indies. Nowadays high levels of this pesticide are still found in soils which represent a subsequent source of contamination for outdoor-reared animals. In that context, sequestering matrices like biochars or activated carbons (ACs) are believed to efficiently decrease the bioavailability of such compounds when added to contaminated soils. The present study intends to test the respective efficiency of soil amendment strategies using commercial ACs or biochars (obtained by a 500 °C or 700 °C pyrolysis of 4 distinct type of wood). This study involved three experimental steps. The first one characterized specific surface areas of biochars and ACs. The second one assessed CLD-availability of contaminated artificial soils (50 µg g-1 of Dry Matter) amended with 5% of biochar or AC (mass basis). The third one assessed CLD bioavailability of those artificial soils through an in vivo assay. To limit ethically the number of animals, selections of the most promising media were performed between each experimental steps. Forty four castrated male 40-day-old piglets were exposed during 10 day by amended artificial soils according to their group (n = 4). Only treatment groups exposed through amended soil with AC presented a significant decrease of concentrations of CLD in liver and adipose tissue in comparison with the control group (p < 0.001). A non-significant decrease was obtained by amending artificial soil with biochars. This decrease was particularly high for a coconut shell activated carbon were relative bioavailability was found lower than 3.2% for both tissues. This study leads to conclude that AC introduced in CLD contaminated soil should strongly reduce CLD bioavailability.

Sources, nature, and fate of heavy metal-bearing particles in the sewer system.

A preliminary insight into metal cycling within the urban sewer was obtained by determining both the heavy metal concentrations (Cu, Zn, Pb, Cd, Ni, Cr) in sewage and sediments, and the nature of metal-bearing particles using TEM-EDX, SEM-EDX and XRD. Particles collected from tap water, sump-pit deposits, and washbasin siphons, were also examined to trace back the origin of some mineral species. The results show that the total levels in Cu, Pb, Zn, Ni, and Cr in sewage are similar to that reported in the literature, thus suggesting that a time-averaged heavy metal fingerprint of domestic sewage can be defined for most developed cities at the urban catchment scale. Household activities represent the main source of Zn and Pb, the water supply system is a significant source of Cu, and in our case, groundwater infiltration in the sewer system provides a supplementary source of Ni and Cd. Concentrations in heavy metals were much higher in sewer sediments than in sewage suspended solids, the enrichment being due to the preferential settling of metal-bearing particles of high density and/or the precipitation of neoformed mineral phases. TEM and SEM-EDX analyses indicated that suspended solids, biofilms, and sewer sediments contained similar heavy metal-bearing particles including alloys and metal fragments, oxidized metals and sulfides. Copper fragments, metal carbonates (Cu, Zn, Pb), and oxidized soldering materials are released from the erosion of domestic plumbing, whereas the precipitation of sulfides and the sulfurization of metal phases occur primarily within the household connections to the sewer trunk. Close examination of sulfide phases also revealed in most cases a complex growth history recorded in the texture of particles, which likely reflects changes in physicochemical conditions associated with successive resuspension and settling of particles within the sewer system.

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.