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.

Floc compaction during ballasted aggregation.

Ballasted aggregation, a process using the addition of a ballasting agent to improve the settling performance of flocs, appears particularly appropriate for the treatment of humic rich waters that leads to low-density aggregates. In that context, using an aquagenic humic acid coagulated by ferric chloride in the presence of pozzolana particles as ballasting agent, we show that the origin of improved floc settling in ballasted aggregation is not simply related to an increased specific weight of flocs, but also to a significant restructuring of flocs to a more compact structure induced by the added particles. The floc restructuring is evidenced from the increased lag time before measurable floc growth in the presence of the ballasting agent, the higher fractal dimension of flocs above the micron scale range after incorporation of the particles into the aggregates, and a much smaller sediment volume after settling. A simple model of floc compaction based on the turbulent viscous effects that act on an elastic floc, is described.

Interaction of Cocos nucifera cream casein with humic acid suspensions.

Two caseins labelled as CaSMG (casein without fats) and CaMG (casein with fats) were extracted from coconut cream. Both caseins were used as coagulants for the aggregation of humic acid (HA) particles in synthetic water at pH = 6 during the jar-test essays. The optimum dosage of CaMG or CaSMG and the residual turbidities of treated water obtained depend on the type of used casein (CaMG or CaSMG) and the concentration of particles in solution. The optimal doses of CaMG and CaSMG are respectively 280 and 180 mg/L for solution S(1) (HA aqueous solution at 15 mg/L), and then 340 and 240 mg/L for solution S(2) (HA aqueous solution at 25 mg/L). The residual turbidities of treated water are respectively 6.88 and 3.85 NTU for solution S(1) and 4.52 and 2.53 NTU for solution S(2). The collected sediment volumes are respectively 1.2 and 1.5 mL for solutions S(1) and S(2). The electrophoretic mobility measurement and transmission electron microscopy images of flocs formed during the flocculation essays suggest that both caseins operate through both mechanisms (charge neutralisation and bridging process mechanism), this last one seems to be predominant. The aggregates formed are the large clusters and result from adsorption of HA particles by the casein molecules.

MnCl2 and MgCl2 for the removal of reactive dye Levafix Brilliant Blue EBRA from synthetic textile wastewaters: an adsorption/aggregation mechanism.

Two divalent cation-based coagulants, magnesium chloride and manganese chloride, were used to treat synthetic textile wastewaters containing the azo-dye pigment Levafix Brilliant Blue EBRA. The jar-tests were performed in the presence or absence of auxiliary dyeing chemicals. They proved that (i) both divalent cation-based coagulants were effective in the treatment of those alkaline effluents, (ii) better performances in terms of color removal, residual turbidity, and settled volume, were achieved with manganese chloride, and (iii) the presence of dyeing auxiliaries significantly increases the required coagulant demand for treating the textile effluent. The dye removal mechanisms were investigated by combining observations of freeze-dried sediments with transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy and selected area electron diffraction, Fourier transform infrared spectroscopy, adsorption experiments, and aggregates size measurements with a laser sizer under cyclic shear conditions. The results show that brucite (Mg(OH)(2)) particles are formed when applying MgCl(2) to the textile wastewaters, whereas a mixture of feitknechite (ß-MnOOH) and hausmannite (Mn(3)O(4)) is obtained when using MnCl(2). More poorly crystallized particles are formed in presence of auxiliary dyeing chemicals. The adsorption experiments suggested that the azo-dye pigment adsorbs onto the surface of precipitating phases, whereas the aggregation dynamics indicated that a charge-neutralization mechanism underlies the formation of aggregates. The dye removal is then consistent with a precipitation/adsorption mechanism.

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.

Floc cohesive force in reversible aggregation: a Couette laminar flow investigation.

A simple theoretical model is proposed to describe the limiting size of aggregates attained at steady state under given shear conditions. The stable size is assumed to be the result of a dynamic equilibrium between simultaneous aggregate growth and breakup that are represented as first-order processes. The theory establishes that the evolution of steady-state aggregate size versus shear rate is written as the sum of two exponential laws. The validity of the model is verified by direct observation of the coagulation behavior of latex particles in the stagnant plane of a counter-rotating Couette reactor. The influence of latex elementary particle size, initial particle volume fraction, and inner gap spacing of Couette reactor, are investigated. In all cases, the model shows good agreement with the experimental results. Aggregate growth proceeds with a monomodal size distribution that exhibits a scaling behavior. Such monomodal distribution evolves toward broad and even bimodal steady-state distributions at both low and high shear rates, whereas a narrow monomodal pattern is observed at intermediate shear gradients. The aggregate cohesive force F(C) can be calculated from the critical shear rate of dislocation defined by the model. In contrast to the broadly accepted view that larger flocs should be more fragile than smaller aggregates, we find that F(C) scales as D(3/2) where D is the aggregate characteristic diameter. The latter relationship may be derived by assuming linear elasticity of aggregates.

Interaction of pyrene fluoroprobe with natural and synthetic humic substances: Examining the local molecular organization from photophysical and interfacial processes.

The direct and indirect interaction mechanisms of pyrene with: (i) various molecular weight fractions of a synthetic humic-like substance (SyHA) and (ii) extracts of natural humic acids (NHA) from Moselle River suspended matter were investigated using quenching fluorescence and surface tension measurements. Humic materials were characterized in a previous study. The Stern-Volmer associative constants were determined from the quenching technique. Surface tension measurements revealed an increase in surface activity as a function of concentration for each humic fraction independently of the pyrene presence in solution, even during the formation of humic micelles. The results obtained suggest the possibility of specific intermolecular interactions occurring during pyrene entrapment within humic acids. In addition, we show that molecular weight, aliphatic chains (especially those containing nitrogen groups) and number of acidic groups are determinant characteristics for pollutant entrapment capacity at concentrations below the critical micellar concentration (CMC) of humic substances.

Isotopic tracing of clear water sources in an urban sewer: A combined water and dissolved sulfate stable isotope approach.

This paper investigates the potential of stable isotopes of both water (deltaD and deltaOH(2)O18) and dissolved sulfate (delta(34)S and deltaOSO(4)18) for determining the origin and the amount of clear waters entering an urban sewer. The dynamics of various hydrological processes that commonly occur within the sewer system such as groundwater infiltration, rainwater percolation, or stormwater release from retention basins, can be readily described using water isotope ratios. In particular, stable water isotopes indicate that the relative volumes of infiltrated groundwater and sewage remain approximately constant and independent of wastewater flow rate during the day, thus demonstrating that the usual quantification of parasitic discharge from minimal nocturnal flow measurements can lead to completely erroneous results. The isotopic signature of dissolved sulfate can also provide valuable information about the nature of water inputs to the sewage flow, but could not be used in our case to quantify the infiltrating water. Indeed, even though the microbial activity had a limited effect on the isotopic composition of dissolved sulfate at the sampling sites investigated, the dissolved sulfate concentration in sewage was regulated by the formation of barite and calcium-phosphate mineral species. Sulfate originating from urine was also detected as a source using the oxygen isotopic composition of sulfate, which suggests that deltaOSO(4)18 might find use as a urine tracer.

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.

Phosphate dynamics in an urban sewer: a case study of Nancy, France.

The nature of phosphate phases present in suspended matter, biofilm, and sediment of Greater Nancy sewer system was investigated over a period of two years. The phosphate speciation was determined by two approaches: a direct identification of phosphorus mineral phases was conducted by Transmission Electron Microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDXS), whereas a chemical extraction of samples provided an estimate of phosphorus pools defined by the fractionation scheme. Quantitative analysis of 1340 individual particles by TEM-EDXS allowed to draw a picture of phosphate species distributions along the sewer system and over time. Amorphous Ca-phosphates (brushite, whitlockite, octacalcium phosphate, Mg-brushite, hydroxyapatite and carbapatite) were ubiquitous although brushite dominated upstream, and octacalcium phosphate and apatite prevailed downstream and in sediments. Al-Ca-phosphate minerals such as foggite, bearthite, gatumbaite, and crandallite appeared downstream and in biofilms. Ca-phosphate phase assemblages in the different locations of the sewer system were dependent on phase transformations from brushite to hydroxyapatite that were shown to be kinetically driven. The restriction of Al-Ca-phosphates to downstream of the sewer system was most probably related to the lower pHs measured at these sites. The pH dependency was confirmed by stability calculations. Chemical extractions were not reliable. TEM examination of extraction residues revealed the presence of neoformed Al-Ca-phosphate species that invalidated the fractionation scheme. Nonetheless, it confirmed that phosphate phases may undergo significant geochemical changes over a short time scale.

Changes in humic acid conformation during coagulation with ferric chloride: implications for drinking water treatment.

Electrophoretic mobility, pyrene fluorescence, surface tension measurements, transmission electron microscopy on resin-embedded samples, and X-ray microscopy (XRM) were combined to characterize the aggregates formed from humic colloids and hydrolyzed-Fe species under various conditions of pH and mixing. We show that, at low coagulant concentration, the anionic humic network is reorganized upon association with cationic coagulant species to yield more compact structures. In particular, spheroids about 80nm in size are evidenced by XRM at pH 6 and 8 just below the optimal coagulant concentration. Such reorganization of humic colloids does not yield surface-active species, and maintains negative functional groups on the outside of humic/hydrolyzed-Fe complex. We also observe that the humic network remains unaffected by the association with coagulant species up to the restabilization concentration. Upon increasing the coagulant concentration, restructuration becomes limited: indeed, the aggregation of humic acid with hydrolyzed-Fe species can be ascribed to a competition between humic network reconformation rate and collision rate of destabilized colloids. A decrease in stirring favors the shrinkage of humic/hydrolyzed-Fe complexes, which then yields a lower sediment volume. Elemental analyses also reveal that the iron coagulant species are poorly hydrolyzed in the destabilization range. This suggests that destabilization mechanisms such as sweep flocculation or adsorption onto a hydroxyde precipitate are not relevant to our case. A neutralization/complexation destabilization mechanism accompanied by a restructuration of flexible humic network is then proposed to occur in the range of pHs investigated.

Chemical coagulation of combined sewer overflow: heavy metal removal and treatment optimization.

The coagulation of combined sewer overflow (CSO) was investigated by jar-testing with two commercial coagulants, a ferric chloride solution (CLARFER) and a polyaluminium chloride (WAC HB). CSO samples were collected as a function of time during various wet-weather events from the inlet of Boudonville retention basin, Nancy, France. Jar-tests showed that an efficient turbidity removal can be achieved with both coagulants, though lower optimum dosages and higher re-stabilization concentrations were obtained with the aluminum-based coagulant. Optimum turbidity removal also yielded effective heavy metal elimination. However, the evolution with coagulant dosage of Cu, Zn, Pb, Cr, soluble and suspended solids contents followed various patterns. The removal behaviors can be explained by a selective aggregation of heavy metal carriers present in CSO and a specific interaction between hydrolyzed coagulant species and soluble metals. Stoichiometric relationships were established between optimal coagulant concentration, range of optimal dosing, and CSO conductivity, thus providing useful guidelines to adjust the coagulant demand during the course of CSO events.

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.

Coagulation of humic substances and dissolved organic matter with a ferric salt: an electron energy loss spectroscopy investigation.

Transmission electron microscopy (TEM) coupled with electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDXS) was used to investigate the coagulation of natural organic matter with a ferric salt. Jar-test experiments were first conducted with a reconstituted water containing either synthetic or natural extracts of humic substances, and then with a raw water from Moselle River (France). The characterization of the freeze-dried coagulated sediment by EELS in the 250-450 eV range, showed that Fe-coagulant species predominantly associate with the carboxylic groups of organic matter, and that this interaction is accompanied by a release of previously complexed calcium ions. The variation of Fe/C elemental ratio with iron concentration provides insightful information into the coagulation mechanism of humic substances. At acid pH, Fe/C remains close to 3 over the whole range of iron concentrations investigated, while a much lower atomic ratio is expected from the value of optimal coagulant dosage. This suggests that a charge neutralization/complexation mechanism is responsible for the removal of humic colloids, the aggregates being formed with both iron-coagulated and proton-neutralized organic compounds. At pH 8, the decrease in Fe/C around optimal coagulant concentration is interpreted as a bridging of stretched humic macromolecules by Fe-hydrolyzed species. Aggregation would then result from a competition between reconformation of humic chains around coagulant species and collision of destabilized humic material. EELS also enabled a fingerpriting of natural organic substances contained in the iron-coagulated surface water, N/C elemental analyses revealing that humic colloids are removed prior to proteinic compounds.

Incorporation of hydrophobized mineral particles in activated sludge flocs: a way to assess ballasting efficiency.

The role of mineral surface hydrophobicity in attachment to activated sludge flocs was investigated. Fluorite and quartz particles of similar granulometry were hydrophobized by adsorbing sodium oleate and dodecylamine chloride, respectively. Mineral hydrophobicity was assessed by flotation expriments. The attachment of particles to microbial flocs was determined by optical microscopy. The results indicate that hydrophobized particles are always better incorporated within activated sludge flocs than non-coated particles. A comparison with Aquatal particles used as sludge ballast reveals that hydrophobized minerals are associated with microbial flocs to the same extent.

Trace element carriers in combined sewer during dry and wet weather: an electron microscope investigation.

The nature of trace element carriers contained in sewage and combined sewer overflow (CSO) was investigated by TEM-EDX-Electron diffraction and SEM-EDX. During dry weather, chalcophile elements were found to accumulate in sewer sediments as early diagenetic sulfide phases. The sulfurization of some metal alloys was also evidenced. Other heavy metal carriers detected in sewage include metal alloys, some iron oxihydroxide phases and neoformed phosphate minerals such as anapaite. During rain events, the detailed characterization of individual mineral species allowed to differentiate the contributions from various specific sources. Metal plating particles, barite from automobile brake, or rare earth oxides from catalytic exhaust pipes, originate from road runoff, whereas PbSn alloys and lead carbonates are attributed to zinc-works from roofs and paint from building siding. Soil contribution can be traced by the presence of clay minerals, iron oxihydroxides, zircons and rare earth phosphates. However, the most abundant heavy metal carriers in CSO samples were the sulfide particles eroded from sewer sediments. The evolution of relative abundances of trace element carriers during a single storm event, suggests that the pollution due to the "first flush" effect principally results from the sewer stock of sulfides and previously deposited metal alloys, rather than from urban surface runoff.

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.

Evolution of size distribution and transfer of mineral particles between flocs in activated sludges: an insight into floc exchange dynamics.

The aggregation behavior of activated sludge flocs was investigated by monitoring the size distribution of flocs and transfer of mineral particles between flocs, under various conditions of agitation and dilution. The results showed that (i) the shape of the floc size distribution can be fitted with a gamma function, (ii) a steady-state mean floc size is reached for a given stirring rate, (iii) this stable floc size is shifted towards floc growth as sludge concentration is increased, (iv) under cycled-shear conditions, microbial aggregates break up and re-form in an almost reversible manner, (v) blending of raw sludge and sludge spiked with Aquatal mineral particles results in particle exchange between flocs and (vi) the detailed study of exchange kinetics indicates that some flocs do not participate to the aggregation dynamics. These experimental results suggest that the activated sludge floc size is governed by a flocculation/deflocculation balance, implying an exchange of floc constituents between microbial aggregates.

Ferric chloride and lime conditioning of activated sludges: an electron microscopic study on resin-embedded samples.

Ferric chloride and lime conditioning of sewage sludge is usually interpreted in terms of enhanced aggregation of sludge components. In this study, transmission electron microscopy was used to investigate the conditioning mechanism at a submicronic scale. Samples were collected from two municipal wastewater treatment plants at different stages of the process, embedded in an epoxy resin, and sectioned with an ultramicrotome. Transmission electron microscopy examination of thin sections revealed that clumps of crystalloids develop on external surfaces of flocs after the application of both conditioners. This precipitate creates a rigid structure around the flocs which, upon mechanical dewatering, transmits the stresses applied to the inner parts of flocs. The porous structure of the precipitate may also participate to the withdrawal of water as a draining media. Energy dispersive X-ray spectroscopy revealed that Fe, P, and Ca are the dominant elements in the precipitate with Fe/P and Fe/Ca elemental ratios close to 2.8-3 and 1.1-3, respectively.

Composition, structure and size distribution of suspended particulates from the Rhine River.

Fluvial suspended particulates collected from the Rhine River were investigated in terms of composition, structure and size distribution. Elemental analysis and Diffuse Reflectance Infrared Spectroscopy reveal that most particulate organic matter is formed from material derived from microorganisms. Transmission Electron Microscopy observations on resin-embedded samples and structural characterization from break-up experiments, show that fluvial particulate matter should be viewed as fractal aggregates organized by bacterial exopolymeric substances. The shape of particulate size distribution suggests that the formation and dynamics of suspended particulate matter are controlled mainly by physical processes. Finally, particulate growth and structure are consistent with a cluster-cluster aggregation scheme.