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Research is presented describing the study of Ga13 Keggin ion to determination its formation structure.

Analytical scanning and transmission electron microscopy, sequential chemical extraction, and pyrolysis-gas chromatography on solvent-extractable organic matter are used to provide both direct and indirect speciation of heavy metals and organic matter in sewage-suspended solids and in biofilms taken from an urban sewer in an emerging country. Compared to developed countries where the domestic activities represent the main source of heavy metal pollution in wastewater, the combined sewer system of an emerging country also integrates significant contributions originating from the private drinking water supply system (Zn, Cu, Cr, and Ni), industrial discharges (Cu, Mn), and road dust transported by street washing (Pb). The relative importance of those sources changes drastically over time as evidenced by the difference in metal levels recorded between weekday and weekend effluents. Nevertheless, sewer biofilms are found to provide a good averaging of contaminant loads and they can be used as environmental archives. The speciation study reveals the predominance of neoformed minerals such as sulfides and phosphates and highlights the strong biogeochemical dynamics that takes place within the sewer system. Electron microscope observations of heavy metal-bearing phases proved to be necessary to provide a consistent interpretation of chemical extraction results. The molecular characterization of the solvent-extractable organic matter from biofilms reveals the presence of classical fingerprints of domestic activity such as fecal sterols and detergents but also confirms a major contribution of petroleum by-products consistent with a traffic-related pollution. [ABSTRACT FROM AUTHOR]

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 experiments. 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 noncoated particles. A comparison with Aquatal particles used as sludge ballast reveals that hydrophobized minerals are associated with microbial flocs to the same extent. [ABSTRACT FROM AUTHOR]

Light Microscopy, Transmission Electron Microscopy (TEM, EDXS), and Fourier Transform Infra Red MicroSpectroscopy (FTIRMS) were used to describe the organization and chemical distribution of major constituents in a sludge filtration cake. Samples were obtained from a municipal wastewater treatment plant using conventional ferric chloride and lime sludge conditioning. Various samples collected at different stages of the process were embedded in an Epoxy resin after acetone-dehydration, and sectioned using an ultra-microtome. The thickness of the sections was adapted to the experimental techniques used. [ABSTRACT FROM AUTHOR]

Impacts of the acid mine drainage (AMD) remediation are investigated on the largest gold mine in Latin America, located in the Dominican Republic. Geochemical analysis of suspended matter in water performed in 2022 on water bodies located downstream to the mine, namely, the Margajita River and Lake Hatillo, are compared with analyses made in 2007, before the AMD remediation. The results for the Margajita River show a strong decrease in heavy metal and metalloid concentrations in the dissolved phase for Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd, Sb, and Pb (between 89.1 and 99.9%) which is correlated with a pH neutralization (from a pH of 2 to 7.5). However, the concentrations of Cd and sulfate in the dissolved fraction remain higher than their environmental standard values, and a high concentration of K is also observed. High contributions in terms of mass are identified for Cs, Tl, Cd, and Li in the Margajita River. Concentrations of Al, Fe, Ni, Zn, and As in suspended sediments are higher than the environmental standard values in 2022. Modeling of the chemical speciation shows that the higher pH leads to the formation of suspended particles in the form of hydroxides and sulfates. The concentrations in suspended sediments are highly correlated between Margajita River and Lake Hatillo in 2022 for Fe, Cd, Li, and Ca (R 2 between 0.9 and 0.99 with p ≤ 0.05). In Lake Hatillo, principal component analysis shows that invariant elements Fe, P, Ti, Zr, and Al are correlated, as they precipitate between the inlet and outlet of the lake., Competing Interests: Declarations. Conflict of interest: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Radon-222, a radioactive noble gas with a half-life of 3.8 days produced by radium-226, is a health hazard in caves, but also a powerful tracer of atmospheric dynamics. Here we show how airborne radon-222 can be analysed in a cave with multiple openings, the Pech Merle Cave in South-West France. This two-level cave hosts prehistoric remains and Gravettian paintings in its lower level. Radon concentration, monitored at 15 points with one-hour sampling intervals for more than one year, including two points for more than three years, showed mean values from 1274 ± 11 to 5281 ± 20 Bq m -3 , with transient values above 15,000 Bq m -3 . Seasonal variations were observed, with a weak normal cycle (low in winter) at two points in the upper level and a pronounced inverse seasonal cycle (low in summer) at the other points in the cave. The radon-222 source (effective radium-226 concentration, EC Ra ) was measured in the laboratory for floor deposits, soil and rock samples. While EC Ra values obtained for rocks and speleothems are smaller than 1 Bq kg -1 , most EC Ra values for soils are larger than 10 Bq kg -1 . Quantitative modelling confirms that the floor fillings inside the cave are responsible for the stationary lower concentrations, while the higher concentrations observed in winter are explained by percolation of outside air, which collects radon-222 as it passes through the soil layers. In addition, Stored Available Radon (SAR) is sufficient to account for transient variations. While air currents occur when visitors enter the cave or when the cave is deliberately ventilated, the climatic processes revealed by their radon-222 signatures appear to be essentially natural. These processes, enhanced by global climate change, could cause or accelerate the deterioration of prehistoric paintings. Radon-222 source analysis using EC Ra -based modelling and SAR appears essential for the preservation of underground heritage., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The colloidal stability of non-motile algal cells in water drives their distribution in space. An accurate description of the interfacial properties of microalgae is therefore critical to understand how microalgae concentrations can change in their biotope or during harvesting processes. Here, we probe the surface charges of three unicellular algae─ Chlorella vulgaris , Nannochloropsis oculata , and Tetraselmis suecica ─through their electrophoretic mobility. Ohshima's soft particle theory describes the electrokinetic properties of particles covered by a permeable polyelectrolyte layer, a usual case for biological particles. The results appear to fit the predictions of Ohshima's theory, proving that all three microalgae behave electrokinetically as soft particles. This allowed us to estimate two characteristic parameters of the polyelectrolyte external layer of microalgae: the volume charge density and the hydrodynamic penetration length. Results were compared with transmission electron microscopy observations of the algal cells' surfaces, and in particular of their extracellular polymeric layer, which was identified with the permeable shell evidenced by electrophoretic measurements. Noticeably, the algal surface potentials estimated from electrophoretic mobility using the soft particle theory are less negative than the apparent zeta potentials. This finding indicates that electrostatics are expected to play a minor role in phenomena of environmental and industrial importance, such as microalgae aggregation or adhesion.

Natural apatites have previously shown a great capacity for phosphate retention from wastewater. However, its fine particle size distribution may lead to a premature clogging of the filter. Accordingly, a granulated apatite product was developed and manufactured in order to control the particle size distribution of the media. Experiments were conducted on laboratory columns to assess their phosphorus retention capacity, to identify the processes involved in phosphorus retention and to evaluate their kinetic rates. The results showed phosphorus retention capacities of 10.5 and 12.4 g PO 4 -P·kg -1 and kinetic rate coefficients in the range of 0.63 and 0.23 h -1 involving lower values than those found for natural apatites in previous studies. Scanning Electron Microscopy images showed that apatite particles in the granules were embedded in the binder and were not readily accessible to act as seeds for calcium phosphate precipitation. The retention processes differ depending on the supersaturation of the solution with respect to calcium phosphate phases: at low calcium concentrations (69.8 ± 3.9 mg·L -1 ), hydroxyapatite precipitates fill up the porosity of the binder up to a depth of 100-300 μm from the granule surface; at higher calcium concentrations (112.7 ± 7.4 mg·L -1 ) precipitation occurs at the granule surface, forming successive layers of hydroxyapatite and carbonated calcium phosphates.

Carbon dioxide (CO 2 ) concentration (CDC) is an essential parameter of underground atmospheres for safety and cave heritage preservation. In the Chauvet cave (South France), a world heritage site hosting unique paintings dated 36,000 years BP, a high-sensitivity monitoring, ongoing since 1997, revealed: 1) two compartments with a spatially uniform CDC, a large volume (A) (40,000 to 80,000 m 3 ) with a mean value of 2.20 ± 0.01% vol. in 2016, and a smaller remote room (B) (2000 m 3 ), with a higher mean value of 3.42 ± 0.01%; 2) large CDC annual variations with peak-to-peak amplitude of 2% and 1.6% in A and B, respectively; 3) long-term changes, with an increase of CDC and of its annual amplitude since 1997, then faster since 2013, reaching a maximum of 4.4% in B in 2017, decreasing afterwards. While a large effect of seasonal ventilation is ruled out, monitoring of seepage at two dripping points indicated that the main control of CDC seasonal reduction was transient infiltration. During periods of water deficit, calculated from surface temperature and rainfall, CDC systematically increased. The carbon isotopic composition of CO 2 , correlated with water excess, is consistent with a time-varying component of CO 2 seeping from above. The CO 2 flux, which is the primary driver of CDC in A and B, inferred using box modelling, was found to confirm the relationship between water excess and reduced CO 2 flux into A, compatible with a more constant flux into B. A buoyancy-driven horizontal CO 2 flow model in the vadose zone, hindered by water infiltration, is proposed. Similarly, pluri-annual and long-term CDC changes can likely be attributed to variations of water excess, but also to increasing vegetation density above the cave. As CDC controls the carbonate geochemistry, an increased variability of CDC raises concern for the preservation of the Chauvet cave paintings., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

We investigated the relationships between inherent and apparent optical properties (IOP and AOP, respectively) and suspended sediment concentrations (SSC) in the main Amazonian river waters. In situ measurements of SSC, remote sensing reflectance (R rs ), the diffuse light attenuation coefficient (K d ) and the total and non-algal particle (NAP) absorption coefficients (a TOT and a NAP , respectively) were conducted during three sampling trips along different streams of the Amazon River catchment (104 stations). The size distribution and chemical characteristics of the suspended sediment were also determined for 85 stations. We show that the particle size distribution (PSD) in the river water is best described by a segmented Junge power law distribution with a smaller slope value for the smallest particles (J 1 = 2.4) and a larger slope value (J 2 = 4.1) for the largest particles (> 10 µm). A strong relationship was found between AOPs and IOPs and SSC when the entire data set was considered. However, for the Madeira River, the primary Amazon River tributary in terms of suspended sediment discharge, a significant dispersion was detected for the R rs - SSC relationship but not for the K d - SSC relationship. This dispersion has been shown by a previous study, using MODIS data, to display a seasonal pattern, which we investigated in this study using Mie modeling calibrated with suspended sediment characteristics. In the Madeira River, suspended sediment had a finer distribution size and a different mineralogy (e.g., a greater smectite content and a lower kaolinite content) during the rising water stage. Spectral variations of the imaginary part n ' (λ) of the refraction index also showed significant differences during the rising water stage. In contrast, other streams of the Amazon basin had very stable properties with respect to granulometry and mineralogy. Model simulations made possible to reproduce both field and satellite observations, showing that the R rs hysteresis observed in the Madeira River in the near infrared was mainly due to n ' (λ) seasonal variations, leading to a decrease of absorption during the rising water stage. K d was shown to remain stable because of its strong dependency on scattering processes. The model was used to further understand how suspended sediment size distribution and refraction index drive the IOPs in large rivers: n ' (λ) variations were shown to control primarily the reflectance variability; R rs (850) presented limited variations as a function of PSD in the range typical of large rivers (J 1 < 3) although it remained sensitive to particle mineralogical composition; R rs (670) showed the opposite behavior with a higher sensitivity to PSD variation for coarser PSD. Finally, we demonstrate that the use of the R rs ratio between the red and infrared channels allowed a reduction of the R rs sensitivity in all cases, by an average of 50% with respect to changes in the mineral composition or size distribution of suspended sediment. In particular, the R rs ratio varied by less than 5% for PSD representative of surface river waters.

The contamination of edible leafy vegetables by atmospheric heavy metal-bearing particles is a major issue in environmental toxicology. In this study, the uptake of lead by cladodes of Opuntia ficus-indica (Ofi), traditionally used in Mexican cuisine and in livestock fodder, is investigated after a 4-months exposure of either cladodes or roots to synthetic Pb-fluorapatite particles. Atomic Absorption Spectroscopy (AAS) for the quantitative analysis of Pb levels, Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) for the examination of the cladode surface and fate of particles, and Micro-X-ray fluorescence (μXRF) measurements for elemental mapping of Pb in cladodes, were used. The results evidence that foliar contamination may be a major pathway for the transfer of Pb within Ofi cladodes. The stomata, areoles, and cuticle of cladode surface, play an obvious role in the retention and the incorporation of lead-bearing apatite, thus revealing the hazard of eating contaminated cladodes. The possibility of using series of successive cladodes for biomonitoring the atmospheric pollution in arid and semi-arid regions is also rapidly discussed., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Aggregation tests between bacteria and Polyethyleneimine (PEI) of low (600g/mol) and high (750,000g/mol) molecular weight were performed in order to address the physico-chemical mechanisms underlying the interactions between cationic polymer and bacterial membranes. The selected strain, Schewanella oneidensis MR-1, produces a lipopolysaccharide (LPS) of various lengths depending on the growth conditions. Optical density, bioaggregate size, electrophoretic mobility measurements, TEM and AFM observations, and cell lysis tests (crystal violet release), were collected to describe the PEI-mediated aggregation of LPS-O-antigen-free and LPS-O-antigen-decorated bacteria. The results show that PEI of low molecular weight (600g/mol) fails to aggregate bacteria, whereas PEIs of higher molecular weight (60,000 and 750,000g/mol) lead to flocculation at low polymer concentrations. In addition, the LPS-O antigen bacterial superstructure is shown to act as a protective barrier, thus delaying the harmful effects of the cationic polymer. Despite this protection, the interaction of bacterial membranes with increasing concentrations of PEI leads to a series of deleterious processes including biosurface modification (peeling, membrane permeabilization and/or lysis), aggregation of bacterial cells, and complexation of PEI with both released biosurface fragments and cytoplasmic residues issued from lysis., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Opuntia ficus-indica (Ofi) is a long-domesticated cactus that is widespread throughout arid and semiarid regions. Ofi is grown for both its fruits and edible cladodes, which are flattened photosynthetic stems. Young cladodes develop from mother cladodes, thus forming series of cladodes of different ages. Therefore, successive cladodes may hold some potential for biomonitoring over several years the local atmospheric pollution. In this study, cladodes, roots, dust deposited onto the cladodes, and soil samples were collected in the vicinity of three heavily polluted sites, i.e., a fertilizer industry, the road side of a highway, and mine tailings. The lead content was analyzed using atomic absorption spectroscopy (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS). Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) was used to characterize the cladode surfaces and the nature of dust deposit, and the lead isotopes were analyzed to identify the origin of Pb. The results show that (i) Ofi readily bioaccumulates Pb, (ii) the lead isotopic composition of cladodes evidences a foliar pathway of lead into Ofi and identifies the relative contributions of local Pb sources, and (iii) an evolution of air quality is recorded with successive cladodes, which makes Ofi a potential biomonitor to be used in environmental and health studies.

One of the most important sources of solid waste in the Mediterranean Basin ecosystem originated from the phosphate fertilizer industries, which discharge phosphogypsum (PG) directly into aquatic environments or are stacked on stockpiles. The present study investigates metal release from PG under the influence of variable pH, increasing PG mass content, and complexing organic matter ligands. Major ions from PG leachates, grain size and charge, main functional groups along with metal leachability (Pb, Cd, Cr, Cu, and Zn) were determined using ion chromatography, laser diffraction, zetameter, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy, respectively. The complete dissolution of PG recorded is at 2 g/L. Saturation and supersaturation with respect to PG may occur at concentrations of 3 and 4 g/L, respectively, revealing a clustering phenomenon leading to heavy metal encapsulation within the aggregates. Organic ligands such as citrate may trigger the cationic exchange within the PG suspension leading to ion release. As these factors are considered as specific process involving the release of contaminants from PG during storage under natural conditions, this study could set the foundations for PG remediation in aquatic environment. Organic ligands under controlled pH conditions could be utilized in treating fertilizer industrial wastes by taking into consideration the particularity of the receiving area, thus decreasing metal hazardous impact on natural media.

Fugitive dust emission, transport and deposition from phosphate fertilizer industries may pose an environmental hazard to the surrounding environment, particularly to soil. This study is to evaluate such hazard by investigating the fate of airborne pollutants, their transfer from atmosphere to soil surface, and their contamination potential. Concentrations of elements were measured in soil samples. Elemental analyses were carried out using ICP-AES and ICP-MS. Analysis of speciation of trace elements, using a sequential extraction method, was performed on the plant's raw material (apatite), product and waste (phosphate fertilizer and phosphogypsum). A model estimating local atmospheric dry deposition was formulated. Statistical analyses were performed on sample data. Measured phosphorus accumulated considerably to the north-east of the plant, mainly due to the prevailing wind and associated dry deposition. Results exhibited considerably above-threshold enrichments in potentially toxic, bio-available trace elements (Cd, Zn) (2.5-6.9, 295-506 mg kg(-1)) and radionuclide (U, 20-98.69 mg kg(-1)) within a major deposition area. Speciation results revealed Zn and Cd occurring predominantly in mobile phases within the pollution source materials. Dry deposition calculation showed extensive input fluxes of Sr, Zn, Cr, U, Ni and Cd. Significant correlation was established between measured trace elements concentrations and their calculated deposition fluxes. Phosphorus species were the principal carriers of trace elements in soils. The phosphate industry poses a serious soil pollution hazard, with deposited contaminants being potentially hazardous to plants and groundwater. This study serves as a basis to assess the phosphate industry's risk impact on soil, while it introduces combined analytical methodologies for such assessment.

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 (β-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., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.