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

International audienceThe 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 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) are 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. Changes in Ca-phosphate phase distribution were related to 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. TEM examination of chemical extraction residues revealed the presence of neoformed Al-Ca-phosphate species that invalidate the fractionation scheme. On the other hand, it confirmed that phosphate phases may undergo significant geochemical changes over a short time scale

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

International audienceThe 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

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

International audienceThe 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

Hydrolysis and flocculation : a structural approach through small-angle X-ray scattering

The flocculation of silica by coagulation with hydrolyzed aluminum salt and the flocculation of aluminum salt in the presence of organic acids at pH 6.5 have been studied by using Small-Angle X-ray Scattering. The flocculation of silica at pH 4.5 by isolated Al13 is very similar to its flocculation by nonhydrolyzable salt as Ca++ ; the fractal dimension Df of the flocs is 2.20. At pH 7.5, Al13 is hydrolyzed and strongly aggregated through hydroxo bridges, and the structure of the flocs is that of Al13 aggregates, i.e Df = 1.7. The flocculation of aluminum in the presence of organics such as acetate, salicylate, lactate and oxalate (organics/Al = 0.25, 0.5 and 1.0) occurs at lower pH values than in the absence of organics. The SAXS curves display a crossover region in the Q-range 0.05 to 0.15 Å-1, due to the presence of small, loose -Al-OH-Al-aggregates. The simulation of the outermost part of the SAXS curves shows that the organic ligands limit the Al hydrolysis at the stage of the monomers and small oligomers by competing with the OH- ions. This charge screening results in high coordination numbers and in high density of the flocs ([MATH])

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

International audienceThe role of mineral surface hydrophobicity on attachment to activated sludge flocs was investigated. Fluorite and quartz particles of similar granulometry were hydrophobized by adsorbing sodium oleate and docecylamine 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

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

International audienceThis paper investigates the potential of stable isotopes of both water (δD and δ18OH2O) and dissolved sulfate (δ34S and δ18OSO4) 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 δ18OSO4 might find use as a urine tracer

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

International audienceThe 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 acidity are determinant characteristics for pollutant entrapment capacity at concentrations below the critical micellar concentration (CMC) of humic substances

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

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

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