Catherine Faur

Analysis of endocrine disrupting compounds in wastewater and drinking water treatment plants at the nanogram per litre level.

Abstract The determination of steroid hormones, alkylphenolic compounds and bisphenol A at the ng l−1 level in environmental water samples (surface water and WasteWater Treatment Plant samples (WWTP)) is performed by a specific analytical procedure. Pre‐concentration by solid‐phase extraction conditions was optimized using C18 cartridges for steroid hormones and polymeric Oasis HLB cartridges for phenolic compounds. Identification and quantification were performed using a LC‐MS/MS system with electrospray ionization in the negative mode for both compound families. For steroid hormones, the need to have limits of detection lower than 0.5 ng l−1 in WWTP samples led to the improvement of a purification step on silica cartridges. In the case of the phenolic compounds, no purification was required because of their lower estrogenicity. The limits of detection in WWTP effluents ranged between 0.02 ng l−1 and 0.21 ng l−1 for steroid hormones and 0.4 and 10.2 ng l−1 for phenolic compounds. The method was then applied to determine concentrations of the target compounds at each step of a WWTP. The process efficiencies were evaluated. Finally, concentrations were measured in influents and effluents of a Drinking Water Treatment Plant showing the complete removal of estrogenicity.

Removal of nickel ions from aqueous solution by low energy-consuming sorption process involving thermosensitive copolymers with phosphonic acid groups

In order to remove metal ions from wastewaters, thermosensitive copolymers bearing sorption properties toward metal cations were prepared by free radical copolymerization between the N-n-propylacrylamide (NnPAAm) and the (dimethoxyphosphoryl)methyl 2-methylacrylate (MAPC1), followed by a hydrolysis of the phosphonated esters into phosphonic diacid groups ((h)MAPC1). The thermosensitivity and the sorption abilities of the resulting poly(NnPAAm-stat-(h)MAPC1) copolymers were studied. Lower Critical Solution Temperatures (LCST) of these copolymers ranged from 22 °C to 26 °C, depending on the molar ratio of phosphonated monomers and were lower than those obtained with usual poly(N-isopropylacrylamide)-based polymers. The influence of both the temperature and the pH on the sorption properties of the copolymers was evaluated for Ni(2+) cations. The most interesting results were obtained for temperatures around the LCST, i.e. when the proximity of the complexing groups favored the sorption of metallic cations. Concerning the pH effect, the maximum sorption capacity was obtained at pH 7, i.e. in the absence of competition between the sorption of H(+) and Ni(2+) ions on the phosphonic acid groups. The influence of the molar ratio of metal ions and phosphonate moieties was also studied and different sorption mechanisms were proposed.

Synthesis by RAFT of innovative well-defined (co)polymers from a novel phosphorus-based acrylamide monomer

The present contribution reports on the synthesis and controlled polymerization of a novel acrylamide monomer containing phosphonated moieties, namely diethyl-2-(acrylamido)ethylphosphonate. This monomer appears to be of great interest due to the phosphonated moieties, which can lead to a wide range of applications, associated with the chemical stability of the acrylamide compared to more common (meth)acrylate monomers. Reversible Addition–Fragmentation Transfer (RAFT) polymerization of this monomer was investigated using two different trithiocarbonate chain transfer agents, and it allowed the synthesis of poly(diethyl-2-(acrylamido)ethylphosphonate) with controlled molecular weight and low dispersity. Additionally, a diblock copolymer was successfully prepared by a similar RAFT procedure using thermosensitive poly(N-n-propylacrylamide) as a macro-chain transfer agent. A combination of both stimuli-responsive and phosphonated ester or phosphonic diacid (after hydrolysis) containing blocks appears valuable for drug delivery or water treatment, for instance.

Alginate and Algal-Based Beads for the Sorption of Metal Cations: Cu(II) and Pb(II)

Alginate and algal-biomass (Laminaria digitata) beads were prepared by homogeneous Ca ionotropic gelation. In addition, glutaraldehyde-crosslinked poly (ethyleneimine) (PEI) was incorporated into algal beads. The three sorbents were characterized by scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX): the sorption occurs in the whole mass of the sorbents. Sorption experiments were conducted to evaluate the impact of pH, sorption isotherms, and uptake kinetics. A special attention was paid to the effect of drying (air-drying vs. freeze-drying) on the mass transfer properties. For alginate, freeze drying is required for maintaining the porosity of the hydrogel, while for algal-based sorbents the swelling of the material minimizes the impact of the drying procedure. The maximum sorption capacities observed from experiments were 415, 296 and 218 mg Pb g−1 and 112, 77 and 67 mg Cu g−1 for alginate, algal and algal/PEI beads respectively. Though the sorption capacities of algal-beads decreased slightly (compared to alginate beads), the greener and cheaper one-pot synthesis of algal beads makes this sorbent more competitive for environmental applications. PEI in algal beads decreases the sorption properties in the case of the sorption of metal cations under selected experimental conditions.

Removal of metal ions from aqueous effluents involving new thermosensitive polymeric sorbent.

In this work, new thermosensitive copolymers bearing phosphonated groups were synthesized and used to remove metal pollution. Sorption properties are brought by hydrolyzed (dimethoxyphosphoryl)methyl 2-methylacrylate (hMAPC1) monomer. N-n-propylacrylamide (NnPAAm) led to the thermoresponsive properties of the copolymers. Low lower critical solution temperature (LCST) values were observed, ranging between 20 and 25 °C depending on the molar ratio of each monomer in the copolymer. Sorption properties of these copolymers towards nickel ions were evaluated for increasing temperatures (10-40 °C), Ni ion concentrations of 20 mg L(-1) and pH values between 3 and 7. Best results were observed for temperatures just lower than the LCST (20 °C), when the copolymer was fully soluble in water solution. For temperature higher than the LCST, phosphonic diacid groups accessibility was considerably reduced by the precipitation of the thermosensitive part of the copolymer leading to lower sorption properties. In these conditions, the highest Ni removal by the copolymer was observed for pH = 7, when there was almost no competition between the sorption of H(+) and Ni(2+) ions on the phosphonic acid groups. These optimal conditions enabled removal of about 70% of the nickel in the synthetic effluent.

BIODEGRADATION OF ENDOCRINE DISRUPTERS: CASE OF 17BETA-ESTRADIOL AND BISPHENOL A.

Abstract The biodegradation of 17 β‐estradiol (E2) and bisphenol A (BPA) was compared to that of a reference pollutant, sodium benzoate (SB), known for its high biodegradability. The biodegradation was measured using the Sturm test (ISO 9439 modified Sturm test). The susceptibility of the target pollutants to be degraded by microorganisms of activated sludge from a wastewater treatment plant (WWTP) was evaluated by the production of carbon dioxide (CO2). Sorption experiments onto inactivated sludge were carried out to assess the contribution of sorption in E2 and BPA removal during biological treatment in a WWTP. E2 was more adsorbed than BPA onto inactivated sludge, probably making it less accessible to assimilation by microorganisms. In fact, E2 was less biodegradable than BPA with 66 % and 74 % of theoretical CO2 formation (ThCO2) in 28 days, respectively. However, E2 showed faster biodegradation than BPA due to the shorter adaptation time of the microorganisms to start the assimilation. Final concentrations were measured and revealed that, under Sturm test conditions, E2 was totally removed from the aqueous phase while some traces of BPA were detected. This result could be explained by the lower adsorbability of BPA observed in adsorption experiments onto inactivated sludge. To investigate competition in a bi‐component solution, Sturm tests were carried out with BPA/SB and E2/SB. Moreover, the biodegradation curves obtained did not indicate a toxicity of the target compounds towards microorganisms, which rapidly degraded SB. In the case of BPA/SB, an inflection in the curve confirmed the adaptation time of 4–5 days for BPA to be degraded.

Sorption properties of a new thermosensitive copolymeric sorbent bearing phosphonic acid moieties in multi-component solution of cationic species

In this paper, original thermosensitive copolymers bearing phosphonic acid groups, namely the poly(N-n-propylacrylamide-stat-2-(methacryloyloxy)methylphosphonic acid) (P(NnPAAm-stat-hMAPC1)) were synthesized, and their sorption properties for three divalent cations (Ni(2+), Ca(2+), Cd(2+)) and one trivalent cation (Al(3+)) have been investigated. The sorption experiments were performed with increasing relative amount of cationic pollution compared to the amount of sorption sites (C(n+)/P ratio) in mono and multi-component solutions to investigate the sorption mechanisms. C(n+)/P proved to strongly affect the sorption capacity and high capacities were obtained for all cations at highest C(n+)/P ratios, reaching one mole of C(sorbed)(n+) per phosphonated moiety. For divalent cations, sorption mechanisms were likely to be described by electrostatic interactions only, whereas for aluminum trivalent cation the sorption not only resulted from electrostatic interactions but also from the formation of coordination binding. The selectivity of the phosphonic acid moieties for aluminum cations was demonstrated, highlighting the interest of P(NnPAAm-stat-(h)MAPC1) for their use for the treatment of metallic pollution from wastewater.

Modeling competitive sorption of lead and copper ions onto alginate and greenly prepared algal-based beads

The binary sorption of Pb(II) and Cu(II) onto calcium alginate, algal biomass and algal/glutaraldehyde-crosslinked polyethyleneimine (PEI) composite beads was studied in the absence and presence of Ca(II). Different competitive models were compared for predicting the equilibrium data. Results show that all the sorbents have a significant preference for Pb(II) over Cu(II) in Pb-Cu system: the separation factors reach 14.1, 9.1 and 3.6 for alginate, algal biomass and algal/PEI beads, respectively. Kinetic studies confirm the occurrence of an ion-exchange mechanism between Pb(II) and Cu(II) as the sorption sites are progressively saturated. Competitive Sips model predicts well the sorption data for all the sorbents. In Pb-Cu-Ca system, the Cu(II) sorption by algal beads was negligible, while algal/PEI still maintained a significant sorption of Cu(II) sorption under these conditions.

Dynamic Mechanisms of the Bactericidal Action of an Al2O3-TiO2-Ag Granular Material on an Escherichia coli Strain.

ABSTRACT The bactericidal activity of an Al2O3-TiO2-Ag granular material against an Escherichia coli strain was confirmed by a culture-based method. In particular, 100% of microorganisms were permanently inactivated in 30 to 45 min. The present work aimed to investigate the mechanisms of the bactericidal action of this material and their dynamics on Escherichia coli using different techniques. Observations by transmission electron microscopy (TEM) at different times of disinfection revealed morphological changes in the bacteria as soon as they were put in contact with the material. Notably highlighted were cell membrane damage; cytoplasm detachment; formation of vacuoles, possibly due to DNA condensation, in association with regions exhibiting different levels of electron density; and membrane lysis. PCR and flow cytometry analyses were used to confirm and quantify the observations of cell integrity. The direct exposure of cells to silver, combined with the oxidative stress induced by the reactive oxygen species (ROS) generated, was identified to be responsible for these morphological alterations. From the first 5 min of treatment with the Al2O3-TiO2-Ag material, 98% of E. coli isolates were lysed. From 30 min, cell viability decreased to reach total inactivation, although approximately 1% of permeable E. coli cells and 1% of intact cells (105 genomic units · ml−1) were evidenced. This study demonstrates that the bactericidal effect of the material results from a synergic action of desorbed and supported silver. Supported silver was shown to generate the ROS evidenced.

Membrane process treatment for greywater recycling: investigations on direct tubular nanofiltration.

On-site greywater recycling and reuse is one of the main ways to reduce potable water requirement in urban areas. Direct membrane filtration is a promising technology to recycle greywater on-site. This study aimed at selecting a tubular nanofiltration (NF) membrane and its operating conditions in order to treat and reuse greywater in buildings. To do so, a synthetic greywater (SGW) was reconstituted in order to conduct experiments on a reproducible effluent. Then, three PCI NF membranes (AFC30, AFC40 and AFC80) having distinct molecular weight cut-offs were tested to recycle this SGW with a constant concentration at 25°C at two different transmembrane pressures (20 and 35 bar). The best results were obtained with AFC80 at 35 bar: the flux was close to 50 L m⁻²  h⁻¹, retentions of 95% for chemical oxygen demand and anionic surfactants were observed, and no Enterococcus were detected in the permeate. The performances of AFC80 were also evaluated on a real greywater: fluxes and retentions were similar to those observed on SGW. These results demonstrate the effectiveness of direct nanofiltration to recycle and reuse greywater.