Understanding Aging Mechanisms in the Context of UV Irradiation of a Low Fouling and Self-Cleaning PVDF-PVP-TiO2 Hollow-Fiber Membrane.

In the context of designing a photocatalytic self-cleaning/low-fouling membrane, the stability of PVDF-PVP-TiO2 hollow-fiber membranes under UV irradiation has been studied. The effect of irradiation power, aqueous environment composition and fouling state on the properties of the membranes has been investigated. With this aim, SEM observations, chemical analysis and tensile strength measurements have been conducted. The results indicate that pristine membranes that undergo UV irradiation in ultra-pure water are significantly degraded due to attacks of OH° radicals. However, when methylene blue, used as a model pollutant, is introduced in the aqueous environment, OH° radicals preferentially react with this molecule rather than the membranes, successfully preserving the original properties of the latter. The presence of an adsorbed BSA layer (pre-fouling by immersion) on the surface of the membrane delays membrane aging, as the BSA layer is degraded by radicals instead of the membrane material. The degradation of the BSA layer also validates the self-cleaning properties of the membrane. However, when membranes are pre-fouled by filtration of a 2 g/L BSA solution, delay to aging is less. This is because OH° radicals do not reach BSA molecules that are trapped inside the membrane pores, and therefore react with the membrane material.

Performance of PVDF-TiO2 Membranes during Photo-Filtration in the Presence of Inorganic and Organic Components.

In this study, the anti-fouling performance of PVDF-TiO2 composite membranes, indicated by their permeate flux, was studied with different types of synthetic feed solutions. Photo-filtration (filtration under continuous UV irradiation) of solutions containing inorganic and organic components, which are ubiquitous in drinking/natural water, was performed to evaluate their influence on the photo-induced properties and performance of the membranes. The results indicated that inorganic fouling was unlikely to occur on PVDF-TiO2 membranes, and the presence of common inorganic ions in drinking water did not hinder their performance. However, in the particular case where a small amount of Cu2+ coexisted alongside HCO3- in the feed solution, inorganic fouling occurred, causing severe flux decline and prohibiting the photo-induced properties of the membranes. On the other hand, when used to filter organic fouling solutions, the membranes showed strong resistance to sodium alginate fouling, and less so for humic acids. In terms of separation efficiency, the membranes showed no advantages when operated in photo-filtration mode, as the rejection rate of both foulants under photo-filtration was not higher than that under normal filtration. In the case of humic acids, the photodegradation of humic substances into smaller compounds that were able to enter the permeate stream led to a lower rejection rate. Nevertheless, photo-filtration of these organic foulants still offered a higher permeate flux than normal filtration, up to a certain concentration level (5 mg/L for humic acids and 50 mg/L for sodium alginate).

Influence of Preparation Temperature on the Properties and Performance of Composite PVDF-TiO2 Membranes.

Composite PVDF-TiO2 membranes are studied extensively in literature as effective anti-fouling membranes with photocatalytic properties. Yet, a full understanding of how preparation parameters affect the final membrane structure, properties and performance has not been realized. In this study, PVDF-TiO2 membranes (20 wt% TiO2/PVDF) were fabricated via the non-solvent-induced phase separation (NIPS) method with an emphasis on the preparation temperature. Then, a systematic approach was employed to study the evolution of the membrane formation process and membrane properties when the preparation temperature changed, as well as to establish a link between them. Typical asymmetric membranes with a high porosity were obtained, along with a vast improvement in the permeate flux compared to the neat PVDF membranes, but a reduction in mechanical strength was also observed. Interestingly, upon the increase in preparation temperature, a significant transition in membrane morphology was observed, notably the gradual diminution of the finger-like macrovoids. Other membrane properties such as permeability, porosity, thermal and mechanical properties, and compression behavior were also influenced accordingly. Together, the establishment of the ternary phase diagrams, the study of solvent-nonsolvent exchange rate, and the direct microscopic observation of membrane formation during phase separation, helped explain such evolution in membrane properties.

Boosted Cr(VI) sorption coupled reduction from aqueous solution using quaternized algal/alginate@PEI beads.

APEI beads (algal/alginate-PEI) were quaternized for enhancing the sorption of Cr(VI) (Q-APEI). The readily reduction of Cr(VI) into Cr(III) in acidic solution and in the presence of organic material constitute an additional phenomenon to be taken into account for the removal of Cr(VI) by Q-APEI. The optimal pH value for both the sorption and reduction of Cr(VI) was close to 2. The sorption isotherm was well described by the Sips model in batch system; the experimental maximum Cr(VI) sorption capacity of Q-APEI was 334 mg Cr(VI) g-1, including a reduction yield close to 25%. The pseudo-second-order kinetic model (PSORE) and the Yan model fit the uptake kinetics and breakthrough curves, in a fixed-bed system with circulation or single-path modes, respectively. The mechanism of reduction-assisted sorption allows boosting the global removal of chromate. Furthermore, the testing of Cr(VI) for three successive sorption and desorption cycles shows the remarkable stability of the sorbent for Cr(VI) removal. The Cr(VI) sorption coupled reduction mechanism and interactions between the sorbent and Cr(VI) were further explained using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS).

Investigation of mercury(II) and copper(II) sorption in single and binary systems by alginate/polyethylenimine membranes.

This study investigates Hg(II) and Cu(II) sorption in single and binary systems by alginate/polyethylenimine membranes. Batch experiments are conducted to assess the metal sorption performance. FTIR and SEM-EDX analyses are used to identify metal binding mechanism. The sorption kinetics are better fitted by the pseudo-second-order-equation compared to the pseudo-first-order-equation. Three isotherms are compared for fitting the sorption in mono-component solutions and the Sips model gives the best simulation of experimental data. The competitive-Sips model fits well sorption data in Hg-Cu binary solutions and finds that the Cu uptake is drastically reduced by Hg competition. Copper(II) uptake remains negligible at low pH whereas it increases with pH up to 6 because of material deprotonation. Mercury(II) sorption behaves differently, it slightly changes from pH 1 (qeq: 0.76 mmol g-1) to pH 6 (qeq: 0.84 mmol g-1) due to chloro-anion formation. Therefore, playing with the pH allows separating Hg(II) from Cu(II).

Pb doped ZnO nanoparticles for the sorption of Reactive Black 5 textile azo dye.

In this study, Pb doped ZnO nanoparticles were synthesized by a sol-gel technique for the sorption of Reactive Black 5 (RB5) textile dye in aqueous solution. The ZnO:Pb (2 and 4%) nanoparticles have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and cryogenic nitrogen adsorption method. The average size of the synthesized nanoparticles was less than 100 nm and the surface areas were 18.8 and 20.8 m2/g, respectively for ZnO:Pb 2% and ZnO:Pb 4%. Batch sorption experiments were performed for color removal of RB5 dye at ambient temperature and 30 mg/L dye concentration. The central composite design with response surface methodology was used to study the effect of sorption condition (pH, nanoparticles dose and contact time). The significance of independent variables and their interactions was tested by analysis of variance. The optimum conditions of color removal were pH = 7, 2 g/L dose of nanoparticles and a contact time of 79 min. The color removal performance was 79.4 and 98.1% for ZnO:Pb 2 and 4% respectively. The pseudo-second-order model described well the removal rates while the Langmuir model fitted well the adsorption isotherms.

Selenium(VI) and copper(II) adsorption using polyethyleneimine-based resins: Effect of glutaraldehyde crosslinking and storage condition.

This study synthesizes polyethyleneimine-glutaraldehyde (PEI-GA) resins using different amounts of GA to crosslink with a certain amount of PEI and compares these adsorbents for the adsorption of Cu(II) (cations) and Se(VI) (anions). Moreover, the stability of adsorption affinity of PEI-GA resins stored in open or sealed conditions is also studied. Results show that the amount of GA for PEI crosslinking does not affect the adsorption performance for Se(VI), especially when PEI/GA mass ratio is less than 2, while for Cu(II), the increase on GA amount decreases Cu(II) adsorption capacity. This difference is directly correlated to the change in the adsorption mechanism from electrostatic attraction to chelation. The primary and secondary amine groups on PEI can easily react with CO2 in the air to form carbamate, potentially affecting the adsorption performance of PEI. Results also indicate that the adsorption efficiency for Se(VI) is hardly affected by the storage condition, while that for Cu(II) decreases significantly after 20-day storage compared to the freshly prepared ones. In addition, all of the adsorbents can selectively remove Se(VI) from Se(VI)-As(V) system and Cu(II) from Pb(II)-Cu(II) system, indicating that the crosslinking has no significant influence on the selectivity.

Se(VI) sorption from aqueous solution using alginate/polyethylenimine membranes: Sorption performance and mechanism.

New high percolating alginate membranes are designed without using sophisticated drying methods: negatively charged alginate reacts with positively charged polyethylenimine (PEI), prior to be crosslinked with glutaraldehyde and air-dried. This is sufficient to obtain a highly macroporous structured membrane. Highly percolating properties of these new A-PEI membranes make the material applicable in natural drainage systems. The high density of amine groups in composite membranes explain their high affinity for anions in acidic solutions. FTIR, SEM-EDX and XPS analysis are used to explore the sorption mechanism. Se(VI) is sorbed through electrostatic attraction between positive amine groups and negative selenium anions; in a second step, bound Se(VI) is reduced by amine and hydroxyl groups in acidic conditions. A-PEI membranes are successfully used for recovering Se(VI) anions at pH 2. The maximum sorption capacity is close to 83 mg Se g-1; the sorption isotherm is described by the Sips and Langmuir equations. The membranes are poorly sensitive to flow rate in the range 15-50 mL min-1. The kinetic profiles are fitted by the pseudo-first order rate equation. Solute desorption is operated using NaOH solutions; the sorbent shows a remarkable stability in sorption and desorption properties for a minimum of 4 cycles.

New highly-percolating alginate-PEI membranes for efficient recovery of chromium from aqueous solutions.

Highly percolating membranes are prepared by the interaction of polyethylenimine and alginate (with glutaraldehyde crosslinking). SEM illustrates the macroporous structure of the material. The material is characterized by FTIR before and after chromate anions sorption. Batch-simulated continuous sorption experiments revealed that the maximum sorption occurred at pH 2 and the flow rate has limited effect on sorption efficiency. Uptake kinetics and sorption isotherms are well fitted by the pseudo-second-order rate and Sips equations, respectively. Maximum sorption is found close to 314 mg g-1. Competition effects from Ca(II), Cu(II), Cl-, NO3-, and SO42- are investigated to evaluate sorbent selectivity. The membranes are applied to remediate a simulate of Cr(VI) contaminated electroplating wastewater. Successive cycles of sorption and desorption show that the membranes maintain sorption capacity higher than 200 mg Cr g-1 for both Cr(VI) and total chromium for the first two cycles. These new highly percolating membranes have promising performances for Cr(VI) removal.

Algal Foams Applied in Fixed-Bed Process for Lead(II) Removal Using Recirculation or One-Pass Modes.

The incorporation of brown algae into biopolymer beads or foams for metal sorption has been previously reported. However, the direct use of these biomasses for preparing foams is a new approach. In this study, two kinds of porous foams were prepared by ionotropic gelation using algal biomass (AB, Laminaria digitata) or alginate (as the reference) and applied for Pb(II) sorption. These foams (manufactured as macroporous discs) were packed in filtration holders (simulating fixed-bed column) and the system was operated in either a recirculation or a one-pass mode. Sorption isotherms, uptake kinetics and sorbent reuse were studied in the recirculation mode (analogous to batch system). In the one-pass mode (continuous fixed-bed system), the influence of parameters such as flow rate, feed metal concentration and bed height were investigated on both sorption and desorption. In addition, the effect of Cu(II) on Pb(II) recovery from binary solutions was also studied in terms of both sorption and desorption. Sorption isotherms are well fitted by the Langmuir equation while the pseudo-second order rate equation described well both sorption and desorption kinetic profiles. The study of material regeneration confirms that the reuse of the foams was feasible with a small mass loss, even after 9 cycles. In the one-pass mode, for alginate foams, a slower flow rate led to a smaller saturation volume, while the effect of flow rate was less marked for AB foams. Competitive study suggests that the foams have a preference for Pb(II) over Cu(II) but cannot selectively remove Pb(II) from the binary solution.

Praseodymium sorption on Laminaria digitata algal beads and foams.

Algal (Laminaria digitata) beads and algal foams have been prepared by a new synthesis mode and the sorbents were tested for praseodymium sorption in batch and fixed-bed like systems (recirculation or one-pass modes), respectively. Metal binding occurs through ion-exchange with Ca(II) ions used for ionotropic gelation of alginate contained in the algal biomass and eventually with protons. Sorption isotherms at pH 4 are described by the Langmuir and the Sips equations with maximum sorption capacities close to 110-120mgPrg-1. Uptake kinetics are fitted by the pseudo-second order reaction rate equation for both beads and foams; in the case of beads the Crank equation also gives good fit of experimental data. Metal is successfully desorbed using 2M HCl/0.05M CaCl2 solutions and the sorbent can be efficiently re-used for a minimum of 5 cycles with negligible decrease in sorption/desorption properties and appreciable concentrating effect (around 8-10 times the initial metal concentration). Tested in continuous mode, the algal foam shows typical breakthrough curves that are fitted by the Yan method; desorption is also efficient and allows under the best conditions to achieve a concentration factor close to 8.

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.

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.

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

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 (10(5) 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.

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.

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.

Formulation of synthetic greywater as an evaluation tool for wastewater recycling technologies.

On-site greywater recycling is one of the main ways of preserving water resources in urban or arid areas. This study aims to formulate model synthetic greywater (SGW) in order to evaluate and compare the performances of several recycling processes on a reproducible effluent. The formulated SGW is composed of septic effluent to provide indicators of faecal contamination, and technical quality chemical products to simulate organic pollution of greywater. To ensure that the SGW developed is representative of household greywater, its analysis was compared to real greywater collected and analysed (RGWs) and to real greywater mentioned in previous publications (RGW(L)). The performance of a direct nanofiltration process with a concentration factor of 87.5% at 35 bar was then tested on both real greywater and SGW. The laboratory experimental results are promising: fluxes and retention rates were high, and similar for both effluents. The permeation flux was higher than 50 L h(-1) m(-2). Retentions greater than 97% for biochemical oxygen demand for 5 days (BOD5) and 92% for anionic surfactants were observed. No Enterococcus were detected in the two permeates. These results confirm that the model SGW developed in this study shows the same behaviour as real greywater when recycled. Thus, the use of this SGW developed in this study was validated for the evaluation of membrane efficiency to treat greywater. This new tool will be a real asset for future studies.

Development and statistical validation of a quantitative method for the determination of steroid hormones in environmental water by column liquid chromatography/tandem mass spectrometry.

This paper presents an analytical method applied to the determination of 3 natural steroid hormones, estrone, 17 beta-estradiol, and 16 alpha-hydroxyestrone, and the contraceptive estrogen, 17 alpha-ethynylestradiol, at the sub-ng/L level in water samples [surface water and wastewater treatment plant (WWTP) samples]. The solid-phase extraction conditions were optimized using C18 cartridges. Identification and quantification were performed using a column liquid chromatographic/tandem mass spectrometric system with electrospray ionization in the negative mode. Before analyzing steroids in complex matrixes, statistical tools permitted a fine validation of the analytical method, and performance was evaluated for spring water in terms of recovery, specificity, trueness, repeatability, and intralaboratory reproducibility. The results showed the accuracy of the method, and limits of detection (LOD) ranged between 0.02 and 0.21 ng/L. The determination of steroids in WWTP effluents, which contain high levels of organic matter, required an additional purification step on silica cartridges. The high efficiency of the purification was proved with LOD < 0.3 ng/L from 200 mL sample. Specificity of the entire analytical procedure was shown by repeatable recoveries at low and high levels of the calibration range.

Adsorption of dyes onto activated carbon cloth: using QSPRs as tools to approach adsorption mechanisms.

The present study aimed to investigate the adsorption of dyes onto activated carbon cloths. Kinetics and isotherms were studied based on results of batch reactors to constitute databases for the adsorption rates and capacities of 22 commercial dyes. Added to a qualitative analysis of experimental results, quantitative structure property relationships (QSPRs) were used to determine the structural features that influence most adsorption processes. QSPRs consisted of multiple linear regressions correlating adsorption parameters with molecular connectivity indices (MCIs) as molecular descriptors. Results related to adsorption kinetics showed that the size of molecules was the significant feature, the high order MCIs involved in QSPRs indicating the influence of a critical size on adsorption rate. Improved statistical fits were obtained when the database was divided according to the chemical classes of dyes. As regards to adsorption isotherms, their particular form led to the use of saturation capacity as the adsorption parameter. By contrast with adsorption kinetics, molecular overcrowding seemed to be of less influence on adsorption equilibrium. In this case, MCIs included in the QSPR were more related to details of the molecular structure. The robustness of the QSPR assessed for azo dyes was studied for the other dyes. Although the small size of the database limited predictive ability, features relevant to the influence of the database composition on QSPRs have been highlighted.