Probing the reduction of adhesion forces between biofilms and anti-biofouling filtration membrane surfaces using FluidFM technology.

Biofouling is a persistent problem in many sectors (healthcare, medicine, marine, and membrane filtration processes). To control the biofouling of surfaces, it is essential to overcome or reduce the adhesion forces between biofilms and surfaces. To access and understand the molecular basis of these interactions, atomic force microscopy (AFM) is a well-suited technology that can measure adhesion forces at the piconewton level. However, AFM-based existing methods only probe interactions between individual cells and surfaces, which is not representative of realistic conditions given that bacteria mainly exist in biofilms. We develop here an original method using FluidFM, a combination of AFM and microfluidics, to probe the adhesion forces between biofilms and filtration membranes modified with an anti-biofouling agent, vanillin. This strategy involves i) growing bacterial biofilms on micrometer-sized polystyrene beads, ii) aspirating these biofilm beads at the aperture of microfluidic cantilevers and iii) using them as probes in force spectroscopy experiments. The results obtained first showed that COOH-functionalized polystyrene beads are more suitable for bacterial growth, and that biofilms obtained after 3 h of incubation could be used with FluidFM. Then, biofilm-scale force spectroscopy experiments showed a significant decrease in adhesion forces, adhesion work, and adhesion events after membrane modification, demonstrating the potential of vanillin-coated membranes to reduce biofouling. In addition, the comparison between results at the individual cell and biofilm scales highlighted the complexity of polymeric matrix unbinding and/or unfolding in the biofilm, showing that individual cells behave differently from biofilms. Overall, this method could have implications in the fields of materials science, chemical engineering, health, and the environment.

pH-Dependent Adsorption of Human Serum Albumin Protein on a Polystyrene-Block-Poly(acrylic acid)-Coated PVDF Membrane.

This study reports the investigation of human serum albumin (HSA) adsorption on a poy-styrene-block-poly(acrylic acid) (PS-b-PAA)-coated PVDF membrane, which is a potential smart material for biomedical applications. First, copolymer coating on the membrane surface was successfully performed, due to the hydrophobic interaction of the PS anchoring group with the PVDF membrane. This was confirmed by Fourier transform infrared spectroscopy (FTIR) characterization of the membrane. Then, HSA adsorption onto the coated membrane was assessed and was proved to be strongly dependent on the pH of the protein solution. Indeed, both FTIR mapping and mass balance calculation using UV-visible spectroscopy displayed a greater HSA adsorption on the membrane at pH 5, even though it still took place at higher pH, but to a lower extent. Afterwards, an ionic strength influence study evinced the role of electrostatic interactions between HSA and the PAA layer on HSA adsorption. Dead-end filtration of HSA through the coated membrane confirmed the pH dependence of HSA adsorption on the coated membrane.

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.

Pearl-necklace assembly of human serum albumin with the poly(acrylic acid) polyelectrolyte investigated using small angle X-ray scattering (SAXS).

In this comprehensive study, the interaction of human serum albumin (HSA) with poly(acrylic acid) (PAA) was explored using small angle X-ray scattering (SAXS) combined with chromatography. The results revealed the formation of a complex between HSA macromolecules and PAA chains but solely under some specific conditions of the ionic strength and pH of the medium. In fact, this binding was found to take place only at pH close to 5 and at low ionic strength (0.15 M). Otherwise, for a higher pH and a salt concentration of 0.75 M the HSA-PAA complex tends to dissociate completely showing the reversibility of the complexation. The assessment of the influence of the HSA/PAA molar ratio on the radius of gyration of the complex suggests that 4 HSA molecules could bind to each 100 kDa PAA chain. In addition, the Porod volume evaluation for the same range of the HSA/PAA ratio confirms this assumption. Finally, an all-atom SAXS modelling study using the BUNCH program was conducted to find a compatible model that fits the HSA-PAA complex scattering data. This model allows us to portray the HSA/PAA complex as a pearl-necklace assembly with 4 HSA molecules on the 100 kDa PAA chain.

Nanofiltration performances after membrane bioreactor for hospital wastewater treatment: Fouling mechanisms and the quantitative link between stable fluxes and the water matrix.

Treatment combining membrane bioreactors (MBR) and nanofiltration (NF) is becoming an emerging wastewater treatment strategy. The combined process is capable of producing high quality water potentially reusable; however, diverse compositions of MBR effluents induce several types and degrees of NF membrane fouling that impacts process productivity. Moreover, since MBR effluent composition for one type of wastewater source is variable depending on the MBR efficiency at different periods, downstream NF membrane fouling types and degrees may consequently change over time. In that context, the present paper aims at developing effective fouling control strategies of NF membrane in the case of the filtration of MBR effluents taken from a MBR system installed in a French hospital. These effluents were filtrated under various transmembrane pressures, and stable fluxes during these filtrations were determined. Several types and degrees of fouling mechanisms were then identified through surface morphology observation and the analysis of chemical compositions of fouled membranes. The diverse flux behaviour was further associated with the fouling mechanisms and foulant compositions. Based on the study of these mechanisms, the quantitative link between stable fluxes and calcium phosphate concentrations in MBR effluents has been established.

Electro-oxidation of organic pollutants by reactive electrochemical membranes.

Electro-oxidation processes are promising options for the removal of organic pollutants from water. The major appeal of these technologies is the possibility to avoid the addition of chemical reagents. However, a major limitation is associated with slow mass transfer that reduces the efficiency and hinders the potential for large-scale application of these technologies. Therefore, improving the reactor configuration is currently one of the most important areas for research and development. The recent development of a reactive electrochemical membrane (REM) as a flow-through electrode has proven to be a breakthrough innovation, leading to both high electrochemically active surface area and convection-enhanced mass transport of pollutants. This review summarizes the current state of the art on REMs for the electro-oxidation of organic compounds by anodic oxidation. Specific focuses on the electroactive surface area, mass transport, reactivity, fouling and stability of REMs are included. Recent advances in the development of sub-stoichiometric titanium oxide REMs as anodes have been made. These electrodes possess high electrical conductivity, reactivity (generation of •OH), chemical/electrochemical stability, and suitable pore structure that allows for efficient mass transport. Further development of REMs strongly relies on the development of materials with suitable physico-chemical characteristics that produce electrodes with efficient mass transport properties, high electroactive surface area, high reactivity and long-term stability.

Mineralization of organic pollutants by anodic oxidation using reactive electrochemical membrane synthesized from carbothermal reduction of TiO2.

Reactive Electrochemical Membrane (REM) prepared from carbothermal reduction of TiO2 is used for the mineralization of biorefractory pollutants during filtration operation. The mixture of Ti4O7 and Ti5O9 Magnéli phases ensures the high reactivity of the membrane for organic compound oxidation through •OH mediated oxidation and direct electron transfer. In cross-flow filtration mode, convection-enhanced mass transport of pollutants can be achieved from the high membrane permeability (3300 LMH bar-1). Mineralization efficiency of oxalic acid, paracetamol and phenol was assessed as regards to current density, transmembrane pressure and feed concentration. Unprecedented high removal rates of total organic carbon and mineralization current efficiency were achieved after a single passage through the REM, e.g. 47 g m-2 h-1 - 72% and 6.7 g m-2 h-1 - 47% for oxalic acid and paracetamol, respectively, at 15 mA cm-2. However, two mechanisms have to be considered for optimization of the process. When the TOC flux is too high with respect to the current density, aromatic compounds polymerize in the REM layer where only direct electron transfer occurs. This phenomenon decreases the oxidation efficiency and/or increases REM fouling. Besides, O2 bubbles sweeping at high permeate flux promotes O2 gas generation, with adverse effect on oxidation efficiency.

Effects of sodium hypochlorite exposure mode on PES/PVP ultrafiltration membrane degradation.

Drinking water production plants using membrane filtration processes report membrane failure issues. According to the literature, membrane degradation is often induced by exposure to sodium hypochlorite, an oxidant widely used during in-place cleanings. The present study focused on quantifying the effect of membrane exposure mode to hypochlorite on properties modifications of a PES/PVP ultrafiltration membrane widely used for drinking water production. For this purpose effects of sodium hypochlorite concentration, contact duration and exposure mode (static or dynamic) were investigated. The pH of the hypochlorite solution was set to 8 as it was demonstrated in numerous previous works that the pH range 7-8 leads to the most severe modification in the membrane characteristics. Membrane degradation was monitored at molecular scale by attenuated total reflectance infrared spectroscopy and at macroscopic scale by pure water permeability and elongation at break measurements. The results obtained in static (soaking) and dynamic (filtration and filtration/backwashing cycles) hypochlorite exposure modes indicated that PES/PVP membrane degradation progress was predominantly governed by hypochlorite oxidation rate. In the tested conditions, mechanical stress (pressure differentials) did not significantly contribute to membrane ageing. The correlation between molecular and macroscopic characterizations demonstrated that PVP degradation is responsible for the membrane integrity loss. A linear relationship between the loss of ductility of the membrane and the progress of the PVP degradation was obtained whatever the exposure mode. Thanks to experiments conducted at various hypochlorite concentrations and exposure durations, the hypochlorite dose parameter (hypochlorite concentration times contact time), widely used in the literature, was demonstrated to be inappropriate to describe the degradation rate: the hypochlorite concentration impact was shown to be dominating the exposure time's one on the degradation rate.

Formation of bacterial streamers during filtration in microfluidic systems.

Bacterial behavior during filtration is complex and is influenced by numerous factors. The aim of this paper is to report on experiments designed to make progress in the understanding of bacterial transfer in filters and membranes. Polydimethylsiloxane (PDMS) microsystems were built to allow direct dynamic observation of bacterial transfer across different microchannel geometries mimicking filtration processes. When filtering Escherichia coli suspensions in such devices, the bacteria accumulated in the downstream zone of the filter forming long streamers undulating in the flow. Confocal microscopy and 3D reconstruction of streamers showed how the streamers are connected to the filter and how they form in the stream. Streamer development was found to be influenced by the flow configuration and the presence of connections or tortuosity between channels. Experiments showed that streamer formation was greatest in a filtration system composed of staggered arrays of squares 10 µm apart.

Effects of ionic strength on bacteriophage MS2 behavior and their implications for the assessment of virus retention by ultrafiltration membranes.

Bacteriophage MS2 is widely used as a surrogate to estimate pathogenic virus elimination by membrane filtration processes used in water treatment. Given that this water technology may be conducted with different types of waters, we focused on investigating the effects of ionic strength on MS2 behavior. For this, MS2 was analyzed while suspended in solutions of various ionic strengths, first in a batch experiment and second during membrane ultrafiltration, and quantified using (i) quantitative reverse transcriptase PCR (qRT-PCR), which detects the total number of viral genomes, (ii) qRT-PCR without the RNA extraction step, which reflects only particles with a broken capsid (free RNA), and (iii) the PFU method, which detects only infectious viruses. At the beginning of the batch experiments using solutions containing small amounts of salts, losses of MS2 infectivity (90%) and broken particles (20%) were observed; these proportions did not change during filtration. In contrast, in high-ionic-strength solutions, bacteriophage kept its biological activity under static conditions, but it quickly lost its infectivity during the filtration process. Increasing the ionic strength decreased both the inactivation and the capsid breakup in the feed suspension and increased the loss of infectivity in the filtration retentate, while the numbers of MS2 genomes were identical in both experiments. In conclusion, the effects of ionic strength on MS2 behavior may significantly distort the results of membrane filtration processes, and therefore, the combination of classical and molecular methods used here is useful for an effective validation of the retention efficiency of ultrafiltration membranes.

[Removal of bisphenol A and tetrabromobisphenol A membrane by nanofiltration from water source].

The removal efficiency of BPA and TBBPA by nanofiltration membrane Desal 5 DK has been investigated with a lab-scale dead-end filtration module and the role of adsorption of two molecules on membrane was also explored to understand the filtration mechanism. The results showed that the R(obs) of BPA decreased from 89% to 47% as the accumulated adsorption quantity of BPA onto the membrane increased to 30 microg x m(-2). The high BPA concentration in adsorption layer caused the water flux decline especially at high pressure. The high TBBPA rejection of over 95% by Desal 5 DK was obtained due to the molecular weight and molecular structure although the accumulated adsorption quantity of TBBPA reached 50 microg x m(-2). The desorption test showed that the TBBPA could not pass through the membrane for its structure at the 5 x 10(5) Pa, while BPA could diffuse through the membrane and the peak concentration was obtained after 30 mL filtration. The quantity of BPA released from the membrane contributed 30% of the total amount adsorbed by the membrane Desal 5 DK.

Photochemical degradation of diethyl phthalate with UV/H2O2.

The decomposition of diethyl phthalate (DEP) in water using UV-H2O2 process was investigated in this paper. DEP cannot be effectively removed by UV radiation and H2O2 oxidation alone, while UV-H2O2 combination process proved to be effective and could degrade this compound completely. With initial concentration about 1.0mg/L, more than 98.6% of DEP can be removed at time of 60 min under intensity of UV radiation of 133.9 microW/cm2 and H2O2 dosage of 20mg/L. The effects of applied H2O2 dose, UV radiation intensity, water temperature and initial concentration of DEP on the degradation of DEP have been examined in this study. Degradation mechanisms of DEP with hydroxyl radicals oxidation also have been discussed. Removal rate of DEP was sensitive to the operational parameters. A simple kinetic model is proposed which confirms to pseudo-first order reaction. There is a linear relationship between rate constant k and UV intensity and H2O2 concentration.