The effect of temperature on fouling in anaerobic membrane bioreactor: SMP- and EPS-membrane interactions.

Biofouling is the main challenge in the operation of anaerobic membrane bioreactors (AnMBRs). Biofouling strongly depends on temperature; therefore, we hypothesize that the interactions and viscoelastic properties of soluble microbial products (SMP) and extracellular polymeric substances (EPS) vary with temperature, consequently influencing membrane permeability. This study compares the performance of an AnMBR operated at a similar permeate flux at two temperatures. The transmembrane pressure (TMP) rose rapidly after 5 ± 2 days at 25 °C but only after 18 ± 2 days at 35 °C, although the reactor's biological performance was similar at both temperatures, in terms of the efficiency of dissolved organic carbon removal and biogas composition, which were obtained by changing the hydraulic retention time. Using confocal laser scanning microscopy (CLSM), a higher biofilm amount was detected at 25 °C than at 35 °C, while quartz crystal microbalance with dissipation (QCM-D) showed a more adhesive, but less viscous and elastic EPS layer. In situ optical coherence tomography (OCT) of an ultra-filtration membrane, fed with the mixed liquor suspended solids (MLSS) at the two temperatures, revealed that while a higher rate of TMP increase was obtained at 25 °C, the attachment of biomass from MLSS was markedly less. Increased EPS adhesion to the membrane can accelerate TMP increase during the operation of both the AnMBR and the OCT filtration cell. EPS's reduced viscoelasticity at 25 °C suggests reduced floc integrity and possible increased EPS penetration into the membrane pores. Analysis of the structures of the microbial communities constituting the AnMBR flocs and membrane biofilms reveals temperature's effects on microbial richness, diversity, and abundance, which likely influence the observed EPS properties and consequent AnMBR fouling.

Pseudo-bottle-brush decorated thin-film composite desalination membranes with ultrahigh mineral scale resistance.

High water recovery is crucial to inland desalination but is impeded by mineral scaling of the membrane. This work presents a two-step modification approach for grafting high-density zwitterionic pseudo-bottle-brushes to polyamide reverse osmosis membranes to prevent scaling during high-recovery desalination of brackish water. Increasing brush density, induced by increasing reaction time, correlated with reduced scaling. High-density grafting eliminated gypsum scaling and almost completely prevented silica scaling during desalination of synthetic brackish water at a recovery ratio of 80%. Moreover, scaling was effectively mitigated during long-term desalination of real brackish water at a recovery ratio of 90% without pretreatment or antiscalants. Molecular dynamics simulations reveal the critical dependence of the membrane's silica antiscaling ability on the degree to which the coating screens the membrane surface from readily forming silica aggregates. This finding highlights the importance of maximizing grafting density for optimal performance and advanced antiscaling properties to allow high-recovery desalination of complex salt solutions.

Microporous Polyethersulfone Membranes Grafted with Zwitterionic Polymer Brushes Showing Microfiltration Permeance and Ultrafiltration Bacteriophage Removal.

Virus removal from water using microfiltration (MF) membranes is of great interest but remains challenging owing to the membranes' mean pore sizes typically being significantly larger than most viruses. We present microporous membranes grafted with polyzwitterionic brushes (N-dimethylammonium betaine) that combine bacteriophage removal in the range of ultrafiltration (UF) membranes with the permeance of MF membranes. Brush structures were grafted in two steps: free-radical polymerization followed by atom transfer radical polymerization (ATRP). Attenuated total reflection Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) verified that grafting occurred at both sides of the membranes and that the grafting increased with increasing the zwitterion monomer concentration. The log reduction values (LRVs) of the pristine membrane increased from less than 0.5 LRV for T4 (∼100 nm) and NT1 (∼50 nm) bacteriophages to up to 4.5 LRV for the T4 and 3.1 LRV for the NT1 for the brush-grafted membranes with a permeance of about 1000 LMH/bar. The high permeance was attributed to a high-water fraction in the ultra-hydrophilic brush structure. The high measured LRVs of the brush-grafted membranes were attributed to enhanced bacteriophages exclusion from the membrane surface and entrapment of the ones that penetrated the pores due to the membranes' smaller mean pore-size and cross-section porosity than those of the pristine membrane, as seen by scanning electron microscopy (SEM) and measured using liquid-liquid porometry. Micro X-ray fluorescence (µ-XRF) spectrometry and nanoscale secondary ion mass spectrometry showed that 100 nm Si-coated gold nanospheres accumulated on the surface of the pristine membrane but not on the brush-coated membrane and that the nanospheres that penetrated the membranes were entrapped in the brush-grafted membrane but passed the pristine one. These results corroborate the LRVs obtained during filtration experiments and support the inference that the increased removal was due to a combined exclusion mechanism and entrapment. Overall, these microporous brush-grafted membranes show potential for use in advanced water treatment.

Biofilm Formation and Biofouling Development on Different Ultrafiltration Membranes by Natural Anaerobes from an Anaerobic Membrane Bioreactor.

Biofouling in anaerobic membrane bioreactors (AnMBRs) has not been studied widely. Moreover, the effect of membrane surface properties on biofilm formation beyond initial deposition is controversial. We investigated biofouling with polyvinyldifluoride, polyacrylonitrile, and zwitterion-modified polyethersulfone ultrafiltration membranes having different properties during 72 h filtration using natural anaerobes isolated from AnMBR and analyzed biofilm characteristics by physicochemical and molecular techniques. A decrease in membrane performance was positively correlated with biofilm formation on polyvinyldifluoride and polyacrylonitrile membranes, and as expected, physical cleaning effectively mitigated biofilm on hydrophilic and low-roughness membranes. Surprisingly, while the biofilm on the hydrophilic and low-surface roughness zwitterion-modified membrane was significantly impaired, the impact on transmembrane pressure was the highest. This was ascribed to the formation of a soft compressible thin biofilm with high hydraulic resistance, and internal clogging and pore blocking due to high pore-size distribution. Anaerobe community analysis demonstrated some selection between the bulk and biofilm anaerobes and differences in the relative abundance of the dominant anaerobes among the membranes. However, correlation analyses revealed that all membrane properties studied affected microbial communities' composition, highlighting the system's complexity. Overall, our findings indicate that the membrane properties can affect biofilm formation and the anaerobic microbial population but not necessarily alleviate biofouling.

Zwitterionic hydrogel modified reduced graphene oxide/ZnO nanocomposite blended membrane with high antifouling and antibiofouling performances.

Membrane fouling and biofouling are major challenges in the application of membrane technology for wastewater treatment. The synthesis of antifouling and antibiofouling dual functionality membranes is a promising approach to tackling these problems. In this work, we fabricated a high-efficiency dual functionality polyethersulfone (PES) ultrafiltration membrane by blending an antibacterial reduced graphene oxide-ZnO nanocomposite into a PES matrix (rGO/ZnO-PES) followed by surface grafting of a low-fouling polyampholyte hydrogel (rGO/ZnO-z-PES). The antibacterial activity of the blended membrane was optimized by changing the nanocomposite fraction in the PES dope solution. Surface characterizations (SEM-EDS, XPS, ATR-FTIR, contact angle, and Zeta potential) confirmed the successful grafting of the zwitterionic hydrogel on the rGO/ZnO-PES membrane surface. Contact killing assays revealed that the polyampholyte hydrogel grafting did not affect the high antibacterial activity of the rGO/ZnO-PES membrane. Dynamic filtration experiments demonstrated the very high antifouling and antibiofouling of the rGO/ZnO-z-PES membrane, and significantly higher than those of the rGO/ZnO-PES and pristine PES membranes. The measured concentration of zinc ions in the permeate was low. Overall, our results demonstrate that the rGO/ZnO-z-PES membrane has excellent antifouling and antibiofouling performance and is stable and safe, and therefore very promising for wastewater treatment.

Advanced near-zero waste treatment of food processing wastewater with water, carbon, and nutrient recovery.

A near-zero waste treatment system for food processing wastewater was developed and studied. The wastewater was treated using an anaerobic membrane bioreactor (AnMBR), polished using an outdoor photobioreactor for microalgae cultivation (three species were studied), and excess sludge was treated using hydrothermal carbonization. The study was conducted under arid climate conditions for one year (four seasons). The AnMBR reduced the total organic carbon by 97%, which was mostly recovered as methane (~57%) and hydrochar (~4%). Microalgal biomass productivity in the AnMBR effluent ranged from 0.25 to 0.8 g·L-1·day-1. Nitrogen (N) and phosphorous (P) uptake varied seasonally, from 18 to 45 mg·L-1·day-1 and up to 5 mg·L-1·day-1, respectively. N and P mass balance analysis demonstrated that the process was highly efficient in the recovery of nitrogen (~77%), and phosphorus (~91%). The performance of the microalgal culture changed among seasons because of climatic variation, as a result of variation in the wastewater chemistry, and possibly due to differences among the microalgal species. Effluent standards for irrigation use were met throughout the year and were achieved within two days in summer and 4.5 days in winter. Overall, the study demonstrated a near-zero waste discharge system capable of producing high-quality effluent, achieving nutrient and carbon recovery into microalgae biomass, and energy production as biogas and hydrochar.

Facile activation of sludge-based hydrochar by Fenton oxidation for ammonium adsorption in aqueous media.

Lately, there has been a growing interest in converting low-cost biomass residuals, including wastewater sludge, into char-like materials for various applications. In this research, ammonium (NH4+) adsorption and desorption potential of hydrochar activated via Fenton oxidation were systematically investigated. Hydrochar was prepared from domestic wastewater treatment plant sludge and activated by Fenton oxidation using different H2O2 concentrations, H2O2/Fe2+ ratios, and activation times. The activated hydrochars (AHs) were characterized by ATR-FTIR, high-resolution XPS, BET specific surface area, and SEM, and their NH4+ adsorption capacity was analyzed. The NH4+ adsorption isotherms and kinetics, adsorption in the presence of competing ions (with and without humic acid), and NH4+ desorption were investigated. The results show that following hydrochar activation, the acidic groups' concentration and the BET surface area increased, but the morphology remained essentially unchanged. It was also found that the activation occurs within a few minutes when using a relatively low concentration of reagents, and without extensive post-treatment steps. The NH4+ adsorption onto AH at equilibrium fitted the Langmuir isotherm model, with a maximum adsorption capacity of 30.77 mg g-1, and the NH4+ adsorption kinetics fitted the pseudo-second-order model. NH4+ adsorption in the presence of competing ions decreased by up to 33 ± 3%. NH4+ desorption experiments demonstrated that NH4+ recovery can reach 33 ± 5% with ultrapure water and 67 ± 2% with 2 M KCl. The results of this study indicate that Fenton oxidation is a promising alternative for hydrochar activation, and can be used as an adsorbent for NH4+ remediation in wastewater treatment processes.

Molecular insight into the interfacial chemical functionalities regulating heterogeneous calcium-arsenate nucleation.

Heterogeneous nucleation induced by natural organic matter (NOM) can lower the energy barrier for calcium arsenate (Ca-As) precipitation, which aids in immobilizing arsenate (AsⅤ). However, it remains unclear how certain chemical functionalities of NOM affect Ca-As nucleation at the molecular scale. By analyzing changes in the local supersaturation and/or interfacial energy, the present work investigates the Ca-As heterogeneous nucleation kinetics and mechanisms on functional-group-modified model surfaces. Mica surfaces modified by functional groups of amine (NH2), hydroxyl (OH), or carboxyl (COOH) through self-assembled monolayers were used to investigate how chemical functionalities affect the Ca-As heterogeneous nucleation, in which the distributions of formation kinetics and size (as measured by the change in particle height) of nucleated Ca-As particles were measured by using in situ atomic force microscopy. In a parallel analysis, a quartz-crystal microbalance with dissipation was used to detect the buildup of Ca2+ and/or HAsO42- ions at the solid-fluid interface. PeakForce quantitative nanomechanical mapping and dynamic force spectroscopy using functional-group-modified tips made it possible to calculate the binding energies holding functional groups to Ca-As particles. Nucleated Ca-As particles were characterized by using Raman spectroscopy and high-resolution transmission electron microscopy. The results indicate that the height of amorphous Ca-As particles formed on a modified mica surface may be ranked in descending order as NH2 > OH > bare mica > COOH, as determined by the buildup of Ca2+ and HAsO42- ions at the solid-fluid interface and the decrease of interfacial energy due to the functional groups. These nanoscale observations and molecular-scale determinations improve our understanding of the roles played by chemical functionalities on NOM in immobilizing dissolved As through heterogeneous nucleation in soil and water.

Initial Deposition and Pioneering Colonization on Polymeric Membranes of Anaerobes Isolated from an Anaerobic Membrane Bioreactor (AnMBR).

Membrane biofouling constitutes a great challenge in anaerobic membrane bioreactor (AnMBR). Here, we studied the initial deposition of anaerobes, the first step in biofilm formation, with a consortium isolated from an AnMBR on membranes with different surface properties and under two shear rate conditions without filtration. We found that the cell transfer coefficient, calculated from the initial deposition experiments, was similar under the two shear rates for the hydrophobic membranes, but much higher under low shear rate and much lower under high shear rate, for the hydrophilic membrane. The cell transfer coefficient measured under filtration mode and at a higher shear rate showed a similar trend. The pioneer bacteria and archaea (without filtration) were identified by next-generation sequencing. The results showed that the selective force for the dissimilarity of the pioneer bacterial and archaeal diversity was the shear rate and the membrane surface properties, respectively. However, statistical analyses revealed minor changes in the pioneer bacteria (class level) and archaea (order level) populations under the various conditions. These results shed light on the first step of biofilm formation on the membranes in AnMBRs and emphasize the importance of hydrodynamic shear and membrane surface properties on the initially deposited anaerobes.

Graphene Oxide-Functionalized Membranes: The Importance of Nanosheet Surface Exposure for Biofouling Resistance.

Surface functionalization using two-dimensional (2D) graphene oxide (GO) materials is a promising technique to enhance the biofouling resistance of membranes used in water purification and reuse. However, the role of GO exposure, which is crucial for the contact-mediated toxicity mechanism, has not been well evaluated or elucidated in previous studies. Herein, we employ bioinspired polydopamine chemistry to fabricate GO-functionalized membranes through two strategies: coating and blending. The two types of GO-functionalized membranes displayed comparable roughness, hydrophilicity, water permeability, and solute retention properties but different degrees of GO nanosheet exposure on the membrane surface. When in contact with the model bacterium, Escherichia coli, the GO-coated membrane exhibited enhanced biofouling resistance compared to that of the GO-blended membrane, as evidenced by lower viable cells in static adsorption experiments, and lower water flux decline and higher flux recovery in dynamic biofouling experiments. Moreover, the development of biofilm on the GO-coated membrane was also inhibited to a greater extent than on the GO-blended membrane. Taken together, our findings indicate the paramount importance of GO exposure on the membrane surface in conferring antibacterial activity and biofouling resistance, which should be considered in the future design of antibiofouling membranes using 2D nanomaterials.

Characterization and utilization of hydrothermal carbonization aqueous phase as nutrient source for microalgal growth.

This study investigated the feasibility of using hydrothermal carbonization (HTC) aqueous phase as an alternative nutrient source for microalgae cultivation, and the microalgae cultivation capability to treat this complex medium to a level enabling its reuse or discharge. HTC of activated sludge was optimized in terms of the energy content of the solid hydrochar and the nutrient content of the HTC aqueous phase adequate for microalgal growth. Growth rates of Coelastrella sp. and Chlorella sp. in the HTC aqueous phase based growth medium and a control medium (mBG11) were similar, indicating that the HTC aqueous phase does not inhibit the microalgae growth. Nitrogen and phosphorus concentrations were reduced by >90% and dissolved organic carbon by 80% after 6 days of cultivation, resulting in water quality suitable for reuse or discharge. This study confirms the microalgae high potential in a circular bio-economy to valorize wet bio-waste streams from various treatment methods.

Effect of the membrane exclusion mechanism on phosphate scaling during synthetic effluent desalination.

Calcium phosphate scaling is one of the main limitations in effluent desalination using membranes. This may be overcome by tailoring membranes with lower rejection of the scalant ions. In this study, we systematically examined the use of negatively and positively charged membranes, rejecting ions mainly based on Donnan exclusion, as a low-scaling alternative to dielectric-exclusion-dominated polyamide NF membranes for effluent desalination. The two charged membranes exhibited a lower calcium and especially phosphate rejection than the polyamide membrane. Consequently, the calcium phosphate supersaturation and then the propensity to scaling of the charged membranes were much lower than the polyamide membrane. This also allowed filtering at a much higher recovery ratio with the charged membranes. It was also found that, despite the fact that the charged membranes had an opposite fixed charge, their scaling behavior was similar. Apparently, although these membranes showed opposite selectivity towards scalant ions (phosphate and calcium) in single salt solutions, the rejection pattern in mixed salt solutions resulted in similar saturation indices, much lower than for polyamide membrane. The scale formed on all three membranes was identified as amorphous calcium phosphate (ACP), although its saturation index was lower than its solubility factor. This was explained by concentration polarization which increases the saturation index in the solution adjacent to the membrane surface. Tests in absence of permeate flux showed a much slower precipitation that took a few days compared with filtration conditions (few hours). In addition, under these conditions, the effect of the scaling on the membrane permeability was generally reduced and the scale contained crystalline calcium phosphate products, different from ACP. The results indicate that the ion rejection and resulting polarization next to the membrane surface plays a crucial role in scaling. Thus, tuning ion selectivity of NF membranes towards scalant ions presents a promising alternative for scaling mitigation during effluent desalination.

Surface and anti-fouling properties of a polyampholyte hydrogel grafted onto a polyethersulfone membrane.

Zwitterion polymers have anti-fouling properties; therefore, grafting new zwitterions to surfaces, particularly as hydrogels, is one of the leading research directions for preventing fouling. Specifically, polyampholytes, polymers of random mixed charged subunits with a net-electric charge, offer a synthetically easy alternative for studying new zwitterions with a broad spectrum of charged moieties. Here, a novel polyampholyte hydrogel was grafted onto the surface of polyethersulfone membrane by copolymerizing a mixture of vinylsulfonic acid (VSA) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METMAC) as the negatively and positively charged monomers, respectively, using various monomer ratios in the polymerization solution, and with N,N'-methylenebisacrylamide as the crosslinker. The physicochemical, morphological and anti-fouling properties of the modified membranes were systematically investigated. Hydrophilic hydrogels were successfully grafted using monomers at different molar ratios. A thin-film zwitterion hydrogel (∼90 nm) was achieved at a 3:1 [VSA:METMAC] molar ratio in the polymerization solution. Among all examined membranes, the zwitterion polyampholyte-modified membrane demonstrated the lowest adsorption of proteins, humic acid, and sodium alginate. It also had low fouling and high flux recovery following filtration with a protein or with an extracellular polymeric substance solution. These findings suggest that this polyampholyte hydrogel is applicable as a low fouling surface coating.

'Should I stay or should I go?' Bacterial attachment vs biofilm formation on surface-modified membranes.

A number of techniques are used for testing the anti-biofouling activity of surfaces, yet the correlation between different results is often questionable. In this report, the correlation between initial bacterial deposition (fast tests, reported previously) and biofilm growth (much slower tests) was analyzed on a pristine and a surface-modified reverse osmosis membrane ESPA-1. The membrane was modified with grafted hydrophilic polymers bearing negatively charged, positively charged and zwitter-ionic moieties. Using three different bacterial strains it was found that there was no general correlation between the initial bacterial deposition rates and biofilm growth on surfaces, the reasons being different for each modified surface. For the negatively charged surface the slowest deposition due to the charge repulsion was eventually succeeded by the largest biofilm growth, probably due to secretion of extracellular polymeric substances (EPS) that mediated a strong attachment. For the positively charged surface, short-term charge attraction by quaternary amine groups led to the fastest deposition, but could be eventually overridden by their antimicrobial activity, resulting in non-consistent results where in some cases a lower biofilm formation rate was observed. The results indicate that initial deposition rates have to be used and interpreted with great care, when used for assessing the anti-biofouling activity of surfaces. However, for a weakly interacting 'low-fouling' zwitter-ionic surface, the positive correlation between initial cell deposition and biofilm growth, especially under flow, suggests that for this type of coating initial deposition tests may be fairly indicative of anti-biofouling potential.

UV-photo graft functionalization of polyethersulfone membrane with strong polyelectrolyte hydrogel and its application for nanofiltration.

A strong polyelectrolyte hydrogel was graft copolymerized on a polyethersulfone (PES) ultrafiltration (UF) membrane using vinyl sulfonic acid (VSA) as the functional monomer, and N,N'-methylenbisacrylamide (MBAA) as the cross-linker monomer. This was carried out in one simple step using the UV photoirradiation method. The effect of the polymerization conditions on the degree of grafting (DG) was investigated using the gravimetric method which measures the total hydrogel grafted on the membrane, and with ATR-FTIR spectroscopy which indicates the functional monomer fraction in the hydrogel layer. The VSA could not graft polymerize without the cross-linker as comonomer. An increase in the cross-linker fraction from 0.25 to 2.5 mol % (relative to the functional monomer VSA) resulted in a higher DG. Although the surface morphology changed upon modification, the resulting surface roughness as measured by AFM was very low. From the monitoring of DG with UV time (4.5-30 min) at constant conditions, it was deduced that during the early stages of the polymerization mainly the cross-linker was grafted, thus inducing the graft copolymerization of the functional monomer. Polymerization using a higher monomer concentration (12.5-40% VSA) at constant monomer/cross-linker ratio resulted in a higher VSA fraction in the grafted hydrogel, although the gravimetric DG was similar. Ion exchange capacity and X-ray photoelectron spectroscopy measured after modification under the different conditions supported these findings. The new membranes were tested under nanofiltration (NF) conditions. A NF membrane could be obtained when the MBAA fraction was above 0.25%. The Na2SO4 rejection was 90-99% and the permeability 10-1 L m(-2) h(-1) bar(-1) when the MBAA fraction increased from 0.75 to 2.5%. The order of rejection of single salts solution was Na2SO4 > MgSO4 ≈ NaCl > CaCl2, as expected on the basis of Donnan exclusion for negatively charged NF membranes. An increase in the salts rejection with increasing degree of cross-linking and VSA fraction was attributed to an increase in the membrane charge density and to steric exclusion that also resulted in an increase of rejection for uncharged solutes such as sucrose or glucose. The new membrane presented a high, essentially unchanged Na2SO4 rejection (>97%) in the range of salt concentrations up to 4 g/L, and only slightly reduced rejection (>92%) at a concentration of 8 g/L; this can be related to its high barrier layer charge density measured by ion exchange capacity. In addition, because poly(vinyl sulfonic acid) (PVSA) is a strong polyelectrolyte the membrane separation performance was stable in the range of pH 1.5 to pH 10.

Bacterial attachment to RO membranes surface-modified by concentration-polarization-enhanced graft polymerization.

Concentration polarization-enhanced radical graft polymerization, a facile surface modification technique, was examined as an approach to reduce bacterial deposition onto RO membranes and thus contribute to mitigation of biofouling. For this purpose an RO membrane ESPA-1 was surface-grafted with a zwitterionic and negatively and positively charged monomers. The low monomer concentrations and low degrees of grafting employed in modifications moderately reduced flux (by 20-40%) and did not affect salt rejection, yet produced substantial changes in surface chemistry, charge and hydrophilicity. The propensity to bacterial attachment of original and modified membranes was assessed using bacterial deposition tests carried out in a parallel plate flow setup using a fluorescent strain of Pseudomonas fluorescens. Compared to unmodified ESPA-1 the deposition (mass transfer) coefficient was significantly increased for modification with the positively charged monomer. On the other hand, a substantial reduction in bacterial deposition rates was observed for membranes modified with zwitterionic monomer and, still more, with very hydrophilic negatively charged monomers. This trend is well explained by the effects of surface charge (as measured by ζ-potential) and hydrophilicity (contact angle). It also well correlated with force distance measurements by AFM using surrogate spherical probes with a negative surface charge mimicking the bacterial surface. The positively charged surface showed a strong hysteresis with a large adhesion force, which was weaker for unmodified ESPA-1 and still weaker for zwitterionic surface, while negatively charged surface showed a long-range repulsion and negligible hysteresis. These results demonstrate the potential of using the proposed surface- modification approach for varying surface characteristics, charge and hydrophilicity, and thus minimizing bacterial deposition and potentially reducing propensity biofouling.

Toward improved boron removal in RO by membrane modification: feasibility and challenges.

Membrane modification by concentration polarization (CP)-enhanced radical graft polymerization using a dilute aqueous solution of appropriate monomer was examined as a method for increasing rejection of boric acid by reverse osmosis (RO) membranes. On the basis of suggested physicochemical rationales a number of monomers were examined in order to determine those with the lowest affinity toward boric acid as compared to water. The improvement in the modified membrane performance was mainly attributed to sealing less selective areas ("defects") inherently present in the original low pressure RO (LPRO) membranes. However, the effect clearly differed for different monomers. Among the examined monomers glycidyl methacrylate (GMA) exhibited the lowest affinity and the largest improvement in removal of boric acid along with a moderate loss of permeability and slightly improved NaCl rejection. Modification of LPRO membrane thus resulted in a membrane with a permeability in the brackish water RO (BWRO) range but with removal of boric acid and salt superior to those reported for most commercial BWRO membranes.

Surface modification of dense membranes using radical graft polymerization enhanced by monomer filtration.

Surface graft polymerization is a promising way to modify membranes for improved performance. Redox-initiated graft polymerization of vinyl monomers is a facile and inexpensive method carried out at room temperature in aqueous media; however, its use is often limited by slow kinetics, low surface specificity, and excessive consumption of chemicals on undesired homopolymerization. It is shown that in the case of RO or NF membranes these drawbacks may be eliminated by utilizing the selectivity of the membranes toward monomers and carrying out the polymerization while applying pressure, i.e., under filtration conditions. Concentration polarization that ensues raises the concentration of reagents near the membrane surface and thereby drastically increases the rate of reaction and preferentially directs it towards surface grafting. Grafting experiments using 2-hydroxyethyl methacrylate and other monomers and characterization of modified membranes using permeability measurements, ATR-FTIR, AFM, XPS, and contact angle demonstrate that the required monomer concentrations can be drastically reduced, particularly when a small fraction of a cross-linker is added. As an additional benefit, this approach enables broadening the spectrum of utilizable monomers to sparingly soluble hydrophobic, charged, and macro-monomers, as was demonstrated using sparingly soluble ethyl methacrylate and 2-ethoxyethyl methacrylate and other monomers. Even though the kinetics of the process is substantially complicated by evolution and concentration polarization of oligomeric and polymeric species, especially in the presence of a cross-linker, it is well offset by the benefits of higher rate, specificity, and reduced monomer consumption.