Mechanisms and Strategies of Advanced Oxidation Processes for Membrane Fouling Control in MBRs: Membrane-Foulant Removal versus Mixed-Liquor Improvement.

Membrane bioreactors (MBRs) are well-established and widely utilized technologies with substantial large-scale plants around the world for municipal and industrial wastewater treatment. Despite their widespread adoption, membrane fouling presents a significant impediment to the broader application of MBRs, necessitating ongoing research and development of effective antifouling strategies. As highly promising, efficient, and environmentally friendly chemical methods for water and wastewater treatment, advanced oxidation processes (AOPs) have demonstrated exceptional competence in the degradation of pollutants and inactivation of bacteria in aqueous environments, exhibiting considerable potential in controlling membrane fouling in MBRs through direct membrane foulant removal (MFR) and indirect mixed-liquor improvement (MLI). Recent proliferation of research on AOPs-based antifouling technologies has catalyzed revolutionary advancements in traditional antifouling methods in MBRs, shedding new light on antifouling mechanisms. To keep pace with the rapid evolution of MBRs, there is an urgent need for a comprehensive summary and discussion of the antifouling advances of AOPs in MBRs, particularly with a focus on understanding the realizing pathways of MFR and MLI. In this critical review, we emphasize the superiority and feasibility of implementing AOPs-based antifouling technologies in MBRs. Moreover, we systematically overview antifouling mechanisms and strategies, such as membrane modification and cleaning for MFR, as well as pretreatment and in-situ treatment for MLI, based on specific AOPs including electrochemical oxidation, photocatalysis, Fenton, and ozonation. Furthermore, we provide recommendations for selecting antifouling strategies (MFR or MLI) in MBRs, along with proposed regulatory measures for specific AOPs-based technologies according to the operational conditions and energy consumption of MBRs. Finally, we highlight future research prospects rooted in the existing application challenges of AOPs in MBRs, including low antifouling efficiency, elevated additional costs, production of metal sludge, and potential damage to polymeric membranes. The fundamental insights presented in this review aim to elevate research interest and ignite innovative thinking regarding the design, improvement, and deployment of AOPs-based antifouling approaches in MBRs, thereby advancing the extensive utilization of membrane-separation technology in the field of wastewater treatment.

Green Solvent Cleaning Removes Irrecoverable Foulants from End-of-Life Membranes in Membrane Bioreactors: Efficacy and Mechanisms.

Removal of irrecoverable foulants, which cannot be removed by conventional chemical cleaning, from end-of-life (EOL) membranes remains a substantial challenge due to the strong interaction between the foulants and membrane matrix. Herein, we developed a green solvent cleaning strategy based on Hansen solubility parameters to achieve the removal of irrecoverable foulants from the EOL polyvinylidene fluoride (PVDF) membranes serving for 6 years in a large-scale membrane bioreactor (MBR). We selected methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (MDMO) as the green solvent due to its strong interaction with the PVDF material, which might enable the substitution of binding sites of irrecoverable foulants. After the MDMO cleaning, the water permeance of the EOL membrane recovered from 47.6 ± 4.7 to 390.9 ± 8.2 L m-2 h-1 bar-1 (with a flux recovery ratio of ∼100%), with its rejection ability and stability maintained. The main components of irrecoverable fouling were humic acid-like substances revealed by spectroscopic characterization. Molecular dynamic simulation further elucidated the cleaning mechanisms: the strong interaction of MDMO-PVDF enabled substitution of binding sites of irrecoverable foulants by MDMO, followed by desorption of the irrecoverable foulants from PVDF and diffusion of the irrecoverable foulants into the bulk phase of MDMO. Evaluation in a lab-scale MBR treating real municipal wastewater verified the reusability of green solvent cleaned-EOL membranes. This study provides a novel, effective, and green cleaning strategy to remove irrecoverable foulants and prolong the service life of membranes in MBRs, facilitating sustainable wastewater treatment using membrane-based processes.

Fouling mechanisms in anoxic-aerobic sequencing batch membrane bioreactor based on adapted Hermia models and main foulant characteristics.

Various derivatives of Hermia models (complete pore blocking, intermediate pore blocking, cake layer formation, and standard pore blocking) and different assessments of foulant characteristics have long been used to determine the membrane fouling mechanisms. Accordingly, this study aims to adapt Hermia models and their combination according to the operating conditions of an anoxic-aerobic sequencing batch membrane bioreactor (A/O-SBMBR). In addition, fouling mechanisms of the A/O-SBMBR were assessed using these models along with the main foulant characteristics. Models fitting with the transmembrane pressure (TMP) data indicated that the intermediate-standard model was accounting for the increased fouling during the whole regular operating period, with the residual sum of squares (RSS) of 58.3. A more detailed study on the distinct stages of TMP curve showed that the intermediate-standard model had the best fit in stages of 2 and 3, with the RSS equal to 2.6 and 2.8, respectively. Also, the complete-standard model provided the best description of the fouling mechanism in stage 4, with the RSS of 12.5. Different analyzes revealed how the main foulant characteristics affect the occurrence of intermediate, complete and standard fouling mechanisms in the A/O-SBMBR, which is consistent with the fitting results of the adapted Hermia models. The modeling and experimental methods used in the presented study provided a valuable basis to prevent and control membrane fouling in membrane bioreactors.

Critical fractions in reclaimed water responsible for membrane fouling: Isolation, fouling characteristics, quantitative and qualitative variations in practical application.

Considering the different fouling characteristics between model foulants and organic components in real reclaimed water, it is of great importance to identify the critical foulants responsible for membrane fouling. This study identified and isolated the fraction with molecular weight (MW) > 100 kDa as the critical foulant in secondary effluent by MW cut-off membrane of 100 kDa with high efficiency. This fraction accounted for 92.2% membrane fouling of raw water, including 28.7%, 29.7% and 33.8% fouling contribution by subfractions with MW between 100-300, 300-500 and > 500 kDa. Specifically, the critical fraction with MW > 100 kDa were mainly distributed in two parts: < 0.22 µm and > 0.45 µm, corresponding to 41.9% and 56.9% fouling contribution of this fraction. Furthermore, both total organic carbon (TOC) and fouling potential of fraction with MW > 100 kDa were monitored, presenting about threefold increase from September to January in next year. Membrane fouling contribution of this critical fraction in raw secondary effluent were mainly distributed in 85∼95% throughout the 5 months, demonstrating its predominant fouling propensity. Moreover, the TOC concentration of fraction with MW > 100 kDa presented distinct positive correlation with the fouling potential of raw secondary effluent (R2 = 0.947), which was promising to be a surrogate for predicting membrane fouling in practical application.

Role of inorganic foulants in the aging and deterioration of low-pressure membranes during the chemical cleaning process in surface water treatment: A review.

Low-pressure membrane (LPM) filtration, including microfiltration (MF) and ultrafiltration (UF), is a promising technology for the treatment of surface water for drinking and other purposes. Various configurations and operational sequences have been developed to ensure the sustainable provision of clean water by overcoming fouling problems. In the literature, various periodic physical and/or chemical approaches to the cleaning of LPMs have been reported, but little data is available on the aging of MF/UF membranes that results from the interaction between the foulants and the cleaning agent. Periodic physical cleaning of the membrane is expected to return the membrane to its original performance capacity, but it only recovers to a certain level because the remaining foulants cause irreversible fouling. Chemical cleaning can then be employed to recover the membrane from this irreversible fouling but, in the process, it can cause irrecoverable damage to the membrane. In this review, the foulants responsible for irrecoverable damage to MF/UF membranes are summarized, and their interaction with cleaning agents and other foulants is described. The impact of these foulants on various membrane parameters, including filtration efficiency, flux decline, permeability, membrane characterization, and membrane integrity are also summarized and discussed in detail. In addition, mitigation options and future prospects are also discussed with regard to increasing the operational life span of a membrane in a cost-effective manner. Ultimately, this review suggests an advanced control system based on membrane-foulant interactions under the impact of various operational parameters to mitigate the integrity loss of membranes.

Fouling and Mitigation Behavior of Foulants on Ion Exchange Membranes with Surface Property in Reverse Electrodialysis.

In this study, two different types of ion exchange membranes are used to investigate the tendency of membrane fouling with respect to surface roughness and hydrophilicity. Commercially available membranes reinforced by electrospun nanofiber have rough and hydrophilic surfaces, and lab-made pore-filling membranes exhibit a smooth and hydrophobic surface. Three different organic surfactants (i.e., cationic, anionic and non-ionic surfactants) are chosen as foulants with similar molecular weights. It is confirmed that membrane fouling by electrical attraction mainly occurs, in which anionic and cationic foulants influence anion and cation exchange membranes, respectively. Thus, less fouling is obtained on both membranes for the non-charged foulant. The membranes with a rough surface show a higher fouling tendency than those with a smooth surface in the short-term continuous fouling tests. However, during the cyclic operations of fouling and mitigation of the commercially available membranes, the irregularities of a rough membrane surface cause a rapid increase in electrical resistance from the beginning of fouling due to excessive adsorption on the surface, but the fouling is easily mitigated due to the hydrophilic surface. On the other hand, the membranes with a smooth surface show alleviated fouling from the beginning of fouling, but the irreversible fouling occurs as foulants accumulate on the hydrophobic surface which causes membrane fouling to be favorable.

Towards bio-utilization and energy recovery potential exploration of membrane foulant from membrane bioreactor by using microbial fuel cell-centered technology.

The utilization of membrane foulant is expected to push forward the developments of membrane bioreactor (MBR). In this study, the combination of microbial fuel cell (MFC) with bio-electrochemical enhanced hydrolysis process was proposed, and three systems were conducted to utilize the membrane foulant and simultaneously harvest electricity. Polysaccharides (PS), proteins (PN) and humic acid (HA) concentration variations and the fluorescent compound changes in different chambers revealed the biodegradability of membrane foulant. Optimized HRT improved the hydrolysis of membrane foulant while allowing MFC to utilize the biodegradable components efficiently. MFC-MFC system had the highest voltage and satisfactory effluent quality at HRT of 1 d. Microbial community structure analysis indicated that Proteobacteria, Planctomycetes and Bacteroidetes were the majority phyla and network analysis further revealed that Proteobacteria played a key role in membrane foulant utilization. This study suggests that MFC hybrid systems has potential application for synchronous membrane foulant reuse and energy recovery.

Influence of Molecular Structures of Organic Foulants on the Antifouling Properties of Poly(2-methoxyethyl acrylate) and Its Analogs: A Molecular Dynamics Study.

Elucidating the fouling phenomena of polymer surfaces will facilitate the molecular design of high-performance biomedical devices. Here, we investigated the remarkable antifouling properties of two acrylate materials, poly(2-methoxyethyl acrylate) (PMEA) and poly(3-methoxypropionic acid vinyl ester) (PMePVE), which have a terminal methoxy group on the side chain, via molecular dynamics simulations of binary mixtures of acrylate/methacrylate trimers with n-pentane or 2,2-dimethylpropane (neopentane), that serve as the nonpolar organic probe (organic foulants). The second virial coefficient (B2) was determined to assess the aggregation/dispersion properties in the binary mixtures. The order of the B2 values for the trimer/pentane mixtures indicated that the terminal methoxy group of the side chain plays an important role in enhancing the fouling resistance to nonpolar organic foulants. Here, we hypothesized that the antifouling properties of PMEA/PMePVE surfaces originate from the resistance. To evaluate the molecular-level accessibility of organic foulants to acrylate/methacrylate materials, we examined the radial distribution functions (RDFs) of the terminal methyl groups of neopentane around the main chains of the acrylate/methacrylate trimers. As a result, the third distinct RDF peaks are observed only for the methacrylate trimers. The peaks are attributed to the hydrophobic interactions between the methyl group of neopentane and that of the main chain of the trimer. Accordingly, the methyl group of the main chain of methacrylate materials, such as poly(2-hydroxyethyl methacrylate) and poly(2-methoxyethyl methacrylate), unfavorably induces fouling with organic foulants. In this study, we clarify that preventing hydrophobic interactions between an organic foulant and polymeric material is essential for enhancing the antifouling property. Our approach has great potential for evaluating the molecular-level affinities of organic foulant with polymer surfaces for the molecular design of excellent antifouling polymeric materials.

Process- and Product-Related Foulants in Virus Filtration.

Regulatory authorities place stringent guidelines on the removal of contaminants during the manufacture of biopharmaceutical products. Monoclonal antibodies, Fc-fusion proteins, and other mammalian cell-derived biotherapeutics are heterogeneous molecules that are validated based on the production process and not on molecular homogeneity. Validation of clearance of potential contamination by viruses is a major challenge during the downstream purification of these therapeutics. Virus filtration is a single-use, size-based separation process in which the contaminating virus particles are retained while the therapeutic molecules pass through the membrane pores. Virus filtration is routinely used as part of the overall virus clearance strategy. Compromised performance of virus filters due to membrane fouling, low throughput and reduced viral clearance, is of considerable industrial significance and is frequently a major challenge. This review shows how components generated during cell culture, contaminants, and product variants can affect virus filtration of mammalian cell-derived biologics. Cell culture-derived foulants include host cell proteins, proteases, and endotoxins. We also provide mitigation measures for each potential foulant.

The Limitations in Current Studies of Organic Fouling and Future Prospects.

Microfiltration and ultrafiltration for water/wastewater treatment have gained global attention due to their high separation efficiency, while membrane fouling still remains one of their bottlenecks. In such a situation, many researchers attempt to obtain a deep understanding of fouling mechanisms and to develop effective fouling controls. Therefore, this article intends to trigger discussions on the appropriate choice of foulant surrogates and the application of mathematic models to analyze fouling mechanisms in these filtration processes. It has been found that the commonly used foulant surrogate (sodium alginate) cannot ideally represent the organic foulants in practical feed water to explore the fouling mechanisms. More surrogate foulants or extracellular polymeric substance (EPS) extracted from practical source water may be more suitable for use in the studies of membrane fouling problems. On the other hand, the support vector machine (SVM) which focuses on the general trends of filtration data may work as a more powerful simulation tool than traditional empirical models to predict complex filtration behaviors. Careful selection of foulant surrogate substances and the application of accurate mathematical modeling for fouling mechanisms would provide deep insights into the fouling problems.

A Review on Ion-Exchange Membrane Fouling during the Electrodialysis Process in the Food Industry, Part 1: Types, Effects, Characterization Methods, Fouling Mechanisms and Interactions.

Electrodialysis (ED) was first established for water desalination and is still highly recommended in this field for its high water recovery, long lifetime and acceptable electricity consumption. Today, thanks to technological progress in ED processes and the emergence of new ion-exchange membranes (IEMs), ED has been extended to many other applications in the food industry. This expansion of uses has also generated several problems such as IEMs' lifetime limitation due to different ageing phenomena (because of organic and/or mineral compounds). The current commercial IEMs show excellent performance in ED processes; however, organic foulants such as proteins, surfactants, polyphenols or other natural organic matters can adhere on their surface (especially when using anion-exchange membranes: AEMs) forming a colloid layer or can infiltrate the membrane matrix, which leads to the increase in electrical resistance, resulting in higher energy consumption, lower water recovery, loss of membrane permselectivity and current efficiency as well as lifetime limitation. If these aspects are not sufficiently controlled and mastered, the use and the efficiency of ED processes will be limited since, it will no longer be competitive or profitable compared to other separation methods. In this work we reviewed a significant amount of recent scientific publications, research and reviews studying the phenomena of IEM fouling during the ED process in food industry with a special focus on the last decade. We first classified the different types of fouling according to the most commonly used classifications. Then, the fouling effects, the characterization methods and techniques as well as the different fouling mechanisms and interactions as well as their influence on IEM matrix and fixed groups were presented, analyzed, discussed and illustrated.

Alginate to simulate biofouling in submerged fluidized ceramic membrane reactor: Effect of solution pH and ionic strength.

Membrane fouling was investigated experimentally by fluidizing non-adsorbed plastic scouring media on flat-tubular ceramic membrane treating a sodium alginate solution as a representative of polysaccharides in wastewater. Fouling rate increased with set-point permeate flux, but it was remarkably reduced by fluidizing the scouring agent regardless of the flux applied. Higher solution pH resulted in more reduction in membrane fouling due to electrostatic repulsion enhanced between alginate foulant and membrane surface which are both negatively charged. The addition of divalent cations such as Ca2+ and Cu2+ mitigated alginate fouling significantly due to the back transport associated with formation of larger particles away from membrane. However, the addition of monovalent cations accelerated the membrane fouling with less effectiveness of the media fluidization in fluidized bed membrane reactor. Adding monovalent ions was thought to transform rigid, compact and spherocolloidal macromolecular structure of alginate into the intramolecular charge shielding to neutralize functional groups.

Light sheet fluorescence microscopy applied for in situ membrane fouling characterization: The microscopic events of hydrophilic membrane in resisting DEX fouling.

Membrane fouling restricts the wide applications of membrane technology and therefore, it is essential to develop novel analytical techniques to characterize membrane fouling and to further understand the mechanism behind it. In this work, we demonstrate a capability of high-resolution large-scale 3D visualization and quantification of the foulants on/in membranes during fouling process based on light sheet fluorescence microscopy as a noninvasive reproducible optical approach. The adsorption processes of dextran (DEX) on/in two polyvinylidene fluoride membranes with similar pore structure but distinct surface hydrophilicity were clearly observed. For a hydrophilic polyvinylidene fluoride (PVDF) membrane, the diffusion and adsorption of the DEX in membrane matrix were much slower compared to that for a hydrophobic membrane. A concentrated foulant layer was observed in the superficial potion of the hydrophilic membrane matrix while the foulants were observed quickly penetrating across the overall hydrophobic PVDF membrane during a short adsorption process. Both the inner concentrated fouling layer (in membrane superficial portion) and the foulant penetration (in membrane asymmetric structure) presented correlations with membrane fouling irreversibility, which could elucidate the microscopic events of hydrophilic membrane in resisting fouling. In addition, the imaging results could be correlated with the XDLVO analysis, suggesting how the membrane-foulant and foulant-foulant interfacial interactions resulted in a time-dependent membrane fouling process. This work provides a fast, highly-sensitive and noninvasive imaging platform for in situ characterization of membrane fouling evolution and should be useful for a wide range of membrane-based process explorations.

Seeing is believing: Insights from synchrotron infrared mapping for membrane fouling in osmotic membrane bioreactors.

We employed synchrotron infrared (IR) mapping to resolve forward osmosis (FO) membrane fouling in osmotic membrane bioreactor (OMBR). Synchrotron IR mapping offers a unique perspective to elucidate the fouling mechanisms and associated consequences in OMBR operation. We demonstrated the spatial distribution and relative intensity of carbohydrate and protein longitudinally along of the fouled FO membrane at the conclusion of OMBR operation. Both transmission and attenuated total reflection (ATR) modes were used to map the cross-section and surface of the fouled FO membrane. Micro X-ray computed tomography revealed patchy, "sand-dune" features on the membrane surface at the conclusion of OMBR operation. Synchrotron IR-ATR mapping demonstrated that the development of membrane fouling layer in OMBR operation was initiated by polysaccharide-like carbohydrate, followed by layering with protein-like substance, resulting in a characteristic "sand-dune" three dimensional feature. Synchrotron FTIR mapping shed light on foulant occurrence and accumulation in the draw solution. Strong penetration of protein-like substance into membrane matrix was visualised, resulting the detection of protein adsorption in the region of membrane supporting layer.

Foulant Analysis of Three RO Membranes Used in Treating Simulated Brackish Water of the Iraqi Marshes.

In this work, three different types of Reverse Osmosis (RO) (Thin-Film Composite (SE), Cellulose Acetate (CE), and Polyamide (AD)) were used to perform foulant analysis (autopsy) study on the deposited materials from three different simulated brackish surface feed waters. The brackish surface water qualities represented the water quality in Iraqi marshes. The main foulants from the simulated feed waters were characterized by using Scanning Electron Microscope (SEM) images and Energy-Dispersive X-ray Spectroscopy (EDXS) spectra. The effect of feed water temperatures (37 °C and 11 °C) on the formation of the fouled material deposited on the membrane surface was examined in this study. Also, pretreatment by a 0.1 micron microfiltration (MF) membrane of the simulated feed water in advance of the RO membrane on the precipitated material on the membrane surface was investigated. Finally, Fourier Transform Infrared Spectroscopy (FTIR) analysis was used to identify the functional groups of the organic matter deposited on the RO membrane surfaces. The SEM images and EDSX spectra suggested that the fouled material was mainly organic matter, and the major crystal deposited on the RO membrane was calcium carbonate (CaCO3). The FTIR spectra of the fouled RO membranes suggested that the constituents of the fouled material included aliphatic and aromatic compounds.

Surface pattern by nanoimprint for membrane fouling mitigation: Design, performance and mechanisms.

Imparting water treatment membrane with surface pattern by nanoimprint offered a novel approach to fouling resistance. We employed nanoimprint to fabricate line-shape nanostructure on membrane distillation (MD) membrane surface. Patterned MD membrane exhibited strong antifouling property to Bovine Serum Albumin (BSA) protein during MD separation. Water flux decline and protein deposition were substantially minimized on the patterned MD membrane in comparison with the pristine one. Such lower fouling propensity on the patterned MD membrane was mainly driven by the weak hydrophobic interaction between BSA protein and patterned MD membrane surface. Weaker adhesion force mapping of the patterned MD membrane was quantified. Representative force-distance curve of pristine MD membrane showed a strong attractive depletion force comparing with that of patterned one. The simple, chemical-free, and scalable nanofabrication approach enables varying designs on membrane surface for special membrane properties.

Fouling analysis of membrane bioreactor treating antibiotic production wastewater at different hydraulic retention times.

Membrane fouling, including foulants and factors, was investigated during hydraulic retention time (HRT) optimization of a membrane bioreactor (MBR) that treated wastewater from the production of antibiotics. The results showed that HRT played an important role in membrane fouling. Trans-membrane pressure (TMP), membrane flux, and resistance were stable at -6 kPa, 76 L m-2 h-1 bar-1, and 4.5 × 1012 m-1 when HRT was at 60, 48, and 36 h, respectively. Using Fourier transform infrared spectroscopy, foulants were identified as carbohydrates and proteins, which correlated with effluent organic matter and effluent chemical oxygen demand (COD) compounds. Therefore, membrane fouling trends would benefit from low supernatant COD (378 mg L-1) and a low membrane removal rate (26 %) at a HRT of 36 h. Serious membrane fouling at 72 and 24 h was related to soluble microbial products and extracellular polymeric substances in mixed liquor, respectively. Based on the TMP decrease and flux recovery after physical and chemical cleaning, irremovable fouling aggravation was related to extracellular polymeric substances' increase and soluble microbial products' decrease. According to changes in the specific oxygen uptake rate (SOUR) and mixed liquor suspended solids (MLSSs) during HRT optimization in this study, antibiotic production wastewater largely inhibited MLSS growth, which only increased from 4.5 to 5.0 g L-1 when HRT was decreased from 72 to 24 h, but did not limit sludge activity. The results of a principal component analysis highlighted both proteins and carbohydrates in extracellular polymeric substances as the primary foulants. Membrane fouling associated with the first principal component was positively related to extracellular polymeric substances and negatively related to soluble microbial products. Principal component 2 was primarily related to proteins in the influent. Additional membrane fouling factors included biomass characteristics, operational conditions, and feed characteristics.

Performance assessment of a submerged membrane bioreactor using a novel microbial consortium.

The performance of a submerged membrane bioreactor (MBR) with and without a novel microbial consortium (NMBR vs. CMBR) was compared to provide deeper insights into the effects of changes in water quality and dissolved organic matter (DOM) characteristics by a novel microbial consortium on the fouling characteristics of MBR processes. Despite similar operating conditions and identical DOM properties in the feed waters, NMBR exhibited a lower propensity to release polysaccharide-like compounds with low molecular weight by bacterial activities compared to CMBR. These compounds have a great fouling potential for MBR processes. Therefore, an increase in the transmembrane pressure (TMP) of NMBR (normalized TMP (TMP/TMP0): 1.14) was much slower and less significant than that observed in CMBR (TMP/TMP0: 2.61). These observations imply that the novel microbial consortium can efficiently mitigate membrane fouling by hydrophilic DOM in MBR processes.

Biofilm increases permeate quality by organic carbon degradation in low pressure ultrafiltration.

We investigated the influence of biofouling of ultrafiltration membranes on the removal of organic model foulants and ultimately on the quality of permeate. Gravity Driven Membrane ultrafiltration (GDM) membrane systems were operated with modified river water during five weeks without control of the biofilm formation. Three GDM systems were studied: two systems with biofilms exposed to (A) variable or (B) constant load of organic foulants, and (C) one system operated without biofilm and exposed to constant foulant loading. Biodegradable dextran or non-biodegradable polystyrene sulfonate model foulants were tested. Substrate biodegradability was confirmed by Size Exclusion Chromatography (SEC) and by degradation batch tests (D). The GDM systems (A) and (B) were fed with pre-filtered river water supplemented with dextran (Dex) of 1, 150 or 2000 kDa, or polystyrene sulfonate (PSS) of 1 or 80 kDa at concentrations of 2-3.5 mgC L(-1). In exp. (C) the feed water consisted of deionized water with 25 mgC L(-1) of either PSS 1, 80 kDa or Dex 2000 kDa. The biofilm formation on UF membrane surfaces controlled the foulant permeation and thus the permeate quality. Biofilms exposed to continuous foulant loading (exp. B) degraded low molecular weight (LMW) biodegradable foulants (1 kDa Dex), which improved the permeate quality. For high molecular weight (HMW) substrates (150, 2000 kDa Dex), the improvement of the permeate quality was observed after 7 days of biofilm formation, and resulted from the foulant hydrolysis followed by degradation. For non-biodegradable foulants, an improvement of 20% of the retention was observed for the polystyrene (1, 80 kDa PSS) due to the presence of biofilms on membrane surfaces. For variable foulant loading (exp. A) the biofilms hydrolysed the large biodegradable foulants but did not degraded them fully, which resulted a deterioration of the permeate quality (except for the LMW dextran (1 kDa) that was fully degraded). Overall, the "biofilm + membrane" composite retained a larger amount of biodegradable foulant than the membrane alone, due to the activity of the biofilm. However, this resulted in an increased biofilm accumulation and reduced flux. In presence of the biofilm, the highest fluxes were observed for control (no foulant) and for small non-biodegradable foulants (PSS 1 kDa). Low fluxes were observed for the accumulating on membrane surface or degradable foulants (exp. B). But, the lowest fluxes were observed in absence of the biofilm (exp. C) due to physical accumulation of the foulants (PSS 80 kDa and Dextran 2000 kDa). Overall our study demonstrates that the presence of biofilms on membrane surfaces has some benefits: (i) biofilm helps to increase the permeate quality and (ii) biofilms protect the membrane from further fouling. Permeate flux stabilizes in the case of biofilm-membrane composite, while it continuously declines in the case of the membrane only.

Understanding the fouling of algogenic organic matter in microfiltration using membrane-foulant interaction energy analysis: effects of organic hydrophobicity.

Fouling caused by algogenic organic matter (AOM) in membrane filtration is a critical problem in algae-rich waters, and understanding fouling mechanisms, particularly by identifying the predominant membrane foulants, could have significant effects on algal fouling prediction and pretreatment. In this work, the fouling behavior of Aphanizomenon flos-aquae (APF)- and Anabaena flos-aquae (ANF)-AOM fractions was analyzed using the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory. The results show that the interfacial energy of membranes and foulants could be used for AOM membrane fouling analysis. The attractive energy was highest between the membrane and the neutral hydrophilic fractions (N-HPI) on clean membrane surfaces, followed by the energy associated with the hydrophobic fractions (HPO) and the transphilic fractions (TPI) in both of the AOMs; on the other hand, the negatively charged hydrophilic organics (C-HPI) in the APF-AOM suffered from repulsive interactions when nearing the membrane surface, which was consistent with their initial filtration flux. After the formation of an initial fouling layer on the membrane surface, membrane fouling was controlled mainly by the cohesion free energy between the approaching foulants and the foulants on the fouled membranes. In addition, it was observed that the interfacial energy between foulants was the dominant factor controlling membrane fouling in AOM filtration. Finally, the interfacial energies between the N-HPI fractions had the greatest effect on both APF-AOM and ANF-AOM membrane fouling.