Degradation of Polyamide Nanofiltration Membranes by Bromine: Changes of Physiochemical Properties and Filtration Performance.

The potential coexistence and interaction of bromine and polyamide membranes during membrane-based water treatment prompts us to investigate the effect of bromine on membrane performance. For fully aromatic polyamide membrane NF90 exposed under a mild bromination condition (10 mg/L), bromine incorporation resulted in more negatively charged (-13 vs -25 mV) and hydrophobic (55.2 vs 58.9°) surfaces and narrower pore channels (0.3 vs 0.29 nm). The permeabilities of water and neutral solutes were reduced by 64 and 69-87%, respectively, which was attributed to the decreased effective pore radius and hydrophilicity. NaCl permeability was reduced by 90% as a synergistic result of enhanced size exclusion and charge repulsion. The further exposure (100 and 500 mg/L bromine) resulted in a more hydrophobic surface (61.7 and 65.5°) and the minor further reduction for water and solute permeabilities (1-9%). Compared with chlorine, the different incorporation efficiency and properties (e.g., atomic size, hydrophilicity) of bromine resulted in opposite trends and/or different degrees for the variation of physicochemical properties and filtration performance of membranes. The bromine incorporation, the shift and disappearance of three characteristic bands, and the increased O/N ratio and calcium content indicated the degradation pathways of N-bromination and bromination-promoted hydrolysis under mild bromination conditions (480 mg/L·h). The further ring-bromination occurred after severe bromine exposure (4800-24,000 mg/L·h). The semi-aromatic polyamide membrane NF270 underwent a similar but less significant deteriorated filtration performance compared with NF90, which requires a different explanation.

Enhancing proton transport in polyvinylidenedifluoride membranes and reducing biofouling for improved hydrogen production in microbial electrolysis cells.

Hydrophilic porous membranes, exemplified by polyvinylidene fluoride (PVDF) membranes, have demonstrated significant potential for replacing ion exchange membranes in microbial electrolysis cells (MECs). Membrane fouling remains a major challenge in MECs, impeding proton transport and consequently limiting hydrogen production. This study aims to investigate a synergistic antifouling strategy for PVDF membrane through the incorporation of a coating composed of polydopamine (PDA), polyethyleneimine (PEI), and silver nanoparticles (AgNPs). The PDA-PEI-Ag@PVDF membrane not only effectively mitigates fouling through steric and electrostatic repulsion forces, but also amplifies ion transport by facilitating water diffusion and electromigration. The PDA-PEI-Ag@PVDF membrane exhibited a reduced membrane resistance of 1.01 mΩ m2 and PDA-PEI-Ag modifying PVDF membrane was found to be effective in enhancing the proton transportation of PVDF membrane. Therefore, the enhanced hydrogen production rate of 2.65 ± 0.02 m3/m3/d was achieved in PDA-PEI-Ag@PVDF-MECs.

The structural and functional properties of polysaccharide foulants in membrane fouling.

Polysaccharide foulant is known to play a crucial role in membrane fouling, however the detailed influential mechanisms and the pertinence to specific structure of polysaccharides, as well as intermolecular interactions among them with and without divalent cation are still indistinct. In this study, seven polysaccharides including agarose, sodium alginate, carrageenan, pectin, starch, sodium carboxymethylcellulose (CMC) and xanthan gum, with different chain and molecular structures, were used as model foulants to investigate the role of structural and functional features of polysaccharides in membrane fouling. Two Hermia's models (classical and mass-transfer models) as well as the resistance-in-series model were used to analyze the fouling mechanism. Results show that the spatial configuration of foulant molecule is significant in membrane fouling which actually controls the resistance of gel layer formed on membrane. Polysaccharides with different properties show distinct fouling mechanisms which are in accordance with the four models described by Hermia respectively. Cations may change the interaction of polysaccharide foulant which further leads to the structural change of the gel layer. It turns out that mass-transfer model is more suitable for interpreting of crossflow filtration data. So far, little has been known about the effects of molecule structure of polysaccharides on membrane fouling. In this paper, we provide a basic database for polysaccharide fouling which will work as a theoretical basis for finding more effective measures to prevent and control membrane fouling.

Phosphate recovery from the P-enriched brine of AnMBR-RO-IE treating municipal wastewater via an innovated phosphorus recovery batch reactor with nano-sorbents.

Municipal wastewater is a very unique pool full of energy and useful substances. Though the innovative integrated anaerobic membrane bioreactor and reverse osmosis-ion exchange (AnMBR-RO-IE) process can produce high-grade reclaimed water with high energy efficiency, phosphorus resources recovery in the WWTPs has been rarely reported thus far. This study evaluated the feasibility of a phosphorus recovery batch reactor (PRBR) as an approach for the phosphate production from the P-enriched brine from AnMBR-RO-IE. With operating PRBR for 162 cycles, high to 85% of P recovery rate was obtained for 145 cycles, leading to a P production rate of 6.17 g/m3 domestic wastewater with nano-sorbents (NSs) consumption rate of 10.2 g/m3. Acidification pretreatment efficiently improved the adsorption capacity and reduced the NSs renewing frequency. High adsorption selectivity of NSs contributed to low impurities (<0.3%) in the P-enriched reclaimed solution. Moreover, the integrated AnMBR-RO-IE-PRBR process saved 47% of energy consumption compared to the present NEWater production process in Singapore. The innovative PRBR reactor was competitive compared to the commonly-used chemical precipitation methods in conventional WWTPs in terms of phosphorus recovery/loss and energy balance. It is expected that the proposed integrated process can offer new insights into the direction of phosphorus reclamation in the future WWTPs.

The role of transparent exopolymer particles (TEP) in membrane fouling: A critical review.

Transparent exopolymer particles (TEP) as gel-like particulate acidic polysaccharide have been commonly found in marine, surface water and wastewater. Currently, increasing interest has been devoted to TEP-associated membrane fouling in different membrane systems for water and wastewater treatment, thus this review attempts to provide a holistic view and critical analysis with regard to the definition, formation, detection and properties of TEP, which could ultimately determine its fouling potential. It appears that there is not a common consensus on the actual role of TEP in membrane fouling development due to the subjective definition and highly debatable detection method of TEP. It was clearly demonstrated in this review that the formation of TEP was largely related to cations in water and wastewater which indeed determined the cross-linking degree of precursor materials (e.g. polysaccharides) via intermolecular interactions, and subsequently the quantity of TEP formed. The binding between cations ions (e.g. monovalent, divalent and trivalent cations) and polysaccharide not only depends on the functional groups of polysaccharide, but also its spatial configuration. These in turn suggest that the formation, property and ultimate fouling potential of TEP would be closely related to the type and concentration of cations, while well explaining the controversial reports on TEP-associated fouling in the literature. In addition, the fouling mechanisms of TEP are also elucidated with details in this review, including (i) the formation of TEP-associated gel layer on membrane surface; (ii) carrying microorganisms to membrane surface via protobiofilm and (iii) trapping of deformable TEP in membrane pores. Consequently, it is apparent that TEP is an ignored determinant of membrane fouling, which has not yet been seriously addressed in the design and operation of membrane systems for water and wastewater treatment.

Intermolecular interactions of polysaccharides in membrane fouling during microfiltration.

Membrane technology has been widely employed for seawater desalination, water and wastewater reclamation, while membrane fouling still remains as a major challenge. The polysaccharides in extracellular polymeric substances (EPS) have been recognized as an important foulant that causes serious membrane fouling, while the detailed structure of polysaccharides and the intermolecular interactions between them have not been adequately disclosed. In this study, two different polysaccharides and their mixtures were used to study the intermolecular cross-linking of polysaccharides as well as its effects on membrane fouling. Results demonstrated that the fouling propensities of distinct polysaccharides were completely different, which was attributed to the different intermolecular interactions lying in polysaccharides. The cross-linking among molecules of polysaccharide, regardless of the homogeneity, was found to form complex networks and determine the effective dimension of polysaccharides. Depending on the effective dimension of foulants, pore blocking and cake layer occurred subsequently during filtration processes. In light of this, it potentially gives new insights into the fouling behaviours by combining the structure-function knowledge of polysaccharides with their fouling propensity. In addition, transparent exopolymeric particles (TEP) measurement was found to provide an intuitionistic evaluation of the complex networks formed from polysaccharides, so that may act as a good indicator of fouling during membrane filtration.

Transparent exopolymer particles (TEP)-associated membrane fouling at different Na+ concentrations.

Membrane filtration has been widely applied for water treatment, wastewater reclamation and seawater desalination. Although extensive research work has been conducted to better understand the fouling mechanism under various conditions, little has been known about the transparent exopolymer particles (TEP)-associated membrane fouling at different Na+ concentrations. In this study, the influence of Na+ concentration on the TEP formation as well as the filtration behaviors of alginate blocks was investigated. Results showed that increasing Na+ concentration substantially reduced the TEP formation from all types of alginate blocks, thus preventing the cake layer development on the membrane surface. As a result, the TEP-associated membrane fouling was found to be kinetically slower and much less at higher Na+ level. Furthermore, filtration tests of alginate blocks at freshwater and seawater conditions were also conducted, showing that TEP-associated fouling in freshwater is much server than that in seawater at the defined conditions. This study reveals that the TEP formation is significantly influenced by the chemistry condition of bulk solution and membrane fouling is profoundly affected by the TEP levels in feed water.

Ultrafiltration behaviors of alginate blocks at various calcium concentrations.

Alginate, a linear copolymer, is composed of 1,4-linked ß-d-mannuronic acid (M) and α-l-guluronic acid (G), which are combined into homopolymeric blocks (MM-block and GG-block) and heteropolymeric block (MG-block). It has been widely used as a model foulant in various studies of membrane fouling, thus this study investigated the impacts of calcium ion on MG-, MM- and GG-blocks of alginate and the filtration behaviors of the three types of alginate blocks at different concentrations of calcium ion. Results showed that calcium ion had the most serious effects on GG-blocks and significantly promotes the formation of transparent exopolymeric particles (TEP) from GG-blocks which in turn led to rapid formation of thick cake layer on membrane surface during the filtration of GG-blocks. As for MM-blocks, it was found that the formation of TEP was proportional to the Ca(2+) concentration in MM-blocks solution, while the membrane fouling was enhanced by Ca(2+) in the filtration of MM-blocks solution. Unlike MM- and GG-blocks, MG-blocks were nearly not affected by addition of calcium ion, as the result, there was no significant increase in TEP. The initial fouling rates and the mass of foulants deposed on the membrane surfaces further revealed a close correlation between the TEP concentration and the membrane fouling propensity. The observations by field emission scanning electron microscope (FESEM) and atomic force microscope (AFM) further confirmed the formation process of the cake layer by TEP on the membrane surface. This study offers deep insights into the development of membrane fouling by different alginate blocks in the presence of calcium ion, and suggests that TEP formed from alginate blocks played a very significant role in the fouling development.

Alginate block fractions and their effects on membrane fouling.

Alginate has been commonly used as a model foulant in studies of membrane organic fouling. As a complex polymer, alginate is composed of two different monomers, namely M ((1 → 4) linked ß-D-mannopyranuronic acid) and G ((1 → 4) linked α-L-gulopyranuronic acid) which are randomly arranged into MG-, MM- and GG-blocks. So far, little information is available about fouling propensity of each block in microfiltration. In this study, microfiltration experiments were conducted respectively with MG-, MM- and GG-blocks separated from alginate under defined conditions. Results showed the severest fouling in the filtration of MG-block, and the least flux decline in the filtration of MM-block. The initial pore blocking was found to be responsible for the fouling observed in MG-block filtration, while the cake layer formed on membrane surface during the MM-block filtration could serve as a pre-filter that prevented membrane from further pore blocking. In order to look into fouling mechanisms, the effects of transparent exopolymeric particles (TEP) on membrane fouling were also studied. TEP were found to form through aggregation or cross-link of alginate blocks. As TEP were bigger than original alginate blocks, they could facilitate the formation of cake layer on membrane surface. It was observed that more TEP were produced from MM-blocks than from MG-blocks in solutions. This in turn explained why cake resistance was dominant in the filtration of MM-blocks as compared to MG-blocks. The analysis by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory further revealed that MM-blocks had lowest cohesive interaction energy among all three alginate blocks, which favoured aggregation of MM-blocks, and ultimately leading to the formation of more TEP. This study provided insights into the roles of different alginate blocks in development of membrane fouling, and suggested that the membrane fouling would be related to molecular structure of alginate.