Engineering Multinanochannel Polymer-Intercalated Graphene Oxide Membrane for Strict Volatile Sieving in Membrane Distillation.

Graphene oxide (GO) membranes enabled by subnanosized diffusion channels are promising to separate small species in membrane distillation (MD). However, the challenge of effectively excluding small volatiles in MD persists due to the severe swelling and subsequent increase in GO interlamination spacing upon direct contact with the hot feed. To address this issue, we implemented a design in which a polymer is confined between the GO interlaminations, creating predominantly 2D nanochannels centered around 0.57 nm with an average membrane pore size of 0.30 nm. Compared to the virginal GO membrane, the polymer-intercalated GO membrane exhibits superior antiswelling performance, particularly at a high feed temperature of 60 °C. Remarkably, the modified membrane exhibited a high flux of approximately 52 L m-2 h-1 and rejection rates of about 100% for small ions and 98% for volatile phenol, with a temperature difference of 40 °C. Molecular dynamics simulations suggest that the sieving mechanisms for ions and volatiles are facilitated by the narrowed nanochannels within the polymer network situated between the 2D nanochannels of GO interlaminations. Concurrently, the unrestricted permeation of water molecules through the multinanochannel GO membrane encourages high-flux desalination of complex hypersaline wastewater.

Evaluation of Front-Face Fluorescence for Assessing Cyanobacteria Fouling in Ultrafiltration.

Cyanobacteria fouling in ultrafiltration (UF) drinking water treatment poses a significant threat to the stability and sustainability of the process. Both phycocyanin found in cyanobacteria and the polymer membrane exhibit strong fluorescence, which could be readily detected using front-face excitation-emission matrix (FF-EEM) spectroscopy. In this study, FF-EEM was employed for the nondestructive and in situ characterization of algae fouling evolution in UF, while also analyzing fouling mechanisms and reversibility. The results indicated that phycocyanin fluorescence on the membrane surface showed a linear correlation with the specific algal cell count on the membrane surface before reaching saturation. As fouling progressed, membrane fluorescence decreased, which was associated with the extent of the surface coverage on the membrane. The plateau in membrane fluorescence indicated full coverage, coinciding with the cake filtration mechanism, cake compression, and deterioration of fouling reversibility. These findings highlight the promise of FF-EEM as a valuable tool for monitoring and evaluating fouling of cyanobacteria in UF systems.

Dual-Bioinspired Design for Constructing Membranes with Superhydrophobicity for Direct Contact Membrane Distillation.

Water flux and durability are the two critical parameters that are closely associated with the practical application of membrane distillation (MD). Herein, we report a facile approach to fabricate superhydrophobic polyimide nanofibrous membranes (PI NFMs) with hierarchical structures, interconnected pores, and high porosity, which was derived from the electrospinning, dual-bioinspired design, and fluorination processes. Bioinspired adhesive based on polydopamine /polyethylenimine (PDA/PEI) composite was first linked onto membrane substrates and then assembled lotus leaf hierarchical structure by binding the negatively charged silica nanoparticles (SiO2 NPs) via electrostatic attraction. The resultant superhydrophobic PI NFMs exhibit a water contact angle of 152°, robust hot water resistance of 85 °C, and high water entry pressure of 42 kPa. Moreover, the membrane with omniphobicity presents high water flux over 31 L m-2 h-1 and high salts rejection of ∼100% as well as robust durability for treating high salinity wastewater containing typical low surface tension and dissolved contaminants (Δ T = 40 °C). Significantly, the novel dual-bioinspired method can be used as a universal tool to modify various materials with hierarchical structures, which is expected to provide more effective alternative membranes for MD and even for other selective wetting separation fields.

Membrane Fouling and Rejection of Organics during Algae-Laden Water Treatment Using Ultrafiltration: A Comparison between in Situ Pretreatment with Fe(II)/Persulfate and Ozone.

In this study, in situ pretreatments with ozone and Fe(II)/persulfate were employed to suppress membrane fouling during the filtration of algae-laden water and to improve the rejection of metabolites. Both ozonation and Fe(II)/persulfate pretreatments negatively impacted the cell integrity, especially ozonation. Fe(II)/persulfate pretreatment improved the removal of dissolved organic carbon and microcystin-LR, but ozonation resulted in a deterioration in the quality of the filtered water. This suggests that the Fe(II)/persulfate oxidation is selective for organic degradation over cell damage. With ozonation, 2-methylisoborneol and geosmin were detected in the filtered water, and the irreversible fouling increased. The intracellular organic release and generation of small organic compounds with ozonation may be the reason for the increased membrane fouling. Fe(II)/persulfate oxidation substantially mitigated the membrane-fouling resistance at concentrations over 0.2 mM compared to the membrane-fouling resistance without oxidation. The combined effect of oxidation and coagulation is likely the reason for the excellent fouling control with Fe(II)/persulfate pretreatment. Membrane fouling during the filtration of algae-laden water is successively governed by complete-blocking and cake-filtration mechanisms. Ozonation caused a shift in the initial major mechanism to intermediate blocking, and the Fe(II)/persulfate pretreatment (>0.2 mM) converted the dominant mechanism into single-standard blocking.

Comparison of Hydrophilicity and Mechanical Properties of Nanocomposite Membranes with Cellulose Nanocrystals and Carbon Nanotubes.

The inherent properties of hydrophilicity and mechanical strength of cellulose nanocrystals (CNCs) make them a possible alternative to carbon nanotubes (CNTs) that may present fewer objections to application water-treatment membranes. In this work, the hydrophilicity and mechanical properties of CNCs and CNTs nanocomposite poly(ether sulfone) (PES) membranes were characterized and compared. Membrane pore geometry was analyzed by scanning electron microscopy (SEM). Overall porosity and mean pore radius were calculated based on a wet-dry method. Results showed that PES polymers were loosely packed in the top layer of both the CNC- and CNT-composite membranes (CNC-M and CNT-M). The porosity of the CNC-M was greater than that of the CNT-M. Membrane hydrophilicity, measured by water-contact angle, free energy of cohesion, and water flux, was increased through the addition of either CNCs or functionalized CNTs to an otherwise hydrophobic polymer membrane. The hydrophilicity of the CNC-M was greater than the CNT-M. In addition, the Young's modulus and tensile strength was enhanced for both the CNC-M and CNT-M. While smaller concentrations of CNTs were required to achieve an equal increase in Young's modulus compared with the CNCs, the elasticity of the CNC-composite membranes was greater.

Biofouling control by biostimulation of quorum-quenching bacteria in a membrane bioreactor for wastewater treatment.

Bacterial quorum quenching (QQ) has been shown to be effective in controlling biofouling in membrane bioreactors (MBRs) for wastewater treatment. However, the encapsulation of a sufficient level of QQ bacteria is complicated and difficult. In plant research, gamma-caprolactone (GCL), which is structurally similar to the quorum signal, N-acyl homoserine lactone (AHL), was successfully used to specifically stimulate AHL-degrading bacteria (biostimulation) in hydroponic systems to control blackleg and soft rot diseases in potato. In this study, the feasibility of enriching QQ bacteria from activated sludge by GCL was examined, and the effect of biostimulation on biofouling control in MBR treating domestic wastewater was investigated. The results showed that after enrichment with GCL, activated sludge could effectively degrade AHLs, and a QQ gene (qsdA) was augmented. The proposed biostimulation QQ strategy, by introducing and continuously dosing GCL, could significantly increase QQ activity, decrease AHL, control the secretion of extracellular polymeric substances (EPS), and thus, effectively control biofouling in an MBR. This biostimulation QQ strategy provides a more convenient option for biofouling control in MBR applications. Biotechnol. Bioeng. 2016;113: 2624-2632. © 2016 Wiley Periodicals, Inc.

Effect of solid retention time on membrane fouling in membrane bioreactor: from the perspective of quorum sensing and quorum quenching.

Solid retention time (SRT) is one of the most important operational parameters in membrane bioreactor (MBR), which significantly influences membrane fouling. It is widely recognized that SRT mainly changes biomass characteristics, and then, influences membrane fouling. Effect of SRT on quorum sensing (QS) in MBR, which could also influence fouling by coordinating biofilm formation, has not been reported. In this study, fouling, QS, soluble microbial products (SMP), and extracellular polymer substances (EPS) in MBRs operated under SRTs of 4, 10, and 40 days were investigated. The results showed that as SRT increased, the abundance of quorum quenching (QQ) bacteria increased, the quorum signal degradation activity of activated sludge increased, the concentrations of signal molecules in MBR decreased, the excretion of SMP and EPS decreased, and thus membrane biofouling was alleviated. Therefore, besides altering the biomass physiochemical properties, SRT also changed the balance between QS and QQ in MBR, and in this way, influenced membrane biofouling.

Towards a better hydraulic cleaning strategy for ultrafiltration membrane fouling by humic acid: Effect of backwash water composition.

As a routine measurement to alleviate membrane fouling, hydraulic cleaning is of great significance for the steady operation of ultrafiltration (UF) systems in water treatment processes. In this work, a comparative study was performed to investigate the effects of the composition of backwash water on the hydraulic cleaning performance of UF membranes fouled by humic acid (HA). Various types of backwash water, including UF permeate, Milli-Q water, NaCl solution, CaCl2 solution and HA solution, were compared in terms of hydraulically irreversible fouling index, total surface tension and residual HA. The results indicated that Milli-Q water backwash was superior to UF permeate backwash in cleaning HA-fouled membranes, and the backwash water containing Na(+) or HA outperformed Milli-Q water in alleviating HA fouling. On the contrary, the presence of Ca(2+) in backwash water significantly decreased the backwash efficiency. Moreover, Ca(2+) played an important role in foulant removal, and the residual HA content closely related to the residual Ca(2+) content. Mechanism analysis suggested that the backwash process may involve fouling layer swelling, ion exchange, electric double layer release and competitive complexation. Ion exchange and competitive complexation played significant roles in the efficient hydraulic cleaning associated with Na(+) and HA, respectively.

Effects of poly aluminum chloride dosing positions on the performance of a pilot scale anoxic/oxic-membrane bioreactor (A/O-MBR).

The effects of poly aluminum chloride (PACl) dosing positions on the performance of a pilot scale anoxic/oxic membrane bioreactor were investigated. PACl dosage was optimized at 19.5 mg Al2O3/L by jar test. Nutrients removal efficiencies and sludge properties were systematically investigated during periods with no PACl dosing (phase I), with PACl dosing in oxic tank (phase II) and then in anoxic tank (phase III). The results showed that total phosphorus removal efficiency increased from 18 to 88% in phase II and 85% in phase III with less than 0.5 mg P/L in effluent. Ammonia nitrogen removal efficiencies reached 99% in all phases and chemical oxygen demand removal efficiencies reached 92%, 91% and 90% in the three phases, respectively. Total nitrogen removal efficiency decreased from 59% in phase I to 49% in phases II and III. Dosing PACl in the oxic tank resulted in smaller sludge particle size, higher zeta potential, better sludge settleability and lower membrane fouling rate in comparison with dosing PACl in the anoxic tank.

Enhancing electron transfer in anaerobic process by supercapacitor materials: Polyaniline functionated activated carbon.

Strengthening the direct interspecies electron transfer (DIET) is an effective strategy to improve the performance of anaerobic digestion (AD) process. In this study, the polyaniline functionated activated carbon (AC-PANi) was prepared by chemical oxidative polymerization. This material possessed pseudo-capacitance properties as well as excellent charge transfer capability. The experimental results demonstrated that the incorporation of AC-PANi in AD process could efficiently increase the chemical oxygen demand (COD) removal (18.6 %) and daily methane production rate (35.3 %). The AC-PANi can also act as an extracellular acceptor to promote the synthesis of adenosine triphosphate (ATP) and secretion of extracellular enzymes as well as cytochrome C (Cyt-C). The content of coenzyme F420 on methanogens was also shown to be increased by 60.9 % with the addition of AC-PANi in AD reactor. Overall, this work provides an easy but feasible way to enhance AD performance by promoting DIET between acetate-producing bacteria and methanogens.

Moderate oxidation of algae-laden water: Principals and challenges.

The occurrence of seasonal algae blooms represents a huge dilemma for water resource management and has garnered widespread attention. Therefore, finding methods to control algae pollution and improve water quality is urgently needed. Moderate oxidation has emerged as a feasible way of algae-laden water treatment and is an economical and prospective strategy for controlling algae and endogenous and exogenous pollutants. Despite this, a comprehensive understanding of algae-laden water treatment by moderate oxidation, particularly principles and summary of advanced strategies, as well as challenges in moderate oxidation application, is still lacking. This review outlines the properties and characterization of algae-laden water, which serve as a prerequisite for assessing the treatment efficiency of moderate oxidation. Biomass, cell viability, and organic matter are key components to assessing moderate oxidation performance. More importantly, the recent advancements in employing moderate oxidation as a treatment or pretreatment procedure were examined, and the suitability of different techniques was evaluated. Generally, moderate oxidation is more promising for improving the solid-liquid separation process by the reduction of cell surface charge (stability) and removal/degradation of the soluble algae secretions. Furthermore, this review presents an outlook on future research directions aimed at overcoming the challenges encountered by existing moderate oxidation technologies. This comprehensive examination aims to provide new and valuable insights into the moderate oxidation process.

Feasibility of replacing proton exchange membranes with pressure-driven membranes in membrane electrochemical reactors for high salinity organic wastewater treatment.

Membrane electrochemical reactor (MER) shows superiority to electrochemical oxidation (EO) in high salinity organic wastewater (HSOW) treatment, but requirement of proton exchange membranes (PEM) increases investment and maintenance cost. In this work, the feasibility of using low-cost pressure-driven membranes as the separation membrane in MER system was systematically investigated. Commonly used pressure-driven membranes, including loose membranes such as microfiltration (MF) and ultrafiltration (UF), as well as dense membranes like nanofiltration (NF) and reverse osmosis (RO), were employed in the study. When tested in a contamination-free solution, MF and UF exhibited superior electrochemical performance compared to PEM, with comparable pH regulation capabilities in the short term. When foulant (humic acid, Ca2+ and Mg2+) presented in the feed, UF saved the most energy (43 %) compared to PEM with similar removal rate of UV254 (∼85 %). In practical applications of MER for treating nanofiltration concentrate (NC) of landfill leachate, UF saved 27 % energy compared to PEM per cycle with the least Ca2+ and Mg2+ retention in membrane and none obvious organics permeation. For fouled RO and PEM with ion transport impediment, water splitting was exacerbated, which decreased the percentage of oxidation for organics. Overall, replacing of PEM with UF significantly reduce the costs associated with both the investment and operation of MER, which is expected to broaden the practical application for treating HSOW.

Enhanced anaerobic digestion performance and sludge filterability by membrane microaeration for anaerobic membrane bioreactor application.

Slow dissolution/hydrolysis of insoluble/macromolecular organics and poor sludge filterability restrict the application potential of anaerobic membrane bioreactor (AnMBR). Bubble-free membrane microaeration was firstly proposed to overcome these obstacles in this study. The batch anaerobic digestion tests feeding insoluble starch and soluble peptone with and without microaeration showed that microaeration led to a 65.7-144.8% increase in methane production and increased critical flux of microfiltration membrane via driving the formation of large sludge flocs and the resultant improvement of sludge settleability. The metagenomic and bioinformatic analyses showed that microaeration significantly enriched the functional genes and bacteria for polysaccharide and protein hydrolysis, microaeration showed little negative effects on the functional genes involved in anaerobic metabolisms, and substrate transfer from starch to peptone significantly affected the functional genes and microbial community. This study demonstrates the dual synergism of microaeration to enhance the dissolution/hydrolysis/acidification of insoluble/macromolecular organics and sludge filterability for AnMBR application.

UV/Fe(II)/S(IV) Pretreatment for Ultrafiltration of Microcystis aeruginosa-Laden Water: Fe(II)/Fe(III) Triggered Synergistic Oxidation and Coagulation.

Ultrafiltration (UF) has been proven effective in removing algae during seasonal algal blooms, but the algal cells and the metabolites can induce severe membrane fouling, which undermines the performance and stability of the UF. Ultraviolet-activated sulfite with iron (UV/Fe(II)/S(IV)) could enable an oxidation-reduction coupling circulation and exert synergistic effects of moderate oxidation and coagulation, which would be highly preferred in fouling control. For the first time, the UV/Fe(II)/S(IV) was systematically investigated as a pretreatment of UF for treating Microcystis aeruginosa-laden water. The results showed that the UV/Fe(II)/S(IV) pretreatment significantly improved the removal of organic matter and alleviated membrane fouling. Specifically, the organic matter removal increased by 32.1% and 66.6% with UV/Fe(II)/S(IV) pretreatment for UF of extracellular organic matter (EOM) solution and algae-laden water, respectively, while the final normalized flux increased by 12.0-29.0%, and reversible fouling was mitigated by 35.3-72.5%. The oxysulfur radicals generated in the UV/S(IV) degraded the organic matter and ruptured the algal cells, and the low-molecular-weight organic matter generated in the oxidation penetrated the UF and deteriorated the effluent. The over-oxidation did not happen in the UV/Fe(II)/S(IV) pretreatment, which may be attributed to the cyclic redox Fe(II)/Fe(III) coagulation triggered by the Fe(II). The UV-activated sulfate radicals in the UV/Fe(II)/S(IV) enabled satisfactory organic removal and fouling control without over-oxidation and effluent deterioration. The UV/Fe(II)/S(IV) promoted the aggregation of algal foulants and postponed the shift of the fouling mechanisms from standard pore blocking to cake filtration. The UV/Fe(II)/S(IV) pretreatment proved effective in enhancing the UF for algae-laden water treatment.

Mineral scaling induced membrane wetting in membrane distillation for water treatment: Fundamental mechanism and mitigation strategies.

The scaling-induced wetting phenomenon seriously affects the application of membrane distillation (MD) technology in hypersaline wastewater treatment. Unlike the large amount of researches on membrane scaling and membrane wetting, scaling-induced wetting is not sufficiently studied. In this work, the current research evolvement of scaling-induced wetting in MD was systematically summarized. Firstly, the theories involving scaling-induced wetting were discussed, including evaluation of scaling potential of specific solutions, classical and non-classical crystal nucleation and growth theories, observation and evolution of scaling-induced processes. Secondly, the primary pretreatment methods for alleviating scaling-induced wetting were discussed in detail, focusing on adding agents composed of coagulation, precipitation, oxidation, adsorption and scale inhibitors, filtration including granular filtration, membrane filtration and mesh filtration and application of external fields including sound, light, heat, electromagnetism, magnetism and aeration. Then, the roles of operation conditions and cleaning conditions in alleviating scaling-induced wetting were evaluated. The main operation parameters included temperature, flow rate, pressure, ultrasound, vibration and aeration, while different types of cleaning reagents, cleaning frequency and a series of assisted cleaning measures were summarized. Finally, the challenges and future needs in the application of nucleation theory to scaling-induced wetting, the speculation, monitoring and mitigation of scaling-induced wetting were proposed.

Integrated membrane electrochemical reactor-membrane distillation process for enhanced landfill leachate treatment.

Treatment of recalcitrant landfill leachate (LFL) induces huge energy consumption and carbon emissions due to its complex composition. Although membrane distillation (MD) exhibits good potential in LFL treatment with waste heat utilization, membrane fouling and ammonia rejection are still the major problems encountered that hinder its application. Herein, membrane electrochemical reactor (MER) was coupled with MD for simultaneous membrane fouling control and resource recovery. LFL pretreatment with membrane-less electrochemical reactor (EO) and without pretreatment were also purified by MD for comparison. Results showed that the MER-MD system rejected almost all CODCr, total phosphorus, metal salts, and ammonia nitrogen (increased by 33.5%-43.5% without chemical addition), and recovered 31% of ammonia nitrogen and 48% of humic acid in the raw LFL. Owing to the effective removal of hardness (61%) and organics (77%) using MER, the MER-MD system showed higher resistance to the membrane wetting and fouling, with about 61% and 14% higher final vapor flux than those of the MD and EO-MD systems, respectively, and the pure water flux could be fully recovered by alkaline solution cleaning. Moreover, SEM-EDS, ATR-FTIR and XRD characterization further demonstrated the superiority of the MD membrane fouling reversibility of the MER-MD system. Energy consumption and carbon emissions analysis showed that the MER-MD system reduced the total energy consumption/carbon emissions by ∼20% and ∼8% compared to the MD and EO-MD systems, respectively, and the ammonia nitrogen recovered by MER could offset 8.25 kg carbon dioxide equivalent. Therefore, the introduction of MER pretreatment in MD process would be an option to decrease energy consumption and reduce carbon emissions for MD treatment of LFL.

Simultaneous ammonium and water recovery from landfill leachate using an integrated two-stage membrane distillation.

Resources recovery from landfill leachate (LFL) has been attracting growing attention instead of merely purifying the wastewater. An integrated two-stage membrane distillation (ITMD) was proposed to simultaneously purify LFL and recover ammonia in this study. The results showed that organics could be always effectively rejected by the ITMD regardless of varying feed pH, with COD removal higher than 99%. With feed pH increased from 8.64 to 12, the ammonia migration (50-100%) and capture (36-75%) in LFL were considerably enhanced, boosting the separated ammonia enrichment to 1.3-1.7 times due to the improved ammonium diffusion. However, the corresponding membrane flux of the first MD stage decreased from 13.7 to 10.5 L/m2·h. Elevating feed pH caused the deprotonation of NOM and its binding with inorganic ions, constituting a complex fouling layer on the membrane surface in the first MD stage. In contrast, the membrane permeability and fouling of the second MD were not affected by feed pH adjustment because only volatiles passed through the first MD. More importantly, it was estimated that ITMD could obtain high-quality water and recover high-purity ammonium from LFL with relatively low ammonium concentration at an input cost of $ 2-3/m3, which was very competitive with existing techniques. These results demonstrated that the ITMD can be a valuable candidate strategy for simultaneous water purification and nutrient recovery from landfill leachate.

The influence of environmental factor on the coagulation enhanced ultrafiltration of algae-laden water: Role of two anionic surfactants to the separation performance.

With the acceleration of urbanization and the improvement of people's living standards, more chemicals that humans rely on are entering the city and surrounding water bodies. Anionic surfactants are one of the essential products for human beings. It is also one of the inducements that cause the eutrophication. The algae-laden water caused by eutrophication is a headache in the traditional water treatment process. To solve the problem, ultrafitration combined process was widely investigated to treat the algae-laden water. The presence of stimuli, low concentration anionic surfactant, probably interfere the performance of ultrafiltration process during algae-laden water treatment. In this study, the influence of two typical anionic surfactants, sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (LAS), on the performance of coagulation-enhanced ultrafiltration was investigated. The aluminum sulfate hydrate and iron sulfate hydrate were respectively employed as coagulant. Based on the residual turbidity and zeta potential, 4 mg/L Al and 8 mg/L Fe were determined as the optimal coagulant dosage. The floc morphology confirmed that Al-algae flocs with lower fractal dimension (Df) were looser and more porous compared to Fe-algae flocs. More coagulant was depleted by LAS due to the better hydrophobicity of LAS. During the filtration process, LAS caused a larger flux reduction compared with SDS regardless of the coagulant that was used. More organic compounds penetrate into membrane pores and block the pores with the presence of LAS since algal cell aggregation was weakened. Finally, the rejection of organic compounds by the coagulation-enhanced ultrafiltration process was studied, and the co-existing surfactants can cause effluent deterioration. Therefore, the presence of surfactants has a negative effect to the ultrafiltration treatment of algae-laden water.

Efficient biostimulants for bacterial quorum quenching to control fouling in MBR.

Quorum quenching (QQ), which disrupts bacterial communication and biofilm formation, could alleviate biofouling in MBR. QQ bio-stimulus possessing similar conserved moiety as the signal molecule could promote indigenous QQ bacteria, and thus successfully alleviate biofouling in MBR. However, efficient biostimulant has been barely explored for QQ enhancement in activated sludge system. This study extensively enumerated the potential QQ bio-stimuli, and examined their efficacy on QQ promotion for activated sludge. Moreover, the effect of the QQ consortia on fouling mitigation was also investigated. The results indicated that gamma-caprolactone (GCL), d-xylonic acid-1,4-lactone (XAL), gamma-heptalactone (GHL), urea, and acetamide proved effective in promoting AHLs inactivating activity of activated sludge. GCL, XAL, and GHL intensified the lactonase activity, while urea and acetamide augmented acylase activity. While coupled with beads entrapment, GCL consortia beads, XAL consortia beads, and urea consortia beads effectively disrupted quorum sensing (QS) and controlled membrane fouling in MBR. This work found out several optional bio-stimuli valid for tuning QQ in activated sludge system, and provided easily available and economical alternatives for QQ biostimulation, meanwhile the proposed QQ-MBR approach through QQ biostimulation and consortia entrapment also proved effective and practical.

Confining Nano-Fe3O4 in the Superhydrophilic Membrane Skin Layer to Minimize Internal Fouling.

Membrane surface fouling is often reversible as it can be mitigated by enhancing the crossflow shear force. However, membrane internal fouling is often irreversible and thus more challenging. In this study, we developed a new superhydrophilic poly(vinylidene fluoride) (P-PVDF) membrane confined with nano-Fe3O4 in the top skin layer via reverse filtration to reduce internal fouling. The surface of the P-PVDF membrane confined with nano-Fe3O4 had superwetting properties (water contact angle reaching 0° within 1 s), increased roughness (from 182 to 239 nm), and enhanced water affinity. The Fe3O4@P-PVDF membrane surface showed a thicker and enhanced hydration layer, which prevented foulants from approaching membrane surfaces and pores, thereby improving the rejection. For example, when 50 ppm humic acid (HA) solution was used as the feed, the removal efficiency of the Fe3O4@P-PVDF membrane was ∼67%, while the HA removal of the P-PVDF membrane was only ∼20%. The results from the resistance-in-series model showed that nanoconfinement of Fe3O4 in the top skin layer of the membrane allowed foulants to accumulate on the membrane surface (i.e., surface fouling) rather than within the internal pores (i.e., internal fouling). The filtration results under crossflow fouling and cleaning confirmed that the Fe3O4@P-PVDF membrane had higher surface fouling but it was much more reversible and much lower internal fouling compared with the control membrane. Our fouling analysis offers new insights into mass transfer mechanisms of the membrane with a nanoconfinement-enhanced hydration layer. This study provides an effective strategy to develop membranes with low internal fouling propensities.