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.

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.

Improving membrane distillation performance by Fe(II) activated sodium percarbonate oxidation during the treatment of shale gas produced water.

Membrane distillation (MD) offers promise for recycling shale gas produced water (SGPW), while membrane fouling is still a major obstacle in standalone MD. Herein, sodium percarbonate (SPC) oxidation was proposed as MD pretreatment, and the performance of the single MD, SPC-MD hybrid process and Fe(II)/SPC-MD hybrid process for SGPW treatment were systematically evaluated. Results showed that compared to raw SGPW, the application of SPC and Fe(II)/SPC led to the decrease of the fluorescent organics by 28.54 % and 54.52 %, respectively. The hydrophobic fraction decreased from 52.75 % in raw SGPW to 37.70 % and 27.20 % for SPC and Fe(II)/SPC, respectively, and the MD normalized flux increased from 0.19 in treating raw SGPW to 0.65 and 0.81, respectively. The superiority of SPC oxidation in reducing the deposited membrane foulants and restoring membrane properties was further confirmed through scanning electron microscopy observation, attenuated total reflection fourier transform infrared, water contact angle and surface tension analyses of fouled membranes. Correlation analysis revealed that hydrophobic/hydrophilic matters and fluorescent organics in SGPW took a crucial role in MD fouling. The mechanism of MD fouling mitigation by Fe(II)/SPC oxidation was attributed to the decrease in concentrations and hydrophobicity of organic by synergistic oxidation, coagulation and adsorption.

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.