Surface modification of nanofiltration membranes to improve the removal of organic micropollutants: Linking membrane characteristics to solute transmission.

Surface modification of nanofiltration (NF) membranes has great potential to improve the removal of organic micropollutants (OMs) by NF membranes. This study used polydopamine (PDA) as a model coating to comprehensively link the changes in membrane properties with the changes in transmission of 34 OMs. The membrane characterization demonstrated that a thicker, denser, and more hydrophilic PDA coating can be achieved by increasing the PDA deposition time from 0.5 to 4 hours. Overall, the transmissions of target OMs were reduced by PDA-coated NF membranes compared to unmodified NF membranes. The neutral hydrophobic compounds showed lower transmissions for longer PDA coating (PDA4), while the neutral hydrophilic compounds tended to show lower transmissions for shorter PDA coating (PDA0.5). To explain this, competing effects provided by the PDA coatings are proposed including sealing defects, inducing cake-enhanced concentration polarization in the coating layer for neutral hydrophilic compounds, and weakened hydrophobic adsorption for neutral hydrophobic compounds. For charged compounds, PDA4 with the greatest negative charge among the PDA-coated membranes showed the lowest transmission. Depending on the molecular size and hydrophilicity of the compounds, the transmission of OMs by the PDA4 coating could be reduced by 70% with only a 26.4% decline in water permeance. The correlations and mechanistic insights provided by this work are highly useful for designing membranes with specific surface properties via surface modification to improve the removal of OMs without compromising water production.

Mitigation of membrane particulate fouling by nano/microplastics via physical cleaning strategies.

Membrane fouling by nano/microplastics (NP/MPs) is an emerging concern threatening the performance of water and wastewater treatment facilities. The NP/MPs can lead to surface adsorption, fouling and potential mechanical abrasion of the membranes. In this work, periodic gas scouring was applied during the filtration of nano/microplastics across ultrafiltration membranes to investigate the impact of shear forces on the adsorption of nano/microplastics. A series of surface energy and chemistry-modified membranes were also used including acrylic acid, cyclopropylamine and hexamethyldisiloxane plasma-modified membranes, allowing for a set of materials with controlled hydrophilicity, roughness and surface charge. Bubbling gas within the system at a gas flow rate of 0.5 to 1 L·min-1 and a water flow rate of 2 L·min-1 was found to limit the water flux decline across the pristine and hydrophobic membranes compared to the filtration experiments performed without cleaning from 38 to 22 and 23%, respectively. The adsorption of nano/microplastics onto the surface of the membranes was also simultaneously decreased from 40 to 25 and 19%, respectively. Interestingly, for the hydrophilised membranes no enhancement in permeance was observed when performing gas scouring due to the already low tendency for selective adsorption of the nano/microplastics onto their surface. The correlation of a dimensionless fouling number to the shear stress number suggested that the shear forces induced by gas scouring reduced nano/microplastics adsorption up to a gas injection ratio (volume fraction of gas) of 0.3, where the wall shear stress at the surface of the membrane was limited. This work offers an advanced physical strategy to reduce and control membrane fouling by nano/microplastics, with potential for this strategy to be adapted for more complex water matrices and plastic particles.

Optimization of Aquaporin Loading for Performance Enhancement of Aquaporin-Based Biomimetic Thin-Film Composite Membranes.

The aquaporin-based biomimetic thin-film composite membrane (ABM-TFC) has demonstrated superior separation performance and achieved successful commercialization. The larger-scale production of the ABM membrane requires an appropriate balance between the performance and manufacturing cost. This study has systematically investigated the effects of proteoliposome concentration, protein-to-lipid ratio, as well as the additive on the separation performance of ABM for the purpose of finding the optimal preparation conditions for the ABM from the perspective of industrial production. Although increasing the proteoliposome concentration or protein-to-lipid ratio within a certain range could significantly enhance the water permeability of ABMs by increasing the loading of aquaporins in the selective layer, the enhancement effect was marginal or even compromised beyond an optimal point. Alternatively, adding cholesterol in the proteoliposome could further enhance the water flux of the ABM membrane, with minor effects on the salt rejection. The optimized ABM not only achieved a nearly doubled water flux with unchanged salt rejection compared to the control, but also demonstrated satisfactory filtration stability within a wide range of operation temperatures. This study provides a practical strategy for the optimization of ABM-TFC membranes to fit within the scheme of industrial-scale production.

Membrane-based separation for oily wastewater: A practical perspective.

The large volumes of oily wastewater generated by various industries, such as oil and gas, food and beverage, and metal processing, need to be de-oiled prior to being discharged into the environment. Compared to conventional technologies such as dissolved air flotation (DAF), coagulation or solvent extraction, membrane filtration can treat oily wastewater of a much broader compositional range and still ensure high oil removals. In the present review, various aspects related to the practical implementation of membranes for the treatment of oily wastewater are summarized. First, sources and composition of oily wastewater, regulations that stipulate the extent of treatment needed before discharge, and the conventional technologies that enable such treatment are appraised. Second, commercially available membranes, membrane modules, operation modes and hybrids are overviewed, and their economics are discussed. Third, challenges associated with membrane filtration are examined, along with means to quantify and mitigate membrane fouling. Finally, perspectives on state-of-the-art techniques to facilitate better monitoring and control of such systems are briefly discussed.

Gravity-driven membrane filtration for water and wastewater treatment: A review.

Gravity-driven membrane (GDM) filtration has been investigated for almost 10 years. The technology is characterized not only by relatively lower transmembrane pressures which can be achieved by gravity (extremely low energy consumption), but also by the phenomenon of flux stabilization: A biofilm is allowed to form on the membrane and a stabilization of flux occurs which is related to biological processes within the biofilm layer on the membrane. This enables stable operation during a year or longer without any cleaning or flushing. Initially, the technology was developed mainly for household drinking water treatment, but in the meantime, the research and application has expanded to the treatment of greywater, rainwater, and wastewater as well as the pretreatment of seawater for desalination. This review covers the field from the rather fundamental research on biofilm morphology and microbial community analysis to the impact of feedwater composition, process parameters and organic removal performance. Not only household applications, but also for community-scale treatment and full-scale applications are discussed. In addition, the application potential is highlighted in comparison to conventional ultrafiltration. Finally, an overall assessment is illustrated and the research and development needs are identified.

Online monitoring of transparent exopolymer particles (TEP) by a novel membrane-based spectrophotometric method.

The presence of transparent exopolymer particles (TEP) in water bodies has been related to several adverse impacts in various water treatment processes. In recent years, there have been an increasing number of publications relating to TEP. Unfortunately, this increased interest in TEP measurement has not been accompanied by significant improvement in the analysis method or TEP monitoring. Currently, the most common method to analyze and quantify TEP only allows offline, and often offsite measurement, causing delays and slow response times. This paper introduces an improved method for TEP monitoring using a membrane-based spectrophotometric technique to quantify TEP in various water bodies. The proposed TEP monitor involves a crossflow filtration unit, reagent injection and a spectrophotometer system. The TEP retained on the membrane surface is stained by Alcian blue and the amount deposited is quantified directly using an optic fibre reflectance probe coupled with a spectrophotometer. The novel method shows a linear relationship with various concentrations of Xanthan gum (a model representing TEP). When tested with various water samples, the proposed method was found to correlate well with the conventional method. Several advantages of this novel method are shorter analysis time, increased accuracy, and the potential to be further developed into an online system.

Succession of biofilm communities responsible for biofouling of membrane bio-reactors (MBRs).

Biofilm formation is one of the main factors associated with membrane biofouling in membrane bioreactors (MBRs). As such, it is important to identify the responsible organisms to develop targeted strategies to control biofouling. This study investigated the composition and changes in the microbial communities fouling MBR membranes over time and correlated those changes with an increase in transmembrane pressure (TMP). Based on qPCR data, bacteria were the dominant taxa of the biofilm (92.9-98.4%) relative to fungi (1.5-6.9%) and archaea (0.03-0.07%). NMDS analysis indicated that during the initial stages of operation, the biofilm communities were indistinguishable from those found in the sludge. However, the biofilm community significantly diverged from the sludge over time and ultimately showed a unique biofilm profile. This suggested that there was strong selection for a group of organisms that were biofilm specialists. This pattern of succession and selection was correlated with the rapid increase in TMP, where bacteria including Rhodospirillales, Sphingomonadales and Rhizobiales dominated the biofilm at this time. While most of the identified fungal OTUs matched Candida sp., the majority of fungal communities were unclassified by 18S rRNA gene sequencing. Collectively, the data suggests that bacteria, primarily, along with fungi may play an important role in the rapid TMP increase and loss of system performance.

Rubidium extraction from seawater brine by an integrated membrane distillation-selective sorption system.

The ultimate goal of seawater reverse osmosis (SWRO) brine management is to achieve minimal liquid discharge while recovering valuable resources. The suitability of an integrated system of membrane distillation (MD) with sorption for the recovery of rubidium (Rb+) and simultaneous SWRO brine volume reduction has been evaluated for the first time. Polymer encapsulated potassium copper hexacyanoferrate (KCuFC(PAN)) sorbent exhibited a good selectivity for Rb+ sorption with 10-15% increment at 55 °C (Langmuir Qmax = 125.11 ± 0.20 mg/g) compared to at 25 °C (Langmuir Qmax = 108.71 ± 0.20 mg/g). The integrated MD-KCuFC(PAN) system with periodic membrane cleaning, enabled concentration of SWRO brine to a volume concentration factor (VCF) of 2.9 (65% water recovery). A stable MD permeate flux was achieved with good quality permeate (conductivity of 15-20 µS/cm). Repeated cycles of MD-KCuFC(PAN) sorption with SWRO brine enabled the extraction of 2.26 mg Rb+ from 12 L of brine (equivalent to 1.9 kg of Rb/day, or 0.7 tonne/yr from a plant producing 10,000 m3/day brine). KCuFC(PAN) showed a high regeneration and reuse capacity. NH4Cl air stripping followed by resorcinol formaldehyde (RF) resin filtration enabled to recover Rb+ from the desorbed solution.

Preparation of Superhydrophilic and Underwater Superoleophobic Nanofiber-Based Meshes from Waste Glass for Multifunctional Oil/Water Separation.

The deterioration of water resources due to oil pollution, arising from oil spills, industrial oily wastewater discharge, etc., urgently requires the development of novel functional materials for highly efficient water remediation. Recently, superhydrophilic and underwater superoleophobic materials have drawn significant attention due to their low oil adhesion and selective oil/water separation. However, it is still a challenge to prepare low-cost, environmentally friendly, and multifunctional materials with superhydrophilicity and underwater superoleophobicity, which can be stably used for oil/water separation under harsh working conditions. Here, the preparation of nanofiber-based meshes derived from waste glass through a green and sustainable route is demonstrated. The resulting meshes exhibit excellent performance in the selective separation of a wide range of oil/water mixtures. Importantly, these meshes can also maintain the superwetting property and high oil/water separation efficiency under various harsh conditions. Furthermore, the as-prepared mesh can remove water-soluble contaminants simultaneously during the oil/water separation process, leading to multifunctional water purification. The low-cost and environmentally friendly fabrication, harsh-environment resistance, and multifunctional characteristics make these nanofiber-based meshes promising toward oil/water separation under practical conditions.

Improved performance of gravity-driven membrane filtration for seawater pretreatment: Implications of membrane module configuration.

As a low energy and chemical free process, gravity-driven membrane (GDM) filtration has shown a potential for seawater pretreatment in our previous studies. In this study, a pilot submerged GDM reactor (effective volume of 720 L) was operated over 250 days and the permeate flux stabilized at 18.6 ± 1.4 L/m2h at a hydrostatic pressure of 40 mbar. This flux was higher than those in the lab-scale GDM reactor (16.3 ± 0.2 L/m2h; effective volume of 8.4 L) and in the filtration cell system (2.7 ± 0.6 L/m2h; feed side volume of 0.0046 L) when the same flat sheet membrane was used. Interestingly, when the filtration cell was submerged into the GDM reactor, the flux (17.2 L/m2h) was comparable to the submerged membrane module. Analysis of cake layer morphology and foulant properties indicated that a thicker but more porous cake layer with less accumulation of organic substances (biopolymers and humics) contributed to the improved permeate flux. This phenomenon was possibly associated with longer residence time of organic substances and sufficient space for the growth, predation, and movement of the eukaryotes in the GDM reactor. In addition, the permeate flux of the submerged hollow fibre membrane increased with decreasing packing density. It is thought that the movement of large-sized eukaryotes could be limited when the space between hollow fibres was reduced. In terms of pretreatment, the GDM systems effectively removed turbidity, viable cells, and transparent exopolymer particles from the feed seawater. Importantly, extending the reactor operation time produced a permeate with less assimilable organic carbon and biopolymers. Thus, the superior quality of the GDM permeate has the potential to alleviate subsequent reverse osmosis membrane fouling for seawater treatment.

Quorum quenching bacteria can be used to inhibit the biofouling of reverse osmosis membranes.

Over the last few decades, significant efforts have concentrated on mitigating biofouling in reverse osmosis (RO) systems, with a focus on non-toxic and sustainable strategies. Here, we explored the potential of applying quorum quenching (QQ) bacteria to control biofouling in a laboratory-scale RO system. For these experiments, Pantoea stewartii was used as a model biofilm forming organism because it was previously shown to be a relevant wastewater isolate that also forms biofilms in a quorum sensing (QS) dependent fashion. A recombinant Escherichia coli strain, which can produce a QQ enzyme, was first tested in batch biofilm assays and significantly reduced biofilm formation by P. stewartii. Subsequently, RO membranes were fouled with P. stewartii and the QQ bacterium was introduced into the RO system using two different strategies, direct injection and immobilization within a cartridge microfilter. When the QQ bacterial cells were directly injected into the system, N-acylhomoserine lactone signals were degraded, resulting in the reduction of biofouling. Similarly, the QQ bacteria controlled biofouling when immobilized within a microfilter placed downstream of the RO module to remove QS signals circulating in the system. These results demonstrate the proof-of-principle that QQ can be applied to control biofouling of RO membranes and may be applicable for use in full-scale plants.

Carbon-Based Functional Materials Derived from Waste for Water Remediation and Energy Storage.

Carbon-based functional materials hold the key for solving global challenges in the areas of water scarcity and the energy crisis. Although carbon nanotubes (CNTs) and graphene have shown promising results in various fields of application, their high preparation cost and low production yield still dramatically hinder their wide practical applications. Therefore, there is an urgent call for preparing carbon-based functional materials from low-cost, abundant, and sustainable sources. Recent innovative strategies have been developed to convert various waste materials into valuable carbon-based functional materials. These waste-derived carbon-based functional materials have shown great potential in many applications, especially as sorbents for water remediation and electrodes for energy storage. Here, the research progress in the preparation of waste-derived carbon-based functional materials is summarized, along with their applications in water remediation and energy storage; challenges and future research directions in this emerging research field are also discussed.

Effects of spacer orientations on the cake formation during membrane fouling: Quantitative analysis based on 3D OCT imaging.

Spacer design plays an important role in improving the performance of membrane processes for water/wastewater treatment. This work focused on a fundamental issue of spacer design, i.e., investigating the effects of spacer orientations on the fouling behavior during a membrane process. A series of fouling experiments with different spacer orientation were carried out to in situ characterize the formation of a cake layer in a spacer unit cell via 3D optical coherence tomography (OCT) imaging. The cake layers formed at different times were digitalized for quantitatively analyzing the variation in the cake morphology as a function of time. In particular, the local deposition rates were evaluated to determine the active regions where the instantaneous changes in deposit thickness were significant. The characterization results indicate that varying the spacer orientation could substantially change the evolution of membrane fouling by particulate foulants and thereby result in a cake layer with various morphologies; the competition between growth and erosion at different locations would instantaneously respond to the micro-hydrodynamic environment that might change with time. This work confirms that the OCT-based characterization method is a powerful tool for exploring novel spacer design.

The roles of bacteriophages in membrane-based water and wastewater treatment processes: A review.

Membrane filtration processes have been widely applied in water and wastewater treatment for many decades. Concerns related to membrane treatment effectiveness, membrane lifespan, and membrane fouling control have been paid great attention. To achieve sustainable membrane operation with regards to low energy and maintenance cost, monitoring membrane performance and applying suitable membrane control strategies are required. As the most abundant species in water and wastewater, bacteriophages have shown great potential to be employed in membrane processes as (1) indicators to assess membrane performance considering their similar properties to human pathogenic waterborne viruses; (2) surrogate particles to monitor membrane integrity due to their nano-sized nature; and (3) biological agents to alleviate membrane fouling because of their antimicrobial properties. This study aims to provide a comprehensive review on the roles of bacteriophages in membrane-based water and wastewater treatment processes, with focuses on their uses for membrane performance examination, membrane integrity monitoring, and membrane biofouling control. The advantages, limitations, and influencing factors for bacteriophage-based applications are reported. Finally, the challenges and prospects of bacteriophage-based applications in membrane processes for water treatment are highlighted.

Single-stage versus two-stage anaerobic fluidized bed bioreactors in treating municipal wastewater: Performance, foulant characteristics, and microbial community.

This study examined the receptive performance, membrane foulant characteristics, and microbial community in the single-stage and two-stage anaerobic fluidized membrane bioreactor (AFMBR) treating settled raw municipal wastewater with the aims to explore fouling mechanisms and microbial community structure in both systems. Both AFMBRs exhibited comparable organic removal efficiency and membrane performances. In the single-stage AFMBR, less soluble organic substances were removed through biosorption by GAC and biodegradation than those in the two-stage AFMBR. Compared to the two-stage AFMBR, the formation of cake layer was the main cause of the observed membrane fouling in the single-stage AFMBR at the same employed flux. The accumulation rate of the biopolymers was linearly correlated with the membrane fouling rate. In the chemical-cleaned foulants, humic acid-like substances and silicon were identified as the predominant organic and inorganic fouants respectively. As such, the fluidized GAC particles might not be effective in removing these substances from the membrane surfaces. High-throughout pyrosequencing analysis further revealed that beta-Proteobacteria were predominant members in both AFMBRs, which contributed to the development of biofilms on the fluidized GAC and membrane surfaces. However, it was also noted that the abundance of the identified dominant in the membrane surface-associated biofilm seemed to be related to the permeate flux and reactor configuration.

Analyzing the Evolution of Membrane Fouling via a Novel Method Based on 3D Optical Coherence Tomography Imaging.

The development of novel tools for studying the fouling behavior during membrane processes is critical. This work explored optical coherence tomography (OCT) to quantitatively interpret the formation of a cake layer during a membrane process; the quantitative analysis was based on a novel image processing method that was able to precisely resolve the 3D structure of the cake layer on a micrometer scale. Fouling experiments were carried out with foulants having different physicochemical characteristics (silica nanoparticles and bentonite particles). The cake layers formed at a series of times were digitalized using the OCT-based characterization. The specific deposit (cake volume/membrane surface area) and surface coverage were evaluated as a function of time, which for the first time provided direct experimental evidence for the transition of various fouling mechanisms. Axial stripes were observed in the grayscale plots showing the deposit distribution in the scanned area; this interesting observation was in agreement with the instability analysis that correlated the polarized particle groups with the small disturbances in the boundary layer. This work confirms that the OCT-based characterization is able to provide deep insights into membrane fouling processes and offers a powerful tool for exploring membrane processes with enhanced performance.

Application of Hollow Fiber Forward Osmosis Membranes for Produced and Process Water Volume Reduction: An Osmotic Concentration Process.

Produced and process water (PPW) from oil and gas operations, specifically in Qatar, are disposed of by deep well injection in onshore facilities. Disposing large volumes of PPW may affect deep well formation sustainability highlighting the need for effective PPW management. Forward osmosis (FO) was applied as an "osmotic concentration" process to reduce PPW injection volumes by 50% using brines and seawater as draw solutions (DS). The energy intensive step of restoring the salinity of the DS was eliminated; the diluted DS would be simply discharged to the ocean. Both hollow fiber and flat sheet FO membranes were tested and the former exhibited better flux and rejection; they are the focus of this study. Optimization experiments, conducted using Box-Behnken statistical design, confirmed that temperature and DS concentration had a substantial effect on performance. To validate the concept, a long-term experiment, under optimized conditions, was conducted with PPW as feed and brine from thermal desalination plant as DS which yielded an average flux of 24 L/m(2)h. The results confirmed that low-energy osmotic concentration FO has the potential for full-scale implementation to reduce PPW injection volumes. Pilot testing opportunities are being evaluated to demonstrate the effectiveness of this technology under field conditions.

Sandwich-Architectured Poly(lactic acid)-Graphene Composite Food Packaging Films.

Biodegradable food packaging promises a more sustainable future. Among the many different biopolymers used, poly(lactic acid) (PLA) possesses the good mechanical property and cost-effectiveness necessary of a biodegradable food packaging. However, PLA food packaging suffers from poor water vapor and oxygen barrier properties compared to many petroleum-derived ones. A key challenge is, therefore, to simultaneously enhance both the water vapor and oxygen barrier properties of the PLA food packaging. To address this issue, we design a sandwich-architectured PLA-graphene composite film, which utilizes an impermeable reduced graphene oxide (rGO) as the core barrier and commercial PLA films as the outer protective encapsulation. The synergy between the barrier and the protective encapsulation results in a significant 87.6% reduction in the water vapor permeability. At the same time, the oxygen permeability is reduced by two orders of magnitude when evaluated under both dry and humid conditions. The excellent barrier properties can be attributed to the compact lamellar microstructure and the hydrophobicity of the rGO core barrier. Mechanistic analysis shows that the large rGO lateral dimension and the small interlayer spacing between the rGO sheets have created an extensive and tortuous diffusion pathway, which is up to 1450-times the thickness of the rGO barrier. In addition, the sandwiched architecture has imbued the PLA-rGO composite film with good processability, which increases the manageability of the film and its competency to be tailored. Simulations using the PLA-rGO composite food packaging film for edible oil and potato chips also exhibit at least eight-fold extension in the shelf life of these oxygen and moisture sensitive food products. Overall, these qualities have demonstrated the high potential of a sandwich-architectured PLA-graphene composite film for food packaging applications.

Recent Development of Advanced Materials with Special Wettability for Selective Oil/Water Separation.

The increasing number of oil spill accidents have a catastrophic impact on our aquatic environment. Recently, special wettable materials used for the oil/water separation have received significant research attention. Due to their opposing affinities towards water and oil, i.e., hydrophobic and oleophilic, or hydrophilic and oleophobic, such materials can be used to remove only one phase from the oil/water mixture, and simultaneously repel the other phase, thus achieving selective oil/water separation. Moreover, the synergistic effect between the surface chemistry and surface architecture can further promote the superwetting behavior, resulting in the improved separation efficiency. Here, recently developed materials with special wettability for selective oil/water separation are summarized and discussed. These materials can be categorized based on their oil/water separating mechanisms, i.e., filtration and absorption. In each section, representative studies will be highlighted, with emphasis on the materials wetting properties and innovative aspects. Finally, challenges and future research directions in this emerging and promising research field will be briefly described.

Optimization of gravity-driven membrane (GDM) filtration process for seawater pretreatment.

Seawater pretreatment by gravity-driven membrane (GDM) filtration at 40 mbar has been investigated. In this system, a beneficial biofilm develops on the membrane that helps to stabilize flux. The effects of membrane type, prefiltration and system configuration on stable flux, biofilm layer properties and dissolved carbon removal were studied. The results show that the use of flat sheet PVDF membranes with pore sizes of 0.22 and 0.45 µm in GDM filtration achieved higher stabilized permeate fluxes (7.3-8.4 L/m(2)h) than that of flat sheet PES 100 kD membranes and hollow fibre PVDF 0.1 µm membranes. Pore constriction and cake filtration were identified as major membrane fouling mechanisms, but their relative contributions varied with filtration time for the various membranes. Compared to raw seawater, prefiltering of seawater with meshes at sizes of 10, 100 and 1000 µm decreased the permeate flux, which was attributed to removal of beneficial eukaryotic populations. Optical coherence tomography (OCT) showed that the porosity of the biofouling layer was more significantly related with permeate flux development rather than its thickness and roughness. To increase the contact time between the biofilm and the dissolved organics, a hybrid biofilm-submerged GDM reactor was evaluated, which displayed significantly higher permeate fluxes than the submerged GDM reactor. Although integrating the biofilm reactor with the membrane system displayed better permeate quality than the GDM filtration cells, it could not effectively reduce dissolved organic substances in the seawater. This may be attributed to the decomposition/degradation of solid organic substances in the feed and carbon fixation by the biofilm. Further studies of the dynamic carbon balance are required.