Demystifying the Role of Surfactant in Tailoring Polyamide Morphology for Enhanced Reverse Osmosis Performance: Mechanistic Insights and Environmental Implications.

Surfactant-assisted interfacial polymerization (IP) has shown strong potential to improve the separation performance of thin film composite polyamide membranes. A common belief is that the enhanced performance is attributed to accelerated amine diffusion induced by the surfactant, which can promote the IP reaction. However, we show enhanced membrane performance for Tween 80 (a common surfactant), even though it decreased the amine diffusion. Indeed, the membrane performance is closely related to its polyamide roughness features with numerous nanovoids. Inspired by the nanofoaming theory that relates the roughness features to nanobubbles degassed during the IP reaction, we hypothesize that the surfactant can stabilize the generated nanobubbles to tailor the formation of nanovoids. Accordingly, we obtained enlarged nanovoids when the surfactant was added below its critical micelle concentration (CMC). In addition, both the membrane permeance and selectivity were enhanced, thanks to the enlarged nanovoids and reduced defects in the polyamide layer. Increasing the concentration above CMC resulted in shrunken nanovoids and deteriorated performance, which can be ascribed to the decreased stabilization effect caused by micelle formation. Interestingly, better antifouling performance was also observed for the surfactant-assisted membranes. Our current study provides mechanistic insights into the critical role of surfactant during the IP reaction, which may have important implications for more efficient membrane-based desalination and water reuse.

Does Surface Roughness Necessarily Increase the Fouling Propensity of Polyamide Reverse Osmosis Membranes by Humic Acid?

Surface roughness has crucial influence on the fouling propensity of thin film composite (TFC) polyamide reverse osmosis (RO) membranes. A common wisdom is that rougher membranes tend to experience more severe fouling. In this study, we compared the fouling behaviors of a smooth polyamide membrane (RO-s) and a nanovoid-containing rough polyamide membrane (RO-r). Contrary to the traditional belief, we observed more severe fouling for RO-s, which can be ascribed to its uneven flux distribution caused by the "funnel effect". Additional tracer filtration tests using gold nanoparticles revealed a more patchlike particle deposition pattern, confirming the adverse impact of "funnel effect" on membrane water transport. In contrast, the experimentally observed lower fouling propensity of the nanovoid-containing rough membrane can be explained by: (1) the weakened "funnel effect" thanks to the presence of nanovoids, which can regulate the water transport pathway through the membrane and (2) the decreased average localized flux over the membrane surface due to the increased effective filtration area for the nanovoid-induced roughness features. The current study provides fundamental insights into the critical role of surface roughness in membrane fouling, which may have important implications for the future development of high-performance antifouling membranes.

Impact of Polymer Chain Rearrangements in the PA Structure of RO Membranes on Water Permeability and N-Nitrosamine Rejection.

The use of solvents is overall recognized as an efficient method to improve the water permeability of polyamide thin film composite membranes (PA-TFC). The objective of this work was to test the performance of the membranes after exposing them to n-propanol (n-PrOH) to improve the permeability of the membranes while maintaining the rejection factor for small uncharged organic molecules, namely N-nitrosamines (NTRs). After the membranes were exposed to n-PrOH, the water permeability of the UTC73AC membrane increased by 98%, with minimal change in rejection. N-nitrosodiethylamine (NDEA) rejection decreased (3.4%), while N-nitrosodi-n-propylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) rejection increased by 0.9% and 2.8%, respectively. In contrast, for the BW30LE membrane, water permeability decreased (by 38.7%), while rejection factors increased by 14.5% for NDEA, 6.2% for NDPA, and 15.0% for NDBA. In addition, the morphology of the membrane surface before and after exposure to n-PrOH was analyzed. This result and the pore size distribution (PSD) curves obtained indicate that the rearrangement of polymer chains affects the network or aggregate pores in the PA layer, implying that a change in pore size or a change in pore size distribution could improve the permeability of water molecules, while the rejection factor for NTRs is not significantly affected.

Cosolvent-Assisted Interfacial Polymerization toward Regulating the Morphology and Performance of Polyamide Reverse Osmosis Membranes: Increased m-Phenylenediamine Solubility or Enhanced Interfacial Vaporization?

Cosolvent-assisted interfacial polymerization (IP) can effectively enhance the separation performance of thin film composite (TFC) reverse osmosis (RO) membranes. However, the underlying mechanisms regulating the formation of their polyamide (PA) rejection films remain controversial. The current study reveals two essential roles of cosolvents in the IP reaction: (1) directly promoting interfacial vaporization with their lower boiling points and (2) increasing the solubility of m-phenylenediamine (MPD) in the organic phase, thereby indirectly promoting the IP reaction. Using a series of systematically chosen cosolvents (i.e., diethyl ether, acetone, methanol, and toluene) with different boiling points and MPD solubilities, we show that the surface morphologies of TFC RO membranes were regulated by the combined direct and indirect effects. A cosolvent favoring interfacial vaporization (e.g., lower boiling point, greater MPD solubility, and/or higher concentration) tends to create greater apparent thickness of the rejection layer, larger nanovoids within the layer, and more extensive exterior PA layers, leading to significantly improved membrane water permeance. We further demonstrate the potential to achieve better antifouling performance for the cosolvent-assisted TFC membranes. The current study provides mechanistic insights into the critical roles of cosolvents in IP reactions, providing new tools for tailoring membrane morphology and separation properties toward more efficient desalination and water reuse.

A simple reaction-diffusion model for initial stages of biofouling in reverse osmosis membranes.

Biofouling is a critical issue in membrane water and wastewater treatment as it greatly compromises the efficiency of the treatment processes and consequently increases operational and maintenance costs. It is difficult to control this operational challenge, so the development of effective biofouling monitoring and control methods and strategies is a critical issue for membrane technology and applications. In this work, we develop a simulation approach for evaluating the operational time of reverse osmosis (RO) membranes based on a reaction-diffusion (RD) type of model. This approach would help to understand different factors involved in the formation of biofilms including microbial population dynamics (replication and death rates of microbial cells) and nutrient consumption. The model is focused on the initial stages of the membrane biofouling that is initiated by attachment of microbial species to the membrane leading to pore blocking followed by the formation of thick cake layer. We applied this approach to study the RO membrane biofouling by Picochlorum algae, the most common biofouling agent in the seawater of the Arabian Gulf, at known contents of total organic carbon and essential nutrients. We found that the biofilm growth dynamics on an RO membrane is mainly defined by the ratio of the replication and death rates of microbial cells. The proposed approach should be useful for fast evaluation of the RO membrane performance in different environmental conditions without using significant computational resources. This methodology allows generalization for multi-microbial and multi-nutrient systems. The establishment of effective fouling control strategies should decrease operational and maintenance costs of RO membrane systems.

Maximizing N-Nitrosamine Rejection via RO Membrane Plugging with Hexylamine and Hexamethylenediamine.

The rapid expansion of urban areas and the increasing demand for water resources necessitate substantial investments in technologies that enable the reuse of municipal wastewater for various purposes. Nonetheless, numerous challenges remain, particularly regarding disinfection by-products (DBPs), especially carcinogenic compounds such as N-nitrosamines (NTRs). To tackle the ongoing issues associated with reverse osmosis (RO) membranes, this study investigated the rejection of NTRs across a range of commercially available RO membranes. In addition, the research aimed to improve rejection rates by integrating molecular plugs into the nanopores of the polyamide (PA) layer. Hexylamine (HEX) and hexamethylenediamine (HDMA), both linear chain amines, have proven to be effective as molecular plugs for enhancing the removal of NTRs. Given the environmental and human health concerns associated with linear amines, the study also aimed to assess the feasibility of diamine molecules as potential alternatives. The application of molecular plugs led to changes in pore size distribution (PSD) and effective pore number, resulting in a decrease in membrane permeability (from 5 to 33%), while maintaining levels suitable for RO processes. HEX and HDMA exhibited a positive effect on NTR rejection with ACM1, ACM5 and BW30LE membranes. In particular, NDMA rejection, the smallest molecule of the tested NTRs, with ACM1 was improved by 65.5% and 70.6% after treatment with HEX and HDMA, respectively.

Synergistic effect of GO/ZnO loading on the performance of cellulose acetate/chitosan blended reverse osmosis membranes for NOM rejection.

Declining freshwater resources along with their pollution are threatening the life existence on earth. To meet the freshwater demand, one of the most appropriate and possible ways which has been adopted all over the world is to reuse wastewater by removing its impurities. Among many water pollutants, natural organic matter (NOM) is found to be responsible as major precursor for the formation of other pollutants. Removal of NOM from wastewater is being done by using membrane filtration systems incorporated with certain nanofillers to increase membranes efficiency and permeability. In this study, novel nanocomposite reverse osmosis (RO) membranes were prepared using cellulose acetate and chitosan in N,N-Dimethyl formamide. Graphene oxide (GO) nanosheets and zinc oxide (ZnO) in different concentration were loaded to modify the membranes for tuning their RO performance. The confirmation of the functional groups is demonstrated by Fourier transform infrared spectroscopy which revealed the specific peaks indicating the formation of the nano-composite membranes. The surface morphology was studied by scanning electronic microscopy which shows a gradual transformation of the membrane surface from voids-free to macro-voids filled surface up to threshold concentration of GO and ZnO. The thermal properties of GO based membranes were analyzed using thermogravimetric analysis and differential scanning calorimetry. The uniform interaction of the GO and ZnO with polymers induced the remarkable thermal properties of the synthesized membranes. Permeate flux and contact angle measurements were considered to estimate their water content (96%) capacity and NOM rejection (96%) using 0.1 ppm humic acid solution. The permeate flux, NOM rejection and the water content changed directly with GO and inversely with ZnO wt% in the membranes up to GO5 (GO:0.14: ZnO:0.03) whereas the contact angle exhibited the inverse relationship with GO and ZnO concentration in casting solution of the synthesized membranes. Hence it can be concluded that prepared RO membranes are suitable for NOM rejection and recommended for water treatment.

Fouling in reverse osmosis membranes: monitoring, characterization, mitigation strategies and future directions.

Water scarcity has been a global challenge for many countries over the past decades, and as a result, reverse osmosis (RO) has emerged as a promising and cost-effective tool for water desalination and wastewater remediation. Currently, RO accounts for >65% of the worldwide desalination capacity; however, membrane fouling is a major issue in RO processes. Fouling reduces the membrane's lifespan and permeability, while also increases the operating pressure and chemical cleaning frequency. Overall, fouling reduces the quality and quantity of desalinated water, and thus hinders the sustainable application of RO membranes by disturbing its efficacy and economic aspects. Fouling arises from various physicochemical interactions between water pollutants and membrane materials leading to foulants' accumulation onto the membrane surfaces and/or inside the membrane pores. The current review illustrates the main types of particulates, organic, inorganic and biological foulants, along with the major factors affecting its formation and development. Moreover, the currently used monitoring methods, characterization techniques and the potential mitigation strategies of membrane fouling are reviewed. Further, the still-faced challenges and the future research on RO membrane fouling are addressed.

A pilot application of recycled discarded RO membranes for low strength gray water reclamation.

Reuse of recycled RO membranes after oxidative treatment as ultrafiltration membranes promise to bring membrane filtration at par with conventional treatment processes in terms of cost-effectiveness. Although the treatment process in which discarded RO membranes are converted into ultrafiltration membranes is well documented, limited pilot data are available for their application in different filtration applications. This research gap is felt because most commercially available RO membranes are spiral, wound while the ultrafiltration membranes commonly used for water filtration applications are hollow fiber. Pilot-scale data will help to develop performance guidelines and predict fouling characteristics of different types of feed waters. In the current paper, converted RO membranes are subjected to filtration with domestic gray water as the feed source. The results show that the converted membranes performed at par with conventional filtration while also providing a consistent filtrate turbidity of < 1 NTU. The reduction in cost and physical footprints and recycling of membranes that would otherwise have ended up in landfills are added advantages that makes this an attractive proposition for gray water filtration applications.

Characterization of Selected Polymeric Membranes Used in the Separation and Recovery of Palladium-Based Catalyst Systems.

Membrane separation processes tender a capable option for energy-demanding separation processes. Nanofiltration (NF) and reverse osmosis (RO) membranes are among the most explored, with a latent use in the chemical industry. In this study, four commercial membranes (NF90, NF270, BW30, and XLE) were investigated for their applicability based on the key structural performance characteristics in the recycling of Pd-based catalysts from Heck coupling post-reaction mixture. Pure water and organic solvent permeabilities, uncharged solute permeability, swelling, and catalyst rejection studies of the membranes were conducted as well as the morphological characterization using Fourier transform infrared, field emission gun scanning electron microscopy, and atomic force microscopy. Characterization results showed trends consistent with the manufactures' specifications. Pure water and organic solvent fluxes generally followed the trend NF270 > NF90 > BW30 > XLE, with the solvent choice playing a major role in the separation process. Pd(PPh3)2Cl2 was well rejected by almost all membranes in 2-propanol; however, XLE rejects Pd(OAc)2 better at high pressure in acetonitrile. Our study, therefore, revealed that the separation and reuse of the two catalysts by NF90 at 10 bar resulted in 97% and 49% product yields with 52% and 10% catalyst retention for Pd(OAc)2 while Pd(PPh3)2Cl2. gave 87% and 6% yields with 58% and 36% catalyst retention in the first and second cycles, respectively. Considering, the influence of membrane-solute interactions in Pd-catalyst rejection, a careful selection of the polymeric membrane and solvent, a satisfactory separation, and recovery can be achieved.

Morphology of Thin Film Composite Membranes Explored by Small-Angle Neutron Scattering and Positron-Annihilation Lifetime Spectroscopy.

The morphology of thin film composite (TFC) membranes used in reverse osmosis (RO) and nanofiltration (NF) water treatment was explored with small-angle neutron scattering (SANS) and positron-annihilation lifetime spectroscopy (PALS). The combination of both methods allowed the characterization of the bulk porous structure from a few Å to µm in radius. PALS shows pores of 4.5 Å average radius in a surface layer of about 4 m thickness, which become 40% smaller at the free surface of the membranes. This observation may correlate with the glass state of the involved polymer. Pores of similar size appear in SANS as closely packed pores of 6 Å radius distributed with an average distance of 30 Å. The main effort of SANS was the characterization of the morphology of the porous polysulfone support layer as well as the fibers of the nonwoven fabric layer. Contrast variation using the media H2O/D2O and supercritical CO2 and CD4 identified the polymers of the support layers as well as internal heterogeneities.

Anti-Biofouling and Desalination Properties of Thin Film Composite Reverse Osmosis Membranes Modified with Copper and Iron Nanoparticles.

The anti-biofouling and desalination properties of thin film composite reverse osmosis membranes (TFC-RO), modified by the incorporation of copper and iron nanoparticles, were compared. Nanoparticles of metallic copper (CuNPs) and an iron crystalline phase mix (Fe and Fe2O3, FeNPs) were obtained by oxide-reduction-precipitation and reduction reactions, respectively, and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. Modified membranes (PA+0.25Cu-PSL and PA+0.25Fe-PSL) were obtained by incorporating these nanoparticles during the interfacial polymerization process (PI). These membranes were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and contact angle measurements. Bactericidal tests by a Colony Forming Unit (CFU) were performed using Escherichia coli, and anti-adhesion properties were confirmed by fluorescence microscopy estimating the percentage of live/dead cells. The permeate flow and rejection of salts was evaluated using a crossflow cell. An increase of the membrane's roughness on the modified membrane was observed, influencing the desalination performance more strongly in the presence of the FeNPs with respect to the CuNPs. Moreover, a significant bactericidal and anti-adhesion effect was obtained in presence of both modifications with respect to the pristine membrane. An important decrease in CFU in the presence of modified membranes of around 98% in both modifications was observed. However, the anti-adhesion percentage and reduction of live/dead cells were higher in the presence of the copper-modified membrane in comparison to the iron-modified membrane. These facts were attributed to the differences in antimicrobial action mechanism of these types of nanoparticles. In conclusion, TFC-RO membranes modified by the incorporation of CuNPs during PI represent one alternative material to attend to the biofouling impact in the desalination process.

N-nitrosamine rejection by reverse osmosis membranes: a full-scale study.

This study aims to provide longitudinal and spatial insights to the rejection of N-nitrosamines by reverse osmosis (RO) membranes during sampling campaigns at three full-scale water recycling plants. Samples were collected at all individual filtration stages as well as at a cool and a warm weather period to elucidate the impact of recovery and feed temperature on the rejection of N-nitrosamines. N-nitrosodimethylamine (NDMA) was detected in all RO feed samples varying between 7 and 32 ng/L. Concentrations of most other N-nitrosamines in the feed solutions were determined to be lower than their detection limits (3-5 ng/L) but higher concentrations were detected in the feed after each filtration stage. As a notable exception, in one plant, N-nitrosomorpholine (NMOR) was observed at high concentrations in RO feed (177-475 ng/L) and permeate (34-76 ng/L). Overall rejection of NDMA among the three RO systems varied widely from 4 to 47%. Data presented here suggest that the feed temperature can influence rejection of NDMA. A considerable variation in NDMA rejection across the three RO stages (14-78%) was also observed. Overall NMOR rejections were consistently high ranging from 81 to 84%. On the other hand, overall rejection of N-nitrosodiethylamine (NDEA) varied from negligible to 53%, which was considerably lower than values reported in previous laboratory-scale studies. A comparison between results reported here and the literature indicates that there can be some discrepancy in N-nitrosamine rejection data between laboratory- and full-scale studies probably due to differences in water recoveries and operating conditions (e.g. temperature, membrane fouling, and hydraulic conditions).