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Enzyme-mediated systems have been widely employed for the biotransformation of environmental contaminants. However, the catalytic performance of free enzymes is restricted by the rapid loss of their catalytic activity, stability, and reusability. In this work, we developed an enzyme immobilization platform by elaborately anchoring fungal laccase onto arginine-functionalized boron nitride nanosheets (BNNS-Arg@Lac). BNNS-Arg@Lac showcased â¼75% immobilization yield and enhanced stability against fluctuating pH values and temperatures, along with remarkable reusability across six consecutive cycles, outperforming free natural laccase (nlaccase). A model pollutant, atrazine, was selected for a proof-of-concept demonstration, given the substantial environmental and public health concerns in agriculture runoff. BNNS-Arg@Lac-catalyzed atrazine degradation rate was nearly twice that of nlaccase. Moreover, BNNS-Arg@Lac consistently demonstrated superior atrazine degradation in synthetic agricultural wastewater and various mediator systems compared to nlaccase. Comprehensive product analysis unraveled distinct degradation pathways for BNNS-Arg@Lac and nlaccase. Overall, this research provides a foundation for the future development of enzyme-nanomaterial hybrids for degrading environmental chemicals and may unlock new potential for green and efficient resource recovery and waste management strategies.
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Pervaporation (PV) is an effective membrane separation process for organic dehydration, recovery, and upgrading. However, it is crucial to improve membrane materials beyond the current permeability-selectivity trade-off. In this research, we introduce machine learning (ML) models to identify high-potential polymers, greatly improving the efficiency and reducing cost compared to conventional trial-and-error approach. We utilized the largest PV data set to date and incorporated polymer fingerprints and features, including membrane structure, operating conditions, and solute properties. Dimensionality reduction, missing data treatment, seed randomness, and data leakage management were employed to ensure model robustness. The optimized LightGBM models achieved RMSE of 0.447 and 0.360 for separation factor and total flux, respectively (logarithmic scale). Screening approximately 1 million hypothetical polymers with ML models resulted in identifying polymers with a predicted permeation separation index >30 and synthetic accessibility score <3.7 for acetic acid extraction. This study demonstrates the promise of ML to accelerate tailored membrane designs.
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Aprendizaje Automático , Polímeros , Polímeros/química , Membranas Artificiales , PermeabilidadRESUMEN
This study set out to uncover which interfacial properties have the greatest impact on membrane organic fouling, biofouling, and fouling resistance. A relatively simple manipulation of the basic equations used in determining Lifshitz-van der Waals (LW) and Lewis acid-base (AB) surface tensions for solid materials reveals that the high electron accepticity of water makes the electron donicity of membrane and biofouling materials the key component governing their interfacial free energy of adhesion (ΔG132), which defines the favorability (or unfavorability) of one material (1) adhering to another (2) when immersed in a liquid (3). Various biofoulant and membrane LW and AB surface tensions were systematically characterized. Static bacterial adhesion, alginic acid filtration, and wastewater filtration tests were conducted to determine the fouling propensities of three different polymeric membrane materials. Experimental results of microbial adhesion, alginate fouling, and biofouling tests all correlated well with membrane electron density, where higher electron density produced less organic fouling or biofouling. These combined theoretical and experimental results confirm the importance of surface electron donicity in determining the fouling propensity of polymeric membranes.
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Water reuse is rapidly becoming an integral feature of resilient water systems, where municipal wastewater undergoes advanced treatment, typically involving a sequence of ultrafiltration (UF), reverse osmosis (RO), and an advanced oxidation process (AOP). When RO is used, a concentrated waste stream is produced that is elevated in not only total dissolved solids but also metals, nutrients, and micropollutants that have passed through conventional wastewater treatment. Management of this RO concentrateâdubbed municipal wastewater reuse concentrate (MWRC)âwill be critical to address, especially as water reuse practices become more widespread. Building on existing brine management practices, this review explores MWRC management options by identifying infrastructural needs and opportunities for multi-beneficial disposal. To safeguard environmental systems from the potential hazards of MWRC, disposal, monitoring, and regulatory techniques are discussed to promote the safety and affordability of implementing MWRC management. Furthermore, opportunities for resource recovery and valorization are differentiated, while economic techniques to revamp cost-benefit analysis for MWRC management are examined. The goal of this critical review is to create a common foundation for researchers, practitioners, and regulators by providing an interdisciplinary set of tools and frameworks to address the impending challenges and emerging opportunities of MWRC management.
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Ultrafiltración , Aguas Residuales , Epiclorhidrina , Nutrientes , AguaRESUMEN
Recovery of carbon-based resources from waste is a critical need for achieving carbon neutrality and reducing fossil carbon extraction. We demonstrate a new approach for extracting volatile fatty acids (VFAs) using a multifunctional direct heated and pH swing membrane contactor. The membrane is a multilayer laminate composed of a carbon fiber (CF) bound to a hydrophobic membrane and sealed with a layer of polydimethylsiloxane (PDMS); this CF is used as a resistive heater to provide a thermal driving force for PDMS that, while a highly hydrophobic material, is known for its ability to rapidly pass gases, including water vapor. The transport mechanism for gas transport involves the diffusion of molecules through the free volume of the polymer matrix. CF coated with polyaniline (PANI) is used as an anode to induce an acidic pH swing at the interface between the membrane and water, which can protonate the VFA molecule. The innovative multilayer membrane used in this study has successfully demonstrated a highly efficient recovery of VFAs by simultaneously combining pH swing and joule heating. This novel technique has revealed a new concept in the field of VFA recovery, offering promising prospects for further advancements in this area. The energy consumption was 3.37 kWh/kg for acetic acid (AA), and an excellent separation factor of AA/water of 51.55 ± 2.11 was obtained with high AA fluxes of 51.00 ± 0.82 g.m-2hr-1. The interfacial electrochemical reactions enable the extraction of VFAs without the need for bulk temperature and pH modification.
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Ácido Acético , Ácidos Grasos Volátiles , Ácidos Grasos Volátiles/química , Gases , Fenómenos Físicos , CarbonoRESUMEN
Ammonia is considered a contaminant to be removed from wastewater. However, ammonia is a valuable commodity chemical used as the primary feedstock for fertilizer manufacturing. Here we describe a simple and low-cost ammonia gas stripping membrane capable of recovering ammonia from wastewater. The material is composed of an electrically conducting porous carbon cloth coupled to a porous hydrophobic polypropylene support, that together form an electrically conductive membrane (ECM). When a cathodic potential is applied to the ECM surface, hydroxide ions are produced at the water-ECM interface, which transforms ammonium ions into higher-volatility ammonia that is stripped across the hydrophobic membrane material using an acid-stripping solution. The simple structure, low cost, and easy fabrication process make the ECM an attractive material for ammonia recovery from dilute aqueous streams, such as wastewater. When paired with an anode and immersed into a reactor containing synthetic wastewater (with an acid-stripping solution providing the driving force for ammonia transport), the ECM achieved an ammonia flux of 141.3 ± 14.0 g.cm-2.day-1 at a current density of 6.25 mA.cm-2 (69.2 ± 5.3 kg(NH3-N)/kWh). It was found that the ammonia flux was sensitive to the current density and acid circulation rate.
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Amoníaco , Compuestos de Amonio , Amoníaco/análisis , Amoníaco/química , Aguas Residuales , Compuestos de Amonio/química , Electricidad , IonesRESUMEN
Perfluorooctanesulfonic acid (PFOS) is a persistent organic substance that has been extensively applied in many industries and causes severe, widespread adverse health impacts on humans and the environment. The development of an effective PFOS treatment method with affordable operational costs has been expected. This study proposes the biological treatment of PFOS using microbial capsules enclosing a PFOS-reducing microbial consortium. The objective of this study was to evaluate the performance of the polymeric membrane encapsulation technique for the biological removal of PFOS. First, a PFOS-reducing bacterial consortium, composed of Paracoccus (72%), Hyphomicrobium (24%), and Micromonosporaceae (4%), was enriched from activated sludge by acclimation and subsequent subculturing with PFOS containing media. The bacterial consortium was first immobilized in alginate gel beads, then enclosed in membrane capsules by coating the gel beads with a 5% or 10% polysulfone (PSf) membrane. The introduction of microbial membrane capsules could increase PFOS reduction to between 52% and 74% compared with free cell suspension, which reduced by 14% over three weeks. Microbial capsules coated with 10% PSf membrane demonstrated the highest PFOS reduction at 80% and physical stability for six weeks. Candidate metabolites including perfluorobutanoic acid (PFBA) and 3,3,3- trifluoropropionic acid were detected by FTMS, suggesting the possible biological degradation of PFOS. In microbial membrane capsules, the initial adsorption of PFOS on the shell membrane layer enhanced subsequent biosorption and biological degradation by PFOS-reducing bacteria immobilized in the core alginate gel beads. The 10%-PSf microbial capsules exhibited a thicker membrane layer with the fabric structure of a polymer network, which maintained longer physical stability than 5%-PSf microbial capsules. This outcome suggests the potential application of microbial membrane capsules to PFOS-contaminated water treatment.
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Polímeros , Sulfonas , Humanos , Polímeros/química , Sulfonas/química , Bacterias , Alginatos/química , Cápsulas/químicaRESUMEN
Concentration polarization (CP) should limit the energy and cost reducing benefits of high permeability seawater reverse osmosis (SWRO) membranes operating at a water flux higher than normal one. Herein, we propose a multiscale optimization framework coupling membrane permeability, feed spacer design (sub-millimeter scale) and system design (meter scale) via computational fluid dynamics and system level modeling using advanced supercomputing in conjunction with machine learning. Simulation results suggest energy consumption could be reduced by 27.5% (to 1.66 kWh m-3) predominantly through the use of high permeability SWRO membranes (12.2%) and a two-stage design (14.5%). Without optimization, CP approaches 1.52 at the system inlet, whereas the optimized CP is limited to 1.20. This work elucidates the optimized permeability, module design, operating scheme and benefits of high permeability SWRO membranes in seawater desalination.
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Surface-heated membrane distillation (MD) enhances the energy efficiency of desalination by mitigating temperature polarization (TP). However, systematic investigations of larger scale, multistage, surface-heated MD system with high water recovery and heat recycling are limited. Here, we explore the design and performance of a multistage surface-heated vacuum MD (SHVMD) with heat recovery through a comprehensive finite difference model. In this process, the latent heat of condensation is recovered through an internal heat exchanger (HX) using the retentate from one stage as the condensing fluid for the next stage and an external HX using the feed as the condensing fluid. Model results show that surface heating enhances the performance compared to conventional vacuum MD (VMD). Specifically, in a six-stage SHVMD process, 54.44% water recovery and a gained output ratio (GOR) of 3.28 are achieved with a surface heat density of 2000 W m-2, whereas a similar six-stage VMD process only reaches 18.19% water recovery and a GOR of 2.15. Mass and energy balances suggest that by mitigating TP, surface heating increases the latent heat trapped in vapor. The internal and external HXs capture and reuse the additional heat, which enhances the GOR values. We show for SHVMD that the hybrid internal/external heat recovery design can have GOR value 1.44 times higher than that of systems with only internal or external heat recovery. Furthermore, by only increasing six stages to eight stages, a GOR value as high as 4.35 is achieved. The results further show that surface heating can reduce the energy consumption of MD for brine concentration. The multistage SHVMD technology exhibits a promising potential for the management of brine from industrial plants.
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Purificación del Agua , Agua , Calor , Vacio , Destilación/métodos , Membranas Artificiales , Purificación del Agua/métodosRESUMEN
The influence of growth medium water chemistry, specifically carbon/nitrogen (C/N) molar ratios, on the characteristics and development of biofilms of the model microorganism Pseudomonas aeruginosa was investigated. C/N = 9 had a unique effect on biofilm composition as well as quorum sensing (QS) pathways, with higher concentrations of carbohydrates and proteins in the biofilm and a significant upregulation of the QS gene lasI in planktonic cells. The effect of C/N ratio on total attached biomass was negligible. Principal component analysis revealed a different behavior of most outputs such as carbohydrates and QS chemicals at C/N = 9, and pointed to correlations between parameters of biofilm formation and steady state distribution of cells and extracellular components. C/N ratio was also shown to influence organic compound utilization by both planktonic and sessile organisms, with a maximum chemical oxygen demand (COD) removal of 83% achieved by biofilms at C/N = 21. Planktonic cells achieved higher COD removal rates, but greater overall rates after six days occurred in biofilms. The development of a dual-species biofilm of P. aeruginosa and Nitrobacter winogradskyi was also influenced by C/N, with increase in the relative abundance of the slower-growing N. winogradskyi above C/N = 9. These results indicate that altering operational parameters related to C/N would be relevant for mitigating or promoting biofilm formation and function depending on the desired industrial application or treatment configuration.
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Carbono , Nitrógeno , Carbono/metabolismo , Nitrógeno/farmacología , Biopelículas , Percepción de Quorum , Carbohidratos , Pseudomonas aeruginosaRESUMEN
Specific-ion selectivity is a highly desirable feature for the next generation of membranes. However, existing membranes rely on differences in charge, size and hydration energy, which limits their ability to target individual ion species. Here we demonstrate a nanocomposite ion-exchange membrane material that enables a reverse-selective transport mechanism that can selectively pass a single ion species. We demonstrate this transport mechanism with phosphate ions selectively transporting across negatively charged cation exchange membranes. Selective transport is enabled by the in situ growth of hydrous manganese oxide nanoparticles throughout a cation exchange membrane that provide a diffusion pathway via phosphate-specific, reversible outer-sphere interactions. On incorporating the hydrous manganese oxide nanoparticles, the membrane's phosphate flux increased by a factor of 27 over an unmodified cation exchange membrane, and the selectivity of phosphorous over sulfate, nitrate and chloride reaches 47, 100 and 20, respectively. By pairing ion-specific outer-sphere interactions between the target ions and appropriate nanoparticles, these nanocomposite ion-exchange materials can, in principle, achieve selective transport for a range of ions.
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Óxidos , Fosfatos , Intercambio Iónico , CationesRESUMEN
Membrane distillation (MD) is an emerging thermal desalination technology capable of desalinating waters of any salinity. During typical MD processes, the saline feedwater is heated and acts as the thermal energy carrier; however, temperature polarization (as well as thermal energy loss) contributes to low distillate fluxes, low single-pass water recovery and poor thermal efficiency. An alternative approach is to integrate an extra thermal energy carrier as part of the membrane and/or module assembly, which can channel externally provided heat directly to the membrane-feedwater interface and/or along the feed channel length. This direct-heat delivery has been demonstrated to increase single-pass water recovery and enhance the overall thermal efficiency. We developed a bench-scale direct-heated vacuum MD (DHVMD) process to desalinate pre-treated oil and gas "produced water" with an initial total dissolved solids of 115,500 ppm at a feed temperature ranging between 24 and 32 °C. We evaluated both water flux and specific energy consumption (SEC) as a function of water recovery. The system achieved a 50% water recovery without significant scaling, with an average flux >6 kg m-2 hr-1 and a SEC as low as 2,530 kJ kg-1. The major species of mineral scales (i.e., NaCl, CaSO4, and SrSO4) that limited the water recovery to 68% were modeled in terms of thermodynamics and identified by scanning electron microscopy and energy-dispersive X-ray spectroscopy. In addition, we further developed and employed a physics-based process model to estimate temperature, salinity, water transport and energy flows for full-scale vacuum MD and DHVMD modules. Model results show that a direct-heat input rate of 3,600 W can increase single-pass water recovery from 2.1% to 3.1% while lowering the thermal SEC from 7,800 kJ kg-1 to 6,517 kJ kg-1 in an unoptimized module. Finally, the scaling up potential of DHVMD process is briefly discussed.
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Destilación , Purificación del Agua , Destilación/métodos , Calor , Membranas Artificiales , Vacio , AguaRESUMEN
Microplastics are continuously released into the terrestrial environment from sources where they are used and produced. These microplastics accumulate in soils, sediments, and freshwater bodies, and some are conveyed via wind and water to the oceans. The concentration gradient between terrestrial inland and coastal regions, the factors that influence the concentration, and the fundamental transport processes that could dynamically affect the distribution of microplastics are unclear. We analyzed microplastic concentration reported in 196 studies from 49 countries or territories from all continents and found that microplastic concentrations in soils or sediments and surface water could vary by up to eight orders of magnitude. Mean microplastic concentrations in inland locations such as glacier (191 n L-1) and urban stormwater (55 n L-1) were up to two orders of magnitude greater than the concentrations in rivers (0.63 n L-1) that convey microplastics from inland locations to water bodies in terrestrial boundary such as estuaries (0.15 n L-1). However, only 20% of studies reported microplastics below 20 µm, indicating the concentration in these systems can change with the improvement of microplastic detection technology. Analysis of data from laboratory studies reveals that biodegradation can also reduce the concentration and size of deposited microplastics in the terrestrial environment. Fiber percentage was higher in the sediments in the coastal areas than the sediments in inland water bodies, indicating fibers are preferentially transported to the terrestrial boundary. Finally, we provide theoretical frameworks to predict microplastics transport and identify potential hotspots where microplastics may accumulate.
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Microplásticos , Contaminantes Químicos del Agua , Monitoreo del Ambiente , Agua Dulce , Océanos y Mares , Plásticos , Suelo , Contaminantes Químicos del Agua/análisisRESUMEN
The growth of mineral crystals on surfaces is a challenge across multiple industrial processes. Membrane-based desalination processes, in particular, are plagued by crystal growth (known as scaling), which restricts the flow of water through the membrane, can cause membrane wetting in membrane distillation, and can lead to the physical destruction of the membrane material. Scaling occurs when supersaturated conditions develop along the membrane surface due to the passage of water through the membrane, a process known as concentration polarization. To reduce scaling, concentration polarization is minimized by encouraging turbulent conditions and by reducing the amount of water recovered from the saline feed. In addition, antiscaling chemicals can be used to reduce the availability of cations. Here, we report on an energy-efficient electrophoretic mixing method capable of nearly eliminating CaSO4 and silicate scaling on electrically conducting membrane distillation (ECMD) membranes. The ECMD membrane material is composed of a percolating layer of carbon nanotubes deposited on porous polypropylene support and cross-linked by poly(vinyl alcohol). The application of low alternating potentials (2 Vpp,1Hz) had a dramatic impact on scale formation, with the impact highly dependent on the frequency of the applied signal, and in the case of silicate, on the pH of the solution.
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Nanotubos de Carbono , Purificación del Agua , Destilación , Membranas Artificiales , MineralesRESUMEN
Graphene oxide (GO) membranes have great potential for separation applications due to their low-friction water permeation combined with unique molecular sieving ability. However, the practical use of deposited GO membranes is limited by the inferior mechanical robustness of the membrane composite structure derived from conventional deposition methods. Here, we report a nanostructured GO membrane that possesses great permeability and mechanical robustness. This composite membrane consists of an ultrathin selective GO nanofilm (as low as 32 nm thick) and a postsynthesized macroporous support layer that exhibits excellent stability in water and under practical permeability testing. By utilizing thin-film lift off (T-FLO) to fabricate membranes with precise optimizations in both selective and support layers, unprecedented water permeability (47 L·m-2·hr-1·bar-1) and high retention (>98% of solutes with hydrated radii larger than 4.9 Å) were obtained.
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Conjugated polyaniline has shown anticorrosive, hydrophilic, antibacterial, pH-responsive, and pseudocapacitive properties making it of interest in many fields. However, in situ grafting of polyaniline without harsh chemical treatments is challenging. In this study, we report a simple, fast, and non-destructive surface modification method for grafting tetraaniline (TANI), the smallest conjugated repeat unit of polyaniline, onto several materials via perfluorophenylazide photochemistry. The new materials are characterized by nuclear magnetic resonance (NMR) and electrospray ionization (ESI) mass spectroscopy. TANI is shown to be covalently bonded to important carbon materials including graphite, carbon nanotubes (CNTs), and reduced graphene oxide (rGO), as confirmed by transmission electron microscopy (TEM). Furthermore, large area modifications on polyethylene terephthalate (PET) films through dip-coating or spray-coating demonstrate the potential applicability in biomedical applications where high transparency, patternability, and low bio-adhesion are needed. Another important application is preventing biofouling in membranes for water purification. Here we report the first oligoaniline grafted water filtration membranes by modifying commercially available polyethersulfone (PES) ultrafiltration (UF) membranes. The modified membranes are hydrophilic as demonstrated by captive bubble experiments and exhibit extraordinarily low bovine serum albumin (BSA) and Escherichia coli adhesions. Superior membrane performance in terms of flux, BSA rejection and flux recovery after biofouling are demonstrated using a cross-flow system and dead-end cells, showing excellent fouling resistance produced by the in situ modification.
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Azide-functionalized graphene oxide (AGO) was covalently anchored onto commercial reverse osmosis (RO) membrane surfaces via azide photochemistry. Surface modification was carried out by coating the RO membrane with an aqueous dispersion of AGO followed by UV exposure under ambient conditions. This simple process produces a hydrophilic, smooth, antibacterial membrane with limited reduction in water permeability or salt selectivity. The GO-RO membrane exhibited a 17-fold reduction in biofouling after 24 h of Escherichia coli contact and almost 2 times reduced BSA fouling after a 1 week cross-flow test compared to its unmodified counterpart.
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Incrustaciones Biológicas/prevención & control , Grafito/química , Membranas Artificiales , Óxidos/química , Antibacterianos/química , Antibacterianos/farmacología , Ósmosis , Óxidos/farmacología , FotoquímicaRESUMEN
Application of forward osmosis (FO) membrane to microalgae cultivation processes enables concentration of microalgae and nutrients with low energy consumption. To understand fouling characteristics of FO membrane in concentration of microalgae culture, we studied flux decline, flux recovery by cleaning, and foulants characteristics, in different membrane orientation of active-layer-facing-feed-solution (AL-FS) and active-layer-facing-draw-solution (AL-DS) modes. Batch concentration of Chlorella vulgaris was conducted with a cellulose-triacetate FO membrane. Rapid flux decline and lower flux recovery was observed in AL-DS mode because of inner-membrane fouling including internal pore clogging, adsorption and internal concentration polarization in the support layer. A proportion of polysaccharides in extracellular polymeric substances to soluble microbial products were larger in chemical cleaning effluent than physical one in AL-DS mode, although those were not significantly different in AL-FS mode. Excitation-emission matrix analysis revealed that proteins and humic-like substances were also possible irreversible foulants both in AL-DS and AL-FS modes.
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Técnicas de Cultivo Celular por Lotes/instrumentación , Chlorella vulgaris/crecimiento & desarrollo , Membranas Artificiales , Microalgas/crecimiento & desarrollo , Adsorción , Acuicultura/instrumentación , Acuicultura/métodos , Técnicas de Cultivo Celular por Lotes/métodos , Celulosa/análogos & derivados , Ósmosis , Polisacáridos/química , SolucionesRESUMEN
We present a method to produce anti-fouling reverse osmosis (RO) membranes that maintains the process and scalability of current RO membrane manufacturing. Utilizing perfluorophenyl azide (PFPA) photochemistry, commercial reverse osmosis membranes were dipped into an aqueous solution containing PFPA-terminated poly(ethyleneglycol) species and then exposed to ultraviolet light under ambient conditions, a process that can easily be adapted to a roll-to-roll process. Successful covalent modification of commercial reverse osmosis membranes was confirmed with attenuated total reflectance infrared spectroscopy and contact angle measurements. By employing X-ray photoelectron spectroscopy, it was determined that PFPAs undergo UV-generated nitrene addition and bind to the membrane through an aziridine linkage. After modification with the PFPA-PEG derivatives, the reverse osmosis membranes exhibit high fouling-resistance.