Charge Exclusion Research Articles

Ion-Selective Transport Promotion Enabled by Angstrom-Scale Nanochannels in Dendrimer-Assembled Polyamide Nanofilm for Efficient Electrodialysis.

The ion permeability and selectivity of membranes are crucial in nanofluidic behavior, impacting industries ranging from traditional to advanced manufacturing. Herein, we demonstrate the engineering of ion-conductive membranes featuring angstrom-scale ion-transport channels by introducing ionic polyamidoamine (PAMAM) dendrimers for ion separation. The exterior quaternary ammonium-rich structure contributes to significant electrostatic charge exclusion due to enhanced local charge density; the interior protoplasmic channels of PAMAM dendrimer are assembled to provide additional degrees of free volume. This facilitates the monovalent ion transfer while maintaining continuity and efficient ion screening. The dendrimer-assembled hybrid membrane achieves high monovalent ion permeance of 2.81 mol m-2 h-1 (K+), reaching excellent mono/multivalent selectivity up to 20.1 (K+/Mg2+) and surpassing the permselectivities of state-of-the-art membranes. Both experimental results and simulating calculations suggest that the impressive ion selectivity arises from the significant disparity in transport energy barrier between mono/multivalent ions, induced by the "exterior-interior" synergistic effects of bifunctional membrane channels.

Chromium (III) and chromium (VI) removal and organic matter interaction with nanofiltration

Chromium (Cr) is a toxic inorganic contaminant for drinking water, in which the concentration has to be controlled for human health and safety. Cr retention was investigated with stirred cell experiments using sulphonated polyethersulfone nanofiltration (NF) membranes of different molecular weight cut-off (MWCO). Cr(III) and Cr(VI) retention follow the order of the MWCO of the studied NF membranes; HY70–720 Da > HY50–1000 Da > HY10–3000 Da with a pH dependency, especially for Cr(III). The importance of the charge exclusion was highlighted when Cr(OH)4− (for Cr(III)) and CrO42− (for Cr(VI)) was the predominant species in the feed solution.In presence of organic matter, namely humic acid (HA), Cr(III) retention increased by 60 %, while no influence of HA was observed for Cr(VI). HA did not induce major modifications on the membrane surface charge for these membranes. Solute-solute interaction, in particular Cr(III)-HA complexation, was the responsible mechanism for the increase in Cr(III) retention. This was confirmed by asymmetric flow field-flow fractionation, coupled with inductively coupled plasma mass spectrometry (FFFF-ICP-MS) analysis. Cr(III)-HA complexation was significant at HA concentrations as low as 1 mgC/L. The chosen NF membranes were able to achieve the EU guideline (25 μg/L) for Cr in drinking water for a feed concentration of 250 μg/L.

A Comparative Study of PMETAC-Modified Mesoporous Silica and Titania Thin Films for Molecular Transport Manipulation.

The manipulation and understanding of molecular transport across functionalized nanopores will take us closer to mimicking biological membranes and thus to design high-performance permselective separation systems. In this work, Surface-initiated atom transfer radical polymerization (SI-ATRP) of (2-methacryloyloxy)-ethyltrimethylammonium chloride (METAC) was performed on both mesoporous silica and mesoporous titania thin films. Pores were proven to be filled using ellipsometry and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Furthermore, the employed method leads to a polymer overlayer, whose thickness could be discriminated using a double-layer ellipsometry model. Cyclic voltammetry experiments reveal that the transport of electrochemically active probes is affected by the PMETAC presence, both due to the polymer overlayer and the confined charge of the pore-tethered PMETAC. A more detailed study demonstrates that ion permeability depends on the combined role of the inorganic scaffolds' (titania and silica) surface chemistry and the steric and charge exclusion properties of the polyelectrolyte. Interestingly, highly charged negative walls with positively charged polymers may resemble zwitterionic polymer behavior in confined environments.

Experimental measurement of the exclusion-diffusion potential in sandstone and shaly sand samples at full and partial water saturation

The exclusion-diffusion potential (EDP) arises in response to concentration gradients and is one of the key components of the self-potential (SP) observed in subsurface environments. However, few data are available to characterize the EDP in reservoir rocks saturated with complex natural brines and at partial brine saturation. We report experimental measurements of the EDP across fully and partially brine-saturated sandstone samples and fully brine-saturated shaly sand samples, using natural saline brine (2.2 Mol/L), seawater (0.5 Mol/L), and natural crude oil. When fully saturated, the EDP across the samples is diffusion-dominated, with the shaly samples exhibiting a small contribution from charge exclusion. The contribution of charge exclusion to the measured EDP increases as permeability decreases. At the residual oil saturation, the measured EDP is diffusion-dominated, consistent with our findings at full saturation. However, the EDP is more exclusive at the irreducible water saturation, and the polarity of the excluded ions depends on the polarity of the charged oil-brine interface. A charge exclusion is more significant at lower irreducible water saturation. Our results support recent studies suggesting that the oil-brine interface can be positively charged in contact with natural brines. The EDP trends reported have not been observed previously and have broad implications for geophysical monitoring of subsurface flow and transport, such as transport of nonaqueous phase contaminants in aquifers and water flow during hydrocarbon production.

Anionic covalent organic framework engineered high-performance polyamide membrane for divalent anions removal

Porous framework materials hold great promise in tuning the chemical and physical structure of polyamide membranes for efficient nanofiltration. In this work, anionic covalent organic framework (aCOF) with abundant sulfonic acid groups was embedded into polyamide matrix via interfacial polymerization to modulate both membrane charge property and thickness for the removal of divalent ions. Benefiting from the high negative charged density, aCOF not only enhanced the membrane electronegativity from −25.6 mV to −71.5 mV but also slowed down the diffusion rate of piperazine by electrostatic interaction to decrease the membrane thickness from 93 nm to 18 nm. The enhanced electronegativity can intensify the charge exclusion to divalent anions (Na2SO4 rejection above 97%), while the ultrathin structure endows membrane with high water permeance of up to 39 L m−2 h−1 bar−1, about 2.4 times higher than that of pristine PA membrane. Our membranes provide a new path to rational design and controllable construction of high-performance nanofiltration membranes.

Immigration Law, Public Health, and the Future of Public Charge Policymaking

U.S. immigration law has excluded noncitizens likely to become a "public charge" since 1882. When the Trump administration proposed a new Rule expanding the interpretation of that exclusion in 2018, over 55,000 people wrote public comments. These comments, overwhelmingly opposed to the change, are the subject of Rachel Fabi and Lauren Zahn's insightful article in this issue of The Journal of Law, Medicine, and Ethics. The themes they identify resonate with the history of the public charge exclusion, which has always reflected a tension between two aims of American governance - to provide for those in need of assistance, and to shape the nation's citizenry according to ideals of self-sufficiency.

Enhanced removal of perfluorooctane sulfonic acid and perfluorooctanoic acid via polyelectrolyte functionalized ultrafiltration membrane: Effects of membrane modification and water matrix

This study investigated the mechanisms of removal of perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) using polyelectrolyte (PE) functionalized ultrafiltration (UF) membranes, performed through a fluidic method of layer-by-layer (LbL) deposition of polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA) multilayer coatings. The effects of source water composition (humic acids [HA] and cations [Ca2+ and Mg2+]) on PFOS and PFOA removal efficiency by the functionalized membrane were determined. PAH/PAA modification resulted in approximately 38 % and 9.2 % reduction in membrane molecular weight cut-off (MWCO) and porosity, respectively, leading to approximately 30 % increase in the removal of PFOS and PFOA primarily due to size exclusion. The presence of only HA led to 10–12 % higher removal of PFOS/A when compared to DI water; however, an increase in HA concentration did not further influence their removal efficiency. The coexistence of cations and HA resulted in significantly higher removal of PFOS and PFOA (up to 23 % higher for PFOS). Further enhancement of PFOS removal (14 % higher) was observed when cation concentrations were doubled, attributable to the interactions of PFOS/A with the source water components and the functionalized membrane, resulting in enhanced size and charge exclusion of macromolecular complexes including PFOS-cation-PFOS, PFOS-cation-HA, and PFOA-cation-HA.

Progress in Research and Application of Nanofiltration (NF) Technology for Brackish Water Treatment.

Brackish water is a potential fresh water resource with lower salt content than seawater. Desalination of brackish water is an important option to alleviate the prevalent water crisis around the world. As a membrane technology ranging between UF and RO, NF can achieve the partial desalination via size exclusion and charge exclusion. So, it has been widely concerned and applied in treatment of brackish water during the past several decades. Hereon, an overview of the progress in research on and application of NF technology for brackish water treatment is provided. On the basis of expounding the features of brackish water, the factors affecting NF efficiency, including the feed water characteristics, operating conditions and NF membrane properties, are analyzed. For the ubiquitous membrane fouling problem, three preventive fouling control strategies including feed water pretreatment, optimization of operating conditions and selection of anti-fouling membranes are summarized. In addition, membrane cleaning methods for restoring the fouled membrane are discussed. Furthermore, the combined utilization of NF with other membrane technologies is reviewed. Finally, future research prospects are proposed to deal with the current existing problems. Lessons gained from this review are expected to promote the sustainable development of brackish water treatment with NF technology.

Removal of arsenic(III) via nanofiltration: contribution of organic matter interactions

The removal of arsenic(III) (As(III)) with nanofiltration (NF) was investigated with emphasis on the role of salinity, pH and organic matter on retention mechanisms. While no measurable impact of salinity on As(III) retention with NF membranes (NF270 and NF90) was observed, a significant increase in As(III) retention occurred from pH 9 to pH 12. This was explained by As(III) deprotonation at pH > 9 that enhanced Donnan (charge) exclusion. Of the five different organic matter types investigated at 10 mgC/L, only humic acid (HA) increased As(III) retention by up to 10%. Increasing HA concentration to 100 mgC/L enhanced As(III) retention by 40%, which was attributed to As(III)-HA complexation. Complexation was confirmed by field-flow fractionation inductively coupled plasma mass spectrometry (FFF-ICP-MS) measurements, which showed that the bound As(III) increased with HA concentration. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that NF90, which exhibited lower permeability reduction than NF270, has accumulated a lower amount of As(III) in the presence of HA, where As(III)-HA complex was formed in the feed solution. This finding implies that As(III) retention with NF technology can be enhanced by complexation, instead of using other methods such as oxidation or pH adjustement.

Asymmetric layer‐by‐layer polyelectrolyte nanofiltration membranes with tunable retention

AbstractNanofiltration (NF) membrane processes are attractive to remove multivalent ions. As ion retention in NF membranes is determined by both size and charge exclusion, negatively charged membranes are required to reject negatively charged ions. Layer‐by‐layer assembly of alternating polycation (PC) and polyanion layers on top of a support is a versatile method to produce membranes. Especially the polyelectrolyte (PE) couple polydiallyldimethylammoniumchloride and poly(sodium‐4‐styrenesulfonate) (PDADMAC/PSS) is extensively investigated. This PE couple cannot form highly negatively charged membrane surfaces, due to interdiffusion and charge overcompensation of PDADMAC into the PSS layers, which limits the operational window to tailor membrane properties. We propose the use of asymmetric layer formation and show how combining two charge densities of one PC can produce negatively charged NF membranes. Starting from hollow fiber ultrafiltration supports coated with base layers of PDADMAC/PSS, they are coated with PDADMAC/PSS or poly(acrylamide‐co‐diallyldimethylammoniumchloride), P(AM‐co‐DADMAC)/PSS layers. P(AM‐co‐DADMAC) has a charge density of only 32% compared to 100% for PDADMAC. The particular novel membranes coated with P(AM‐co‐DADMAC) have a highly negatively charged surface and high permeabilities (7–19 L/[m2hbar]), with high retentions for Na2SO4 of up to 95%. These values position the developed membranes in the top range compared to commercial and other layer‐by‐layer membranes.

Removal of arsenic(V) by nanofiltration: Impact of water salinity, pH and organic matter

Climate change will affect water quality through a change in salinity, pH and organic matter (OM) content due to seawater intrusion, temperature change and subsurface biological processes. Therefore, a systematic evaluation of the impact of water quality variations is of particular importance to maintain the performance of a treatment process designed for drinking water. In this work, nanofiltration (NF) was investigated for the treatment of arsenic (As) contaminated water with the emphasis on water chemistry. Water salinity variations had no impact on the high rejection of As(V) with the studied NF membranes (NF270, NF90). The pH affects speciation and this significantly influenced the rejection of As(V) with NF270 (10–86%). The predominant mechanism was charge exclusion, while no effect was observed with NF90 (85–94%) where size exclusion plays the major role in rejection. The presence of humic acid (HA) in water has enhanced the rejection As(V) overall (10–20%) depending on water chemistry (pH, salinity) and membrane type. This study showed that NF technology was effective for As(V) rejection from water where seasonal changes in water quality can occur.

Fabrication of soft-etched nanoporous polyimide membranes for ionic conduction and discrimination

Ionic selectivity in nanopores is usually based either on steric or charge exclusion mechanisms. By simultaneously incorporating both mechanisms into a functionalized membrane, an improved control over selectivity can be achieved. We describe the fabrication and experimental characterization of alkali metal cation-selective nanopores in heavy ion-tracked polyimide (PI) membranes using the soft-etching (SE) technique. The latent ion tracks in the PI membrane are selectively dissolved by an organic solvent to form tiny pores without affecting the bulk material. The ionic transport properties of SE-PI membranes are characterized using different electrolyte solutions containing alkali metals, divalent metals, and organic cations under symmetric and asymmetric electrolyte conditions. Under symmetric conditions, the pores exhibit ohmic behavior when exposed to alkali metal chlorides and ammonium chloride solutions while divalent cations cannot pass through the pores as evidenced from the current-voltage curves. For the case of asymmetric electrolyte conditions, current rectification suggests pore blockage from the side of membrane exposed to divalent cations and tetraalkylammonium (TAA) cations. The experimental data show that the SE-PI membranes efficiently discriminate alkali cations from divalent metal cations and ammonium cation from TAA cations. The ionic conduction of the membranes is also sensitive to the mole fraction of Ca2+ in multi-ionic solutions. The ionic transport experiments further confirm that the nanopores allow significant alkali cation fluxes while rejecting divalent cations. Based on the good stability and high selectivity, the solvent treated PI membranes constitute remarkable candidates to be employed in applications concerning a wide range of electrolyte solutions.

Application of polyamide thin-film composite layered on polysulfone-GO/TiO2 mixed matrix membranes for removal of nitrotoluene derivatives from petrochemical wastewaters.

Release of harmful organic intermediates or byproducts during the manufacture of petrochemical compounds is a serious problem in petrochemical plants. In this work, polysulfone membranes blended with GO/TiO2 nanocomposite were synthesized by phase inversion method and coated with a polyamide layer formed by interfacial polymerization to prepare a thin-film composite (TFC) sample. Analysis and characterization of the sample were carried out by XRD, FE-SEM, BET, FTIR/ATR, AFM, TGA, and zeta potential. Results indicated that incorporation of GO/TiO2 into the membrane structure enhanced porosity, surface roughness, and macrovoid formation along the cross-section of the sublayer and permeability of the membrane. The TFC membranes were applied to remove mononitrotoluene (MNT) and dinitrotoluene (DNT) as the basic intermediates of toluene diisocyanate (TDI). The membranes demonstrated high efficiency (> 90%) for the removal of MNT and DNT according to the charge exclusion mechanism and Donnan effect. Application of the TFC membrane for treatment of wastewater in the TDI plant showed that the removal of pollutants is variable in the range of 45-65% and 53-69% for the membrane with the highest flux and highest rejection in different transmembrane pressure, respectively.

Charge exclusion as a strategy to control retention of small proteins in polyelectrolyte-modified ultrafiltration membranes

While retention in commercial ultrafiltration membranes is commonly governed by size exclusion, addition of charged polyelectrolytes to the membrane surface has been proposed as a facile and inexpensive method to modulate retention during filtration of charged compounds, such as proteins. This study demonstrates that selected combinations of common polyelectrolytes can be efficiently used to control the retention of proteins. We show how the retention of positively charged lysozyme increased from ~7% to ~50% when a negatively charged polyelectrolyte was deposited on a commercial polysulfone membrane, most probably due to a combination of associated pore narrowing effect and protein adsorption onto the membrane. By contrast, the retention decreased again (from ~50% to ~30%) upon further addition of a positively charged polyelectrolyte onto the membrane. The electrostatic repulsion between the positively charged surface and proteins prevented protein adsorption onto the membrane, while pore size was still large enough that size exclusion was limited. The retention decreased further to ~22% when increasing amounts of polyelectrolytes of the same charge as the protein were deposited on the membrane. In addition, variations in pH revealed that the negative effect of polyelectrolytes of the same charge as the protein on lysozyme retention was reversed when the charge density of lysozyme reached a certain level beyond which the positively charged electrolyte promoted dramatic increases of rejection. The results of this study suggest that use of polyelectrolyte-modified ultrafiltration membranes with a much larger pore size than the charged solute to be filtered could be a strategy to control retention of such solutes by minimizing the effect of size exclusion and fouling.

Permeation Properties of Ions through Inorganic Silica-Based Membranes.

The development of inorganic membranes has mainly found applicability in liquid separation technologies. However, only a few reports cite the permeation and separation of liquids through inorganic nanofiltration membranes compared with the more popular microfiltration membranes. Herein, we prepared silica membranes using 3,3,3-trifluoropropyltrimethoxysilane (TFPrTMOS) to investigate its liquid permeance performance using four different ion solutions (i.e., NaCl, Na2SO4, MgCl2, and MgSO4). The TFPrTMOS-derived membranes were deposited above a temperature of 175 °C, where the deposition behavior of TFPrTMOS was dependent on the organic functional groups decomposition temperature. The highest membrane rejection was from NaCl at 91.0% when deposited at 200 °C. For anions, the SO42− rejections were the greatest. It was also possible to separate monovalent and divalent anions, as the negatively charged groups on the membrane surfaces retained pore sizes >1.48 nm. Ions were also easily separated by molecular sieving below a pore size of 0.50 nm. For the TFPrTMOS-derived membrane deposited at 175 °C, glucose showed 67% rejection, which was higher than that achieved through the propyltrimethoxysilane membrane. We infer that charge exclusion might be due to the dissociation of hydroxyl groups resulting from decomposition of organic groups. Pore size and organic functional group decomposition were found to be important for ion permeation.

Model assessment of a nanofiltration membrane for the removal metal ions from simulated wastewater

This paper accords the likelihood of applying Donnan and Steric Partitioning Pore Model (DSPM) together with extended Nernst-Planck model to elucidate the capacity of charge and Donnan exclusion mechanisms in removing ions from simulated wastewater in Nano-Pro-3012 membrane filtration process. The extended Nernst-Planck model reports the transportation of cations across Nano-Pro-3012 with respect to electrical potential gradient, movement of solutes and pressure difference through the membrane. The working principle of these two equations is dependent on the adsorption of the charged surface, diffusion and convective transport. This principle was established with a software called Comsol multi-physic 4.3b to explain the capacity of charge and Donnan exclusion mechanism of Nano-Pro-3012. The extended Nernst-Planck model and the Darcy law model were applied to evaluate the physical interrelationship amidst NanoPro-3012 and ionic solutions with the aim of having a good understanding of the transport and rejection working operation of the ions. The principle of these equations was first used to envisage the capability of Nano-Pro-3012. The data obtained were validated with the laboratory data. There was an establishment that movement of solutes across the membrane bring about diffusion transport. The total flux in solution increases due to the working operation of the diffusion which in turns reduces the electrical potential, as a result, reduces the flux in the membrane. Ions smaller than pore sizes are rejected and the theoretical data is in conformity with the experimental data.

Influence of Chemical Cleaning on Physicochemical Characteristics and Ion Rejection by Thin Film Composite Nanofiltration Membranes.

The impact of membrane cleaning with NaOH and HCl on the characteristics and associated changes in ion rejection was investigated in this study. NaOH affected the zeta potential of membranes with a greater concentration of carboxylic groups so that it was negative across the entire pH range investigated. Exposure to NaOH led to swelling of the active layer after each cleaning, especially for poly(piperazineamide) membranes. A 23% increase in the effective pore radii for these membranes after NaOH cleaning for 18 h led to 25, 36, 53 and 62% decrease in the rejection of magnesium, calcium, sodium, and chloride ions, respectively. Sulfate rejection decreased only slightly even for poly(piperazineamide) membranes (i.e., 7%) despite an appreciable increase in pore radii, which can be explained by the impact of charge exclusion on ion rejection that was enhanced by the 16% reduction in zeta potential. On the other hand, cleaning with HCl had a negligible impact on the zeta potential and performance of all membranes evaluated in this study. The increase in permeability after chemical cleaning was in agreement with the decrease in rejection of inorganic ions and correlated well with the effective pore radii measured using the membrane potential technique. The importance of charge exclusion in the rejection of inorganic ions was highlighted by the observed differences in rejection and permeability values when testing membranes after NaOH cleaning.

Highly Selective Transport of Alkali Metal Ions by Nanochannels of Polyelectrolyte Threaded MIL-53 Metal Organic Framework.

Conventional ion-exchange polymeric membranes have limited selectivity due to their nonuniform and unstable structures. The rigid, regular, high porosity of metal organic framework (MOF) generally provides MOF membrane with exclusion/sieving effect but lack of electrostatic screening. Here we report for the first time a nonbiological highly selective MOF membrane with polyelectrolyte threaded in the nanochannel of metal organic framework (polyelectrolyte∼MOF) and its selective transport of alkali metal cations. Poly(sodium vinyl sulfonated-co-acrylic acid)∼MIL-53(Al) is prepared on anodic aluminum oxide substrate via steps of MOF MIL-53(Al) growth followed by in situ polymerization. The poly(VS-co-AA)∼MIL-53(Al) membrane demonstrates highly specific selectivity in transport of alkali metal cations. Rate of ion transport correlates inversely with the hydrated diameter of the ion reaching a low limiting rate near 0.7 nm hydrated diameter. Charge exclusion is demonstrated with blockage of anion transport under a concentration gradient. The highly uniform porous nanostructure of MOF and ionic function of polyelectrolyte offers the MOF membrane with synergistic selectivity based on exclusion forces of the framework and Coulomb forces from fixed charges of polyelectrolytes in nanochannels.

Performance of thin-film composite hollow fiber nanofiltration for the removal of dissolved Mn, Fe and NOM from domestic groundwater supplies

Groundwater (GW) is one of the most abundant water resources and around 1.5 billion people rely on GW as their main water supply. Manganese (Mn) and iron (Fe) are very common GW contaminants. Even though their presence is considered mainly as an organoleptic and operational nuisance, water with elevated Mn content may also lead to adverse health impacts. Amongst the most common treatment processes currently used to treat domestic GW supplies: catalytic filtration may lead to Mn leaching if improperly maintained; while ion exchange consumes a considerable amount of salt and produces a brine waste which pollutes the environment. Thus, it is proposed to design a simple, yet robust treatment system which can be implemented in small/remote communities or even domestic applications. To this end, the main objective of this investigation was to assess the potential application of novel outside-in sulfonated polyethersulfone thin-film composite hollow fiber nanofiltration (HFNF) membranes to remove dissolved Mn, Fe and natural organic matter (NOM) from domestic GW supplies. Of particular interest was the impact of GW matrix on performance of the HFNF membranes. Our experimental findings demonstrated that, in absence of hardness and the cumulative throughput of 1.9 L/m2, above 90% of Mn, Fe and NOM were retained by the examined HFNF membranes (MWCO ∼ 200 Da) regardless of their initial concentrations in the feed solution (250–1000 μ g/L). In contrast, increasing the hardness level reduced the removal of Mn and Fe ions. XPS analysis revealed that the surface properties of the HFNF membranes were altered when the membranes were exposed to calcium and magnesium salts. These observations were attributed to the propensity for Ca and Mg ions to bind to the sulfonic groups present on the surface of the HFNF membranes which, subsequently, weakens rejection by charge exclusion. On the other hand, in the absence of GW hardness, charge exclusion was mainly responsible for rejection of dissolved Mn and Fe. It was also found that GW hardness had no marked impact on the NOM rejection as the later was mostly removed by size exclusion.

Role of Ionic Charge Density in Donnan Exclusion of Monovalent Anions by Nanofiltration.

The main objective of this study is to examine how the charge densities of four monovalent anions-fluoride (F-), chloride (Cl-), bromide (Br-), and nitrate (NO3-)-influence their Donnan (charge) exclusion by a charged nanofiltration (NF) membrane. We systematically studied the rejection behavior of ternary ion solutions containing sodium cation (Na+) and two of the monovalent anions as a function of the pH with a polyamide NF membrane. In the solutions containing F- and Cl- or F- and Br-, F- rejection was higher than Cl- or Br- rejection only when the solution pH was higher than 5.5, suggesting that F- (which has a higher charge density) was repelled more strongly by the negatively charged membrane. The order of change in the activation energy for the transport of the four anions through the polyamide membrane as a response to the increase of the membrane negative charge was the following: F- > Cl- > NO3- > Br-. This order corroborates our main hypothesis that an anion with a smaller ionic radius, and hence a higher charge density, is more affected by the Donnan (charge)-exclusion mechanism in NF. We conclude with a proposed mechanism for the role of ionic charge density in the rejection of monovalent anions in NF.