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Award ID contains: 1822130

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  1. Per- and polyfluoroalkyl substances (PFAS) have garnered attention as a pressing environmental issue due to their enduring presence and suspected adverse health effects. This study assessed the rejection or removal ef- ficacy of PFAS by commercial reverse osmosis (RO) and nanofiltration (NF) membranes and examined the im- pacts of surfactants, ion valency and solution temperature that are inadequately explored. The results reveal that the presence of cationic surfactants such as cetyltrimethylammonium bromide (CTAB) increased the rejection of two selected PFAS compounds, perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA), by binding with negatively charged PFAS and preventing them from passing through membrane pores via size exclusion, whereas the presence of anionic surfactants such as sodium dodecyl sulfate (SDS) increased the PFAS rejection because the increased electrostatic repulsion prevented PFAS from approaching and adsorbing onto the mem- brane surface. Moreover, aqueous ions (e.g., Al³⁺ and PO³−) with higher ion valency enabled higher rejection of PFOA and PFBA through increased effective molecular size and increased electronegativity. Finally, only high solution temperature at 45 ◦C significantly reduced PFAS rejection efficiency because of the thermally expanded membrane pores and thus the increased leakage of PFAS. Overall, this research provides valuable insights into the various factors impacting PFAS rejection in commercial RO and NF processes. These findings are crucial for developing efficient PFAS removal methods and optimizing existing treatment systems, thereby contributing significantly to the ongoing efforts to combat PFAS contamination. 
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  2. The paper presents a new methodology for short-term (5–25 min) benchtop tests to evaluate the effectiveness of magnetic treatment of feed water for reducing mineral scaling on a reverse osmosis (RO) membrane. Scale deposition is measured at a controlled level of salt supersaturation in water flowing through an RO unit in once-through mode. A magnetic water conditioner is tested in a transient flow regime when variations of the permeate flux along the flow path are insignificant. Scale formation under these conditions is governed by salt crystallization on the membrane surface. The proposed method was implemented to investigate the influence of magnetic treatment on gypsum deposition on RO membranes in supersaturated aqueous CaSO4/NaCl solutions. The effects of magnetic water treatment on scale formation under our experimental conditions were found to be statistically insignificant with a confidence level of 95%. However, this outcome should not be considered to negate the potential efficiency of magnetic water treatment in specific applications. The proposed methodology of testing under a controlled level of salt supersaturation will also be useful for evaluating the efficiency of other water treatment technologies. 
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  3. Nghiem, Long (Ed.)
    Porous membranes having a particular wetting characteristic, hydrophobic or hydrophilic, are used for nondispersive membrane solvent extraction (MSX) where two immiscible phases flow on two sides of the membrane. The aqueous-organic phase interface across which solvent extraction/back extraction occurs remains immobilized on one surface of the membrane. This process requires the pressure of the phase not present in membrane pores to be either equal to or higher than that of the phase present in membrane pores; the excess phase pressure should not exceed a breakthrough pressure. In countercurrent MSX with significant flow pressure drop in each phase, this often poses a problem. To overcome this problem, flat porous Janus membranes were developed using either a base polypropylene (PP) or polyvinylidene fluoride (PVDF) or polyamide (Nylon) membrane, one side of which is hydrophobic and the other being hydrophilic. Such membranes were characterized using the contact angle, liquid entry pressure (LEP) and the droplet breakthrough pressure from each side of the membrane along with characterizations via scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR). Nondispersive solvent extractions were carried out successfully for two systems, octanol-phenol (solute)-water, toluene-acetone (solute)-water, with either flowing phase at a pressure higher than that of the other phase. The phenol extraction system had a high solute distribution coefficient whereas acetone prefers both phases almost identically. The potential practical utility of the MSX technique will be substantially enhanced via Janus MSX membranes. 
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  4. null (Ed.)
    Polymeric membranes for separation of pharmaceutical intermediates/products by organic solvent nanofiltration (OSN) have to be highly resistant to many organic solvents including high-boiling polar aprotic ones, e.g., N- methyl-2-pyrollidone (NMP), dimethylsulfoxide (DMSO), dimethylformamide (DMF). Unless cross-linked, few polymers resist swelling or dissolution in such solvents; however particular perfluoropolymers are resistant to almost all solvents except perfluorosolvents. One such polymer, designated AHP1, a glassy amorphous hydrophobic perfluorinated polymer, has been studied here. Additional perfluoropolymers studied here are hydrophilically modified (HMP2 and HMP3) versions to enhance the flux of polar aprotic solvents. OSN performances of three types of membranes including the hydrophilically modified ones were studied via solvent flux and solute rejection at pressures up to 5000 kPa. The solutes were four active pharmaceutical ingredients (APIs) or pharmaceutical intermediates having molecular weights (MWs) between 432 and 809 Da and three dyes, Oil Blue N (378 Da), Sudan Black B (456 Da), Brilliant Blue R (826 Da). Solvents used were: ethyl acetate, toluene, n- heptane, iso-octane, DMSO, tetrahydrofuran (THF), DMF, acetone, NMP, methanol. Test cells included stirred cells and tangential flow cells. Pure solvent fluxes through three membrane types were characterized using a particular parameter employing various solvent properties. All three membranes achieved high solute rejections around 91–98% at ambient temperatures. HMP2 membrane achieved 95% solute rejection for an API (809 Da) in DMSO at a high temperature, 75 ◦C. A two-stage simulated nanofiltration process achieved 99%+ rejection of a pharmaceutical intermediate (MW, 432 Da) in 75v% NMP-25v% ethyl acetate solution. 
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  5. null (Ed.)
    Sometimes NH₃ is stripped from process/effluent streams through hydrophobic porous hollow-fiber-membranes (HFMs) via a supported-gas-membrane (SGM) process and recovered in concentrated H₂SO₄ solution as (NH₄)₂SO₄. To recover relatively purified (NH₄)₂SO₄, one can avoid excess H₂SO₄ with a more dilute H₂SO₄ strip solution. Neglect of strip-side mass-transfer resistance for low-pH strip H₂SO₄ solutions is not desirable with higher-pH H₂SO₄ strip solutions. Small hollow-fiber membrane modules (HFMMs) were used with a higher-pH H₂SO₄ strip solution. Mass transfer was successfully modeled using reaction-enhanced mass transport in higher-pH H₂SO₄ solution. Employing larger-scale crossflow HFMMs, time-dependent ammonia removal from a large tank having ammonia-containing process effluent was modeled for batch recirculation operation. The larger-scale modules employ shell-side feed liquid in crossflow with an overall countercurrent flow pattern and acid flow in the tube side. Modeling ammonia transport without water vapor transfer can cause substantial errors in batch recirculation method. Water vapor transport was considered here for low-pH and high-pH H₂SO₄ strip solutions for ammonia-containing feed in a large tank. Model results describe literature-based experimentally observed mass transfer behavior in industrial-treatment systems well. Model calculations were also made for continuous ammonia recovery from industrial effluents by a number of series-connected HFMMs without any batch recirculation. 
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  6. null (Ed.)
    Defense against small molecule toxic gases is an important aspect of protection against chemical and biological threat as well as chemical releases from industrial accidents. Current protective respirators/garments cannot effectively block small molecule toxic gases and vapors and retain moisture transmission capability without a heavy burden. Here, we developed a nanopacked bed of nanoparticles of UiO-66-NH₂ metal organic framework (MOF) by synthesizing them in the pores of microporous expanded polytetrafluoroethylene (ePTFE) membranes. The submicron scale size of membrane pores ensures a large surface area of MOF nanoparticles which can capture/adsorb and react with toxic gas molecules efficiently. It was demonstrated that the microporous ePTFE membrane with UiO-66-NH₂ MOF grown inside and around the membrane can defend against ammonia for a significant length of time while allowing passage of moisture and nitrogen. It was also demonstrated that the MOF-loaded ePTFE membrane could provide significant protection from Cl₂ intrusion as well as intrusion from 2-chloroethyl ethyl sulfide (CEES) (a simulant for sulfur mustard). Such MOF-filled membranes exhausted by NH₃ breakthrough experiments were regenerated conveniently by heating at 60 °C for one week under vacuum for further/repeated use; a single regenerated membrane could block NH₃ for 200–300 min. The moisture permeability of such a membrane/nanopacked bed was considerably above the breathability threshold value of 2000 g/m² -day. The results suggest that microporous membranes filled with reactive MOF nanoparticles could be designed as protective barriers against toxic gases/vapors, e.g., NH₃ and Cl₂ and yet be substantially permeable to H₂O and air. 
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  7. Membrane processes are widely used in industrial applications such water purification, food processing and pharmaceutical manufacturing. During their operation, the accumulation of foulants in membrane pores and on membrane surfaces lead to the reduction in flux, membrane lifetime and increase in operational cost, and the understanding of the fouling phenomenon is important for mitigating these problems. In this paper we report the application of Raman chemical imaging as a means of identify and map foulants on a membrane surface. The surface of a Polytetrafluoroethylene (PTFE) membrane was studied by Raman chemical imaging before and after fouling during desalination via membrane distillation. Information about location and concentration of three different salts namely CaSO4, BaSO4 and CaCO3 was studied. The three salts showed different distribution patterns, and their distribution was analyzed by correlation mapping and multivariate curve resolution. It was observed that CaSO4 agglomerated in specific places while the BaSO4 and CaCO3 were more distributed. Raman imaging appears to be a powerful tool for studying membrane foulants and can be effective in identifying the distribution of different species on a membrane surface. 
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