Search Results (65)

Nanofiltration (NF) is considered a competitive purification method for acidic stream treatments. However, conventional thin-film composite NF membranes degrade under acid exposures, limiting their applications in industrial acid treatment. For example, wet-process phosphoric acid contains impurities of multivalent metal ions, but NF membrane technologies for impurity removal under harsh conditions are still immature. In this work, we develop a novel strategy of acid-resistant nanofiltration membranes based on interfacial polymerization (IP) of polyethyleneimine (PEI) and cyanuric chloride (CC) with the s-triazine ring. The IP process was optimized by orthogonal experiments to obtain positively charged PEI-CC membranes with a molecular weight cut-off (MWCO) of 337 Da. We further applied it to the approximate industrial phosphoric acid purification condition. In the tests using a mixed solution containing 20 wt% P₂O₅, 2 g/L Fe³⁺, 2 g/L Al³⁺, and 2 g/L Mg²⁺ at 0.7 MPa and 25 °C, the NF membrane achieved 56% rejection of Fe, Al, and Mg and over 97% permeation of phosphorus. In addition, the PEI-CC membrane exhibited excellent acid resistance in the 48 h dynamic acid permeation experiment. The simple fabrication procedure of PEI-CC membrane has excellent acid resistance and great potential for industrial applications. Full article

Traditional pre-clinical drug evaluation methods, including animal experiments and static cell cultures using human-derived cells, face critical limitations such as interspecies differences, ethical concerns, and poor physiological relevance. More recently, microphysiological systems (MPSs) that use microfluidic devices to mimic in vivo conditions have emerged as promising platforms. By enabling perfusion cell culture and incorporating human-derived cells, MPSs can evaluate drug efficacy and toxicity in a more human-relevant manner. However, standard MPS protocols rely on discrete medium changes, causing abrupt changes in drug concentrations that do not reflect the continuous pharmacokinetics seen in vivo. To overcome this limitation, we developed a Dialysis Membrane-integrated Microfluidic Device (DMiMD) which maintains continuous drug concentrations through selective medium change via a dialysis membrane. The membrane’s molecular weight cut-off (MWCO) enables the retention of high-molecular-weight drugs while facilitating the passage of essential low-molecular-weight nutrients such as glucose. We validated the membrane’s molecular selectivity and confirmed effective nutrient supply using cells. Additionally, anticancer drug efficacy was evaluated under continuously changing drug concentrations, demonstrating that the DMiMD successfully mimics in vivo drug exposure dynamics. These results indicate that the DMiMD offers a robust in vitro platform for accurate assessment of drug efficacy and toxicity, bridging the gap between conventional static assays and the physiological complexities of the human body. Full article

This study examined total ammoniacal nitrogen (TAN) rejection by two reverse osmosis (RO) and two nanofiltration (NF) membranes as a function of pH for three ammonium salts to optimize conditions for a hybrid membrane system that can produce high-purity TAN streams suitable for reuse. The results showed that TAN rejection was significantly influenced by membrane type, feed pH, and the ammonium salt used. This study represents the first attempt to simulate real manure wastewater conditions typically found in pig manure. TAN rejection for (NH₄)₂SO₄ and NH₄HCO₃ reached up to 95% at pH values below 7, with the SW30 membrane showing the highest performance (99.5%), attributed to effective size exclusion and electrostatic repulsion of SO₄²⁻ and HCO₃⁻ ions. In contrast, lower rejection was observed for NH₄Cl, particularly with the MPF-34 membrane, due to its higher molecular weight cut-off (MWCO), which diminishes both exclusion mechanisms. TAN rejection decreased markedly with increasing pH across the BW30, NF90, and MPF-34 membranes as the proportion of uncharged NH₃ increased. The lowest rejection rates (<15%) were recorded at pH 11.5 for both NF membranes. These results reveal a notable shift in separation behavior, where NH₃ permeation under alkaline conditions becomes dominant over the commonly reported NH₄⁺ retention at low pH. This novel insight offers a new perspective for optimizing membrane-based ammonia recovery in systems simulating realistic manure wastewater conditions. TAN recovery was evaluated using a hybrid membrane system, where NF membranes operated at high pH promoted NH₃ permeation, and the SW30 membrane at pH 6.5 enabled TAN rejection as (NH₄)₂SO₄. This hybrid system insight offers a new perspective for optimizing membrane-based ammonia recovery in systems simulating realistic manure wastewater conditions. Based on NH₃ permeation and membrane characteristics, the NF90 membrane was operated at pH 9.5, achieving a TAN recovery of 48.3%, with a TAN concentration of 11.7 g/L, corresponding to 0.9% nitrogen. In contrast, the MPF-34 membrane was operated at pH 11.5. The NF90–SW30 system also achieved a TAN recovery of 48.3%, yielding 11.7 g/L of TAN with a nitrogen content of 1.22%. These nitrogen concentrations indicate that both retentate streams are suitable for use as liquid fertilizers in the form of (NH₄)₂SO₄. A preliminary economic assessment estimated the chemical consumption cost at 0.586 EUR/kg and 0.729 EUR/kg of (NH₄)₂SO₄ produced for the NF90–SW30 and MPF-34–SW30 systems, respectively. Full article

Stimuli-responsive polysulfone (PSf) ultrafiltration (UF) membrane was developed via surface modification with tethered hydrophilic polyacrylic acid (PAA) chains of length greater than the native membrane pore size. The surface nano-structured (SNS) membrane was synthesized via atmospheric pressure plasma-induced graft polymerization (APPIGP) to form a surface tethered PAA brush layer. The SNS-PAA-PSf UF membrane demonstrated hydraulic permeability and selectivity in the ranges of 0.74–2.29 × 10¹³ m⁻¹ and 1.8–15.0 kDa, respectively, in response to changes in pH (3–11) and ionic strength (~0.02–547 mM). Membrane performance characterization showed that, for the above ranges of pH and salinity, the SNS-PAA-PSf UF membrane can overcome the typical membrane perm-selectivity tradeoff. The above performance is attributed to the swelling of the tethered PAA chains, upon ionic strength decrease or pH increase, which provides a less hindered transmembrane solute transport path, but increased hydraulic resistance. Conversely, at high ionic stress or low pH tethered chain collapse leads to lower molecular weight cutoff (MWCO) but with hydraulic resistance below that of the swollen state. The study results suggest that there is merit for further tailoring and improving the performance of stimuli-responsive UF membranes, developed via APPIGP, for applications over selected ranges of pH and ionic strength. Full article

Fucoidan, a sulphated polysaccharide from brown seaweed composed of several monosaccharides, has been stated to have several bioactive properties such as antioxidant, antiviral, anticancer, antithrombic, anti-inflammatory, and immunomodulatory effects. This paper provides research findings on green extraction methods, structural analysis of fucoidan, and its associated bioactivities. Fucoidans from brown seaweeds, Fucus vesiculosus and Ascophyllum nodosum, were extracted using green solvents such as citric acid (CA) followed by MWCO (molecular weight cut-off) filtration to obtain high-purity polysaccharides. The presence of functional groups typical to fucoidans, namely, fucose, sulfate, and glycosidic bonds, in the extracts were confirmed through the data obtained from FTIR (Fourier-transform infrared spectroscopy), TGA (thermogravimetric analysis), DSC (differential scanning calorimetry), and solid-state CP–MAS (cross-polarization magic angle spinning) analysis. The MWCO analysis identified that the >300 kDa fraction can have better content of fucoidan (FV-CA 79.16%, FV-HCl 63.59%, AN-CA 79.21%, AN-HCl 80.70%) than the conventional extraction process. Furthermore, the >300 kDa fraction showed significantly higher antioxidant activities compared to crude fucoidan extracts. Crude fucoidan extracts showed significant inhibition of cell viability in human lung (A459 lung carcinoma cells) and colorectal adenocarcinoma (Caco-2) cells at higher concentrations. The fucoidan extracted with green solvents and avoiding alcohol-based precipitation has substantial antioxidant/antitumor action, so, due to this activity, it can be employed as functional foods in food applications. Full article

Car wash wastewaters (CWWs) contain various pollutants with different contents. Hence, selecting an appropriate process for their treatment is a great challenge. Undoubtedly, the ultrafiltration (UF) process is one of the most interesting and reliable choices. Therefore, the main aim of the current study was to investigate the performance of the UF membranes used for the long-term treatment of real CWWs. For this purpose, two polyethersulfone (PES) membranes with molecular weight cut-off (MWCO) values equal to 10 and 100 kDa were applied. As expected, a significant decrease in the permeate flux during the UF run was observed. However, it was immediately demonstrated that the systematic cleaning of membranes (every day) with Insect agent (pH = 11.5) prevented a further decline in the process’s performance. In addition, this study focused on the relative flux during the process run with breaks lasting a few days when the UF installation was filled with distilled water. The results of this research indicated that aqueous media favor microorganism adherence to the surface which leads to the formation of biofilms inside processing installations. As a consequence, many attempts have been made to restore the initial membrane performance. It has been found that the application of several chemical agents is required. More precisely, the use of an Insect solution, P3 Ultrasil 11 agent, and phosphoric acid increases the relative flux to a value of 0.8. Finally, it has been indicated that the membranes used in this work are resistant to the long-term exposure to bacteria and chemical agents. However, during the separation of CWWs for the membrane with an MWCO of 10 kDa, a lesser fouling influence and higher effectiveness of cleaning were obtained. Finally, the present study demonstrates a novel analysis and innovative implications towards applying the UF process for the CWW treatment. Full article

Low-molecular-weight (LMW, <1000 Da) dissolved organic matter (DOM) plays a significant role in metal/organic pollutant complexation, as well as photochemical/microbiological processes in freshwater ecosystems. The micro size and high reactivity of LMW-DOM hinder its precise characterization. In this study, Suwannee River fulvic acid (SRFA), a commonly used reference material for aquatic DOM, was applied to examine the optical features and molecular composition of LMW-DOM by combining membrane separation, ultraviolet–visible absorption and Orbitrap mass spectrometry (MS) characterization. The 100–500 Da molecular weight cut-off (MWCO) membrane had a better performance in regard to separating the tested LMW-DOM relative to the 500–1000 Da MWCO membrane. The ultraviolet–visible absorbance decreased dramatically for the retentates, whereas it increased for the dialysates. Specifically, carbohydrates, lipids and peptides exhibited high selectivity to the 100–500 Da MWCO membrane in early dialysis. Lignins, tannins and condensed aromatic molecules displayed high permeability to the 500–1000 Da MWCO membrane in late dialysis. Overall, the retentates were dominated by aromatic rings and phenolic hydroxyls with high O/C_wa (weighted average of O/C) and low H/C_wa. Conversely, such dialysates had numerous aliphatic chains with high H/C_wa and low O/C_wa compared to SRFA. In particular, LMW-DOM below 200 Da was identified by Orbitrap MS. This work provides an operational program for identifying LMW-DOM based on the SRFA standard and MS analysis. Full article

The removal of persistent organic micropollutants (OMPs) from secondary effluent in wastewater treatment plants is critical for meeting water reuse standards. Traditional treatment methods often fail to adequately degrade these contaminants. This study explored the efficacy of a hybrid ozonation membrane filtration (HOMF) process using CeO₂ and CeTiO_x-doped ceramic crossflow ultrafiltration ceramic membranes for the degradation of OMPs. Hollow ceramic membranes (CM) with a 300 kDa molecular weight cut-off (MWCO) were modified to serve as substrates for catalytic nanosized metal oxides in a crossflow and inside-out operational configuration. Three types of depositions were tested: a single layer of CeO₂, a single layer of CeTiO_x, and a combined layer of CeO₂ + CeTiO_x. These catalytic nanoparticles were distributed uniformly using a solution-based method supported by vacuum infiltration to ensure high-throughput deposition. The results demonstrated successful infiltration of the metal oxides, although the yield permeability and transmembrane flow varied, following this order: pristine > CeTiO_x > CeO₂ > CeO₂ + CeTiO_x. Four OMPs were examined: two easily degraded by ozone (carbamazepine and diclofenac) and two recalcitrant (ibuprofen and pCBA). The highest OMP degradation was observed in demineralized water, particularly with the CeO₂ + CeTiO_x modification, suggesting O₃ decomposition to hydroxyl radicals. The increased resistance in the modified membranes contributed to the adsorption phenomena. The degradation efficiency decreased in secondary effluent due to competition with the organic and inorganic load, highlighting the challenges in complex water matrices. Full article

A validation study using recycled ultrafiltration membranes (r-UF) on an aerobic membrane bioreactor (aMBR) was conducted for the first time. Four different polyethersulfone (PES) membranes were tested using synthetic urban wastewater (COD 0.4–0.5 g/L) during two experimental periods: (i) recycled ultrafiltration membrane (r-UF) and commercial UF membrane (molecular weight cut-off (MWCO) 150 kDa) (c-150 kDa); (ii) r-UF membrane modified by dip-coating using catechol (CA) and polyethyleneimine (PEI) (mr-UF) and c-20 kDa membrane. Permeability, fouling behavior, and permeate quality were evaluated. Extensive membrane characterization was conducted using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy-dispersive X-ray (EDX), and confocal laser scanning microscopy (CLSM). Permeate quality for r-UF and mr-UF membranes was excellent and comparable to that obtained using commercial membranes under similar conditions. Additionally, r-UF and mr-UF membranes presented a steadier performance time. Additionally, r-UF membrane demonstrated less tendency to be fouled (R_f, m⁻¹) r-UF 7.92 ± 0.57 × 10¹²; mr-UF 9.90 ± 0.14 × 10¹², c-150 kDa 1.56 ± 0.07 × 10¹³ and c-20 kDa 1.25 ± 0.50 × 10¹³. The r-UF membrane showed an excellent antibiofouling character. Therefore, r-UF membranes can be successfully implemented for wastewater treatment in aMBR, being a sustainable and cost-effective alternative to commercial membranes that can contribute to overcome membrane fouling and membrane replacement issues. Full article

Clarification and stabilisation processes are routinely performed post-fermentation to ‘finish’ wines, but traditional methods are slow and energy intensive, create waste, and can affect wine volume and quality. New methods that ‘finish’ wine rapidly, with higher recovery rates, and reduced waste and input costs, are therefore needed. Ultrafiltration is a separation process that fractionates liquids, nominally, according to molecular weight. By comparing the composition of permeate and retentate derived from pilot-scale fractionation of white and red wine using 75, 20, or 10 kDa membranes and different degrees of permeation (50, 80, 90, or 95%), this study sought to evaluate ultrafiltration as an innovative approach to the clarification and stabilisation of wine. Mass balance analysis confirmed that titratable acidity and alcohol were fractionated according to the degree of permeation; however, proteins, polysaccharides, and phenolic compounds (including anthocyanins for red wine) were concentrated in retentate due both to the membrane molecular weight cut-off (MWCO) specifications and degree of permeation. The retention of wine constituents smaller than the nominal MWCO suggests that interaction with other macromolecules or the membrane surface occurred. Red wine permeates were stripped of much of their essential character and were no longer considered commercially acceptable. In contrast, the removal of protein and phenolic compounds from white wine demonstrated the potential for ultrafiltration to remediate heat unstable or excessively phenolic wines. Findings enabled the identification of other winemaking applications of ultrafiltration technology that could enhance wine quality, process efficiency, and profitability. Full article

Membrane technology allows the separation of active compounds, providing an alternative to conventional methods such as column chromatography, liquid–liquid extraction, and solid–liquid extraction. The nanofiltration of a Muérdago (Tristerix tetrandus Mart.) fruit juice was realized to recover valuable metabolites using three different membranes (DL, NFW, and NDX (molecular weight cut-offs (MWCOs): 150~300, 300~500, and 500~700 Da, respectively)). The metabolites were identified by ESI-MS/MS. The results showed that the target compounds were effectively fractionated according to their different molecular weights (MWs). The tested membranes showed retention percentages (RPs) of up to 100% for several phenolics. However, lower RPs appeared in the case of coumaric acid (84.51 ± 6.43% (DL), 2.64 ± 2.21% (NFW), 51.95 ± 1.23% (NDX)) and some other phenolics. The RPs observed for the phenolics cryptochlorogenic acid and chlorogenic acid were 99.74 ± 0.21 and 99.91 ± 0.01% (DL membrane), 96.85 ± 0.83 and 99.20 ± 0.05% (NFW membrane), and 92.98 ± 2.34 and 98.65 ± 0.00% (NDX membrane), respectively. The phenolic quantification was realized by UHPLC-ESI-MS/MS. The DL membrane allowed the permeation of amino acids with the MW range of about 300~100 Da (aspartic acid, proline, tryptophan). This membrane allowed the highest permeate flux (22.10–27.73 L/m²h), followed by the membranes NDX (16.44–20.82 L/m²h) and NFW (12.40–14.45 L/m²h). Moreover, the DL membrane allowed the highest recovery of total compounds in the permeate during the concentration process (19.33%), followed by the membranes NFW (16.28%) and NDX (14.02%). Permeate fractions containing phenolics and amino acids were identified in the membrane permeates DL (10 metabolites identified), NFW (13 metabolites identified), and NDX (10 metabolites identified). Particularly, tryptophan was identified only in the DL permeate fractions obtained. Leucine and isoleucine were identified only in the NFW permeate fractions, whereas methionine and arginine were identified only in the NDX ones. Liquid permeates of great interest to the food and pharmaceutical industries were obtained from plant resources and are suitable for future process optimization and scale-up. Full article

A combination of straw filtration and nanofiltration was investigated for the first time as a sustainable approach aimed at valorizing olive mill wastewaters (OMWs) within a circular economy strategy. Ground straw filters with different granulometry (120, 250 and 500 μm) were tested in the first step to clarify the raw wastewater. The 500 μm filter offered the best performance due to a lower exposed surface of the filtering fibers and a shorter filtering time, allowing us to reduce about 70% of the chemical oxygen demand (COD) of the raw wastewater. Three different commercial membranes in a flat-sheet configuration with a molecular weight cut-off (MWCO) in the range 150–500 Da were tested to fractionate the clarified wastewater according to a dead-end configuration. Among the investigated membranes, a polymeric membrane of 500 Da (NFA-12A) exhibited the highest productivity in selected operating conditions (steady-state values of 11.4 L/m² h at 20 bar and 24 ± 2 °C). In addition, flux decays for this membrane were lower than the other two tested membranes, indicating a lower propensity to fouling phenomena. Higher rejections towards total polyphenols and total antioxidant activity (TAA) (76.6% and 73.2%, respectively) were also observed for this membrane. Flavanols and hydroxycinnamic acids were retained by more than 99%. The combination of straw filtration and NF with the NFA-12A membrane allowed us to reduce the COD of raw OMWs up to 97.6%. The retentate fraction of this membrane exhibited a TAA of 18.9 ± 0.7 mM Trolox, supporting its propensity for the development of innovative formulations of interest in food and nutraceutical applications. Full article

The present work investigates nanofiltration (NF) and ultrafiltration (UF) for the removal of three widely used pharmaceutically active compounds (PhACs), namely atenolol, sulfamethoxazole, and rosuvastatin. Four membranes, two polyamide NF membranes (NF90 and NF270) and two polyethersulfone UF membranes (XT and ST), were evaluated in terms of productivity (permeate flux) and selectivity (rejection of PhACs) at pressures from 2 to 8 bar. Although the UF membranes have a much higher molecular weight cut-off (1000 and 10,000 Da), when compared to the molecular weight of the PhACs (253–482 Da), moderate rejections were observed. For UF, rejections were dependent on the molecular weight and charge of the PhACs, membrane molecular weight cut-off (MWCO), and operating pressure, demonstrating that electrostatic interactions play an important role in the removal of PhACs, especially at low operating pressures. On the other hand, both NF membranes displayed high rejections for all PhACs studied (75–98%). Hence, considering the optimal operating conditions, the NF270 membrane (MWCO = 400 Da) presented the best performance, achieving permeate fluxes of about 100 kg h⁻¹ m⁻² and rejections above 80% at a pressure of 8 bar, that is, a productivity of about twice that of the NF90 membrane (MWCO = 200 Da). Therefore, NF270 was the most suitable membrane for this application, although the tight UF membranes under low operating pressures displayed satisfactory results. Full article

The nanofiltration performance of three commercial membranes was analyzed by the Steric Pore Model (SPM) and the extended Nernst–Planck diffusion equation inside membrane pores. The model was completed with the equation to predict the concentration polarization, and the mass transfer coefficient was determined by considering the presence of a feed spacer. The model parameters that characterized the performance of the membrane were the hydrodynamic coefficient, which accounts for the possible variations in solute size and membrane pore radius, the effective membrane thickness, and the water permeability coefficient. All experiments were conducted at fixed feed pH of 6. The rejections of uncharged solutes (glucose for membranes with a high molecular weight cut-off (MWCO) and glycerol and ethylene glycol for membranes with a low MWCO) allowed the model parameters to be determined. We found that glycerol and ethylene glycol overestimate the membrane pore radius due to their ability to interact with the membrane matrix. Therefore, the rejection of glycine as a small amino acid was explored to characterize the membranes with low MWCO since these molecules do not interact with the membrane matrix and have an almost zero charge at pH values between 4.5 and 6.5. Based on the experimental rejections, it was stated that glucose and glycine could be separated by these membranes operating in continuous diafiltration mode. Full article

The present study investigates the molecular characteristics of fucoidan obtained from the brown Irish seaweed Ascophyllum nodosum, employing hydrothermal-assisted extraction (HAE) followed by a three-step purification protocol. The dried seaweed biomass contained 100.9 mg/g of fucoidan, whereas optimised HAE conditions (solvent, 0.1N HCl; time, 62 min; temperature, 120 °C; and solid to liquid ratio, 1:30 (w/v)) yielded 417.6 mg/g of fucoidan in the crude extract. A three-step purification of the crude extract, involving solvents (ethanol, water, and calcium chloride), molecular weight cut-off filter (MWCO; 10 kDa), and solid-phase extraction (SPE), resulted in 517.1 mg/g, 562.3 mg/g, and 633.2 mg/g of fucoidan (p < 0.05), respectively. In vitro antioxidant activity, as determined by 1,1-diphenyl-2-picryl-hydrazyl radical scavenging and ferric reducing antioxidant power assays, revealed that the crude extract exhibited the highest antioxidant activity compared to the purified fractions, commercial fucoidan, and ascorbic acid standard (p < 0.05). The molecular attributes of biologically active fucoidan-rich MWCO fraction was characterised by quadruple time of flight mass spectrometry and Fourier-transform infrared (FTIR) spectroscopy. The electrospray ionisation mass spectra of purified fucoidan revealed quadruply ([M+4H]⁴⁺) and triply ([M+3H]³⁺) charged fucoidan moieties at m/z 1376 and m/z 1824, respectively, and confirmed the molecular mass 5444 Da (~5.4 kDa) from multiply charged species. The FTIR analysis of both purified fucoidan and commercial fucoidan standard exhibited O-H, C-H, and S=O stretching which are represented by bands at 3400 cm⁻¹, 2920 cm⁻¹, and 1220–1230 cm⁻¹, respectively. In conclusion, the fucoidan recovered from HAE followed by a three-step purification process was highly purified; however, purification reduced the antioxidant activity compared to the crude extract. Full article