Protein adsorption onto an inorganic microfiltration membrane: Solute–solid interactions and surface coverage

The mass of γ-globulin deposited onto an Anodisc^® alumina membrane with a nominal pore diameter of 0.1 μm has been measured at several concentrations and pH. This deposition resulted from filtering through the membrane in a continuous recirculation device.The low concentration deposition can be assigned mainly to adsorption, that can be studied as a function of the electrostatic forces between the solute and the membrane. A sharp maximum in the adsorbed mass for zero electrostatic force was obtained. At high concentrations, accumulation (non-adsorptive deposition) has also to be taken into account at alkaline pH as confirmed by flux decay experiments and retention measurements.The irreversible deposition (understanding irreversible as referring to deposition that do not disappear when the flux through the membrane stops) has been studied by imaging the surface of the membrane after filtration using atomic force microscopy (AFM). These images give insights into how and where adsorption takes place.     

Ultrafiltration of protein and humic substances: effect of solution chemistry on fouling and flux decline

The rate and extent of adsorption of a protein and a humic acid onto membranes was measured at varying conditions of pH and ionic strength. The resistance-in-series approach was used to calculate reversible and irreversible fouling resistances, which were then compared for static (no flow) and dynamic runs in order to determine the effect of convective flow and electrostatic interactions on fouling behavior. Although convective forces tended to increase the amount of material accumulated near the membrane surface, electrostatic interactions played a stronger role, as evident in the irreversible adsorption results for the static and dynamic cases. Electrostatic interactions affected reversible and irreversible resistances. Both resistances were higher at the isoelectric point (iep) of the protein and decreased at higher pH values. Humic acid adsorption decreased as pH was increased from 4.7 to 10. Humic acid filtration resulted in a higher resistance per unit mass than protein filtration.     

The role of foulant–foulant electrostatic interaction on limiting flux for RO and NF membranes during humic acid fouling—Theoretical basis,experimental evidence,and AFM interaction force measurement

A limiting flux model has been recently developed for predicting the fouling behavior of reverse osmosis and nanofiltration membranes by organic macromolecules [C.Y. Tang, J.O. Leckie, Membrane independent limiting flux for RO and NF membranes fouled by humic acid, Environmental Science and Technology 41 (2007) 4767–4773]. Several interesting results have been observed: (a) there was a maximum pseudo-stable flux (the limiting flux) beyond which further increase in applied pressure did not translate to a greater stable flux; (b) all membrane samples attained the limiting flux under constant pressure conditions as long as their initial flux was greater than the limiting flux; (c) the limiting flux did not depend on the properties of membranes; (d) the limiting flux had strong dependence on the feedwater composition, such as pH, ionic strength, and divalent ion concentration. The current study investigates the dependence of limiting flux on intermolecular interaction between foulant molecules. It was observed that the limiting flux was directly proportional to the intermolecular electrostatic repulsive force and that conditions enhancing foulant-deposited-foulant repulsion resulted in greater limiting flux values. Such observations agree well with a theoretical model capturing both hydrodynamic and DLVO interactions. Interaction force measurements by atomic force microscopy (AFM) were also performed. The limiting flux correlated reasonably well with AFM interaction force between the model foulant and the fouled membrane surface.     

Performance of partially permeable microfiltration membranes under low fouling conditions

Controlling the onset of fouling and concentration polarization is critical in many membrane operations, particularly in the bioseparation area. By using stepping and constant flux experiments, the fouling threshold or `incipient fouling' region was studied for various microfiltration membranes, pH's, and bulk concentrations using bovine serum albumin. Experiments were conducted to try to decouple effects such are porosity and pore size on incipient fouling by using a combination of tracked etched and polyvinylidene difluoride membranes. Changes in protein transmission and wall concentrations near the fouling threshold were also compared across these membranes. While porosity determined the fouling rate after the exceeding the fouling threshold, pore size appear to be an dominant factor in determining level of the fouling threshold itself. The effect of pH also supports the hypothesis that the rejections are initially dominated by membrane–solute interactions but are subsequently modified by protein adsorption to the surface as the wall concentration increases. Repulsive forces between membrane and solute allow greater rejection (greater wall concentration) to be maintained without fouling but did not increase the critical flux substantially. Attractive electrostatic forces allow greater passage of solute (lower wall concentration), but the protein adsorption soon dominated and the onset of fouling occurred much more quickly. Using a conventional concentration polarization model, analysis of the results indicates that the onset of fouling is occurring at a relatively low wall concentrations.     

基于XDLVO理论解析MBR膜污染研究进展

膜污染问题严重制约了膜生物反应器(MBR)的广泛应用,因此膜污染机制的研究对于有效控制膜污染十分重要。XDLVO理论合理地解析了范德华力、极性作用力、双电层作用力在膜污染过程中的贡献,有效地揭示了膜污染机理。本文首先阐述了XDLVO理论;然后运用XDLVO理论,解析界面微距离范围内膜表面凝胶层及泥饼层形成过程;最后总结了XDLVO理论在MBR膜污染方面的应用,并对该领域未来的研究方向进行了展望。     

Free-solvent model shows osmotic pressure is the dominant factor in limiting flux during protein ultrafiltration

In protein ultrafiltration (UF), the limiting flux phenomenon has been generally considered a consequence of the presence of membrane fouling or the perceived formation of a cake/gel layer that develops at high operating pressures. Subsequently, numerous theoretical models on gel/cake physics have been made to address how these factors can result in limiting flux. In a paradigm shift, the present article reestablishes the significance of osmotic pressure by examining its contribution to limiting flux in the framework of the recently developed free solvent osmotic pressure model. The resulting free-solvent-based flux model (FSB) uses the Kedem–Katchalsky model, film theory and the free solvent representation for osmotic pressure in its development. Single protein tangential-flow diafiltration experiments (30 kDa MWCO CRC membranes) were also conducted using ovalbumin (OVA, 45 kDa), bovine serum albumin (BSA, 69 kDa), and immuno-gamma globulin (IgG, 155 kDa) in moderate NaCl buffered solutions at pH 4.5, 5.4, 7 and 7.4. The membrane was preconditioned to minimize membrane fouling development during the experimental procedure. The pressure was randomly selected and flux and sieving were determined. The experimental results clearly demonstrated that the limiting flux phenomenon is not dominated by membrane fouling and the FSB model theoretically illustrates that osmotic pressure is the primary factor in limiting flux during UF. The FSB model provides excellent agreement with the experimental results while producing realistic protein wall concentrations. In addition, the pH dependence of the limiting flux is shown to correlate to the pH dependency of the specific protein diffusion coefficient.     

Surfactant fouling of nanofiltration membranes: measurements and mechanisms.

Fouling of nanofiltration membranes is studied during filtration of aqueous surfactant solutions under different conditions. To this purpose, four typical nanofiltration membranes (Desal51HL, NF270, NTR7450 and NFPES10) and three typical surfactants (nonionic neodol, anionic SDBS and cationic cetrimide) are selected. Fouling is studied as a function of the surfactant concentration, with and without addition of an electrolyte (NaCl), at different pH and when filtering a mixture of surfactants. Adsorption experiments and hydrophobicity measurements (to study the orientation of the surfactants on the membrane surface) are also performed under the different conditions. The least membrane fouling is found for the anionic surfactant SDBS, while for the cationic surfactant cetrimide very low relative fluxes are observed. Neodol shows an intermediate degree of fouling. Both hydrophobic and electrostatic interactions (in the case of ionic surfactants) between the membrane surface and the surfactant explain the degree of adsorption and hence fouling, as membrane fouling is correlated with the amount of adsorbed surfactant. The difference between cetrimide and SDBS becomes especially visible when changing the pH: increasing the pH leads not only to an opposite orientation of the adsorbed surfactants, but also to an opposite trend in adsorbed amount and membrane fouling. This study permits selection of an optimal nanofiltration membrane to recycle wastewater containing surfactants in the carwash industry. The optimal choice would be a hydrophilic membrane with a low molecular weight cut-off and a small negative surface charge at neutral pH. Cationic surfactants in the wastewater should also be avoided as much as possible.     

Microfiltration of amphoteric surfactant using ceramic membranes

The microfiltration of commercially available amphoteric surfactant using ceramic membranes has been investigated. Various combinations operating conditions such as pH, electrolyte and surfactant concentrations were employed. Zeta potential and adsorption isotherms were obtained for the components of membrane surfactant system as functions of pH using surfactant or indifferent electrolyte (KCl). The shift in the membrane isoelectric point induced by the surfactant is linked to the carboxylic groups present on the surfactant which are believed to play a dominant role in the net surface charge of the membrane. A minimum in the permeate flux was found at the pH corresponding to the isoelectric point of the zwitterionic surfactant. This behaviour is ascribed to the interactions occurring between the surfactant–surfactant molecules and the surfactant–membrane. The higher fluxes obtained at low pH as compared to high pH arise from different fouling mechanisms and ionic strengths. Lower fluxes were found when inorganic electrolytes were used in conjunction with surfactant. However, as the valency of the salt increases, flux behaviour of the zwitterionic surfactant (close to isoelectric point) does not vary whilst the cationic and anionic state of the surfactants are much more affected. Interactions between surfactant molecules as a result of the charge screening effects by the larger valence ions are encouraged. The permeate flux declines with an increasing surfactant concentration even though some concentrations fall under the critical micelle concentration (c.m.c.). This is attributed to concentration polarisation in which the accumulated surfactant concentration at the membrane surface could form a stable viscous phase which is resistant to permeate flow in the secondary layer next to the membrane surface. This paper demonstrates the role interactions such as surfactant–surfactant and surfactant–membrane play in influencing the filterability of surfactant solutions using ceramic membranes.     

Critical flux in NF of high molar mass polysaccharides and effluents from the paper industry

High molar mass polysaccharides (locust bean gum and karaya gum) and effluents from a mechanical pulp mill and a paper mill were nanofiltered with commercially available nanofiltration (NF) membranes. The effect of the filtration conditions on the flux (critical flux), retention, and the fouling of the membranes was studied. The experiments were conducted by increasing and decreasing the pressure and measuring the flux thus obtained.

The critical flux was observed to increase with increasing flow velocity and decreasing concentration. An increase in pH increased the electrostatic repulsion between the membrane and the dissociated (charged) components in the paper mill effluents. As a result, a higher critical flux was obtained and also the retentions of the charged substances improved. Only a weak form of the critical flux was observed with the mill effluents. The permeate flux deviated from the pure water flux even at the lowest pressure, but increased linearly with pressure until the weak form of the critical flux was exceeded. The small decrease in flux immediately after filtration was started was probably caused by the plugging of the free spaces in the membranes or by the adsorption of foulants onto the membrane surface.

In the filtrations with the high molar mass polysaccharides, a strong form of the critical flux as well as a weak form were observed. The significant irreversible fouling of the most hydrophobic membrane was due to adsorption of the model substances by hydrophobic interaction. A precleaning of the membranes with an alkaline cleaning agent improved the pure water fluxes by up to 30%, but it had only a small effect on the critical or the limiting flux. The pure water fluxes of precleaned membranes after filtration were still higher than the pure water fluxes of the untreated membranes before filtration.     

Physico-chemical study of fouling mechanisms of ultrafiltration membrane on Biwa lake (Japan)

Many studies have been undertaken to understand the fouling of the ultrafiltration membranes in drinking water treatment. Physico-chemical fouling of membranes depends on characteristics of the raw water and membrane surface properties. In the case of Biwa lake, some chemical parameters as Si and Fe concentrations change with temperature (season) causing irreversible fouling. While some exits on the influence of the particle mineralogy on the fouling, little work has been developed to elucidate the relation between the physicochemical complexity of the cake and the fouling. Generally clays or oxides are known to lead to a reversible fouling. In this work, the interactions between a UF organic membrane with minerals leading to a hardly reversible fouling are studied. In the case of the Biwa lake water, fouling of ultrafiltration membranes results from the formation of a Si-rich ferric gel directly deposited on the membrane surface and a secondary allophanic gel layer at a bigger distance. The deposit nature and the membrane/cake interactions were studied using infra-red, X-ray diffraction, Al and Si NMR and EXAFS technics. The effect of mineral particles, especially ferric oxides associated with silica, has been demonstrated. The formation of Fe---Si gel directly on the membrane surface is mainly responsible for the fouling. The change of these particles is less negative than the membrane surface. The structure of such a material is complex. The low permeability of the gel is at the prime origin of the fouling.     

Properties of protein adsorption onto pore surface during microfiltration: Effects of solution environment and membrane hydrophobicity

Properties of bovine serum albumin (BSA) adsorption onto pore surface during the filtration of BSA containing solution with the Sirasu porous glass membrane with a pore size of 0.1 μm were studied. The effects of pH, ionic strength, and surface modification on the flux decline and breakthrough curves were observed. The adsorption properties of BSA were estimated quantitatively by using the internal fouling model, which relates the filtration performance to the adsorption interaction, the adsorption capacity, and the thickness of the adsorption layer. The electrostatic interaction between BSA and pore surface was estimated by the streaming potential measurement. The BSA adsorption involved a rapid adsorption in the early stage of filtration followed by a slow multilayer adsorption that dominates the long-term filtration performance. The electrostatic repulsive force reduced the overall adsorption interaction but the electrostatic attractive force did not affect the adsorption interaction. The effect of ionic strength on the BSA adsorption could be explained in terms of the shift of the IEP of BSA toward lower pH with the increase in ionic strength. The hydrophobicity of membrane did not affect the adsorption properties except for the adsorption interaction in the early stage of the filtration.     

Quantifying the effect of ionic strength on colloidal fouling potential in membrane filtration

Ultrafiltration experiments were conducted to study the fouling potential of colloidal suspensions under different ionic strengths and colloid concentrations. A linear relationship was found relating the colloidal fouling potential to the logarithm of the Debye-Huckel parameter, a characteristic for electrical double layers of colloids. This finding provided a useful quantitative linkage between the colloidal fouling potential and the water chemistry. Considering the linear dependence of colloidal fouling potential on the colloid concentration, a bilinear model was proposed to explain the coupling effects of colloid concentration and ionic strength of the suspension on the fouling potential. The model predictions of fouling potential were found to fit accurately with experimentally determined fouling potential values. Further analysis of the model showed that ionic strength can significantly affect colloidal fouling, for example, a 10-fold increase in ionic strength from 0.001 to 0.01 M for a given feed concentration has the same membrane fouling effect as doubling the feed concentration. The model allows for a quick and reliable assessment of fouling potential without even performing any experiments. This could then be used to design the membrane process or pretreatment stages required to mitigate membrane fouling.     

Irreversible membrane fouling in microfiltration membranes filtering coagulated surface water

Chemical coagulation has been widely used as a method to mitigate membrane fouling in MF/UF membranes used for drinking water treatment. Optimization of coagulation as pre-treatment of membrane processes has not been achieved yet: the optimum condition of coagulation for conventional treatment systems is not necessarily applicable to membrane-based treatment systems. This study investigated (physically) irreversible membrane fouling in an MF membrane used with pre-coagulation by aluminum salt. In a series of bench-scale filtration tests, feed water containing commercially available humic acid or organic matter isolated from surface water was coagulated with polyaluminum chloride (PACl) under various conditions and subsequently filtered with an MF membrane with the nominal pore size of 0.1 μm. It was found that coagulation conditions had great impacts on the degree of physically irreversible fouling. Acidic conditions improved the quality of treated water but generally caused greater physically irreversible fouling than did neutral or alkaline conditions. Also, dosage of coagulant was found to be influential on the degree of membrane fouling: high dosage of coagulant frequently caused more severe irreversible fouling. Sizes of flocs seemed to become small under acidic conditions in this study, which was indicated by high concentrations of aluminum in the permeate under acidic conditions. It is thought that small flocs produced under acidic conditions could migrate into micropores of the membrane and caused physically irreversible fouling by plugging or adsorption. These findings obtained in the bench-scale tests were verified in a long-term pilot-scale test.     

Protein fouling in microfiltration: deposition mechanism as a function of pressure for different pH

The influence of applied pressure on the fouling mechanism during bovine serum albumin (BSA) dead-end microfiltration (MF) has been investigated for a polyethersulfone acidic negatively charged membrane (ICE-450) from Pall Co. BSA solutions at pH values of 4, 5 (almost equal to the protein isoelectric point, IEP), and 6 were microfiltered through the membrane at different applied transmembrane pressures. Results have been analyzed in terms of the usual blocking filtration laws and a substantial change in the fouling mechanism was observed as the pressure was increased, this change can be related to the specific membrane-protein and protein-protein interactions.     

Adsorption of highly charged polyelectrolytes onto an oppositely charged porous substrate

The adsorption behavior of highly charged cationic polyelectrolytes onto porous substrates is electrostatic in nature and has been shown to be highly dependent on the polyelectrolyte properties. Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC) were synthesized to have a range of macromolecular properties (i.e., charge density and molecular mass). Traditional titration methods have been complemented by fluorescence labeling techniques that were developed to directly observe the extent that fluorescently labeled poly(AM- co-DADMAC) adsorbs into the pore structure of a cellulosic substrate. Although contributing to the electrostatic driving force, the charge density acts to limit adsorption to the outermost surface under electrolyte-free conditions. However, adsorption into the pores can occur if both the molecular mass and charge density of poly(AM- co-DADMAC) are sufficiently low. Adsorption initially increases as the electrolyte concentration is increased. However, the electrostatic persistence length of poly(AM- co-DADMAC) restricts the polyelectrolyte from entering the pores. Therefore, changes in the adsorption behavior at moderate electrolyte concentrations have been attributed to swelling of the polyelectrolyte layer at the fiber exterior. The adsorption behavior changes again at high electrolyte concentrations such that poly(AM- co-DADMAC) could adsorb into the pore structure. This occurred when the electrolyte concentration was sufficient to screen the electrostatic persistence length of poly(AM- co-DADMAC), provided that the entropic driving force for adsorption still existed. It is suggested that adsorption into the pore structure is a kinetic process that is governed by localized electrostatic interactions between poly(AM- co-DADMAC) and the charges located within the pores.     

Direct contact membrane distillation of humic acid solutions

Direct contact membrane distillation process has been conducted for the treatment of humic acid solutions using microporous polytetrafluoroethylene and polyvinylidene fluoride membranes. The membranes were characterized in terms of their non-wettability, pore size and porosity. Water advancing and receding contact angles on the top membrane surfaces were measured. Experiments were also carried out employing pure water as feed at different mean temperatures and the water vapor permeance of each membrane was determined. Different humic acid concentrations in the feed solution, pH values and transmembrane temperature difference were tested. The direct contact membrane distillation technique is more adequate for the treatment of humic acid solutions than the applied pressure-driven separation processes, as lower membrane fouling was detected.     

Characterization and theoretical analysis of protein fouling of cellulose acetate membrane during constant flux dead-end microfiltration

A rapid characterization method was used to study protein fouling of cellulose acetate membrane during dead-end, in-line, constant flux microfiltration. Based on pressure-permeate volume profiles, two fouling phases could be identified and compared at different permeate fluxes. Using protein staining dyes, the model foulant (bovine serum albumin) was found to deposit on the upstream side of the membrane as a loose cake at its isoelectric point. The effects of solution pH on both the nature and extent of membrane fouling, and membrane cleaning were examined. To further understand and quantitatively analyze the fouling behavior, a combined mathematical model which took into account pore blocking, cake formation and pore constriction was developed based on existing fouling models. The data obtained by modeling was in good agreement with experimental fouling data. Theoretical analysis of data clearly indicated that cake formation was the main fouling mechanism. Using methods such as dynamic light scattering, the significant role of large protein aggregates in membrane fouling was confirmed. The dimer composition of protein did not change significantly during the fouling experiments, clearly indicating that smaller aggregates played less important role in membrane fouling.     

Characterizing the pH-responsive behavior of thin films of diblock copolymer micelles at the silica/aqueous solution interface

The pH-responsive behavior of cationic diblock poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate) copolymer micelles adsorbed at the silica/aqueous solution interface has been characterized. The micellar morphology of this copolymer, initially adsorbed at pH 9, can be dramatically altered by lowering the solution pH. The original micelle-like morphology of the adsorbed copolymer chains at pH 9 completely disappears as the pH is decreased to 4, and a brush-like layer structure is produced. This change results from protonation of the copolymer chains: the subsequent electrostatic repulsions within the film drive the copolymer chains to expand into the aqueous phase. Returning the solution pH from 4 to 9 causes this brush-like layer to collapse, with atomic force microscopy images suggesting degradation of the film. Hence, the pH-responsive behavior of the copolymer film exhibits irreversible morphological changes. Measurements of the adsorbed/desorbed amounts of the copolymer film were conducted using both a quartz crystal microbalance with dissipation monitoring (QCM-D) and optical reflectometry (OR). After an initial rinse at both pH values, the OR adsorbed mass becomes almost constant during subsequent pH cycling, whereas the corresponding QCM-D adsorbed mass changes significantly but reversibly in response to the solution pH. Since the QCM-D measures a bound mass that moves in tandem with the surface, the discrepancy with the OR data is due to changes in the amount of bound water in the copolymer film as a result of the pH-induced changes in surface morphology. The larger effective mass observed at pH 4 suggests that the brush-like layer contains much more entrapped water than the micellar films at pH 9. The pH dependence of the contact angle of the adsorbed film is consistent with the changes observed using the other techniques, regardless of whether the solution pH is altered in situ or the aqueous solution is completely replaced. In fact, comparison of these two approaches provides direct evidence of the exposure of adsorbed micelle core blocks to the solution during pH cycling and the concomitant impact upon all the other measurements.