Fouling of nanofiltration, reverse osmosis, and ultrafiltration membranes by protein mixtures: the role of inter-foulant-species interaction

Protein fouling of nanofiltration (NF), reverse osmosis (RO), and ultrafiltration (UF) membranes by bovine serum albumin (BSA), lysozyme (LYS), and their mixture was investigated under cross-flow conditions. The effect of solution chemistry, membrane properties, and permeate flux level was systematically studied. When the solution pH was within the isoelectric points (IEPs) of the two proteins (i.e., pH 4.7-10.4), the mixed protein system experienced more severe flux decline compared to the respective single protein systems, which may be attributed to the electrostatic attraction between the negatively charged BSA and positively charged LYS molecules. Unlike a typical single protein system, membrane fouling by BSA-LYS mixture was only weakly dependent on solution pH within this pH range, and increased ionic strength was found to enhance the membrane flux as a result of the suppressed BSA-LYS electrostatic attraction. Membrane fouling was likely controlled by foulant-fouled-membrane interaction under severe fouling conditions (elevated flux level and unfavorable solution chemistry that promotes fouling), whereas it was likely dominated by foulant-clean-membrane interaction under mild fouling conditions. Compared to nonporous NF and RO membranes, the porous UF membrane was more susceptible to dramatic flux decline due to the increased risk of membrane pore plugging. This study reveals that membrane fouling by mixed macromolecules may behave very differently from that by typical single foulant system, especially when the inter-foulant-species interaction dominates over the intra-species interaction in the mixed foulant system.     

Recovery and purification of potato proteins from potato starch wastewater by hollow fiber separation membrane integrated process

Potato starch wastewater contains high-concentration potato proteins which have great potential in the fields of food and health care. Most researches on potato protein recovery by membrane separation technique are focused on flat sheet or tubular ultrafiltration (UF) and reverse osmosis (RO) membranes and lack the further protein purification and the in-depth discussions on the fouling behavior. In this laboratory-scale study, potato proteins were recovered and purified from the simulated potato starch wastewater by the self-made hollow fiber (HF) UF and nanofiltration (NF) separation membrane integrated process. 85.62% potato proteins with high molecular weight in the potato starch wastewater could be retained by UF membrane and 92.1% potato proteins with low molecular weight were rejected by NF membrane. The concentrated solution after UF and NF filtration was desalinated and purified by diluting the solution eight times and filtering the diluted solution with UF membrane. Both types of HF membranes, UF and NF, suffered the inevitable membrane fouling. After the traditional physical washing and chemical cleaning, water flux of UF and NF membranes can be effectively recovered. The corresponding recovery rates of UF and NF membranes can reach 93.5% and 84.7%, respectively. The hollow fiber UF-NF separation membrane integrated process was proved to be a promising technique of high-purity potato protein recovery from potato starch wastewater.     

Cake-enhanced concentration polarization: a new fouling mechanism for salt-rejecting membranes

Results from well-controlled colloidal fouling experiments with reverse osmosis (RO) and nanofiltration (NF) membranes suggest the existence of a new source of flux decline for salt-rejecting membranes-cake-enhanced osmotic pressure. The physical mechanisms leading to this enhanced osmotic pressure are a combination of hindered back-diffusion of salt ions and altered cross-flow hydrodynamics within colloidal deposit layers, which lead to an enhanced salt concentration polarization layer. A model that accounts for both hindered diffusion of salt ions and altered hydrodynamics within colloidal deposit ("cake") layers is presented. The model successfully links permeate flux and salt rejection to cake-enhanced concentration polarization and provides new insight into the mechanisms through which salt-rejecting membranes foul. Experimental data support the model calculations and highlight the role of enhanced concentration polarization phenomena in the performance (i.e., water flux and salt rejection) of polymeric thin-film composite RO/NF membranes in environmental applications.     

Effect of flux (transmembrane pressure) and membrane properties on fouling and rejection of reverse osmosis and nanofiltration membranes treating perfluorooctane sulfonate containing wastewater

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns. In this study, reverse osmosis (RO) and nanofiltration (NF) membranes were used to remove this toxic and persistent compound from PFOS-containing wastewater. Five RO membranes and three NF membranes were tested at a feed concentration of 10 ppm PFOS over 4 days, and the PFOS rejection and permeate flux performances were systematically investigated. PFOS rejection was well correlated to sodium chloride rejection. The rejection efficiencies for the RO membranes were > 99%, and those for the NF membranes ranged from 90-99%. Improvement in PFOS rejection, together with mild flux reduction (< 16%), was observed at longer filtration time. Such shifts in rejection and flux performance were probably due to the increased PFOS accumulation at longer duration, as shown by X-ray photoelectron spectroscopy and liquid chromatograph and tandem mass spectrometry results. A fraction of PFOS molecules might be entrapped in the polyamide layer of the composite membranes, which hindered the further passage of both water and other PFOS molecules. In a similar fashion, PFOS rejection and fouling were enhanced for greater initial flux and/or applied pressure, where PFOS accumulation was promoted probably due to increased hydrodynamic permeate drag. Flux reduction was also shown to correlate to membrane roughness, with the rougher membranes tend to experience more flux reduction than the smoother ones.     

Comprehensive bench- and pilot-scale investigation of trace organic compounds rejection by forward osmosis

Forward osmosis (FO) is a membrane separation technology that has been studied in recent years for application in water treatment and desalination. It can best be utilized as an advanced pretreatment for desalination processes such as reverse osmosis (RO) and nanofiltration (NF) to protect the membranes from scaling and fouling. In the current study the rejection of trace organic compounds (TOrCs) such as pharmaceuticals, personal care products, plasticizers, and flame-retardants by FO and a hybrid FO-RO system was investigated at both the bench- and pilot-scales. More than 30 compounds were analyzed, of which 23 nonionic and ionic TOrCs were identified and quantified in the studied wastewater effluent. Results revealed that almost all TOrCs were highly rejected by the FO membrane at the pilot scale while rejection at the bench scale was generally lower. Membrane fouling, especially under field conditions when wastewater effluent is the FO feed solution, plays a substantial role in increasing the rejection of TOrCs in FO. The hybrid FO-RO process demonstrated that the dual barrier treatment of impaired water could lead to more than 99% rejection of almost all TOrCs that were identified in reclaimed water.     

Extra-cellular polysaccharides, soluble microbial products, and natural organic matter impact on nanofiltration membranes flux decline

Extra-cellular polysaccharides (EPS), soluble microbiological products (SMP), dispersed bacterial cells, and a well-characterized natural organic matter (NOM) isolate were observed to determine their influence on the flux decline of model nanofiltration membrane systems. Biofouling tests were conducted using bench-scale, flat-sheet membrane modules, fed with particle-free (laboratory) waters and natural waters, some of which were augmented with readily biodegradable organic carbon. The modules were operated 6.7 x 10(5) Pa, and 21+/- 2 degrees C. Membrane flux-decline was associated with increases in surface EPS mass: between 30 and 80% of normalized flux decline occurred when membrane-associated EPS content increased from 5to 50 microg/ cm2. As judged by standard culturing, heterotrophic cell densities recovered from membrane biofilm samples showed no significant correlations with the different carbon sources present in the feedwaters, or flux decline rates. Results suggested that, in the absence of microbiological activity, SMP and NOM have intrinsic membrane fouling properties at levels that are operationally significant to commercial-scale membrane treatment practices. Results also suggested that SMP may have a biofouling potential significantly greater than some types of NOM. Trends obtained relating these compounds with flux decline were successfully described by expanding existing resistance-in-series models.     

Effects of microbial degradation of biofoulants on microfiltration membrane performance in a membrane bioreactor

In membrane bioreactors (MBRs) for wastewater treatment, membrane fouling, particularly biofouling caused by soluble microbial products (SMP), is a nuisance problem causing decreases in permeation flux. In a previous study, we identified primary biofoulants of microfiltration (MF) membranes in SMP as polysaccharides containing uronic acids that undergo inter- and intramolecular ionic cross-linking by polyvalent cations, forming a gelatinous mass that clogs membrane pores. In the present study, we therefore attempted to isolate biofoulant-degrading microorganisms from activated sludge on a polygalacturonic acid-overlaid agar medium and evaluate their efficiency for preventing biofouling of MF membranes. Among the isolates, the fungal strain HO1 identified as Phialemonium curvatum degraded 30% of polysaccharides containing uronic acids into smaller molecules in a SMP solution containing a high concentration of saccharides after 30 days of cultivation. Microfiltration tests using a laboratory-scale submerged MBR indicated that the filtration resistance of this degraded SMP solution was lower than that of the control SMP solution without fungal inoculation. Importantly, accumulation of gelatinous mass on the membrane responsible for biofouling was avoided in the SMP solution augmented with P. curvatum HO1 during the microfiltration test. This is the first report to describe a new method for avoiding biofouling of MBRs by microbial degradation of primary biofoulants.     

Investigation of seawater reverse osmosis fouling and its relationship to pretreatment type

Desalination of seawater using reverse osmosis (RO) technology is an important option available to water-scarce coastal regions. A major challenge to seawater reverse osmosis (SWRO) is membrane productivity decline due to fouling. Systematic studies in the area of SWRO fouling are lacking as compared to RO fouling by freshwater. The effect of the type of pretreatment employed ahead of the SWRO process has been recognized to be of critical importance in SWRO fouling. The objective of this study was to evaluate the effect of pretreatment on SWRO performance using bench scale experiments. The effect of different pretreatment strategies on SWRO flux decline was simulated using prefiltration of the SWRO feedwater using different filtration size ranges. The prefiltration size ranges used were selected to mimic the size fractions associated with different SWRO pretreatment processes. It was found that particulate matter greater than 1 microm (representing media filtration) caused most of the RO fouling. On the other hand, significant reduction in fouling was observed when membrane filtration was used (microfiltration represented by 0.1 microm prefiltration and ultrafiltration represented by 100 kDa prefiltration). There was no significant difference in flux decline between these two membrane filtration types. The lowest RO flux decline was observed when a tight ultrafiltration membrane (20 kDa) was used as prefiltration. The RO fouling observed was modeled using the gel layertheory, which could be used to satisfactorily describe fouling by different dissolved fractions of seawater. The observed SWRO fouling trends were confirmed using specially adapted attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy of the fouled membrane surface.     

Understanding Nanofiltration Fouling of Phenolic Compounds in Model Juice Solution with Two Membranes

Understanding membrane fouling mechanisms of key nutrition indicators in fruit juices during nanofiltration (NF) are important for quality control of products and manufacture processes. This study evaluated the effects of operating and molecular parameters of six phenolic compounds on fouling resistances during NF with two membranes. Results showed that fouling resistances and mechanisms were significantly different among the six representative phenolic compounds as a result of different molecular parameters such as acidity coefficient, molecular refractive index, octanol-water partition coefficient, and lipo-hydro partition coefficient. Operating time, solution concentration, and transmembrane pressure can also significantly affect the membrane fouling during nanofiltration of gallic acid solution. The images obtained by field emission scanning electron microscopy and atomic force microscopy on new, fouled, and cleaned membranes showed the fouling mechanisms intuitively. For phenolic compounds, a cake/gel layer as a reversible fouling was the main fouling resistance, and the adsorption was a significant role in the irreversible fouling resistance.     

Polyelectrolyte and silver nanoparticle modification of microfiltration membranes to mitigate organic and bacterial fouling

Membrane fouling remains one of the most problematic issues surrounding membrane use in water and wastewater treatment applications. Organic and biological fouling contribute to irreversible fouling and flux decline in these processes. The aim of this study was to reduce both organic and biological fouling by modifying the surface of commercially available poly(ether sulfone) (PES) membranes using the polyelectrolyte multilayer modification method with poly(styrenesulfonate) (PSS), poly(diallyldimethylammonium chloride) (PDADMAC), and silver nanoparticles (nanoAg) integrated onto the surface as stable, thin (15 nm) films. PSS increases the hydrophilicity of the membrane and increases the negative surface charge, while integration of nanoAg into the top PSS layer imparts biocidal characteristics to the modified surface. Fouling was simulated by filtering aqueous solutions of humic acid (5 and 20 mg L(-1)), a suspension of Escherichia coli (10(6) colony-forming units (CFU) mL(-1)), and a mixture of both foulants through unmodified and modified PES membranes under batch conditions. Filtration and cleaning studies confirmed that the modification significantly reduced organic and biological fouling.     

Membrane fouling in pilot-scale membrane bioreactors (MBRs) treating municipal wastewater

The main obstacle for wider use of membrane bioreactors (MBRs) for wastewater treatment is membrane fouling (i.e., deterioration of membrane permeability),which increases operating costs. For more efficient control of membrane fouling in MBRs, an understanding of the mechanisms of membrane fouling is important. However, there is a lack of information on membrane fouling in MBRs, especially information on features of components that are responsible for the fouling. We conducted a pilot-scale experiment using real municipal wastewater with three identical MBRs under different operating conditions. The results obtained in this study suggested that the food-microorganisms ratio (F/M) and membrane filtration flux were the important operating parameters that significantly influenced membrane fouling in MBRs. Neither concentrations of dissolved organic matter in the reactors nor viscosity of mixed liquor, which have been thought to have influences on fouling in MBRs, showed clear relationships with membrane fouling in this study. Organic substances that had caused the membrane fouling were desorbed from fouled membranes of the MBRs at the termination of the operation and were subjected to Fourier transform infrared (FTIR) and 13C nuclear magnetic resonance (NMR) analyses. These analyses revealed that the nature of the membrane foulant changes depending on F/M. It was shown that high F/M would make the foulant more proteinaceous. Carbohydrates were dominant in membrane foulants in this study, while features of humic substances were not apparent.     

Use of reverse osmosis membranes to remove perfluorooctane sulfonate (PFOS) from semiconductor wastewater

Perfluorooctane sulfonate (PFOS) and related substances are persistent, bioaccumulative, and toxic, and thus of substantial environmental concern. PFOS is an essential photolithographic chemical in the semiconductor industry with no substitutes yet identified. The industry seeks effective treatment technologies. The feasibility of using reverse osmosis (RO) membranes for treating semiconductor wastewater containing PFOS has been investigated. Commercial RO membranes were characterized in terms of permeability, salt rejection, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and membrane surface zeta potential (streaming potential measurements). Filtration tests were performed to determine the membrane flux and PFOS rejection. Over a wide range of feed concentrations (0.5 - 1500 ppm), the RO membranes generally rejected 99% or more of the PFOS. Rejection was better for tighter membranes, but was not affected by membrane zeta potential. Flux decreased with increasing PFOS concentration. While the flux reduction was severe for a loose RO membrane probably due to its higher initial flux, very stable flux was maintained for tighter membranes. At a very high feed concentration (about 500 ppm), all the membranes exhibited an identical stable flux. Isopropyl alcohol, present in some semiconductor wastewaters, had a detrimental effect on membrane flux. Where present it needs to be removed from the wastewater prior to using RO membranes.     

Organic fouling and chemical cleaning of nanofiltration membranes: measurements and mechanisms

Fouling and subsequent chemical cleaning of nanofiltration (NF) membranes used in water quality control applications are often inevitable. To unravel the mechanisms of organic fouling and chemical cleaning, it is critical to understand the foulant-membrane, foulant-foulant, and foulant-cleaning agent interactions at the molecular level. In this study, the adhesion forces between the foulant and the membrane surface and between the bulk foulant and the fouling layer were determined by atomic force microscopy (AFM). A carboxylate modified AFM colloid probe was used as a surrogate for humic acid, the major organic foulant in natural waters. The interfacial force data were combined with the NF membrane water flux measurements to elucidate the mechanisms of organic fouling and chemical cleaning. A remarkable correlation was obtained between the measured adhesion forces and the fouling and cleaning behavior of the membrane under various solution chemistries. The AFM measurements further confirmed that divalent calcium ions greatly enhance natural organic matter fouling by complexation and subsequent formation of intermolecular bridges among organic foulant molecules. Efficient chemical cleaning was achieved only when the calcium ion bridging was eliminated as a result of the interaction between the chemical cleaning agent and the fouling layer. The cleaning efficiency was highly dependent on solution pH and the concentration of the chemical cleaning agent.     

Removal of pharmaceutical and personal care products from reverse osmosis retentate using advanced oxidation processes

The application of reverse osmosis (RO) in water intended for reuse is promising for assuring high water quality. However, one significant disadvantage is the need to dispose of the RO retentate (or reject water). Studies focusing on Pharmaceutical and Personal Care Products (PPCPs) have raised questions concerning their concentrations in the RO retentate. Advanced oxidation processes (AOPs) are alternatives for destroying these compounds in retentate that contains high concentration of effluent organic matter (EfOM) and other inorganic constituents. Twenty-seven PPCPs were screened in a RO retentate using solid phase extraction (SPE) and UPLC-MS/MS, and detailed degradation studies for 14 of the compounds were obtained. Based on the absolute hydroxyl radical (HO?) reaction rate constants for individual pharmaceutical compounds, and that of the RO retentate (EfOM and inorganic constituents), it was possible to model their destruction. Using excitation-emission matrix (EEM) fluorescence spectroscopy, the HO? oxidation of the EfOM could be observed through decreases in the retentate fluorescence. The decrease in the peak normally associated with proteins correlated well with the removal of the pharmaceutical compounds. These results suggest that fluorescence may be a suitable parameter for monitoring the degradation of PPCPs by AOPs in RO retentates.     

Flux decline during nanofiltration of organic components in aqueous solution

Flux decline due to interaction of the membrane with the feed solution is a major drawback for the use of nanofiltration in environmental applications. This paper studies different mechanisms of flux decline for the nanofiltration of aqueous solutions containing organic compounds. The resistance model for flux decline is used: different mechanisms contribute through an increase of the resistance of the membrane against mass transport. The focus in this research is on pore blocking and adsorption inside the membrane pores. Osmotic pressure is also taken into account as it decreases the driving force. The nanofiltration membranes used were NF70 (Dow), UTC-20 and UTC-60 (Toray Ind.), and NTR 7450 (Nitto-Denko). Experiments with different organic components in aqueous solution showed that adsorption resulted in a strong decrease of the water flux. The results of the flux decline as a function of the concentration could well be fitted with the Freundlich equation for adsorption. The components that showed the largest effect had the highest polarity (permanent dipole moment or polarizability), which indicates that adsorption is favored by the polarity of the components in solution. Moreover, the molecules with a size similar to the pore size had a stronger effect on the water flux than other molecules. This can be explained by blocking of the pores by adsorbed compounds.     

Evaluation of membrane fouling for in-line filtration of oil sands process-affected water: the effects of pretreatment conditions

Membrane filtration is an effective reclamation option for oil sands process-affected water (OSPW). However, fresh OSPWs contain suspended solids and inorganic constituents in suspended and dissolved forms that can severely foul membranes. Pretreatment of OSPW with coagulation-flocculation (CF) was investigated to determine the effects of different coagulant aids (anionic, cationic, and nonionic polymers) on membrane surface properties and fouling. Our results showed that CF pretreatment effectively enhanced nanofiltration (NF) and reverse osmosis (RO) membrane permeate flux and salt rejection ratio through reducing membrane fouling. It was shown that coagulants and coagulant aids applied to OSPW feedwater can affect membrane physicochemical properties (surface hydrophilicity, zeta potential, and morphology), membrane performance, and the fouling indexes. Membrane rejection of ionic species increased significantly with the inclusion of an anionic coagulant aid and slightly with a cationic coagulant aid. Among three coagulant aids tested, anionic coagulant aids led to the most enhanced membrane performance through increasing membrane surface negativity and decreasing the formation of a fouling layer. Conversely, although cationic coagulant aids were the most effective in reducing OSPW turbidity, the application of cationic coagulant aids promoted the adsorption of foulants on membrane surfaces.     

Membrane Processing Technology in the Food Industry: Food Processing,Wastewater Treatment,and Effects on Physical,Microbiological, Organoleptic,and Nutritional Properties of Foods

Membrane processing technology (MPT) is increasingly used nowadays in a wide range of applications (demineralization, desalination, stabilization, separation, deacidification, reduction of microbial load, purification, etc.) in food industries. The most frequently applied techniques are electrodialysis (ED), reverse osmosis (RO), nanofiltration (NF), ultrafiltration (UF), and microfiltration (MF). Several membrane characteristics, such as pore size, flow properties, and the applied hydraulic pressure mainly determine membranes’ potential uses. In this review paper the basic membrane techniques, their potential applications in a large number of fields and products towards the food industry, the main advantages and disadvantages of these methods, fouling phenomena as well as their effects on the organoleptic, qualitative, and nutritional value of foods are synoptically described. Some representative examples of traditional and modern membrane applications both in tabular and figural form are also provided.     

Influence of flocculation and adsorption as pretreatment on the fouling of ultrafiltration and nanofiltration membranes: application with biologically treated sewage effluent

Membrane fouling is a critical limitation on the application of membranes to wastewater reuse. This work aims to understand the fouling phenomenon which occurs in ultrafiltration (UF; 17500 molecular weight cutoff (MWCO)) and nanofiltration (NF; 250 MWCO) membranes, with and without pretreatment. For this purpose, the molecular weight (MW) distribution of the organics has been used as a parameter to characterize the influent, the permeate, and the foulant on the membrane surface. The variation of foulant concentration on the membrane due to pretreatment of the influent by flocculation and/or adsorption was investigated in detail. With the UF membrane, the peak of the MW distribution of organics in the permeate depended on the pretreatment; for example, the weight-averaged MW (Mw) of 675 without pretreatment shifted down to 314 with pretreatment. In the case of the NF membrane, the Mw of organics in the permeate was 478 (without pretreatment) and 310 (with flocculation followed by adsorption). The Mw of the organics in the foulant on the membrane surface was 513 (UF) and 192 (NF) without pretreatment and 351 (UF) and 183 (NF) after pretreatment with flocculation followed by adsorption, respectively. Without the pretreatment, the foulant concentration was higher on both membranes. The difference was more significant on the UF membrane than on the NF membrane. For both membranes, the flocculation-and-then-adsorption pretreatment proved very effective.     

Selective coagulant recovery from water treatment plant residuals using Donnan membrane process

Fouling of membrane surfaces by particulate matter and large organic molecules is relatively common for pressure-driven membrane processes, namely, reverse osmosis (RO), nanofiltration (NF), and ultrafiltration (UF). Donnan membrane process (DMP) or Donnan Dialysis is driven by electrochemical potential gradient across a semipermeable ion exchange membrane. Theoretically, DMP is not susceptible to fouling by fine particulates and/or large organic molecules. According to information available in the open literature, however, DMP has not been tried to treat slurry or sludge with relatively high concentration of suspended solids or large organic molecules. This study presents the salient results of an extensive investigation pertaining to selective alum recovery from water treatment residuals (WTR) using DMP. Water treatment plants use alum, Al2(SO4)3 x 14H2O, as a coagulant, alum being finally converted and discharged as insoluble aluminum hydroxide along with natural organic matters (NOM), suspended solids, and other trace impurities. One commercial cation exchange membrane, namely Nafion 117 from DuPont Chemical Co., was used in the study for treating WTR obtained from two different water treatment plants in Pennsylvania. A series of laboratory tests confirmed that over 70% of alum is easily recoverable, and recovered alum is essentially free of particulate matter, NOM, and other trace metals. Most importantly, after repeated usage in the presence of high concentration of NOM and suspended solids, there was no noticeable decline in aluminum flux through the membrane, i.e., membrane surface fouling was practically absent. The DMP process involves coupled transport of Al3+ and H+ across the cation exchange membrane, and intramembrane transport was the rate-limiting step. Experimentally determined aluminum-hydrogen interdiffusion coefficient (D(Al-H)) values within the membrane were quite high (approximately 10(-6) cm2/s) under representative conditions, thus confirming high alum recovery rate. DMP was also found equally effective in recovering Fe(III) based coagulants from WTR.     

黄浆水中功能性成分和主要污染物在组合膜分离中的再分布

为了进一步开展豆制品加工高浓废水的再资源化研究,对黄浆水进行超滤、纳滤和反渗透组合膜处理,并分析各个膜分离单元功能性成分的再分布情况和主要污染物指标的变化。结果显示,超滤单元可以实现糖与蛋白质的分离、不同分子量蛋白质的分离,纳滤单元可截留原液中绝大部分的大豆低聚糖,大豆异黄酮和大豆皂苷的再分离贯穿了所有膜分离单元,纳滤截留液中活性成分多、相对含量高,可进一步分离纯化,反渗透单元出水COD累计去除率达99.6%。