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.     

Relating organic fouling of reverse osmosis membranes to intermolecular adhesion forces

Organic fouling of reverse osmosis (RO) membranes and its relation to foulant--foulant intermolecular adhesion forces has been investigated. Alginate and Suwannee River natural organic matter were used as model organic foulants. Atomic force microscopy was utilized to determine the adhesion force between bulk organic foulants and foulants deposited on the membrane surface under various solution chemistries. The measured adhesion force was related to the RO fouling rate determined from fouling experiments under solution chemistries similar to those used in the AFM measurements. A remarkable correlation was obtained between the measured adhesion force and the fouling rate under the solution chemistries investigated. Fouling was more severe at solution chemistries that resulted in larger adhesion forces, namely, lower pH, higher ionic strength, presence of calcium ions (but not magnesium ions), and higher mass ratio of alginate to Suwannee River natural organic matter. The significant adhesion force measured with alginate in the presence of calcium ions indicated the formation of a crossed-linked alginate gel layer during fouling through intermolecular bridging among alginate molecules.     

Mechanism involved in the evolution of physically irreversible fouling in microfiltration and ultrafiltration membranes used for drinking water treatment

Control of membrane fouling is important for more efficient use of membranes in water treatment. Control of physically irreversible fouling, which is defined as fouling that requires chemical cleaning to be cancelled, is particularly important for reduction of operation cost in a membrane process. In this study, a long-term filtration experiment using three different types of MF and UF membranes was carried out at an existing water purification plant, and the evolution of physically irreversible fouling was investigated. The experimental results demonstrated that the extent of physically irreversible fouling differed significantly depending on the membrane type. Cleaning of the fouled membranes with various chemical reagents demonstrated that organic matter was mainly responsible for physically irreversible fouling. Organic matter that had caused physically irreversible fouling in the long-term operation was desorbed from the fouled membranes and was subjected to Fourier transform infrared and 13C nuclear magnetic resonance analyses. These analyses revealed that carbohydrates were dominant in the membrane foulant regardless of the type of membrane. Based on measurements of molecular weight distribution of organic matter in the feedwater and the permeates from the membranes, a two-step fouling mechanism is proposed to explain the dominance of carbohydrates in the foulant: hydrophobic (humic-like) components with small molecular weight are first adsorbed on the membrane and, consequently, narrow the size of micro-pores of membranes, and then hydrophilic (carbohydrate-like) compounds with larger molecular weight plug the narrowed pores or the hydrophilic compounds are adsorbed onto the membrane surface conditioned by the hydrophobic components.     

Modes of natural organic matter fouling during ultrafiltration

The fouling of ultrafiltration membranes by natural organic matter (NOM), isolated from a potable surface water source, was studied with an emphasis on elucidating fouling modes and the role of aggregates. NOM size was related to membrane pore sizes using parallel membrane fractionation and size exclusion chromatography, such analyses confirmed the predominance of low MW species and identified the presence of aggregates in concentrated NOM solutions. Cake formation was the dominant mode of fouling by the unfiltered feed, which contained aggregates. This was identified by a constant rate of increase in membrane resistance with permeate throughput and was independent of pore size over a 10-1000 kDa molecular weight cutoff (MWCO) range. Prefiltration (to remove aggregates) and dilution (to reduce aggregate concentration) reduced the rate of increase in membrane resistance for the low MWCO membranes but did not change the fouling mode. In contrast, such pretreatment prevented cake formation on the larger MWCO membranes and shifted the mode of fouling to pore blockage. The date lend support for the idea that an initial fouling layer of large aggregates can catalyze the fouling by lower MW species. The fouling layer could be removed from the large MWCO membranes by backwashing, but the lower MWCO membranes exhibited some irreversible fouling, suggesting that low MW species penetrated into the pore structure. A combined pore blockage-cake formation model described the data well and provided insight into how fouling modes evolve during filtration.     

Effects of palm oil-based fatty acids on fouling of ultrafiltration membranes during the clarification of glycerin-rich solution

Ultrafiltration (UF) is an alternative option that can be used to clarify glycerin-rich solutions in the oleochemical industry. However, the UF membranes used in the process were observed to have been seriously fouled in our preliminary study. Thus, the ultrafiltration of a glycerol-water-fatty acid mixture was carried out to investigate the membrane binding properties of the components and their contributions to membrane fouling. Palmitic, stearic, and oleic acid were used as fouling substances in the glycerol-water mixture. The flux decline experiments were carried out using polyvinylidenefluoride (PVDF) as well as polyethersulphone (PES) membranes with a MWCO of 30 and 25 kDa, respectively at specific conditions (T = 40 °C; ΔP = 2 bar). It was found that the PES membrane exhibited severe fouling for all types of fatty acids in solution with glycerol-water. As the pH decreased to acidic conditions, the PES membrane tended to exhibit more severe fouling than the PVDF membrane.     

Fouling and natural organic matter removal in adsorbent/membrane systems for drinking water treatment

Adsorbent particles added to ultrafiltration (UF) systems treating drinking water can remove natural organic matter (NOM) and some other contaminants from the water, but their effect on membrane fouling is inconsistent-in some cases, fouling is reduced, and in others, it is exacerbated. This research investigated the behavior of UF systems to which powdered activated carbon (PAC), heated iron oxide particles (HIOPs), or (nonadsorbent) SiO2 particles were added. On a mass basis, the PAC removed the most NOM from solution, the HIOPs removed less, and the SiO2 removed essentially none. However, in the case of both PAC and SiO2, increasing the dose of solids led to a steady increase in fouling, whereas the opposite trend applied when HIOPs were added. In the absence of NOM, none of the solids fouled the membrane significantly. Thus, even though NOM is a causative agent for fouling, removing it from solution does not necessarily reduce fouling; the mechanism of removal can be just as important as the absolute amount removed, if the removal occurs in a cake layer near the membrane surface. Scanning electron microscopy images of the cake layers formed in the three systems suggest that the NOM binds PAC or SiO2 particles to one another and to the membrane surface, so that the particles become part of the foulant in the system. By contrast, the NOM appears to bind HIOPs to one another but not to the membrane. This process leaves enough pore space in the cake layer for water to reach the membrane with minimal resistance, and it reduces the tendency for either the NOM or the HIOPs to foul the membrane surface.     

Membrane fouling during filtration of milk––a microstructural study

The surface morphology and internal microstructure of a membrane are the result of membrane manufacturing processes and subsequent use during fluid processing in industry. Both these structural factors have a great effect on fouling and filtration performance.

In this study, scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy were used to comprehensively characterise the surface of unused microfiltration and ultrafiltration membranes, the fouled layer on the surface of membranes used for milk filtration and the internal fouling within the used membranes.

A simple and effective sample preparation method was developed to study the internal membrane structure using high-resolution field emission SEM with low-accelerating voltage. Various methods of structural characterisation were compared and the results showed that for flat sheet membranes AFM is an appropriate and convenient technique for examining the surface topography of membranes. In contrast SEM is a very appropriate technique for examining the cross-sectional and internal structure of a membrane, either unused or fouled.

Using these complimentary techniques it has been shown that internal fouling, during filtration of skim milk, proceeds by protein–polymer and protein–protein interactions. A gel layer forms on the surface of the membrane and has been imaged using SEM. This layer is slightly compressible and densifies as it grows. Fouling initiation commences after a very short filtration time.     

NOM fractionation and fouling of low-pressure membranes in microgranular adsorptive filtration

Membrane fouling by natural organic matter (NOM) was investigated in microgranular adsorptive filtration (μGAF) systems, in which a thin layer of adsorbent is predeposited on low-pressure membranes. The adsorbents tested included heated aluminum oxide particles (HAOPs), ion exchange (IX) resin, and powdered activated carbon (PAC). Size exclusion chromatography (SEC) separated the NOM into four apparent MW fractions with significant UV???. HAOPs and the IX resin performed almost identically with respect to removal of these fractions, and differently from PAC. However, while HAOPs and PAC reduced fouling substantially, IX resin did not, indicating that fouling could not be attributed to the NOM fractions detected by SEC. Rather, the key foulants appear to comprise a very small fraction of the NOM with almost no UV??? absorbance. Alginate, a strongly fouling surrogate for natural polysaccharides, is adsorbed effectively by HAOPs, but not by IX resin or PAC, suggesting that polysaccharides sometimes play a key role in membrane fouling by NOM.     

Formation of N-nitrosodimethylamine (NDMA) from humic substances in natural water

N-nitrosodimethylamine (NDMA)formation in chloraminated Iowa River water (IRW) is primarily attributed to reactions with natural organic matter (NOM) generally classified as humic substances. Experiments were conducted to determine the contribution of various NOM humic fractions to the NDMA formation potential (NDMA FP) in this drinking water source. NOM was concentrated by reverse osmosis (RO) and humic fractions were obtained by a series of resin elution procedures. Mass balances showed that nearly 90% of the NDMA formation potential could be recovered in the NOM concentrate and in water reconstituted using additions of the various humic fractions. Generally, the hydrophilic fractions tended to form more NDMA than hydrophobic fractions, and basic fractions tend to form more NDMA than acid fractions when normalized to a carbon basis. Overall, the hydrophobic acid fraction was the dominant source of NDMA when both formation efficiency and water composition were considered. The amount of NDMA formed in a sample was found to correlate linearly with an oxidation-induced decrease in specific UV absorbance (SUVA) value at 272 nm. This is consistent with a mechanism in which precursors are formed as the direct consequence of the oxidation of NOM. The NDMA FP estimated using the slope of this relationship and the initial SUVA value compared closely to the value obtained by measuring the NDMA formed in solutions dosed with excess concentrations of monochloramine that presumably exhaust all potential precursor sources. However, the NOMA FP could not be correlated to the SUVA value of the individual humic fractions indicating that the relationship of the NDMA FP to SUVA value is probably a water-specific parameter dependent on the exact composition of humic fractions. It is hypothesized that either specific NDMA precursors are distributed among the various humic fractions or that the humic material itself represents a "generic" nonspecific precursor source that requires some degree of oxidation to eventually produce NDMA. The nonmonotonic behavior of NOM fluorescence spectra during chloramination and lack of correlation between NOM fluorescence characteristics and NDMA formation limited the usage of fluorescence spectra into probing NDMA formation.     

Influence of the composition of natural organic matter on Pb bioavailability to microalgae

The current work examines the effects of model allochtonous (humic substances) and autochtonous (microbial polysaccharides) natural organic matter (NOM) on Pb speciation and bioaccumulation. The results demonstrated that polysaccharides, in particular alginic acid, had complexing properties and effects on Pb bioaccumulation by the green alga Chlorella kesslerii that were similar to equivalent complexing capacity of humic substances. Pb uptake decreased in the presence of humic, alginic, and polygalacturonic acids with respect to noncomplexed Pb, but accumulated Pb was higher than predicted from measured Pb2+ concentrations or from previous results obtained in the presence of simple synthetic ligands. An improved fit between experimental observations and Pb speciation was obtained by taking into account the formation of a ternary complex at the algal surface. The contribution of the ternary complexes to Pb bioaccumulation was dependent on the relative binding constants of the Pb to the NOM and to the binding sites on the biological surface. In the presence of the humic acid, a decreased surface charge and increased membrane permeability were considered to be of secondary importance to explain the observation of increased Pb uptake with respect to that predicted on the basis of [Pb2+]. The environmental implications of the results are discussed with respect to the development of site-specific water quality criteria.     

Effect of coagulation on the size of MF and UF membrane foulants

Microfiltration (MF) and ultrafiltration (UF) have become common water treatment technologies for the removal of particles from natural waters. Many water utilities are now integrating MF/UF with other treatment processes to provide treatment for nonparticulate contaminants. Research is needed to understand the impact that other processes have on MF/UF performance. This study was conducted to investigate the interactions between water quality, coagulation, and membrane fouling. The study examined the fouling of MF/UF membranes by natural waters with and without coagulation by specific fractions of constituents in natural water, separated by size. This research found thatthe component of natural organic matter (NOM) smaller than 100 kDa contributes relatively little to fouling during filtration of either raw or coagulated water. The fraction between 1 microm and 100 kDa contributes a significant portion of the fouling. After coagulation pretreatment, fouling due to various size fractions in the feedwater can change.     

纳米AI203溶胶的稳定性及PVDF／AI203杂化膜的性能研究

以异丙醇铝（AIP）为原料,采用溶胶-凝胶法,制备了纳米氧化铝（A1203）溶胶。研究了酸解剂、酸铝比[n（H＋）／n（Al3＋）]、陈化时间等因素对溶胶粒径和稳定性的影响,得到了制备稳定、透明纳米A1203溶胶的最佳工艺条件,即酸解剂HN03;n（H＋）／n（Al3＋）=0.18～0．25;陈化时间20h。为了改善聚偏氟乙烯（PVDF）膜的性能,通过PVDF与AIP的原位聚合,制备了不同PⅥ）F含量的PVDF／A1203杂化膜。采用扫描电镜（SEM）、原子力显微镜（AFM）、红外光谱（FI-IR）、差示扫描量热法（DSC）、热失重分析（TGA）等手段对膜的结构和性能进行了表征。结果表明：杂化膜的纯水通量随着PVDF浓度的增大呈下降趋势,截留率则随着PVDF浓度的增大逐渐升高;AIP的加入使得杂化膜两相之间存在键合,可以增强Al2O3和PVDF之间的化学连接,从而提高杂化膜的亲水性和机械强度;添加AIP后,杂化膜的热分解温度向低温移动,即杂化膜的热稳定性下降;而AIP对PVDF膜的熔点影响不明显。     

纳米Al2O3溶胶的稳定性及PVDF/Al2O3杂化膜的性能研究

以异丙醇铝(AIP)为原料,采用溶胶-凝胶法,制备了纳米氧化铝(Al2O3)溶胶。研究了酸解剂、酸铝比[n(H+)/n(Al3+)]、陈化时间等因素对溶胶粒径和稳定性的影响,得到了制备稳定、透明纳米Al2O3溶胶的最佳工艺条件,即酸解剂HNO3;n(H+)/n(Al3+)=0.18~0.25;陈化时间20 h。为了改善聚偏氟乙烯(PVDF)膜的性能,通过PVDF与AIP的原位聚合,制备了不同PVDF含量的PVDF/Al2O3杂化膜。采用扫描电镜(SEM)、原子力显微镜(AFM)、红外光谱(FI-IR)、差示扫描量热法(DSC)、热失重分析(TGA)等手段对膜的结构和性能进行了表征。结果表明:杂化膜的纯水通量随着PVDF浓度的增大呈下降趋势,截留率则随着PVDF浓度的增大逐渐升高;AIP的加入使得杂化膜两相之间存在键合,可以增强Al2O3和PVDF之间的化学连接,从而提高杂化膜的亲水性和机械强度;添加AIP后,杂化膜的热分解温度向低温移动,即杂化膜的热稳定性下降;而AIP对PVDF膜的熔点影响不明显。     

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.     

Membrane independent limiting flux for RO and NF membranes fouled by humic acid

The flux decline of reverse osmosis and nanofiltration membranes was investigated under constant pressure conditions during humic acid fouling tests. For a given membrane type under a given feedwater composition, increasing pressure resulted in increased flux reduction and foulant accumulation. A limiting flux seems to exist beyond which the membrane flux cannot be sustained. Membranes with initial fluxes greater than the limiting flux experienced severe fouling and their pseudo stable fluxes approached the limiting flux. Flux reduction was much milder when the initial flux was lower than the limiting flux. Furthermore, the limiting flux seems to be independent of membrane properties, probably due to the dominance of foulant--deposited-foulant interaction upon complete foulant coverage over membrane surfaces. On the other hand, strong dependence of the limiting flux on the feedwater composition was observed. The limiting flux was reduced at higher proton, calcium, and/or background electrolytes concentrations, likely due to reduced electrostatic repulsion under these conditions.     

Biodegradability, DBP formation, and membrane fouling potential of natural organic matter: characterization and controllability

Various natural organic matter (NOM) constituents were evaluated in terms of their biodegradability, disinfection byproduct (DBP) formation potentials, and membrane fouling. The biodegradability of NOM was evaluated with respect to biodegradable dissolved organic carbon (BDOC) and its inhibition control. NOM was divided into (i) colloidal and noncolloidal NOM, using a dialysis membrane with a molecular weight cutoff of 3500 Da and (ii) hydrophobic, transphilic, and hydrophilic NOM constituents, using XAD-8/4 resins. The colloidal, and noncolloidal hydrophilic, NOM were identified as being more problematic than the other components, exhibiting relatively higher biodegradability and reactivity toward DBP formation potential. A higher biodegradability especially can provide a high risk of membrane biofouling, if a membrane is fouled by highly biodegradable NOM. Colloidal, and noncolloidal hydrophilic, NOM constituents were also shown as major foulants of negatively charged membranes due to their high neutral fractions. Filter adsorber (F/A) types of activated carbons were evaluated in terms of removals of NOM, DBP formation potential, and BDOC and were compared to conventional processes and a nanofiltration membrane. The F/A process exhibited a comparatively good efficiency, especially in DBP and BDOC control, but was not so good at removing NOM. This suggests that F/A could potentially be combined with a membrane process to minimize the DBP formation potential and bio-/organic-fouling (i.e., F/A process as a pretreatment for a membrane process).     

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.     

Investigation of interparticle forces in natural waters: effects of adsorbed humic acids on iron oxide and alumina surface properties

The nature of interparticle forces acting on colloid particle surfaces with adsorbed surface films of the internationally used humic acid standard material, Suwannee River Humic Acid (SHA), has been investigated using an atomic force microscope (AFM). Two particle surfaces were used, alumina and a hydrous iron oxide film coated onto silica particles. Adsorbed SHA dominated the interactive forces for both surface types when present. At low ionic strength and pH > 4, the force curves were dominated by electrostatic repulsion of the electrical double layers, with the extent of repulsion decreasing as electrolyte (NaCl) concentration increased, scaling with the Debye length (kappa(-1)) of the electrolyte according to classical theory. At pH approximately 4, electrostatic forces were largely absent, indicating almost complete protonation of carboxylic acid (-COOH) functional groups on the adsorbed SHA. Under these conditions and also at high electrolyte concentration ([NaCl] > 0.1 M), the absence of electrostatic forces allowed observation of repulsion forces arising from steric interaction of adsorbed SHA as the oxide surfaces approached closely to each other (separation < 10 nm). This steric barrier shrank as electrolyte concentration increased, implying tighter coiling of the adsorbed SHA molecules. In addition, adhesive bridging between surfaces was observed only in the presence of SHA films, implying a strong energy barrier to spontaneous detachment of the surfaces from each other once joined. This adhesion was especially strong in the presence of Ca2+ which appears to bridge SHA layers on each surface. Overall, our results show that SHA is a good model for the NOM adsorbed on colloids.     

Quantifying the adhesion and interaction forces between Pseudomonas aeruginosa and natural organic matter

Atomic force microscopy (AFM) was used to characterize interactions between natural organic matter (NOM), and glass or bacteria. Poly(methacrylic acid) (PMA), soil humic Acid (SHA), and Suwannee River humic Acid (SRHA), were adsorbed to silica AFM probes. Adhesion forces (Fadh) for the interaction of organic-probes and glass slides correlated with organic molecular weight (MW), but not with radius of the organic aggregate (R), charge density (Q), or zeta potential (zeta). Two Pseudomonas aeruginosa strains with different lipopolysaccharides (LPS) were chosen: PAO1 (A+B+), whose LPS have common antigen (A-band) + O-antigen (B-band); and mutant AK1401 (A+B-). Fadh between bacteria and organics correlated with organic MW, R, and Q, but not zeta. PAO1 had lower Fadh with silica than NOM, which was attributed to negative charges from the B-band polymers causing electrostatic repulsion. AK1401 adhered stronger to silica than to the organics, perhaps because the absence of the B-band exposed underlying positively charged proteins. DLVO calculations could not explain the differences in the two bacteria or predict qualitative or quantitative trends in interaction forces in these systems. Molecular-level information from AFM studies can bring us closer to understanding the complex nature of bacterial-NOM interactions.     

采用AFM法表征芳纶短切纤维和沉析纤维表面黏附力

采用原子力显微镜(AFM)探针修饰技术,用芳纶沉析纤维薄膜对探针进行修饰,在水中测定了芳纶短切纤维和沉析纤维的表面黏附力,探究了不同pH值对芳纶短切纤维和沉析纤维表面黏附力的影响.实验结果表明,芳纶沉析纤维薄膜修饰的探针与芳纶短切纤维和沉析纤维之间的黏附力分别为1.71 nN和9.20 nN,沉析纤维分子间黏附作用力大于其与芳纶短切纤维间的黏附力,认为探针针尖与芳纶短切纤维和沉析纤维-NH-之间的相互作用与pH值相关,芳纶沉析纤维修饰的探针与芳纶沉析纤维之间的黏附力受pH值的影响较大.