Recent advances in membrane bioreactors (MBRs): Membrane fouling and membrane material

Membrane bioreactors (MBRs) have been actively employed for municipal and industrial wastewater treatments. So far, membrane fouling and the high cost of membranes are main obstacles for wider application of MBRs. Over the past few years, considerable investigations have been performed to understand MBR fouling in detail and to develop high-flux or low-cost membranes. This review attempted to address the recent and current developments in MBRs on the basis of reported literature in order to provide more detailed information about MBRs. In this paper, the fouling behaviour, fouling factors and fouling control strategies were discussed. Recent developments in membrane materials including low-cost filters, membrane modification and dynamic membranes were also reviewed. Lastly, the future trends in membrane fouling research and membrane material development in the coming years were addressed.     

Influence of filtration conditions on membrane fouling and scouring aeration effectiveness in submerged membrane bioreactors to treat municipal wastewater

Membrane fouling and scouring aeration effectiveness were studied using three large pilot-scale submerged membrane bioreactors (MBRs) operated at a series of permeate fluxes, scouring aeration intensities and cyclic aeration frequencies to treat municipal wastewater. The results showed that when operated at the sustainable conditions, the MBRs had a stable reversible fouling resistance. At unsustainable conditions, the reversible fouling resistance increased exponentially as filtration progressed. For each of above two cases, the fouling ratios newly defined by Eqs. (7) and (8) were calculated from the transmembrane pressure increases to compare the relative reversible fouling rates. With the range of sustainable filtration conditions, the fouling ratios at the same reference scouring aeration intensity were found to be proportional to permeate flux. Similarly, the fouling ratios calculated with the same reference permeate flux decreased exponentially with increasing scouring aeration intensity. Moreover, the effects of scouring aeration intensity and permeate flux on the fouling ratios were found to be independent of one another. As a result, an empirical relationship was derived to relate the stable reversible fouling resistance to sustainable permeate fluxes and scouring aeration intensities. Its application was demonstrated by constructing transmembrane pressure contours overlaid with scouring aeration effectiveness contours to aid in the selection of optimal MBR filtration conditions.     

Sludge properties and their effects on membrane fouling in submerged anaerobic membrane bioreactors (SAnMBRs)

Two submerged anaerobic membrane bioreactors (SAnMBRs) (thermophilic vs. mesophilic) were operated for a period of 3.5 months with kraft evaporator condensate at a feed chemical oxygen demand of 10,000 mg/L. The results show that the filtration behavior of the two systems was significantly different. The filtration resistance in the thermophilic SAnMBR was about 5–10 times higher than that of the mesophilic system when operated under similar hydrodynamic conditions. Comparison of sludge properties and cake layer structure from the two systems was made to elucidate major factors governing the different filtration characteristics. There were more soluble microbial products (SMP) and biopolymer clusters (BPC) produced and a larger portion of fine flocs (<15 μm) in the thermophilic SAnMBR. Analysis of bound extracellular polymeric substances (EPS) showed that the thermophilic sludge had a higher protein/polysaccharide ratio in EPS, as compared to that in the mesophilic sludge. A series of analyses, including Fourier transform infrared (FTIR) spectroscopy, energy dispersive X-ray spectroscopy (EDX), confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), atomic force microscopy (AFM) and particle size analyzer showed that the cake layer formed in the thermophilic SAnMBR contained higher levels of both organic and inorganic foulants, smaller particle sizes, and especially, a denser and more compact sludge cake structure. These results indicate that floc size, SMP, BPC, bound EPS as well as cake layer structure are the major factors governing membrane fouling in SAnMBR systems.     

Extracellular polymeric substances (EPS) properties and their effects on membrane fouling in a submerged membrane bioreactor

A pilot-scale submerged membrane bioreactor (MBR) for real municipal wastewater treatment was operated for over one year in order to investigate extracellular polymeric substances (EPS) properties and their role in membrane fouling. The components and properties of bound EPS were examined by the evaluation of mean oxidation state (MOS) of organic carbons, Fourier transform infrared (FT-IR) spectroscopy, three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy, and gel filtration chromatography (GFC), etc. Test results showed that MOS of organic carbons in the bound EPS was ranging from −0.14 to −0.51, and major components could be assessed as proteins and carbohydrates. FT-IR analysis confirmed the presence of proteins and carbohydrates in the bound EPS. The organic substances with fluorescence characteristics in the bound EPS were identified as proteins, visible humic acid-like substances and fulvic acid-like substances by EEM technology. GFC analysis demonstrated that EPS had part of higher MW molecules and a broader MW distribution than the influent wastewater. It was also found that a high shear stress imposed on mixed liquor could result in the release of EPS, which would in turn influence membrane fouling in MBRs. Bound EPS solution was observed to have a stronger potential of fouling than mixed liquor. During long-term operation of the MBR, bound EPS demonstrated positive correlations with membrane fouling while temperature was verified as a negative factor affecting EPS concentration. Compared to tightly bound EPS (TB-EPS), loosely bound EPS (LB-EPS) showed more significant correlations with membrane fouling. This critical investigation would contribute towards a better understanding of the behavior, composition and fouling potential of EPS in MBR operation.     

Fate of aromatic hydrocarbons in Italian municipal wastewater systems: An overview of wastewater treatment using conventional activated-sludge processes (CASP) and membrane bioreactors (MBRs)

We studied the occurrence, removal, and fate of 16 polycyclic aromatic hydrocarbons (PAHs) and 23 volatile organic compounds (VOCs) in Italian municipal wastewater treatment systems in terms of their common contents and forms, and their apparent and actual removal in both conventional activated-sludge processes (CASP) and membrane bioreactors (MBRs). We studied five representative full-scale CASP treatment plants (design capacities of 12 000 to 700 000 population-equivalent), three of which included MBR systems (one full-scale and two pilot-scale) operating in parallel with the conventional systems. We studied the solid-liquid partitioning and fates of these substances using both conventional samples and a novel membrane-equipped automatic sampler. Among the VOCs, toluene, ethylbenzene, xylenes, styrene, 1,2,4-trimethylbenzene, and 4-chlorotoluene were ubiquitous, whereas naphthalene, acenaphthene, fluorene, and phenanthrene were the most common PAHs. Both PAHs and aromatic VOCs had removal efficiencies of 40-60% in the headworks, even in plants without primary sedimentation. Mainly due to volatilization, aromatic VOCs had comparable removal efficiencies in CASP and MBRs, even for different sludge ages. MBRs did not enhance the retention of PAHs sorbed to suspended particulates compared with CASPs. On the other hand, the specific daily accumulation of PAHs in the MBR’s activated sludge decreased logarithmically with increasing sludge age, indicating enhanced biodegradation of PAHs. The PAH and aromatic VOC contents in the final effluent are not a major driver for widespread municipal adoption of MBRs, but MBRs may enhance the biodegradation of PAHs and their removal from the environment.     

Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment

In this paper we report on the performances of full-scale conventional activated sludge (CAS) treatment and two pilot-scale membrane bioreactors (MBRs) in eliminating various pharmaceutically active compounds (PhACs) belonging to different therapeutic groups and with diverse physico-chemical properties. Both aqueous and solid phases were analysed for the presence of 31 pharmaceuticals included in the analytical method. The most ubiquitous contaminants in the sewage water were analgesics and anti-inflammatory drugs ibuprofen (14.6-31.3 μg/L) and acetaminophen (7.1-11.4 μg/L), antibiotic ofloxacin (0.89-31.7 μg/L), lipid regulators gemfibrozil (2.0-5.9 μg/L) and bezafibrate (1.9-29.8 μg/L), β-blocker atenolol (0.84-2.8 μg/L), hypoglycaemic agent glibenclamide (0.12-15.9 μg/L) and a diuretic hydrochlorothiazide (2.3-4.8 μg/L). Also, several pharmaceuticals such as ibuprofen, ketoprofen, diclofenac, ofloxacin and azithromycin were detected in sewage sludge at concentrations up to 741.1, 336.3, 380.7, 454.7 and 299.6 ng/g dry weight. Two pilot-scale MBRs exhibited enhanced elimination of several pharmaceutical residues poorly removed by the CAS treatment (e.g., mefenamic acid, indomethacin, diclofenac, propyphenazone, pravastatin, gemfibrozil), whereas in some cases more stable operation of one of the MBR reactors at prolonged SRT proved to be detrimental for the elimination of some compounds (e.g., β-blockers, ranitidine, famotidine, erythromycin). Moreover, the anti-epileptic drug carbamazepine and diuretic hydrochlorothiazide by-passed all three treatments investigated.Furthermore, sorption to sewage sludge in the MBRs as well as in the entire treatment line of a full-scale WWTP is discussed for the encountered analytes. Among the pharmaceuticals encountered in sewage sludge, sorption to sludge could be a relevant removal pathway only for several compounds (i.e., mefenamic acid, propranolol, and loratidine). Especially in the case of loratidine the experimentally determined sorption coefficients (K_ds) were in the range 2214-3321 L/kg (mean). The results obtained for the solid phase indicated that MBR wastewater treatment yielding higher biodegradation rate could reduce the load of pollutants in the sludge. Also, the overall output load in the aqueous and solid phase of the investigated WWTP was calculated, indicating that none of the residual pharmaceuticals initially detected in the sewage sludge were degraded during the anaerobic digestion. Out of the 26 pharmaceutical residues passing through the WWTP, 20 were ultimately detected in the treated sludge that is further applied on farmland.     

Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM)

An understanding of natural organic matter (NOM) as a membrane foulant and the behavior of NOM components in low-pressure membrane fouling are needed to provide a basis for appropriate selection and operation of membrane technology for drinking water treatment. Fouling by NOM was investigated by employing several innovative chemical and morphological analyses.

Source (feed) waters with a high hydrophilic (HPI) fraction content of NOM resulted in significant flux decline. Macromolecules of a relatively hydrophilic character (e.g. polysaccharides) were effectively rejected by low-pressure membranes, suggesting that macromolecular compounds and/or colloidal organic matter in the hydrophilic NOM fraction may be a problematic foulant of low-pressure membranes. Moreover, the significant organic fouling that is contributed by polysaccharides and/or proteins in macromolecular and/or colloidal forms depends on molecular shape (structure) as well as size (i.e. molecular weight). More significant flux decline was observed in microfiltration (MF) compared to ultrafiltration (UF) membrane filtration. MF membrane fouling may be caused by pore blockage associated with large (macromolecular) hydrophilic molecules and/or organic colloids. In the case of UF membranes, the flux decline may be caused by sequential or simultaneous processes of surface (gel layer) coverage during filtration. Morphological analyses support the notion that membrane roughness may be considered as a more important factor in membrane fouling by controlling interaction between molecules and the membrane surface, compared to the hydrophobic/hydrophilic character of membranes. Membrane fouling mechanisms are not only a function of membrane type (MF versus UF) but also depend on source (feed) water characteristics.     

Surface modification of polypropylene macroporous membrane to improve its antifouling characteristics in a submerged membrane-bioreactor: H(2)O plasma treatment

To improve the antifouling characteristics of polypropylene hollow fiber macroporous membranes in a submerged membrane-bioreactor for wastewater treatment, the membranes were surface modified by H₂O plasma treatment. Structural and morphological changes on the membrane surface were characterized by X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE-SEM). The change of surface wettability was monitored by contact angle measurement. The static water contact angle of the modified membrane reduced obviously with the increase of plasma treatment time. The total surface free energy and its dispersive component decreased, while the polar component increased with the increase of treatment time. The relative pure water flux for the modified membranes increased gradually with the increase of plasma treatment time. The tensile strength and the tensile elongation at break for the membranes decreased after plasma treatment. After continuous operation in a submerged membrane-bioreactor for about 68 h, flux recovery after water and caustic cleaning, flux ratio after fouling were improved by 2.0, 3.6 and 22.0%, while reduction of flux was reduced by 1.1% for the 1 min H₂O plasma treated membrane, compared to those of the unmodified membrane.     

Ultrafiltration membrane fouling by extracellular organic matters (EOM) of Microcystis aeruginosa in stationary phase: influences of interfacial characteristics of foulants and fouling mechanisms

This paper focused on the membrane fouling caused by extracellular organic matters (EOM) which was extracted from lab-cultured Microcystis aeruginosa in stationary phase. The characteristics of EOM such as molecular weight distribution, hydrophobicity and fluorescence were measured. It was found that high molecular weight (MW) and hydrophilic organics accounted for the major parts of algal EOM which was comprised of protein-like, polysaccharide-like and humic-like substances. Ultrafiltration (UF) experiments were carried out in a stirring cell and hydrophobic polyethersulfone (PES) membranes which carried negative charge were used. Prefiltration, calcium addition and XAD fractionation were employed to change the interfacial characteristics of EOM. Then the effects of these interfacial characteristics on flux decline, reversibility and mass balance of organics were compared. Algal EOM proved to cause serious membrane fouling during UF. The fraction of algal EOM between 0.45 μm and 100 kDa contributed a significant portion of the fouling. Hydrophobic organics in EOM tended to adhere to membrane surface causing irreversible fouling, while the cake layer formed by hydrophilic organics caused greater resistance to water flow due to hydrophilic interaction such as hydrogen bond and led to faster flux decline during UF. The results also indicated that the algal EOM was negatively charged and the electrostatic repulsion could prevent organics from adhering to membrane surface. In term of fouling mechanisms, cake layer formation, hydrophobic adhesion and pore plugging were the main mechanisms for membrane fouling caused by algal EOM.     

Persistent organic pollutants (POPs) in the sewage treatment plant of Thessaloniki, northern Greece: occurrence and removal

The occurrence and the removal of persistent organic pollutants (POPs) during the conventional activated sludge treatment process were investigated in the wastewater treatment plant of the city of Thessaloniki, northern Greece. POPs of interest were seven polychlorinated biphenyls (PCBs) and 19 organochlorine pesticides. Target compounds were determined at six different points across the treatment system. Most abundant compounds in raw wastewater at all treatment stages were PCB-52, PCB-110, PCB-180 and Heptachlor-exo-epoxide. Quintozene occurred frequently but in relatively low concentrations. Hexachlorocyclohexanes, DDT and its metabolites (DDE, DDD) and Aldrin, Dieldrin, Endrin, Isodrin ("Drins") were found at medium or low frequencies and in concentrations close to their detection limits. Removal percentages throughout the whole treatment process ranged from 65% to 91% for individual POP species. Significant linear relationship was observed between removal efficiency and log Kow for PCBs suggesting that compounds with a strong hydrophobic character are principally removed through sorption to sludge particles and transfer to the sludge processing systems. Total PCBs' concentrations in sewage sludge ranged between 185 and 765 ng g(-1) dw being below the EU limit for use of sludge in agriculture.     

Analysis of N-nitrosamines and other nitro(so) compounds in water by high-performance liquid chromatography with post-column UV photolysis/Griess reaction

Despite their potential carcinogenicity and probable formation during water disinfection processes, little is known about the occurrence of other nitro(so) compounds than a few specific N-nitroso compounds such as N-nitrosodimethylamine (NDMA). An analytical method was developed to monitor various nitro(so) compounds including N-nitrosamines based on the Griess colorimetric determination of nitrite generated by UV-254 nm photolysis of nitro(so) compounds after separation by HPLC (HPLC-Post Column UV photolysis/Griess reaction (HPLC-PCUV)). To differentiate N-nitro(so) compounds (i.e. UV-labile) from other nitro(so) and N-containing compounds (i.e. UV-resistant), a pre-treatment was established by photolyzing solid-phase extracted samples at 254 nm (1000 mJ/cm²) and thus removing N-nitro(so) compounds selectively. Considering a 1000-fold concentration factor and extraction efficiencies (57–83%) during solid phase extraction, the method detection limits ranged from 4 to 28 ng/L for dimethylnitramine and eight N-nitrosamines (EPA 8270 nine nitrosamines mixture except for N-nitrosodiphenylamine). For four pool waters, the UV-resistant groups accounted for more than 78% of the estimated total concentration of nitro(so) and other N-containing compounds (6.1–48.6 nM). Only one unknown UV-labile compound was detected in one pool water (2.0–7.9 nM). NDMA was most frequently detected and N-nitrosodipropylamine (NDPA) and N-nitrosodibutylamine (NDBA) were additionally detected in one pool water. Chloramination of a secondary wastewater effluent with NDMA (0.2 nM) and UV-resistant compounds (7.9 nM) from a pilot-scale municipal wastewater treatment plant led to a significant formation of not only unidentified UV-resistant compounds (67.8 nM) and UV-labile compounds (14.6 nM), but also identified nitrosamines such as NDMA (4.3 nM), N-nitrosopiperidine (1.8 nM), NDPA (0.5 nM), and NDBA (0.5 nM). Overall, the novel HPLC-PCUV system is a powerful screening tool for the detection of (un)known N-nitro(so) as well as other nitro(so) and UV-induced nitrite-producing compounds.