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.     

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.     

Characterization of intracellular & extracellular algae organic matters (AOM) of Microcystic aeruginosa and formation of AOM-associated disinfection byproducts and odor & taste compounds

Algae organic matters (AOM), including intracellular organic matters (IOM) and extracellular organic matters (EOM), are causing numerous water quality issues, among which formation of disinfection byproducts (DBPs) and odor & taste (O&T) compounds are of particular concern. In this study, physiochemical properties of IOM and EOM of Microcystic aeruginosa under an exponential growth phase (2.01 × 10¹¹/L) were comprehensively characterized. Moreover, the yields of DBPs during AOM disinfection and O&T-causing compounds were quantified. Hydrophilic organic matters accounted for 86% and 63% of DOC in IOM and EOM, respectively. Molecular weight (MW) fractions of IOM in <1 kDa, 40-800 kDa, and >800 kDa were 27%, 42%, and 31% of DOC, respectively, while EOM primarily contained 1-100 kDa molecules. Besides, a low SUVA (0.84 L/mg m) and the specific fluorescence spectra suggested that AOM (especially IOM) was principally comprised of protein-like substances, instead of humic-like matters. The formation potentials of chloroform, chloroacetic acid, and nitrosodimethylamine were 21.46, 68.29 and 0.0096 μg/mg C for IOM, and 32.44, 54.58 and 0.0189 μg/mg C for EOM, respectively. Furthermore, the dominant O&T compound produced from EOM and IOM were 2-MIB (68.75 ng/mg C) and β-cyclocitral (367.59 ng/mg C), respectively. Of note, dimethyltrisulfide became the prevailing O & T compound following anaerobic cultivation.     

Effects of mass retention of dissolved organic matter and membrane pore size on membrane fouling and flux decline

Ultrafiltration (UF) fouling has been attributed to concentration polarization, gel layer formation as well as outer and inner membrane pore clogging. It is believed that mass of humic materials either retained on membrane surface or associated with membrane inner pore surface is the primary cause for permeate flux decline and filtration resistance build-up in water supply industries. While biofilm/biofouling and inorganic matter could also be contributing factors for permeability decline in wastewater treatment practices. The present study relates UF fouling to mass of dissolved organic matter (DOM) retained on membrane and quantifies the effect of retained DOM mass on filtration flux decline. The results demonstrate that larger pore membranes exhibit significant flux decline in comparison with the smaller ones. During a 24-h period, dissolved organic carbon mass retained in 10 kDa membranes was about 1.0 g m⁻² and that in 100 kDa membranes was more than 3 times higher (3.6 g m⁻²). The accumulation of retained DOM mass significantly affects permeate flux. It is highly likely that some DOMs bind or aggregate together to form surface gel layer in the smaller 10 kDa UF system; those DOMs largely present in inner pore and serving as pore blockage on a loose membrane (100 kDa) are responsible for severe flux decline.     

Low-pressure membrane (MF/UF) fouling associated with allochthonous versus autochthonous natural organic matter

Natural organic matter (NOM) isolates/fractions; organic colloids, and hydrophobic (HPO), transphilic (TPI), and hydrophilic (HPI) fractions; isolated from a natural surface water as an allochthonous source, and in the form of algal organic matter (AOM) derived from blue green algae as an autochthonous source, were investigated in low-pressure membrane filtration. The most significant flux decline was caused by organic colloids, with an intermediate flux decline caused by AOM derived (isolated) from ground and sonicated blue green algae. 3D fluorescence excitation-emission matrix (EEM) analyses revealed that colloids and AOM contain protein-like substances, and FTIR analyses showed overlapping peaks associated with the peptide bonds in proteins and alcohols in polysaccharides originating from extra- and/or intra-cellular materials. HP-SEC results also support a high content of apparently macromolecular compounds in the colloid fraction. The presence of a divalent cation (Ca(2+)), hypothesized to enhance fouling by NOM acids by a reduction in molecular charge, showed little effect. Morphological analyses indicated that the surface topography of fouled UF membranes was elevated, presumably due to deposition of NOM on the membrane surface. The pores of MF membranes were reduced, suggesting pore blockage and/or constriction by NOM aggregates.     

Granular iron oxide adsorbents to control natural organic matter and membrane fouling in ultrafiltration water treatment

Fine iron oxide particles (IOPs) are effective in removing natural organic matter (NOM) that causes membrane fouling in water treatment, but the separation of used IOPs is problematic. This study focused on the fabrication and use of granular iron oxide adsorbents, in combination with ultrafiltration (UF) membranes while investigating the NOM removal efficiency and fouling control. Sulfonated styrene-divinylbenzene copolymer beads were coated with two types of iron oxides (ferrihydrite and magnetite) and their performances were compared to that of fine IOPs. A significant amount of iron oxide coating (52–63 mg of Fe per g bead) was achieved by means of electrostatic binding and hydrolysis of iron ions. Iron oxide coated polymer (IOCP) beads were able to remove some amounts (～20%) of dissolved organic carbon (DOC) comparable to that achieved by IOPs within a short period of time (<15 min). Regenerated IOCPs exhibited the same sorption capacity as the fresh ones. The integrated IOCP/UF system operation with a 15-min empty bed contact time and 10-h cyclic regeneration maintained the 20% DOC removal with no sign of significant membrane fouling. In contrast, a sharp transmembrane pressure buildup occurred in the UF system when no iron oxide pretreatment was applied, regardless of the types of membranes tested. Iron oxide adsorbed the NOM fraction with molecular weights of >1000 kDa which is believed to be responsible for severe UF fouling.     

A polishing hybrid AER/UF membrane process for the treatment of a high DOC content surface water

The efficacy of a combined AER/UF (Anion Exchange Resin/Ultrafiltration) process for the polishing treatment of a high DOC (Dissolved Organic Carbon) content (>8 mgC/L) surface water was investigated at lab-scale using a strong base AER. Both resin dose and bead size had a significant impact on the kinetic removal of DOC for short contact times (i.e. <15 min). For resin doses higher than 700 mg/L and median bead sizes below 250 μm DOC removal remained constant after 30 min of contact time with very high removal rates (80%). Optimum AER treatment conditions were applied in combination with UF membrane filtration on water previously treated by coagulation-flocculation (i.e. 3 mgC/L). A more severe fouling was observed for each filtration run in the presence of AER. This fouling was shown to be mainly reversible and caused by the progressive attrition of the AER through the centrifugal pump leading to the production of resin particles below 50 μm in diameter. More important, the presence of AER significantly lowered the irreversible fouling (loss of permeability recorded after backwash) and reduced the DOC content of the clarified water to l.8 mgC/L (40% removal rate), concentration that remained almost constant throughout the experiment.     

Algal-derived organic matter as precursors of disinfection by-products and mutagens upon chlorination

Algal-derived organic materials (including algal cells, hydrophilic and hydrophobic proteins) from Chlamydomonas sp. (a common green alga in local reservoirs), were chlorinated in the laboratory (20 °C, pH 7, Cl₂/DOC ratio of 20 mg Cl₂ mg⁻¹). Levels of disinfection by-products and mutagenicity (via Salmonella T100 mutation assay, -S9) over 2 h of chlorination time were determined. The hydrophilic proteins were more effective precursors of chloroform (35.9 μmol L⁻¹ at 120 min), 35 times greater than that from the hydrophobic proteins; whereas the hydrophobic proteins were more potent precursors of direct-acting mutagens (maximum level of 50.1 rev μL⁻¹ at 30 s) than the hydrophilic proteins (maximum level of 3.38 rev μL⁻¹ at 60 min). The mutagenicity of the chlorinated solutions generally reached a peak level shortly after chlorination and then declined afterwards, a pattern different from that of chloroform generation. The results indicate that algal hydrophilic proteins, containing low aromaticity and difficult to be removed via coagulation/flocculation, are important chloroform precursors. It is also suggested that hydrophobic organic intermediates with low molecular weight formed during chlorination may serve as the direct-acting mutagens.     

Assessing PAC contribution to the NOM fouling control in PAC/UF systems

This paper investigates the powdered activated carbon (PAC) contribution to the fouling control by natural organic matter (NOM) in PAC/UF hybrid process, as well as the foulant behaviour of the PAC itself. Solutions of NOM surrogates (humic acids, AHA, and tannic acid, TA) and AOM/EOM (algogenic organic matter/extracellular organic matter) fractions from a Microcystis aeruginosa culture were permeated through an ultrafiltration (UF) hollow-fibre cellulose acetate membrane (100 kDa cut-off). The greatest impairment on flux and the poorest rejection were associated with polysaccharide-like EOM substances combined with mono and multivalent ions. PAC, either in the absence or in the presence of NOM, did not affect the permeate flux nor the reversible membrane fouling, regardless of the NOM characteristics (hydrophobicity and protein content) and water inorganics. However, PAC controlled the irreversible membrane fouling, minimising the chemical cleaning frequency. Furthermore, PAC enhanced AHA and TA rejections and the overall removal of AOM, although it was apparently ineffective for the highly hydrophilic EOM compounds.     

Characterization of algal organic matter and formation of DBPs from chlor(am)ination

The frequent occurrence of algal blooms in drinking water reservoirs causes problems to water supply, one of which is the release of algal organic matter in high concentrations to affect drinking water quality. Algal organic matter, including extracellular organic matter (EOM) and intracellular organic matter (IOM), was characterized. The formation of a variety of disinfection by-products (DBPs) in chlorination and chloramination of EOM, IOM and algal cells was evaluated. Natural organic matter (NOM) isolated from Suwannee River was also studied for comparison. EOM and IOM were rich in organic nitrogen, which consisted of high (over 10 kDa) and low (70–1000 Da) molecular weight (MW) organic matter, whilst the MW of organic carbon in EOM and IOM was relatively lower. IOM had a higher fraction of total organic nitrogen, with larger proportions of higher MW and more hydrophobic contents than did EOM. IOM also contained higher fractions of free amino acids but lower fractions of aliphatic amines than did EOM. During chlorination of EOM and IOM, organic chloramines were first formed and then became undetectable after 1 d. Chlorination of EOM and IOM produced more nitrogenous DBPs (N-DBPs) and haloaldehydes and less carbonaceous DBPs (C-DBPs) than did chlorination of NOM. Organic chloramines were found after 3-d chloramination of EOM and IOM. The amounts of N-DBPs and C-DBPs formed from chloramination of EOM or IOM were much less than that from NOM. EOM produced less DBPs (except for trichloronitromethane) than did IOM and algal cells in chlorination and chloramination.     

Adsorption combined with ultrafiltration to remove organic matter from seawater

Organic fouling and biofouling are the major severe types of fouling of reverse osmosis (RO) membranes in seawater (SW) desalination. Low pressure membrane filtration such as ultrafiltration (UF) has been developed as a pre-treatment before reverse osmosis. However, UF alone may not be an effective enough pre-treatment because of the existence of low-molecular weight dissolved organic matter in seawater. Therefore, the objective of the present work is to study a hybrid process, powdered activated carbon (PAC) adsorption/UF, with real seawater and to evaluate its performance in terms of organic matter removal and membrane fouling. The effect of different PAC types and concentrations is evaluated. Stream-activated wood-based PAC addition increased marine organic matter removal by up to 70% in some conditions. Moreover, coupling PAC adsorption with UF decreased UF membrane fouling and the fouling occurring during short-term UF was totally reversible. It can be concluded that the hybrid PAC adsorption/UF process performed in crossflow filtration mode is a relevant pre-treatment process before RO desalination, allowing organic matter removal of 75% and showing no flux decline for short-term experiments.     

Autopsy of high-pressure membranes to compare effectiveness of MF and UF pretreatment in water reclamation

A pilot-plant study was designed to compare the effectiveness of microfiltration (MF) and ultrafiltration (UF) as pretreatment for high-pressure membranes in reclamation of biologically treated wastewater effluent. Granular media, filtered secondary effluent from a full-scale wastewater treatment plant, was fed to MF and UF units that operated in parallel. Each of these filtrates served as the feedwater to two reverse osmosis (RO) units and one nanofiltration (NF) unit that operated in parallel. The decline in specific flux was substantially lower for high-pressure membranes receiving UF than MF pretreatment over the course of each of four pilot plant runs that lasted from 1 to 7 weeks. The removal of organic matter as measured by dissolved organic carbon (DOC) was somewhat higher by UF than MF pretreatment (about 15% by UF compared with 11% by MF). Addition of ferric chloride ahead of the UF unit, but not ahead of the MF unit, may account for this additional removal of organic matter. However, the additional DOC removal appeared insufficient to explain the differential in foulant accumulation between high-pressure membranes receiving UF and MF pretreatment. Extensive autopsy analyses of these high-pressure membranes showed from 35% to 56% less organic carbon on those receiving UF rather than MF pretreatment. A more specific indicator of a differential in organic fouling was the accumulation of polysaccharides and this showed from 27% to 38% less on UF- than on MF-pretreated membranes. Yet another possible source of foulants is inorganic material given that the inorganic and organic weight percentages were nearly equal (56% vs. 44%) on the membrane surface. One specific source was aluminum added for phosphorus removal. Less fouling of high-pressure membranes pretreated by UF than MF could be due to the following: (1) a small, but very important, colloidal fouling fraction may have passed through MF but was rejected by UF pretreatment; (2) organic fouling was not related to organics in either the MF or UF filtrates but rather to organics that are generated in situ by microbial activity on the membrane surface; and/or (3) less passage of colloidal Al-P that carried over from secondary wastewater treatment.     

Photodegradation of estrone enhanced by dissolved organic matter under simulated sunlight

In the present work the degradation of estrone (E1) a natural estrogenic hormone has been studied under simulated solar irradiation. The photodegradation of E1 has been investigated in the absence and in the presence of 7.7-8.9 mg L⁻¹ of dissolved organic carbon (DOC), under solar light simulation with irradiance approximating that of the sun. DOC extracts from different origins have been used. Half-lives ranging between 3.9 h and 7.9 h were observed. Results indicated that E1 was photodegraded even in the absence of DOC. The presence of DOC was found to enhance the degradation of E1. Experiments performed with the addition of reactive species scavengers (azide ions and 2-propanol) have shown that these two species play a significant role in the photodegradation. Some experiments have been performed with a DOC previously submitted to solar irradiation. Changes in optical and physico-chemical properties of DOC strongly affect its photoinductive properties, and hence its efficiency on E1 degradation. A part of the study consisted in the investigation of photoproducts structures. Five photoproducts were shown by chromatographic analysis: one arising from direct photolysis and the four others from DOC photoinduced degradation.     

Characterizing algogenic organic matter (AOM) and evaluating associated NF membrane fouling

Occasional algal blooms, comprised of blue-green algae and/or green algae, cause significant challenges in drinking water treatment due to the release of algogenic organic matter (AOM) into water extracellularly and, upon cell lysis, intracellularly. AOM has been extracted from blue-green algae (cyanobacteria) by various means and analyzed by UV absorbance scanning, HPSEC-UV-fluorescence-DOC, UV absorbance ratio index (URI), FTIR, and fluorescence excitation emission matrix (EEM). AOM extracted in water as a solvent exhibited a high hydrophilic fraction (57.3%) with a low SUVA (1.0 L/m-mg). The molecular weight (MW) distribution showed a significant heterogeneity (high value of polydispersivity) and high protein content (as indicated by specific fluorescence). Significant amounts of proteinaceous components such as mycosporine-like amino acids (MAAs, UV-screening components) and phycobilins (light-harvesting pigment) were detected by UV/visible absorption. The presence of proteins was confirmed by FTIR (at 1661 and 1552 cm(-1)), EEM spectra (EX:278-282 nm and EM:304-353 nm), and high URI values (3.1-6.0). A bench-scale cross-flow unit, employing a flat-sheet membrane specimen, was used to examine nanofiltration (NF) membrane fouling and removal of natural organic matter (NOM) derived from different blends of Suwannee River humic acid (SRHA) and AOM: SRHA 10 mgC/L, AOM 3mg C/L + SRHA 7 mgC/L, AOM 7 mgC/L + SRHA 3 mgC/L, and AOM 10 mgC/L. The study focused mainly on the effects of two different sources of organic matter on NF (NF 200) membrane fouling under otherwise similar conditions. Flux decline and organic matter rejection as a function of delivered DOC (cumulative mass of feed DOC per unit area) showed significantly different results depending on the organic matter composition of samples even though the test conditions were the same (organic matter concentration, pH, temperature, inorganic salt composition and concentration, and recovery). A higher flux decline was observed with increasing proportions of AOM. Organic matter rejections also decreased with higher AOM contributions to the samples, indicating that lower molecular weight (MW) AOM components were not well rejected by the NF 200 membrane having a 360 Da MWCO. However, SRHA that exhibited a relatively high MW (1000-5000 Da range) and high SUVA (7.4 L/m-mg) was preferentially rejected through electrostatic repulsion/size exclusion by the NF 200 membrane, having a high negative charge, low MWCO, and relatively low hydrophobicity. Even though the DOC concentration of feed water is a decisive factor for membrane fouling along with membrane properties and operating conditions, the characteristics of organic matter are more influential in fouling potential. Protein-like and polysaccharide-like substances were found as major foulants by FTIR.     

Effective removal of effluent organic matter (EfOM) from bio-treated coking wastewater by a recyclable aminated hyper-cross-linked polymer

Effluent organic matter (EfOM) is a complex matrix of organic substance mainly from bio-treated sewage effluent and is considered as the main constraint to further advanced treatment. Here a recyclable aminated hyper-cross-linked polymeric adsorbent (NDA-802) featured with aminated functional groups, large specific surface area, and sufficient micropore region was synthesized for effective removal of EfOM from the bio-treated coking wastewater (BTCW), and its removal characteristics was investigated. It was found that hydrophobic fraction was the main constituent (64.8% of DOC) in EfOM of BTCW, and the hydrophobic-neutral fraction had the highest SUVA level (7.06 L mg^?1 m^?1), which were significantly different from that in the domestic wastewater. Column adsorption experiments showed that NDA-802 exhibited much higher removal efficiency of EfOM than other polymeric adsorbents D-301, XAD-4, and XAD-7, and the efficiency could be readily sustained according to continuous 28-cycle batch adsorption–regeneration experiments. Moreover, dissolved organic matter (DOM) fractionation and excitation-emission matrix (EEM) fluorescence spectroscopy study indicated that NDA-802 showed attractive adsorption preference as well as high removal efficiency of hydrophobic and aromatic compounds. Possibly ascribed to the presence of functional aminated groups, relatively large specific surface area and micropore region of the unique polymer, NDA-802 possesses high and sustained efficiency for the removal of EfOM, and provides a potential alternative for the advanced treatment.     

High-performance thin-layer hydrogel composite membranes for ultrafiltration of natural organic matter

Thin-layer hydrogel composite (TLHC) ultrafiltration (UF) membranes were synthesized by photo-grafting of either poly(ethylene glycol) methacrylate (PEGMA) or N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium betaine (SPE) onto commercial polyethersulfone (PES) UF membranes. The performance of TLHC UF membranes was evaluated for natural organic matter (NOM) filtration and compared to commercial PES UF membranes. The fouling evaluation was done by investigation of membrane-solute interactions (adsorptive fouling) and membrane-solute-solute interactions (UF). The results suggest that the TLHC membranes convincingly displayed a higher adsorptive fouling resistance than unmodified PES UF membranes. In long-term stirred dead-end UF, a much lower fouling was observed for TLHC membranes than for commercial membranes with the same flux and rejection. Further, water flux recovery was also much higher. An analysis using an existing blocking model was performed in order to elucidate the effect of a polymer hydrogel layer on fouling mechanism as well as cake layer characteristics. The TLHC membranes synthesized by photo-grafting of PEGMA (40 g/L) and PEGMA with a low concentration of cross-linker monomer in the reaction mixture (ratio: 40/0.4 (g/L)/(g/L)) showed a much better performance than the other composite membranes. Those membranes could reduce the cake resistance on the membrane surface. This work has relevance for the design of high-performance UF membranes for applications in water treatment.     

Combination of coagulation and ion exchange for the reduction of UF fouling properties of a high DOC content surface water

The treatment of a high DOC content surface water (about 6mg DOC/L) using anion exchange resins (MIEX resin from Orica or IRA958 resin from Rohm and Haas) can remove up to 80% of DOC in less than 45min. The combination of coagulation prior to or after resin treatment only slightly improves the removal of DOC (0.2-0.3mg/L) but eliminates the high MW organic compounds (MW >20kDa) attributed to biopolymers (proteins and polysaccharides) that were not removed using anion exchange resins alone and that were found to be responsible for reversible fouling of UF membranes (YM 100 UF membrane from Millipore with MW cut-off of 100kDa). The combination of treatments then significantly improves the permeability of the UF membrane. Also, the combination of both treatments allows a reduction of the coagulant doses by a factor of 6 with no impact on the DOC removal and the filterability of produced waters.     

Efficacy of relaxation, backflushing, chemical cleaning and clogging removal for an immersed hollow fibre membrane bioreactor

A pilot-scale hollow fibre immersed MBR, challenged with real municipal wastewater, was studied and operated under conditions identical to those prevailing at full-scale to assess the relative influence of backflushing, relaxation, chemical enhanced backflushing (CEB) and declogging on permeability decline and recovery. The influence of relaxation and backflushing was initially assessed using the conventional flux step method; results indicated reversible fouling to be similar for each method, whilst the irreversible fouling rate was significantly reduced by backflushing. For a given total backflush volume, fouling mitigation was found to be marginally better through employing higher backflush fluxes than longer backflush durations.The impact of the CEB on permeability recovery assessed at low and high fluxes indicated operation at more conservative fluxes to yield more sustained permeability. Under more aggressive operating conditions - fluxes of up to 35 L m⁻² h⁻¹ at specific aeration demand values of 0.25 Nm³/(m² h) - long-term permeability decline took place which was not significantly ameliorated by chemical cleaning. On declogging the membrane through gentle agitation permeability recovery was significant, but was followed by a rapid permeability decline over the course of a few hours. Results suggested control of clogging to be of greater importance than that of fouling in sustaining permeability.     

Irreversible membrane fouling during ultrafiltration of surface water

For more efficient use of membranes, the control of irreversible membrane fouling, which can be defined as fouling requiring chemical reagents to be mitigated, is of importance. In this study, irreversible fouling caused by constituents in surface water was investigated, based on a long-term pilot scale study. The membrane employed was a low-pressure hydrophobic ultrafiltration (UF) membrane made of polysulfone and having a molecular weight cutoff of 750,000 Da. Various chemical reagents were examined to overcome the irreversible fouling that had developed through 5 months of continuous filtration. Among the tested cleaning reagents, alkaline (NaOH) and oxidizing reagent (NaClO) showed good performance in the restoration of membrane permeability, which implied that organic matter played an important role in the development of the irreversible fouling in this study. Chemical analysis, adsorptive fractionation methods, fluorescence excitation-emission matrix (EEM) and Fourie-transformed infra-red (FTIR) spectra analysis were applied to elucidate which fraction of organic matter caused the irreversible fouling. All of the analysis indicated that polysaccharide-like organic matter was responsible for the evolution of the irreversible fouling. In addition to organic matter, presumably iron and manganese also contributed to the irreversible fouling to some extent.     

Fouling characteristics of NF and RO operated for removal of dissolved matter from groundwater

A pilot study had been performed for about 6 months in order to investigate the removal efficiency of dissolved matter and its fouling potential during nanofiltration (NF) and reverse osmosis (RO) of local groundwater that was pretreated with an ultrafiltration (UF) membrane system. After pilot plant operation, autopsy tests were performed to identify the characteristics of foulants that were attached to the membrane surface. In the autopsy tests, the flux recovery for each specific cleaning scheme (hydraulic washing, acid cleaning, and alkaline cleaning) was also measured using a dead-end filtration cell unit. The washing solution used in each chemical cleaning was analyzed to identify major components of the foulants, and the membrane surface was observed using the scanning electron microscopy (SEM).Among three kinds of membranes tested, one NF and two RO membranes, the NF and RO1 membranes showed a rapid flux decline after 100 days of operation. Especially, the RO1 membrane showed the more serious flux decline than the NF membrane. The RO2 membrane, with the lowest recovery rate, demonstrated a gradual flux decline. The removal efficiency of dissolved inorganic matter (as conductivity) for each NF, RO1 and RO2 membrane was 76.3%, 88.2% and 95.3%, respectively. The removal of dissolved organic matter (as total organic carbon) was found to be about 80% for both NF and RO membranes used in this study. During the membrane autopsy tests, five sections of the fouled membrane were cut along each NF and RO membrane module from the feed inlet side to the concentrate outlet side, the specific flux for each membrane section was measured before and after each cleaning step. As expected, the degree of fouling was intensified along the membrane surface as the feed flow approached the outlet. Based on the analysis results of wash water used in each cleaning step, the major foulants attached to the membrane surface appeared to be Ca bound with inorganic matter and Si bound with organic matter. Fe seemed to be a great contributor to irreversible fouling. The SEM analysis indicated that the organic matter was forming the first fouling layer close to the membrane and that the inorganic matter was layered top of the organic fouling layer in a tetragonal shape. Any evidence of biofouling was not observed in this study because most of microorganisms had been already removed by the UF pretreatment.