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Journal of Membrane Science 267 (2005) 18–26

Iron and manganese removal and membrane fouling during UF in conjunction with prechlorination for drinking water treatment
Kwang-Ho Choo ∗ , Haebum Lee, Sang-June Choi
Department of Environmental Engineering, Kyungpook National University, 1370 Sankyeok-Dong, Buk-Gu, Daegu 702-701, Republic of Korea Received 7 December 2004; received in revised form 17 May 2005; accepted 24 May 2005 Available online 24 June 2005

Abstract The removal of various levels of iron and manganese along with chlorine dosages from lake water was investigated using different ultrafiltration (UF) systems in conjunction with an in-line prechlorination step. In particular membrane fouling, caused by oxidized iron and manganese particles, was assessed in depth with visualization of the membrane surfaces. For feedwater containing 1.0 mg/L of Fe and/or 0.5 mg/L of Mn, substantial iron removal was achieved even without the addition of chlorine due to the oxidation of ferrous iron to ferric by dissolved oxygen and the consequent formation of less soluble iron hydroxide particles. Only negligible amounts of manganese removal occurred in the absence of chlorine, but with a dose of chlorine the manganese removal efficiency increased markedly and reached a level of more than 80% (corresponding to less than 0.1 mg/L Mn) at a chlorine dosage of 3 mg/L as Cl2 . With a higher dosage of chlorine (e.g., 5 mg/L Cl2 ), there was no significant increase in the removal of metal ions but more serious membrane fouling occurred. Also, oxidized manganese claimed a greater responsibility for membrane fouling during UF with chlorination. This phenomenon was in close association with the kinetics of manganese oxidation and its oxidized particles’ deposition inside the pores during backwashing, rather than its accumulation on top of the membrane skin layer. Turbidity and natural organic matter (NOM) removal levels of efficiency were enhanced with the addition of chlorine in the presence of iron and manganese because the metal oxides, created by chlorination, could serve as adsorbents. © 2005 Elsevier B.V. All rights reserved.
Keywords: Ultrafiltration; Iron and manganese; Chlorination; Membrane fouling; Backwashing

1. Introduction Ultrafiltration (UF) technologies recently have become more popular in drinking water treatment, since they can control small pathogenic microorganisms such as viruses very effectively. The use of UF membranes and their hybrid processes is thus considered as an attractive option in solving the issues related to viruses and protozoan oocysts as well as disinfection/disinfection by-products [1–5]. UF alone, however, is still unable to fully eliminate dissolved inorganic constituents such as iron and manganese that can deteriorate the quality of water with respect to taste and color. Groundwater and some water from the bottom anoxic zones

Corresponding author. Tel.: +82 53 950 7585; fax: +82 53 950 6579. E-mail address: chookh@knu.ac.kr (K.-H. Choo).

of reservoirs often contain such metal ions as reduced forms of Fe2+ and Mn2+ or their complexes with natural organic matter (NOM) [6]. In conventional treatment, the oxidation of iron and manganese was thus carried out using various oxidants such as oxygen, chlorine, ozone, or potassium permanganate, the precipitates of which could be then removed by either clarification or sand filtration, or both. The chemistry of oxidation becomes complicated when background species such as phosphate and fulvic acid are involved, so that even the oxidation of ferrous ion, that can be normally readily oxidized, is retarded [7]. The removal of metals by oxidation followed by depth filtration is greatly dependent on the size of the metal precipitates. In recent years, various treatment technologies have been employed to enhance water quality by removing inorganic contaminants. Ion exchange resins are able to remove many

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in conjunction with a prechlorination step was evaluated using different concentration levels of iron and manganese and chlorine. UF with in-line prechlorination was investigated with regard to the removal of iron and manganese from water since little information is available on this approach. The membranes were made of cellulose acetate and had a molecular weight cut-off (MWCO) of 100 kDa (corresponding to a nominal pore size of 10 nm).45 0. alkaline solution containing NH3 was selected in order to avoid manganese precipitation [10].5.014–0.5–10.71–3.9–7.1 mg/L Mn) [10].93 mm.035 m2 . iron and manganese levels were adjusted to approximately 1. the RO membrane removes manganese better than the NF one. One module had ten fibers with an effective surface area of 0. and disinfection with chlorine before distribution.34 .1. Tight reverse osmosis (RO) filtration and nanofiltration (NF) membranes were used and compared in the tests of the treatment of contaminated water and wastewater containing Mn2+ and Fe2+ [10. which is a water supply source for the eastern part of the city of Daegu. Choo et al. the characteristics and dynamics of oxidized particles were explored systematically in the laboratory using scanning electron microscopy (SEM). Also.2.5 1. Through the spiking of each metal into the feedwater. Each single fiber in the module was 1. but large amounts of the metal ions (more than 74%) passed through the membrane when humic acid or precipitation were not involved [12]. filtered water (FW) samples taken from the rapid gravity filter were also used as feedwater for some dead-end UF experiments (see Table 3).2 m long and had an inner diameter of 0. the polymeric NF membrane provided almost 100% removal of manganese and iron. The water treatment plant consists of the following typical physico-chemical processes: coagulation/flocculation. Before use. Feedwater Water samples used for this study were obtained from the Gosan Water Treatment Plant that receives raw water (RW) from the Unmoon Dam. it is still not clear as to how those metals sometimes exacerbate membrane fouling but sometimes do not. but it still could not meet the WHO guidelines (0.3 7.18].-H. therefore.0–93. It was reported. The actual levels of concentration of iron and manganese present in the source water were nearly negligible.11]. and manganese sand filtration was performed to remove iron and/or manganese from groundwater [13. A laboratory-made ion exchange UF membrane was tested to remove Fe2+ and Mn2+ . Japan) and/or MnCl2 (Daejung Chemicals and Metals Co. / Journal of Membrane Science 267 (2005) 18–26 19 inorganic metal ions from drinking water including iron and manganese.14].98 0.3 6. the efficiency of turbidity and NOM removal was also examined along with the monitoring of membrane perme- ability change. The removal of up to 94% manganese was achieved at long retention times but it decreased in the presence of ammonia and iron [9]. in NF for the treatment of chlorine-free pulp mill bleaching effluent.64–3. 2. Materials and methods 2. Korea) were spiked depending on the experimental conditions tested (which are specified in Tables 2 and 3). To illuminate membrane fouling mechanisms. and the formation of insoluble metal oxides improves the performance delaying the breakthrough of the column [8]. UF membranes The UF hollow fiber membrane modules used in this study were supplied from Aquasource (France).K.33 0. So. membrane fouling still needed to be rectified though levels were reduced with the Mn sands.9–14.0 12.. hydrogen peroxide. that oxidized iron and manganese particles reduced or prevented membrane fouling by NOM while forming a protective coat layer on top of the membrane [3.9–7. the membranes were rinsed using distilled water.4 <0. The removal of manganese from potable water was tested using a biological tricking filter.9 0. clarification. The flat Table 1 Quality of the water sources tested Parameter pH Temperature (◦ C) Turbidity (NTU) Alkalinity (mg/L as CaCO3 ) Fe (mg/L) Mn (mg/L) DOC (mg/L) UV254 (cm−1 ) SUVA (L/mg m) ND: not detectable Raw water 6. so a weak. Ltd. although the ceramic NF membrane only provided a low removal of metals [11]. In the case that KMnO4 was used as an oxidizing agent.3 ND ND 1. Manganese and iron were found to cause membrane fouling in the treatment of drinking water and membrane gas transfer applications in addition to NOM [15–17]. the MF experiments were conducted only with a suspension containing the already oxidized iron and manganese [13].8–15.040 0. In this paper. Manganese sand filtration followed by MF was more promising in the removal of Mn than H2 O2 /MF. so that additional FeCl2 (Wako Pure Chemical Industries.69 Filtered water 6.14–1. there was sufficient removal of the metals. whereby both performances relied on a pH of solution and reaction time [14]. however.2 12.39–3.. Some water samples collected were also moved to the laboratory for further analyses and tests. The key water quality characteristics are given in Table 1. Obviously.0 mg/L as Fe and 0. The removal of iron and manganese from lake water using bench-scale UF systems.. Thus. Membrane cleaning is also an issue because simple water flushing is unable to remove manganese. During long-term UF experiments at the real water treatment plant. but it seemed unrealistic from a practical point of view for the treatment of drinking water. rapid gravity filtration. respectively (which are often found in groundwater in Korea). Needless to say.5 mg/L as Mn.1 ND 1.017–0. Microfiltration (MF) after oxidation using potassium permanganate (KMnO4 ). Ltd. However. 2.

0 7.5 0.0 bar using a nitrogen cylinder.7 6.7 0 . a UF unit.8 6.2 1.1 7.5 0 0.0 0.2 1.9 5.02 0.9 1.025 0.5 bar using N2 gas with a 40-min cycle as follows: permeation. The system operation and data collection were automated using a programmable logic controller and an on-line computer.7 1.9 UV254 (cm−1 ) 0. and final flush. The overall water recovery corresponded to 91% of the water injected.6 5.9 2.019 0.0 0.9 6.059 0. 3 s.7 2.7 cm2 .8 2.3.022 0.0 6.2 7.8 Fe (mg/L) 0. The whole system was mainly composed of a feed tank.0 0.07 0.5 0.9 1.0 1.9 Chorine dose (mg Cl2 /L) Removal (%) Fe Mn Turb.8 – – – – 79 −13 75 96 84 4 75 5 73 14 82 81 86 – 90 – – 8 – 31 66 31 90 2 92 81 91 99 UF membranes (YM 100) used in the laboratory tests were purchased from Amicon (USA).5 Turb. 3 s.9 9.3 6.0 5.2 5.0 7.9 7.1 7.0 1. Stirred cell UF experiments were also performed using a 180-mL stirred cell plus an 800-mL reservoir (Amicon 8200.2 1.0 1.5 0.5 0. 2.7 1.0 3.0 7.3 6.0 3.09 0.7 7. and a data acquisition system.8 6.9 6.0 3.065 0.-H. USA). The single fiber system used in the lab for membrane fouling evaluation was designed in the same manner.5 0.025 0.0 1. the permeate mass Table 3 Summary of operating conditions and removal efficiency by dead-end UF with and without prechlorination Phase Time period (day) Feedwater Source RW RW RW RW RW RW RW RW FW FW FW FW FW FW FW pH 6.5 2. The UF system was designed to operate at a constant flux of 69 L/m2 h (corresponding to 40 mL/min). 95 99 99 99 99 99 – – −31 40 50 68 60 63 36 – – −6 7 16 4 10 6 15 UV254 9 39 55 63 65 47 – – 8 7 0 15 9 −7 −18 DOC 12 26 16 13 11 24 A1 A2 A3 A4 B1 B2 B3 B4 C1 C2 C3 D1 D2 D3 D4 0–40 40–52 52–55 55–59 59–64 64–73 73–73 73–75 75–78 78–85 85–89 89–93 93–97 97–101 101–105 0 0 1 3 0 0 3 0 0 0 3 0 3 0 3 .0 0.025 0.6 1.5 0.8 2.0 0.6 1.5 7.6 0.08 0. The stirring speed was adjusted to 160 rpm using a magnetic stirrer.0 1. 39 min and 24 s.4 8.0 1.1 7.0 0.1 7.7 6.5 0.2 2.4 1.02 0.1 0.5 0.3 3.05 0.0 0.062 0.5 0.5 Turb.5 0 0 0. 1.20 K.2 0.7 1.3 8.051 0.02 0.8 7.4 0. Periodic backwashing was performed at 1.04 0. Choo et al.7 1.05 0.4 4.0 6.05 0.5 1.6 0.08 0.8 1.0 7.5 1.2 1.057 0.0 0.8 1.8 3.050 DOC (mg/L) 1.5 0.2 2.3 0. 30 s.5 0 0.9 7.1 2. The membranes were made of regenerated cellulose and had an MWCO of 100 kD and an effective filtration area of 28. During stirred flow UF.6 6.6 1.0 3. For prechlorination.0 0.3 2. To stress the lab system.4 2. The working volume of the batch unit was 980 mL.0 1.2 Chorine dose (mg Cl2 /L) Removal (%) Fe – 97 97 87 – 98 – – – 100 99 97 99 – – Mn – 36 26 81 – 7 – – – 1 86 – – 5 84 Turb.5 0. the circulation pump was operated to maintain a tangential velocity of 1 m/s inside the hollow fibers.1 1.02 0.052 0.9 6. / Journal of Membrane Science 267 (2005) 18–26 Table 2 Summary of operating conditions and removal efficiency by crossflow UF with and without prechlorination Phase Time period (day) Feedwater Source RW RW RW RW RW RW RW RW RW RW RW RW RW RW RW RW pH 7.07 0. backwash.1 7. During crossflow UF.2 0 .0 0.1 7. Membrane system operation The bench-scale UF system used in this work is shown in Fig.0 0. (NTU) 7 20 12 18 20 21 21 21 0.6 1. while the pressure applied was kept at 1. (NTU) 2.2 0.2 UV254 (cm−1 ) 0. but it stopped during dead-end UF.6 6.02 0.2 7.5 0.4 0.0 7.3 2.049 0.1 0.0 Mn (mg/L) 0.0 Fe (mg/L) 0 1 1 1 0 1 1 1 0 1 1 1 1 0 0 Mn (mg/L) 0 0.0 0. first flush. 83 73 93 98 96 96 96 97 96 97 98 98 98 98 98 99 UV254 0 19 66 73 37 47 55 53 34 73 19 31 20 73 74 75 DOC 14 22 30 14 19 28 13 24 – – 27 29 17 27 34 39 A B1 B2 B3 C1 C2 C3 C4 D1 D2 D3 D4 D5 E1 E2 E3 0–11 11–25 25–27 27–32 32–34 34–36 36–37 37–37 37–38 38–38 38–40 40–41 41–43 43–45 45–46 46–48 0.1 6.0 5. dead-end UF was conducted at a substantially high flux of 150 L/m2 h.5 0.2 1.0 4.02 DOC (mg/L) 1.1 7.052 0.045 0.3 8.4 0.0 0.6 0.0 0. a chlorine solution with 100 mg/L as Cl2 was injected before the feeding pump (P2) using a peristaltic pump (P1).7 2.059 0.

Since the residual chlorine measured decreased from 1. . USA). 1. and dissolved organic carbon (DOC). 2. however. The surface of the membrane tested was visualized using a field emission scanning electron microscope (S-4300. The manganese removal efficiency was. not as effective as that for iron.5–2. Removal efficiency of: (a) iron and (b) manganese over time at different chlorine dosages.0 to 0. Hitach. Fig. Analytical methods Feedwater and permeate samples were analyzed for key water-quality parameters such as iron. 2. UV absorbance at 254 nm. Japan). PlasmaQuad 3. USA) to remove particles before the measurements of UV absorbance and DOC concentration level. As shown in Fig. The chlorine dose was determined by the DPD method using a Hach spectrophotometer and reagent pillows. Feedwater samples were filtered through a 0. Choo et al.45-␮m membrane (Millipore. The turbidity measurement was taken on a Hach turbidmeter (2100P.0 mg/L Fe and 0. while the DOC concentration level was measured using a TOC analyzer (Sievers 8200. turbidity. / Journal of Membrane Science 267 (2005) 18–26 21 Fig. A cake layer containing 100 mg as Fe and/or Mn was first formed at 0.4. Batch chlorination test To determine an appropriate dose of chlorine for the oxidation of iron and manganese.5 mg/L as Cl2 . USA). manganese. Kontron.5 mg/L Mn were conducted.39 mg/L.2 bar and then the specific cake layer resistance corresponding to the cake resistance per unit mass of particles was determined at a wide pressure range of 0.-H. Italy).K. 2.0 bar [19]. was monitored and recorded using an electronic balance and a personal computer to evaluate the change of flux. Results and discussion 3. batch tests with feedwater containing 1. Schematic of a bench-scale UF system in combination with a prechlorination step.1. The specific cake resistance of particles was also measured using the stirred cell unit in an unstirred mode. The UV absorbance was determined using a UV/VIS spectrophotometer (Uvicon 942. The levels of iron and manganese concentration were analyzed using an inductively coupled plasma mass spectrometer (VG Elemental. some other constituents in raw water were oxidized preferentially at the low chlorine 3. the removal efficiency of dissolved iron increased very rapidly and reached nearly 100% within 20 min even with a chlorine dose of as little as 0. UK).

it was necessary to examine the effect of chlorination on UF for the treatment of water containing different levels of iron and manganese. 3. Manganese was relatively difficult to oxidize but normal. 3. Choo et al. In Phases D and E. At first.22]. UV removal was much more substantial than that of DOC. Consequently. The turbidity was nearly completely removed since UF can reject most of the colloidal particles present in raw water. the turbidity and UV removal efficiency levels were also monitored. This result is indicative of large amounts of chlorine required to remove both iron and manganese if manganese exists in the feedwater.. 3. In one case (condition D4). A relatively high chlorine dosage of approximately 2 mg/L as Cl2 was required in order to achieve a desirable manganese removal efficiency of greater than 40% (corresponding to the current Korean maximal contamination level of 0. was very low. This is probably due to the extremely low turbidity of filtered water. but further investigation regarding manganese removal was needed. the chlorine dose was changed stepwise from 0 to 3 mg/L throughout Phase C. some variations of data were unavoidable. UV254 .21. during the UF treatment with the addition of chlorine. the quality of the UF permeate could be guaranteed to meet the regulation criterion of 0. membrane fouling seemed to occur when the oxidation of manganese was sped up. This is possibly due to the oxidative degradation of the aromatic groups of NOM by chlorine that have strong UV absorbance at 254 nm [20]. pressure was maintained at a constant level as presented in the early stages of Phase B.e. D1. it did not change the overall trend of the experimental results. the increase of pressure always coincided with the increase of manganese removal. To further clarify it. i. so small fluctuations of their concentration may give negative removal efficiency.22 K. As expected. physical and chemical cleanings were performed. Fig. Variation of inlet transmembrane pressure over time in crossflow UF. substantial iron removal was achieved even without prechlorination (conditions B2. E1). The above results imply that the material precipitated by oxidation (e.3. it could be hypothesized that the deposition of oxidized manganese precipitates claimed a greater amount of responsibility for membrane fouling (which will be discussed later in detail). Crossflow UF with prechlorination Table 2 summarizes the overall performances of the combined prechlorination/crossflow UF process under different operating conditions. This could be attributed to the oxidation of ferrous iron to ferric by dissolved oxygen and the subsequent formation of iron hydroxide precipitates which were rejected by UF. The pressure started increasing when a large amount of chlorine was dosed (C4). Dead-end UF with prechlorination The efficiency of water treatment through chlorination followed by dead-end UF is summarized in Table 3. Thus.-H. It was reported elsewhere that iron oxides could remove Fig. It would be an additional benefit of the oxidation of iron and manganese followed by the removal of the precipitates by UF. ferrihydrite) can play a part in removing NOM from water by sorption. Moreover. The iron removal efficiency was mostly kept at its highest level regardless of the feedwater quality and whether the water was chlorinated or not. However.5. the combined process operation removed approximately more than 70% of iron. 3 displays the change of the transmembrane pressure during the 48-day UF operation in combination with chlorination. They deteriorated when the feedwater was switched to filtered water obtained from the sand filters. and DOC. During the combined process operation. In Phase A.. satisfactory manganese removal occurred with chlorination at a larger chlorine dosage of 3 mg/L. / Journal of Membrane Science 267 (2005) 18–26 dosage. the removal efficiency of iron and manganese was well observed at a high level based on the batch tests conducted in the laboratory. and DOC also indicated similar trends as those in the crossflow UF when raw water was fed into the system. particularly when iron was present in feedwater. large colloidal particles in raw water contributed to the for- .3 mg/L Fe. 1). After placing a strainer starting from Phase B (refer to Fig. It is interesting to note that relatively great UV and DOC removal was also observed.. The characteristic of manganese removal behaved roughly in the same manner. Mn. this might be ascribed to the deposition of iron and manganese precipitates at the UF membrane.3 mg/L). however. C1. A sharp rise in pressure occurred again when the water was chlorinated in the presence of iron and manganese (B3). respectively.g. Although we tried our best to eliminate any errors during experiments. organic substances from river and lake water and wastewater effluent [3. At the points of (*) and CC. i. As a result.e. particularly related to Fe. negligible amounts of manganese was removed. as being in agreement with that of the crossflow UF. there were several significant increases in pressure.2. Other parameters such as turbidity. only 31% of manganese was removed by a dose of approximately 3 mg/L Cl2 and with low chlorine dosages. which were caused by membrane lumen clogging alone. which was slightly dependent on the initial iron concentration. Overall. The concentration of each item in feedwater and permeate.

the two sudden leaps in pressure were caused by a malfunction of the in-line strainer. which might be in association with the concentration level of colloids in feedwater [20]. began to increase steadily without chlorination (Phase B2). respectively. the size of the particles in the filtered water from the sand filter is smaller than that in the raw water. the DOC level of UF permeate was sometimes higher than that of raw water as shown in Fig. Considering the variations of turbidity during Phases A and C Fig. But one possible explanation is that during dead-end UF. as opposed to the previous results. its energy consumption would be much less than that of the crossflow membrane process. Nevertheless. At the points of (*) and CC. there was a question as to why the two inorganic precipitates had a different effect on fouling. Variation of turbidity in raw water and permeate over time in deadend UF. The pressure. Variation of DOC in raw water and permeate over time in dead-end UF. Changes in transmembrane pressure during the constantflux UF operation are shown in Fig.0 bar) along the fiber during crossflow UF. Another possibility is that chlorine can affect the chemistry of NOM in water leading to the reduction in NOM rejection by UF.-H. However. / Journal of Membrane Science 267 (2005) 18–26 23 Fig. the performance of dead-end UF with prechlorination seemed to be more stable in terms of the removal of contaminants and membrane permeability. A similar finding was also reported elsewhere [3]. there was a significant pressure drop (∼1. dead-end UF seemed to be more economical and reliable for water treatment from a practical point of view. 4. In Phase A. 6. Thus.K. filtered water was used as feedwater during Phases C through D. Since the dead-end UF process did not have a circulation pump. serious membrane fouling occurred simultaneously (Phase A4) as mentioned above. relatively uniform deposit layers can be formed under even distribution of transmembrane pressure inside the hollow fiber leading to higher stability in removal and permeability with backwashing. Choo et al. but it did not change the overall trend of the experimental results as mentioned above. mation of secondary dynamic layers on top of the membrane surface while providing additional rejection of turbidity and NOM. it was believed that the higher NOM concentration was more responsible for the membrane fouling in Phase B2. When a significant amount of manganese was removed by chlorination. Fouling became much worse with chlorination during the rest of Phase B. On the other hand. . It is unclear why dead-end UF is more stable and we need to further examine this phenomenon. Fig. the turbidity level appeared not to directly affect it. 6. but after fixing it there were not any technical problems in the system. physical and chemical cleanings were performed. however. 5. which seemed to be related to the increase of either turbidity or the NOM levels or both (Figs. With the tests. so their rejection by UF membrane is of course lower. Also. The negative removal efficiencies may occur due to very low level of concentration and its fluctuations. In addition. probably resulting in the formation an irregular deposit layer at the membrane. it was clear that oxidized manganese did affect membrane fouling a lot more than the iron oxides. 4. even though the fouling caused by oxidized manganese was still occurring. 5 and 6). It is still not clear but it might be caused by the concentration polarization of DOC at the membrane surface resulting in some fluctuations in the DOC level of permeate during UF. Variation of transmembrane pressure over time in dead-end UF. Thus. In order to minimize the effect of turbidity and NOM on membrane permeability. through D.

7). Illustration of possible mechanisms of membrane fouling caused by oxidized particles during prechlorination with and without backwashing (BW). particularly by manganese oxide particles. 8. Membrane fouling mechanisms To elucidate the cause of membrane fouling during chlorination/UF.24 K. however. As shown in Fig. Specific cake resistance of iron and manganese particles and a 1:1 ratio mixture (in mass base). Effect of chlorination on pressure build-up during single hollow fiber UF along with backwashing. / Journal of Membrane Science 267 (2005) 18–26 Fig. while 3 mg/L Cl2 was dosed for runs 2 and 3.5 mg/L Mn was fed for all runs. There might be several possibilities related to the geometry and hydrodynamics of the modules: (1) hollow fibers can be easily clogged. the manganese oxide particles offered a relatively low specific resistance of the cake compared to the iron oxide particles and their mixture (Fig. 8). batch stirred cell UF was conducted with different combinations of iron and manganese levels in the feedwater (Fig. oxidation of the iron and manganese was always beneficial with regard to membrane permeability Fig. 7. no chlorine was added. Effect of chlorination on pressure differential during single hollow fiber UF of feedwater containing different amounts of iron and manganese. For run 3. Choo et al. 9. In run 1. even when hollow fibers were used. Filtered water containing 0. It could be assumed that the difference between the continuous and batch tests stemmed from modular types such as hollow fibers and flat sheets. which had never been referred to as a cause of membrane Fig. This seemed to contradict the findings from the previous.-H. 3. Effect of chlorination on membrane permeability during stirred flow UF of feedwater containing different amounts of iron and manganese. This revealed that our reasoning given above turned out to be incorrect. Also. 9. 11. The only possibility left to consider would be backwashing. continuous tests. backwashing was done with chlorine-free acidic solution (pH 3). the membrane permeability always increased whenever amounts of oxidized iron and/or manganese were present in feedwater. . Fig.4. 10. Fig. Unexpectedly. and (2) the tangential flow inside the hollow fibers may change the deposition of particles and fouling behavior may occur. Results of the batch tests suggest that manganese particles contribute barely to membrane fouling as compared to the iron ones. No backwashing was applied to any of the tests.

as shown in Fig. UF of chlorinated water with normal backwashing aggravated membrane fouling unlike those without backwashing and with backwashing using an acidic solution (pH 3). This is possible because the oxide particles can sorb NOM. Fig. Choo et al. instead of chlorine addition (run 3 of Fig. (c) used membrane (lumen side). 10. They can grow continuously later on and thereby. 2). the speed of the oxidation of manganese is relatively slow (refer to Fig. Unlike iron.5]. Similar findings by other researchers reported that metal oxide adsorption contributed to the reduction in fouling [3. Consequently. so some of the manganese particles are still small enough to pass through pores after chlorination. plug the pores during the backwashing stage. Conclusions Prior to UF. Thus. and (d) used membrane (shell side). The SEM pictures of the UF membranes used confirmed the deposition of manganese precipitates on the shell side of the membrane during UF with chlorination (Fig.K. 4. fouling but rather it was believed it could prevent it. which is also known as a foulant. 12. / Journal of Membrane Science 267 (2005) 18–26 25 Fig. 12).-H. (b) virgin membrane (shell side). SEM pictures of the UF hollow fiber membranes tested: (a) virgin membrane (lumen side). it could be claimed that fouling was affected by the kinetics of the oxidation of manganese and the operation of backwashing. it was necessary to explain why normal backwashing increased the level of fouling in this work. Surprisingly. 10). If an additional dose of chlorine into the permeate during backwashing is done as it normally does to prevent microbial growth at the membrane. Thus backwashing with an acidic solution can help reduce fouling caused by inorganic precipitation. 11 illustrates a possible mechanism of the fouling phenomenon during water treatment by prechlorination/UF. The accumulation of the metal oxide particles on the membrane surface may not bring about severe fouling but rather can improve permeability. it may accelerate the growth of manganese oxides inside the pores. The effects of chorine doses and different levels of iron and manganese on treatment efficiency . chlorine was added to remove iron and manganese from drinking water.

W. Iron fouling in membrane gas transfer applications. [18] M. L. Membr. W. Lantagne. [14] Z. 37 (2003) 1663. 112 (1996) 287. G. [15] Y.Y. Zhang. Mn2+ and humic acid) in water. Desalination 154 (2003) 139. J. Desalination 138 (2001) 271. H. Sci. Lehto. Use of ultrafiltration membranes for the separation of TiO2 photocatalysts in drinking water treatment.H. Grohmann. Teng. Lee of the Korea Basic Science Institute and Mr. S. Kabsch-Korbutowicz. Ha. Korea. D.J. Ellis. Choi.K. dead-end UF with prechlorination seemed more feasible than crossflow UF. Lee. [2] G. Choi. [8] K. K. Fouling and natural organic removal in adsorbent/membrane systems for drinking water treatment. D.I. 40 (2001) 1712. Technol. Conjunctive use of ultrafiltration with powdered activated carbon adsorption for removal of synthetic and natural organic matter. Appl. Studies on interactions between membranes (RO and NF) and pollutants (SiO2 . Membr. 32 (1998) 2442. G´ omeza. Chellam.H. This was an unusual case because backwashing aggravated membrane fouling due to the reaction kinetics of manganese. Zaw. Heijnen. S. Benjamin.A. Molinari. Anderson.M. C. K.2 to 90 NTU. a relatively stable operation and low pressure were maintained during longtime in situ testing compared to that with the latter.J. Lee. Fujita. Li. E. Kang.W. [6] M. K. 6 (2000) 357. NO3 − . 102 (1995) 65. Chang. [4] S. Chem. while substantial iron removal was possible even without chlorine addition. Colloid Interface Sci. J.S. [13] D. Choo. Chiswell. M. Removal of metals and anions from drinking water by ion exchange. Madaeni. Winnicki.M. Choo. Using ultrafiltration membrane technology to meet UK Cryptosporidium regulations. Choo. Sci. ´ Alvarez. [10] R.M. [16] W. Manganese removal by hollow fiber micro-filter. Ind. Romeo. Environ. J. Development of an integrated iron oxide adsorption/membrane separation system for water treatment. Application of modified polysulfone membranes to the treatment of water solutions containing humic substances and metal ions. / Journal of Membrane Science 267 (2005) 18–26 [3] Y. Indirect evidence for deposit rearrangement during dead-end microfiltration of iron coagulated suspensions. References [1] S. Chang. Membrane separation for drinking water. Lastra. With the former. Choo et al. 205 (2002) 45. Han of Gosan Water Works for their assistance in instrumental analyses and UF system operations. H. Membr. Effect of chlorine on adsorption/ultrafiltration treatment for removing organic matter in drinking water treatment. J. Takizawa. probably because of sorption of the oxidized particles. K. Kwon. D.H. Benjamin. Desalination 106 (1996) 71. K.J. [11] A. [22] M. Xu. S. Kosmidis. S. [12] M. Technol. Removal of Mn and simultaneous removal of NH3 . Lyberatos.R. K.-H. Choo. Study on fouling materials in the membrane treatment process for potable water. and membrane permeability were investigated using batch and continuous membrane systems. had a minimal effect on fouling. The authors thank Mr. Sci. [5] K. [19] S. C.A. Removal of metal complexes by nanofiltration in a TCF pulp mill: technical and economic feasibility. Eng.M. Removal of residual organic matter from secondary effluent by iron oxides adsorption. Choo. Temminghoff. G. C.I. Lee. respectively. Weng. Luque. Membrane fouling caused by oxidized manganese particles did not occur because of the formation of their cake layers on top of the membrane surface but because the particles that were grown after passing through the pores blocked them up during backwashing. Ind. The provision of laboratory-scale hollow fiber UF modules from Aquasource (France) is also appreciated. Membr. Lee. Johnson. Water Res.S. Desalination 105 (1996) 41. C.26 K. the oxidized manganese caused serious membrane fouling during crossflow and deadend UF.J.V. ranging from 0. 33 (1999) 1900. along with slight contribution by NOM. while turbidity levels in feedwater. Sci. Kinna. [7] A. Choi. J. A. J. P. J. Technol. Desalination 130 (2000) 255. Reiber. Water Sci. Desalination 139 (2001) 411. Francisco. Lee. Vayenas. Choo. Chem. Colloid formation in groundwater: effect of phosphate. Geochem. For iron and manganese removal in drinking water treatment. 19 (2004) 611. K. S.K. manganese. [21] K. Combined adsorption/UF process increases TOC removal. J.L. Reckhouse. silicate and dissolved organic matter on the dynamic heterogeneous oxidation of ferrous iron.H.H. J. D.H. Yamamoto. S. 141 (2002) 6. T. Formation of dynamic membranes with crossflow microfiltratioin. J.H. Takizawa. Fujita. G.H. J. J. Clifford. Vaaramaa. Fane. 239 (2004) 243. J.K. S. Sci. the following conclusions could be drawn: A relatively large dosage (approximately 3 mg/L as Cl2 ) of chlorine was required to remove manganese by means of oxidation followed by UF. it was found that tangential flow was not always necessary for a stable UF operation during water treatment. The formation of the precipitated material by chlorination contributed to an increase in turbidity and NOM removal. Res. Iron and manganese dynamics in lake water. Wolthoorn. AWWA 90 (5) (1998) 90.W. K.H.H. van Riemsdijk. Membr. Huang. J. G. Water Res. Membr. Removal of iron and manganese from groundwater by oxidation and microfiltration. Al-Malack. . Sci. J. Kaiya. Eng. [17] C. [9] A. Hyeon. Thus. [20] T. Thus. W. Pearce. S. Unlike iron oxide particles.H. Gouzinis. Virus removal from water and wastewater using membranes. T. Desalination 155 (2003) 157.W. Romerob. L. 274 (2004) 587. Fe and Mn from potable water using a trickling filter. Acknowledgements This work was supported by the Korea Research Foundation Grant (KRF-2003-042-D20083) and the MOE. 2 (2002) 293. M.J. 242 (2004) 97. Bouchard. B. Y. Arguiro. Lee.H. J. M.G. N. Water Sup.