Research Article

Received: 28 January 2009 Revised: 16 March 2009 Accepted: 17 March 2009 Published online in Wiley Interscience: 28 April 2009

(www.interscience.wiley.com) DOI 10.1002/jctb.2195

Membrane autopsy to investigate CaCO3 scale formation in pilot-scale, submerged membrane bioreactor treating calcium-rich wastewater
Mooseok Leea and Jeonghwan Kimb
Abstract
BACKGROUND: Membrane scaling is an area of research interest because it can deteriorate membrane performance. The extent to which membrane scaling is produced varies depending upon the concentration of scale-forming species such as calcium on the membrane surface. Bench-scale tests have been conducted to better understand membrane scaling in submerged membrane reactors (MBR). However, relatively few studies of membrane scaling in pilot-scale, submerged MBR have been reported. The objective of this study was to perform membrane autopsy work to analyze membrane scaling in a submerged MBR treating calcium-rich wastewater. RESULTS: Membrane autopsy work provided evidence that deposition of calcium carbonate (CaCO3 ) scale occurred on the membrane surface at the completion of pilot-scale, submerged MBR operation. The CaCO3 scaling resulted in signicant external fouling on the surface of the membrane. The membrane scaling increased the rejection of calcium with MF membranes. However, the level of CaCO3 scaling as internal fouling (in the pores) was almost negligible. This autopsy work also showed that aeration did not play a major role in controlling CaCO3 scaling at the membrane surface in a submerged MBR. Chemical cleaning using citric acid solution efciently removed CaCO3 scale from the membrane. Combining citric acid with sodium hypochlorite pretreatment provided synergistic effects, further reducing CaCO3 scale formation. CONCLUSION: The carbonate salt of calcium leads to precipitation resulting in surface fouling of membranes, and this cannot be removed physically by aeration in a submerged MBR treating calcium-rich wastewater. It is necessary to combine properlyselected cleaning strategies with submerged MBR treating wastewater containing a high potential for inorganic chemical precipitates. c 2009 Society of Chemical Industry Keywords: membrane bioreactor; wastewater; membrane autopsy; calcium carbonate scale

INTRODUCTION
The submerged membrane bioreactor (MBR) is a biological wastewater treatment process in which microltration and ultraltration membranes immersed in the mixed liquor are used for solidliquid separation. In addition to the removal of biodegradable organics, suspended solids and inorganic nutrients, the MBR retains particulate and slow-growing organisms and removes a very high percentage of pathogens.1 Higher biomass concentration in the MBR results in a smaller footprint and excellent efuent quality, thereby enabling many wastewater treatment applications without further treatments.2,3 Although there has been an upsurge of interest in MBRs for the treatment of wastewater, the occurrence of membrane fouling caused by deposition of foulants on the membrane surface and/or foulant adsorption within the membrane pores is a major problem of this innovative technology. Membrane fouling results in poor membrane performance by decreasing the specic permeate ux and subsequently increasing capital and operational costs.4,5 Therefore, an understanding of membrane fouling is critical for the application of MBR to achieve efcient operation. Signicant efforts have been made not only to investigate the effects of operating conditions on membrane fouling4 7 but also to identify membrane

foulants.8,9 Nevertheless, membrane fouling in submerged MBR still requires further research. The impact of divalent cations such as calcium on membrane fouling in the application of submerged MBR remains controversial. It has been reported that interaction of hydrophobic organic compounds such as extracellular polymeric substances (EPS) and soluble microbial products (SMP) with calcium helped bioocculation.10,11 Bioocculation with calcium bridges was found to be related to membrane fouling through EPS characterization.3 In addition, calcium can play an important role as a coagulant to produce colloidal ocs via charge neutralization.10 In this regard, external fouling by calcium on the membrane

Correspondence to: Jeonghwan Kim, Department of Environmental Engineering, INHA University, Nam-gu, Yonghyun-dong 253, Incheon, Republic of Korea 407-751. E-mail: jeonghwankim@inha.ac.kr

a Eco Research Institute, KOLON Central Research Park, Mabuk-dong, Giheungku, Yongin-city, Kyungi-do, Republic of Korea 446-797

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www.soci.org surface can be signicant if the colloidal ocs are larger than the membrane pore size. Recent studies have shown that membrane scaling could be a serious problem in the performance of submerged MBR. In a membrane-coupled anaerobic bioreactor, the bioreactor is typically enclosed and thus CO2 partial pressure in the gaseous space of the anaerobic tank increases. As a result, alkalinity in the anaerobic reactor needs to be supplemented to maintain neutral pH for microorganisms. Calcium in the form of Ca+2 interacts with alkalinity and forms CaCO3 leading to sludge displacement and membrane scaling.2 Given that the concentrations of dissolved inorganic solutes increase in the direction of the feed ow, the concentrations of sparingly soluble salts exceeds their solubility limit. Crystallization may occur either directly on the membrane surface or in the bulk and subsequently deposit on the membrane. The resulting membrane scaling leads to the decline of specic permeate ux and eventually shorter membrane lifetime.12,13 While membrane scaling has been investigated by performing membrane autopsy work, previous research still falls short of strong support for their practical implications in submerged MBR. Because most studies were based on bench-scale modules treating synthetic wastewater,5 11 direct observation and analysis of membrane scale in pilot-scale units of submerged, aerobic MBR treating real wastewater are very limited. In particular, little autopsy work has been performed with hollow-ber membranes treating calcium-rich wastewater discharged from industries that utilize chemical substances including additives and salts.15 Calcium-rich wastewater (5001500 mg L1 calcium concentration) can be associated with industries such as paper recycling, landll leachates and textile processing.15 17 Such high calcium concentrations are problematic because they can lead to membrane fouling owing to the formation of inorganic scaling. The aim in this study was to perform membrane autopsies extensively to observe membrane scaling in the application of pilot-scale, submerged MBR treating wastewater containing a high potential for scale formation. A submerged, aerobic MBR was operated at pilot scale for the treatment of calciumrich wastewater discharged from the textile industry. During operation of the submerged MBR, a signicant decline in membrane performance was observed. Evidence was sought via membrane autopsies to investigate how the scaling formation affected membrane fouling and rejection of calcium ions. Membrane autopsy measurements included identication of inorganic foulants deposited on and within the membranes using microscopic and surface analysis techniques. In this study, chemical cleaning strategies were also sought to improve the efciency of removal of membrane scaling from fouled membranes in submerged MBR.

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concentration in the reactor was about 5 g L1 . The temperature of the mixed liquor was maintained within the range 20 to 25 C during operation of the MBR. The MBR system consisted of an activated sludge bioreactor and hollow-ber MF membrane modules submerged in the reactor. The membrane modules were directly installed into the aeration tank with a horizontal conguration and the aeration pipe with 6 mm hole was tted below the module to generate coarse bubbles at the surface of the membrane. Aeration was provided at the bottom of the reactor at an air ow rate of 0.75 Nm3 m2 min1 . Filtration was performed at a constant ux of about 17 L m2 h1 using an automatically controlled suction pump. Relaxation was performed every 10 min during ltration by stopping suction pressure and continuing aeration into the reactor. Results for MBR operation between September and November 2008 are discussed in this paper. Membranes The submerged, hollow-ber membrane module was manufactured by KOLON industries Inc., (Gwacheon-city, Korea) and four modules were applied for the operation of MBR. The hollow-ber membrane was fabricated from polyvinylideneuoride (PVDF) with braid reinforcement to improve the integrity of the membrane module by preventing damage typically caused by movement of membranes in the bioreactor. Reinforced hollow-ber membranes have shown ideal performance in MBR systems in terms of lterability and mechanical properties, attributed to the thin layer PVDF membrane and braid reinforcement, respectively. The nominal pore size of the membrane is 0.1 m. The hollow-ber membrane has an inner diameter of 0.8 mm, outer diameter of 2.0 mm and length of 1 m. The surface area of the hollow-ber membrane per module is 20 m2 . Accordingly, the total surface area of membrane is 80 m2 . Measurement of inorganic fractions in foulant materials Membrane autopsies were performed to investigate membrane scaling at the end of MBR operation. At the completion of MBR operation, a coupon of hollow-ber membrane was placed on a sample mount and examined by scanning electron microscope (SEM). The SEM (Model: Hitachi S430, Hitach High Technologies, Japan) was applied with an accelerating voltage of 5 kV and a working distance of 13.216.0 mm, depending upon magnication. A magnication of 50120 was applied to obtain the appropriate resolution of membrane samples. The membrane sample cut from fouled membrane was mounted with double-side tape on aluminum stubs, and coated with a thin layer of conductive metal (Au) using a high vacuum sputter coating unit. Secondary electron (SE) images were taken at high magnication (120). The targeted energy dispersive X-ray analysis (T-EDXA Model: Noran EDX System, Noran-Voyager System, Middleton, WI, USA) uses the SE image to determine the inorganic elemental composition of foulants. The wavelength of the X-rays produced was used to identify the presence and relative amounts of chemical elements in the foulants. A small portion of foulant was removed from the fouled membrane for Fourier transform infrared analysis (FTIR, Model: Nicolet/Thermo Electron Avatar 360, Thermo Electron Co. Ltd., Waltham, MA, USA). The FTIR spectra were interpreted by library search of chemicals to identify functional groups within foulant structures. Functional groups in the foulants can be identied from the adsorption peaks generated by the frequencies of vibrations between chemical bonds of atoms making

EXPERIMENTAL
Design and operation of MBR pilot plant The MBR was installed at pilot scale and operated to treat wastewater discharged from a glove manufacturing plant. The industrial wastewater from the plant, located in the city of Sooncheon in South Korea, was pumped at a rate of 30 m3 day1 into an activated sludge basin. The pH of feed wastewater ranged from 7 to 8. Average solid retention time (SRT) and hydraulic retention time (HRT) of the reactor were 7 days and 8 h, respectively. The mixed liquor suspended solids (MLSS)

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Membrane autopsy to investigate CaCO3 scale formation in submerged MBR

(a) (b)

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Scale formation

Membrane

Figure 1. SEM images of scale formations on the hollow-ber MF membranes in (a) normal direction, and (b) cross-sectional direction.

Figure 2. Results of targeted energy dispersive X-ray analysis in normal direction of fouled membrane.

up the foulant materials. FTIR analysis was also applied to virgin membrane for reference to compare the results obtained from chemically cleaned membrane. Inductively coupled plasma mass spectroscopy (ICP-MS Model: Perkin Elmer Elan DRCII, Waltham, MA, USA) was used to analyze trace elements in feed wastewater. Atomic absorption spectrophotometry (AAS, Model: Shimadzu AA-680, Kyoto, Japan) analysis was also performed to measure calcium concentration in the eluate after chemical cleaning procedure with fouled membranes.

RESULTS AND DISCUSSION

Saturation index of feed wastewater The ICP-MS results for the feed wastewater tested in pilot-scale operation of the MBR are given in Table 1, which shows that the most prevalent inorganic ion in the feed wastewater is calcium. Thus, precipitation of calcium carbonate can be expected and it may subsequently scale the membrane. The feed wastewater is categorized as calcium-rich wastewater (5001500 mg L1 ) by considering that calcium concentrations found in industrial and domestic wastewater typically ranges from 20 to 500 mg

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Figure 3. Results of targeted energy dispersive X-ray analysis in cross-sectional direction of fouled membrane.

L1 .15 17 Calcium-rich wastewater is associated mainly with textile wastewater processed with lime, detergents and dyes.15 The saturation index measures the propensity of feed solution to result in scale formation, which is abiotic fouling. Specically, it attempts to estimate the potential of a sparingly soluble salt, CaCO3 , to precipitate from bulk solution.12 The Langelier Saturation Index (LSI) as shown in Equation (1) is the most commonly used index for determining the potential for CaCO3 scale formation.14,18 LSI = pH pHs

ionic strength. Saturation pH can be described as follows:19 pHs = pK2 + pCa+2 pKs log(2[Alk]) log 2902.39 + 0.02379T 6.498 pK2 = T pKs = 0.0183(T 273) + 8.03 (2) (3) (4)

(1)

where , Alk and T are activity coefcient of calcium, alkalinity (mg L1 as CaCO3 ) and absolute temperature (K) of the feed water, respectively. The activity coefcient ( ) was calculated using Equations (5) and (6), known as the Davies relationship:16 I 0.31I 1+ I

where pH is the actual pH of feed water, pHs is the calculated pH of the water corresponding to the CaCO3 precipitation at given calcium and alkalinity concentrations, temperature, and

log = AZ

(5) (6)

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Table 1. Concentrations of inorganic species in feed wastewater by ICP-MS analysis Component Li Na Mg Ca K Mn Fe Co Cu Concentration, mg/L 0.04 161 3.5 1303 37 0.09 9.8 0.13 0.03

Small CaCO3 crystals may be formed on the membrane surface during the initial stage of ltration and then developed on the membrane surface over time.13,20 The CaCO3 crystals tend to increase in size, with a deformed shape compared with the initial rhombohedral shape, exhibiting step features on the rounded shape,20 which can be observed on the SEM images in Fig. 1. As also shown in Fig. 1(a), the scale grew in all directions and coalesced to form a rather coherent and thick deposit on the membrane surface, supporting the notion that the CaCO3 scale occurs mostly on the membrane surface rather than in the bulk. Inorganic chemicals in foulant materials SEM-targeted energy dispersive X-ray analysis (T-EDXA) was performed to identify specically inorganic chemicals in foulant materials. The T-EDXA results obtained from normal and crosssectional observations of fouled membrane are given in Figs 2 and 3, respectively. As expected, the dominant inorganic ion in foulants deposited on the surface of membrane was calcium, as is shown in Fig. 2. As also discussed above, the LSI value of feed wastewater is greater than zero indicating that the water should be supersaturated with CaCO3 and subsequently should scale the membrane.17 However, the T-EDXA obtained from cross-sectional observation of the fouled membrane revealed that the calcium appeared not to be fouling within the membrane pores (Fig. 3). The importance of inorganic scaling on the surface of membranes has been investigated previously in submerged MBR treating synthetic wastewater.2,22 However, solid evidences that calcium can contribute to internal fouling has been lacking. T-EDXA in the cross-sectional direction of fouled membrane (indicated as position 5) demonstrates that the predominant component within membranes is uoride, not calcium, although local observations using microscopic techniques may not be representative of the full morphological characteristics inside membranes. Since uoride is detected as a component of the PVDF membrane material, calcium contributes to the external fouling of the membrane surface considerably more than to internal fouling within the membrane pore matrix. By performing ICP-MS analysis of membrane permeates, the rejection of calcium by MF membrane was found to be about 93%. This rejection efciency cannot be achieved by MF membrane alone. Strong rejection of calcium also supports the nding that calcium should be rejected as an aggregated form of scaling on

Table 2. Characteristics of feed wastewater Characteristics pH Temp ( C) Ca+2 (mg L1 ) Alkalinity (mg L1 as CaCO3 ) Conductivity (mho cm1 ) Ionic strength (mol L1 ) Wastewater 78 20 1303 500 1000 0.016

where D is dielectric constant, which is equal to 78.3 for the water. The ionic strength (I) was estimated by measuring conductivity of the feed water (C) and using the equation described below: I = 1.6 105 C(mhos/cm) (7)

Based on the characteristics of feed wastewater listed in Table 2, the LSI value was calculated as about 2.2. A value of LSI above zero can be interpreted as having the potential for scale-forming, while a value of LSI below zero means that the water is undersaturated with respect to CaCO3 . The result here indicates that the feed wastewater should be supersaturated and have a tendency to deposit CaCO3 on the membrane surface. SEM observations of fouled membrane SEM images of the hollow-ber membranes at the end of MBR operation are presented in Fig. 1. The magnication was adjusted to 50 to observe the normal surface of the fouled membrane (Fig. 1(a)), and to 120 to observe the cross-sectional surface (Fig. 1(b)). The SEM images in Fig. 1 demonstrate that signicant accumulation of foulants occurs on the membrane surface. The SEM images also show clearly the stratied-crystal structure of the foulant layer on the membrane surface, typical of mineral scale deposits.20 From the SEM images, the accumulation of inorganic material appears particulate based, resulting from scale formation on the membrane surface. Based on the high concentration of calcium (1.3 g L1 ) and LSI value of 2.2 in the feed wastewater, membrane scaling originating from calcium was thought to be caused by the formation of CaCO3 . The SEM images also imply that the aeration generated at the bottom of the reactor does not play an important role in mitigating membrane scaling because the CaCO3 particles are cohesive, and deposits of CaCO3 particles on the membrane surface can be regarded as physically irreversible.20,21

120 100 Reflectance (%) 80 60 40

872 1396 840 879 1072 1173 1276 1400

20 0 600

Used-washed

Virgin

Foulant

800

1000

1200

1400

1600

Wavelength(cm-1)
Figure 4. FTIR spectra for used membrane after chemical cleaning (usedwashed) with citric acid solution following sodium hypochlorite pretreatment, virgin membrane, and foulant detached from the membrane.

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Figure 5. SEM images of hollow ber membranes after citric acid cleaning ((a) and (b)) and after citric acid cleaning following sodium hypochlorite cleaning ((c) and (d)).

the membrane surface, otherwise dissolved calcium would pass through the membrane pores. In a previous study, the rejection of calcium was observed to be about 80% in a submerged anaerobic MBR using UF membrane, regardless of calcium concentration in the feed stream ranging from 50 to 400 mg L1 . The MBR typically contained higher CO2 partial pressure than that in an aerobic MBR (about 30% vs. 0.03%), which may lead to higher potential for CaCO3 scaling due to high concentration of carbonate ions.2 However, in the present study, CaCO3 scaling was also found to be signicant in the submerged, aerobic MBR. These results conrmed that the rejection of calcium should be enhanced considerably (more than 90%) by the formation of CaCO3 scaling on the MF membrane surface when applied to treat calcium-rich wastewater in which the LSI value is high and positive. FTIR analysis The FTIR spectra for virgin membrane, foulant and membrane after chemical cleaning of it by citric acid solution following sodium hypochlorite pretreatment are shown in Fig. 4. The spectra show the same strong absorbance peaks for both membranes. The fact that the FTIR spectra are the same for both virgin membrane and chemically cleaned membrane indicates that foulants are removed from the membrane effectively by chemical cleaning. The

adsorption bands at 1276 and 840 are characteristic of -form CF bond and CH2 rocking of the PVDF membrane, respectively.23 The FTIR spectrum of foulants detached from the membrane and the indication of carbonates at the adsorption bands 872 and 1396 reinforces the evidence of CaCO3 scale formation.19 It is known that CaCO3 scale formation can be controlled by acid addition, which lowers the pH to prevent scale formation. However, anti-scalant has very often been selected to supplement the traditional addition of acid. The anti-scalant application can also often be integrated into the overall implementation of a pH adjustment strategy to control CaCO3 scale formation by permitting the formation of scale that can easily be removed during backwashing of the membranes.12 As the MBR is applied to treat wastewater containing a high potential for CaCO3 scale, it may be necessary to combine properly selected anti-scalant and MBR. However, some commercially available anti-scalants can also increase the fouling rate of organic foulants such as humic acids on reverse osmosis or nanoltration membranes as the MBR is applied as a pretreatment for feeding these high-pressure driven membranes.12 Efciency of chemical cleaning SEM images were taken of chemically cleaned membranes and AAS measurements were performed to evaluate the conditions of

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Figure 6. Results of SEM-targeted energy dispersive X-ray analysis for membrane after citric acid cleaning alone.

chemical cleaning by determining calcium concentration in the eluates. Samples of fouled membrane at the end of operation were soaked in a citric acid solution (3 g L1 ) and sonicated for 2 h. The combined effect of sodium hypochlorite solution and citric acid solution on the removal of CaCO3 scale from the membrane was also investigated. As shown in Fig. 5, citric acid solution is an effective agent for the removal of CaCO3 scale from the membrane surface. However, chemical cleaning with citric acid solution following hypochlorite pretreatment provided better results. Although membrane scale was removed effectively by applying citric acid solution, some of the foulant still remained on the membrane surface (Fig. 5(a) and 5(b)). T-EDXA was performed to identify the components of the remaining foulant materials located at position 1 on the membrane surface. As shown in Fig. 6, the most prevalent inorganic ion of the foulant materials at position 1 is calcium. The predominance of calcium in the foulant materials can be explained by the growth of CaCO3 scale on the membrane surface. In addition, the inorganic fraction of the materials located at position 2 is quantied as

uoride, which is a component of the PVDF membrane used in this study. It was reported that particle size of washed liquid from fouled membrane using tap water was smaller than that of feed wastewater in a submerged MBR treating synthetic municipal wastewater.22 Although the previous study was not performed for the observation of CaCO3 scaling specically, the particle size which deposited on the membrane surface preferentially ranged from 10 to 40 m, while the larger particles (about 100 m) were detached more easily from the membrane surface by aeration. Conclusions may not be reached about the exact size of calcium carbonate scale. However, the SEM image in Fig. 1 shows that the aggregated form of scale appeared to be about 100 m in size and even somewhat bigger. This suggests that the aeration generated at the bottom of the reactor does not signicantly reduce membrane scaling due to its cohesive characteristics at the membrane surface. For the calcium-rich wastewater tested in this study, in particular, inorganic precipitates such as CaCO3 have a strong tendency to deposit on the membrane surface, thereby requiring appropriate

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www.soci.org cleaning strategies to remove the CaCO3 scaling from the membrane. The AAS results after chemical cleaning of fouled membranes provided higher concentrations of calcium in the eluate obtained when combining citric acid solution following hypochlorite (NaOCl) solution than that obtained when applying citric acid solution prior to NaOCl solution (350 vs. 200 mg L1 ). Combining NaOCl solution with anti-scalant EDTA was reported to increase permeate ux recovery by applying the sequence EDTA-NaOCl.2 Based on the measurement of calcium concentration in the eluate in this study, however, the addition of citric acid solution prior to NaOCl solution was less efcient in the removal of CaCO3 scaling than applying the sequence NaOClcitric acid solution. These current results suggest that the order sequence of chemical cleaning needs to be evaluated to determine optimal cleaning strategies for removing membrane scaling in submerged MBR. For calcium-rich wastewater, this study also suggested that the sequence baseacid is preferred for the removal of calcium carbonate scaling from the membrane. Oxidant cleaners such as sodium hypochlorite are generally considered effective against biolm and organic fouling because they cause hydrophilicity of the organic components and reduce the surface charge of the membrane.24 The effectiveness may be due to the formation of oxygen-containing groups leading to higher hydrophilicity of the components.24 A possible explanation is that the structure of hydrophobic organic foulant materials combined with calcium becomes loose due to the addition of NaOCl. As a result, the calcium can be released easily from the organic foulant and then subsequently detached from the membrane by applying citric acid solution.

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REFERENCES
1 DiGiano FA, Andreotolla G, Adham S, Buckley C, Cornel P, Daigger GT, et al, Safe water for everyone. Water Environ Technol June: 3135 (2004). 2 You HS, Huang CP, Pan JR and Chang SC, Behavior of membrane scaling during crossow ltration in the anaerobic MBR system. Sep Sci Technol 41:12651278 (2006). 3 Arabi S and Nakhla G, Impact of calcium on the membrane fouling in membrane bioreactors. J Membrane Sci 314:134142 (2008). 4 Guibert D, Ben Aim R, Rabie H and Cote P, Aeration performance of immersed hollow-ber membranes in a bentonite suspension. Desalination 148:395400 (2002). 5 Tardieu E, Grasmick A, Geaugey V and Manem J, Hydrodynamic control of bioparticle deposition in a MBR applied to wastewater treatment. J Membrane Sci 147:112 (1998). 6 Liu R, Huang X, Sun YF and Qian Y, Hydrodynamic effect on sludge accumulation over membrane surfaces in a submerged membrane bioreactor. Process Biochem 39:157163 (2003). 7 Shimizu Y, Uryu K, Okuno YI, Ohtubo S and Watanabe A, Effect of particle size distributions of activated sludges on cross-ow microltration ux for submerged membranes. J Fermentation Bioeng 83:583589 (1997). 8 Chu HP and Li XY, Membrane fouling in a membrane bioreactor (MBR): sludge cake formation and fouling characteristics. Biotechnol Bioeng 90:323331 (2005). 9 Germain E, Stephenson T and Pearce P, Biomass characteristics and membrane aeration: toward a better understanding of membrane fouling in submerged membrane bioreactors (MBRs). Biotechnol Bioeng 90:316322 (2005). 10 Kim IS and Jang NJ, The effect of calcium on the membrane biofouling in the membrane bioreactor. Water Res 40:27562764 (2006). 11 Nagaoka H, Ueda S and Miya A, Inuence of bacteria extracellular polymers on the membrane separation activated sludge process. Water Sci Technol 34:165172 (1996). 12 Reardon RD, Paranjape SV, Foussereau XJ, DiGiano FA, Aitken MD, Kim JH, et al, Membrane Treatment of Secondary Efuent for Subsequent Reuse. IWA Publishing, UK (2005). 13 Uchymiak M, Lyster E, Glater J and Cohen Y, Kinetics of gypsum crystal growth on a reverse osmosis membrane. J Membrane Sci 314:163172 (2008). 14 Langelier WF, The analytical control of anti-corrosion water treatment. J Am Water Works Assoc 28:15001521 (1936). 15 Hammes F, Seka A, Knijf S and Verstaete W, A novel approach to calcium removal from calcium-rich industrial wastewater. Water Res 37:699704 (2003). 16 Habets LHA and Knelissen HJ, In line biological water regeneration in a zero-discharge recycle paper mill. Water Sci Technol 35:4148 (1997). 17 Van Langerak EPA, Hamelers HVM and Lettinga G, Inuent calcium removal by crystallization reusing anaerobic efuent alkalinity. Water Sci Technol 36:341348 (1997). 18 Snoeyink VL and Jenkins D, Water Chemistry. John Wiley & Sons, New York (1980). 19 Beneeld LD, Judkins JF and Weand BL, Process Chemistry for Water and Wastewater Treatment. Prentice-Hall, Inc., New Jersey (1982). 20 Tzotzi C, Pahiadaki T, Yiantsios SG, Karabelas AJ and Andritsos N, A study of CaCO3 scale formation and inhibition in RO and NF membrane processes. J Membrane Sci 296:171184 (2007). 21 Kim IS and Jang NJ, The effect of calcium on the membrane biofouling in the membrane bioreactor. Water Res 40:27562764 (2006). 22 Meng F, Zhang H, Yang F and Liu L, Characterization of cake layer in submerged membrane bioreactor. Environ Sci Technol 41:40654070 (2009). 23 Boccaccio T, Bottino A, Capannelli G and Piaggio P, Characterization of PVDF membranes by vibrational spectroscopy. J Membrane Sci 210:315329 (2002). 24 Strugholtz S, Sundaramoorthy K, Panglisch S, Lerch A, Brugger A and Gimbel R, Evaluation of the performance of different chemicals for cleaning capillary membranes. Desalination 179:191202 (2005).

CONCLUSIONS
Membrane autopsies of MF hollow-ber membranes at the end of operation of an MBR treating wastewater containing high calcium concentration provided evidence that signicant deposition of CaCO3 scale could occur on the membrane surface. SEM-TEDX results showed that calcium was the most prevalent inorganic component in the foulant materials deposited on the membrane surface. A comparison library search of the FTIR spectrum of the foulant samples taken from a fouled membrane suggested a possible match with carbonate, reinforcing the evidence of CaCO3 scale. The main component detected within membrane pores was uoride, which is a component of the PVDF membrane material. The fact that a large portion of the calcium that could pass through the MF membrane pores was rejected on the membrane surface supported the fact that calcium was rejected in the form of CaCO3 scale on the membrane surface. Citric acid solution was an efcient cleaning agent to remove CaCO3 scale from the membrane at the end of submerged MBR operation. However, the cleaning efciency using citric acid solution was improved further by combination with sodium hypochlorite as oxidant. Although further research is needed, this result may be attributed to the loose binding of calcium associated with organic foulant by the addition of oxidant, thereby leading to the release of calcium from the fouled membrane.

ACKNOWLEDGEMENT
This work was supported by INHA UNIVERSITY Research Grant.

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