HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU NATIONAL UNIVERSITY OF SINGAPORE 2009 HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU (M. Eng., Beijing Univ. of Civil Eng. & Arch.) A THESIS SUBMITTED FOR THE DEGREE OF PHILOSOPHIAE DOCTOR DEPARTMENT OF CIVIL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2009 ACKNOWLEDGEMENT I wish to express my deepest appreciation and gratitude to my supervisor, Assoc. Prof. Ng How Yong, for his invaluable guidance, support, and encouragement throughout the entire research work. I would also like to extend my sincere gratitude to all technicians, staff and students, especially Mr. S.G. Chandrasegaran, Ms. Lee Leng Leng, Ms. Tan Xiaolan, Ms. Tan Hwee Bee, Ms. Ng Mei Joo and Mr. Tan Eng Hin, Michael, at the Environmental Engineering Laboratory of Division of Environmental Science and Engineering, National University of Singapore, for their assistance and cooperation in the many ways that made this research study possible. In addition, I wish to express my deep gratitude to National University of Singapore for financial support of my Ph.D study and various opportunities in academic activities. Special thanks also to be given to the Bedok and Ulu Pandan Water Reclamation Plant for the provision of raw water used in this study. Finally, I want to express my sincerest respect and thankfulness to my parents Mr LIU LianKao, Ms QI FuZhen, Elder sister LIU XiaoLuan and grandfather . I am deeply indebted to them for their everlasting support and encouragement in my study at Singapore. Without their endless encouragement and support, it would not be possible for me to complete my study. i TABLE OF CONTENTS Pages ACKNOWLEDGEMENT i TABLE OF CONTENTS .ii SUMMARY vi LIST OF TABLES .x LIST OF FIGURES xi LIST OF PLATES . xviii NOMENCLATURE .xix CHAPTER INTRODUCTION 1.1 Background 1.2 Objective and Scope 1.3 Organization of Thesis .5 CHAPTER LITERATURE REVIEW .8 2.1 Membrane Fouling .8 2.2 Membrane Fouling by EfOM .9 2.3 Membrane Fouling by NOM .15 2.4 Fouling Control Strategies .21 2.4.1 Conventional Pretreatment 21 2.4.2 Biofouling Prevention 23 2.4.3 MF/UF Membrane Pretreatment .25 2.5 Photocatalytic Reaction .27 2.6 Hybrid Membrane/Photocatalysis Process 33 2.7 Membrane Fouling Reduction by Photocatalytic Pretreatment .34 2.8 Summary 36 CHAPTER MATERIALS AND METHODS .39 ii 3.1 Photocatalysis Experiments .39 3.1.1 Catalysts .39 3.1.2 Feed Water .39 3.1.3 Photoreactor and UV Source .41 3.2 Crossflow RO Membrane Filtration Units .45 3.3 RO Membrane Fouling Experiments .47 3.4 Analytic Methods .48 3.4.1 Total Organic Carbon 48 3.4.2 Molecular Weight (MW) Distribution .48 3.4.3 UVA254, and Colour measurement (UVA430) 49 3.4.4 Contact Angle 50 3.4.5 Zeta Potential .50 3.4.6 Fourier Transform Infrared Spectroscopy (FTIR) .51 3.4.7 Excitation emission matrix (EEM) fluorescence spectroscopy and Synchronous fluorescence (SF) spectroscopy .52 CHAPTER NANO-SIZE TITANIA PHOTOCATALYSIS FOR ORGANIC FOULING ABATEMENT IN RO PROCESS IN THE RECLAMATION OF SECONDARY MUNICIPAL EFFLUENT .54 4.1 Introduction 54 4.2 Photocatalytic Oxidation of EfOM 57 4.3 EfOM Fouling on RO Membrane 65 4.3.1 Fouling Potential 65 4.3.2 Effect of Photocatalysis on Fouling Behaviors of EfOM 68 4.4 Changes in the Physicochemical Properties of EfOM .72 4.4.1 Molecular Weight Distribution 72 4.4.2 Hydrophobicity (SUVA and Contact angles) and Color of EfOM iii 74 4.4.3 Fluorescence Spectrum of EfOM 80 4.4.4 FTIR Spectrum 83 4.5 Conclusion .85 CHAPTER PHOTOCATALYTIC PRETREATMENT OF LOW CONCENTRATION SODIUM ALGINATE AND IMPACT ON ITS FOULING BEHAVIORS 88 5.1 Introduction 88 5.2 Photocatalytic Oxidation of Polysaccharide 90 5.3 Polysaccharide Fouling on RO Membrane 95 5.3.1 Fouling Potential 95 5.3.2 Influence of Electrolytes on Fouling .99 5.3.2.1 No External Electrolytes 100 5.3.2.2 Ionic Strength .102 5.3.2.3 The Effect of Calcium 103 5.3.3 Influence of Feed Foulant Composition on Fouling 106 5.3.4 Influence of Initial Concentration of Polysaccharides on Fouling 109 5.3.5 Influence of UV Sources on Fouling .112 5.3.6 Influence of Reaction Time on Fouling .113 5.3.7 Influence of Catalyst Concentrations on Fouling 116 5.4 Changes in the Physicochemical Properties of Polysaccharides .118 5.4.1 Molecular Weight Distribution 118 5.4.2 Zeta Potential .120 5.4.3 FTIR Spectrum 123 5.5 Conclusion .124 iv CHAPTER IMPACT OF PHOTOCATALYTIC PRETREATMENT ON REVERSE OSMOSIS MEMBRANE FOULING BY LOW CONCENTRATION NATURAL ORGANIC MATTERS .126 6.1 Introduction 126 6.2 Photocatalytic Oxidation of SRNOM 128 6.3 SRNOM Fouling on RO Membrane 133 6.3.1 Influence of Electrolytes on Fouling .133 6.3.1.1 No External Electrolytes 134 6.3.1.2 Ionic Strength .136 6.3.1.3 The Effect of Calcium 137 6.3.2 Influence of Feed Foulant Composition on Fouling 142 6.3.3 Influence of UV Sources on Fouling .143 6.4 Changes in the Physicochemical Properties of SRNOM .145 6.4.1 Hydrophobicity (SUVA values) and Color of SRNOM 145 6.4.2 Fluorescence Spectrum of SRNOM 149 6.4.3 Molecular Weight Distribution 155 6.4.4 Zeta Potential .157 6.4.5 FTIR Spectrum 160 6.5 Conclusion .162 CHAPTER CONCLUSIONS AND RECOMMENDATIONS 164 7.1 Conclusions 164 7.2 Recommendations for further research 166 REFERENCES 170 v SUMMARY Organic fouling caused by aqueous organic matters (AOM) from secondary effluents or natural water bodies has been the prime bottleneck hindering the widespread applications of RO membrane technology. These organic matters tend to absorb or deposit on RO membrane surface and often cause reversible or irreversible fouling. The costs associated with organic fouling abatement and the resultant flux decrease usually contribute to a significant fraction of the total cost of the membrane processes. The conventional pretreatment methods, such as coagulation/flocculation, have never satisfactorily prevented the fouling associated with aqueous biopolymers, such as the polysaccharides, protein, and natural organic matter (NOM). Moreover, due to the abundance and complexity of AOM in aquatic environment, conventional pretreatment measures cannot readily achieve stable performances. Even emerging membrane pretreatment system using low pressure driven membranes, such as microfiltration (MF), ultrafiltration pretreatment, or nanofiltration, which itself is susceptible to organic fouling by AOM, cannot address the problem over a long-term operation. Hence, it is timely and important to develop an alternative method for effective alleviation and control of organic fouling in RO process. The primary objective of this study was to develop a novel pretreatment method - hybrid photocatalysis and microfiltration process - for RO membrane fouling control in the water reclamation process. In this study, TiO2-based photocatalytic reaction combined with MF process was employed as pretreatment process for fouling reduction of RO membrane, vi with effluent organic matters (EfOM), a model hydrophilic polysaccharide (sodium alginate), a model protein (Bovine serum albumin) and Suwannee River NOM of hydrophobic propensity as foulants operated in a lab-scale cross flow RO membrane filtration system. Factors influencing the fouling potential of the feed solution were investigated. The hybrid system provided a good alternative to effectively control the organic fouling development on RO membrane. In the presence of UV light and nano-size TiO2, photocatalytic reaction within relatively short reaction time favorably changed the physicochemical properties of the reactants, such as the molecular weight distribution, functional groups, charge densities, etc, which were revealed by the tests of chromatography, high pressure Fluorescence liquid chromatography-size excitation–emission-matrix exclusion spectrum, Synchronous fluorescence spectrum, Fourier transform infrared spectroscopy, UV spectrum and Zeta potential, etc. At relatively low TOC concentration, the fouling potential, k, on RO membrane, a parameter for qualitative measurement of fouling tendency, was significantly lowered in the fouling tests with EfOM, polysacchrides and SRNOM, especially in the presence of calcium by photocatalytic pretreatment. This reduction could be ascribed to the changes in the properties of AOM introduced by photocatalysis, leading to attenuated intermolecular actions among organic molecules and reduced interactions between the organic molecules and RO membrane surface. The macromolecules of the hydrophobic matters could be degraded into less hydrophobic micromolecules, resulting in the decrease in their fouling potentials. These reductions were also significant for hydrophilic polysaccharides in the presence of Ca2+ due to the weakened intermolecular vii bridging effect on micromolecules, leading to a less dense fouling layer on membrane surface. These findings are of crucial importance in starting a new scenario in the study of organic fouling alleviation. In addition, the effects of solution chemistry, operation, and configuration parameters on the fouling behaviors of major organic foulants on RO membrane were also investigated. viii References  REFERENCES [1] Hilal N, Ogunbiyi OO, Miles NJ, Nigmatullin R. Methods employed for control of fouling in MF and UF membranes: A comprehensive review. Separation Science and Technology 2005;40(10):1957-2005. [2] Ma HM, Bowman CN, Davis RH. Membrane fouling reduction by backpulsing and surface modification. Journal of Membrane Science 2000;173(2):191-200. [3] Vrouwenvelder JS, Kappelhof J, Heijman SGJ, Schippers JC, van der Kooij D. Tools for fouling diagnosis of NF and RO membranes and assessment of the fouling potential of feed water. Conference on Desalination and the Environment - Fresh Water for All, Malta, Italy, 2003. p. 361-65. [4] Le-Clech P, Lee EK, Chen V. Hybrid photocatalysis/membrane treatment for surface waters containing low concentrations of natural organic matters. Water Research 2006;40(2):323-30. [5] Hoffmann MR, Martin ST, Choi WY, Bahnemann DW. Environmental Applications of Semiconductor Photocatalysis. Chemical Reviews 1995;95(1):69-96. [6] Peral J, Domenech X, Ollis DF. Heterogeneous photocatalysis for purification, decontamination and deodorization of air. Journal of Chemical Technology and Biotechnology 1997;70(2):117-40. [7] Scott JP, Ollis DF. Integration of chemical and biological oxidation processes for water treatment: Review and recommendations. Environmental Progress 1995;14(2):88-103. [8] Okamoto K, Yamamoto Y, Tanaka H, Tanaka M, Itaya A. Heterogeneous photocatalytic decomposition of phenol over TiO2 powder. Bulletin of the Chemical Society of Japan 1985;58(7):201522. [9] Alekabi H, Serpone N, Pelizzetti E, Minero C, Fox MA, Draper RB. Kinetic-studies in heterogeneous photocatalysis .2. TiO2-mediated degradation of 4-chlorophenol alone and in a 3-component mixture of 4-chlorophenol, 2,4-dichlorophenol, and 2,4,5-trichlorophenol in airequilibrated aqueous-media. Langmuir 1989;5(1):250-55. [10] Sabate J, Anderson MA, Kikkawa H, Edwards M, Hill CG. A kinetic study of the photocatalytic degradation of 3-chlorosalicylic acid over TiO2 membranes supported on glass. Journal of Catalysis 1991;127(1):167-77. 170 References  [11] Hidaka H, Zhao J. Photodegradation of surfactants catalyzed by a TiO2 semiconductor. Colloids and Surfaces 1992;67:165-82. [12] Percherancier JP, Chapelon R, Pouyet B. Semiconductor-sensitized photodegradation of pesticides in water - the case of Carbetamide. Journal of Photochemistry and Photobiology a-Chemistry 1995;87(3):261-66. [13] Taniguchi M, Kilduff JE, Belfort G. Modes of natural organic matter fouling during ultrafiltration. Environmental Science & Technology 2003;37(8):1676-83. [14] Hong SK, Elimelech M. Chemical and physical aspects of natural organic matter (NOM) fouling of nanofiltration membranes. Journal of Membrane Science 1997;132(2):159-81. [15] Jones KL, O'Melia CR. Protein and humic acid adsorption onto hydrophilic membrane surfaces: effects of pH and ionic strength. Journal of Membrane Science 2000;165(1):31-46. [16] Yuan W, Zydney AL. Humic acid fouling during microfiltration. Journal of Membrane Science 1999;157(1):1-12. [17] Lin CF, Lin TY, Hao OJ. Effects of humic substance characteristics on UF performance. Water Research 2000;34(4):1097-106. [18] Carroll T, King S, Gray SR, Bolto BA, Booker NA. The fouling of microfiltration membranes by NOM after coagulation treatment. Water Research 2000;34(11):2861-68. [19] Al-Ahmad M, Aleem FAA, Mutiri A, Ubaisy A. Biofuoling in RO membrane systems Part 1: Fundamentals and control. Conference on Membranes in Drinking and Industrial Water Production, Paris, France, 2000. p. 173-79. [20] Shon HK, Vigneswaran S, Kim IS, Cho J, Ngo HH. The effect of pretreatment to ultrafiltration of biologically treated sewage effluent: a detailed effluent organic matter (EfOM) characterization. WATER RESEARCH 2004;38(7):1933-39. [21] Shon HK, Vigneswaran S, Ngo HH, Aim RB. Is semi-flocculation effective as pretreatment to ultrafiltration in wastewater treatment? WATER RESEARCH 2005;39(1):147-53. [22] Lee S, Lee CH. Microfiltration and ultrafiltration as a pretreatment for nanofiltration of surface water. Separation Science and Technology 2006;41(1):1-23. [23] Schiener P, Nachaiyasit S, Stuckey DC. Production of soluble microbial products (SMP) in an anaerobic baffled reactor: Composition, biodegradability, and the effect of process parameters. Environmental Technology 1998;19(4):391-99. 171 References  [24] Barker DJ, Salvi SML, Langenhoff AAM, Stuckey DC. Soluble microbial products in ABR treating low-strength wastewater. Journal of Environmental Engineering-Asce 2000;126(3):239-49. [25] Drewes JE, Fox P. Fate of natural organic matter (NOM) during groundwater recharge using reclaimed water. IAWQ/IWSA International Conference on Removal of Humic Substances from Water, Trondheim, Norway, 1999. p. 241-48. [26] Park N, Kwon B, Kim IS, Cho JW. Biofouling potential of various NF membranes with respect to bacteria and their soluble microbial products (SMP): Characterizations, flux decline, and transport parameters. Journal of Membrane Science 2005;258(1-2):43-54. [27] Shon HK, Vigneswaran S, Ben Aim R, Ngo HH, Kim IS, Cho J. Influence of flocculation and adsorption as pretreatment on the fouling of ultrafiltration and nanofiltration membranes: Application with biologically treated sewage effluent. Environmental Science & Technology 2005;39(10):3864-71. [28] Rittmann BE, Bae W, Namkung E, Lu CJ. A critical-evaluation of microbial product formation in biological processes. Water Science and Technology 1987;19(3-4):517-28. [29] Manka J, Rebhun M, Mandelbaum A, Bortinger A. Characterization of organics in secondary effluents. Environmental Science & Technology 1974;8(12):1017-20. [30] Jarusutthirak C, Amy G, Croue JP. Fouling characteristics of wastewater effluent organic matter (EfOM) isolates on NF and UF membranes. International Congress on Membranes and Membrane Processes (ICOM), Taulouse, France, 2002. p. 247-55. [31] Barker DJ, Stuckey DC. A review of soluble microbial products (SMP) in wastewater treatment systems. Water Research 1999;33(14):3063-82. [32] Hejzlar J, Chudoba J. Microbial polymers in the aquatic environment .2. isolation from biologically non-purified and purified municipal waste-water and analysis. Water Research 1986;20(10):1217-21. [33] Flemming HC, Schaule G, Griebe T, Schmitt J, Tamachkiarowa A. Biofouling - the Achilles heel of membrane processes. Workshop on Membranes in Drinking Water Production - Technical Innovations and Health Aspects, Laquila, Italy, 1997. p. 215-25. [34] Jarusutthirak C, Amy G. Role of Soluble Microbial Products (SMP) in Membrane Fouling and Flux Decline. Environ. Sci. Technol. 2006;40(3):969-74. 172 References  [35] Lee S, Ang WS, Elimelech M. Fouling of reverse osmosis membranes by hydrophilic organic matter: implications for water reuse. Desalination 2006;187(1-3):313-21. [36] Lee S, Elimelech M. Relating organic fouling of reverse osmosis membranes to intermolecular adhesion forces. Environmental Science & Technology 2006;40(3):980-87. [37] Xie RJ, Gomez MJ, Xing YJ, Klose PS. Fouling assessment in a municipal water reclamation reverse osmosis system as related to concentration factor. Journal of Environmental Engineering and Science 2004;3(1):61-72. [38] Schneider RP, Ferreira LM, Binder P, Ramos JR. Analysis of foulant layer in all elements of an RO train. Journal of Membrane Science 2005;261(1-2):152-62. [39] Boerlage SFE, Kennedy MD, Witkamp GJ, van der Hoek JP, Schippers JC. BaSO4 solubility prediction in reverse osmosis membrane systems. Journal of Membrane Science 1999;159(1-2):4759. [40] Li JX, Hallbauer-Zadorozhnaya VY, Hallbauer DK, Sanderson RD. Cake-layer deposition, growth, and compressibility during microfiltration measured and modeled using a noninvasive ultrasonic technique. Industrial & Engineering Chemistry Research 2002;41(16):4106-15. [41] Thurman EM, Malcolm RL. Preparative isolation of aquatic humic substances. Environmental Science & Technology 1981;15(4):463-66. [42] Nilson JA, DiGiano FA. Influence of NOM composition on nanofiltration. Journal American Water Works Association 1996;88(5):53-66. [43] Aiken GR, McKnight DM, Thorn KA, Thurman EM. Isolation of hydrophilic organic-acids from water using nonionic macroporous resins. Organic Geochemistry 1992;18(4):567-73. [44] Owen DM, Amy GL, Chowdhury ZK, Paode R, McCoy G, Viscosil K. NOM - Characterization and treatability. Journal American Water Works Association 1995;87(1):46-63. [45] Stevenson IL, Schnitzer M. Transmission electron-microscopy of extracted fulvic and humic acids. Soil Science 1982;133(3):179-85. [46] Jucker C, Clark MM. Adsorption of aquatic humic substances on hydrophobic ultrafiltration membranes. Journal of Membrane Science 1994;97:37-52. [47] Beckett R, Jue Z, Giddings JC. Determination of molecular-weight distributions of fulvic and humic acids using flow field-flow 173 References  fractionation. Environmental Science & Technology 1987;21(3):28995. [48] Chin Y-P, Aiken G, O'Loughlin E. Molecular Weight, Polydispersity, and Spectroscopic Properties of Aquatic Humic Substances. Environ. Sci. Technol. 1994;28(11):1853-58. [49] Maurice PA, Pullin MJ, Cabaniss SE, Zhou QH, NamjesnikDejanovic K, Aiken GR. A comparison of surface water natural organic matter in raw filtered water samples, XAD, and reverse osmosis isolates. WATER RESEARCH 2002;36(9):2357-71. [50] Howe KJ, Clark MM. Fouling of microfiltration and ultrafiltration membranes by natural waters. Environmental Science & Technology 2002;36(16):3571-76. [51] Kaiya Y, Itoh Y, Fujita K, Takizawa S. Study on fouling materials in the membrane treatment process for potable water. International Water Specialists Conference, Perth, Australia, 1994. p. 71-77. [52] Yuan W, Zydney AL. Humic acid fouling during ultrafiltration. Environmental Science & Technology 2000;34(23):5043-50. [53] Lin CF, Liu SH, Hao OJ. Effect of functional groups of humic substances on UF performance. Water Research 2001;35(10):2395402. [54] Fan LH, Harris JL, Roddick FA, Booker NA. Influence of the characteristics of natural organic matter on the fouling of microfiltration membranes. Water Research 2001;35(18):4455-63. [55] Crozes G, Anselme C, Mallevialle J. Effect of adsorption of organicmatter on fouling of ultrafiltration membranes. Journal of Membrane Science 1993;84(1-2):61-77. [56] Yamagiwa K, Kobayashi H, Ohkawa A, Onodera M. Membrane fouling in ultrafiltration of hydrophobic nonionic surfactant. Journal of Chemical Engineering of Japan 1993;26(1):13-18. [57] Speth TF, Summers RS. Evaluating membrane foulants from conventionally-treated drinking waters. Abstracts of Papers of the American Chemical Society 1996;212:6-ENVR. [58] Childress AE, Elimelech M. Effect of solution chemistry on the surface charge of polymeric reverse osmosis and nanofiltration membranes. Journal of Membrane Science 1996;119(2):253-68. [59] Seidel A, Elimelech M. Coupling between chemical and physical interactions in natural organic matter (NOM) fouling of nanofiltration membranes: implications for fouling control. Journal of Membrane Science 2002;203(1-2):245-55. 174 References  [60] Ghosh K, Schnitzer M. Macromolecular structures of humic substances. Soil Science 1980;129(5):266-76. [61] Gur-Reznik S, Katz I, Dosoretz CG. Removal of dissolved organic matter by granular-activated carbon adsorption as a pretreatment to reverse osmosis of membrane bioreactor effluents. Water Research 2008;42(6-7):1595-605. [62] López-Ramírez JA, Sahuquillo S, Sales D, Quiroga JM. Pre-treatment optimisation studies for secondary effluent reclamation with reverse osmosis. Water Research 2003;37(5):1177-84. [63] van der Hoek JP, Hofman JAMH, Bonné PAC, Nederlof MM, Vrouwenvelder HS. RO treatment: selection of a pretreatment scheme based on fouling characteristics and operating conditions based on environmental impact. Desalination 2000;127(1):89-101. [64] Wend CF, Stewart PS, Jones W, Camper AK. Pretreatment for membrane water treatment systems: a laboratory study. Water Research 2003;37(14):3367-78. [65] Maartens A, Swart P, Jacobs EP. Feed-water pretreatment: methods to reduce membrane fouling by natural organic matter. Journal of Membrane Science 1999;163(1):51-62. [66] Al-Malack MH, Anderson GK. Coagulation-crossflow microfiltration of domestic wastewater. Journal of Membrane Science 1996;121(1):59-70. [67] Lahoussineturcaud V, Wiesner MR, Bottero JY, Mallevialle J. Coagulation pretreatment for Ultrafiltration of a surface-water. Journal American Water Works Association 1990;82(12):76-81. [68] Kerry JH, Mark MC. Effect of coagulation pretreatment on membrane filtration performance. American Water Works Association. Journal 2006;98(4):133. [69] Kim SH, Moon SY, Yoon CH, Yim SK, Cho JW. Role of coagulation in membrane filtration of wastewater for reuse. Desalination 2005;173(3):301-07. [70] Mores WD, Davis RH. Direct visual observation of yeast deposition and removal during microfiltration. Journal of Membrane Science 2001;189(2):217-30. [71] Campbell P, Srinivasan R, Knoell T, Phipps D, Ishida K, Safarik J, et al. Quantitative structure-activity relationship (QSAR) analysis of surfactants influencing attachment of a Mycobacterium sp to cellulose acetate and aromatic polyamide reverse osmosis membranes. Biotechnology and Bioengineering 1999;64(5):527-44. 175 References  [72] Kang ST, Subramani A, Hoek EMV, Deshusses MA, Matsumoto MR. Direct observation of biofouling in cross-flow microfiltration: mechanisms of deposition and release. Journal of Membrane Science 2004;244(1-2):151-65. [73] Li QL, Elimelech M. Organic fouling and chemical cleaning of nanofiltration membranes: Measurements and mechanisms. Environmental Science & Technology 2004;38(17):4683-93. [74] Gabelich CJ, Yun TI, Ishida KP, Leddy MB, Safarik J. The effect of naturally occurring biopolymers on polyamide membrane fouling during surface water treatment. Desalination 2004;161(3):263-76. [75] Bull RJ, Birnbaum LS, Cantor KP, Rose JB, Butterworth BE, Pegram R, et al. Water Chlorination: Essential Process or Cancer Hazard? Fundamental and Applied Toxicology 1995;28(2):155-66. [76] Ng WJ, Ong SL, Hu JY. The effects of water reclamation technologies on biological stability of industrial water. 3rd International Symposium on Wastewater Reclamation, Recycling and Reuse held in Conjunction with the 1st IWA World Congress, Paris, France, 2000. p. 327-34. [77] Hu JY, Song LF, Ong SL, Phua ET, Ng WJ. Biofiltration pretreatment for reverse osmosis (RO) membrane in a water reclamation system. Chemosphere 2005;59(1):127-33. [78] Gabelich CJ, Yun TI, Coffey BM, Suffet IH. Pilot-scale testing of reverse osmosis using conventional treatment and microfiltration. Desalination 2003;154(3):PII S0011-9164(03)00222-4. [79] Wilf M, Schierach MK. Improved performance and cost reduction of RO seawater systems using UF pretreatment. International Conference on Seawater Desalination Technologies on the Threshold of the New Millennium, Kuwait, 2000. p. 61-68. [80] Speth TF, Summers RS, Gusses AM. Nanofiltration foulants from a treated surface water. Environmental Science & Technology 1998;32(22):3612-17. [81] Kimura K, Hane Y, Watanabe Y, Amy G, Ohkuma N. Irreversible membrane fouling during ultrafiltration of surface water. Water Research 2004;38(14-15):3431-41. [82] Crozes GF, Jacangelo JG, Anselme C, Laîné JM. Impact of ultrafiltration operating conditions on membrane irreversible fouling. Journal of Membrane Science 1997;124(1):63-76. [83] Kamp PC, Kruithof JC, Folmer HC. UF/RO treatment plant Heemskerk: from challenge to full scale application. Conference on 176 References  Membranes in Drinking and Industrial Water Production, Paris, France, 2000. p. 27-35. [84] Ericsson B, Hallmans B. Membrane applications in raw watertreatment with and without reverse-osmosis desalination. IDA and WRPC World Conference on Desalination and Water Treatment, Yokohama, Japan, 1993. p. 3-16. [85] Brehant A, Bonnelye V, Perez M. Comparison of MF/UF pretreatment with conventional filtration prior to RO membranes for surface seawater desalination. International Congress on Membranes and Membrane Processes (ICOM), Taulouse, France, 2002. p. 353-60. [86] Mills A, LeHunte S. An overview of semiconductor photocatalysis. Journal of Photochemistry and Photobiology a-Chemistry 1997;108(1):1-35. [87] Hashimoto K, Irie H, Fujishima A. TiO2 photocatalysis: A historical overview and future prospects. Japanese Journal of Applied Physics Part 1-Regular Papers Brief Communications & Review Papers 2005;44(12):8269-85. [88] Herrmann JM. Heterogeneous photocatalysis: fundamentals and applications to the removal of various types of aqueous pollutants. Catalysis Today 1999;53(1):115-29. [89] Cabrera MI, Alfano OM, Cassano AE. Absorption and scattering coefficients of titanium dioxide particulate suspensions in water. Journal of Physical Chemistry 1996;100(51):20043-50. [90] Arana J, Nieto JLM, Melian JAH, Rodriguez JMD, Diaz OG, Pena JP, et al. Photocatalytic degradation of formaldehyde containing wastewater from veterinarian laboratories. Chemosphere 2004;55(6):893-904. [91] Brandi RJ, Alfano OM, Cassano AE. Rigorous model and experimental verification of the radiation field in a flat-plate solar collector simulator employed for photocatalytic reactions. 15th International Symposium on Chemical Reaction Engineering (ISCRE 15), Newport Beach, California, 1998. p. 2817-27. [92] Arancibia-Bulnes CA, Cuevas SA. Modeling of the radiation field in a parabolic trough solar photocatalytic reactor. Solar Energy 2004;76(5):615-22. [93] Wiszniowski J, Robert D, Surmacz-Gorska J, Miksch K, Weber JV. Photocatalytic decomposition of humic acids on TiO2 Part I: Discussion of adsorption and mechanism. Journal of Photochemistry and Photobiology a-Chemistry 2002;152(1-3):267-73. 177 References  [94] Fu XZ, Zeltner WA, Anderson MA. The gas-phase photocatalytic mineralization of benzene on porous titania-based catalysts. Applied Catalysis B-Environmental 1995;6(3):209-24. [95] Fujishima A, Rao TN, Tryk DA. Titanium dioxide photocatalysis. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 2000;1(1):1-21. [96] Zheng H, Maness PC, Blake DM, Wolfrum EJ, Smolinski SL, Jacoby WA. Bactericidal mode of titanium dioxide photocatalysis. Journal of Photochemistry and Photobiology a-Chemistry 2000;130(2-3):163-70. [97] Maness PC, Smolinski S, Blake DM, Huang Z, Wolfrum EJ, Jacoby WA. Bactericidal activity of photocatalytic TiO2 reaction: Toward an understanding of its killing mechanism. Applied and Environmental Microbiology 1999;65(9):4094-98. [98] Wolfrum EJ, Huang J, Blake DM, Maness PC, Huang Z, Fiest J, et al. Photocatalytic oxidation of bacteria, bacterial and fungal spores, and model biofilm components to carbon dioxide on titanium dioxidecoated surfaces. Environmental Science & Technology 2002;36(15):3412-19. [99] Blake DM, Maness PC, Huang Z, Wolfrum EJ, Huang J, Jacoby WA. Application of the photocatalytic chemistry of titanium dioxide to disinfection and the killing of cancer cells. Separation and Purification Methods 1999;28(1):1-50. [100] Molinari R, Mungari M, Drioli E, Di Paola A, Loddo V, Palmisano L, et al. Study on a photocatalytic membrane reactor for water purification. 2nd World Congress of Environmental Catalysis, Miami, Florida, 1998. p. 71-78. [101] Molinari R, Palmisano L, Drioli E, Schiavello M. Studies on various reactor configurations for coupling photocatalysis and membrane processes in water purification. Journal of Membrane Science 2002;206(1-2):399-415. [102] Matthews RW, McEvoy SR. Photocatalytic degradation of phenol in the presence of near-UV illuminated titanium dioxide. Journal of Photochemistry and Photobiology A: Chemistry 1992;64(2):231-46. [103] Molinari R, Borgese M, Drioli E, Palmisano L, Schiavello M. Hybrid processes coupling photocatalysis and membranes for degradation of organic pollutants in water. Catalysis Today 2002;75(1-4):77-85. [104] Chatterjee D, Dasgupta S. Visible light induced photocatalytic degradation of organic pollutants. Journal of Photochemistry and Photobiology C-Photochemistry Reviews 2005;6(2-3):186-205. 178 References  [105] Navio JA, Testa JJ, Djedjeian P, Padron JR, Rodriguez D, Litter MI. Iron-doped titania powders prepared by a sol-gel method. Part II: Photocatalytic properties. Applied Catalysis a-General 1999;178(2):191-203. [106] Liu HY, Song L. Titania based photocatalysis as the pretreatment for ultrafiltration of secondary municipal effluent with low concentration of organic matters. The Proceedings of Water Resources Management IV, Greece, May 2007. p. 411-20. [107] Huang X, Leal M, Li Q. Degradation of natural organic matter by TiO2 photocatalytic oxidation and its effect on fouling of lowpressure membranes. Water Research 2008;42(4-5):1142-50. [108] Song W, Ravindran V, Koel BE, Pirbazari M. Nanofiltration of natural organic matter with H2O2/UV pretreatment: fouling mitigation and membrane surface characterization. Journal of Membrane Science 2004;241(1):143-60. [109] Lee S, Cho JW, Elimelech M. Combined influence of natural organic matter (NOM) and colloidal particles on nanofiltration membrane fouling. Journal of Membrane Science 2005;262(1-2):2741. [110] Lee S, Elimelech M. Salt cleaning of organic-fouled reverse osmosis membranes. Water Research 2007;41(5):1134-42. [111] PeulaGarcia JM, HidaldoAlvarez R, delasNieves FJ. Protein coadsorption on different polystyrene latexes: Electrokinetic characterization and colloidal stability. Colloid and Polymer Science 1997;275(2):198-202. [112] Ci SX, Huynh TH, Louie LW, Yang A, Beals BJ, Ron N, et al. Molecular mass distribution of sodium alginate by high-performance size-exclusion chromatography. Journal of Chromatography A 1999;864(2):199-210. [113] Bosco MV, Callao MP, Larrechi MS. Simultaneous analysis of the photocatalytic degradation of polycyclic aromatic hydrocarbons using three-dimensional excitation-emission matrix fluorescence and parallel factor analysis. Analytica Chimica Acta 2006;576(2):184-91. [114] Rinnan A, Booksh KS, Bro R. First order Rayleigh scatter as a separate component in the decomposition of fluorescence landscapes. Analytica Chimica Acta 2005;537(1-2):349-58. [115] JiJi RD, Booksh KS. Mitigation of Rayleigh and Raman Spectral Interferences in Multiway Calibration of Excitation-Emission Matrix Fluorescence Spectra. Anal. Chem. 2000;72(4):718-25. 179 References  [116] Gourley L, Britten M, Gauthier SF, Pouliot Y. Characterization of adsorptive fouling on ultrafiltration membranes by peptides mixtures using contact-angle measurements. Journal of Membrane Science 1994;97:283-89. [117] Shon HK, Vigneswaran S, Kim IS, Cho J, Ngo HH. Fouling of ultrafiltration membrane by effluent organic matter: A detailed characterization using different organic fractions in wastewater. JOURNAL OF MEMBRANE SCIENCE 2006;278(1-2):232-38. [118] Escobar IC, Hoek EM, Gabelich CJ, DiGiano FA, Le Gouellec YA, Berube P, et al. Committee Report: Recent advances and research needs in membrane fouling. Journal American Water Works Association 2005;97(8):79-89. [119] Mills A, Davies RH, Worsley D. Water-purification by semiconductor photocatalysis. Chemical Society Reviews 1993;22(6):417-25. [120] Carp O, Huisman CL, Reller A. Photoinduced reactivity of titanium dioxide. Progress in Solid State Chemistry 2004;32(1-2):33177. [121] Sclafani A, Herrmann JM. Comparison of the photoelectronic and photocatalytic activities of various anatase and rutile forms of titania in pure liquid organic phases and in aqueous solutions. Journal of Physical Chemistry 1996;100(32):13655-61. [122] Pekakis PA, Xekoukoulotakis NP, Mantzavinos D. Treatment of textile dyehouse wastewater by TiO2 photocatalysis. Water Research 2006;40(6):1276-86. [123] Paz Y. Preferential photodegradation - why and how? Comptes Rendus Chimie 2006;9(5-6):774-87. [124] Gumy D, Morais C, Bowen P, Pulgarin C, Giraldo S, Hajdu R, et al. Catalytic activity of commercial of TiO2 powders for the abatement of the bacteria (E. coli) under solar simulated light: Influence of the isoelectric point. Applied Catalysis B: Environmental 2006;63(12):76-84. [125] Yang H-G, Li C-Z, Gu H-C, Fang T-N. Rheological Behavior of Titanium Dioxide Suspensions. Journal of Colloid and Interface Science 2001;236(1):96-103. [126] Foissy A, El Attar A, Lamarche JM. Adsorption of polyacrylic acid on titanium dioxide. Journal of Colloid and Interface Science 1983;96(1):275-87. [127] Kormann C, Bahnemann DW, Hoffmann MR. Photolysis of chloroform and other organic molecules in aqueous titanium dioxide 180 References  suspensions. Environmental Science & Technology 1991;25(3):494500. [128] Song LF, Chen KL, Ong SL, Ng WJ. A new normalization method for determination of colloidal fouling potential in membrane processes. Journal of Colloid and Interface Science 2004;271(2):42633. [129] Lee S, Ang WS, Elimelech M. Novel salt cleaning of organic fouled reverse osmosis membranes. Abstracts of Papers of the American Chemical Society 2005;229:U633-U33. [130] Israelachvili JN. Intermolecular and surface forces. Academic Press, 1992. [131] Schwarzenbach RP, Gschwend PM, Imboden DM. Environmental organic chemistry. Wiley-Interscience publication, 1993. [132] Jarusutthirak C, Amy G, Croue JP. Fouling characteristics of wastewater effluent organic matter (EfOM) isolates on NF and UF membranes. Desalination 2002;145(1-3):247-55. [133] Lee NH, Amy G, Croue JP, Buisson H. Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM). Water Research 2004;38(20):4511-23. [134] Bennett LE, Drikas M. The evaluation of color in natural-waters. Water Research 1993;27(7):1209-18. [135] Arana J, Melian JAH, Rodriguez JMD, Diaz OG, Viera A, Pena JP, et al. TiO2-photocatalysis as a tertiary treatment of naturally treated wastewater. Catalysis Today 2002;76(2-4):279-89. [136] Uyguner CS, Bekbolet M. Implementation of spectroscopic parameters for practical monitoring of natural organic matter. Desalination 2005;176(1-3):47-55. [137] Uyguner CS, Bekbolet M. Evaluation of humic acid photocatalytic degradation by UV-vis and fluorescence spectroscopy. Catalysis Today 2005;101(3-4):267-74. [138] Coble PG. Characterization of marine and terrestrial DOM in seawater using excitation emission matrix spectroscopy. Marine Chemistry 1996;51(4):325-46. [139] Swietlik J, Sikorska E. Application of fluorescence spectroscopy in the studies of natural organic matter fractions reactivity with chlorine dioxide and ozone. Water Research 2004;38(17):3791-99. [140] Sierra MMD, Giovanela M, Parlanti E, Soriano-Sierra EJ. Fluorescence fingerprint of fulvic and humic acids from varied 181 References  origins as viewed by single-scan and excitation/emission matrix techniques. Chemosphere 2005;58(6):715-33. [141] Zhang T, Lu J, Ma J, Qiang Z. Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation. Chemosphere 2008;71(5):911-21. [142] Chen J, LeBoef EJ, Dai S, Gu BH. Fluorescence spectroscopic studies of natural organic matter fractions. Chemosphere 2003;50(5):639-47. [143] Cabaniss SE. Synchronous fluorescence-spectra of metal-fulvic acid complexes. Environmental Science & Technology 1992;26(6):1133-39. [144] Hu Y-J, Liu Y, Pi Z-B, Qu S-S. Interaction of cromolyn sodium with human serum albumin: A fluorescence quenching study. Bioorganic & Medicinal Chemistry 2005;13(24):6609-14. [145] Senesi N. Molecular and quantitative aspects of the chemistry of fulvic-acid and its interactions with metal-ions and organicchemicals .2. the fluorescence spectroscopy approach. Analytica Chimica Acta 1990;232(1):77-106. [146] Ghatak H, Mukhopadhyay SK, Jana TK, Sen BK, Sen S. Interactions of Cu (II) and Fe (III) with mangal humic substances studied by synchronous fluorescence spectroscopy and potentiometric titration. Wetlands Ecology and Management 2004;12(3):145-55. [147] McMurry J. Organic chemistry. Thomson Brooks/Cole, 2008. [148] Kuptsov AH, Zhizhin GN. Handbook of fourier transform Raman and infrared spectra of polymers. Elsevier Science, 1998. [149] Lee S, Lee CH. Effect of membrane properties and pretreatment on flux and NOM rejection in surface water nanotiltration. Separation and Purification Technology 2007;56(1):1-8. [150] Kumar M, Adham SS, Pearce WR. Investigation of seawater reverse osmosis fouling and its relationship to pretreatment type. Environmental Science & Technology 2006;40(6):2037-44. [151] Ang WS, Lee SY, Elimelech M. Chemical and physical aspects of cleaning of organic-fouled reverse osmosis membranes. Journal of Membrane Science 2006;272(1-2):198-210. [152] Carman PC. Fundamental principles of industrial filtrantion. Trans. Inst. Chem. Eng. 1938;16:168-87. 182 References  [153] de Kerchove AJ, Elimelech M. Formation of polysaccharide gel layers in the presence of Ca2+ and K+ ions: Measurements and mechanisms. Biomacromolecules 2007;8(1):113-21. [154] Ang WS, Elimelech M. Protein (BSA) fouling of reverse osmosis membranes: Implications for wastewater reclamation. JOURNAL OF MEMBRANE SCIENCE 2007;296(1-2):83-92. [155] Elimelech M, Chen WH, Waypa JJ. Measuring the zeta (electrokinetic) potential of reverse-osmosis membranes by a streaming potential analyzer. Desalination 1994;95(3):269-86. [156] Al-Amoudi A, Lovitt RW. Fouling strategies and the cleaning system of NF membranes and factors affecting cleaning efficiency. Journal of Membrane Science 2007;303(1-2):4-28. [157] Pongsawatmanit R, Harnsilawat T, McClements DJ. Influence of alginate, pH and ultrasound treatment on palm oil-in-water emulsions stabilized by [beta]-lactoglobulin. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2006;287(1-3):59-67. [158] Harnsilawat T, Pongsawatmanit R, McClements DJ. Characterization of [beta]-lactoglobulin-sodium alginate interactions in aqueous solutions: A calorimetry, light scattering, electrophoretic mobility and solubility study. Food Hydrocolloids 2006;20(5):577-85. [159] Li QL, Xu ZH, Pinnau I. Fouling of reverse osmosis membranes by biopolymers in wastewater secondary effluent: Role of membrane surface properties and initial permeate flux. Journal of Membrane Science 2007;290(1-2):173-81. [160] Zhan J, Liu Z, Wang BG, Ding FX. Modification of a membrane surface charge by a low temperature plasma induced grafting reaction and its application to reduce membrane fouling. Separation Science and Technology 2004;39(13):2977-95. [161] Wilf M, Alt S. Application of low fouling RO membrane elements for reclamation of municipal wastewater. Conference on Membranes in Drinking and Industrial Water Production, Paris, France, 2000. p. 11-19. [162] Clark MM, Allgeier S, Amy G, Chellam S, DiGiano F, Elimelech M, et al. Committee report: Membrane processes. Journal American Water Works Association 1998;90(6):91-105. [163] Hilal N, Al-Zoubi H, Darwish NA, Mohammad AW, Abu Arabi M. A comprehensive review of nanofiltration membranes: Treatment, pretreatment, modelling, and atomic force microscopy. DESALINATION 2004;170(3):281-308. 183 References  [164] Childress AE, Elimelech M. Relating nanofiltration membrane performance to membrane charge (electrokinetic) characteristics. Environmental Science & Technology 2000;34(17):3710-16. [165] Everett CR, Chin YP, Aiken GR. High-pressure size exclusion chromatography analysis of dissolved organic matter isolated by tangential-flow ultrafiltration. Limnology and Oceanography 1999;44(5):1316-22. [166] Hudson N, Baker A, Reynolds D. Fluorescence analysis of dissolved organic matter in natural, waste and polluted waters - A review. River Research and Applications 2007;23(6):631-49. [167] Peuravuori J, Koivikko R, Pihlaja K. Characterization. differentiation and classification of aquatic humic matter separated with different sorbents: synchronous scanning fluorescence spectroscopy. Water Research 2002;36(18):4552-62. [168] Duarte R, Santos EBH, Duarte AC. Spectroscopic characteristics of ultrafiltration fractions of fulvic and humic acids isolated from an eucalyptus bleached Kraft pulp mill effluent. Water Research 2003;37(17):4073-80. [169] Collins MR, Amy GL, Steelink C. Molecular-weight distribution, carboxylic acidity, and humic substances content of aquatic organicmatter - implications for removal during water-treatment. Environmental Science & Technology 1986;20(10):1028-32. [170] Chandrakanth MS, Amy GL. Effects of NOM source variations and calcium complexation capacity on ozone-induced particle destabilization. Water Research 1998;32(1):115-24. [171] Benson SW, -. Thermochemical kinetics ; methods for the estimation of thermochemical data and rate parameters, Wiley, 1968 (xii, 223 p . illus . 23 cm. pp.). [172] Chen J, Gu BH, LeBoeuf EJ, Pan HJ, Dai S. Spectroscopic characterization of the structural and functional properties of natural organic matter fractions. Chemosphere 2002;48(1):59-68. 184 185 [...]... minor modification of the functional groups of the substrate and decreasing membrane fouling by biopolymers associated with microorganism Therefore it is a possible process for organic fouling control in membrane process Our aim in this research was to develop a novel pretreatment measure for organic fouling control of RO process by a hybrid photocatalysis process and low-pressure-driven membrane process,... also associated with membrane fouling The current understanding of all of these chemical and physical interactions is still insufficient to provide a comprehensive and systematic understanding of membrane fouling Organic fouling by aqueous organic matters and biofouling caused by an active biofilm remain as the major problems in membrane- related water and wastewater processes Organic foulants in aqueous... because of its high effectiveness in removing particles, including microorganisms, organic pollutants, inorganic salts, and achieving a biologically stable water However, membrane fouling is still a major obstacle for wide-scale application of this technology Several types of fouling can occur in membrane systems including inorganic fouling, particulate and colloidal fouling, organic fouling, and biofouling... LITERATURE REVIEW 2.1 Membrane Fouling Membrane systems - Microfiltration/ Ultrafiltration (MF/UF) and Nanofiltration/ Reverse Osmosis (NF/RO) - are increasingly being applied for water and wastewater treatment and water reclamation The choice of membrane, module configuration, process and operating parameters, and pretreatment are very important factors affecting efficiency of separation Membrane technology... effects of membrane fouling [1-3] 1 Chapter 1  The costs associated with fouling control and abatement usually contribute to a significant fraction of the total cost of the membrane processes Membrane fouling is inevitable in membrane filtration processes [1-3] and the reduction of fouling propensity of the feed water with the appropriate treatment is one of the most serious considerations of membrane. .. hydrophilic polysaccharides and effluent organic matters, and to investigate the possible mechanisms of changes in fouling potentials and the correlation between physicochemical property changes and fouling behaviors (iv) RO membrane fouling alleviation with hybrid pretreatment - to compare and optimize the fouling control efficiency for various membrane /photocatalysis configuration factors, and to investigate... process Fouling control mechanisms was elucidated for major organic matters in the biologicallytreated sewage effluent, such as polysaccharides, protein, and natural organic matter (NOM), and the fouling control efficiency was optimized 1.2 Objective and Scope The overall objective of this proposed study was to develop a hybrid photocatalysis/ membrane pretreatment system for effective alleviation and control. .. Accordingly, SMP fouling is one of the major types of fouling in the RO process and it was found to provide high membrane fouling potential during water reclamation/reuse [26] Microorganisms and their SMP have been found to be the major source of membrane biofouling in the wastewater reclamation system especially in the RO, NF processes Biofouling is more complicated than other membrane fouling phenomena Fouling. .. processes Organic fouling and biofouling are regarded as the two major types of fouling for membrane related to water and wastewater treatment that can be less effectively abated by common pretreatment measures The common pretreatment measures, such as coagulation/flocculation, sedimentation, and filtration, are more effective for particulate and colloidal foulants At very low concentrations, aqueous organic. .. blocking and cake formation are considered as the two main mechanisms of membrane fouling while other factors such as adsorption, particle deposition within the pores, etc also have some effect on the fouling formation [13] Membrane fouling is an extremely complex physicochemical phenomenon Fouling of membrane is determined by the composition of the feed water and the physical-chemical properties of membranes . HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU NATIONAL UNIVERSITY OF SINGAPORE. 2009 HYBRID PHOTOCATALYSIS AND MICROFILTRATION PRETREATMENT FOR ORGANIC FOULING CONTROL OF REVERSE OSMOSIS MEMBRANE LIU HONGYU (M. Eng., Beijing Univ. of Civil Eng method for effective alleviation and control of organic fouling in RO process. The primary objective of this study was to develop a novel pretreatment method - hybrid photocatalysis and microfiltration