Rejection of steriod hormone estrone by NF RO membranes

REJECTION OF STEROID HORMONE ESTRONE BY NF/RO MEMBRANES JIN XUE NATIONAL UNIVERSITY OF SINGAPORE 2007 Founded 1905 REJECTION OF STEROID HORMONE ESTRONE BY NF/RO MEMBRANES BY JIN XUE (B.Eng. Tsinghua Univ.) A THESIS SUBMITTED FOR THE DEGREE OF PHILOSOPHIAE DOCTOR DEPARTMENT OF CIVIL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2007 ACKNOWLEDGEMENT The author wishes to express her deepest appreciation and gratitude to her supervisors, Associate Professor Hu Jiangyong and Professor Ong Say Leong for their invaluable guidance and encouragement throughout the entire course of the research project. The author would like to thank cordially Dr Shan Junhong for her helpful insights and suggestions, which led to the solution of a critical issue of this study. Thanks are also due to all technicians, staff and students, especially Mr. S.G. Chandrasegaran, Ms. Lee Leng Leng, Ms. Tan Xiaolan at the Environmental Engineering Laboratory of Department of Civil Engineering, National University of Singapore, for their assistance and cooperation in the many ways that made this research study possible. Finally and foremost, I would like to express my deepest gratitude and love from the bottom of my heart to my parents Mr. Jin Huaying and Ms. Zhang Ran, and my husband Mr. Liu Xiaopeng. Without their love, encouragement and understanding, this work could not have been completed. i TABLE OF CONTENTS ACKNOWLEDGEMENT .I TABLE OF CONTENTS II SUMMARY .VI NOMENCLATURE IX LIST OF FIGURES XII LIST OF TABLES .XVI LIST OF PLATES XVIII CHAPTER ONE INTRODUCTION 1.1 BACKGROUND 1.2 PROBLEM STATEMENT . 1.3 OBJECTIVE AND SCOPE OF STUDY CHAPTER TWO LITERATURE REVIEW . 2.1 ENDOCRINE DISRUPTING CHEMICALS (EDCS) . 2.1.1 Classification of EDCs 2.1.2 Occurrence of EDCs in Aquatic Environments 12 2.1.3 Adverse Effects of EDCs on Ecosystem and Human Health . 16 2.1.4 Techniques for Detection of Trace EDCs . 17 2.1.5 Advanced Treatment Technologies in Removing EDCs in Aquatic Environment 20 2.2 DOM IN AQUATIC ENVIRONMENTS . 23 2.2.1 Concentration of DOM in Aquatic Environments 24 2.2.2 Characteristics of DOM in Natural Waters and Wastewater Effluents 24 ii 2.2.3 Binding of Organic Pollutants to DOM 28 2.2.4 Model DOM 30 2.3 ORGANICS REJECTION BY NF/RO MEMBRANE IN WATER AND WASTEWATER TREATMENT . 31 2.3.1 Size Exclusion Effect . 32 2.3.2 Electric Exclusion Effect . 34 2.3.3 Adsorption Effect 36 2.3.4 Feed Water Composition Effect 37 2.4 REMOVAL OF TRACE EDCS BY MEMBRANE TECHNOLOGY . 39 2.4.1 In Single-Organic Solution . 40 2.4.2 In Solution Containing other DOM 43 CHAPTER THREE MATERIALS AND METHODS 46 3.1 EXPERIMENTAL SET-UP 46 3.1.1 Cross-flow Membrane Test Cell System . 46 3.1.2 Fractionation Process . 49 3.2 CHEMICALS AND SOLUTION CHEMISTRY . 51 3.3 SAMPLING AND ANALYSIS METHODS 54 3.3.1 Water Sampling . 54 3.3.2 Estrone Detection 54 3.3.3 TOC and UV254 Analysis . 57 3.3.4 Conductivity Analysis 58 3.3.5 pH Analysis . 58 3.3.6 Molecular Weight Analysis . 58 3.3.7 Ion Analysis . 59 3.3.8 Charge Measurement 60 iii 3.3.9 Structural Characterization 61 3.3.10 Membrane Characterization . 62 CHAPTER FOUR RESULTS AND DISCUSSIONS 67 4.1 MEMBRANE CHARACTERIZATION 67 4.2 REJECTION OF ESTRONE IN SINGLE-ORGANIC SOLUTION BY NF/ RO MEMBRANES 69 4.2.1 Filtration of Estrone by Four Kinds of NF/RO Membranes . 70 4.2.2 Effect of pH on Estrone Rejection . 79 4.2.3 Effect of Ionic Strength on Estrone Rejection . 85 4.2.4 Effect of Calcium Ion Concentration on Estrone Rejection 87 4.3 REJECTION OF ESTRONE IN THE PRESENCE OF NATURAL ORGANIC MATTER (NOM) . 89 4.3.1 Characteristics of Selected Natural Organic Matter 90 4.3.2 Effect of the selected NOM on Estrone Removal 94 4.3.3 pH Effect on the Influence of Humic Acid on Estrone Removal by DL 104 4.3.4 Calcium Ion Concentration Effect on the Influence of Humic Acid on the Fate of Estrone during Filtration Process 112 4.3.5 Ionic Strength Effect on the Influence of HA on Estrone Removal by DL 116 4.4 REJECTION OF ESTRONE IN SECONDARY EFFLUENT FROM WASTEWATER TREATMENT PLANT . 119 4.4.1 Characteristics of Treated Effluent . 119 4.4.2 Rejection of Estrone by NF/RO Membranes in Secondary Effluent Matrix 121 4.4.3 Effects of Different Organic Fractions Derived from Secondary Effluent iv on Estrone Removal 126 4.4.4 Effect of Solution Chemistry on the “Enhancement Effect” of Hydrophobic Acid Fraction on Estrone Removal . 146 4.5 RELATIONSHIP BETWEEN HUMIC SUBSTANCES’ STRUCTURAL CHARACTERISTICS AND THEIR EFFECTS ON ESTRONE REMOVAL BY NF/RO MEMBRANES . 163 CHAPTER FIVE SUMMARY, CONCLUSIONS AND RECOMMENDATIONS . 169 5.1 SUMMARY AND CONCLUSIONS . 169 5.2 RECOMMENDATIONS FOR FURTHER STUDIES . 174 REFERENCES 176 v SUMMARY Recently the use of treated wastewater for groundwater recharge and indirect potable water reuse has been initialized worldwide. However, the presence of wastewaterderived contaminants, especially endocrine disrupting chemicals (EDCs), in treated effluent and the receiving aquatic environment has caused great consumer concern due to their potential health risk. Membrane technology such as nanofiltration (NF) and reverse osmosis (RO) are likely to play an important role in removal of those pollutants. A laboratory-scale crossflow membrane filtration system was used to investigate the effect of other dissolved organic matter (DOM) on the rejection of steroid hormone estrone in complicated water matrix during NF/RO membrane separation processes. In single-organic solution, the initial excellent removal performances of all the membranes could be attributed to their adsorption capabilities and steric hindrance, while when the adsorption of estrone into membrane reached equilibrium, size exclusion would become the overriding removal mechanism. In addition, water chemistry (such as pH, ionic strength (IS) and Ca2+ ion concentration) was found to be important in determining the extent of estrone rejection at later stage of filtration. Higher estrone rejection was observed at pH 10.4, higher IS and Ca2+ ion concentration. In natural organic matter (NOM)-containing solutions, estrone rejection depended on the type of NOM co-present in a feed matrix. Dextran without aromatic functional vi groups showed little effects on the fate and transport of estrone during nanofiltration processes. In contrast, the presence of humic acid (HA) with great aromaticity improved estrone adsorption on membrane significantly, while the improvement in estrone rejection was limited. The “enhancement effect” of HA on estrone adsorption and rejection was observed under all the pH conditions investigated in this study, with the greatest “enhancement effect” at pH 4. Moreover, the influence of HA on the fate and transport of estrone during filtration process was observed to be less noticeable with elevation of Ca2+ ion concentration in feed solution. In addition to pH and Ca2+ ion concentration, IS in feed solution played a critical role in HA effect. Less noticeable “enhancement effect” of HA on estrone adsorption and rejection was observed at higher IS. In treated effluent, estrone removal efficiencies were consistently higher than the results obtained in single-organic solution. To elucidate how the effluent organic matter (EfOM) affect the target estrone removal more clearly, investigations were then conducted on the effect of specific organic fraction isolated from secondary effluent on estrone removal in solutions. Results showed that the highest “enhancement effect” on estrone rejection was associated with the presence of hydrophobic acid (HpoA) fraction which possessed phenolic groups and high aromaticity. Furthermore, the “enhancement effect” of HpoA was depended on the feed water chemistry. The strongest enhanced effect on estrone rejection was observed at pH 10.4 and 100 mM NaCl. However, the presence of Ca2+ ion tended to diminish the “enhancement effect” of HpoA on estrone rejection. Keywords: Nanofiltration (NF), Reverse Osmosis (RO), Endocrine Disrupting vii Chemicals (EDCs), Estrone, Rejection, Treated Effluent, Interaction, Dissolved Organic Matter (DOM). viii References Kingdom inland waters. Environmental Toxicology and Chemistry 1996, 15, 19932002. Harries, J.E.; Janbakhsh, A.; Jobling, S. Matthiessen, P.; Sumpter, J.P. and Tyler, C.R. Estrogenic potency of effluent from two sewage treatment works in the United Kingdom. Environmental Toxicology and Chemistry 1999, 18, 932-937. Hofman, J.; Beerendonk, E.F.; Folmer, H.C. and Kruithof, J.C. Removal of pesticides and other micropollutants with cellulose acetate, polyamide and ultra-low pressure reverse osmosis membranes. Desalination 1997, 113, 209-214. Hong, S. and Elimelech, M. Chemical and physical aspects of natural organic matter (NOM) fouling of nanofiltration membranes. Journal of Membrane Science 1997, 132, 159-181. Hu, J.Y.; Ong, S.L.; Shan, J.H.; Kang, J.B. and Ng, W.J. Treatability of organic fractions derived from secondary effluent by reverse osmosis membrane. Water Research 2003, 37, 4801-4809. Hu, J.Y.; Ng, W.J.; Jin, X. and Tan, X. Reverse osmosis and nanofiltration membrane rejection of endocrine disrupting chemicals. Advances in Asian Environmental Engineering 2006, 5, 53-59. Huber, M.M.; Canonica, S.; Park, G.Y. and Gunten, V.U. Oxidation of pharmaceuticals during ozonation and advanced oxidation processes. Environmental 185 References Science and Technology 2003, 37, 1016-1024. Iguchi, T.; Watanabe, H. and Katsu, Y. Developmental effects of estrogenic agents on mice, fish, and frogs: a mini-review. Hormones and Behavior 2001, 40, 248-251. Illés, E. and Tombácz, E. The role of variable surface charge and surface complexation in ;the adsorption of humic acid on magnetite. Colloids and Surface A: Physicochem. Eng. Aspects 2004, 230, 99-109. Imai, A.; Fukushima, T.; Matsushige, K.; Kim, Y.H. and Choi, K. Characterization of dissolved organic matter in effluents from wastewater treatment plants. Water Research 2002, 36, 859-870. Ingrand, V.; Herry, G.; Beausse, J. and Roubin, M.D. Analysis of steroid hormones in effluents of wastewater treatment plants by liquid chromatography–tandem mass spectrometry. Journal of Chromatography A 2003, 1020, 99-104. Iwasaki, S.; Fukuhara, T.; Abe, I.; Yanagi, J.; Mouri, M.; Iwashima, Y.; Tabuchi, T. and Shinohara, O. Adsorption of alkylphenols onto microporous carbons prepared from coconut shell. Synthetic Metals 2001, 125, 207-211. Jada, A.; Akbour, A.R. and Douch, J. Surface charge and adsorption from water onto quartz sand of humic acid. Chemosphere 2006, 64, 1287-1295. Jeannot, R.; Sabik, H.; Sauvard, E.; Dagnac, T. and Dohrendorf, K. Determination of 186 References endocrine-disrupting compounds in environmental samples suing gas and liquid chromatography with mass spectrometry. Journal of Chromatography A 2002, 974, 143-159. Jobling, S.; Nolan, M.; Tyler, C.R.; Brighty, G.; Sumpter, J.P. Widespread sexual disruption in wild fish. Environmental Science and Technology 1998, 32, 2498-2506. Johnson, A.C. and Sumpter, J.P. Removal of endocrine-disrupting chemicals in activated sludge treatment works. Environmental Science and Technology 2001, 35, 4697-4703. Katarzyna, M. N.; Malgorzata, K. K.; Monika, D. and Tomasz, W. The influence of organic carbon concentration on atrazine removal by UF membranes. Desalination 2002, 147, 117-122. Kennedy, D.M.; Chun, K.H.; Yangali, V.A.Q.; Heijman, B.G.J. and Schippers, C.J. Natural organic matter (NOM) fouling of ultrafiltration membranes: fractionation of NOM in surface water and characterization by LC-OCD. Desalination 2005, 178, 7383. Kim, K.J.; Fane, A.G.; Fell, C.J.D. and Joy, D.C. Fouling mechanisms of membranes during protein ultrafiltration. Journal of Membrane Science 1992, 68, 79-91. Kimura, K.; Amy, G.L.; Drewes, J. and Watanabe, Y. Adsorption of hydrophobic compounds onto NF/RO membranes – an artifact leading to overestimation of 187 References rejection. Journal of Membrane Science 2003a, 221, 89-101. Kimura, K.; Amy, G.; Drewes, J.E.; Heberer, T.; Kim, T.U. and Watanabe, Y. Rejection of organic micropollutants (disinfection by-products, endocrine disrupting compounds, and pharmaceutically active compounds) by NF/RO membranes. Journal of Membrane Science 2003b, 227, 113-121. Kimura, K.; Toshima, S.; Amy, G. and Watanabe, Y. Rejection of neutral endocrine disrupting compounds (EDCs) and pharmaceutical active compounds (PhACs) by RO membranes. Journal of Membrane Science 2004, 245, 71-78. Kiso, Y. Factors affecting adsorption of organic solutes on cellulose in an aqueous solution system. Chromatographia 2001, 22, 55-58. Kiso, Y.; Kitao, T.; Kiyokatsu, J. and Miyagi, M. The effects of molecular width on permeation of organic solute through cellulose acetate reverse osmosis membrane. Journal of Membrane Science 1992, 74, 95-103. Kiso, Y.; Nishimura, Y.; Kitao, T. and Nishimura, K. Rejection properties of nonphenylic pesticides with nanofiltration membranes. Journal of Membrane Science 2000, 171, 229-237. Kiso, Y.; Kon, T.; Kitao, T. and Nishimura, K. Rejection properties of alkyl phthalates with nanofiltration membranes. Journal of Membrane Science 2001a, 182, 205-214. 188 References Kiso, Y.; Sugiura, Y.; Kitao, T and Nishmura, K. Effects of hydrophobicity and molecular size on rejection of aromatic pesticides with nanofiltration membranes. Journal of Membrane Science 2001b, 192, 1-10. Körner, W.; Hanf, V.; Schuller, W.; Kempter, C.; Metzger, J. and Hagenmaier, H. Development of a sensitive E-screen assay for quantitative analysis of estrogenic activity in municipal sewage plant effluents. The Science of the Total Environment 1999, 225, 33-48. Körner, W.; Bolz, U.; Süssmuth, W.; Hiller, G.; Schuller, W.; Hanf, V. and Hagenmaier, H. Input/output balance of estrogenic active compounds in a major municipal sewage plant in Germany. Chemosphere 2000, 40, 1131-1142. Ko uti , K. and Kunst, B. Removal of organics from aqueous solutions by commercial RO and NF membranes of characterized porosities. Desalination 2002, 142, 47-56. Kukkonen, J. and Oikari, A. Bioavailability of organic pollutants in boreal waters with varying levels of dissolved organic material. Water Research 1991, 25, 455-463. Kulikova, N.A. and Perminova, I.V. Binding of atrazine to humic substances from soil, peat, and coal related to their structure. Environmental Science and Technology 2002, 36, 3720-3724. Laganà, A.; Bacaloni, A.; Leva, I.D.; Faberi, A.; Fago, G.; and Marino, A. Analytical methodologies for determining the occurrence of endocrine disrupting chemicals in 189 References sewage treatment plants and natural waters. Analytica Chimica Acta 2004, 501, 79-88. Lai, K.M.; Johnson, K.L.; Scrimshaw, M.D. and Lester, J.N. Binding of Waterborne Steroid Estrogens to Solid Phases in River and Estuarine Systems. Environmental Science and Technology 2000, 34, 3890-3894. Laufenberg, G., Hausmanns, S. and Kunz, B. The influence of intermolecular interactions on the selectivity of several organic acids in aqueous multicomponent systems during reverse osmosis. Journal of Membrane Science 1996, 110, 59-68. Layton, A.C.; Gregory, B.W.; Seward, J.R.; Schultz, T.W. and Sayler, G.S. Mineralization of steroidal hormones by biosolids in wastewater treatment systems in Tennessee U.S.A. Environmental Science & Technology 2000, 34, 3925-3931. Leenheer, J.A. Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and used waters. Environmental Science and Technology 1981, 15, 578-587. Li, Z.; Wang, S.; Lee, N.A.; Allan, R.D. and Kennedy, I.R. Development of a solidphase extraction—enzyme-linked immunosorbent assay method for the determination of estrone in water. Analytica Chimica Acta 2004, 503, 171-177. Li, Q.; Xu, Z. and 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, 173-181. 190 References Liu, R.; Zhou, J.L. and Wilding, A. Simultaneous determination of endocrine disrupting phenolic compounds and steroid in water by solid-phase extraction-gas chromatography-mass spectrometry. Journal of Chromatography A 2004, 1022, 179189. Liu, X.Y.; Nakamura, C.; Tanimoto, I.; Miyake, S.; Nakamura, N.; Hirano, T. and Miyake, J. High sensitivity detection of bisphenol A using liposome chromatography. Analytica Chimica Acta 2006, 578, 43-49. López de Alda, M.J. and Barceló, D. Determination of steroid sex hormones and related synthetic compounds considered as endocrine disrupters in water by liquid chromatography–diode array detection–mass spectrometry. Journal of Chromatography A 2000, 892, 391-406. Ma, Y.G., Tian, W.J. and Shen, J.C. Control of the molecular interaction in the emitting layer of organic light-emitting device. Materials Science and Engineering: C 1999, 10, 19-24. Ma, H.Z., Allen, H.E. and Yin, Y.J. Characterization of isolated fractions of dissolved organic matter from natural waters and a wastewater effluent. Water Research 2001, 35, 985-996. Matsumoto, G.; Isbiwatari, R. and Hayna, T. Gas chromatographic-mass spectrometric identification of phenols and aromatic acids in river waters. Water Research 1977, 11, 191 References 693-698. Matsumoto, G. Comparative study on organic constituents in polluted and unpolluted island aquatic environments-III. Water Research 1982, 16, 551-557. Nakanishi, A.; Tamai, M.; Kawasaki, N.; Nakamura, T. and Tanada, S. Adsorption characteristics of bisphenol A onto carbonaceous materials produced from wood chips as organic waste. Journal of Colloid and Interface Science 2002, 252, 393-396. Nakashima, T.; Ohko, Y.; Tryk, D.A. and Fujishima, A. Decomposition of endocrinedisrupting chemicals in water by use of TiO2 photocatalysts immobilized on polytetrafluoroethylene mesh sheets. Journal of Photochemistry and Photobiology A: Chemistry 2002, 151, 207-212. Namour, Ph. and Műller, M.C. Fractionation of organic matter from wastewater treatment plants before and after 21-day biodegradability test: a physical-chemical method for measurement of the refractory part of effluents. Water Research 1997, 32, 2224-2231. Ng, H.Y. and Elimelech, M. Effect of colloidal fouling on removal of trace organics by RO. Journal of Membrane Science 2004, 244, 215-226. Nghiem, L.D.; Schäfer, A.I. and Elimelech, M. Removal of natural hormones by nanofiltration membranes: measurement, modeling, and mechanisms. Environmental Science and Technology 2004a, 38, 1888-1896. 192 References Nghiem, L.D.; Manis, A.; Soldenhoff, K. and Schäfer, A. I. Estrogenic hormone removal from wastewater using NF/RO membranes. Journal of Membrane Science 2004b, 242, 37-45. Nghiem, L.D.; Schäfer, A.I. and Elimelech, M. Pharmaceutical retention mechanisms by nanofiltration membranes. Environmental Science and Technology 2005, 39, 76987705. Onda, K.; Yang, S.Y.; Miya, A. and Tanaka, T. Evaluation of estrogen-like activity on sewage treatment processes using recombinant yeast. Proceeding of 1st IWA Asian Waterqual 2001, Japan, 441-446. Ozaki, H. and Li, H.F. Rejection of organic compounds by ultra-low pressure reverse osmosis membrane. Water Research 2002, 36, 123-130. Paolis, D.F. and Kukkonen, J. Binding of orgnaic pollutants to humic and fulvic acids: influence of pH and the structural of humic material. Chemosphere 1997, 34, 16931704. Peterson, E.W.; Davis, R.K. and Orndorff, H.A. 17 β -Estradiol as an indicator of animal waste contamination in mantled karst aquifers. Journal of Environmental Quality 2001, 29, 826-834. Purdom, C.E.; Hardiman, P.A.; Bye, V.J.; Eno, N.C.; Tyler, C.R. and Sumpter, J.P. 193 References Estrogenic effects of effluents from sewage treatment works. Journal of Chemical Ecology 1994, 8, 275-285. Pusch, W. Performance of RO membranes in correlation with membrane structure, transport mechanisms of matter and module design (fouling). State of the art. Desalination 1990, 77, 35-54. Schäfer, A.I.; Fane, A.G. and Waite, T.D. Nanofiltration of natural organic matter: removal, fouling and the influence of multivalent ions. Desalination 1998, 118, 109122. Schäfer, A.I.; Nghiem, L.D. and Waite, T.D. Removal of the Natural Hormone Estrone from Aqueous Solutions Using Nanofiltration and Reverse Osmosis. Environmental Science and Technology 2003, 37, 182-188. Schäfer, A.I.; Pihlajamäki, A.; Fane, A.G.; Waite, T.D. and Nyström, M. Natural organic matter removal by nanofiltration: effects of solution chemistry on retention of low molar mass acids versus bulk organic matter. Journal of Membrane Science 2004, 242, 73-85. Schäfer, A.I.; Fane, A.G. and Waite, T.D. Nanofiltration – principles and applications. 2005, New York: Elsevier Inc. Schlautman, M.A. and Morgan, J.J. Effects of aqueous chemistry on the binding of polycyclic aromatic hydrocarbons by dissolved humic materials. Environmental 194 References Science and Technology 1993, 27, 961-969. Shan, J.H. Rejection of organic matters by RO/NF membrane. Ph.D. Thesis, National University of Singapore, 2005. Shim, Y.; Lee, G.H.; Lee, S.; Moon, S.H. and Cho, J. Effects of NOM and ionic species on membrane surface charge. Environmental Science and Technology 2002, 36, 3864-3871. Shishida, K.; Echigo, S.; Kosaka, K.; Tabasaki, M.; Matsuda, T. and Takigami, H. Evaluation of advanced sewage treatment processes for reuse of wastewater using bioassays. Environmental Technology 2000, 21, 553-560. Shon, H.K.; Vigneswaran, S.; Kim, In.S.; Cho, J. and Ngo, H.H. Fouling of ultrafiltration membrane by effluent organic matter: A detailed characterization using different organic fractions in wastewater. Journal of Membrane Science 2005, 278, 232-238. Soto, A.M.; Sonnenschein, C.; Chung, K.L.; Fernandez, M.F.; Olea, N. and Serrano, F.O. The E-SCREEN assay as a tool to identify estrogens: an update on estrogenic environmental pollutants. Environmental Health Perspectives 1995, S103, 113-122. Staples, C.A.; P Dorn, P.B.; Klecka, G. M.; O'Block, S.T.; Branson, D.R. and Harris, L.R. Bisphenol A concentrations in receiving waters near US manufacturing and processing facilities. Chemosphere 2000, 40, 521-525. 195 References Tang, C.; Kwon, Y.N. and Leckie, J.O. Fouling of reverse osmosis and nanofiltration membranes by humic acid—Effects of solution composition and hydrodynamic conditions. Journal of Membrane Science 2007, 290, 86-94. Tanninen, J. and Nystrom, M. Separation of ions in acidic conditions using NF. Desalination 2002, 147, 295-299. Taylor, J.S. and Jacobs, E.P. Reverse osmosis and nanofiltration. In: Mallevialle, J.; Odendaal, P.E. and Wiesner, M.R. editors. Water Treatment Membrane Processes, New York, NY: McGraw-Hill 1996, 41-20. Teixeira, R.M. and Rosa, J.M. The impact of the water background inorganic matrix on the natural organic matter removal by nanofiltration. Journal of Membrane Science 2006, 279, 513-520. Ternes, T.A.; Stumpf, M.; Mueller, J.; Haberer, K.; Wilken, R.D. and Servos, M. Behavior and occurrence of estrogens in municipal sewage treatment plants--I. Investigations in Germany, Canada and Brazil. The Science of the Total Environment 1999, 225, 81-90. Ternes, T.A.; Stüber, J.; Herrmann, N.; McDowell, D.; Ried, A.; Kampmann, M. and Teiser, B. Ozonation: a tool for removal of pharmaceuticals, contrast media and musk fragrances from wastewater. Water Research 2003, 37, 1976-1982. 196 References Thurman, E.M. Organic geochemistry of natural waters, 1985, Martinus Nijhoff/Dr W.Junk Publishers, Dordrecht. Tilton, F.; Benson, W.H. and Schlenk, D. Evaluation of estrogenic activity from a municipal wastewater treatment plant with predominantly domestic input. Aquatic Toxicology 2002, 61, 211-224. Tim, Z. In vitro bioassays for assessing estrogenic substances. Environmental Science and Technology, 1997, 31, 613-623 Tombácz, E.; Libor, Z.; Illés, E.; Majzik, A. and Klumpp, E. The role of reactive surface sites and complexation by humic acids in the interaction of clay mineral and iron oxide particles. Organic Geochemistry 2004, 35, 257-267. Vanderford, B.J.; Pearson, R.A.; Rexing, D.J. and Snyder, S.A. Analysis of endocrine disruptors, pharmaceuticals, and personal care products in water using liquid chromatography/tandem mass spectrometry. Analytical Chemistry 2003, 75, 62656274. Violleau, D.; Tome,H.; Habaroiu, H.; Croue, J.P. and Pontie, M. Fouling studies of a polyamide nanofiltration membrane by selected natural organic matter: analytical approach. Desalination 2005, 173, 223-238. Wershaw, R.L. and Pinckney, D.J. Determination of the association and dissociation of humic acid fractions by small angle X-ray scattering. U.S. Geological Survey Journal 197 References of Research 1973, 1, 701-707. Williams, R.J.; Johnson, A.C.; Smith, J.J.L. and Kanda, R. Steroid Estrogens Profiles along River Stretches Arising from Sewage Treatment Works Discharges. Environmental Science and Technology 2003, 37, 1744-1750. Wintgens, T.; Gallenkemper, M. and Melin, T. Endocrine disrupter removal from wastewater using membrane bioreactor and nanofiltration technology. Desalination 2002, 146, 387-391. Wintgens, T.; Gallenkemper, M. and Melin, T. Occurrence and removal of endocrine disrupters in landfill leachate treatment plants. Water Science and Technology 2003, 48, 127-134. Wu, S.H. and Pendleton, P. Adsorption of anionic surfactant by activated carbon: effects of surface chemistry, ionic strength and hydrophobicity. Journal of Colloid Interface Science 2001, 243, 306-315. Yamamoto, H.; Liljestrand, H.M.; Shimizu, Y. and Morita, M. Effects of physicalchemical characteristics on the sorption of selected endocrine disruptors by dissolved organic matter surrogates. Environmental Science and Technology 2003, 37, 26462657. Yamamoto, H. and Liljestrand, H.M. The fate of estrogenic compounds in the aquatic environment: sorption onto organic colloids. Water Science and Technology 2003, 47, 198 References 77-84. Yan, W.L. and Bai, R.B. Adsorption of lead and humic acid on chitosan hydrogel beads. Water Research 2005, 39, 688-698. Ying, G.G. and Kookana, R.S. Endocrine disruption: an Australian perspective. Australian Water Association Journal Water 2002, 29, 42-45. Ying, G.G.; Kookana, R.S. and Ru, Y.J. Occurrence and fate of hormone steroid in the environment. Environment International 2002a, 28, 545-551. Ying, G.G.; Williams, B. and Kookana, R.S. Environmental fate of alkylphenols and alkylphenol ethoxylates – a review. Environment International 2002b, 28, 215-226. Yoon, Y., Westerhoff, P., Yoon, J. and Snyder, S. A. Removal of 17β estradiol and fluoranthene by nanofiltration and ultrafiltration. Journal of Environmental Engineering, 2004, 130, 1460-1467. Yoon, Y.; Westerhoff, P.; Snyder, S.A. and Wert, E.C. Nanofiltration and ultrafiltration of endocrine disrupting compounds, pharmaceuticals and personal care products. Journal of Membrane Science 2006, 270, 88-100. Zhang, Y.; Bruggen, B.V.; Chen, G.X.; Braeken, L. and Vandecasteele, C. Removal of pesticides by nanofiltration: effect of the water matrix. Separation and Purification Technology 2004, 38, 163-172. 199 References Zwiener, C. and Frimmel, F.H. Oxidative treatment of pharmaceuticals in water. Water Research 2000, 34, 1881-1885. 200 [...]... concentrations of estrone in electrolyte background solution as a function of filtration time for (A) DL, (B) CK, (C) AK and (D) CG 72 Figure 4.3 Estrone rejection in electrolyte background solution by 4 NF/ RO membranes as a function of time 75 Figure 4.4 Transport of estrone across NF/ RO membranes 78 Figure 4.5 Speciation of estrone 80 Figure 4.6 DL membrane surface zeta potential measured background solution... separation processes 7 Chapter One-Introduction Estrone Rejection by NF/ RO membranes Different feed matrix Single-organic solution NOM-containing solution Fate and transport of estrone during NF/ RO membrane separation processes Influence of two kinds of selected NOM on estrone adsorption and rejection Effect of water chemistry on estrone rejection: pH effect; Ionic strength effect; Ca2+ ion effect Effect of. .. 4.15 Rejection of estrone with the presence of HpoA by DL membrane at different pH levels 155 Table 4.16 Rejection of estrone with the presence of HpoA by DL membrane at different ionic strength 157 Table 4.17 Rejection of estrone with the presence of HpoA by DL membrane at different Ca2+ ion concentrations 162 xvii LIST OF PLATES Pages Plate 3.1 The photo of cell membrane system (A) front view of the... Effect of pH on estrone concentrations in feed and permeate during DL membrane filtration test in single-organic solution 82 Figure 4.8 Influence of pH on estrone rejection by DL membrane in single-organic solution 83 Figure 4.9 Influence of ionic strength on estrone rejection by DL membrane in single-organic solution 87 Figure 4.10 Influence of calcium ion concentration on estrone rejection by DL membrane... concentrations of estrone in HAcontaining solution as a function of filtration time for (A) DL and (B) CK 98 Figure 4.18 Estrone rejection in HA-containing solution by (A) DL and (B) CK 100 Figure 4.19 DOC rejection in HA-containing solution by DL and CK membranes 103 Figure 4.20 Feed and permeate concentrations of estrone as a function of filtration time for DL membrane at pH 4 105 Figure 4.21 Rejection of estrone. .. derived from treated effluent which makes crucial contribution to the ‘enhancement effect’ on estrone removal in treated effluent; To examine the effects of solution chemistry (pH, IS and Ca2+ ion concentration) on estrone removal by NF/ RO membranes; and To identify how the two kinds of interaction introduced by other DOM (estroneDOM and DOM-membrane) as mentioned earlier influence the behaviour of estrone. .. bonding between phenolic groups 139 Figure 4.37 Hydrogen bonding between phenolic group and aromatic amine group 141 Figure 4.38 Estrone rejection with different hydrophobic organic fractions by (A) DL, (B) CK and (C) CG 142 Figure 4.39 DOC rejection for different hydrophobic organic fractions by (A) DL, (B) CK and (C) CG 144 Figure 4.40 Influence of HpoA on estrone rejection by DL membrane at different... Influence of HpoA on estrone rejection by DL membrane at different Ca2+ ion concentrations (A) 0 mM Ca2+, (B) 0.3 160 C-NMR spectra for HpoA derived from treated effluent xiv mM Ca2+ and (C) 0.6 mM Ca2+ Figure 4.48 Rejection of estrone with the presence of different humic substances by (A) DL and (B) CK 165 Figure 4.49 Schematic illustration of the effects of HA and HpoA on estrone rejection by membrane... 4.6 Predicted estrone fraction sorbed onto HA and estimated estrone rejection at the later stage of filtration in HAcontaining solution 102 Table 4.7 Summary of HA effects on estrone adsorption and rejection 111 Table 4.8 Summary of HA effects on estrone final adsorption and rejection at different Ca2+ ion concentrations 114 Table 4.9 Summary of HA effects on estrone final adsorption and rejection at... Characteristics of MF filtered SE 120 xvi Table 4.11 DOC fractionation results 120 Table 4.12 Characteristics of specific organic fractions derived from secondary effluent 128 Table 4.13 Rejection of estrone with the presence of different hydrophobic organic fractions by DL and CK membranes 132 Table 4.14 The “enhancement effect” of DOM on estrone rejection in different solutions for NF/ RO membranes 146 . CHARACTERIZATION 67 4.2 REJECTION OF ESTRONE IN SINGLE-ORGANIC SOLUTION BY NF/ RO MEMBRANES 69 4.2.1 Filtration of Estrone by Four Kinds of NF/ RO Membranes 70 4.2.2 Effect of pH on Estrone Rejection 79. REJECTION OF STEROID HORMONE ESTRONE BY NF/ RO MEMBRANES JIN XUE NATIONAL UNIVERSITY OF SINGAPORE 2007 Founded 1905 REJECTION OF STEROID HORMONE ESTRONE BY. the Influence of Humic Acid on the Fate of Estrone during Filtration Process 112 4.3.5 Ionic Strength Effect on the Influence of HA on Estrone Removal by DL 116 4.4 REJECTION OF ESTRONE IN