REMOVAL OF ENDOCRINE DISRUPTING COMPOUNDS IN MUNICIPLE WASTEWATER BY MEMBRANE BIOREACTOR SYSTEMS CHEN XIA NATIONAL UNIVERSITY OF SINGAPORE 2009 i REMOVAL OF ENDOCRINE DISRUPTING COMPOUNDS IN MUNICIPLE WASTEWATER BY MEMBRANE BIOREACTOR SYSTEMS CHEN XIA (B. Eng., Tongji Univ.; M. Sc., Stuttgart Unv.) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CIVIL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2009 ii ACKNOWLEDGEMENT The author wishes to express her deepest appreciation and gratitude to her supervisor, Associate Professor Hu Jiangyong for her invaluable guidance and encouragement throughout the entire course of the research project. The author would also like to extend her sincere gratitude to all laboratory officers and students, especially Mr. S.G. Chandrasegaran, Ms. Tan Xiaolan and Ms. Lee Leng Leng at the Laboratory of Water Science & Technology at Division of Environmental Science & Engineering, National University of Singapore, for their assistance and cooperation in the many ways that made this research study possible. Thanks are also due to the Bedok Wastewater Treatment Plant for the provision of wastewater and sludge samples used in this study. The assistance and cooperation of the staff there are greatly appreciated. Also, the authors would like to acknowledge Associate Professor Ng How Yong, Mr. Tan Teck Wee and Ms. Tiew Siow Woon for their kind assistance in providing the lab-scale MBRs and STPs samples. The author also appreciates Prof. Chung Tai-Shung Neal at the Department of Chemical & Biomolecular Engineering for me to use his equipment to analyze the contact angle of the activated sludge. The author would also like to extend her sincere gratitude to the Center for Advanced Water Technology (CAWT), Public Utilities Board (PUB) Singapore for their financial support on the pilot study. i TABLE OF CONTENTS Page ACKNOWLEDGEMENT .i TABLE OF CONTENTS .ii SUMMARY .viii NOMENCLATURE xiii LIST OF FIGURES .xvii LIST OF TABLES xx LIST OF PLATES xxii CHAPTER INTRODUCTION 1.1 BACKGROUND 1.2 OBJECTIVES AND SCOPE OF STUDY CHAPTER LITERATURE REVIEW . 2.1 ENDOCRINE DISRUPTING COMPOUNDS 2.1.1 General Comments 2.1.2 Classification of EDCs 10 2.1.2.1 Natural and Synthetic Steroid Hormones . 10 2.1.2.2 Man-made Chemicals . 14 2.1.2.3 Phytoestrogens 17 2.1.3 Affecting Mechanisms of EDCs to Organisms 19 2.1.4 Negative Influences of EDCs on Wildlife and Human Beings 20 2.1.5 Detection of EDCs 22 2.1.5.1 Chemical Analysis 22 ii 2.1.5.2 Biological Assays 25 2.1.6 Occurrence of EDCs in Sewage Treatment Plants Effluent . 28 2.2 TREATMENT OF EDCS IN SEWAGE TREATMENT PLANTS . 30 2.2.1 General Comments 30 2.2.2 Elimination of EDCs during Biological Wastewater Treatment 30 2.2.2.1 Biodegradation of EDCs . 30 2.2.2.2 Adsorption of EDCs to Activated Sludge . 32 2.2.3 Formation of EDCs during Biological Wastewater Treatment 33 2.2.4 Potential Advanced Treatment Technologies in Removing EDCs in Aquatic Environment 36 2.2.4.1 Removal by Activated Carbon 37 2.2.4.2 Removal by Oxidation Process . 38 2.2.4.3 Removal by Membrane Filtration . 38 2.2.4.4 Removal by Membrane Bioreactor . 39 2.3 INFLUENCE OF OPERATION PARAMETERS ON EDCS REMOVAL . 42 2.3.1 Influence of MLSS and Biomass Characteristics 42 2.3.2 Influence of Sludge Retention Time 43 2.3.3 Influence of pH 45 2.3.4 Influence of Initial Concentration of Substances 46 2.3.5 Influence of Anoxic Zone 47 2.3.6 Influence of Hydraulic Retention Time . 47 2.4 MEMBRANE BIOREACTORS FOR WASTEWATER TREATMENT . 48 2.4.1 General Comments 48 2.4.2 Classification of Membrane Bioreactors 50 iii 2.4.2.1 MBR with external membrane filtration . 51 2.4.2.2 MBR with internal, submerged membrane filtration 51 2.4.3 Anoxic-Aerobic Membrane Bioreactor Systems . 53 2.5 CURRENT STATUS AND RESEARCH NEEDS . 54 CHAPTER MATERIALS AND METHODS 64 3.1 INTRODUCTION 64 3.2 EXPERIMENTAL SET-UP FOR ANAEROBIC SYSTEMS . 64 3.3 EXPERIMENTAL SET-UP FOR PILOT-SCALE STUDY . 66 3.3.1 Set-up, Configuration and Operation of MBR Pilot Plants 66 3.3.2 Set-up of Complementary Lab-scale MBRs for Pilot-scale Study 68 3.4 EXPERIMENTAL SET-UP FOR LAB-SCALE MBRS 70 3.4.1 Set-up, Configuration and Operation of Lab-scale MBRs 70 3.4.2 Batch Experiment for Lab-scale MBRs Performance Confirmation 73 3.5 EXPERIMENTAL SET-UP FOR BATCH STUDY . 74 3.5.1 Set-up of Degradation Test for EDCs and Conjugates . 74 3.5.1.1 Activated Sludge Preparation . 74 3.5.1.2 Degradation Test Procedure 75 3.5.2 Set-up of Adsorption Test for EDCs and Conjugates . 76 3.5.2.1 Activated Sludge Preparation . 76 3.5.2.2 Adsorption Test Procedure . 76 3.6 SAMPLE COLLECTION AND PREPARATION FOR PILOT AND LAB-SCALE MBRS 77 3.7 DETECTION OF EDC AND CONJUGATE COMPOUNDS－CHEMICAL ANALYSIS 78 3.7.1 Pre-treatment of Liquid Phase Samples . 78 3.7.2 Pre-treatment of Solid Phase Samples 80 iv 3.7.3 LC-MS-MS Analysis 82 3.8 DETECTION OF OVERALL ESTROGENICITY－ YES BIOASSAY . 83 3.8.1 Preparation of Standard Chemicals . 84 3.8.2 Yeast Cultivation . 85 3.8.3 YES Assay Procedure and Optimisation . 86 3.8.4 Development of E2 Standard Curve . 90 3.8.5 Statistical Analysis 91 3.9 MEASUREMENT OF MBR SYSTEMS PERFORMANCE . 92 3.9.1 Chemical Oxygen Demand . 92 3.9.2 Nitrogen 92 3.9.3 Total Suspended Solids . 92 3.9.4 Transmembrane Pressure . 92 3.9.5 pH 93 3.10 MEASUREMENT OF PHYSICOCHEMICAL CHARACTERISTICS OF ACTIVATED SLUDGE 93 3.10.1 Mixed Liquor Suspended Solids & Mixed Liquor Volatile Suspended Solids …………………………………………………………………………… 93 3.10.2 Extra cellular Polymeric Substance 93 3.10.3 Surface Charge . 95 3.10.4 Hydrophobicity . 96 3.10.5 Floc Size 97 3.11 MEASUREMENT OF BIOLOGICAL CHARACTERISTICS OF ACTIVATED SLUDGE 97 3.11.1 Oxygen Uptake Rate and Specific Oxygen Uptake Rate . 97 3.11.2 Non-flocculating Microorganisms 98 3.12 DEGRADATION KINETICS . 98 v ADSORPTION ISOTHERM AND COEFFICIENTS 99 3.13 CHAPTER RESULTS AND DISCUSSIONS . 102 4.1 INTRODUCTION 102 4.2 REMOVAL OF EDCS IN MEMBRANE BIOREACTORS AND CONVENTIONAL SEWAGE TREATMENT PROCESSES 103 4.2.1 Removal Efficiencies of EDCs in MBRs & STPs 103 4.2.2 Effect of HRT on EDCs Removal Efficiencies 109 4.2.3 Adsorption of EDCs by Sludge in MBRs & STPs . 111 4.3 THE FATE OF EDCS IN PILOT-SCALE MBR SYSTEMS 113 4.3.1 Evaluation of Overall Estrogenicity in MBR Systems 113 4.3.2 Fate of Estrogen Compounds in MBR Systems . 115 4.3.2.1 Fate of Hormones and Their Conjugates 115 4.3.2.2 Fate of Alkylphenols . 122 4.3.3 Mass Balance Analysis . 125 4.3.3.1.Pilot-Scale MBR Systems 126 4.3.3.2.Lab-scale MBR Systems 129 4.3.4 Comparison of Bioassay and Chemical Analysis . 130 4.4 REMOVAL OF EDCS BY LAB-SCALE MBR SYSTEM . 132 4.4.1 Overall Performance of MBRs 133 4.4.2 Physicochemical and Biological Characteristics of Activated sludge . 135 4.4.2.1 Biomass Concentration . 135 4.4.2.2 EPS 136 4.4.2.3 Floc Size 139 4.4.2.4 Surface Charge of Sludge . 139 vi 4.4.2.5 Hydrophobicity of Sludge . 141 4.4.2.6 OUR and SOUR of Sludge . 142 4.4.2.7 Non-flocculating Microorganisms 144 4.4.3 Influence of SRT on the Removal of EDCs and Conjugates . 145 4.4.4 Influence of Anoxic Zone on the Removal of EDCs and Conjugates 150 4.4.5 Further Batch Study for Confirmation of Lab-scale MBR Performance 151 4.4.5.1 Batch Results for Adsorption Performance 151 4.4.5.2 Batch Results for Removal Performance 156 4.5 DEGRADATION AND ADSORPTION OF ESTROGENS AND CONJUGATES BY BATCH STUDY 160 4.5.1 Degradation of Estrogens and Conjugates by Activated Sludge 160 4.5.1.1 Effect of Initial Concentration 160 4.5.1.2 Effect of MLSS . 165 4.5.1.3 Metabolic Products . 169 4.5.2 Adsorption of Estrogens and Conjugates by Activated Sludge . 172 4.5.2.1 Adsorption of Natural Estrogens 172 4.5.2.2 Adsorption of Natural Estrogen Conjugates . 181 4.5.2.3 Effect of Experimental Settings on Adsorption 183 CHAPTER CONCLUSIONS AND RECOMMENDATIONS . 187 5.1 CONCLUSIONS 187 5.2 RECOMMENDATIONS 190 References ……………………………………………………………………… 192 Publications ……………………………………………………………………….214 vii SUMMARY Environmental pollution with persistent chemicals becomes an increasingly important issue worldwide. 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(2006), Long-term comparison of trace organics removal performances between conventional and membrane activated sludge processes, Water Environ. Res., vol. 78 (13), pp. 24802486. 212 Publications Parts of this thesis have been published in scientific journals or are submitted for publication: - Chen X. and Hu J.Y. (2009), Batch degradation of 17ß-Estradiol (E2) and its conjugates by activated sludge affected by spiking initial concentrations and MLSS. (aceepted by Process Biochemistry) - Chen X. and Hu J.Y. (2009), Removal of Estrogenic Endocrine Disruptors in Membrane Bioreactors and Conventional wastewater Treatment Processes. (submitted to Desalination) - Chen X. and Hu J.Y. (2009), Adsorption of natural estrogens and their conjugates by the activated sludge, Water Air and Soil Pollution, DOI: 10.1007/s11270-009-0102-0. - Hu J.Y., Chen X., Tao G., Kekred K. (2007), Fate of endocrine disrupting compounds in membrane bioreactor systems, Environmental Science& Technology, vol. 41(11), pp. 4097 – 4102. - Hu J.Y., Chen X. (2006), Detection and removal of emerging contaminants in water reclamation process, Water Science & Technology: Water Supply, vol. 6(6), pp. 19 – 26. - Hu J.Y., Chen X. (2006), Evaluation of overall estrogenicity in lab- and pilot-scale membrane bioreactors, The 15th Joint Kaist-Kyoto-NTU-NUS Symposium on Environmental Engineering, June 2006, Kyoto, Japan, pp.11–18. 213 Publications 214 [...]... This kind of study is important for determining EDCs removal in real wastewater matrix and evaluating the best operational parameters for EDCs removal in MBR systems In brief, although there are some reports available in literature, there is a general lack of fundamental understanding in terms of removal of EDCs by MBRs in a real wastewater 4 Chapter One: Introduction matrix More specifically, the removal. .. of different MBR systems to eliminate EDCs in the wastewater More importantly, the results obtained from this investigation would also contribute to improvements in EDCs removal in membrane bioreactor processes 7 Chapter One: Introduction Removal of EDCs in Municipal Wastewater by MBR Systems Detection Methods & Lab-scale Systems Setup Comparison of MBR and STP on EDCs Removal, (including HRT effect)... potentially harmful EDCs into the aquatic environment 1.2 Objectives and Scope of Study In view of the above, the overall objective of this research is to investigate the removal of EDCs in municipal wastewater by MBR systems To understand how EDCs are removed in MBRs, this study will investigate the fate of EDCs and conjugates in MBR systems, elimination kinetics of EDCs, and the influence of operational parameters... capacity of EDCs by lab-scale MBR systems study This study focused on the removal mechanisms of EDCs in MBR systems including biodegradation of EDCs, absorption of EDCs to activated sludge and de-conjugation of EDC conjugates The study of removal mechanisms was able to gather information on the removal efficiency of EDCs and predict the removal efficiency of EDCs in MBR systems A more fundamental insight into... potentially contains thousands of compounds Some of the synthetic organic compounds that are common in treated wastewater have been shown in laboratory studies to induce endocrine disrupting effects These endocrine disrupting compounds (EDCs) include natural hormones such as natural estrogens, e.g 17β-estradiol (E2) and estrone (E1) from urinary excretion; synthetic compounds used in medicine as contraceptives... study the influence of operation parameters on the elimination kinetics of EDCs by the lab experiments The overall work conducted in this study would provide an in- depth and a better understanding of the removal mechanisms and capacity of EDCs in a complex real wastewater matrix by MBRs The study of influence of operation factors on EDCs treatment yield a more detailed insight for practical use of different... would be slightly higher because of the experimental settings This study obtained a more in- depth understanding of EDCs removal in MBR systems With the in- depth understanding, MBRs can be operated with best EDCs removal performance Keywords: Membrane Bioreactor (MBR), Endocrine Disrupting Compound (EDC), Conjugate, Overall Estrogenicity, Adsorption, Degradation, Fate, Removal, Operational Parameter xii...performance of estrone (E1), 17ß-estradiol (E2), 17α-ethinylestradiol (EE2), Bisphenol A (BPA), 4-Nonylphenol (NP) and overall estrogenicity from municipal wastewater in MBRs and STPs; examination of the fate of EDCs in anoxic-aerobic pilot MBR systems; study of the elimination kinetics of EDCs, including biodegradation of EDCs, and deconjugation of EDC conjugates under different initial concentration... the mechanisms of EDCs removal in MBRs will help in further development of future MBR plants This offers a broader perspective and an important boost to this study It will also result in a better safeguarding of the quality of the treated water effluent regarding EDCs The interaction between membrane and EDCs was neglected, because the pore size of membranes in MBR systems could not retain EDCs, and... EDCs and conjugates removal The specific-objectives are listed as follows: • To compare the removal performance of EDCs by lab-scale MBR and STP The influence of HRT on EDCs removal was also investigated • To investigate the removal performance of particular compounds, E1, E2, EE2, BPA, NP and natural EDC conjugates, and overall estrogenicity in municipal wastewater by the examination of anoxic-aerobic . REMOVAL OF ENDOCRINE DISRUPTING COMPOUNDS IN MUNICIPLE WASTEWATER BY MEMBRANE BIOREACTOR SYSTEMS CHEN XIA NATIONAL UNIVERSITY OF SINGAPORE. UNIVERSITY OF SINGAPORE 2009 ii REMOVAL OF ENDOCRINE DISRUPTING COMPOUNDS IN MUNICIPLE WASTEWATER BY MEMBRANE BIOREACTOR SYSTEMS CHEN XIA (B. Eng., Tongji. EDCs in Aquatic Environment 36 2.2.4.1 Removal by Activated Carbon 37 2.2.4.2 Removal by Oxidation Process 38 2.2.4.3 Removal by Membrane Filtration 38 2.2.4.4 Removal by Membrane Bioreactor