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. 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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