SELECTIVE REMOVAL OF ESTROGENIC COMPOUNDS FROM AQUEOUS SOLUTION USING NOVEL ADSORBENT-MOLECULARLY IMPRINTED POLYMER BY ZHANG ZHONGBO (Master Tsinghua Univ.) A THESIS SUBMITTED FOR THE DEGREE OF PHILIOSOPHIAE DOCTOR DEPARTMENT OF CIVIL AND ENVIRONMETNAL ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2010 ACKNOWLEGDEMENT The author wishes to express his deepest appreciation and gratitude to his supervisor, Associate Professor Hu Jiangyong, for her invaluable guidance and encouragement thoughout the entire course of the research project. The author would also like to extend his sincere gratitude to all technicians, staff and students, especially Ms. Tan Xiaolan, Ms. Lee Leng Leng, Ms. Tan Hwee Bee and Mr. S.G. Chandrasegaran, at the Environmental Engineering Laboratory of the 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. i ACKNOWLEDGEMENT TABLE OF CONTENTS SUMMARY NOMENCLATURE LIST OF FIGURES LIST OF TABLES LIST OF PLATES Chapter Introduction 1.1 Background 1.2 Objective and scope of this study Chapter Literature review 10 2.1 Micropollution and Endocrine disruption 10 2.2 Categories and properties of estrogenic compounds 13 2.3 Sources and distribution of estrogenic compounds 15 2.4 Detection of estrogenic compounds . 17 2.4.1 Chemical analysis 17 2.4.2 Bioassay . 19 2.5 Removal of estrogenic compounds 22 2.5.1 Biodegradation . 22 2.5.2 Advanced oxidation . 26 2.5.3 Membrane retention . 29 2.5.4 Adsorption . 32 2.5.5 Selective removal of estrogenic compounds . 35 2.6 Molecular imprinted polymer (MIP) . 37 ii 2.6.1 Introduction of MIP . 37 2.6.2 Application of MIP 43 2.7 Current status and research needs 55 Chapter Materials and methods 58 3.1 Introduction 58 3.2 Synthesis of MIP and NIP . 59 3.2.1 Experimental setup . 59 3.2.2 Confirmation of MIP 63 3.3 Immobilization of MIP and NIP 65 3.4 Adsorption experiments 66 3.4.1 Study on adsorption isotherms 66 3.4.2 Study on adsorption mechanisms . 67 3.4.3 Study on effects of environmental factors on adsorption . 67 3.4.3.1 Effect of HA 67 3.4.3.2 Effect of pH 68 3.4.3.3 Effect of ionic strength 69 3.4.3.4 Effect of competing substances 69 3.4.4 Study of adsorption kinetics . 69 3.4.5 Comparison of MIP and activated carbon . 70 3.4.6 Modeling of MIP adsorption 70 3.5 Study on MIP regeneration . 71 3.6 Sample analysis 73 3.6.1 Measurements of E1, E2, EE2 and BPA by HPLC/MS/MS 73 3.6.2 TOC and UV254 analysis . 74 3.6.3 Molecular weight analysis 75 iii 3.6.4 FTIR analysis of functional groups in humic acid . 76 3.7 Characterization of adsorbent 77 3.7.1 Scanning electron micrograph of bare MIP/ NIP and immobilized MIP/ NIP 77 3.7.2 Measurement of specific surface areas of MIP and NIP 78 3.7.3 Measurement of density . 79 3.7.4 Measurement of hydrophobicity . 80 3.7.5 Measurement of Zeta potential and particle size . 81 3.7.6 Measurement of leakage of template molecules 82 Chapter Results and discussions . 83 4.1 Introduction 83 4.2 Confirmation of MIP 85 4.3 Characterization of MIP and NIP 89 4.3.1 Characterization of bare MIP and NIP 89 4.3.2 Characterization of immobilized MIP and NIP . 94 4.3.3 Leakage and mass balance of template . 98 4.4 Characterization of powder activated carbon . 101 4.5 Study on adsorption isotherms 101 4.5.1 Adsorption isotherms for E1, E2, EE2 and BPA in aqueous solution . 102 4.5.2 Modeling of adsorption isotherms 110 4.6 Adsorption mechanisms of MIP 118 4.6.1 Physical adsorption model 119 4.6.2 Selective adsorption ratio (SAR) 121 4.6.3 Study of desorption 126 iv 4.7 Effect of environmental factors on MIP adsorption . 136 4.7.1 Effect of HA on adsorption by MIP and NIP 136 4.7.2 Effect of pH on adsorption by MIP and NIP . 141 4.7.3 Effect of ionic strength on adsorptions by MIP and NIP . 146 4.7.4 Effect of competing estrogens on adsorptions of MIP and NIP . 149 4.8 Study of adsorption kinetics in aqueous solution . 152 4.9 Regeneration of MIP . 157 4.9.1 Regeneration of immobilized MIP 159 4.9.2 Adsorption study of immobilized MIP . 164 4.10 Comparison of MIP and powder activated carbon . 167 Chapter Summary, conclusion and recommendations . 171 5.1 Summary 171 5.2 Conclusions 172 5.2.1 Adsorption isotherm and modeling . 172 5.2.2 Physical adsorption model 173 5.2.3 Selective adsorption ratio . 174 5.2.4 Effect of environmental factors 174 5.2.5 Adsorption kinetics 175 5.2.6 Regeneration 176 5.2.7 Comparison of MIP and PAC . 176 5.3 Recommendations . 177 Bibliography . 181 Publications 209 v SUMMARY The removal of estrogenic compounds is an insightful research field in water and wastewater treatment due to the estrogenic effect they induce. In this research, selective adsorption of estrogenic compounds by molecular imprinted polymer (MIP) was proposed. The objective of this research was to synthesize a kind of qualified MIP and to study whether MIP could be effectively used to remove estrogenic compounds from aqueous solution and what factors influenced the removal of these compounds. MIP is a kind of artificially synthesized receptor. Firstly, a template molecule and functional monomers with functional groups complementary to those on templates form template molecule-functional monomer complex in solvent, or porogens. Secondly, cross-linkers are added and used to fix the template molecule-functional monomers complex in a polymer matrix. Finally, the initiator is added. After polymerization, the polymer synthesized undergo extensive extraction and template molecules are cleaved out of the polymer, leaving cavities whose shape, size, and chemical functional groups complementary to template molecules. These cavities can rebind reversibly and selectively template molecules and molecules with similar molecular structure to that of template molecules. A molecular imprinted polymer (MIP) was successfully synthesized in this study and used for selective removal of estrogenic compounds, estrone (E1), 17 β -estradiol (E2), 17 α-ethinylestradiol (EE2) and Bisphenol A (BPA) vi from aqueous solution. The confirmation of MIP was first carried out followed with the characterization of MIP. The study on the mass balance of template as well as template leakage revealed that almost all the template could be extracted out of the polymer and no template leakage could be detected in aqueous solution. The mass balance results of template molecule showed further that 2.172 mg of E2 extracted out from 125 mg MIP. In acetonitrile, MIP could absorb more E2 than non-template imprinted polymer (NIP) by more than 3.5 times. However, in aqueous solution, MIP showed reduced selectivity for E2 with a 10% difference in adsorption capacity between MIP and NIP. The adsorption isotherms of E1, E2, EE2 and BPA were studied at the concentration ranging from ppb to ppm. MIP was able to attain adsorption capacities of 111.7, 106.5, 121.5 and 59.4 µmole/g polymer for E1, E2, EE2 and BPA, respectively. According to the adsorption isotherms for E1, E2, EE2 and BPA, a physical adsorption model containing three types of binding sites, namely, specific binding site, semi-specific binding site and non-specific binding site was proposed to interpret the adsorption performance of MIP. The adsorption mechanisms were interpreted by a physical adsorption model in terms of binding affinity. The adsorption mechanisms were further confirmed by desorption isotherms of E1, E2, EE2 and BPA obtained from static gradient desorption. The kinetics of MIP adsorption was also studied. The results showed that within the first 15 min, the adsorption rate was fast followed by a gradual adsorption process until h. However, the adsorption capacity of MIP for the four estrogenic compounds can almost reach the equilibrium. vii According to the adsorption isotherms and the template molecule’s mass balance, an experimental concept, selective adsorption ratio (SAR), was proposed to assess how many template molecules extracted out of MIP could create selective binding sites in MIP. The SAR is expressed as a ratio of the amount of the template molecules which could create selective binding sites in MIP to all the template molecules extracted out of MIP. This concept links the selective adsorption capacity of MIP with the total amount of template molecules extracted. It could serve as an indicator of the selective adsorption capacity of MIP. SARs of different MIPs may be compared to further improve the synthesis of MIP. The SAR of the MIP used in this study was 16.9, 74.3, 26.8 and 14.2% for E1, E2, EE2 and BPA, respectively. In this study, the effects of environmental factors, including humic acid (HA), pH, ionic strength and the coexistence of competing estrogenic compounds, on the adsorption of four typical estrogenic compounds, estrone (E1), 17βestradiol (E2), 17α-ethinylestradiol (EE2) and Bisphenol A (BPA), were studied by molecularly imprinted polymer (MIP). The adsorption capacities of MIP for E2 were 116.3, 118.5, 127.0 and 109.0 µmole/g at HA concentrations of 0, 5, 15 and 20 mg/L in total organic carbon (TOC), respectively, while the corresponding adsorption capacities of non-template imprinted polymer (NIP) for E2 were 98.1, 109.4, 113.8 and 98.0 μ mole/g. This implied that no significant trend could be found with the increasing HA concentrations. Furthermore, the selective adsorption capacity, represented by the difference in adsorption capacities between MIP and NIP, was not affected significantly. Similar observations were noted for E1, EE2 and BPA in the presence of HA. viii Ionic strength did not exert a considerable influence on the adsorption capacities of MIP and NIP for E1, E2 and BPA. However, at mM of NaCl, EE2 adsorption capacities of MIP and NIP were 124.7 and 111.7μmole/g, respectively, while the corresponding adsorption capacities were 144.7 and 138.2 μ mole/g at 10 mM of NaCl due to the increased hydrophobic interactions. Nevertheless, the selective adsorption capacity was not significantly affected by range of ionic strength tested in this study. The study demonstrated that there was no significant effect of pH on the adsorption capacity of both MIP and NIP from pH 3.1 to and that no considerable effect of pH on selective adsorption capacity of MIP could be established. However, the adsorption capacities of MIP and NIP for E2 at pH were 95.1 and 82.9μ mole/g while at the pH 11, the adsorption capacities were 12.1 and 5.9μ mole/g correspondingly. This means adsorption capacity and selective adsorption capacity were influenced significantly due to the ionization of target compounds. Similar trend was observed for E1, EE2 and BPA. Study on the effect of coexistence of competing estrogenic compounds demonstrated that selective adsorption capacities of MIP can be influenced. Differences between MIP and NIP for E1, E1, EE2 and BPA under competing conditions were 8.8, 6.8, 10.2, and 4.2 µmole/g, respectively, while the corresponding differences were 12.6, 18.2, 13.0, and 9.8 µmole/g when adsorbed individually. The immobilization of MIP and NIP was performed with PVA-boric acid in order to carry out the regeneration of MIP. The immobilization had no influence on the adsorption capacity of MIP but facilitated the separation of ix Liu B.and Liu X.L. 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Selective removal of estrogenic compounds by molecular imprinted polymer. Water Research 42(15), 4101-4108. 2. Zhang Zhongbo and Jiangyong Hu. Effect of environmental factors on the molecular recognition of MIP in removing estrogenic compounds. (Water, air and soil pollution, accepted) 3. Jiangyong Hu and Zhongbo Zhang. A quantitative method evaluating the selective adsorption of molecularly imprinted polymer. (Ready for submission) Conference publications 1. Zhang Zhongbo and Jiangyong Hu. Selective removal of estrogenic compounds by molecular imprinted polymer (MIP). The 16th joint KAISTKYOTO-NTU-NUS symposium on environmental engineering. June 2529 2007. 2. J.Y. Hu, Virender K. Sharma, M.L. Tint, Z.B. Zhang and S.L. Ong. Oxidation of Hormone Estrogens in Water Using Potassium Ferrate(VI). The 16th joint KAIST-KYOTO-NTU-NUS symposium on environmental engineering. June 25-29 2007. 3. Monitoring N-Nitrosodimethylamine (NDMA) in Singapore Drinking Water. Zhang Zhongbo, Hu Jiangyong, Josephine Leong Yin Houc, Fang 209 Wei, Andrews Susan. Singapore International Water Week 2010. June 28 –July 2010. 210 [...]... research, selective adsorption of estrogenic compounds by molecular imprinted polymer (MIP) is proposed to selectively adsorb and consequently remove target estrogenic compounds from aqueous solutions 1.2 Objective and scope of this study The objective of this research is to study whether MIP can effectively remove estrogenic compounds from aqueous solution and what factors influence the removal of these compounds. .. Estrogenic compounds have different potential of estrogenic effect For example, E2, usually has 2~3 orders of magnitude of estrogenic effect higher than that of other estrogenic compounds Estrogenic compounds can enter the bodies of organisms though the ways of bioaccumulation and biomagnification The molecular mechanism of the estrogenic effect depends on the molecular structure of estrogenic compounds, ... Plant xi LIST OF FIGURES Fig 1-1 Framework of research 8 Fig 2-1 Molecular structures of some estrogenic compounds 15 Fig 2-2 Schematic diagram of generation and transportation of EDCs 16 Fig 2-3 Schematic diagram of molecularly imprinted polymer preparation 38 Fig 4-1 Adsorption performance of MIP and NIP in acetonitrile solution 86 Fig 4-2 Comparison of adsorption capacity of MIP and... Consequently, the removal of these compounds is still a challenge, especially from the viewpoint of full scale engineering Therefore, new advanced chemical processes and physical operations need to be established One of the promising ideas for the removal of estrogenic compounds is the selective removal This is because the estrogenic effect depends fundamentally on the estrogenic compounds with similar... Effect of HA on the adsorption of E1 140 Fig 4-24 Effect of HA on the adsorption of E2 140 Fig 4-25 Effect of HA on the adsorption of EE2 140 Fig 4-26 Effect of HA on the adsorption of BPA 141 Fig 4-27 Effect of pH on the adsorption of E1 144 Fig 4-28 Effect of pH on the adsorption of E2 145 Fig 4-29 Effect of pH on the adsorption of EE2 145 Fig 4-30 Effect of pH... terms of chemical and mechanical properties So, MIP could be used to selectively adsorb and remove estrogenic compounds (Yan et al., 2005 and Sellergren, 2001) The principle of the selective adsorption of estrogenic compounds by MIP is that MIP can be prepared as artificial ER possessing particular binding sites which can recognize a group of estrogenic compounds Thus, MIP can bind a group of estrogenic. .. more selective adsorption performance of MIP should be done in removing trace estrogenic compounds For example, the adsorption isotherms of typical estrogenic compounds should be established The adsorption kinetics of uniform micro-sized MIP should be investigated due to the small diffusion distance of target compounds in the interior of MIP What is more 6 important is that the removal mechanism of estrogenic. .. remove most of the estrogenic compounds (Nghiem et al., 2002a; 2002b and Thomas et al., 2002) The removal of estrogenic compounds by membrane retention relies on the interactions between the membrane material and the physicochemical properties of target compounds However, this process is not cost-effective Adsorption is also considered as one of the choices for the removal of estrogenic compounds because... the selective 12 adsorption of estrogenic compounds using MIP is based on particular functional group and molecular size As a result, the research on MIP can reveal whether MIP can be used to remove estrogenic compounds, what are the advantages and disadvantages using MIP to remove target compounds, and which aspects of properties of MIP should be improved 2.2 Categories and properties of estrogenic compounds. .. adsorption of single and multiple estrogenic compounds, E1, E2, EE2 and BPA; Adsorption capacity and kinetics study and simulation Effect of competing substances and environmental factors such as NOM, pH and ions on adsorption of estrogenic compounds, E1, E2, EE2 and BPA Adsorption mechanisms of E1, E2, EE2 and BPA Immobilization and regeneration of MIP Selective removal of EDCs in water Fig 1-1 Framework of . SELECTIVE REMOVAL OF ESTROGENIC COMPOUNDS FROM AQUEOUS SOLUTION USING NOVEL ADSORBENT- MOLECULARLY IMPRINTED POLYMER BY ZHANG ZHONGBO . properties of estrogenic compounds 13 2.3 Sources and distribution of estrogenic compounds 15 2.4 Detection of estrogenic compounds 17 2.4.1 Chemical analysis 17 2.4.2 Bioassay 19 2.5 Removal of estrogenic. different potential of estrogenic effect. For example, E2, usually has 2~3 orders of magnitude of estrogenic effect higher than that of other estrogenic compounds. Estrogenic compounds can enter