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Photodegradation of (E)- and (Z)-Endoxifen Kinetics, By-Products

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Photodegradation of (E)- and (Z)-Endoxifen Kinetics, By-Products PHOTODEGRADATION OF (E)- AND (Z)-ENDOXIFEN: KINETICS, BY-PRODUCTS IDENTIFICATION AND TOXICITY ASSESSMENT A Thesis Submitted to the Graduate Faculty of the North Dakota State University of Agriculture and Applied Science By Marina Arino Martin In Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE Major Program: Environmental and Conservational Sciences February 2018 Fargo, North Dakota North Dakota State University Graduate School Title Photodegradation of (E)- and (Z)-Endoxifen in Water by UV-light and Natural Sunlight: Kinetics, Photodegradation By-product, Toxicity Assessment, and Acute Toxicity Study. By Marina Arino Martin The Supervisory Committee certifies that this disquisition complies with North Dakota State University’s regulations and meets the accepted standards for the degree of MASTER OF SCIENCE SUPERVISORY COMMITTEE: Eakalak Khan Chair John McEvoy Thomas DeSutter Approved: April 13, 2018 Craig Stockwell Date Department Chair ABSTRACT Endoxifen is an effective metabolite of tamoxifen, a commonly used chemotherapy drug, and has been detected at the final effluent of a municipal wastewater treatment plant (WWTP). Its presence in the environment could bring negative effects to aquatic lives. This research investigated the use of ultraviolet radiation (253.7 nm) and natural sunlight to photodegrade endoxifen in water and wastewater, the generation of photodegradation by-products (PBPs) and their toxicity. Endoxifen concentration in water was reduced by 99.1% after 35 seconds of UV light generating two toxic PBPs. Experiments in wastewater at UV light doses used for disinfection resulted in reduction of endoxifen by 30 to 71%. Endoxifen concentration in wastewater was reduced by at least 83% after 150 minutes of solar radiation generating eight PBPs. Seven of these PBPs are potentially more toxic than endoxifen itself. Therefore, highly toxic PBPs are potentially generated at WWTPs if endoxifen is present in wastewater. iii ACKNOWLEDGMENTS I would like to thank my advisor Dr. Eakalak Khan for his patience, guidance, and advices during my research at North Dakota State University (NDSU). Without his support and his constant encouragement this research thesis and many other success throughout my graduate study would not have been possible. I am also thankful to Dr. Jayaraman Sivaguru for his invaluable advice and discussion about photodegradation analyses and molecular identification. I would like to take this opportunity to thank Dr. Achintya Bezbaruah for providing me an opportunity to be part of his Graduate Teaching Assistant team. I would like to acknowledge my committee members, Dr. John McEvoy and Dr. Thomas DeSutter, for their continuous support and precious guidance. I am highly obliged to my friends and colleagues for their enormous help along my way as a graduate student. For my research funding, I would like to thank the Civil and Environmental Engineering Department, the Environmental and Conservational Sciences program, the North Dakota Water Research Institute Fellowship and the Center of Excellence for Hazardous Substance Management, Chulalongkorn University. I am eternally grateful to my parents and my sister for their continuously encouragement, love, and unconditional support. They all kept me going through the challenging moments as a graduate student. Last, but by no means the least, I would like to thank my husband Daniel Sanchez for his love, understanding, and most of all for never stopping to believe in me. iv DEDICATION To my parents, Jose Maria and Ana Maria, my sister Laura and my husband Daniel Sanchez. v TABLE OF CONTENTS ABSTRACT ................................................................................................................................... iii ACKNOWLEDGMENTS ............................................................................................................. iv DEDICATION ................................................................................................................................ v LIST OF TABLES .......................................................................................................................... x LIST OF FIGURES ....................................................................................................................... xi LIST OF APPENDIX TABLES .................................................................................................. xiv LIST OF APPENDIX FIGURES ................................................................................................. xv CHAPTER 1. INTRODUCTION ................................................................................................... 1 1.1. Background ........................................................................................................................ 1 1.2. Research objectives ............................................................................................................ 4 1.3. Hypotheses ......................................................................................................................... 5 1.4. Scope of study .................................................................................................................... 5 1.5. Anticipated results and benefits ......................................................................................... 6 CHAPTER 2. LITERATURE REVIEW ........................................................................................ 7 2.1. General background ........................................................................................................... 7 2.2. Endoxifen detection methods ........................................................................................... 10 2.3. Toxicity of endoxifen ....................................................................................................... 11 2.4. Chemical and physical properties of endoxifen ............................................................... 12 2.5. Potential treatment methods for endoxifen in water ........................................................ 15 2.5.1. Photodegradation of endoxifen by UV light ........................................................... 15 2.5.2. Photodegradation of endoxifen by natural sunlight ................................................ 17 2.6. Fate of endoxifen in WWTPs .......................................................................................... 19 CHAPTER 3. MATERIALS AND METHODS .......................................................................... 21 vi 3.1. Materials .......................................................................................................................... 21 3.1.1. Chemicals ................................................................................................................ 21 3.2. Experimental framework ................................................................................................. 21 3.3. Methods............................................................................................................................ 22 3.3.1. Preparations of (E)- and (Z)-endoxifen stock solutions .......................................... 22 3.3.2. Detection and quantification of endoxifen and its photodegradation by-products . 22 3.3.3. Photodegradation with UV light ............................................................................. 25 3.3.4. Photodegradation with natural sunlight .................................................................. 33 3.3.5. Toxicity assessment ................................................................................................ 34 3.3.6. Acute toxicity test ................................................................................................... 34 3.3.7. Statistical analysis ................................................................................................... 35 CHAPTER 4. RESULTS AND DISCUSSION ............................................................................ 36 4.1. Photodegradation with UV light ...................................................................................... 36 4.1.1. Photodegradation standardization method .............................................................. 36 4.1.2. Optimization of photodegradation kinetics and efficiency ..................................... 37 4.1.3. The role of hydroxyl radicals .................................................................................. 43 4.1.4. Quantum yield and emission light intensity ............................................................ 46 4.1.5. Detection and identification of photodegradation by-products .............................. 48 4.1.6. Mineralization of (E)- and (Z)-endoxifen by UV light ........................................... 54 4.1.7. Photodegradation of (E)- and (Z)-endoxifen in wastewater by UV light ............... 56 4.2. Photodegradation with natural sunlight ........................................................................... 62 4.2.1. Photodegradation kinetics and efficiency ............................................................... 62 4.2.2. Photodegradation experiments with wastewater and surface water ....................... 63 4.2.3. Photodegradation by-products of (E)- and (Z)-endoxifen by natural sunlight photodegradation ................................................................................................. 66 vii 4.3. Toxicity study .................................................................................................................
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