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Natural Sunlight Photodegradation of Halogenated Disinfection Byproducts in Water Ibrahim Abusallout South Dakota State University

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Natural Sunlight Photodegradation of Halogenated Disinfection Byproducts in Water Ibrahim Abusallout South Dakota State University South Dakota State University Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange Electronic Theses and Dissertations 2019 Natural Sunlight Photodegradation of Halogenated Disinfection Byproducts in Water Ibrahim Abusallout South Dakota State University Follow this and additional works at: https://openprairie.sdstate.edu/etd Part of the Civil and Environmental Engineering Commons, and the Water Resource Management Commons Recommended Citation Abusallout, Ibrahim, "Natural Sunlight Photodegradation of Halogenated Disinfection Byproducts in Water" (2019). Electronic Theses and Dissertations. 3181. https://openprairie.sdstate.edu/etd/3181 This Dissertation - Open Access is brought to you for free and open access by Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange. For more information, please contact [email protected]. NATURAL SUNLIGHT PHOTODEGRADATION OF HALOGENATED DISINFECTION BYPRODUCTS IN WATER BY IBRAHIM ABUSALLOUT A dissertation submitted in partial fulfillment of the requirements for the Doctor of Philosophy Major in Civil Engineering South Dakota State University 2019 iii بسم هللا الرحمن الرحيم َ ُ م َ ُ َ َ َ َ َ ُ َ َ َ ُ م َ َ ُ ُ ُ َ م ُ م ُ َ (وق ِل اعملوا فسيرى ّللا عملكم ورسوله واْلؤ ِمنون ) صدق هللا العظيم إلهي ﻻ يطيب الليل إﻻ بشكرك و ﻻ يطيب النهار إلى بطاعتك .. و ﻻ تطيب اللحظات إﻻ بذكرك .. وﻻ تطيب اﻵخرة إﻻ بعفوك .. وﻻ تطيب الجنة إﻻ برؤيتك فاياربي لك الحمد والشكر اهداء إلى التي أعطتني من دمها وروحها وعمرها حبا وتصميما ودفعا لغد أجمل إلى ينبوع الصبر والتفاؤل إلى الغالية التي ﻻ نرى اﻷمل إﻻ من عينيها أمي الحبيبة إلى من جرع الكأس فارغا ليسقيني قطرة حب ّ إلى من كلت أنامله ليقدم لي لحظة سعادة إلى من حصد اﻷشواك عن دربي ليمهد لي طريق العلم إلى القلب الكبير والدي العزيز إلى من آثروني على نفسهم إلى من علموني علم الحياة إلى من أظهروا لي ما هو أجمل من الحياة إخوتي To my family iv ACKNOWLEDGMENTS First and most of all, I would like to express my boundless appreciation to my advisor and mentor Dr. Guanghui Hua whose expertise, consistent guidance, ample time spent and consistent advices that brought this dissertation to success. Furthermore, I would like to thank him for introducing me to the field of disinfection byproducts. It was an amazing experience to work in this study area. I would like to extend my appreciation to John R. Andersen, James N. Dornbush, Tanya Miller and HR Green Inc. for their generosity though the several scholarships that I received from them during my graduate studies. To the committee members, Dr. Christopher Schmit and Dr. Suzette Burckhard. Thank you for constructive comments, suggesting and critiquing. Lastly, I would like to thank the staff and students of the Water and Environmental Engineering Research Center at SDSU for their tremendous help and teaching through the years. v TABLE OF CONTENTS LIST OF FIGUERS ............................................................................................................ x LIST OF TABLES ........................................................................................................... xiii ABSTRACT ..................................................................................................................... xiv CHAPTER ONE: INTRODUCTION ............................................................................... 1 1.1 BACKGROUND ........................................................................................................ 1 1.2 FORMATION OF DBPS ............................................................................................. 3 1.3 DEGRADATION OF DBPS IN NATURAL SURFACE WATER ....................................... 7 1.4 PHOTOLYSIS OF DBPS ............................................................................................ 8 1.4.1 Trihalomethanes and Haloacetic acids ............................................................ 8 1.4.2 Haloketones and Haloacetaldehydes ............................................................. 11 1.4.3 Haloacetonitriles, Halonitromethanes and Nitrosamines .............................. 12 1.4.4 Emerging DBPs .............................................................................................. 16 1.4.5 Summary ......................................................................................................... 17 1.5 RESEARCH GAPS ................................................................................................... 18 1.6 RESEARCH OBJECTIVES ........................................................................................ 19 1.7 RESEARCH HYPOTHESES ...................................................................................... 19 1.8 DISSERTATION LAYOUT ........................................................................................ 20 CHAPTER TWO: EVALUATION OF SAMPLE PRESERVATION TECHNIQUES TO IMPROVE TOTAL ORGANIC HALOGEN ANALYSIS .................................. 24 ABSTRACT ...................................................................................................................... 24 2.1 INTRODUCTION ..................................................................................................... 25 vi 2.2 MATERIALS AND METHODS ................................................................................... 27 2.2.1 Chemicals ....................................................................................................... 27 2.2.2 Preparation of TOX and DBP sample ............................................................ 28 2.2.3 Experimental Approach .................................................................................. 29 2.2.4 Analytical Approach ....................................................................................... 30 2.3 RESULTS AND DISCUSSION .................................................................................... 32 2.3.1 Impact of Nitrate Wash Volumes on TOX Recovery ..................................... 32 2.3.2 Impact of Sample Preservation Temperature on TOX and DBPs Recovery . 34 2.3.3 Impact of Quenching Agents on TOX Stability.............................................. 35 2.3.4 Impact of Acidification on TOX Stability ...................................................... 37 2.3.5 Investigation on The Impact of Sulfuric and Phosphoric Acid on TOI Unexpected Formation .............................................................................................. 39 2.4 CONCLUSIONS ....................................................................................................... 41 CHAPTER THREE: NATURAL SOLAR PHOTOLYSIS OF TOTAL ORGANIC CHLORINE, BROMINE AND IODINE IN WATER ................................................ 50 ABSTRACT ...................................................................................................................... 50 3.1 INTRODUCTION ..................................................................................................... 51 3.2 EXPERIMENTAL METHODS.................................................................................... 53 3.2.1 Preparation of TOX Samples.......................................................................... 53 3.2.2 Natural Solar Photolysis Experiments ........................................................... 56 3.2.3 Analytical Methods ......................................................................................... 58 3.3 RESULTS AND DISCUSSION .................................................................................... 59 3.3.1 Degradation Kinetics of TOCl, TOBr and TOI by Solar Photolysis .............. 59 vii 3.3.2 Degradation Kinetics of High and Low MW TOX by Solar Photolysis ......... 62 3.3.3 Effect of Nitrate, Sulfite and Fulvic Acid on TOX Degradation by Solar Photolysis .................................................................................................................. 64 3.3.4 Effect of Natural River Water Matrix on TOX Degradation by Solar Photolysis .................................................................................................................. 68 3.4 CONCLUSIONS ....................................................................................................... 70 CHAPTER FOUR: PHOTOLYTIC DEHALOGENATION OF DISINFECTION BYPRODUCTS IN WATER BY NATURAL SUNLIGHT IRRADIATION ........... 83 ABSTRACT ...................................................................................................................... 83 4.1 INTRODUCTION ..................................................................................................... 84 4.2 EXPERIMENTAL METHODS.................................................................................... 87 4.2.1 Preparation of DBP Samples ......................................................................... 87 4.2.2 Natural Solar Photolysis Experiments ........................................................... 88 4.2.3 Analytical Methods ......................................................................................... 90 4.3 RESULTS AND DISCUSSION .................................................................................... 90 4.3.1 Dehalogenation Kinetics of DBPs by Natural Sunlight Irradiation .............. 90 4.3.2 Effect of Nitrate, Nitrite and pH on Photolytic Dehalogenation of DBPs by Natural Sunlight .......................................................................................................
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