University of South Carolina Scholar Commons Theses and Dissertations 12-15-2014 Application of Various Adsorbents to Remove Micro-Pollutants in Aquatic System Chanil Jung University of South Carolina - Columbia Follow this and additional works at:http://scholarcommons.sc.edu/etd Recommended Citation Jung, C.(2014).Application of Various Adsorbents to Remove Micro-Pollutants in Aquatic System.(Doctoral dissertation). Retrieved from http://scholarcommons.sc.edu/etd/2959 This Open Access Dissertation is brought to you for free and open access by Scholar Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please [email protected]. APPLICATION OF VARIOUS ADSORBENTS TO REMOVE MICRO-POLLUTANTS IN AQUATIC SYSTEM by Chanil Jung Bachelor of Science and Engineering Hanyang University, 2006 Master of Science and Engineering Hanyang University, 2008 Master of Science and Engineering Carnegie Mellon University, 2010 Submitted in Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy in Civil and Environmental Engineering School of Engineering and Computing University of South Carolina 2014 Accepted by: Yeomin Yoon, Major Professor Nicole Berge, Committee Member Joseph R.V. Flora, Committee Member Ahjeong Son, Committee Member Lacy Ford, Vice Provost and Dean of Graduate Studies © Copyright by Chanil Jung, 2014 All Rights Reserved. ii DEDICATION Foremost, I am highly grateful to God for His blessing that continue to flow into my life, and because of You, I made this through against all odds. I dedicate my dissertation work to my family and many friends. First of all, a special feeling of gratitude to my loving parents, Youngchae Jung and Younglee Kim and in law, Kyougjong Hong and Jeongwon Lee, whose words of encouragement and push for tenacity ring in my ear. My sister, Seunghee Jung has never left my side and is very special. I thank you for constant support, encouragement, and interest in what I am doing. To my many friends and church family who have supported me throughout the process, I always appreciate all they have done, especially Linkel Boateng for helping me develop my technology skills and spending the many hours of proofreading. Special thanks to my daughter and son, Dami Jung and Haim Jung. You are the light of my life. I still feel sorry for spending less time with you due to living separately. Nevertheless, your big smiles, hugs and kisses, and love have been encouraging and motivating me to complete this work; both of you have been my best cheerleaders. For the last, to my lovely wife, Eunkyoung Hong, you are my rock in everything and certainly through this four year experience. Without your faith, belief, smiles, hugs, and love, I would not have overcome trials and submitted this dissertation. Thank you for understanding how important this was to me and for supporting me every step of the way. I love you with all that I have. My love and gratitude goes out to you all. iii ACKNOWLEDGEMENTS With a great pleasure I would like to acknowledge the support, assistances and contribution made by individuals from the beginning of the fieldwork, providing me access, data and information, to the writing process until the completion of this thesis. It would not have been possible to write this doctoral thesis without the guidance of my committee members and their assistance and support of the kind people around me, to only some of whom it is possible to give particular mention here. I would like to express my deepest gratitude to my advisor, Dr. Yeomin Yoon, for his excellent guidance, caring, patience, and for providing me with an excellent atmosphere for doing research. I would like to thank Dr. Flora, who gently advised my research and guided me to experience the research of adsorption with molecular modeling in the field and practical issues beyond the textbooks. I would also like to thank Dr. Berge, and Dr. Saleh for guiding my research for the past several years and helping me to develop my background in physiology and water chemistry. Special thank goes to Dr. Son, who was willing to participate in my final defense committee. I would like to thank Linkel Boateng, who as a good friend was always willing to help and give his best suggestions. It would have been a lonely lab without him. Many thanks to Jiyong Heo, Jongkwon Im, Yasir Alhamadani, Liang Li, Caleb Braswell, Seungwoo Nam for their encouragements which help me to focus on my work. My research would not have been possible without their help. iv I would also like to thank my parents, and sister, they were always supporting me and encouraging me with their best wishes. Finally, I would like to thank my wife, Eunkyoung Hong, and lovely daughter, Dami Jung and son, Haim Jung. They were always there cheering me up and stood by me through the good times and bad. v ABSTRACT Untreated or insufficiently treated pharmaceuticals and endocrine disrupting compounds (EDCs) as well as heavy metals have influenced the ecosystem and their exposures in the water system have threatened human health; causing cancers and adverse health effect to immune system. While various water treatment techniques have been applied to solve this problem, adsorption has been considered as one of the most efficient and manageable water purification techniques. Advanced analysis methods for aqueous contaminants have improved comprehension, allowing proficiency about the fate of trace leveled emerging contaminants, thus allowed to reveal the adsorption mechanisms of each pollutant. This dissertation focuses on the investigation of adsorption for micro-pollutants in aquatic environment via the application of different types of carbonaceous (powdered activated carbon, carbon nanotubes, and biochars) and biodegradable (chitosan) adsorbent. The effect of water chemistry conditions such as pH, concentration of ionic strength induced species and natural organic matters were considered as significant factors to increase or decrease the adsorption capacity of each adsorbent. This study also illuminates the use of biochar, byproduct of bio-oil, with simple chemical activation as an efficient adsorbent for pharmaceutical and EDCs removal. In-depth analysis about adsorption between these micro-pollutants and biochars was performed by characterization of physicochemical properties by nuclear magnetic resonance analysis in conjunction with molecular modeling subsequently interpreting the binding energy. Aromaticity and composition of vi carbonaceous structure of adsorbent controlled the adsorption capacity, while hydrophobicity of adsorbates influenced the adsorption affinity toward the adsorbents. More specifically, the presence of adsorption competitors resulted in less effective binding due to a combination of less favorable binding energy, polarity, and π-energy with the adsorbent and electrostatic repulsion from the cosolutes that occupied adsorption sites. vii TABLE OF CONTENTS DEDICATION ....................................................................................................................... iii ACKNOWLEDGEMENTS ........................................................................................................ iv ABSTRACT .......................................................................................................................... vi LIST OF TABLES ....................................................................................................................x LIST OF FIGURES ................................................................................................................ xii LIST OF ABBREVIATIONS ................................................................................................... xvi CHAPTER 1 INTRODUCTION AND MOTIVATION .....................................................................1 CHAPTER 2 OBJECTIVES AND SCOPE .....................................................................................4 CHAPTER 3 LITERATURE REVIEW AND BACKGROUND ..........................................................7 3.1 OCCURRENCE AND EXPOSURE OF MICRO-POLLUTANTS IN THE AQUATIC ENVIRONMENT .......................................................................................................7 3.2 VARIOUS ADSORBENT FOR MICRO-POLLUTANT REMOVAL .................................13 3.3 CHARACTERIZATION OF ADSORBENT AND ADSORBATE ......................................18 3.4 MOLECULAR MODELING FOR STRUCTURE CONFIGURATION IN ADSORPTION STUDY ............................................................................................22 CHAPTER 4 HEXAVALENT CHROMIUM REMOVAL BY VARIOUS ADSORBENTS: POWDERED ACTIVATED CARBON, CHITOSAN, AND SINGLE/MULTI-WALLED CARBON NANOTUBES ......................................................................................................25 4.1 INTRODUCTION ....................................................................................................26 4.2 MATERIALS AND METHODS .................................................................................30 4.3 RESULTS AND DISCUSSION ..................................................................................32 viii 4.4 CONCLUSIONS .....................................................................................................52 CHAPTER 5 ADSORPTION OF SELECTED ENDOCRINE DISRUPTING COMPOUNDS AND PHARMACEUTICALS ON ACTIVATED BIOCHARS ................................................54 5.1 INTRODUCTION ....................................................................................................55 5.2 MATERIALS AND METHODS .................................................................................58 5.3 RESULTS AND DISCUSSION ..................................................................................63 5.4 CONCLUSIONS .....................................................................................................86 CHAPTER 6 COMPETITIVE ADSORPTION OF SELECTED NON-STEROIDAL ANTI-INFLAMMATORY DRUGS ON ACTIVATED BIOCHAR: EXPERIMENTAL AND MOLECULAR MODELING STUDY .......................................................................91 6.1 INTRODUCTION ....................................................................................................92 6.2 MATERIALS AND METHODS .................................................................................94 6.3 RESULTS AND DISCUSSION ...................................................................................99 6.4 CONCLUSIONS ...................................................................................................125 CHAPTER 7 OVERALL CONCLUSIONS AND FUTURE RECOMMENDATIONS .........................127 REFERENCES .....................................................................................................................130 APPENDIX A – PRINTABLE AUTHORSHIP LICENSE ............................................................145 ix