NOVEL HETEROGENEOUS FENTON OXIDATION USING MAGENTIC IRON OXIDE- DECORATED CARBON NANOTUBE TO REMOVE ENDOCRINE DISRUPTING COMPOUNDS IN WASTEWATER AND WATER A THESIS SUBMITTED TO THE GRADUATE DIVISION OF THE UNIVERSITY OF HAWAI‘I AT MĀNOA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN MOLECULAR BIOSCIENCES AND BIOENGINEERING DECEMBER 2014 By Vincent J. Cleveland Thesis Committee Eunsung Kan, Chairperson Jon-Paul Bingham Soojin Jun Keywords: Fenton Oxidation, Carbon Nanotube, Wastewater, BPA Acknowledgments It has been said that producing a thesis is like giving birth. I can hardly say this has been an easy labor, and I would not of been able to complete it without the assistance of my coworkers and friends. My labmates Jihyun “Rooney” Kim and Stuart Watson were essential for keeping my sanity through the process and acted as critical sounding boards for developing my half-baked ideas. I would also like to thank Patrick Gasda for use of the Raman lasers. My use of magnetic separation was greatly facilitated by Jonathan Moroney through supplying me with several rare earth hard drive magnets. Finally I wouls like thank my parents for their support throughout my education. i Abstract Endocrine disrupting compounds are becoming a growing concern in our modern world. Bisphenol A, a known estrogen mimic, is produced on a massive scale exposing it to humans and the environment on a daily basis. Recent studies since 1995 have shown that bisphenol A has negative effects even at ultra-low concentrations. Unfortunately, bisphenol A is biologically recalcitrant and passes through most traditional waste water treatment methods. In order to develop an effective and efficient treatment method, a combined approach is proposed. Iron amended carbon nanotubes can act as a heterogeneous Fenton catalyst and as an adsorbent of the contaminant. This project synthesized and characterized a magnetite decorated carbon nanotube catalyst. Additionally the adsorption kinetics and thermodynamics were investigated in both batch adsorption and column adsorption reactors. ii Table of Contents Table of Contents Acknowledgments ......................................................................................................................................... i Abstract ........................................................................................................................................................ ii Table of Contents ........................................................................................................................................ iii List of Tables ................................................................................................................................................ vi List of Figures .............................................................................................................................................. vii Chapter 1 Description of Thesis ............................................................................................................ 1 1. Prologue ............................................................................................................................................ 1 1.1 Description of Chapters ................................................................................................................ 1 1.2 Overall Aims of Research .............................................................................................................. 2 1.3 Impact of This Thesis ..................................................................................................................... 2 Chapter 2 Literature Survey .................................................................................................................. 3 2.1 Endocrine-Disrupting Compounds ................................................................................................ 3 2.2 Bisphenol A ................................................................................................................................... 5 2.3 Sources of Bisphenol A Contamination ......................................................................................... 5 2.4 Effects of Bisphenol A on the Environment .................................................................................. 6 2.5 Effects of Bisphenol A on Living Organisms .................................................................................. 7 2.6 Effects of BPA on Society .............................................................................................................. 9 2.7 State of Research ........................................................................................................................ 10 2.7.1 Biological Treatment of Bisphenol A ................................................................................... 12 2.7.2 Physical Treatment of Bisphenol A ..................................................................................... 14 2.7.3 Nanofiltration/Reverse Osmosis ......................................................................................... 15 2.7.4 Adsorption of BPA onto Activated Carbon, Carbon Nanotubes, Biochar, and Zeolite ....... 16 2.7.5 Zeolite and Mineral Based Adsorbents ............................................................................... 19 2.7.6 Biochar ................................................................................................................................ 19 2.7.7 Activated Carbon................................................................................................................. 20 2.7.8 Graphene ............................................................................................................................ 20 2.7.9 Carbon Nanotubes .............................................................................................................. 20 2.7.10 Chemical Treatment of Bisphenol A ................................................................................... 22 2.7.11 Ozonation ............................................................................................................................ 22 2.7.12 Fenton Oxidation ................................................................................................................ 22 iii 2.7.13 Heterogeneous Fenton Oxidation ....................................................................................... 24 Chapter 3 Proof of Concepts ............................................................................................................... 27 3.1 Introduction ................................................................................................................................ 27 3.2 Methods ...................................................................................................................................... 29 3.2.1 Catalyst Synthesis ................................................................................................................ 29 3.2.2 Electron Microscopy, XRD, and XPS Characterization ........................................................ 30 3.2.3 Fenton Oxidation ................................................................................................................ 31 3.2.4 Toxicology Testing ............................................................................................................... 31 3.2.5 High Preformance Liquid Chromatography ........................................................................ 31 3.3 Results and Discussion ................................................................................................................ 32 3.3.1 Catalyst Characterization .................................................................................................... 32 3.3.2 Heterogeneous oxidation of BPA by the Fe3O4-MWCNT catalyst ....................................... 37 3.3.3 Effect of the presence of radical scavangers on Fenton Oxidation .................................... 43 3.4. Conclusion ................................................................................................................................... 45 Chapter 4 Adsorption of bisphenol A onto Magnetic Iron Oxide-Coated Multi- Walled Carbon Nanotubes. ............................................................................................................. 47 4.1 Introduction ................................................................................................................................ 47 4.2. Methods and Material ................................................................................................................ 47 4.2.1. Catalyst Synthesis ................................................................................................................ 47 4.2.2. Electron Microscopy, XRD, and XPS .................................................................................... 47 4.2.3. Adsorption Isotherms ......................................................................................................... 47 4.2.4. Kinetic Modeling ................................................................................................................. 48 4.2.5. Thermodynamic Analysis .................................................................................................... 49 4.2.6. Column Based Adsorption Studies ...................................................................................... 49 4.2 Results and Discussion