Interactions of tetracycline antibiotics with dissolved metal ions and metal oxides

200 Pages·2008·1.56 MB·English

INTERACTIONS OF TETRACYCLINE ANTIBIOTICS WITH
DISSOLVED METAL IONS AND METAL OXIDES

A Dissertation
Presented to
The Academic Faculty

by

Wan-Ru Chen

In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy in the
School of Civil and Environmental Engineering

Georgia Institute of Technology
August, 2008

COPYRIGHT BY WAN-RU CHEN 2008
INTERACTIONS OF TETRACYCLINE ANTIBIOTICS WITH DISSOLVED
METAL IONS AND METAL OXIDES

Approved by:

Dr. Ching-Hua Huang, Advisor Dr. Spyros G. Pavlostathis
School of Civil and Environmental School of Civil and Environmental
Engineering Engineering
Georgia Institute of Technology Georgia Institute of Technology

Dr. Jaehong Kim Dr. Andrew Stack
School of Civil and Environmental School of Earth and Atmospheric
Engineering Science
Georgia Institute of Technology Georgia Institute of Technology

Dr. Sotira Yiacoumi
School of Civil and Environmental
Engineering
Georgia Institute of Technology

Date Approved: May 7, 2008
[To my parents]
ACKNOWLEDGEMENTS

First of all, I would like to express my deepest sense of gratitude to my advisor Dr.
Ching-Hua Huang for her patient guidance, encouragement and excellent advice
throughout this study. Her constant support and help made this work successful.
I would also like to thank Dr. Jaehong Kim, Dr. Sotira Yiacoumi, Dr. Spyros G.
Pavlostathis and Dr. Andrew Stack for serving as my committer members. Their
comments and suggestions are very helpful in improving this thesis.
I am deeply indebted to Dr. Guangxuan Zhu for his guidance and assistance
throughout my five year of research in the lab. He showed me a lot invaluable knowledge
regarding instrument operation and maintenance which will be very helpful and useful in
my future research.
I am thankful to my lab members, Judy Zhang, Amisha Shah, Sanghyuck Park,
Lokesh Padhye and Pei Wang for being so helpful in the lab. Those long nights in Daniel
lab will not be forgotten. A special thanks goes to Judy for her valuable contributions and
discussion to kinetic model development.
I would like to acknowledge my closest friends Rebecca Chang, Nora Chen and
Pauline Han for proofreading my thesis and providing valuable feedback. I am grateful to
Emily Ko and her family for their generous help and for being with me throughout my
stay at Atlanta. I would also like to thank Chien-Chung Huang and Min Cho for saving
my data and my thesis while my computer crushed. Throughout the preparation of this
thesis and throughout my entire study, I have received help, advice, and encouragement
from all of my friends, especially San-Hui Chi, Chia-Hung Hou, KJ Liao, Jane Li, Gayle
iv
Hagler and Dooil Kim from Georgia Tech and Jessica Leung, Wendy Tung, Yudan Gaw,
Marcia Rhee and Kate Wang from church.
Lastly, I am deeply and forever indebted to my mother Bao-Lian Yang and my
father Tse-Chuan Chen for their unwavering love, support and encouragement throughout
my entire life. I am also very grateful to my brothers Yung-Fu Chen and Yung-Chian
Chen for being with me all this time. I thank them greatly for being so caring and
supportive when I was far away from home. I would never have completed my Ph.D.
study without my family.

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TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iv
LIST OF TABLES xii
LIST OF FIGURES xiii
LIST OF SYMBOLS AND ABBREVIATIONS xv
SUMMARY xixx
CHAPTER
1 INTRODUCTION 1
1.1 Research Issue and Objectives 1
1.2 Background 5
1.2.1 Tetracycline Antibiotics 5
1.2.1.1 Occurrence of Tetracyclines in the Environment 5
1.2.1.2 Chemical Properties of Tetracyclines 6
1.2.1.3 Possible Environmental Fate of Tetracycline Antibiotics 10
1.2.2 Metal Species That Facilitate Transformation of Organic Contaminants in
the Aquatic Environment 12
1.2.2.1 Metal-ligand Complex Formation 13
1.2.2.2 Effects of Adsorption on the Kinetics of Surface Reactions 18
1.2.2.3 Redox Reactions at the Mineral-water Interface 19
1.2.3 Metal Species Used in This Study 22
1.2.3.1 Manganese Oxides 22
1.2.3.2 Aluminum Oxides 24
1.2.3.3 Transition Metal Ions 27
1.3 Research Tasks and Methodology 31
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1.4 Thesis Organization 32
2 TRANSFORMATION OF TETRACYCLINES MEDIATED BY
MANGANESE(II) AND COPPER(II) IONS IN THE PRESENCE
OF OXYGEN 34
2.1 Introduction 34
2.2 Materials and Methods 37
2.2.1 Chemicals 37
2.2.2 Reaction Setup 38
2.2.3 Analysis of TCs, MnII ions, CuI Ions and Metal-TC Complexes 39
2.2.4 Product Analysis 40
2.2.5 Complexation Calculation 41
2.3 Results 42
2.3.1 MnII-Mediated Transformation of TCs 42
2.3.1.1 pH Effect 42
2.3.1.2 Competing Ion Effect and Reactivity Trend 43
2.3.2 CuII-Mediated Transformation of TCs 44
2.3.2.1 pH Effect 44
2.3.2.2 Competing Ion Effect and Reactivity Trend 45
2.3.3 Complexation of TCs with MnII and CuII Ions 45
2.3.4 Transformation Product Evaluation. 47
2.4 Discussion 47
2.4.1 Proposed Mechanism for MnII-Mediated Reaction. 47
2.4.2 Proposed Mechanisms for CuII-Mediated Reaction. 51
2.4.3 Reactive Moieties of TCs 53
3 KINETIC MODELING OF OXIDATION OF ANTIBACTERIAL AGENTS
BY MANGANESE OXIDE 64
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3.1 Introduction 64
3.2 Materials and Methods 67
3.2.1 Chemical Reagents 67
3.2.2 Kinetic Experiments 68
3.2.3 Analytical Methods 69
3.3 Results 69
3.3.1 Kinetic Model 69
3.3.2 Model Comparison and Kinetic Fitting 72
3.3.3 Effect of Reaction Conditions 74
3.3.3.1 Effect of Reactant Loading 74
3.3.3.2 Effect of pH 75
3.3.3.3 Effect of Co-Solutes 75
3.4 Discussion 76
4 TRANSFORMATION OF TETRACYCLINE ANTIBIOTICS BY
MANGANESE OXIDE 95
4.1 Introduction 95
4.2 Experimental Section 98
4.2.1 Chemicals 98
4.2.2 Kinetic Experiments 99
4.2.3 Analysis of TCs and MnII Ions 99
4.2.4 Product Identification 100
4.3 Results and Discussion 101
4.3.1 Kinetics of Oxidation of TCs by MnO . 101
2
4.3.2 Effect of Metal Ion Co-Solutes. 104
4.3.3 Transformation Product Analysis. 106
4.3.3.1 TTC Transformation Products 106
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4.3.3.2 OTC Transformation Products 109
4.3.3.3 CTC Transformation Products 111
4.3.4 Proposed Transformation Pathways. 112
4.4 Environmental Relevance 114
5 ADSORPTION AND TRANSFORMATION OF TETRACYCLINE
ANTIBIOTICS WITH ALUMINUM OXIDE 127
5.1 Introduction 127
5.2 Experimental Section 130
5.2.1 Chemicals 130
5.2.2 Kinetic Experiments 131
5.2.3 Analysis of TCs 131
5.2.4 Product Identification 132
5.3 Results and Discussion 132
5.3.1 Adsorption and Transformation of TCs in the Presence of Al O 132
2 3
5.3.2 Effect of Reaction Conditions 134
5.3.2.1 Reactant Loading Effect 134
5.3.2.2 pH Effect 135
5.3.2.3 The Presence of Oxygen 136
5.3.3 Transformation Product Analysis 137
5.4 Environmental Relevance 141
6 CONCLUSION 150
6.1 Metal Ion-promoted Transformation of TCs 151
6.2 Surface Promoted Transformation of TCs 152
6.3 Reaction Kinetics of Surface Promoted Transformation 154
6.4 Environmental Significance 155
6.5 Future Work 157
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6.5.1 Further Product Characterization 157
6.5.2 Toxicity Analysis of TC Transformation Products 157
6.5.3 Further Development of The MnOII Model 158
6.5.4 Impact of Other Metal Species 159
6.5.5 Environmental Fate of Other Emerging Contaminants 159
6.5.6 Other Oxidation Treatment Processes of TCs 160
6.5.7 Actual Soil Samples 161
REFERENCES 163
VITA 16379

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