IN-SITU AMMONIA REMOVAL OF LEACHATE FROM BIOREACTOR LANDFILLS by NICOLE D. BERGE B.S. University of South Carolina, 1999 M.S. University of South Carolina, 2001 A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Civil and Environmental Engineering in the College of Engineering and Computer Science at the University of Central Florida Orlando, Florida Spring Term 2006 Major Professor: Debra R. Reinhart ABSTRACT A new and promising trend in solid waste management is to operate the landfill as a bioreactor. Bioreactor landfills are controlled systems in which moisture addition and/or air injection are used as enhancements to create a solid waste environment capable of actively degrading the biodegradable organic fraction of the waste. Although there are many advantages associated with bioreactor landfills, some challenges remain. One such challenge is the ammonia-nitrogen concentration found in the leachate. The concentrations of ammonia-nitrogen tend to increase beyond concentrations found in leachate from conventional landfills because recirculating leachate increases the rate of ammonification and results in accumulation of higher levels of ammonia-nitrogen concentrations, even after the organic fraction of the waste is stabilized. Because ammonia-nitrogen persists even after the organic fraction of the waste is stabilized, and because of its toxic nature, it is likely that ammonia-nitrogen will determine when the landfill is biologically stable and when post-closure monitoring may end. Thus an understanding of the fate of nitrogen in bioreactor landfills is critical to a successful and economic operation. Ammonia-nitrogen is typically removed from leachate outside of the landfill. However, additional costs are associated with ex-situ treatment of ammonia, as separate treatment units on site must be maintained or the leachate must be pumped to a publicly owned wastewater treatment facility. Therefore, the development of an in-situ nitrogen removal technique would be an attractive alternative. Several recent in-situ treatment approaches have been explored, but lacked the information necessary for field-scale ii implementation. The objectives of this study were to develop information necessary to implement in-situ ammonia removal at the field-scale. Research was conducted to evaluate the kinetics of in-situ ammonia removal and to subsequently develop guidance for field-scale implementation. An aerobic reactor and microcosms containing digested municipal solid waste were operated and parameters were measured to determine nitrification kinetics under conditions likely found in bioreactor landfills. The environmental conditions evaluated include: ammonia concentration (500 and 1000mg N/L), temperature (25o, 35o and 45oC), and oxygen concentration in the gas-phase (5, 17 and 100%). Results suggest that in-situ nitrification is feasible and that the potential for simultaneous nitrification and denitrification in field-scale bioreactor landfills is significant due to the presence of both aerobic and anoxic areas. All rate data were fitted to the Monod equation, resulting in an equation that describes the impact of pH, oxygen concentration, ammonia concentration, and temperature on ammonia removal. In order to provide design information for a field-scale study, a simple mass balance model was constructed in FORTRAN to forecast the fate of ammonia injected into a nitrifying portion of a landfill. Based on model results, an economic analysis of the in-situ treatment method was conducted and compared to current ex-situ leachate treatment costs. In-situ nitrification is a cost effective method for removing ammonia-nitrogen when employed in older waste environments. Compared to reported on-site treatment costs, the costs associated with the in-situ ammonia removal process fall within and are on the lower end of the range found in the literature. When compared to treating the iii leachate off-site, the costs of the in-situ ammonia removal process are always significantly lower. Validation of the laboratory results with a field-scale study is needed. iv ACKNOWLEDGMENTS First and foremost, I would like to begin by thanking my advisor, Dr. Debra Reinhart, without whom this work would not have been possible. Dr. Reinhart has played many roles during my time here. She has been an extraordinary role model, mentor, friend and critic, exerting an influential impact on my future and helping to shape me both as an aspiring researcher and teacher. She has taught me how to be strong, positive, and have confidence, as she always had immense confidence in me. I have also learned from her the role teaching and research have in life and how much passion for both makes all the difference. I also thank her for providing me with numerous professional development opportunities, such as teaching and attending many conferences. Her willingness to reply to the countless daily emails I sent and for always being available when I needed to blow off steam have been invaluable. One truly could not ask for a better mentor and I feel blessed to have had the opportunity to get to know and work with her. I truly believe that I am leaving UCF not only with a better understanding of theories and as a better researcher, but also as a better person because of all I learned from her. I would also like to thank Dr. John Dietz for all of his help during the past few years. Thank you, Dr. Dietz, for being so helpful and gracious with your time. I have learned so much from you. Dr. Dietz always dropped by my office to help with my, at times quite numerous, problems or to give advice as to how to interpret results. He taught me how to be critical of all results and how to truly understand the inherent limitations associated with them. His help and expertise were invaluable to this work and I really cannot express the immense gratitude I have for all he has done for me. And yes, Dr. Dietz, I did finish before you retired! I just made it…barely! v I also would like to thank my other committee members. Dr. Tim Townsend has offered invaluable guidance to this work. His comments and critiques have made this project better and I greatly appreciate all of his time and support. Thanks also go to Dr. Andrew Randall for agreeing to serve on my committee and for always being willing to help me sort through microbiological issues. I also thank Dr. Ni-Bin Chang, who enthusiastically joined my committee late in the process and was so willing to help and positively contribute to this work. Thank you all so much. I also acknowledge the Florida Center for Solid and Hazardous Waste and the Environmental Research and Education foundation for funding this work. This work would not have possible without your contributions. Thanks also go to Jackie Ceather, who helped me tremendously with some of the laboratory work. Her help and time were greatly appreciated. I would not have slept during the past five years if it weren’t for her. Thanks also go to my fellow research group colleagues, particularly those who spent so much time in the lab with me (Eyad, Lucia and Andrea). I also would like to extend thanks to my dear friends Sara and Bryan Stone. I couldn’t have made it without all of your support. You guys helped to keep me somewhat sane through this process and always reminded me why I was here. Finally, I thank my family for their enduring love and support. My Mom always taught me that if I worked hard and believed in myself, I could accomplish anything. And she was right. Thanks for always being supportive. I also thank my Step-Dad for all of his support and wisdom throughout the years. And, of course, I thank my little brothers, Weber and Mattison, whom I cherish more than anything. I am finally graduating, guys! vi TABLE OF CONTENTS LIST OF TABLES............................................................................................................xi LIST OF FIGURES.........................................................................................................xii CHAPTER 1 INTRODUCTION.......................................................................................1 Background Information..............................................................................................1 Research Objectives and Scope of Work....................................................................4 Dissertation Organization............................................................................................6 References......................................................................................................................7 CHAPTER 2 THE FATE OF NITROGEN IN BIOREACTOR LANDFILLS............11 Introduction.................................................................................................................11 Bioreactor Landfill Operation...................................................................................13 Anaerobic Bioreactor Landfills.................................................................................17 Aerobic Bioreactor Landfills....................................................................................19 Hybrid Bioreactor Landfills......................................................................................21 Facultative Bioreactor Landfills...............................................................................24 Ammonia-Nitrogen in Leachate................................................................................25 Nitrogen Transformation and Removal Processes..................................................27 Ammonification........................................................................................................30 Ammonium Flushing................................................................................................31 Ammonium Sorption................................................................................................32 Volatilization.............................................................................................................36 Nitrification...............................................................................................................38 Nitrification Case Studies in Landfills..................................................................43 Nitrification Kinetics............................................................................................45 Denitrification...........................................................................................................46 Heterotrophic Denitrification................................................................................47 Autotrophic Denitrification...................................................................................49 Denitrification Kinetics.........................................................................................51 ANAMMOX.............................................................................................................51 Dissimilatory Nitrate Reduction to Ammonium......................................................52 Simultaneous Nitrogen Removal Processes..............................................................55 Other Nitrate Processes.............................................................................................56 Future Research Directions.......................................................................................57 References....................................................................................................................58 CHAPTER 3 THE IMPACT OF WASTE ACCLIMATION ON IN-SITU AMMONIA REMOVAL FROM BIOREACTOR LANDFILL LEACHATE....................................70 Introduction.................................................................................................................70 Materials and Methods...............................................................................................73 vii Aerobic Reactor (Waste Acclimation Process) Design and Operation....................73 In-Situ Nitrification Microcosm Studies...................................................................75 Analytical Techniques..............................................................................................77 Results and Discussion................................................................................................79 Aerobic Reactor (Waste Acclimation Process).........................................................79 In-Situ Nitrification Microcosm Studies...................................................................83 Ammonia Sorption................................................................................................84 In-Situ Nitrification Processes..............................................................................85 Simultaneous Nitrogen Removal Processes..........................................................86 Ammonia Removal Kinetics.................................................................................90 Acclimated vs Unacclimated Processes............................................................93 Field-Scale Ammonia Removal Implications...................................................94 Nitrogen Mass Balances.......................................................................................95 Conclusions..................................................................................................................96 References....................................................................................................................97 CHAPTER 4 THE IMPACT OF GAS-PHASE OXYGEN AND TEMPERATURE ON IN-SITU AMMONIA REMOVAL FROM BIOREACTOR LANDFILL LEACHATE .........................................................................................................................................101 Introduction...............................................................................................................101 Experimental Materials and Methods....................................................................103 Microcosm Study Operation...................................................................................104 Analytical Techniques............................................................................................106 Results and Discussion..............................................................................................106 Nitrogen Removal Processes..................................................................................106 Ammonia-Nitrogen Removal Rates........................................................................113 Impact of oxygen and temperature on removal rates..........................................113 Combined effects on ammonia removal.............................................................122 References..................................................................................................................125 CHAPTER 5 ENGINEERING SIGNIFICANCE........................................................128 Introduction...............................................................................................................128 Model Description.....................................................................................................128 Simulation of Laboratory Experiments..................................................................135 Model Results............................................................................................................138 Optimizing Treatment Depth...................................................................................143 In-Situ Denitrification..............................................................................................145 Field Study Plans......................................................................................................146 Economic Analysis....................................................................................................149 In-Situ Treatment Economics.................................................................................149 Cost Comparison With Other Leachate Treatment Systems..................................153 viii References..................................................................................................................156 CHAPTER 6 CONCLUSIONS AND RECOMMENDATIONS..................................159 Conclusions................................................................................................................159 Field-Scale Implementation Recommendations.....................................................161 APPENDIX A MATERIALS AND METHODS...........................................................163 Introduction...............................................................................................................164 Waste Acclimation Process......................................................................................164 Microcosm Studies....................................................................................................169 Failed Microcosm Designs.....................................................................................170 Chosen Microcosm Design.....................................................................................171 Microcosm Sampling Procedure.........................................................................172 Experiments Conducted......................................................................................173 Impact of Waste Acclimation Experiments....................................................173 Impact of Gas-Phase Oxygen and Temperature Experiments........................174 Analytical Techniques..............................................................................................177 pH............................................................................................................................177 Ammonia.................................................................................................................177 Anions (nitrate, nitrite, sulfate)...............................................................................179 Alkalinity................................................................................................................180 Gas-Phase Oxygen and Nitrogen............................................................................180 Gas-Phase Nitrous Oxide........................................................................................181 Chemical Oxygen Demand (COD).........................................................................181 Solid-Phase Organic Nitrogen................................................................................182 Volatile Solids.........................................................................................................183 Moisture Content....................................................................................................183 Gas Volume............................................................................................................183 Ammonia Gas.........................................................................................................184 References..................................................................................................................184 APPENDIX B WASTE ACCLIMATION PROCESS RESULTS................................185 Introduction...............................................................................................................186 Summary of Results..................................................................................................186 Waste Acclimation Process #1................................................................................186 Waste Acclimation Operation at 22oC................................................................186 Waste Acclimation Operation at 35oC................................................................189 Waste Acclimation Process #2................................................................................192 Waste Acclimation Operation at 45oC................................................................193 References..................................................................................................................198 APPENDIX C MODEL VALIDATION STATISTICS................................................199 Introduction...............................................................................................................200 Procedure...................................................................................................................200 ix Discussion of Results.................................................................................................204 Data Sheets................................................................................................................206 References..................................................................................................................246 APPENDIX D CONFIDENCE INTERVAL DETERMINATION.............................247 Introduction...............................................................................................................248 Summary of Results..................................................................................................248 Case #1: Comparison Between Oxygen Levels at Constant Temperature Using the Monod Model Without Temperature and pH Terms..............................................249 Case #2: Comparison Between Oxygen Levels at Constant Temperature Using the Complete Monod Model (including temperature and pH terms)............................249 Case #3: Comparison Between Temperatures at Different Oxygen Levels Using the Complete Monod Model (including temperature and pH terms)............................250 Discussion of Results.................................................................................................250 Data Sheets................................................................................................................252 Comparison Between Oxygen Levels at Constant Temperature Using the Monod Model Without Temperature and pH Terms...........................................................252 Comparison Between Oxygen Levels at Constant Temperature Using the Complete Monod Model (including temperature and pH terms)............................................256 Comparison Between Temperatures at Different Oxygen Levels Using the Complete Monod Model (including temperature and pH terms)............................................260 APPENDIX E MODEL CODE.....................................................................................264 APPENDIX F PLOTS OF ALL MICROCSM DATA..................................................273 Microcosms at 22oC..................................................................................................274 Acclimated Waste...................................................................................................274 Microcosms at 22oC.................................................................................................290 Unacclimated Waste...............................................................................................290 Microcosms at 35oC..................................................................................................293 Microcosms at 45oC..................................................................................................309 APPENDIX G ECONOMIC CALCULATIONS..........................................................322 Air Flowrate Calculations........................................................................................323 Blower Power Requirement Calculations...............................................................326 Air Piping Calculations............................................................................................328 Leachate Injection Pump Calculations...................................................................329 x
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