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FATE AND TRANSPORT OF HYDRAZINE THROUGH COLUMNS OF SATURATED SANDY SOIL By WAYNE DOWNS C. A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 1993 ACKNOWLEDGMENTS I would like to thank Dr. Robert Mansell for his patience and persistence during the data acquisition and document preparation for this manuscript. It would never have happened without him. would also like to thank Dr. Michael I Annable for agreeing to step in at a late date to supervise the document and Dr. Joseph Delfino, Chairman of the Department of Environmental Engineering Sciences, for devising a way to make it all possible. Thanks, too, go to Dr. Brian McNeal who recently agreed to become a member of the committee, and to Dr. Paul Chadik, who patiently waited things out. I would also like to thank Dr. Stephen Bloom for his ion exchange discussions and modeling assistance, and Dr. Wayne Huber for his example and guidance during my graduate career at the University of Florida. He believed in me all along. Several coworkers deserve special mention for their assistance in the research described herein: Ana Moliner, for long and fruitful discussions of soil chemistry, and Denie Augustyn and Robin Roberson for laboratory assistance. Special thanks go to my wife Jill, for her love and patience during the years of graduate school and the weeks of managing the family without me during the preparation of this document. Truly, without her encouragement this work would never have come to pass. I would also like to acknowledge the faculty and technical staff of the Soil and Water Science Department at the University of Florida for their kind assistance and partial support. The U. S. Environmental Protection Agency's Robert S. Kerr Environmental Research Laboratory in Ada, Oklahoma, deserves particular recognition for allowing me the time and providing the equipment to finish the laboratory experiments. Also, thanks go to EG&G Idaho, Inc. for partial support in completing the writing of the manuscript. This work was initiated under a grant to the Soil and Water Science Department of the University of Florida by the U. S. Air Force Environics Division, Tyndall Air Force Base, Florida (No. F08635-83-C-0136, CRT Floyd Wiseman, Project Officer). Ill TABLE OF CONTENTS ACKNOWLEDGMENTS j,- ABSTRACT CHAPTER INTRODUCTION 1. ^ CHAPTER 2. LITERATURE REVIEW 7 Literature Review Objectives 7 Hydrazine Environmental Chemistry 7 ........."...". Hydrazine Fate and Transport Pathways ...lll....!.lll.l..l.l.ll............ i CHAPTER MATERIALS AND METHODS 3. 34 Research Objectives 34 Soil Characterization !.."."..." 35 Miscible Displacement "////////"ZZZ....."""!. 43 CHAPTER RESULTS 4. 53 Soil Properties go Miscible Displacement -^ZZZZZZZZIZ... 73 CHAPTER DISCUSSION 5. gg Introduction o-. Environmental Variables ......"..". 07 Process Variables IZIZ...".'".!..... 97 CHAPTERS. SUMMARY AND CONCLUSIONS II3 Introduction . Summary of Experimental Design "//........ 1 1 o Summary of Experimental Results f ... 1 1 Conclusions ' '^ IV , LIST OF REFERENCES ^22 APPENDIX A ..132 APPENDIX B .138 APPENDIX C .149 APPENDIX D .160 APPENDIX E .181 BIOGRAPHICAL SKETCH .190 Abstract of Dissertation Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy FATE AND TRANSPORT OF HYDRAZINE THROUGH COLUMNS OF SATURATED SANDY SOIL By Wayne C. Downs December, 1993 Chairman: M. D. Annable Cochairman: R. S. Mansell Major Department: Environmental Engineering Sciences The effects of environmental and process variables on the fate and transport of hydrazine were investigated in laboratory columns of three consecutive horizons of a saturated sandy soil. The investigation of consecutive horizons containing successively less organic matter showed hydrazine loss within soil columns to be closely correlated with percentage organic matter. Percentage clay in each horizon was not well correlated with hydrazine loss. The influence of the ion-exchange process was investigated by observing the ionic composition of column effluent. An effective cation exchange capacity (CEC) was determined under column-saturated flow, and found to be an order of magnitude less than CEC values determined from batch studies. The column-determined value was used in computer simulations to VI correctly predict observed hydrazinium breakthrough curves. Results Indicated that ion exchange and ion transport are primary mechanisms that describe the transport of hydrazine during water flow in these calcium-saturated soils. A hydrazine mass balance showed losses of 10 to 37 percent in the columns, depending on the horizon. Losses were found to be correlated with the duration of column experiments, implying a first-order degradation mechanism. Microbial activity also was observed for soil taken from completed column experiments. Hydrazine concentrations as high as 16 mmol L-1 were not observed to reduce active microbial populations. Plate counts of approximately 10^ organisms per gram of soil were observed, compared to 10^ organisms per gram using acridine-orange counting methods. Literature values of first order hydrazine degradation rates due to microbial activity are similar to the rate-controlled losses observed in this study, though specific experiments to isolate microbial activity were not performed. VII CHAPTER 1 INTRODUCTION Background Hydrazine (N2H4) and its derivatives are extremely versatile compounds that have found application for a wide variety of purposes. They are readily oxidizable and endothermic, and for this reason have been used in fuel cells, as propellant for gas turbines, as antioxidants, for the deoxygenation of boiler water, in pharmaceuticals production, and as intermediates for the production of explosives and propellants. The agricultural industry is a major user of hydrazine in pesticide production. Hydrazine, along with its derivatives, monomethyl (MMH) and unsymmetrical dimethyihydrazine (UDMH), also is used by the defense industry as a liquid propellant in missiles, satellites, and aircraft. Hydrazine was first prepared by T. Curtius, a German chemist, in 1887. It remained little more than a laboratory curiosity with few applications for several decades (SchiessI, 1980). The first sample of anhydrous hydrazine was prepared by Lorty DeBruyn in 1893. The method for preparation of hydrazine hydrate by the Raschig process was discovered in 1907 and cleared the way for its production in industrial quantities. Hydrazine did not enjoy significant use, however, until its propellant capabilities were realized by the Germans during World War 11. An energetic propellant was needed for the rocket airplane, the Me-163B, developed in 1937. A mixture of hydrazine hydrate and methanol was used as a fuel, with hydrogen peroxide as the oxidizer in a bipropellant 1 rocket engine (Schmidt, 1987). The first use of hydrazine as a monopropellant was demonstrated in 1954 at the Jet Propulsion Laboratory in Pasadena, California The late 1950s saw a great increase in the production of anhydrous . hydrazine in the United States, and hydrazine production increased again in the 1960s when a blend of UDMH and hydrazine was used to fuel the Titan series rocket engines. Development of the Shell 405 catalyst in 1963 allowed almost unlimited restart capability and opened the way for new hydrazine applications. As a result, most military, commercial, and scientific satellites in earth orbit use hydrazine propulsion systems for attitude control and orbit maintenance. Many unmanned space missions also have used hydrazine propulsion, such as the Viking landers on Mars; the Pioneer and Voyager space probes to Jupiter, Saturn, and Uranus; and the Giotto space probe to Haley's comet. Hydrazine propellant is used extensively for upper-stage rocket propulsion and for impulse corrections after rocket motor burn is complete. The space shuttle uses both hydrazine and monomethyl-hydrazine for its second- stage booster rockets and for orbital maneuvering. Anhydrous hydrazine is used in the Auxiliary Power Unit on both the space shuttle orbiter and on its two solid rocket boosters. Another widespread aviation use of hydrazine is in the Emergency Power Unit on the F-16 fighter (Clewell et al., 1988). Hydrazine decomposition gasses at high pressure are used to expel ballast water from submarine ballast tanks in emergency situations. Such systems are in use on several NATO submarines. Hydrazine systems weigh only a fraction of comparable compressed-gas systems. While hydrazine use was dominated by the military and aerospace industry in the 1960s, by the 1980s other industrial applications were consuming the major share of a!! hydrazine produced. The agricultural industry is a major user of hydrazine in the manufacture of pesticides. Hydrazine is used in the plastics industry as a chemical intermediate for plastic-foam blowing agents, and hydrazine is used as an oxygen scavenger in boiler water for power production. In laboratory animals, exposure to hydrazine may produce either immediate toxicity or delayed kidney and liver injury in animals that survive the exposure. Via inhalation, the 4-hr LC50 of hydrazine is 7.8 mmol L"! for mice and 18.1 mmol L-1 for rats (Clewell etal., 1988). In another study, the 1-hr LC50 in rats was 20 mmol L^i. A six-month inhalation study conducted with dogs, monkeys, rats, and mice suggested that effects were dose related regardless of whether the exposures were intermittent or continuous (WHO, 1987). Hydrazine is a polar molecule, having a high affinity for water. Consequently, it is extremely irritating to eyes and mucus membranes. Hydrazine has also been shown to enter the body through the skin. In anesthetized dogs, topical application of hydrazine in the 100 mg kg-i range produced detectable blood concentrations within 30 seconds and a chemical burn at the site of application (Clewell et al., 1988). A few instances of hydrazine toxicity in humans have been reported. Dermal sensitization after exposure to hydrazine has been cited (WHO, 1987). Accidental ingestion of a concentrated aqueous solution of hydrazine by a workman caused prolonged unconsciousness and seizures; however, he was considered reasonably recovered within two weeks (Clewell et al., 1988). Hydrazine toxicity has been fatal in at least one case where an individual experienced conjunctivitis, nausea, and tremors each time he handled