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Ann Arbor, MI 48106 THE INTERACTION OF IMIDAZOLINONE HERBICIDES WITH SELECTED ADSORBENTS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Ming-Daw Che, B.S., M.S. ***** The Ohio State University 1991 Dissertation Committee : Approved by M.M. Loux T .J . Logan Co-Advi S.J. Traina L.C. Brown T.J. Department of Agronomy ACKNOWLEDGEMENTS I would like to express my appreciation to my adviser, Dr. Mark Loux, for his advice, patience, and financial assistance throughout this research. My deep appreciation is also extended to my co-adviser, Dr. Terry Logan, and to Dr. Sam Traina for their review and opinion of this dissertation, and for allowing me to use the instruments in their laboratories. The support and help of those who have worked with me in the laboratory is greatly appreciated. I want to thank my wife, Shuling, for the sacrifices that she made over the past seven years in helping me through graduate school. Her constant support, encouragement, and understanding gave me the determination to see this work through to its completion. Finally, I thank my children, Harrison, Angela, and Jonathan, for just being there to brighten this father's days. VITA August 16, 1957 .............. Born - Taipei, Taiwan Rep. of China 1979 ......................... B.S., National Chung-Hsing University, Taichung, Taiwan 1979-1981 .................... Platoon Leader, Army in Taiwan 1981-1982 .................... Research Assistant, Taiwan Forestry Institute 1987 ......................... M.S.(Environmental Chemistry) Department of Agronomy The Ohio State University Columbus, Ohio 1987-Present ................. Graduate Research Associate, Department of Agronomy The Ohio State University Columbus, Ohio PUBLICATIONS Hsieh, Y.P., M.D. Che, and C.C. Liu. 1980. Effect of land disposal of sewage sludge on soil environmental qualities : I. Organic matter decomposition. National Science Council Monthly, vol. VIII, No. 10. p. 903-912. Che, M.D., T.J. Logan, S.J. Traina, and J.M. Bigham. 1988. Properties of water treatment lime sludges and their effectiveness as agricultural limestone substituties. J. Water Pollution Control Federation. 60: 674-680. Logan, T.J., B. Harrison, and M.D. Che. 1989. Agronomic effectiveness of cement Kiln dust-stabilized sludge. Ohio Edison Grant Report. Department of Agronomy. The Ohio State Univers ity. Columbus, Ohio. Che, M.D. and M.M. Loux. 1990. The adsorption and desorption of imazaquin and imazethapyr on soil, clay, and humic acid. Proc. North Cent. Weed Sci. Soc. 45 : 11. FIELDS OF STUDY Major Field : Agronomy Studies in Environmental Chemistry, Soil Chemistry, and Weed Science. TABLE OF CONTENTS ACKNOWLEDGEMENTS .................................... ii VITA ...................................... iii LIST OF TABLES ..................................... vii LIST OF FIGURES .................................... ix INTRODUCTION ........................................ 1 CHAPTER PAGE I. LITERATURE REVIEW ........................... 4 Introduction ............................ 4 Imidazolinone Herbicides ................. 5 Introduction ........................ 5 Structure and Synthesis ............. 5 Physical and Chemical Properties .... 8 Mode of Action and Selectivity ..... 10 Toxicology .......................... 13 Environmental Fate .................. 16 General Adsorption Concepts .............. 16 D e f i n i t i o n .......................... 16 Adsorption Isotherms ................ 19 Adsorption Constants ................ 21 Metal Cation Adsorption and Adsorption Edge ..................... 25 Anion Adsorption, Negative Adsorption and dsorption Envelop ................ 27 Molecular Adsorption ................ 28 Methods for Sorption Study ......... 30 Adsorption Mechanisms for Pesticides in Soil .................................. 31 Cation Exchange ..................... 31 Protonation ......................... 32 Anion Exchange ...................... 33 Ligand Exchange ..................... 34 Water Bridging ...................... 35 Cation Bridging ..................... 35 v Hydrogen Bonding ..................... 36 Van Der Waals Interactions ......... 36 Hydrophobic Effect .................. 37 Factors Affecting the Sorption of Imidazolinone Herbicides in Soils ...... 38 Soil pH ............................. 38 Soil C l a y ........................... 39 Soil Organic Matter ................ 41 Soil Moisture ...................... 42 Soil Temperature ................... 42 Nature of Herbicides ................ 43 Desorption .............................. 45 Introduction ........................ 45 Methods for Desorption Study ....... 46 Hysteresis .......................... 47 References .............................. 50 II. THE ADSORPTION AND DESORPTION OF IMAZAQUIN AND IMAZETHAPYR ON SOIL, CLAY, AND HUMIC ACID ......................................... 54 Introduction ............................ 54 Materials and Methods ................... 56 Results and Discussion ......... 64 sorption ............................ 64 D e s o r p t i o n ........... „ ............. 81 Conclusions ............................. 95 References .............................. 98 III. THE ADSORPTION AND INTERACTION BETWEEN IMIDAZOLINONE HERBICIDES AND SELECTED ADSORBENTS ................................... 104 Introduction ............................ 104 Materials and Methods ................... 106 Results and Discussion .................. 115 Sorption Constant Measurements ..... 115 Colloid-Solution Interface study .... 123 Conclusions ............................. 134 References .............................. 136 CONCLUSIONS ......................................... 138 APPENDICES .......................................... 140 A. Data Relative to Chapter II ................. 141 B. Data Relative to Chapter III ................ 149 REFERENCES .......................................... 162 vi LIST OF TABLES TABLE PAGE 1. Some selected physical and chemical properties of four imidazolinone herbicides ................. 11 2. Metabolism of foliar-applied imazaquin in soybean, cocklebur and velvetleaf 3 days after application ..................................... 14 3. Acute toxicity of imidazolinone herbicides to mammals ...................................... 15 4. Selected properties of adsorbents ................ 57 5. Freundlich adsorption constants (Kd) , 1/n values, and isotherm coefficients of determination (R2) for the sorption of imazaquin and imazethapyr on various adsorbents ....................................... 69 6. The average sorption constants of imazaquin and imazethapyr on various adsorbents .......... 71 7. The effect of initial concentrations of herbicides on the sorption of herbicides on soils at three pH levels ..................... 74 8. The experimental log K values of imazaquin and imazethapyr on soils and humic acids at various pH levels ............................ 77 9. Desorption of imazaquin and imazethapyr from soils (pH = 4.5 or 4.6) ......................... 82 10. The effect of soil moisture variation on herbicide desorption form soils (pH = 4.5 or 4.6) 84 11. The humic acid effect on the desorption of imidazolinone herbicides form soils ............ 86 Vll* • 12. Desorptions of imazaquin and imazethapyr from humic a c i d ................................. 91 13. Desorption of imazaquin and imazethapyr from c l a y ....................................... 92 14. The humic acid effect on the desorption of imidazolinoneherbicides from clays .......... 94 15. The Kd and values for the interactions of three imidazolinone herbicides on humic acids ........................................... 119 16. Kk values for sorption of imidazolinone herbicides on two humic acids at three pH levels ....................................... 121 v m LIST OF FIGURES FIGURES