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INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough,margins, substandard and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road. Ann Arbor. Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9411984 Quantitative structure activity relationships to predict the fate and effects of selected organophosphorus and carbamate insecticides in aquatic systems Kallander, David Brian, Ph.D. The Ohio State University, 1993 UMI 300 N. Zeeb Rd. Ann Arbor, MI 48106 QUANTITATIVE STRUCTURE ACTIVITY RELATIONSHIPS TO PREDICT THE FATE AND EFFECTS OF SELECTED ORGANOPHOSPHORUS AND CARBAMATE INSECTICIDES IN AQUATIC SYSTEMS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By David B. Kallander, B.S., M.S. ***** The Ohio State University 1993 Dissertation Committee: Approved By Dr. Susan W. Fisher Dr. Richard W. Hall Sc. Advisor Dr. David J. Horn Department of Entomology ACKNOWLEDGEMENTS To Dr. Susan Fisher for her advice, guidance, and putting up with me for so long. A special thanks also to my other dissertation committee members Dr. David Horn and Dr. Rich Hall for their help and support over the years. To my co-workers Kathy Bruner, Denise Boulet, Mark Atanasoff, Steve Chordas, Kristen Manter, Lisa Jackson, Xiaosong Zhang, Jane Zumwalt, and Rick Stock. I wish you the best of luck. I'll miss all of you. To Mike and Liz Lydy for advice, suggestions, and years of friendship. I would also like to thank Dr. Bill Collins for the use of his midge cultures and lab space. Finally, I would like to thank my parents for their years of unwavering support. ii VITA November 5, 1963 ................ Born in Hamilton, Ohio 1986 ............................... B.S., Miami University Oxford, Ohio 1989 ............................. M.S., The Ohio State University, Columbus, Ohio PUBLICATIONS Horn, D.J., D.K. Pearl, R. Bartoszynski, and D.B. Kallander 1990. "Refinement of a stochastic model of spider mite predator-prey interactions" in Modern Acarology, F. Dusbabek and V. Bukva, Eds. Volume I, 1991. FIELD OF STUDY Major Field: Entomology iii TABLE OF CONTENTS ACKNOWLEDGEMENTS .................................... ii VITA ............................................... iii LIST OF TABLES .................................... vi LIST OF FIGURES ...................................... viii INTRODUCTION ...................................... 1 CHAPTER PAGE I. QUANTITATIVE STRUCTURE ACTIVITY RELATIONSHIPS FOR PREDICTING THE IN VIVO AND IN VITRO INHIBITION OF ACETYLCHOLINESTERASE IN THE MIDGE, CHIRONOMUS RIPARIUS ................... 17 Introduction...... ......................... 17 Materials and Methods .................... 20 R e s u l t s .....................................27 D i s c u s s i o n ................................ 49 II. SYMPTOMATIC AND ENZYMATIC RECOVERY FROM EXPOSURE TO ORGANOPHOSPHORUS AND CARBAMATE COMPOUNDS IN THE MIDGE, CHIRONOMUS RIPARIUS: TEMPERATURE AND EPISODIC EXPOSURE .......... 64 Introduction...... ......................... 64 Materials and Methods .................... 67 R e s u l t s .....................................76 D i s c u s s i o n ................................ 95 iv III. QUANTITATIVE STRUCTURE ACTIVITY RELATIONSHIPS FOR PREDICTING THE PERSISTENCE OF ORGANOPHOSPHORUS AND CARBAMATE INSECTICIDES IN WATER, WITH AND WITHOUT THE MIDGE, CHIRONOMUS RIPARIUS .......................................104 Introduction ............................ 104 Materials and Methods ................... 107 R e s u l t s .................................... 117 D i s c u s s i o n ................................ 122 CONCLUSIONS ........................................... 135 LIST OF REFERENCES ..................................138 V LIST OF TABLES TABLE PAGE 1. Mean in vivo I50 Values of Organophosphorus and Carbamate Insecticides in the Midge, Chironomus riparius at 10, 20 and 30 "C (± S . E . ) ...........................................28 2. Mean in vivo and in vitro I50 Values of Organophosphorus and Carbamate Insecticides in the Midge, Chironomus riparius at 20 °C (+ S . E . ) ...........................................30 3. Molecular Descriptors used in Regression Analysis with in vivo and in vitro I50 v a l u e s .......................................... 3 3 4. Linear Solvation Energy Relationships for Insecticides used in Regression Analyses .... 36 5. Molecular Connectivity Indices used in Regression Analysis ........................... 38 6. Summary of Best Regression Analyses of In vivo I50 values for LSER, and MC Models......... 40 7. Summary of regression analyses of in vitro I50 values for LSER and MC models........ 42 8. Exposure level (M) of one organophosphorus and four carbamate insecticides at 10, 20 and 30 °C for the midge, Chironomus riparius, producing 50% inhibition of AChE . 72 9. Mean AChE activity (in nmoles substrate hydrolyzed/min/mg protein) for Chironomus riparius at 3, 6, and 12 h following exposure to one of five OP or carbamate insecticides at 10, 20, and 30 ° C ............. 87 vi 1 0 . Mean adjusted percent effect for one Organophosphorus and four carbamate insecticides at 20 °C to the midge, Chironomus riparius following two 1 h exposures separated by 0, 2,6, 12, and 24 h in undosed w a t e r ......................... 90 11. Dose levels of 3 OP and 2 carbamate compounds and sampling dates for determination of abiotic halflives at 10, 20 and 30 ° C .............................. 110 12. Mean abiotic halflives of Organophosphorus and Carbamate Insecticides in sterilized deionized water at 10, 20 and 30 °C (± S . E . ) ........................................ 116 13. Mean halflives of Organophosphorus and Carbamate Insecticides in water with 40 midges (Chironomus riparius) at 10, 20 and 30 °C (± S.E.) ........................... 118 14. Summary of Best Regression Analyses of hydrolysis and biological halflife values for LSER, and MC Mo d e l s ......................... 12 0 vii LIST OF FIGURES FIGURE 1. Some transport and transformation of organic chemicals in aquatic systems......... 2. Regression of in vivo Iso's (20 °C) for 7 OP and 5 carbamate insecticides against corresponding 24 h EC50's..................... 3. Regression of in vitro I50's for 2 OP and 5 carbamate insecticides against corresponding 24 h EC jo's (20 °C)............ .............. 4. Regression of in vivo I50's for 5 carbamate and 2 OP insecticides against corresponding in vitro I50's (20 °C)........................ 5. Reactivation of midge AChE at 10, 20 and 30 °C following exposure to aldicarb. Data points are mean /xmoles substrate hydrolyzed/min/mg protein (+ standard error). Solid lines are mean control activities at respective temperatures .................................. 6. Reactivation of midge AChE at 10, 20 and 30 °C following exposure to propoxur. Data points are mean mmoles substrate hydrolyzed/min/mg protein (+ standard error). Solid lines are mean control activities at respective temperatures .................................. 7. Reactivation of midge AChE at 10, 20 and 30 °C following exposure to carbofuran. Data points are mean ^moles substrate hydrolyzed/min/mg protein (+ standard error). Solid lines are mean control activities at respective temperatures .................................. viii 8. Reactivation of midge AChE at 10, 20 and 30 °C following exposure to carbaryl. Data points are mean /nmoles substrate hydrolyzed/min/mg protein (+ standard error). Solid lines are mean control activities at respective temperatures................................. 83 9. Reactivation of midge AChE at 10, 20 and 30 °C following exposure to parathion. Data points are mean /moles substrate hydrolyzed/min/mg protein (+ standard error). Solid lines are mean control activities at respective temperatures .................................. 85 10. AChE activity (+ S.E.) in 20 fourth instar midges following two 1 h pulsed exposure to carbaryl (T = 20 °C, n = 3). Midges were pulsed at time 0 and 24 h (exposure time not included on graph). Solid line is mean control activity................................. 93 INTRODUCTION More chemicals are being used today than ever before (Jorgensen 1990). In the United States, novel chemicals are

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