Daminozide (Alar) Breakdown During Thermal Processing of Cherry Products T0 Yield, Unsymmetrical Dimethyl— Hydrazine (Udmh)'." "
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.H I n , In»! , a?) 1 ,-~ / p”7’56 .. v] -. V 1")!" h ‘ ._. Illlllllllllllllllllllllllllllll 11‘ l‘lllllllllllllllll 3 129300 r \ LIBRARY Ilium“. State University This is to certify that the dissertation entitled DAMINOZIDE (ALAR) BREAKDOWN DURING THERMAL PROCESSING OF CHERRY PRODUCTS T0 YIELD, UNSYMMETRICAL DIMETHYL— HYDRAZINE (UDMH)'." " presented by CHARLES RICHARD SANTERRE has been accepted towards fulfillment of the requirements for Ph.D. degmin FOOD SCIENCE & ENVIRONMENTAL TOX. Date March 24, 1989 MS U is an Affirmative Action/Equal Opportunity Institution 0-1277 1 ‘~.¢ O’Ntw , record. PLACE IN RETURN isfleckout from your TO AVOID FINES retur on or b ore date d . DATE DUE-ADA15- I DATE DUE Q MSU I. An Affirmative Action/Equal Opportunity Institution email-HM DAMINOZIDE (ALAR) BREAKDOWN DURING THERMAL PROCESSING OF CHERRY PRODUCTS TO YIELD, UNSYMMETRICAL DIMETHYLHYDRAZINE (UDMH). by Charles Richard Santerre A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Food Science a Human Nutrition 1989 “‘3X 5072 ABSTRACT DAMINOZIDE (ALAR) BREAKDOWN DURING THERMAL PROCESSING OF CHERRY PRODUCTS TO YIELD, UNSYMMETRICAL DIMETHYLHYDRAZINE (UDMH). By Charles Richard Santerre Daminozide is applied to tart and sweet cherries to improve fruit color, texture and abscission at harvest. This growth retardant is a system ic compound which is distributed throughout the fruit matrix. Thermal processing of fruit containing daminozide produces a hydrolysis product, unsymmetrical dimethylhydrazine (UDMH), which is a cancer suspect agent. Daminozide was added to a 50 mM NaH2P04-24% sucrose solution at 12.5 ppm (w/w) to determine the influence of heating, pH and processing conditions on hydrolysis of daminozide to UDMH. Daminozide fortified solutions at three pH levels (pH 3.0; 3.6; 4.2) were processed by two regimens. For the first regimen, no. 303 X 404 cans were filled (150 g) with the daminozide fortified solution, sealed, heated for 5, 10, 15 min. at 100°C, and cooled. For the second regimen, cans were filled (150 g) with the daminozide fortified solution which was then heated to 80°C and held for 0, 5, or 10 min. The cans were immediately sealed, heated in 100°C water for 5 min. and cooled. Daminozide concentrations were not decreased at a detectable level in any of the heated solutions. For the daminozide solutions which were heated following can closure, the concentration of UDMH increased with heating time. Approximately 5 ppb UDMH was produced for every 5 min. of heating in 100°C water. However, UDMH concentration was not directly related to heating time for solutions which were heated prior to can closure. This was due to volatilization of UDMH which countered daminozide degradation during heating in the open cans. For the three pH levels, a maximum concentration of UDMH occurred for solutions adjusted to pH 3.6. Tart (Montmorency) and sweet (Napolean and Schmidt) cherry trees were treated 2 wk after full bloom with 3.4 and 6.8 lbs. daminozide/acre at 3 commercial orchards in northwestern Michigan. Daminozide residues in freshly harvested fruit and processed cherry products were less than 13 ppm and 10 ppm, respectively. UDMH residues in freshly harvested fruit and processed cherry products were less than 10 ppb and 500 ppb, respectively. Processing of both sweet and tart cherries reduced the levels of daminozide. However, thermal processing increased the levels of UDMH in canned cherry products. DEDICATION To my parents, Betty and Roland and siblings Michael, Annette, Jeanine, Suzette, Celeste, Roger, Mary, Phyllis, James and Peter. -iv- ACKNOWLEDGEMENTS I would like to express my sincere appreciation to all the people who have supported me in my academic affairs. To my father, Roland, who intrigued me with carpentry, mechanics, and electronics at an early age. To my mother, Betty, who would never tire of questions from a 12 year old as he read through her nursing microbiology text. To my major professor and friend, Dr. Jerry N. Cash, a person of integrity who has earned my respect by his actions. His trust, support, and guidance have helped me to grow as a professional and more importantly, as a person. I shall always be in his debt. To his wife, Stella Cash, who taught me of Southern hospitality even though I am and will always be a Darn Yankee. To Dr. Matt Zabik, who extended my horizons past the laboratory walls. He has taught me to cut through the tripe and seek excellence in every phase of my life. To Dr. Maurice Bennink, who molded me during my undergraduate years. His outstanding teaching ability and concern for students was a pivotal factor which led me down this road. To Dr. Pericles Markakis, who supported my efforts with grace and sophistication. To Dr. James Pestka, for constructive feedback during my studies. In particular, I wish to thank Dr. Gilbert Leveille and Dr. Don Coffey. The influence which they have had on my career can never be put into words. One has shown me the breadth of a career and the other has shown me the importance of a sense of humor in achieving my career goals. I would also like to thank the many graduate students who have endured the journey with me. These include Mark McLellan, David Huang, Touran Cheraghi, Mohammed Kenawi, Ramidan Habiba, Annie Chai, Nirmal Sinha, John Kallas, Amir Zaman, Ahmad Shirazi, Terri Biggerstaff and many others. Finally, I would like to thank Maggie Conner, who helped prepare this dissertation. She has been a good friend for the past 10 years. -v‘i- TABLE OF CONTENTS £5.95 LIST OF TABLES ..................................................... ix LIST OF FIGURES ..................................................... x INTRODUCTION ........................................................ 1 LITERATURE REVIEW ................................................... 3 A. Daminozide as a Plant Growth Retardant .......................... 3 l. Daminozide in Apple and Pear Production ..................... 8 2. Daminozide in Tart and Sweet Cherry Production ............. 11 3. Economice Importance of Daminozide ......................... 13 B. Daminozide Toxicity ............................................ 14 C. UDMH Toxicity .................................................. 17 1. Absorption, Transport and Excretion of UDMH ................ 17 2. Metabolism of UDMH ......................................... 19 3. Mutagenicity of UDMH ....................................... 25 4. Carcinogenicity of UDMH .................................... 26 5. Influence of UDMH on Nervous Function ...................... 27 List of References ................................................. 37 CHAPTER I - The Influence of pH and Heating Time on the Decomposition of Daminozide (Alar) and the Formation.of Unsymmetrical Dimethylhydrazine (UDMH) ................................................. 4S -vii- 2292 Abstract ....................................................... 46 Introduction ................................................... 47 Materials and Methods .......................................... 49 Results and Discussion ......................................... 53 Conclusions .................................................... 57 References ..................................................... 58 Acknowledgement ................................................ 59 CHAPTER 2 - Daminozide (Alar) and Unsymmetrical Dimethyl- hydrazine (UDMH) Residues in Tart and Sweet Cherries and Processed Cherry Products ................. 72 Abstract ....................................................... 73 Introduction ................................................... 74 Materials and Methods .......................................... 76 Results and Discussion ......................................... 81 Conclusions .................................................... 89 References ..................................................... 90 Acknowledgement ................................................ 92 -viii- LIST OF TABLES Ease CHAPTER 1 Table 1. Analysis of variance (AOV) table describing the influence of pH and heating time on the concentration of UDMH in canned samples which were closed prior to heating (100°C) .......................... 60 Table 2. Analysis of variance (ADV) table describing the influence of pH and heating time on the concentration of UDMH in canned samples which were heated before (80°C) and after (100°C) can closure .................................................. 61 CHAPTER 2 Table 1. Daminozide (Alar) and 1,1-dimethylhydrazine (UDMH) residues in tart cherries and cherry products ............ 93 Table 2. Daminozide (Alar) and 1,l~dimethylhydrazine (UDMH) residues in sweet cherries and cherry products ........... 94 -1x- LIST OF TABLES Page CHAPTER 1 Table 1. Analysis of variance (AOV) table describing the influence of pH and heating time on the concentration of UDMH in canned samples which were closed prior to heating (100°C) .......................... 60 Table 2. Analysis of variance (AOV) table describing the influence of pH and heating time on the concentration of UDMH in canned samples which were heated before (80°C) and after (100°C) can closure .................................................. 61 CHAPTER 2 Table 1. Daminozide (Alar) and 1,1-dimethylhydrazine (UDMH) residues in tart cherries and cherry products ............ 93 Table 2. Daminozide (Alar) and 1,1-dimethylhydrazine (UDMH) residues in sweet cherries and cherry products ........... 94 -ix- LIST OF FIGURES £392 LITERATURE