Nuclear Techniques for Studying Chemical Residue Problems in Edible Oil Seeds and Related Products
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IAEA-TECDOC-243 NUCLEAR TECHNIQUES FOR STUDYING CHEMICAL RESIDUE PROBLEMS IN EDIBLE OIL SEEDS AND RELATED PRODUCTS REPORT OF A RESEARCH CO-ORDINATION MEETING ORGANIZEE TH Y DB JOINT FAO/IAEA DIVISION OF ISOTOP RADIATIOD EAN N APPLICATION ATOMIF SO C ENERGY FOR FOOD AND AGRICULTURAL DEVELOPMENT AND HELD IN VIENNA, 9-13 JUNE 1980 A TECHNICAL DOCUMENT ISSUEE TH Y DB INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA, 1981 NUCLEAR TECHNIQUE STUDYINR SFO G CHEMICAL RESIDUE PROBLEMS IN EDIBLE OIL SEEDS AND RELATED PRODUCTS IAEA, VIENNA, 1981 Reproduced by the IAEA in Austria February 1981 PLEASE BE AWARE THAT ALL OF THE MISSING PAGES IN THIS DOCUMENT WERE ORIGINALLY BLANK The IAEA does not maintain stocks of reports in this series. However, microfiche copie f thesso e report obtainee b n sca d from INIS Microfiche Clearinghouse International Atomic Energy Agency Wagramerstrasse 5 P.O. Box 100 A-1400 Vienna, Austria prepaymenn o $1.0S U f againsr 0to o IAEe on t A microfiche service coupon. FOREWORD Bie increasin chemicalf o e g us protectinr sfo g crops, livestocd kan human health against pesdiseasd tan e attac dictates ki neede th sy db of a rapidly growing world population. Notwithstanding these trends there is also a growing public sensitivity to contamination of the agricultural environment. Chemical residues inevitably find their way into human food and the environment. Since 1969> the Joint PAO/IAEA Division of Isotope and Radiation Applications of Atomic Energ Poor Agriculturad yfo dan l Developmen coordinates tha widda e range of isotopic tracer-aided studies of trace contaminant problems. Unde currene rth t programme» whic initiates hwa 1975n di Internationae th » l Atomic Energy Agenc publishes yha d "Radiotracer studie pesticidf so e residues in edible oil seeds and related products" (1979) in i*s technical document series presene Th . t report represent appraisan sa l of a group of studies, with particular emphasis given to the many problems of developing countries. Nuclear techniques have provided powerful research stude tool th thes f yo n s i e problems. generosite Thankth e o st th f yo Swedish International Development Authority (SIDA) bees ha n t ,madi e possibl undertako et numbeea thesf ro e studie developinn si g countries. CONTENTS . 1 COMMUNICATIONS Residue f so C-cyolan cottonseen ei d products ......7 . S.M.A.D. Zayed, I.M.I. Fakhr, M.E. Bahid gan A.Z. Osman Cyolane residues in milk of lactating goats .......... 13 S.M.A.D. Zayed, I.M.I. Osma. FakhA d nran Pate of leptophos residues in milk products .......... 19 S.M.A.D. Zaye S.Id dan . Mohammed Pate of dimethoate in olives and in olive oil ........ 23 Nasri S. Kawar Residue cottonseen si cakd an el resultindoi g froe th m combined applicatio dimethoatd an T DD f eno ..........9 2 . G.A. ElZorgan M.Md ian . Ahmed Monocrotophos residues in cottonseed and related products ............................................7 3 . Jami. M l Qureshi Satta. ,A M.Hd ran . Naqvi Carbaryl residue maizn si processed ean d products ...9 .3 Jami. M l Qureshi Satta. ,A r (Jr. M.Hd )an , Naqvi Carbaryl residues in cottonseed products in the Philippines .......................................... 45 Pelip Pabl. aE o residueT DD groundnun si changed tan residuen si s during processing of groundnut oil ................... *° K. Raghu, N.B.K. Murthy and J. Perreira Pate of technical and C —labelled BHC residues in rice grain ........................................... 55 d Yong-HwSu—Raan e Le e a Kirn Neoasozine residue ricn i s e .........................3 6 . Su—Rae Lee and Yong—Hwa Kim 2. REPORT ............................................... 69 2.1 Introduction ...................................•>•..••• 69 2.2 Meeting objectives ................................... 70 2.3 Some highlights .....................................0 7 . 3. RECOMMENDATIONS .....................................1 7 . 4. CONCLUSIONS .........................................2 ^ . 5. LIST OF P&RTICIPANTS ................................. 75 1. COMMUNICATIONS OP 14C-CYOLANE IN COTTONSEED PRODUCTS S.M.A.D. ZAYED, I.M.I. FAKHR+, M.E. BAKEG4"1" and A.Z. OSMAN M.E. Regional Radioisotope Centre, Dokki, Cairo Arab Republic of Egypt ABSTRACT The systemic insecticide cyolane £2-(0,0-diethylphosphoryl)-imino- 1,3-dithiolane prepares Jwa d from C-ethanol, phosphorus oxychloride and 2-amino-l,3-dithiolane. Cotton plants were treated wito htw application insecticide th f so e under condition locaf so l agricultural practice. 1 4harvestee C-residue th cakd f crudan e eo l th deoi n s i cotto n seeds amounte 1.6o dt 0.01d 3an 4 rog/kg respectivelye th . f o Abou $ 50 t C-activity present in the crude oil was found to be eliminated by simulated commercial processes userefininr oildfo e th .f go Alkal i treatment and bleaching removed 16% and 2f>% of the radioactive residues respectively day3 . r sWinterizatiofo C 7 5- bleachee t th a f l no doi effecte furtheda r eliminatio 13$f no . C-residue cottoe th n nsi seed products and in the samples of the refined oil were characterized and the main constituents identified using chromatographic techniques. INTRODUCTION Cyolane, 2-(0,0-diethyl-phosphoryl)imino-l,3-dithiolane (l) is characterize systemis it y db c activit comparativeld yan y long residual action provet highlI e .b o dt y effective agains differene tth t instars cottoe ofth n leaf worm Spodopter recommendes wa ad littoralian ) (2 d ) s(l for controllin numbega economicallf ro y important cotton pests (3-7). It became, therefore, important to study the possible deposition of cyolane residues in the cotton seed, oil and cake of treated cotton plants. For this purpose, C-cyolane was synthesized in our laboratory. The effects of simulated commercial processing procedures on C-cyolane residues were studied. .V0" //S—CH_/-k2 -CH2 + National Research Centre, Itokki, Cairo, Egypt "*"*" Kept, of Radioisotopes, Atomic Energy Establishment, Cairo, Egypt MATERIALS AM) METHODS 14.C-Cyolane ) a Bthylene dithioovanate; This compoun prepares dwa heatiny db molg1 e ethylene dibromide wit mole3 h 2. potassiu f so m thiocyanat absolutn ei e ethanohours0 1 r .lfo After crystallization from ethano produce lth t melted at 88°(lit.m.p. 90°) ((8) (9). b) Cyclic ethylene dithioimido carbonate (ll); Bfchylene dithiocyanate was cyclized by heating with concentrated hydrochloric acid at 100° for 10 hours to yield the hydrochloride of II. 5br purification of the hydrochloride reactioe ,th n mixtur cooleds ewa , neutralized with potassium carbonat extracted ean d with benzene driee Th .d benzene layes rwa saturated with HC1 gas where the hydrochloride of II separated out (m.p. 208°; lit.m.p. 202°) (10). II was stored in the form of its hydrochloride since the free base decomposes more readily. The free base was liberated by neutralization of the hydrochloride with 10$ potassium carbonate solution and subsequent extraction with benzene. c) Bthyl-l-14C-labelled cyolane (l); Bthanol-l-14C (40 mmol, ImCi) was allowed to react with phosphorus oxychloride (20 mmol) in presence of pyridin givo et e diethyl phosphorochloridate (ill). C-cyolans ewa synthesized by the interaction of III with the equivalent amount of II. The crude produc s purifietwa silica n columl do age n till radiopurity, as determine thiy db n layer chromatography. C.cyolane melte t 39»da ; 5 specifi; yielmg 0 d66 c activity 1.643 mCi/gf R--value thin so n layers of silica gel 0.76 in benzene: ethyl acetate (3:2) and 0.88 in benzenes ethanol:acetic acid (79:14:7). 0 + X'H-P-I l NC XS—CH, HI II Cultivatio analysisd nan ; Cottonseeds were sow alluvian ni l soil under normal field conditions on Februar 1979, y25 * Irrigation, fertilizatio soid nan l management were carried out as practiced in the field. Plants were treated with radioactive cyolane twice wit two-weeha k interval during June 1979» The insecticide was applied as acetone/water suspension to the leaves of isolated five plants at the rate of 20 mg C-oyolane per plant per application harvestt A . , seeds were collecte extracted dan d with ether in a soxhlet apparatus for 6 hours,then with methanol for further 6 hours. Extracts were concentrated under reduced pressur analyzed ean r dfo radioactivity. For characterization purposes, C-residues were extracted from partitioniny b l thoi e g between acetonitril n-hexaned ean . Cyolane and cyolane-derived residues remained in the acetonitrile layer, which analyzes wa papey db r chromatograph solveno tw n yi t systems -using authentic substances as references (Table II). Spots were made visible by spraying with Hanes Isherwood reagent (ll). Commercial processing procedures; Crude cottonsee fortifies wa l doi d with cold dC-cyolanan n a o et end concentration of 7 Alkali refining; - 20 ml samples of the fortified oil were shaken with 2N sodium hydroxid minutes0 3 r eamoune fo solutioTh .° f to 50 t na alkal excesn i i$ thaf so adde10 ts calculatedwa e basie th th f so n d o acid value mixture Th .centrifuges ewa werl aliquotd oi e dan e th f so countod. Bleaching alkale Th ;- i treaterefines wa l ddoi with 0.5$ activated carbon and a factory-grade bleaching earth (l;l). The mixture was stirred vigorously at 80-100 for 20 minutes. The bleached oil was then separated and counted. Winterization winterizes wa l r cleaoi fo e about y Th da 7 r dr ;- t5- day3 s followe centrifugationy db countingd ,an . Samples of oil, after individual treatments were partitioned between acetonitrile and hexane for characterization of ^C-residues. Radiometric measurements; cak d Radioactivitdetermines an e wa l oi e combustioy dth b n yi a n ni Packard-Oxidizer syste d C-activitman 1determine4s ywa Packara n di d Tri-Carb Liquid Scintillation Spectrometer.