PESTICIDE RESIDUES IN FOOD - 1979 Sponsored jointly by FAO and WHO EVALUATIONS 1979 Joint meeting of the FAO Panel of Experts on Pesticide Residues in Food and the Environment and the WHO Expert Group on Pesticide Residues Geneva, 3-12 December 1979 FENITROTHION Explanation Fenitrothion was evaluated in 1969, 1974, 1976 and 1977. At its 11th Session, the CCPR requested the meeting to provide a recommendation for bran (processed) on the basis of new data known to be available: also for clarification of proposals for MRLs in pears and peaches as indicated in paragraphs 107 and 108 of ALINORM 79/24. Further data on the use and fate of fenitrothion was also made available to the meeting by Australia. RESIDUES IN FOOD AND THEIR EVALUATION RESIDUES RESULTING FROM SUPERVISED TRIALS Pre-harvest Having examined the raw data from which a selection was made for presentation in Table 6 of the 1974 monograph, the meeting agreed that although the residues in pears appeared to be somewhat lower than those in apples in the trials carried out in Japan, the differences were small and probably not representative of the true picture world-wide. It was agreed that the MRL for pears should be brought into line with that for apples. The meeting re-examined the raw data from 12 trials carried out on peaches in Japan and which provide the basis for the information contained in Table 6 of the 1974 monograph. The original data were developed by analysis made separately on pulp and peel as is the custom in Japan. The ratio of the weight of pulp to peel averaged 90:10 (range 92/8-85/15). Recalculation of the residue level on the whole fruit indicated that the bulk of the values fall below 1 mg/kg. Residues in Bran In 1974 and 1976 the meeting reviewed the use of fenitrothion for the protection of raw grain against stored-product pests. Among the information reviewed were studies on the fate of fenitrothion residue, on grain subjected to milling and processing. These data (FAO/WHO 1975b page 266, 1977b page 369) showed that the bulk of the insecticide deposited on the grain remains in the epidermis and is removed from the bran during milling. Further studies by Desmarchelier (1979) with fenitrothion and eleven other grain protectant insecticides, showed that the concentration on the bran is from 2 to 3.2 times the concentration on the whole wheat. Except for bioresmethrin and pirimiphosmethyl, where the concentration is 3.2 and 2.9 times that on raw grain respectively, all of the other insecticides tests including fenitrothion residue level all show a concentrating effect from 2 to 2.7 by comparison with the whole wheat. This figure depends to a small extent on the original rate of application of the insecticide and the time in storage prior to milling. Generally the amount of insecticide in the flour is 10% or less of the concentration on the whole wheat. Desmarchelier (1979) extended his studies to determine the percentage loss of residues during processing of bran using a laboratory technique to simulate the least severe industrial process. This consisted of heating the moistened bran for two hours at 90°C. He showed that 42% of the fenitrothion was lost from raw bran by such treatment. With some other insecticides the loss was a high at 96%. None of the insecticides was less subject to degradation than fenitrothion. Murray and Snelson (1978) studied the distribution of fenitrothion and bioresmethrin residues on mill fractions from wheat processed through a commercial flour mill. The results of their investigations are set out in Table 1. These show that the bran from all milling streams when blended together, contained fenitrothion residues 1.5 times as high as those present in raw wheat received into the mill. Snelson (1979) also reports the results of monitoring 13 flour mills processing wheat containing from 5 to 10 mg/kg of fenitrothion. The results, given in Table 2, indicate that 100% of the bran samples contained less than 20 mg/kg but up to 90% contained up to 15 mg/kg. Only 23% of the bran samples contained less than 10 mg/kg. These results are contrasted with the residues found in processed bran. There is no wheat available in Australia without residues of grain protestant insecticides. It was concluded that processed bran available retail would reflect the effect of processing on the residues present in raw bran. A survey was conducted in Australia (Snelson 1979) in which 36 samples of processed bran representing 12 different commercial products available in retail stores of three cities, located over a distance of 2,000 kilometres were analysed. In spite of the fact that all raw bran available for processing contained fenitrothion to a limit of 20 mg/kg, it was found that 80% of the processed bran available in the form of breakfast cereals contained less than 1 mg/kg of fenitrothion residue. 8% of the samples contained more than 3 mg/kg but these (3) represented products which were only partially processed. 36% of the samples contained no detectable residues (less than 0.1 mg/kg) of fenitrothion. In the light of the results of the above survey, a supervised trial was carried out in a factory processing three bran products. The results of the trial are shown in Table 3. These indicate that substantially all of the fenitrothion residues are destroyed in the cooking process which involves prolonged heating under pressure with live steam after the bran has been subjected to wet digestion with malt. The subsequent drying, extrusion, drying and toasting are all vigorous processes employing high temperatures that would be expected to destroy any residues which were not destroyed during the cooking. The trial confirmed that normal commercial processing destroyed the bulk of the residues. Table 1. Residues of Fenitrothion, Mg/kg, in Wheat Milling Fractions (and of Bioresmethrin) Sample No. Treated with 12 mg/kg Treated at harvest and fenitrothion (plus 1 mg/kg with 12 mg/kg Description syngergized bioresmethrin) fenitrothion Laboratory A Laboratory B Laboratory A 1. Wheat before point of pesticide application <0.5 - N.A. 2. Wheat when received into the mill 8 7 (0.7) 7 3. Wheat at first break roll before it enters the rolls 4 4 (0.6) 3 4. Crushed wheat at first break roll after it drops 5 4 (0.6) 3 from the rolls 5. Flour sieved from the sitter fed from first 1 0.8 (<0.05) 1 break roll (clean stream) 6. Flour sieved from the sitter fed by the last break roll (dirty stream) 4 3 (0.1) 2 7. Flour sieved from the sitter fed by the first reduction roll (clean stream) 0.5 0.6 (<0.05) 0.5 8. Flour sieved from the sitter fed by the last reduction roll (dirty stream) 5 5 (0.3) 4 Table 1. Continued... Sample No. Treated with 12 mg/kg Treated at harvest and fenitrothion (plus 1 mg/kg with 12 mg/kg Description syngergized bioresmethrin) fenitrothion Laboratory A Laboratory B Laboratory A 9. Flour from all streams, being fed into bulk flour bins or into packers 2 2 (0.1) 1 10. pollard from all streams before it is mixed with the bran 6 8 (0.7) 7 11. Bran from all streams before it is mixed with the pollard 12 11 (1) 11 12. Wheat germ 10 10 (2) 7 Figures in ( ) are for bioresmethrin. Table 2. Fenitrothion Residues on Raw and Processed Bran (Results from Australian Survey) Raw Bran Processed Bran Range of No. % Range of No. % Residues Residues <10 3 23 <0.1 13 36 10-12 5 38 0-1-0.5 7 19 12-14 1 8 6.5-1.0 9 25 14-16 3 23 1.0-2.0 3 8 16-18 0 0 2.0-3.0 1 3 18-20 1 8 >3.0** 3 8 13 100 36** 100 * Maximum 4.0 ** 12 different brands. Table 3. Effect of Commercial Processing on Fenitrothion Residues on Bran Processing Stage Product A Product B Product C Rep. 1 2 1 2 1 2 1. Raw bran before cooking 5 4 3 4 23 21 2. Cooked bran taken directly from cookers <0.05 <0.05 <0.05 <0.05 2 2 3. Bran taken after initial drying stage <0.05 <0.05 <0.05 <0.05 1 2 4. Finished product taken after bran has been formed into final shape and dried/ toasted through an oven 1 <0.05 <0.05 <0.05 1 1 Tempone (1979) has shown that fenitrothion and other grain protectant insecticides are destroyed during the melting process when grain protectant insecticide residues are present on the raw barley. These investigations have been verified by extensive surveys in which malt from more than 30 maltsters has been monitored for fenitrothion and other insecticide residues. It was already known that all of the barley available for melting contained either malathion or fenitrothion residues at levels up to the maximum residue limits (8 and 10 mg/kg respectively). None of the 36 samples examined contained fenitrothion residues at or above the limit of reporting (0.1 mg/kg). (Snelson, 1979). It is apparent therefore, that the melting process effectively destroys a variety of insecticide residues and no doubt the enzymes of malt which is added to the process to improve the palatability and flavour of the bran, could contribute to the destruction of fenitrothion prior to and during the cooking of raw bran. Residues in Flour Snelson (1979) observed that commercial flour mills could not comply with the national residue limit for fenitrothion in flour (1 mg/kg) particularly when wheat available had been treated within the previous two to three months with fenitrothion at the recommended level of 6 mg/kg. The matter was investigated by Murray and Snelson (1978) and the results, summarised in Table 1, indicate that although the flour sieved from the sifter fed by the first reduction rolls contains residues of the order of 0.5 mg/kg, this is later blended with flour from other streams containing slightly higher residues of fenitrothion due to the higher degree of extraction which occurs in these steps. As a consequence, the commercial flour contained 2 mg/kg of fenitrothion. All of the data examined by the meeting in 1974 and 1976 came from experimental milling equipment which, although designed to reproduce commercial practice, does not give the same high degree of extraction. In view of the extensive commercial experience which shows that commercial flour mills cannot comply with the maximum residue limit of 1 mg/kg, the meeting recommended that the maximum residue limit in flour be raised to 3 mg/kg. Desmarchelier (1979a) and Desmarchelier and Marsden (1979) thoroughly investigated the transfer of fenitrothion residues from wheat via flour into wheat gluten and the fate of these residues during the cooking of many varieties of bread prepared from different recipes. They showed that although gluten represents approximately 10% of the content of raw grain, the residue in the extracted gluten is about 30% of that present in the raw grain, thus representing a threefold concentration above the expected level. This picture is not unique to fenitrothion, but appears to occur with many insecticides of quite different chemical groups. These investigations showed that irrespective of the level of residues in the flour or in gluten and independent of the type of bread, the recipe or the baking process, approximately 50% of the residue was destroyed in the process. Likewise, the processing of oats for the production of rolled oats, involving as it does the removal of the hulls and the heating of the kernel to produce groats, in the removal and destruction of substantially all the insecticide deposited on the grain for protection against stored product pests. Fenitrothion is removed in this operation to an extent exceeding 95% (Desmarchelier, 1979). APPRAISAL New information has been made available concerning the level and fate of fenitrothion residues on bran and other foods processed from raw cereals. The meeting recognised that when fenitrothion was used to protect grain from stored product pests the bulk of the insecticide is deposited on the epidermis and is removed on the bran during the milling process. The concentration on the bran is from 2 to 2.5 times that on the whole wheat. Although some raw, unprocessed bran is marketed for direct consumption or for culinary purposes, the bulk of the bran used for human consumption is first subjected to processes designed to improve the flavour and palatability. These processes subject raw bran to vigorous physical and chemical processes which destroy substantially all of the fenitrothion residues present. The available data indicate that a maximum residue could be established at a lower level on processed bran to assist food processors and food control officials in their monitoring activities. It has been shown that the malting process destroys substantially all of the fenitrothion present on the raw barley. Likewise the removal of the hulls from raw oats and the process involved in converting the hulled oats into groats and rolled oats destroys substantially more than 95% of the residues present on the raw oats. The meeting has reviewed the data on fenitrothion residues on peaches and pears and agrees there is justification for amending the recommendations previously made. RECOMMENDATION The following additional maximum residue limits are recommended: Wheat bran (processed) 2 mg/kg. The maximum residue limits previously proposed are amended as follows: Wheat bran to read wheat bran (raw) 20 Pears 0.5 mg/kg Peaches 1 mg/kg Wheat flour (white) 3 mg/kg REFERENCES Desmarchelier, J.M. - The effect of milling and processing on the level and fate of grain protectant insecticide residues on wheat and oats. Report of CSIRO Division of Entomology, Canberra, Australia, May 1979. Transfer of grain protectant insecticide residues from grain to wheat gluten. Report of CSIRO Division of Entomology, Canberra, Australia, June 1979. Desmarchelier, J.M. and Marsden, P. - Effect of baking on fenitrothion residues in wheat gluten. Report of CSIRO Division of Entomology, Canberra, Australia, May 1979. Murray, D. and Snelson, J.T. - Fenitrothion and bioresmethrin residues in milled products from a commercial flour mill. Report to Department of Primary Industry, Canberra, June 1978. Snelson. J.T. Pesticide Residue Survey, Department of Primary Industry, Canberra, July 1979. The effect of processing on fenitrothion residues on raw bran. Report to Department of Primary Industry, Canberra, October 1979. Tempone, M.J. Studies on the effects of insecticides on barley malting, Government of Victoria. Research Project Series No. 50, January, 1979.
See Also: Toxicological Abbreviations Fenitrothion (EHC 133, 1992) Fenitrothion (HSG 65, 1991) Fenitrothion (ICSC) Fenitrothion (FAO/PL:1969/M/17/1) Fenitrothion (WHO Pesticide Residues Series 4) Fenitrothion (Pesticide residues in food: 1976 evaluations) Fenitrothion (Pesticide residues in food: 1977 evaluations) Fenitrothion (Pesticide residues in food: 1982 evaluations) Fenitrothion (Pesticide residues in food: 1983 evaluations) Fenitrothion (Pesticide residues in food: 1984 evaluations) Fenitrothion (Pesticide residues in food: 1986 evaluations Part II Toxicology) Fenitrothion (Pesticide residues in food: 1988 evaluations Part II Toxicology) Fenitrothion (JMPR Evaluations 2000 Part II Toxicological)