DIQUAT JMPR 1978 Explanation Diquat was evaluated by the 1970, 1972 and 1976 Joint Meetings (FAO/WHO, 1971b, 1973b, 1977b); brief mention is also made in the evaluations of the 1977 Meeting (FAO/WHO, 1978b). The 1972 Meeting indicated that further data on residues occurring in barley, wheat, rye and oats and their products would be required if diquat-treated cereals were to be used for human consumption. The limits recommended at that Meeting for cereals were set on the understanding that the bulk of the treated crops would be used for animal feed or seed purposes only. Similar questions were raised at the 1977 Meeting of the Codex Committee on Pesticides Residues (CCPR, 1978). Data concerning these matters have now been made available and are reviewed together with certain other information, in this monograph addendum. RESIDUES IN FOOD AND THEIR EVALUATION USE PATTERN Cereals are desiccated with diquat to prevent the loss of laid crops. The most important potential source of human intake of diquat residues is wheat, to which this review in primarily directed. Uses on other cereals do not contribute significantly to the potential human Intake of diquat residues. Diquat in recommended for the desiccation of laid barley and laid oats intended for animal feed use only. Moreover, laid barley and laid oats considered to be of generally inferior quality and are not normally used in brewing or in porridge manufacture. Diquat is not currently recommended for use on laid rye but there is some use on rice. Lodging of wheat is not a widespread problem every year. In North-Western Europe, lodging in generally a problem only one year in three. This is because the most important of the several factors which can affect lodging is the weather - heavy wind and rain can result in considerable yield losses, particularly if damage occurs about two months before harvest. Daring the last twenty years, bad weather and heavy lodging occurred in the UK in 1958, 1962, 1965, 1968, 1974 and, to a lesser extent, 1977. 1971 was a year in which wind and rain were insufficient to cause wheat to lodge, but continuing mild, cloudy weather with high humidity resulted in considerable loss owing to grain sprouting in the ears of standing crops. Little data have been published on the extent to which laid cereals are a problem in a bad year. However, on a national basis only a small proportion of the crop in likely to be affected. In the UK in 1965, when laid wheat was widespread, approximately 15% of the crop was estimated to be severely lodged, with moderate lodging in a further 10-20% (Barrett et al., 1967). In France, it is estimated that in a normal year about 1-2% of the cereal acreage can be lodged and that in a wet year, or year following a dry year, up to 10% of the total acreage can be lodged. A similar pattern appears in Germany were estimates indicate that between 0.5% and 5% of the total cereal acreage can be affected, depending upon the year. Although only a small proportion of the crop is likely to be affected nationally, considerable regional variations can occur and lodging can be a matter of agronomic and economic importance in localized areas or to individual growers. In 1965, when laid wheat was a particular problem in the UK, in those regions where lodging occurred up to 70% of the acreage was affected (Barrett et al., 1967). In fields where lodging occurs, up to 70% of the potential yield can be lost (Calidcott, 1966). Although the use of chlormequat and/or short-strawed varieties of wheat is becoming more widespread, they are not used exclusively and it is anticipated that laid wheat will continue to be a matter of economic importance to individual growers in some years. Where serious lodging occurs, diquat can be used to minimize potential yield losses by removing weed growth and secondary tillers. It is effective on wheat, barley and oats at a rate of 0.6-1.2 kg ai per ha, applied at least four days before harvest, under conditions which generally prevail in North-Western Europe. Lower rates, of the order of 0.3-0.4 kg ai per ha, can be effective under conditions of high light intensity, eg in Australia, New Zealand and Canada. RESIDUES RESULTING FROM SUPERVISED TRIALS Wheat Data on diquat residues in desiccated wheat are available from trials in Australia, New Zealand, Canada, Germany, Switzerland and the UK, in the period 1963/75. In the range of effective use rates, a mean residue of 0.5 mg/kg was found (Table 1). More than 200 analytical results are available, only four of which exceeded the maximum residue limit of 2 mg/kg recommended by the 1972 Meeting (FAO/WHO, 1973a,b) and none exceeded 3 mg/kg (Calderbank and Yuen, 1963, Calderbank and McKenna, 1964; Edwards et al., 1976; Gardiner, 1977; Hayward, 1974, 1975; McKenna, 1966, 1967; Reeve, 1972; Ward 1973; Willis, 1968). Barley Unlike wheat, barley does not lose its hull and hence the associated spray-deposited residue of diquat, during threshing. Therefore diquat residues in barley grain are likely to be higher than those in desiccated wheat grains. Trials in Canada, France, Germany, Sweden and the UK in the period 1962-75 showed a mean diquat residue of 1.7 mg/kg in barley grain desiccated at effective use rates (Table 2). Three of the 43 samples analysed contained residues in excess of the 5 mg/kg maximum residue limit recommended by the 1972 Meeting (FA0/WHO, 1973a,b). (Calderbank and Yuen, 1963; Calderbank and McKenna, 1964; Gardiner, 1977; McKenna, 1966; Edwards et al., 1976). TABLE 1. Diquat residues in desiccated wheat Application Residues (mg/kg) of diquat Country Year rate ion (kg diquat ion/ha) Range Mean Australia 1967 0.28 - 0.55 <0.05 <0.05 (6) New Zealand 1966 0.4 0.32 - 1.3 0.63 (23) 0.8 0.91 - 2.3 1.5 (20) 1972-74 0.28 - 0.3 (<0.05 - 0.25 0.10 (26) 0.55 - 0.6 0.05 - 0.8 0.25 (28) 1.2 0.14 - 1.6 0.61 (12) Canada 1973-75 0.28 < 0.02 - 0.08 0.05 (3) 0.56 < 0.02 - 0.12 0.07 (2) Germany 1974-75 0.6 < 0.05 - 0.21 0.11 (4) 1.2 < 0.05 - 0.44 0.19 (4) Switzerland 1965 0.8 - 2.1 (1) UK 1962-65 0.4 - 0.75 < 0.05 - 3.0 0.44 (41) 1.2 0.15 - 1.5 1.3 (5) 1973 0.6 <0.1 - 0.3 0.14 (15) 1.2 <0.1 - 0.8 0.26 (15) Overall mean 0.49 (205) Figures in brackets are the numbers of results upon which each mean is based. In calculating the mean of finite and `non-detectable' results, a value equal to the limit of determination was applied to the `non-detectable' results. TABLE 2. Diquat residues in desiccated barley Application Residues (mg/kg) of diquat Country Year rate ion (kg diquat ion/ha) Range Mean Canada 1965 0.25 0.41 - 0.44 0.43 (2) 0.5 1.2 - 1.5 1.3 (2) France 1963 0.5 - 0.8 1.5 - 1.7 1.6(2) Germany 1974-75 0.6 0.28 - 0.81 0.58 (4) 1.2 1.2 - 2.0 1.6 (4) Sweden 1962 0.5 - 1.1 (1) UK 1962-65 0.4 - 0.75 0.40 - 6.2 1.9 (27) 1.2 1.1 - 7.4 3.2 (5) Overall mean 1.7 (47) Figures in brackets are the numbers of results upon which each mean is based. TABLE 3. Diquat residues in desiccated oats Application Residues (mg/kg) of diquat Country Year rate ion (kg/diquat ion/ha) Range Mean Canada 1975 0.28 0.14 - 0.51 0.33 (2) 0.56 0.14 - 1.4 0.80 (2) UK 1962-63 0.4 - 0.6 0.24 - 1.7 0.93 (5) 1.2 2.4 - 3.8 3.1 (3) Overall mean 1.3 (12) Figures in brackets are the numbers of results upon which each mean is based. Oats Like barley, oats do not lose their hull, and hence the associated spray-deposited residue of diquat, during threshing. In UK and Canadian trials, residues up to 3.8 mg/kg diquat were found in oat grains which had been desiccated with diquat at effective use rates. The mean residue of 1.3 mg/kg was similar to that found in barley (Tables 2 and 3) (Calderbank and Yuen, 1962; Calderbank and McKenna, 1963; Gardiner, 1977). Rice No new data on diquat residues in rice were available to the Meeting. A review of earlier data (FAO/WHO, 1971b. 1973b) confirmed that the bulk of the residue is associated with the husk, residues were seldom detected in de-husked (brown) or polished rice and when observed were below 0.16 mg/kg with a mean level of 0.07 mg/kg. FATE OF RESIDUES In water and on plants Diquat undergoes rapid and extensive photochemical degradation on plants and in water. Photochemical degradation products of diquat are listed in Figure 1 and a proposed scheme for the photochemical degradation of diquat in water is displayed in Figure 2. In water maintained in sunlight, 70% degradation of diquat occurs in 1-3 weeks (Cavell et al., 1978a; Smith and Grove, 1969). The major photochemical degradation product is 1,2,3,4-tetrahydro-1-oxopyrido- 2H-[1,2-a]-5-pyrazinium ion (TOPPS) (II) (Slade and Smith 1967; Smith and Grove, 1969). A four-carbon or smaller moiety must also be formed. On further irradiation, TOPPS is cleaved to yield picolinamide (III) and picolinic acid (IV) (Smith and Grove, 1969). 6-hydroxypicolinic acid (V) is formed from picolinic acid by ultra-violet light (Kurokawa et al.# 1973) and is further degraded by sunlight (Redemann and Youngson, 1968). It is quite likely that the photochemical degradation of 6-hydroxypicolinic acid parallels the known bacterial oxidation of picolinamide, picolinic acid and 6-hydroxypicolinic acid studies by Orpin et al., (1972). During bacterial oxidation, 6-hydroxypicolinic acid is degraded to 2,5-dihydroxypyridine, to maleamic acid and thence to maleic acid which isomerises to fumaric acid (Orpin et al., 1972). Photochemical cleavage of TOPPS also yields glyoxal (VI) which is then oxidised further to oxalic acid (VII), formic acid (VIII) and carbon dioxide (Cavell at al., 1978a).FIGURE 1a;V078PR07.BMP
The photochemical degradation of diquat on plants is more complex than that found in water. On diquat-desiccated wheat and barley more than 90% of the residue has been accounted for. Diquat itself normally constitutes the most important single compound, eg 10-30% of the residue. TOPPS constitutes the most important single photochemical degradation product. No other well-defined major degradation product is formed. Oxalic acid and diquat monopyridone (IX) are minor degradation products, normally constituting approximately 2% of the total residue in each case. A large proportion (eg 50-70%) of the 14C-radiolabel applied as diquat is found as an ill-defined complex mixture of compounds which streak on thin-layer chromatoplates. A spectrum of 14C-products is formed, with molecular weights ranging from less than 700 to greater than 10,000. No individual 14C-labelled component predominates and each generally constitutes less than 5% of the total residue (Cavell et al., 1978a,b; Leahey et al., 1973). At least in part, the higher molecular weight compounds are likely to have been formed by the reaction or incorporation of small molecular weight compounds, for example glyoxal, formic acid and carbon dioxide, with/into natural plant constituents, to yield water soluble polysaccharides and proteins. TOPPS is of low mammalian toxicity (Figure 1). All other degradation products are individually minor. Diquat itself constitutes the single major residue of potential toxicological concern and therefore it is this residue which has been the subject of detailed scrutiny in the other parts of this review. In animals The available data on the fate of diquat and its photoproducts in ruminants and poultry were reviewed at the 1976 Meeting (FA0/WHO, 1977b). Following oral administration, diquat and its photoproducts are rapidly eliminated by ruminants, primarily (90% or more) in the faeces. Diquat undergoes little metabolism in ruminants. Only very small residues are secreted in milk - eg less than 0.02% of a radiolabelled dose of diquat. The radioactivity secreted in milk is due mainly (to 90%) to incorporation into natural milk constituents such as lactose, fats and proteins. Diquat, TOPPS (II) and the monopyridone (IX) have been identified as components of the residue in milk. When diquat-desiccated alfalfa, clover, or sunflower seeds, or silage made from diquat desiccated grass, were fed to cows and sheep for approximately 1-4 months, no ill effects were observed. Diquat residues in meat and milk were consistently within the maximum re residue limits proposed by the 1972 Meeting (0.05 mg/kg in meat, 0.01 mg/kg in milk). Approximately 95% or more of an oral dose of diquat is excreted by hens in 3-5 days, principally (75-80%) as unchanged diquat. Approximately 0.06% of the dose is transferred to the eggs, 35-40% as diquat and 55-60% as the monopyridone (IX). Cereals can form up to 50% of the diet of lactating ruminants, 70% of the diet of poultry and 100% of the diet of animals grown for meat production. The dietary levels used in these studies on residues of diquat in products of animal origin are sufficient to cover the residue levels of diquat which are likely to appear in animal feed-stuffs as a result of laid cereals being desiccated. The maximum residue limits recommended by the 1972 and 1976 Meetings of 0.01 mg/kg in milk and eggs and 0.05 mg/kg in meat are sufficient to cater for the use of diquat as a desiccant of laid cereals (FAO/WHO, 1973b, 1977b). In processing Wheat Extensive data are available from trials conducted in the UK, Germany and New Zealand in the period 1963-75 (Calderbank and McKenna, 1974; Calderbank and Springett, 1971; Edwards et al., 1976; Reeve, 1972). The spray-deposited residue of diquat in desiccated wheat is located primarily in the outer layers of the grain. Overall, residue levels in bran are approximately twice those in whole grains. The highest residue found in bran following desiccation at effective use rates was 2.7 mg/kg (Table 4). Residues in fine offal are comparable to those in whole grains (Table 4). Residues in white flour are generally 20-25% of those in whole grains. At effective use rates all of the 50 samples of white flour analysed contained residues within the maximum residue limit of 0.2 mg recommended by the 1972 Joint Meeting. The highest value recorded was 0.19 mg/kg (Table 4). The baking process does not materially affect diquat residue levels, and diquat residues in white flour and in white bread are essentially the same. Levels in wholemeal bread are slightly smaller than those in whole grains - this is accounted for by the higher moisture content of bread than grain (Tables 4 and 5). Barley As stated previously diquat is recommended for the desiccation of laid barely intended for animal use only. In any case, laid barley is generally considered to be of an inferior quality and not normally used in brewing. Nevertheless to cater for the possibility that a small quantity of treated barley might occasionally be used in beer production, a limited amount of data has been produced on diquat TABLE 4. Diquat residues in processing fractions of wheat Application Residues (mg/kg) of diquat ion Country rate and year (kg diquat ion/ha) Whole grain Bran Fine offal White flour White bread New Zealand 0.28 <0.05 - 0.25 - <0.05 - 0.33 <0.05 - 1972 (Means) 0.10 (4) - 0.19 (4) <0.05 (4) - UK 0.6 <0.1 - 0.3 <0.1 - 1.5 <0.1 - 0.6 <0.05 - 0.08 <0.05 1973 1965 0.75 0.95 - 1.0 1.2 - 2.4 0.57 - 0.58 0.10 - 0.12 0.09 - 0.14 Germany 0.6 <0.05 - 0.21 <0.05 - 0.48 - <0.05 - 0.13 <0.05 - 0.08 1974-75 New Zealand 0.55 - 0.25 - 0.84 - <0.05 - 0.09 - 1971 (means) 0.27 (14) 0.55 (24) 0.28 (10) 0.07 (28) 0.07 (8) UK 1.2 0.71 - 1.5 0.59 - 2.3 0.66 - 1.9 <0.05 - 1963 1973 <0.1 - 0.8 <0.1 - 2.7 0.1 - 0.84 <0.05 - 0.08 <0.05 Germany 1.2 <0.05 - 0.44 0.16 - 1.1 - <0.05 - 0.19 <0.05 - 0.07 1974-75 (means) 0.39 (16) 0.78 (16) 0.43 (16) 0.07 (19) <0.05 (6) Figures in brackets are the numbers of results upon which each mean is based. TABLE 5. Diquat residues in wheat grain and wholemeal bread Application Residues (mg/kg) of diquat Country Year rate ion in (kg diquat ion/ha) Whole grain Wholemeal bread UK 1973 0.6 <0.1 - 0.2 <0.05 - 0.1 1965 0.75 0.95 - 1.0 0.41 - 0.51 Germany 1974-75 0.6 <0.05 - 0.21 0.09 - 0.33 (Means) 0.29 (10) 0.20 (10) UK 1973 1.2 <0.1 - 0.3 <0.05 - 0.6 (Means) 0.16 (5) 0.19 (5) Overall mean 0.25 (15) 0.20 (15) Figures in brackets are the numbers of results upon which each mean in based. TABLE 6. Diquat residues in barley grain and in beer Commodity Residues (mg/kg) of diquat ion analysed whole grain 4.2 2.4 0.94 Beer 0.15, 0.12, 0.14 0.07, 0.06, 0.03, 0.03, 0.03 0.02 0.10, 0.13, 01.3 0.05, 0.06, 0.03, 0.01, 0.04 0.03 0.12 0.05 (Means) 0.13 0.05 0.025 Ratio of Mean residue in beer Residue in grain 3.1% 2.1% 2.7% (expressed as %) residues in melting and brewing (Calderbank and Springett, 1971). The figures indicate that residues in beer would be approximately 2-3% of those found in whole grain (Table 6). With mean residues in barley grain of 1.7 mg/kg at effective use rates (Table 2), it can be anticipated that diquat residues in beer would be of the order of 0.05 mg/kg in the event that treated barley was used for melting and was not diluted with untreated grain first. NATIONAL MAXIMUM RESIDUE LIMITS The following additional national MRLs have been reported to the Meeting. COUNTRY COMMODITY MRL, mg/kg Australia Barley, poppyseed, rice in husk 5 Rapeseed, sorghum, wheat 2 Cottonseed, beans, sunflower seed, rice (polished) 1 Potatoes, wheat flour 0.2 Onions, maize, sugarbeet, peas 0.1 Cottonseed, rape, sesame, sunflower oils, other vegetables crops 0.05 Meat and meat products 0.05 Milk (whole) 0.01 Czechoslovakia Barley for feeding 3 Clover, alfalfa 3 Rye for feeding 2 Silage 1:1 (desilated to non-desilated) 1.5 Rapeseed 1 Peas 0.1 Potatoes 0.05 Milk (smallest detectable quantity of their method) 0.01 COUNTRY COMMODITY MRL, mg/kg Federal Republic Potatoes 0.1 of Germany Rapeseed 0.7 All other crops 0.05 Hungary Animal feed 2 Oily crops 0.8 Other crops 0.5 Netherlands Fruit, vegetables (incl. potatoes) spices 0.05 Sweden Fruit, vegetables, potatoes 0.1 Cereals, beans 0.5 Milled cereal products 0.2 Switzerland Fruit, vegetables 0.02 Appraisal In response to requests from earlier Meetings, further data concerning residues of diquat in some cereals and their products were submitted for evaluation. These data covered the potential use of diquat as a desiccant to rescue lodged wheat for possible human consumption; barley and oats so treated are normally only regarded as suitable for animal feed or seed purposes. Beer made from treated barley contained only 2-3% of the diquat present in the grain. Further information on the degradation of diquat in water, on plants, in animals and during the processing of cereals was also reviewed. The data provided generally confirmed the maximum residue limits recommended by the 1972 and 1976 Meetings with the exceptions of the additions and amendments listed below. RECOMMENDATIONS Commodity Limit, mg/kg diquat ion Wheat bran 5 Wheat flour (wholemeal) 2 Wheat flour (white) rice (hulled and/or polished) 0.2 REFERENCES Barrett, D.W.A., Meens. B.E. and Mees, G.C. The control of lodging in cereals by (2-chloroethyl)-trimethyl ammonium chloride (CCC). J. Agric. Sci., Camb., 68:39-46. Calderbank, A. and Yuen, S.H. Bipyridylium herbicides: residues of (1963) diquat and paraquat in food crops. ICI Plant Protection Ltd., Report No. PP/E/231 (unpublished). Calderbank, A. and McKenna, R.H. Bipyridylium herbicides: residues of (1964) diquat and paraquat in food crops from 1963 trials. ICI Plant Protection Ltd., Report No. PP/E/292 (unpublished). Calderbank, A. and Springett, R.H. Diquat residues in cereal grain (1971) and processed parts (eg flour and malt) following use of `Reglone' as a pre-harvest desiccant. ICI Plant Protection Ltd., Report No. TMJ644A (unpublished). Caldicott, J.J.B. The interaction of Cycocel (2-choroethyl)-trimethyl (1966) ammonium chloride and nitrogen top dressing on the growth lodging and yield of wheat. Proc. 8th Dr. Weed Control Conf., 1:229-239. Cavell, D.B., Francis, P.D., Goddard, C and McIntosh, S. (1978a) Photochemical degradation of diquat in water and on plants. Status report. ICI Plant Protection Division Report No. RJ0038A (unpublished). Cavell, B.D., Francis, P.D. and Goddard, C. Fractionation of the (1978b) photoproducts formed from 14C-diquat on barley ICI Plant Protection Division Report No. RJ0039A (unpublished). CCPR Report of the 1977 Meeting of the Codex Committee on Pesticide (1978) Residues, ALINORM 78/249 para. 91-93. Edwards, M.J., Hayward, G.J. and Ward, R.J. Diquat: residues in (1976) grain, flour and bread - UK and German trials, 1973-5. ICI Plant Protection Division Report No. AR2682A (unpublished). FAO/WHO 1970 evaluations of some pesticide residues in food. (1971) FAO/AGP:1970/M/12/1, WHO Food Add./71.42. FAO/WHO 1972 evaluations of some pesticide residues in food. (1973) FA0/AGP:1972/M/9/1, WHO Pest. Res. Series No, 2. FAO/WHO 1976 evaluations of come pesticide residues in food. (1977) FAO/AGP:1976/M/14. FAO/WHO 1977 evaluations of some pesticide residues in food. (in (1978) press). Gardiner R.P. Summary of residues data from 1975 small plot trials. (1977) Chipman Chemicals Ltd. Canada data (unpublished). Hayward, G.J. Diquat residues data on wheat grain from New Zealand (1974) trials 1974. ICI Plant Protection Division data (unpublished). Hayward G.J. Diquat residues data on wheat grain from Canadian (1975) trial 1973. ICI Plant Protection Division data unpublished). Kurokawa, H., Furihata, T., Takeuchi, F. and Sugimori, A. Photoreactions of heteroaromatic compounds. III Photohydroxylation and alkoxylation of 2-pyridine- carboxylic acid in acidic aqueous and alcohol solutions. Tetrahedron Letters, 28:2623. Leahey, J.P., Griggs, R.E. and Allard, G.B. Diquat: residues of (1973) diquat and its photoproducts on barley and oats after desiccation with 14C-diquat. ICI Plant Protection Ltd. Report No. AR2478B (unpublished). McKenna, R.H. Bipyridylium herbicides: residues of diquat in (1966) food crops from 1964 and 1965 field trials. ICI Agricultural Division Report No. A 126, 493 (unpublished). McKenna, R.H. Diquat residues data on wheat grain from New Zealand (1967) trials, 1966. ICI Plant Protection Ltd, data (unpublished). Orpin, C.G., Knight, M. and Evans, W.C. The bacterial oxidation (1972) of picolinamide, a photolytic product of diquat. Biochem. J., 127:819. Redemenn, C.T. and Youngson, C.R. The partial photolysis of (1968) 6-chloropicolinic acid in aqueous solution. Bull. Env. Cont. and Tox., 3:97. Reeve, M. Diquat residues data on wheat grain, white flour, offal (1972) and bran from New Zealand trials, 1971-72. ICI Plant Protection Ltd. data (unpublished). Slade, P. and Smith, A.E. Photochemical degradation of diquat. (1967) Nature, 213, No. 5079:919. Smith, A.E. and Grove, J. Photochemical degradation of diquat in (1969) dilute aqueous solution and on silica gel. J. Agric. Food Chem. 17, No. 3:609. Ward, R.J. Diquat residues data on wheat grain from New Zealand trials, 1973. ICI Plant Protection Division data (unpublished). Willis G.A. Diquat residues data on wheat grain from Australian (1968) trials 1967. ICI Plant Protection Ltd. data (unpublished).
See Also: Toxicological Abbreviations Diquat (HSG 52, 1991) Diquat (PIM 580F, French) Diquat (AGP:1970/M/12/1) Diquat (WHO Pesticide Residues Series 2) Diquat (Pesticide residues in food: 1976 evaluations) Diquat (Pesticide residues in food: 1977 evaluations) Diquat (Pesticide residues in food: 1993 evaluations Part II Toxicology)