PESTICIDE RESIDUES IN FOOD - 1984 Sponsored jointly by FAO and WHO EVALUATIONS 1984 The monographs Data and recommendations of the joint meeting of the FAO Panel of Experts on Pesticide Residues in Food and the Environment and the WHO Expert Group on Pesticide Residues Rome, 24 September - 3 October 1984 Food and Agriculture Organization of the United Nations Rome 1985 BITERTANOL Explanation Date for the estimation of an acceptable daily intake for bitertanol were evaluated by the 1983 Joint Meeting which estimated a temporary acceptable daily intake. This evaluation considers residues in food and gives details of the identity of the compound. Chemical name: all-rac-1-(biphenyl-4-yloxy)-3,3- dimethyl-1-(1H-1,2,4-triazol- 1-yl)butan-2-ol Registry number [55179-31-2] Synonyms: Baycor, Sibutol Structural formula: KWG 0599Empirical formula: C20H23N3O2 Molecular weight: 337.4 RESIDUES IN FOOD USE PATTERN Bitertanol is a broad-spectrum fungicide said to be effective for the control of scab and Monilinia fruit diseases, banana and peanut leaf spot diseases, and rusts and mildews on a variety of crops. It is available as a wettable powder, emulsifiable concentrate and suspension concentrate, all applied by spraying. It is also used as a seed treatment for cereals. Only the wettable powder is recommended for pome fruit owing to possible foliage or fruit injury by the EC formulation. Bitertanol is said to be registered and marketed in over 20 countries in Europe, Africa and South America and registration is being sought in additional countries. Recommendations by geographical areas are listed in Table 1. RESIDUES RESULTING FROM SUPERVISED TRIALS Residue field trials have been conducted on a variety of crops, primarily fruits and vegetables. Data provided to the JMPR are summarized in Table 2. Pome Fruit Residues trials in apples have been conducted in four countries, although according to Table 1 bitertanol is currently approved for use in only one of the four. The trial in this country reflects European uses. Where reported, controls were <0.01 mg/kg. With maximum residues of 1.0 mg/kg at the recommended 14-day interval, these data and the supporting data from other countries indicate that a 2 mg/kg limit would be required with a 14-day pre-harvest interval. Additional data are desirable from countries with approved uses. Cucumber Trials on cucumbers (under glass) were available from one country with WP application at approximately the approved rate and EC at twice the approved rate. Maximum residues were 0.41 mg/kg at the normal harvest interval. Residues from the two EC applications were similar to those from six with the WP at similar intervals. These limited data indicate a possible need for a 0.5 mg/kg limit at a 3-day pre-harvest interval, but are not sufficient to support a limit. Peanuts In trials in one country reflecting approved application rates (but excessive numbers of applications) no residues were detected (<0.1 mg/kg) 9-14 days after the last application. Analyses were apparently on shelled nuts. Data are not sufficient to support a limit. Beans Data were available from trials in three countries, but approved use information was available from only one of these. From the country with approved uses residues in dry bean pods at 16 days (28-day safety interval required) were 0.1 - 0.18 mg/kg at the normal application rate. This compares with 0.1 mg/kg in untreated controls. Similar application rates in South America resulted in <0.05 mg/kg residues (3 samples) at 26-43 days post-treatment, but it is not clear whether the beans were shelled or in pod. Data are insufficient to support a limit. Table 1. Use Pattern - spray treatment Region and Number of Safety interval, Commodity g a.i./ha treatments days Europe Pome fruit 1, 2 187 - 375 6 - 12 14 - 42 Stone fruit 375 - 562 2 - 3 * Snake gourd ) (Cucumber ) under Peppers ) glass 9003 2 - 6 3 Melons ) South Africa Peanuts 195 - 240 2 - 4 as dry feed 42 Stone fruit 140 - 240 2 - 3 28 Beans 126 - 250** 2 (as dry feed 42) Asia Bananas 125 - 150 26 South America Bananas 125 18 - 26 * Not later than at the end of flowering stage; following this application no residues are expected. ** aerial application 1 Registration (pre-harvest WP on apples) at 0.05 - 1.0% and a 28-day PHI is under way in Finland. 2 Netherlands - 25 WP at 50-80 g a.i./100 1 and 300EC at 22.5 g/l. Both 14-day pre-harvest interval. 3 300 EC in The Netherlands. Seed treatment - Federal Republic of Germany Wheat 75 g a.i./100 kg seed Rye 56 g a.i./100 kg seed Oat 56 g a.i./100 kg seed Table 2. Bitertanol residues in crops resulting from supervised trials Dose a i. No. of Days after Crops (Formulation) Applications Country last Residue (mg/kg) Report (year) Application Range Average No. Pome fruit Bayer Apples 187 - 375 g/ha 10-12 FRG 14 0.13 - 1.8 0.65 (6) 1 10303/79 (25% WP) (1979-1982) 21 0.12 - 1.0 0.43 (6) 10305/79 10313/80 10325/80 10304-5/82 Mobay 1-4 oz/100 gal. 6-14 USA 0 0.53 - 2.54 1.62 (5) 64382+83 (50% WP) (1979) 14 0.24 - 1.5 0.9 (5) 21 0.18 - 1.2 0.8 (4) 28 0.27 - 0.91 0.6 (4) 1-2 oz/100 gal. 5-8 Canada 66-67 0.06 - 0.10 0.07 (4) Mobay (50% WP) (1983) 74-92 < 0.01 - 0.04 0.02 (12) 68282-86 0.8 g/tree 4 Finland Siltanen (1979) 32 0.2 (1) and Makinen (1980= 49 0.1 1980 5 (1981) 67 0.04 Siltanen 6 35 0.1 and Makinen 8 24 0.4 1981 Cucumbers 875 - 1200 g/ha 2(EC) NL 0- 1 0.4 - 0.7 0.54 (4) Bayer (Snake gourds, (200 g/1 EC or 6(WP) (1979-1980) 3- 4 0.25 - 0.41 0.34 (3) 10326/79 under glass) 50% WP) 7-10 0.06 - 0.25 0.15 (5) 10314-15/80 Table 2 (continued) Dose a i. No. of Days after Crops (Formulation) Applications Country last Residue (mg/kg) Report (year) Application Range Average No. Peanuts 250 - 300 g/ha 4-5 S.Africa 9-14 < 0.1 < 0.1 (3) Bayer (Shelled?) (300 g/L EC or (1979-1983) 10301/77 25% WP) 10313/78 10328/80 Beans 225 - 250 g/ha 4 Costa 26 0.05 0.05 (1) Bayer (mature, dry) (300 EC) Rica 37 0.05 0.05 (1) 10332-33/80 Columbia 43 0.05 0.05 (1) 10342/81 (1981) Beans 125 g a.i./ha S. Africa S. Africa (dry) (300 EC) (not avail.) submission whole plt. 1 1 23 : 30 4 2.5 : 3.4 8 3.7 : 3.8 16 0.36 : 0.3 250 g a.i./ha 1 43 : 39.4 (300 EC; 4 6 : 6.8 double rate) 8 4.5 : 5.0 16 0.3 : 0.32 pods 125 g a.i. /ha 1 11 sic? 2.7 : 2.4 (300 EC) 4 0.13: 9.19 8 0.15: 0.13 16 0.18: 0.10 Table 2 (continued) Dose a i. No. of Days after Crops (Formulation) Applications Country last Residue (mg/kg) Report (year) Application Range Average No. 250 g a.i./ha 11? 3.2 : 2.9 (300 EC; 4 0.16: 0.1 double rate) 8 0.4 : 0.4 16 0.23: 0.21 A B Stone fruit A Nectarines 100- 100 g/ha 4 S.Africa 0 0.53 - 1.5 SABS (300 EC) (1982) 3 0.47 - 0.68 (1)* 311/88419 data: 10 0.21 - 0.54 (1) W 212 A = 0.125% a.i. 14 0.18 - 0.51 B = 0.25% a.i. 24 0.18 - 0.37 (1) Peaches 100 - 200 g/ha 3 S. Africa 0 0.6 - 1.8 (1)* SABS (300 EC) (1982-1983) 5 0.4 - 1.2 (1)* 311/88421/ data: 11 0.3 - - (1)* W214 A = 0.125% a.i. 19 0.2 - 0.5 (1)* B = 0.25% a.i. 26 < 0.1 - - (1)* ripe 375 g/ha 3 France 0 1.7 (25& WP) (1979) 7 1.2 14 1.3 21 0.91 300 & 400 g/ha 3 Italy 0 0.8 - 1.2(1)* (3.5cm fruit) Bayer (300 EC) (1981) 7 0.3 - 0.4(1)* 10346-47/81 14 0.2 - 0.2(1)* 20 0.11- 0.13(1)* (5-7cmfruit) Table 2 (continued) Dose a i. No. of Days after Crops (Formulation) Applications Country last Residue (mg/kg) Report (year) Application Range Average No. Plums 250 - 370 g/ha 1 S. Africa 0 0.7 - 0.8(1)* (300 EC) (1982) 3 0.8 - 0.8(1)* data: 9 0.6 - 0.5(1)* A = 0.025% a.i. 16 0.5 - 0.6(1)* B = 0.0375% a.i. Bananas 120 - 300 g/ha 6 - 26 Costa Rica Bayer unbagged (EC 200-300; Columbia 2 0.015 0.015(1) 10309-11/78 pulp WP 25%) Taiwan 4 ND ND (1) 10320-21/80 Kamerun 8 0.014-0.019 0.017(2) 10330-31/80 (1978-1980) 23 < 0.1 < 0.1 (1) 10350-80 40 ND ND (1) 10344-45/81 78 ND ND (1) 10366/81 peel 2 0.14 0.14(1) 4 ND ND (1) 8 0.12 - 0.15 0.14(2) 23 0.025 0.025(1) 40 ND ND (1) 78 ND ND (1) total (calculated) 2 0.06 0.06(1) 4 ND ND (1) 8 0.047-0.055 0.051 (2) 23 < 0.01 < 0.01 (1) 40 ND ND (1) 78 ND ND (1) Table 2 (continued) Dose a i. No. of Days after Crops (Formulation) Applications Country last Residue (mg/kg) Report (year) Application Range Average No. bagged 0 ND ND (2) pulp 2 ND ND (1) 6 ND ND (1) 8 < 0.01 < 0.01 (2) 11 ND ND (2) 12 ND ND (1) peel 0 ND ND (2) 2 0.019 0.019 (1) 6 0.1 0.1 (1) 11 ND ND (2) 12 ND ND (1) Total (calculated) 0 ND 2 < 0.01 6 < 0.01 8 < 0.01-0.015 11 ND 12 ND Bananas, green 125 - 300 g/ha 9 - 12 Honduras 0/3 Mobay unbagged, (300 EC) or Costa 68896-900 unwashed 25 or 50% WP) Rica - 80469-473 pulp (1980-1982 0.03-0.13 0.07(6) peel 0.10-0.76 0.39(6) total 0.06-0.33 0.19(6) unbagged, washed pulp 0.03-0.17 0.09(5) peel 0.09-0.73 0.37(5) total 0.05-0.36 0.19(5) Table 2 (continued) Dose a i. No. of Days after Crops (Formulation) Applications Country last Residue (mg/kg) Report (year) Application Range Average No. bagged, unwashed pulp < 0.01-0.01 < 0.01(4) peel < 0.01-0.05 0.03(4) total < 0.01-0.03 0.02(4) bagged, washed pulp < 0.01-0.02 0.01(5) peel 0.03-0.15 0.06(5) total 0.02-0.06 0.03(5) Bananas, ripe unbagged, unwashed pulp < 0.01-0.08 0.05(3) peel 0.03-0.32 0.19(3) total 0.01-0.17 0.10(3) Bananas, ripe unbagged, unwashed pulp 0.02-0.14 0.09(3) peel 0.05-0.51 0.34(3) total 0.03-0.28 0.18(3) Bananas, ripe bagged-unwashed pulp < 0.01-0.01 < 0.01(3) peel < 0.01-0.12 0.05(3) total < 0.01-0.05 0.02(3) Table 2 (continued) Dose a i. No. of Days after Crops (Formulation) Applications Country last Residue (mg/kg) Report (year) Application Range Average No. bagged, washed pulp < 0.01-0.02 0.02(3) peel 0.03-0.08 0.05(3) total 0.01-0.04 0.03(3) Oats, Green forage 56 g/100 kg seed 1 FRG 94/97 < 0.05 < 0.05(2) Bayer Grain (375 FS) (1983) 140-141 < 0.05 < 0.05(2) 10212+13/83 Straw 140/I41 < 0.05 < 0.05(2) Rye, Green Forage 56 ml/100 kg seed 1 FRG 220/224 < 0.05 < 0.05(2) 10210+11/83 Grain (375 FS) (1983) 291/295 < 0.05 < 0.05(2) Straw 291/295 < 0.05 < 0.05(2) Wheat, Green Forage 75 ml (g)/100 kg seed 1 FRG 56-77 < 0.1 < 0.1 (7) 10341+43/80 Ears (1980-1982) 73-90 < 0.05-0.1 < 0.05-0.1(5) 10370+71/80 Grain q (375 FS) 130-154 < 0.05-0.1 < 0.05-0.1(5) Straw 87-154 < 0.05-0.1 < 0.05-0.1(7) Oats, Green Forage 200g product/100 1 FRG 63-86 < 0.1 < 0.1 (1) 10366+67/82 Ears kg seed (0.132 (1982) 75-86 < 0.1 < 0.1 (2) Grain q kg a.i./ha) 131-139 < 0.05 < 0.05(2) Straw (37.5% DS) 131-139 < 0.05 < 0.05(2) Rye Green Forage 0.08-0.11 kg 1 FRG 219-254 < 0.1 < 0.1 (7) 10363-65/82 Ears a.i./ha(150 g (1981-1982) 228-254 < 0.1 < 0.1 (4) 10372-82 Grain production/100 kg - 291-308 < 0.05 < 0.05(4) Straw seed) (37.5 or 291-308 < 0.05 < 0.05 (4) 3.75 DS) 1 Number in parenthesis = number of samples * One sample per dose level (mean of duplicate analyses) Stone Fruit Data were available from three countries, all of which have approved uses, or are in close geographical proximity to countries with them. While European trials on peaches reflect recommended European dosage rates, applications were apparently made after the end of flowering, and therefore do not appear to reflect the recommended time of application (Table 1) for Europe. South African trials also reflect recommended application rates in that country, but the pre- harvest interval was not available to the meeting. The only available PHI for stone fruit was 21 days for cherries in one European country (see "National maximum residue limits". A 1 mg/kg limit for stone fruit can be supported at a 21-day pre-harvest interval. Additional residue data and good agricultural practice information for stone fruit are desirable, especially for small fruit such as cherries. Residues on peaches were significantly more persistent from WP applications than from EC formulations. Bananas Supervised trials data were available for three Asian and three South American countries and generally reflected the application rates and number of applications (WP or EC) recommended in those geographical areas. Since no national pre-harvest intervals were provided, it must be assumed that application on the day of harvest, as included in the trials, reflects practice. Data were available for both green and ripe, bagged and unbagged, and washed and unwashed bananas and on pulp and peel. In general, average residues were approximately 5-10 times higher in peel than in pulp, whether ripe or green, bagged or unbagged, washed or unwashed. As might be expected, residues were higher on unbagged fruit. Washing (in the field) does not appear to affect average residues significantly. Maximum residues on bagged bananas (whole, green, washed) were 0.06 mg/kg. Maximum residues on whole ripe, unbagged, washed bananas were 0.28 mg/kg as compared to 0.36 mg/kg for green, unbagged, washed bananas. Untreated controls (peel, pulp or whole) were all <0.01 mg/kg. A 0.5 mg/kg limit was estimated. Cereal crops No residues of bitertanol were detected in the green forage, ears, grain or straw of oats, rye or wheat when the seeds were treated pre-plant with recommended rates. The limit of determination ranged from 0.05 - 0.1 mg/kg among the 15 studies. The available data would support a limit of 0.1 mg/kg (at the limit of determination) limit for seed treatments only. Additional data from other countries with approved uses for cereal grains are desirable. FATE OF RESIDUES General The fate of bitertanol has been studied in animals, plants, soil water and light. A proposed metabolic pathway is given in Figure 1. The structures and chemical names are presented in Table 3 which also indicates where the compounds have been identified. Although the metabolic picture is somewhat limited in scope, the data in general demonstrate that metabolism in animals is much more extensive than degradation by other routes. Bitertanol is the predominant residue in plants. Bitertanol and p-hydroxybitertanol are the major residues in animals. In plants Uptake and translocation. Golden Delicious variety apples were individually syringe-treated to run-off with a 50% wettable powder formulation at 0.15 g a.i./l of 14C-bitertanol labelled uniformly (UL) in the biphenyl ring. Sampling was immediately after drying, at 3 and 7-days and thereafter at 7-day intervals through 49 days (Phul and Hurley, 1979c). Analysis was by TLC using radiochromatogram scanning and autoradiography techniques. The peel contained 95% of the total recovered radioactivity even after 49 days, the rest being in the pulp, showing that little migration had occurred. Surface residues decreased from 92% at day 0 to 43% at 49 days while the radioactivity in the peel organic extract increased from 7 to 43.5% of the total. Peel solids increased to 12% in the same interval. The two diasterioisomers of bitertanol were the major residues, in roughly equal proportions throughout the 49-day study. The level of the two combined in peel and pulp ranged from 98.4% of the total radioactivity at day 0 to 83% at 49 days, with lower surface residues and greater peel uptake by the end of that time. The two had penetrated the pulp by day 7 from which time residues were relatively constant at about 3% over the remaining test period. Minor metabolites were bitertanol ketone and 4-hydroxy-biphenyl, together never exceeding 3% of the total radioactivity. All of these metabolites were in the peel. The half-life of bitertanol in this experiment was estimated at approximately 150 days. The metabolism of bitertanol by peanut plants has also been studied (Phul and Hurley, 1981). In preliminary studies, the authors obtained evidence that foliar applications result in poor leaf absorption (96% unchanged bitertanol on the leaf surface after 14 days), with no observable volatility losses. Only very little translocation (acro- and basi-petal) was observed, as well as little translocation to opposite leaves Bitertanol - 14C uniformly labelled in the biphenyl ring was sprayed as a 50% WP formulation to both young (1 mo.) and old (2 mo.) potted peanut plants at an approximate equivalent field rate of 0.5 kg a.i./ha. Young plants were sampled at
Table 3. Bitertanol, its degradation products and their occurrence a Chemical Name Common, trivial or Soil Water Plant Animal Light code name
P-(1,1'-Biphenyl)-4-yloxy-o-(1,1- Bitertanol X X X X X dimethytethyl)-1H-1.2.4-triazole-1- ethanol. Bitertanol
1-[1,1-Biphenyl]-4-yloxy),3,3- Bitertanol ketone X X dimethyl-1-(1H-1,2,4-triazol-1-yl)- BUE 1662 2-butanone 1-(o)-3,3-dimethyl-1-(tr)butan-2-one
4-(1,1'-Biphenyl)-4-yloxy)-2,2- Bitertanol alcohol dimethyl-4-(1H-1,2,4-triazol-1-yl) KWG 1714 X Note 1. 1,3-Butanodiol-1,3-butanediol 4-(o)-2,2.dimethyl-4-tr)butane-1,3- diol Table 3. (continued) Chemical Name Common, trivial or Soil Water Plant Animal Light code name
-([1,1'-Biphenyl]-4-yloxy)-B-hydroxy- Bitertanol acid X dimethyl-1H-1,2,4-triazol-1-butanoic acid4-(Biphenyl-4-yloxy)-3-hydroxy- 2,2-dimethyl-4,4-(1H-1,2,4.triazol.1. 1-yl)butyric acid
-(1,1-Dimethylethyl)- -(4'-hydroxy p-hydroxy-bitertanol X -(1,1'-biphenyl]-4-yloxy)-1H-1,2,4- triazole-1-ethanol 1-(4'-hydroxy o)-3,3-dimethyl-1-(tr) butan-2-ol Table 3. (continued) Chemical Name Common, trivial or Soil Water Plant Animal Light code name
4-(4'Hydroxy-[1-1'-biphenyl]-4-yloxy) X -2,2-dimethyl-4-((1H)-1,2,4-triazol-1- yl)-1,3-butanediol 4-(4'-hydroxyo)-2,2-dimethyl-4- (tr)butane.1,3.diol
-Hydroxy- -(4'-hydroxy-[1,1'- p-Hydroxy-bitertanol biphenyl]-4-yloxy- -dimethyl-1H.1,2 alcohol X 4-triazole-1-butanoic acid 3-hydroxy(4'-hydroxyo)-2,2- dimethyl-4-(tr)butyric acid Table 3. (continued) Chemical Name Common, trivial or Soil Water Plant Animal Light code name
- (1,1-dimethylethyl)-p-(x'-di- Dihydroxy-bitertanol X hydroxy-[1,1'-biphenyl]-4-yloxy)-1H-1, 2,4-triazol-ethanol 1-(dihyvroxyo)-3,3-dimethyl-1-(tr) butan-2-olc(distal biphenyl ring substituted)
-(1,1-Dimethylethyl)-B-(x-hydroxy- Hydroxy, methoxyd x'-methoxy-[1,1'-biphenyl]-4-yloxy)- bitertanol X 1H-1,2,4-triazole-1-ethanol 1-(hydroxymethoxyo)-3,3.dimethyl-1- (tr)butan-2-old (distal biphenyl ring substituted) Table 3. (continued) Chemical Name Common, trivial or Soil Water Plant Animal Light code name
- Hydroxy- -(x'hydroxy-x'-methoxy- Hydroxy,methoxyd [1,1'-biphenyl]-4-yloxy)-d,d-dimethyl bitertanol acid. X 1H-1,2,4-triazole-1-butanoic acid 3-hydroxy-4-(hydroxymethoxyo)-2-2- dimethyl-4,4-(tr)butyric acidd (distal biphenyl ring substituted)
4-([2-Hydroxy-3,3-dimethyl-1-[1H- Bitertanol benzoic X 1,2,4-triazol-l-yl]butoxy)=benzoic acid analogue acid BUE 2684 Note: Butoxybenzoic is one word Table 3. (continued) Chemical Name Common, trivial or Soil Water Plant Animal Light code name
Bitertanol glucoside X
4-Hydroxybiphenyl p-Hydroxybiphenyl X X X X Table 3. (continued) Chemical Name Common, trivial or Soil Water Plant Animal Light code name
4,4'-Dihydroxybiphenyl p,p,'-dihydroxy- biphenyl X X X X
1,2,4-triazol X CO2 Carbon dioxide X Table 3. (continued) a An X indicates that the compound has been found to occur as a degradation product of bitertanol in the substrate concerned (or on irradiation). A blank indicates it has not been found there, but does not exclude its presence in amounts too small to detect. b tr = 1-H-1,2,4-Triazol-l-yl c The position of the hydroxy groups is uncertain d The positions of the hydroxy and methoxy groups are uncertain. 12 and 28 days after treatment and the older plants and nuts after 2.5 months. In young plants, 61-72% of the total recovered radioactivity was surface residue, the remainder being mostly (27-36%) extractable. In the older plants the distribution was 46% surface and 50% extractable. In both cases most of the extractables were organo-soluble. The composition of the residues is shown in Table 4. As in the case of apples most of the residue, both surface and extractable, was bitertanol I and II and a metabolite (R-1) tentatively identified as a bitertanol I glucoside. Low levels of 4- hydroxybiphenyl (0.6% of the total shoot residues) were also detected. The authors conclude that the lower I:II isomer ratios in the surface residues in the older plants compared to the 1.33 ratio of the starting material indicates faster absorption of the I isomer and that the 1.10 ratio of I:II in the combined surface and absorbed residues gives evidence that isomer I is metabolized faster than II. Faster isomer I absorption is supported further by the 1.64 ratio of (bitertanol I + metabolite R-1):bitertanol II in the absorbed residues in the old plants and experimental evidence suggesting increased levels of the tentatively identified glucoside of isomer I (R-1) as opposed to isomer II. There is no convincing evidence as to whether isomeric conversion also occurs to account for the lower bitertanol I:II ratio in the total residue. The half-life in peanuts has been estimated at 141 days. In a similar and related experiment in the same set of studies with 8.9 mg a.i./plant (approximately twice the rate per plant in the above), residues in nut meats were 0.06 mg/kg bitertanol equivalent (0.008% of the total plant residue) 2.5 months after treatment. A similar level was found in the shells. It cannot be concluded from this study whether nut residues resulted from the foliar application or from soil uptake. Seven days after growing peanuts in a 1 mg/l 14C-biphenyl-labelled bitertanol nutrient solution followed by 7 days in an unfortified nutrient solution 94.3% of administered radioactivity was recovered with 28.8% in the roots, 14.9% in the shoots, 40% in the fortified nutrient solution and 10.6% in the non-fortified solution. Radioactivity was concentrated in the veins, but distributed throughout the plant. No translocation to new growth occurred after removal of the fortified solution. Radioactivity in the non-fortified solution suggests desorption from within or from the surface. Of the absorbed radioactivity, 32.1% was in the shoots and 67.9% in the roots with the distribution in the organo-soluble fraction shown in Table 5. Table 4. Composition of bitertanol residues in peanut shoots following spray application of 14C-biphenyl-laballed bitertanol YOUNG PLANTS (1 month) OLD PLANTS (2 months) 12 day2 Ratio3 28 day2 Ratio3 2.5 mos.2 Ratio3 Surface Residues bitertanol II 31.3 1.25 26.7 1.24 20.7 0.98 bitertanol I 39 33 20.5 metabolite R-11 - Absorbed (organosoluble) bitertanol II 11.2 1.64 bitertanol I 11.9 1.27 13.4 1.3 15 metabolite R-1 2.4 13.1 18.9 4.3 5.8 1 Tentatively identified as the 6-0-malonyl-B-D-glucoside of bitertanol I. 2 Interval after treatment. 3 Ratio of bitertanol I to bitertanol II in surface residues; ratio of (bitertanol I + metabolite R-1) to bitertanol II in absorbed residues. Table 5. Distribution of organo-soluble radioactivity absorbed by peanut plants. Compound Shoots Roots Total % of Ratio* % of Ratio* % of Ratio* absorbed absorbed absorbed 14C 14C 14C bitertanol II 10.7 20.4 31.1 1.32 bitertanol I 8.6 1.17 16.1 1.39 24.7 metalite R-1 3.9 12.3 16.2 23.2 48.8 72.0 Ratio of (bitertanol I + metabolite R-i) to bitertanol II. Unextracted residues were 18.3% of the absorbed activity. Assuming R-1 is a glucoside of bitertanol I as postulated the ratio of (I + R-1) to II (1.32) n the total absorbed residue is essentially identical to that in the starting material. This suggests equal root absorption rates of bitertanol I and II. The finding of higher levels of both R-1 and bitertanol I in the roots than in the shoots suggests faster translocation of bitertanol II through-out the plant and/or more rapid metabolism of bitertanol I. There was no evidence of volatility from leaf surfaces. Of the 18.3% unextracted but absorbed residue, 5 and 13.3%, respectively, was in shoots and roots. The metabolite 4-hydroxybiphenyl was detected in both (64% of the root-concentrated residue). Other peanut studies (Scheinpflug and Van den Boom, 1981) also show bitertanol to be slowly absorbed by peanut leaves from surface application with little translocation from petiole applications. In animals The fate of residues in rats and other non-food animals was evaluated by the 1983 meeting. This evaluation considers the fate in cows and chickens. Cow. A single dose of phenyl-UL-14C bitertanol was fed to a 341 kg Holstein dairy cow at 0.2 mg/kg body weight by gelatin capsule, and excreta and milk were analyzed periodically for six days. The I:II isomer ratio was 53:47. Food consumption was not recorded (Obrist et al. 1981). Eighty per cent of the dose was eliminated within 48 hours: urine 8.3%, faeces 70.4% and milk 0.2%, with milk residues becoming steady after 32 hours. Ninety two per cent was eliminated by 6 days. Residues in the blood peaked at 0.13 mg/l after 12 hours. Six days after the single dose the same cow was dosed daily at the same rate for an additional 5 days. The 14C residues (as bitertanol equivalent) in tissues and milk, 2.5 hours after the last dose were: liver 0.82 mg/kg; kidney 0.11 mg/kg; muscle 0.01 mg/kg; fat 0.03 mg/kg; milk 0.008 mg/l. The 0.008 mg/l in milk from the multiple dosing is comparable to 0.009 mg/l found from the single dosing. None of the residues were identified. Summary data were provided on the identity and distribution of residues in the tissues, milk and urine of cows fed UL-14C-phenyl-labelled bitertanol at 0.2 mg/kg, but the study itself was not provided (Obrist, et al, 1983). Chickens. Laying hens (average weight 1170g) were administered single oral doses of 14C-phenyl-UL bitertanol (I:II isomer ratio 53:47) by gelatin capsule at 2.5 mg/kg body weight for excretion studies (5 trials) and blood level determinations (10 birds). Three birds were dosed daily for 5 days at a rate of 8 mg/kg body weight for tissue analyses. Food consumption data were not provided (Obrist et al, 1982). From a single dose, 92% was eliminated in the excreta within 24 hours with <0.1% in eggs (0.2% by 96 hours). Bitertanol equivalents after 4 days were 0.1 and 0.02 mg/kg in liver and kidney respectively (both 2X standard deviation) and <0.006 mg/kg in other tissues. In eggs, residues as bitertanol equivalent from a single dose ranged from <0.002 mg/kg (limit of determination) after 24 hours to 0.061 mg/kg (2X standard deviation) after 96 hours. Dose-dependent residues from the multiple doses ranged from <0.002 to 0.38 mg/kg for the same time interval. Tissue and blood plasma residues, as bitertanol equivalent, 45 minutes after the last of the 5 daily doses varied significantly (by factors of 5-20) among the 3 birds. They are shown in Table 6. The composition of the chicken tissue residues is given in Table 7, where it can be seen that bitertanol and p-hydroxy-bitertanol were by far the main residues, with the latter predominating in liver, kidney and eggs, whereas bitertanol was predominant in the other tissues. Conjugation was also greater in liver, kidney and eggs. Combined unidentified and unextracted residues accounted for up to 19% of the chicken liver residue and less in other tissues. Residues in excreta (single dose) were 69.5% p-hydroxy-bitertanol, 6.7% bitertanol, 13.7% unidentified and <3% each of other identified compounds. The same residues were identified in excreta as in tissues with the exception of dihydroxy-bitertanol, found only in the liver. Bitertanol acid and p-hydroxy-methoxy-bitertanol acid found in rat faeces (Phul and Hurley, 1983) were not identified in chicken excreta or tissues. Summary data provided to the meeting (from Obrist et al 1983) suggest that residues in cow tissues and milk are similar qualitatively, and in some respects quantitatively, to those in chicken tissues except that the dihydroxy-bitertanol found in chicken livers was reportedly not identified in dairy cow tissues or excreta. Cow urine reportedly contained bitertanol acid and p-hydroxy-bitertanol acid, also identified in rat urine (Phul et al 1979b). The cow study itself was not provided. Further evaluation must await availability of the study. Table 6. Tissue and plasma residues in chickens dosed with 14C bitertanol 14C residue Tissue Bitertanol equivalent,mg/kg % organo-soluble Mean Max liver 6.2 12.6 86 kidney 4.3 10.3 91 breast muscle 0.35 0.91 95.2 leg muscle 0.48 1.1 fat 1.4 3.01 93.2 gizzard 0.72 1.7 90.8 heart 1.3 3.2 92.9 skin 0.63 1.4 94.7 blood plasma 1.8 4.5 -- Table 7. Composition of residues in chicken tissues following administration of multiple oral doses of bitertanol-phenyl-UL 14C at 8.0 mg/kg (from Obrist and Phul, 1982) % of 14C in each tissue occurring as named compound Liver Kidney Muscle Gizzard Heart Fat Skin Eggs Bitertanol 34.7 27.2 67.8 62.4 66.0 78.2 74.9 36.6 p-Hydroxy-bitertanol Free 14.7 27.7 23.2 14.8 17.1 12.1 13.2 6.4 Conjugateda 25.4 24.8 1.5 10.4 4.4 - 4.2 37.9 Hydroxy, Methoxy-bitertanol Free 0.2 1.0 - - - - - 0.3 Conjugateda 1.5 1.2 - - - - - 0.7 Bitertanol alcohol Free 1.2 1.8 - - - - - 0.5 Conjugated 0.8 1.1 - - - - - - Dihydroxy-bitertanolb 0.9 - - - - - - - p-Hydroxy-bitertanol alcohol Free 0.4 0.9 - - - - - 0.3 Conjugateda 0.2 - - - - - - - p-Hydroxy bipbenyl 0.2 0.2 - - - - - 1œ3 Table 7. (continued) % of 14C in each tissue occurring as named compound Liver Kidney Muscle Gizzard Heart Fat Skin Eggs p,p'-Dihydroxybiphenyl 0.7 0.2 - - - - - - Unidentified residue 11.9 12.0 4.9 5.9 5.4 2.9 2.4 9.3 Unextracted 7.2 1.9 2.6 6.5 7.1 6.8 5.3 6.7 TOTALS 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 The accumulation, persistence and composition of residues of 14C-bitertanol in bluegill fish maintained in aquarium water fortified at 10 and 10 mg/l for 30 days has been investigated (Lamb, 1979). Residues on a whole fish basis reached a plateau in both cases by three days at 2.1 and 16.2 mg/kg at the 10 and 100 mg/l concentrations respectively, with maximum concentration factors of 203 and 174 respectively. Residues were quantitatively extracted with acetonitrile with 57-66% of the radioactivity in non-edible parts (head, viscera, scales) and 34-43% in edible parts. Residues were characterized by TLC as bitertanol II 40%; bitertanol I 34%; metabolite R-2 (unidentified) 7%; remaining at origin 13%; other unidentified 6%. Approximately 96% of the residues were excreted within 3 days when the fish were transferred to untreated water. In soil Adsorption/desorption. In soil adsorption/desorption studies bitertanol was shown to be strongly adsorbed to three soils in the decreasing order: sand, loam and silty clay with adsorption coefficients (K values) of 39.9, 35.8 and 19.6 (Phul and Hurley, 1979a). The data conformed to the Freundlich equation and in each case >84% was adsorbed under experimental conditions. Only 4-10% of the adsorbed compound was desorbed from sand. Leaching. In TLC leaching experiments six soil types were examined by comparing Rf values (Obrist and Thornton, 1979). The Rf values ranged from 0.04 to 0.22, which places bitertanol in the two lowest mobility ranges of the five classes which have been proposed (Helling and Turner, 1968; Helling et al 1971). This is consistent with the high adsorption determined in adsorption experiments. No significant difference was observed between the two bitertanol isomers. In aged soils (moist sandy loam) 44% of the initial radioactivity was lost during room temperature incubation for 30 days, probably by volatilization (Obrist, 1979). Less than 2% of the aged applied bitertanol was found in the leachate from 30 cm soil columns, leached at an equivalent of 13 mm/day for 45 days. Except for 55% further losses during leaching, most of the remaining residue was in the upper 1.3 cm of the column. Similar results were found in 19 studies with either Dutch polder soil or a standard loamy sand containing aged bitertanol residues leached at an equivalent of 200 mm for 48 hours or up to 500 mm in polder soil after 72 additional hours (Brennecke, 1983). Only 0.8% of the aged soil residue was found in the leachate of polder soil after 48 hours, and 3% after 120 hours. In experiments with 11 standard soils, the leachates contained <6.6% of the original radioactivity in the aged soil in all but one sample, where 48.9% was in the leachate and was identified as the bitertanol soil metabolite 4-[2-hydroxy-3,3-dimethyl-(1H-1,2,4-triazol-1-yl)butoxybenzoic acid (BUE 2684). A repeat of this experiment resulted in only 2.1% or less of aged residue in the leachate, although less leachate (approximately 400 ml) was collected in the repeat, compared with approximately 650 ml in the original experiment. No unchanged bitertanol was found in any leachate. Most leachate residues were BUE 2684 and traces of its methyl ester. The low leaching potential of bitertanol under experimental conditions was supported by 30 additional reports provided to the meeting. Soil persistence. The soil persistence of bitertanol applied to 7 soil types as the 25 WP formulation at 11 kg a.i./ha to field plots in 9 studies in scattered locations in North America was reported in 9 Mobay reports (68296-68304). Half-lives ranged from 10 to 39 days with an average of 25 days, except in one study with Oregon loam in which the half-life was 131 days. The exceptionally long half-life did not appear to be accounted for by temperature, rainfall, pH or geographical area when compared to other studies. Under laboratory aerobic conditions the half-life on silt loam ranged from 14 to 20 days (Phul and Hurley, 1979b). Degradation was slower under anaerobic conditions and there was no significant degradation in sterilized soil after 31 days, showing the importance of soil micro-organisms in bitertanol degradation. Both diasterioisomers of bitertanol were degraded at approximately the same rates. Under laboratory conditions bitertanol decomposed faster in alluvial loam soil (12 day half-life) than volcanic ash loam soil (30 days half-life), while under field conditions decomposition was faster with volcanic ash/sandy loam than with alluvial loam soil (Takase and Yoshimoto, 1980). In other laboratory tests bitertanol had a half-life of 26 days in type 1 soil and 72-days in type 2 (Mobay Report No. 10.317/18), while in field tests half-lives ranged from 19 to 27 days (Mobay Reports NO. 10.324/79, 10.325/79, 10 311/80 and 10.31280). Rotational Crops. The uptake of 14C-biphenyl ring-labelled WP bitertanol by rotational crops planted 31, 118 and 364 days after the last of eight applications to outdoor tub-planted peanuts at an equivalent of 0.56 kg a.i./ha resulted in 14C residues in leafy vegetables at harvest ranging from 0.1 mg/kg bitertanol equivalent in the 118-day planting to 0.02 mg/kg in the 364-day planting (Phul et al. 1981). In sugar beets residues were 0.38 and 0.01 mg/kg for the same plantings, and in wheat heads 0.23 and 0.01 mg/kg for 31-day and 364-day plantings. Residues in wheat straw were 1.4 mg/kg from the 31-day planting. The organo-soluble portion of the residue was <0.04 mg/kg bitertanol equivalent in all at-harvest samples except for 0.51 mg/kg in wheat straw. The benzoic acid derivative of bitertanol, BUE 2684 was identified in the 31-day wheat samples. Soil transformation. The fate of bitertanol has been investigated in silt loam soil (pH 7.4) under aerobic and anaerobic conditions and in sterile soil (Phul and Hurley, 1979b). Soil was fortified at 1 and 10 mg/kg for aerobic conditions and 1 mg/kg for anaerobic and sterile conditions. One mg/kg approximates the maximum residues expected from recommended field rates of 0.56 kg a.i./ha applied to peanuts. In the 1 mg/kg experiment, bitertanol (I + II) and total organo-solubles decreased from 98.6 and 99.8% of the total 14C on the first day to 6 and 8.4% after 121 days, while 14CO2 and unextracted residues increased from 0.8 and 4.6% on day 3 to 45.8 and 45% of the total radioactivity, respectively, after 121 days. A similar trend was observed with the 10 mg/kg fortification over the 29-day period examined. The two diasterioisomers of the bitertanol benzoic acid metabolite were observed at the 10 mg/kg fortification level (8.6% of the total radioactivity) but not at the 1 mg/kg level. Degradation was somewhat slower under anaerobic conditions than aerobic, but the distribution (bitertanol, total organic, 14CO2 and unextracted) was not markedly different at comparable intervals. Bitertanol still accounted for 95.4% of the total 14C in sterile soil after 31 days compared to 11% in non-sterile soil, indicating the importance of soil microbes in the metabolism of bitertanol; this was further demonstrated in another study (Phul et al 1979a). The identity of the microbes present in the soil of the latter study was investigated by Smedly and Hepler (1979). In other studies (Brennecke, 1982) 14C-biphenyl-labelled bitertanol was shown to be mineralized primarily into 14CO2, up to 68% in "standard soil 2.1" and 49% in Netherlands polder soil. The bitertanol benzoic acid metabolite BUE 2684 (<19.1%) and an unknown (<1%) were also found in one of 5 experiments in standard soil. Bitertanol ketone (BUE 1662) was identified by TLC at <1.7% of the total radioactivity in polder soil. In water The stability of bitertanol in sterile aqueous solutions has been studied (Nichols and Thornton, 1979). No apparent degradation was observed after thirty days in sterile aqueous solutions, buffers at pH 4, 7 and 9 and maintained at 25 and 40°C, which contained 0.25 and 2.5 mg/l of bitertanol. After 30 days, 94-109% of the bitertanol was accounted for at the higher concentrations and 85-98% at the lower level. The 85% recovery was from 0.25 mg/l at pH 9 and 40°C. The slightly lower recovery at the lower fortification level was attributed to adsorption to the vials. This is consistent with the adsorption observed at low concentration in other studies (Phul and Hurley, 1979). After using a correction factor to account for vial glass adsorption, the recovery was 100% under all conditions of this study. Additional information on the hydrolytic stability of bitertanol was provided (Stegh, 1980) but not in the working language of the meeting. Photolysis The photolysis of bitertanol has been investigated on soil and silica surfaces and in water. In the soil surface experiment, bitertanol-treated silt loam of 1 mm thickness irradiated for 35 days did not show substantially different extractability (91.5%) from dark controls (96.6%), (Sietsema, 1982). Volatile radioactivity accounted for <0.1% of the original amount. The extracted residue was shown to be bitertanol by mass spectrometry. A study on the photolysis of bitertanol on silica gel places (Stegh and Wilmes, 1982) and two reports on the photolysis in water and on silica gel (Wilmes, 1980; Stegh, 1980) were provided, but not in the working language of the meeting. Another report (Wilmes, 1981) discussed the hydrolytic behaviour and stability of bitertanol in solution. No data were provided, but reference was made to the two studies above which included data. Another bitertanol photolysis study (Sietsema, 1983) was brought to the attention of the meeting, but was not included in the data provided. METHODS OF RESIDUE ANALYSIS An analytical method developed for the analysis of triadimefon in apples (Thornton, 1977) has been used for bitertanol in apples. The sample is ground with dry ice, blended with acetone and filtered. The filter cake is blended with dichloromethane and filtered, and the combined filtrates are partitioned with water, taken to dryness and cleaned up on a Florisil column with 60:40 hexane:ethyl acetate as eluant. The eluate is concentrated and bitertanol determined by GLC using an alkali flame detector. The procedure was validated for bitertanol in apples at 0.05-0.1 mg/kg with recoveries of 86-108% and a blank of <0.01 mg/kg (Morris, 1979a) Although detection was easily attainable at 0.05 mg/kg and probably 0.01 mg/kg, chromatograms showed interferences which would make quantitation below 0.05 mg/kg questionable. Interference studies have demonstrated that the basic procedure above permits analysis of bitertanol at levels equivalent to 0.1 mg/kg in samples in the presence of tolerance levels of 75 pesticides registered in the U.S.A. for apples or peanuts (1979), five compounds registered for bananas (1980) and three compounds registered for cherries, plums, peaches and pears (1981) (Obrist and Nichols,1979). Several compounds interfered, but could be eliminated by a 1-hour reflux with 1 N NaOH and zinc or by partitioning with 0.1 N HC1. However, analytical recoveries from a crop matrix with these steps incorporated were not provided. Another analytical procedure (also suitable for other crop protectants) has been tested for bitertanol on apples, bananas, beans, currants, cherries, damsons, wheat (green, grain and straw) and soil (Specht and Tillkes, 1980). Many of the analyses in the field trials were conducted with this basic procedure. Samples are extracted with 2:1 acetone: water, partitioned with dichloromethane, cleaned up by gel permeation chromatography and analyzed by GLC utilizing a flame alkali detector. Where necessary (e.g. for straw) an additional silica gel column clean-up is used. Analytical recoveries were 74-112%, although fortification levels were described only as "0.02-0.1 ppm (lower limit of determination), and 1.0-3.0 mg/kg". For the compounds tested, the authors concluded that the lower limit of determination was 0.02 to 0.05 mg/kg for plants with >70% water content and 0.1 mg/kg for cereals and soil. The information was not sufficient for the meeting to draw a conclusion on the limit of determination. A method developed for triadimefon in soil and water (Thornton and Lloyd, 1977) is also suitable for bitertanol in soil and water with minor modifications in the GLC column stationary phase (Morris, 1979b). Water is simply extracted with chloroform, the extract is concentrated (a Florisil column clean-up is optional), and analyzed by GLC using a flame-alkali detector. Soil is extracted by refluxing with methanol/water, partitioned with chloroform, washed with water and cleaned up on a Florisil column. Recoveries from water fortified at 0.005 and 0.01 mg/l were 94% and 78% respectively with a blank of <0.001 mg/l. Recoveries from six soils fortified at 0.05-0.5 mg/kg ranged from 76 to 121% (most were >90%) with blanks <0.01 mg/kg (Morris, 1979b). Chromatograms were consistent with the data. In a similar procedure for the analysis of bitertanol and numerous other fungicides in water (Brennecke and Vogeler, 1980), extraction is with dichloromethane and clean-up by gel permeation chromatography. The two recoveries for bitertanol were 108% and 104% for 0.005 and 0.5 mg/l fortifications respectively. The lower limit of determination was said to be 0.005 mg/l, although the meeting could not confirm this with the available data. NATIONAL MAXIMUM RESIDUE LIMITS The following national MRLs were reported to the meeting. Safety interval MRL Country Crop (days) mg/kg Australia Apples 14 1.0 1) Peanuts 14 0.2 1) 2) Belgium Apples 42 0.25 Pears 42 0.25 France Apples 15 1.0 Pears 15 1.0 Germany, Federal Apples 14 Republic Cherries 21 Great Britain Apples 21 Pears 21 Greece Apples 21 Beans 4 crops 14 Pears 5 PHIs 7 Stone fruit 14 10 Israel Apples 14 Italy Pears 14 Beets 30 1.0 Fruit 1.0 Pome fruit 21 Stone fruit 21 Vegetables 14 0.5 Morocco Beans 15 Netherlands Apples 14 Blackberries 0.05 2) Cucumbers 3 Fruiting Vegetables 1.0 Melons 3 Pears 14 Peppers 3 Other commodities 03)(0.05) New Zealand Pome fruit 14 Strawberries 21 Safety interval MRL Country Crop (days) mg/kg South Africa Apricots 56 0.5 Beans 28 0.1 Beans (fodder) 42 Peaches 56 0.5 Peanuts 0.05 Peanuts (fodder) 42 Plums 56 0.5 Spain Pome fruit 15 1) Stone fruit 15 1) Switzerland Pome fruit 42 0.6 Venezuela Apples 15 1.0 Broad beans 28 1.0 Peanuts 0.2 (1) Pears 15 1.0 Stone fruit 42 0.6 Yugoslavia General 28 1) = Preliminary 2) = Level at or about the limit of determination. 3) = No residues should be present. Limit of determination 0.05 mg/kg. APPRAISAL Bitertanol is a relatively new broad-spectrum fungicide introduced and being introduced in a number of countries. Its toxicology was evaluated by the 1983 JMPR which estimated a temporary ADI. The present meeting evaluated residues in food. To date only limited residue trials data have been provided and these have been evaluated. Data were insufficient to estimate residue levels in cucumbers and beans, but temporary limits were estimated for several commodities. The fate of bitertanol has been investigated in plants (apples and peanuts), animals, soil, light and water. In the plant studies bitertanol penetration from surface applications was minimal and there was little volatility. Residues are taken up by roots, although translocation into the plant is relatively low. There are some measurable but not major differences in absorption, translocation and plant metabolism rates of the two diasterioisomeric forms of bitertanol. Bitertanol is by far the main plant residue, with low levels of its ketone and 4-hydroxybiphenyl. In apples, most of the residue in the peel. The fate of residues in non-food animals was evaluated by the 1983 JMPR. The present meeting evaluated metabolism studies on poultry, cows and fish. Bitertanol is metabolized substantially more in animals than in plants. The products are rapidly excreted but low residues can occur in milk, eggs and tissues. These are predominantly in the liver and kidney, as demonstrated with exaggerated feeding levels. Bitertanol and p-hydroxy-bitertanol are by far the predominant residues in chicken tissues and eggs and are reported to be the major residues in cow tissues and milk, although other metabolites occur at significant levels in the latter. Although cow metabolism studies were available to the meeting the only one detailing the distribution of identified residues was received too late for evaluation, until it has been reviewed at a future meeting, no final conclusion can be drawn on the adequacy of information on the fate of residues in animals. The available data indicate that metabolism appears to be similar among rats, poultry and cows. Conventional feeding studies on poultry and ruminants, an analytical method for the analysis of bitertanol in animal products, and information on the fate of residues in apples during processing were all received too late for evaluation. Extensive information was available to the meeting on the fate of bitertanol residues in soil, in which it is of low mobility, and some data were available on water stability and photolysis. The water and photolysis data available in the working language of the meeting indicate a high degree of stability in each case. Other studies provided, but not in the working language of the meeting, were not evaluated. Several analytical methods utilizing solvent extraction, GPC or Florisil clean-up followed by gas chromatography are available for determining residues in crops, soil and water. Further confirmation of the limit of determination is desirable. No information was provided on the fate of residues in storage, in processing, in commerce or at consumption. The meeting examined residue data from supervised trials reflecting good agricultural practice on a number of crops and was able to estimate the maximum residue levels which were likely to occur when bitertanol was used in practice and when the reported intervals between the last application and harvest were observed. These levels refer only to the parent compound. RECOMMENDATIONS COMMODITY MRL (mg/kg)1 Pre-harvest interval on which recommendations are based Apples 2 14 Stone fruit 1 21 Bananas 0.5 0 Oats: grain 0.1* ) forage 0.1* ) straw 0.1* ) Rye: grain 0.1* ) forage 0.1* ) straw 0.1* ) from seed treatment Wheat: grain 0.1* ) forage 0.1* ) straw 0.1* ) * At or about the limit of determination. 1 Temporary irrespective of the status of the ADI. FURTHER WORK OR INFORMATION 1. Except for bananas for which substantial data reflecting approved uses were available, additional information on good agricultural practice and residue data reflecting approved uses for all commodities for which temporary limits have been estimated. Residue data should be from countries from which details of approved uses have been or will be provided, or those in close proximity. 2. Additional plant metabolism studies. 3. Additional residue data reflecting good agricultural practice for additional plant products likely to be used as animal feeds. Desirable 1. Analytical recoveries through the Thornton analytical method utilizing the NaOH and HC1 steps designed to remove interferences. 2. Confirmation of limits of determination for the Specht method. 3. Information on the stability of residues in crops during cold storage. 4. Additional national maximum residue limits and safety intervals. 5. Photolysis/hydrolysis studies in English (Stegh and Wilmes, 1982; Wilmes, 1980; Stegh 1980 and Sietsema, 1983). REFERENCES Mobay Reports are unpublished reports prepared by the Research and Development Dept., Agricultural Chemicals Division, Mobay Chemical Corporation, Kansas City, Mo. 64 120, USA. Nitokuno Reports are unpublished reports prepared by Nihon Tokushu Noyaku Seizo KK., No. 8, 2-chome, Nihonbashi, Chuo-ku, Tokyo, Japan. Bayer Reports: Leaching in Soil 10.314 - 10.316/78 10.342 - 10.334/82 10.318 - 10.320/78 10.348 - 10.350/82a 10.334 - 10.336/80 10.374 - 10.376/82 10.334A - 10.346A/8010.379 - 10.381/82b 10.309 - 10.311/81 10.388 - 10.390/82b Soil Persistence 10.317/78 10.324/7910.3257910.311/8010.312/80 68 296 68 29868 30068 30268 304 68 297 68 29968 30168 303 Brennecke, R. Leaching characteristics of Aged [biphenyl-UL-14C] 1983 bitertanol Soil Residues. Unpublished Bayer Report RA 981/209B, October 1983. Brennecke, R. and Vogeler, K. Method for the Gas Chromatographic 1982 Determination of Residues of Various Fungicides in Water. Bayer AG, Pflanzenschutz-Anwendungstechnik, unpublished Report RA-80, January, 1982. Helling, C.S. and Turner, B.C. Pesticide Mobility: Determination by 1968 Soil Thin-Layer Chromatography, Science 162, 562 (1968). Helling, C.S., Kearney, P.C. and Alexander, M. Behaviour of Pesticides 1971 in soils, Advan. Agron. 23; 147, 1971. Lamb, D.W., BAYCOR-14C Accumulation and Persistence of Residues in 1979 Bluegill. Mobay Report No. 68 343 December 13, 1979. Mobay, Recovery Reports, Apples 68 249, Soil and Water 69 250. Morris, R.A. Recovery of Baycor from Apples. Unpublished Mobay Report 1979a 68 249, November 19, 1979. Morris, R.A. Recovery of Baycor from Soil and Water. Unpublished Mobay 1979b Report 68 250, 1979. Nichols, S.S. and Thornton, J.S. The Behaviour of BAYCOR in Sterile 1979 Aqueous Solutions. Mobay Report No. 68 273. October 22, 1979. Christ, J.J. Leaching Characteristics of Aged BAYCOR Soil Residues 1979a Mobay Report No. 68 271. September 25, 1979. Obrist, J.J. and Nichols, S.S. An Interference Study for the BAYCOR 1979 Residue Method for Apples and Peanuts. Mobay Report No. 68 311. November 27, 1979. Obrist, J.J., Phul, R.J. and Thornton, J.S. Excretion and Tissue 1981 Levels of 14C Following Oral Administration of BAYCOR- Phenyl-UL-14C to a Dairy Cow. Mobay Report NO. 69 400. March 24, 1981. Obrist, J.J., Phul, R.J. and Thornton, J.S. The Metabolism and 1982 Excretion of BAYCOR-Phenyl-UL-14C by Chickens. Mobay Report No 82614. October 8, 1982. Obrist, J.J., Phul R.J. and Thornton, J.S. The Metabolism and 1983 Excretion of BAYCOR-Phenyl-UL-14C Following Oral Administration to a Dairy Cow. Mobay Report, Manuscript in Preparation. 1983. Obrist, J.J. and Thornton, J.S. Soil Thin-Layer Mobility of BAYCOR, 1979 BAYTAN, DYRENE, and PEROPAL. Mobay Report No. 68 272. October 22, 1979. Phul, R.J. and Hurley, J.B. Soil Adsorption and Desorption of BAYCOR. 1979a Mobay Report No. 68 003. July 18, 1979. Phul, R.J. and Hurley, J.B. The Metabolism and Degradation of BAYCOR- 1979b Biphenyl-UL-14C on Soil. Mobay Report NO. 67 998. August 6, 1979. Phul, R.J. and Hurley, J.B. The Metabolism of BAYCOR-Biphenyl-UL-14C 1979c in Apple Fruit. Mobay Report No. 68 305. November 5, 1979, Revised February 3, 1981A. Phul, R.J. and Hurley, J.B. Metabolism of BAYCOR-UL-14C in Peanut 1981 Plants. Mobay Report No. 69 310. October 23, 1979, Revised June 18, 1981b. Phul, R.J. and Hurley, J.B. The Absorption, Excretion and Metabolism 1983 of BAYCOR-Phenyl-UL-14C by Rats. Mobay Report, Manuscript in Preparation, 1983. Phul, R.J., Hurley, J.B. and Close, C.L. Total Radioactive Residues in 1981 Rotational Crops Following a Target Drop of Peanuts Treated with BAYCOR-14C. Mobay Report No.80 059. September 11, 1981. Phul, R.J., Hurley, J.B. and Thornton, J.S. The effect of Soil 1979a Microorganisms on the Degradation of BAYCOR. Mobay Report No. 69 012. July 2, 1979. Phul, R.J., Obrist, J.J. and Pither, K.M. The excretion of 1979b BAYCOR-Phenyl-UL-14C Following Administration of a Single Oral Dose to Rats. Mobay Report NO. 68 307. November 19, 1979. Scheinpflug, H. and van den Boom, T. BAYCOR, A New Fungicide for 1981 Tropical and Subtropical Crops. PflanzenschutzNachrichten Bayer 34, 8-28.1981. Sietsema, W.K. Photodecomposition of BAYCOR on a Soil Surface. Mobay 1982 Report No. 82 572. November 16, 1982. Sietsema, W.K. Photodegradation of BAYCOR in Water. Mobay Report (in 1983 Preparation). 1983. Smedly, L.A. and Hepler, D.I. Identification of Microorganisms in 1979 Samples of Kansas Loam Soil. Mobay Report No. 67 814. May 1, 1979. Specht, W. and Tillkes, M. Determination of Agrochemicals After 1980 Clean-up using Gel Permeation Chromatography and Mini-Silica Gel Column Chromatography. Pflanzenschutz-Nachrichten Bayer 33, 61 - 85. 1980. Stegh, R. Versuche zum Abbau von KWG 0599 in wässerigen Salzlosungen. 1980 Bayer Experimental Notice. January 24, 1980. Stegh, R. and Wilmes, R. Light Induced Degradation of Agrochemical 1982 Parent Compounds on Silica Gel as a Model for Degradation on Soil. Bayer Ag. Pflanzenschutz-Anwendungstechnik unpublished report PF1666. February 10, 1982. Takase, I. and Yoshimoto, Y. Residues of KWG 0599 in Upland Soils 1980 Under Laboratory and Field Conditions. Nitokuno Report No. 1134. December 5, 1980. Thornton, J.S. A Gas Chromatographic Method for BAYLETON and its 1977a Metabolite in Apples. Mobay Report No. 54 166. December 30, 1977. Thornton, J.S. A Gas Chromatographic Method for BAYLETON and KWG 0599 1977 in Soil and Water. Mobay Report NO. 51 231. January 31, 1977. Wilmes, R. Preliminary Studies on Stability to Light. Bayer Pharma 1980 Unpublished Report, 1980. Wilmes, R. Abiotic Degradation of Bitertanol. Bayer summary Report. 1981 March 31, 1981.
See Also: Toxicological Abbreviations Bitertanol (Pesticide residues in food: 1983 evaluations) Bitertanol (Pesticide residues in food: 1987 evaluations Part II Toxicology) Bitertanol (JMPR Evaluations 1998 Part II Toxicological)