MANCOZEB (50) Mancozeb was scheduled for re-evaluation in 1993 in the CCPR periodic review programme.

Transcription

1 5 MANCOZEB (50) EXPLANATION Mancozeb was originally evaluated in 96, and has been reviewed several times since. MRLs for dithiocarbamate fungicides were consolidated by the CCPR into a combined list in 9 under the heading DITHIOCARBAMATES (5). Mancozeb was scheduled for re-evaluation in 99 in the CCPR periodic review programme. The Meeting was provided with extensive information on use patterns, supervised residues trials, fate of residues, and miscellaneous studies by the Mancozeb Task Force and basic manufacturers. Information was also supplied by Australia, Canada, Finland, Germany and Spain. IDENTITY ISO common name: Chemical name: mancozeb IUPAC manganese ethylenebis(dithiocarbamate)(polymeric) complex with zinc salt CA [[,-ethanediylbis[carbamodithioato]](-)]manganese mixture with [[,-ethanediylbis[carbamodithioato]](-)]zinc CAS No: CIPAC No: CIPAC-4 Synonyms: Dithane M-45 R, Penncozeb, Manzate R 00 Structural formula: [-Mn(:S)NHCHCHNHC(:S)S-]x Zny where x/y = A polymer coordination complex of zinc and manganese ethylenebis(dithiocarbamate) containing 0% manganese and.5% zinc. Molecular weight per monomer unit:. Physical and chemical properties Pure active ingredient Vapour pressure: Solubility: Hydrolysis: Negligible Water, 6 mg/l at 5 C (Schweitzer, 98). Essentially insoluble in most organic solvents. Half-lives for aqueous hydrolysis of mg/l suspended in distilled water:

2 5 mancozeb ph 5: 6 hours ph : 55 hours ph 9: 6 hours Technical material Dithane M-45 is a polymeric, non-crystalline solid, a light yellow free-flowing powder with decomposition occurring at 50 C, a slight sulphurous odour, and an active ingredient content of about 80%. Bulk density: 0.4 (loose), 0.48 (packed). Stability: Stable in the absence of moisture, heat, flame, oxidising agents and acids. Decomposed by water under acidic conditions. Thermal decomposition may yield carbon disulphide and hydrogen sulphide. USE PATTERN Mancozeb is a protective fungicide effective against a wide range of foliar fungal diseases. It is registered for use in many countries on horticultural and agricultural food crops as well as on ornamentals and tobacco, and in forestry. The registered uses of mancozeb are summarized in Tables -. Table. Table. Table. Table 4. Table 5. Table 6. Table. Table 8. Table 9. Table. Table. Citrus fruits. Pome fruits. Stone fruits. Berries and other small fruits. Tropical and subtropical fruits. Bulb vegetables and root and tuber vegetables. Brassica vegetables, leafy vegetables, and stalk and stem vegetables Fruiting vegetables. Legume vegetables. Cereals, tree-nuts and oilseed crops. Miscellaneous crops, including hops, coffee and tea. Table. Registered uses of mancozeb on citrus fruits. CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Citrus fruits Australia Citrus fruits Brazil 4 0. Citrus fruits Chile Citrus fruits Japan Citrus fruits Korea Citrus fruits Spain 0. 5 Citrus fruits Taiwan Table. Registered uses of mancozeb on pome fruits. CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Apple Australia Apple Brazil 0.6 Apple Canada Apple Chile Apple France Apple Japan

3 mancozeb 5 CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Apple Korea Apple Netherlands Apple Portugal Apple Spain Apple UK Apple USA not past bloom Apple USA. Crab-apple USA not past bloom Crab-apple USA. Medlar Spain Pear Australia Pear Brazil 0.6 Pear Canada Pear Chile Pear Japan Pear Korea Pear Netherlands Pear Portugal Pear UK Pear USA not past bloom Pear USA. Pome fruits Austria Pome fruits Belgium Pome fruits Bulgaria Pome fruits Eire.6 Pome fruits France 0.6 Pome fruits Germany Pome fruits Greece Pome fruits Hungary Pome fruits Italy. 0.6 Pome fruits Netherlands Pome fruits Romania Pome fruits Switzerland Pome fruits Turkey Pome fruits UK Quince USA not past bloom Quince USA. Table. Registered uses of mancozeb on stone fruits. CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Apricot Australia Apricot Chile Cherry Australia Cherry France Po 0.6 Nectarine Australia Nectarine Chile Peach Australia Peach Brazil 0.6 Peach Chile Peach Spain Plum Australia Plum Brazil Plum Chile Plum France Stone fruits Austria Stone fruits Bulgaria Stone fruits Germany Stone fruits Hungary Stone fruits Portugal Stone fruits Romania Stone fruits Spain Stone fruits Switzerland Po: Post-harvest.

4 54 mancozeb Table 4. Registered uses of mancozeb on berries and other small fruits. CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. applicn. kg ai/hl no. kg ai/ha Black currants Eire 8.4 Black currants and gooseberries Finland 0.6 Black currants and gooseberries UK Cranberry USA Grapes Australia Grapes Austria Grapes Brazil Grapes Bulgaria Grapes Canada Grapes Chile Grapes Columbia Grapes France then.4 0 Grapes Germany Grapes Greece Grapes Hungary Grapes Italy Grapes Japan fg Grapes Korea? Grapes Philippines Grapes Romania Grapes Spain 4.4 Grapes Switzerland st postblossom Grapes Taiwan.0 0. Grapes Turkey Grapes USA Strawberry Chile Strawberry France 5.6 Strawberry Japan 6g Strawberry Spain Vine Portugal T 45, W 5 T: table grapes; W: wine grapes. g: use in glasshouse; fg: use in field and glasshouse. Table 5. Registered uses of mancozeb on tropical and subtropical fruits. CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Avocado Brazil 0.6 Banana Australia oil Banana Brazil Banana Columbia Banana Philippines a Banana Taiwan a Banana USA. 0 Fig Brazil Mango Australia Mango Brazil Mango Malaysia? Mango Philippines Mango Taiwan Olive Greece Olive Spain Papaya Philippines Papaya USA. 0 Passion fruit Australia Persimmon Japan Aerial application. Table 6. Registered uses of mancozeb on bulb vegetables and root and tuber

5 mancozeb 55 vegetables. CROP COUNTRY APPLICATION Max no. Rate per applicn. kg ai/ha Spray concn. kg ai/hl PHI, days Beet Brazil Beet Columbia Beetroot Australia Carrot Australia Carrot Brazil Carrot Canada Carrot Columbia Carrot Portugal Carrot Switzerland.0 0. Carrot UK.4-.8 Celeriac Hungary Chinese yam Japan Garlic Philippines Garlic Brazil Garlic Chile Garlic France 8.6, 0? Garlic Japan Garlic Portugal Garlic Spain Ginseng Canada Leek Belgium 0. Leek Chile Leek France.6 60 Leek Japan Leek Philippines Lotus (East Indian) Japan fg..8 Onion Australia Onion Belgium 8.4 Onion Brazil Onion Canada Onion Chile Onion France Onion Greece Onion Hungary Onion Japan Onion Korea.9 0. Onion Netherlands Onion Philippines Onion Portugal Onion Romania Onion Spain Onion Sweden Onion Switzerland Onion Turkey Onion UK.8-. Onion USA. Potato Australia Potato Austria Potato Bangladesh Potato Belgium.5-. Potato Brazil Potato Bulgaria Potato Canada Potato Chile Potato Columbia Potato Denmark Potato Eire.8 Potato Finland Potato France.6 Potato Germany st Potato Germany 5. Potato Greece Potato Hungary Potato Indonesia Potato Italy Potato Japan Potato Korea.9 0. Potato Netherlands Potato Norway Potato Philippines

6 56 mancozeb CROP COUNTRY APPLICATION Max no. Rate per applicn. kg ai/ha Spray concn. kg ai/hl PHI, days Potato Portugal Potato Romania Potato Spain Potato Sweden Potato Switzerland Potato Turkey Potato UK.4 Potato USA.8 Shallot Belgium 8.4 Shallot France 8 0 Shallot Indonesia Shallot Philippines Sugar beet Canada 5.8 Sugar beet Chile Sugar beet France. 0 Sugar beet Japan Sugar beet Spain.6 Sugar beet USA.8 Use in field and glasshouse. Seed treatment Table. Registered uses of mancozeb on brassica vegetables, leafy vegetables and stalk and stem vegetables. CROP COUNTRY APPLICATION PHI, days

7 mancozeb 5 Max no. Rate per applicn. kg ai/ha Spray concn. kg ai/hl Artichoke Spain Asparagus Belgium 8.8 Asparagus France Asparagus Germany early applic Asparagus Netherlands Asparagus Spain Asparagus USA Asparagus USA (CA, AZ) 4.8 Broccoli Australia Broccoli Brazil Broccoli Chile Broccoli Philippines Brussels sprouts Australia Brussels sprouts Chile Cabbage Australia Cabbage Brazil Cabbage Chile Cabbage Columbia Cabbage Japan Cabbage Malaysia Cabbage Philippines Cauliflower Australia Cauliflower Brazil Cauliflower Chile Cauliflower Malaysia Cauliflower Philippines Celery Australia Celery Belgium Celery Canada Celery Chile Celery Columbia Celery France Celery Philippines Celery Portugal fg Celery Switzerland Celery UK.8 Chard Australia Chinese cabbage Indonesia Chinese cabbage Japan Cole Portugal fg Endive France 5.6 root dip Kale Brazil Lettuce Australia Lettuce Chile Lettuce Columbia Lettuce France.4 Lettuce Malaysia Lettuce Portugal 4fg Lettuce Spain 4fg Lettuce Switzerland 5fg Lettuce UK 8. Lettuce UK g. Rhubarb Australia Spinach Australia Spinach Columbia Spinach Malaysia g: use in glasshouse; fg: use in field and glasshouse. Table 8. Registered uses of mancozeb on fruiting vegetables. CROP COUNTRY APPLICATION PHI, days

8 58 mancozeb Max no. Rate per applicn. kg ai/ha Spray concn. kg ai/hl Cantaloupe Australia Cantaloupe Canada Cantaloupe Columbia Cantaloupe Philippines Cantaloupe USA 8. 5 Cucumber Australia Cucumber Brazil Cucumber Canada Cucumber Chile Cucumber Columbia Cucumber Japan g Cucumber Korea.4 0. Cucumber Philippines Cucumber Spain Cucumber USA 8. 5 Cucurbits Belgium fg 0. Cucurbits France.6 Cucurbits Greece.0 0. Cucurbits Malaysia Cucurbits Turkey fg Eggplant Brazil Eggplant Columbia Eggplant Greece Eggplant Philippines Fruiting vegetables, edible peel Austria Fruiting vegetables, edible peel Romania Melon Australia Melon Canada Melon Chile Melon Japan 5g Melon Philippines Melon Portugal 4fg Melon Spain Melon Turkey Melon USA 8. 5 Peppers Brazil Peppers Columbia Peppers Greece Peppers Malaysia Peppers, chilli Philippines Peppers Portugal 4fg Peppers Spain Pumpkin Australia Pumpkin Brazil Pumpkin Canada Roselle Indonesia 6.-. Squash Australia Squash Canada Squash Chile Squash Japan Squash Philippines Summer squash Australia Summer squash USA 8. 5 Sweet corn Philippines Sweet corn USA 5. Tomato Australia Tomato Belgium 0.6 Tomato Brazil Tomato Bulgaria Tomato Canada fg Tomato Chile Tomato Columbia Tomato Eire.-. 5 Tomato France.6 5 Tomato Germany Tomato Greece Tomato Hungary Tomato Indonesia.-.9 Tomato Italy Tomato Japan 5g Tomato Malaysia 0.4 Tomato Philippines Tomato Portugal 4fg.6 0.6

9 mancozeb 59 CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. applicn. kg ai/hl no. kg ai/ha Tomato Spain Tomato Switzerland Tomato Taiwan.0 0. Tomato Turkey 6fg Tomato UK Tomato USA Watermelon Canada Watermelon Chile Watermelon Columbia Watermelon Japan Watermelon Korea Watermelon Philippines Watermelon Portugal 4fg Watermelon Turkey Watermelon USA 8. 5 g: use in glasshouse; fg: use in field and glasshouse. Table 9. Registered uses of mancozeb on legume vegetables. CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Azuki bean Japan Beans Australia Beans Belgium 0.6 Beans Brazil Beans Chile Beans France.6 Beans Greece Beans Malaysia Beans Philippines Beans Portugal Beans Spain Broad bean Australia Chickpea Chile French bean Brazil Green bean Columbia Green pea Chile Kidney bean Japan Lentil Chile Mung bean Philippines Peas Brazil Peas Columbia Peas France.6 Peas Malaysia Peas Philippines Peas Portugal Peas Spain Soya bean Australia 4.8 Soya bean Hungary Soya bean Philippines Soya bean Taiwan Table. Registered uses of mancozeb on cereals, tree-nuts and oilseed crops. CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Almond Australia Barley Brazil.0 Barley Canada st Barley Chile Barley Columbia.0-0 Barley Eire.0 6 Barley UK.6 gs

10 580 mancozeb CROP COUNTRY APPLICATION PHI, days Max Rate per Spray concn. no. applicn. kg ai/hl kg ai/ha Barley USA.8 6 Cereals Chile st Cereals Spain. Cereals UK Coconut Indonesia Cotton Philippines Cotton USA Flax Canada st Maize Canada st Maize USA. 40 Oats Canada st Oats Chile Oats Eire.0 6 Oats USA.8 6 Peanut Australia Peanut Columbia Peanut Indonesia Peanut Korea.4 Peanut Malaysia Peanut Philippines Peanut Taiwan Peanut Turkey Peanut USA 8.8 Rice Brazil.6 5 Rice Bulgaria Rice Columbia Rice Philippines Rice Taiwan Rye Chile Rye Eire.0 6 Rye USA.8 6 Sesame Korea.4 Sorghum Columbia Wheat Belgium.6 Wheat Brazil.0 Wheat Canada.8 40 Wheat Canada st Wheat Chile Wheat Columbia.0-0 Wheat Eire.0 6 Wheat France. Wheat Netherlands Wheat Portugal. 5 Wheat Romania Wheat UK.6 gs Wheat USA.8 6 Winter oilseed rape UK.4 gs st: seed treatment. gs: growth stage restriction. Table. Registered uses of mancozeb on miscellaneous crops including hops, coffee and tea. CROP COUNTRY APPLICATION PHI, days

11 mancozeb 58 Max no. Rate per applicn. kg ai/ha Spray concn. kg ai/hl Cacao Indonesia Cacao Brazil Coffee Brazil Coffee Columbia Coffee Indonesia Fennel USA 8.8 Hops Belgium Hops Germany Hops Hungary Hops Turkey Tea Indonesia RESIDUES RESULTING FROM SUPERVISED TRIALS Residue data from supervised trials on horticultural and agricultural crops are summarized in Tables to 50. Table. Citrus fruits. Australia, Brazil, Japan and Spain. Table. Citrus fruits. USA. Table. Pome fruits. Australia, Austria, Belgium, Brazil, Hungary, Japan and The Netherlands. Table 5. Pome fruits. France. Table 6. Pome fruits. Germany. Table. Pome fruits. Italy. Table 8. Apples. UK. Table 9. Pome fruits. USA. Table 0. Stone fruits. Australia, Brazil and France. Table. Berry fruits. Australia, Brazil, Hungary, Japan, Portugal and Spain. Table. Cranberries. USA. Table. Grapes. France. Table 4. Grapes. Italy. Table 5. Black currants. UK. Table 6. Tropical and subtropical fruits. Australia, Brazil, Honduras and Japan. Table. Tropical fruits. USA. Table. Bulb vegetables. Australia, Brazil, Finland, France, Japan and The Netherlands. Table 9. Onions. USA. Table 0. Brassica vegetables. Brazil, Germany, Japan and Spain. Table. Cucurbits. Australia, Brazil, France, Germany and Japan. Table. Cucumbers. Australia, Brazil, France, Germany, Japan and Spain. Table. Cucurbits. USA. Table 4. Fruiting vegetables other than cucurbits. Brazil, France, Germany, Italy, Japan, The Netherlands, Portugal and Spain. Table 5. Fruiting vegetables other than cucurbits. USA. Table 6. Leafy vegetables. Brazil and Spain. Table. Legume vegetables. Australia, Brazil, France, Japan, The Netherlands and Spain. Table 8. Root and tuber vegetables. Australia, Brazil, Finland, France, Germany, Italy, Japan, The Netherlands and UK. Table 9. Potatoes. Germany. Table 40. Root and tuber vegetables. USA. Table 4. Stalk and stem vegetables. Australia, France and The Netherlands. Table 4. Stalk and stem vegetables. USA. Table 4. Cereal grains. Brazil, Canada, France, Germany, The Netherlands, Spain and UK. Table 44. Cereal grains. USA. Table 45. Dry hops. Germany. Table 46. Oilseeds. Australia, France, The Netherlands and USA. Table 4. Tree nuts, cocoa and coffee. Australia, Brazil and USA. Table 48. Cereal straws. Canada, France, Germany, The Netherlands and UK. Table 49. Cereal fodder and straw. USA. Table 50. Legume animal feeds and miscellaneous fodder and forage crops. Australia, Italy, Japan and USA.

12 58 mancozeb The information supplied was sometimes only in summary form, but most trials were fully or adequately described. Some residues were adjusted for analytical recoveries and some were not; in summary sheets very often no statement was made either way. Analytical recoveries were mostly high (>80%) for both dithiocarbamates and ETU, so adjustment of results should not influence interpretations. US results were adjusted; Australian were not. Attention is drawn to cases where analytical recoveries were less than 0%. In the French trials of 990, recoveries from crops and wine ( tests) ranged from 46 to %, with a mean recovery of 86%, at concentrations of mg/kg (Wasser, 99n). In the French trials of 99, recoveries from 8 crops and wine ( tests) ranged from 4 to 88%, with a mean recovery of 68%, at concentrations of mg/kg (Mellet, 99a). Dithiocarbamate residues are expressed as mg CS /kg throughout the Tables and text. EBDC is used as an abbreviation for ethylenebis(dithiocarbamate)s in the Tables. Where residues were not detected, data are recorded in the Tables as less than the limit of determination (LOD), e.g. mg/kg. Residues have generally been rounded to significant figures or, near the LOD, to significant figure. When residues were detected in control samples they are recorded in the Tables. In the majority of cases no residues were detected in control samples; these are not recorded. Plot sizes in the Australian trials were usually 8-0 m of - rows (4 replicates) for row crops and tree (4 replicates) for tree crops. Mancozeb was applied with a hand-held high-volume sprayer or a self-propelled small-plot sprayer. Analytical recoveries exceeded 0% except in the following trials: peaches (AUE-9-0, Table 0) dithiocarbamates 6%; bananas (495/89, Table 6) ETU 55-%, dithiocarbamates 58%; watermelon (AUK-9-005, Table ) dithiocarbamates 60%; beans (/88/5, Table ) ETU 5-5%, dithiocarbamates in straw 6%. Mancozeb was applied by a tractor-mounted sprayer in the Canadian trials on onions and lettuce. Plot size was the equivalent of 50- m of row. Plot sizes in the Netherlands trials (PH references) were apples 5 trees, barley 5 m, beans 0 m, onions.6-0 m, potatoes 0-5 m, wheat 5 m - ha. Mancozeb was applied to crops in these trials with a propanepressure knapsack (beans, onions, potato, tomatoes, wheat), a knapsack mist blower (apples) and a motorised compressed air sprayer (potato). Recoveries of dithiocarbamates were all satisfactory. ETU recoveries were sometimes low (<0%). Low recoveries in individual tests were reported in the analysis of apples, barley straw, onions, potatoes, tomatoes and wheat. Dithiocarbamate residues or apparent residues were detected in untreated control samples in US trials on citrus (Table ), apples (Table 9), cranberries (Table ), bananas and papayas (Table ), onions (Table 9), cucurbits (Table ), tomatoes (Table 5), sugar beet (Table 40), celery (Table 4), cereal grains (Table 44), cereal fodder (Table 49) and sugar beet tops (Table 50). Control samples also occasionally showed low residues of ETU: citrus (Table ), cranberries (Table ) and onions (Table 9). In the extensive series of French trials dithiocarbamate or apparent dithiocarbamate residues were detected in untreated control samples. Instances are recorded in the Tables: pome fruits (Table 5), plums (Table 0), grapes (Table ), bulb vegetables (Table ), tomatoes (Table 4), carrots and potatoes (Table 8), asparagus (Table 4), cereal grains (Table 4) and cereal fodder (Table 48). Contamination could have occurred in some cases from a high-level sample during handling or shipment (Wasser, 99n). A coextractive from

13 mancozeb 58 carrots, tomatoes and asparagus may have contributed to a false colour in the Cullen's reagent in the analysis leading to a dithiocarbamate reading for a control sample (Wasser, 99d and related references). Mellet (99d) reported that the extraction-distillation step of potato analysis produces a yellow colour in the sodium hydroxide trap that fades after a few minutes. An excess of that contamination might account for apparent residues in some of the untreated potato samples. Similar explanations were provided for cereal grain and straw, and garlic. ETU was detected (about 0.0 mg/kg) in samples of orange concentrate made from untreated fruit in Brazilian orange trials ( 8-09, Table ). There was some detection of dithiocarbamates in control apples from the Belgian trials (Table ) at mg/kg, which is near the limit of determination. In the UK apple trials (R.6, Table 8) treated areas were - ha in the first four studies, where samples were taken for residue decline measurement. Samples were also taken from commercial orchards with recorded spray programmes (R.6, Table 8). Mancozeb was applied by air-blast equipment in the US apple trials (ETU 9-0, Table 9). The plot size was 8 trees. Cranberries in the US trials (Table ) were grown on plots of -40 m, and were hand-sprayed. In five separate experiments in France in 96 (Haines, 98), wine was produced from grapes treated with mancozeb (6-9 times, final application kg ai/ha) and harvested 50-0 days after the final application. Neither dithiocarbamates (<0.05 mg/kg as CS ) nor ETU ( mg/kg) were detected in the wine. In a similar set of experiments with wines in Germany (Haines, 99) dithiocarbamate residues were not detected (<0.05 mg/kg as CS ) but ETU was detected in one wine at 0. mg/kg and identified by GC-MS. In this case the final mancozeb application had been at. kg ai/ha days before harvest. Samples of wine, 989 vintage ready for commercialisation, were taken from two different French vineyards with accurately recorded pesticide use (R8.85, R8.8, Table ). Dithiocarbamate residues were not detected (Wasser, 99m). The results agreed with a previous similar investigation in 988 reported by Wasser (99l) on three French vineyards (R8.8, R8.89, R9., Table ). UK residue data on black currants are summarized in Table 5. The first three trials were supervised trials on 5 m row plots (4 replicates) with application by a motorised knapsack sprayer. The remainder were grower trials on areas of approximately ha. Analytical recoveries of dithiocarbamates were low (6%). Papayas in the US (Florida) trials were on. ha plots and were ground-sprayed (Table ). The trials in Hawaii were on a smaller scale, 00 m plot, and the papayas were hand-sprayed. The plot size was.-4.4 ha for three of the four onion trials in the USA where mancozeb was applied by aerial and ground equipment (Table 9). The plot sizes in the remaining trials were 5-0 m. Cucurbit vegetables in the US trials (Table ) were mostly sprayed with ground equipment (some hand-spraying). The plot size was in the 5-45 m range. Mellet (99j) reported that an apparent dithiocarbamate residue of 0. mg/kg in untreated tomatoes from a Spanish trial (R80.0, Table 4) could be due to interference in the analytical method by a co-extractive forming a yellow colour with Cullen's reagent, or contamination may have occurred during handling or shipping samples.

14 584 mancozeb Plants in the first five tomato trials listed in Table 5 were handsprayed on m plots. Carrot trials in France (R./4, Table 8) in 990 were carried out on plots of. m. A series of trials on potatoes in 95-6 in 9 States of the USA (Table 40) showed that dithiocarbamate residues were rarely detectable in potatoes even when mancozeb was used at exaggerated application rates. Analytical recoveries for ETU were sometimes down to 60%, but ETU was not detectable in these trials. Plot sizes ranged from 5 m for ground-sprayed carrots to. ha for aerial spraying. Four of the sugar beet trials were on -4 ha plots, while two trials were on 40 ha fields. ETU residues were not detected ( mg/kg) in cooked and processed products (baked potato skin, baked potato, boiled potato, chips, flakes and French fries) produced from potatoes in trials 5-5-0, and (Table 40). ETU residues were not detected ( mg/kg) in cooked and processed products (chips, flakes and French fries) produced from potatoes in trials , and (Table 40). Mancozeb was aerially and ground-applied to celery in US trials (Table 4), with three trials on 4 ha plots and one (85-065) on 80 ha. Detection of apparent dithiocarbamate residues in control wheat straw (Table 48) from the Canadian trials may have been interference in the analytical method by hydrogen sulphide (Frank et al., 986). Wheat trials were conducted in 95 and 98 in 5 different States of the USA with 8 different wheat varieties (Tables 44, 49). Dithiocarbamate residues were detected in some control grain and straw samples, probably as a result of drift to the control plots. Dithiocarbamate residues were detected in bran, flour and bread prepared from control wheat (8-06, 8-068, 8-04, 8-049, 8-040, 8-046, 8-04, 8-0, 8-0). Details of the milling are recorded in Table 5. The US barley trials (Tables 44, 49) in Idaho and Washington State were on 5 ha plots. The other two trials were on 0 m plots. Analytical recoveries were lower than usual for mancozeb in peanuts 69-8% and peanut hay 68-5%, and for ETU in peanuts 5-% and peanut hay 56-58% in a US trial (4--0, Table 46, 50). Mancozeb recoveries were 58-90% from peanuts in trial (Table 46). Table. Mancozeb residues (as CS ) in citrus fruits from supervised trials in Australia, Brazil, Japan and Spain. Underlined residues are from treatments according to GAP. CROP Country, year (Variety) Form Application kg ai/ha kg ai/hl Residues, mg/kg No. EBDC as CS ETU CITRUS "SUMMER" ORANGES, SOUR Japan, 990 (Kawanoamanatsu) Japan, 990 (Amanatsu) LEMONS Spain, 99 (Verna) WP pu 0.0, pe.5 5 pu 0.0, pe. 90 pu 0.006, pe.0 WP pu <0.004, pe pu 0.005, pe pu <0.004, pe 0. WP pu, pe 0.0 pu, pe 0.0 pu, pe pu, pe 0.0 pu, pe 0.0 pu, pe Hei.---5 Hei.---5 MAPA.06.9

15 mancozeb 585 CROP Country, year (Variety) Form Application kg ai/ha kg ai/hl Residues, mg/kg No. EBDC as CS ETU MANDARINS Japan, 9 (Okitsuwase) Japan, 9 (Okitsuwase) Japan, 9 (Miyakawa) Japan, 9 (Miyakawa) Spain, 989 (Clementine) Spain, 989 (Satsuma) Spain, 989 (Clementine) Spain, 989 (Satsuma) Spain, 990 (Clementine) Spain, 990 (Clementine) Spain, 990 (Satsuma) Spain, 990 (Satsuma) ORANGES Australia, 99 (Valencia) Brazil, 989 (Natal) Brazil, 989 (Natal) Spain, 989 (Havelina) Spain, 989 (Havelina) Spain, 989 (Newhall) WP.8-4. WP pu 0.04, pe.6 44 pu 0.04, pe pu 0.06, pe pu 0.06, pe.6 44 pu 0.0, pe.4 60 pu 0.0, pe. WP pu 0., pe.5 46 pu 0.04, pe.5 60 pu 0.0, pe.8 WP pu 0.0, pe. 46 pu 0., pe. 60 pu 0., pe. WP 0. 0 WP WP , w 0.0., w , w 0.6 WP , w , w WP , w , w , w 0.45 WP , w , w 0.. WP , w , w.4 4., w 0.5 WG WG WP. 0 0., j 0.6, j 0.5, j 0.6, j , j WP , j 0.05., j , j 0.59, j 56 0., j WP , w 0.06., w , w pu, pe 0.0 pu, pe 0.05 pu, pe 0.06 pu 0.0, pe 0.08 pu 0.0, pe 0.08 pu 0.0, pe 0.08 pu, pe 0. pu, pe 0.06 pu 0.0, pe 0.08 pu 0.0, pe 0. pu 0.0, pe 0. pu 0.0, pe 0., j 0.0, j, j, j, j 0.0, j 0.04, j 0.0, j, j, j 5P--68 5P--68 5P--68 5P--68 MAPA /5/9 MAPA /5/9 404/VI/89 R. R80.5 R80.5 R80. R80. AUE /VI/89 404/VI/89 R.

16 586 mancozeb CROP Country, year (Variety) Form Application kg ai/ha kg ai/hl Residues, mg/kg No. EBDC as CS ETU 0.66, w 0.09 Spain, 990 (Navel) WP R80.4 Spain, 990 (Navel) WP MAPA /5/9 Spain, 990 (Valencia) WP MAPA /5/9 Spain, 99 (Valencia) WP MAPA /5/9 Spain, 99 (Valencia) WP MAPA /5/9 pu: pulp; pe: peel; w: washed fruit; j: juice. Table. Mancozeb residues (as CS ) in citrus fruits from supervised trials in the USA. CROP State, year (Variety) GRAPEFRUIT TX, 986 (Ruby Red) CA, 986 (Ruby White) CA, 986 (Ruby Red) LEMONS CA, 986 (Eureka) CA, 986 (Eureka) Form Application kg ai/ha kg ai/hl WP WP WP WP WP WP WP WP WP Residues, mg/kg No. EBDC as CS ETU pe pu c pe 0. pe 6 pu pe 0.5 pu c pe 0.4 pu A-88-4A-88-4A WP

17 mancozeb 58 CROP State, year (Variety) FL, 98 (Bearss) FL, 98 (Meyer) FL, 98 (Bearss) LIMES FL, 98 (Persian) FL, 98 (Persian) ORANGES FL, 986 (Valencia) USA (TX), 986 (Valencia) Form Application kg ai/ha kg ai/hl WP WP WP WP WP WP Residues, mg/kg No. EBDC as CS ETU 6.9 c pe WP WP WP WP WP WP pe 6. pu c pe 0.5 pe pu pe. pu c pe pe pu c pe pe pu c 0. c pe 0.69 c pu c CA, 986 W? pe pu c pe pe.4 pu c pe 0. pu pe 0.6 pu c pe 0.4 pu c

18 588 mancozeb CROP State, year (Variety) Form Application kg ai/ha kg ai/hl (Navel) 6 6 FL, 98 (Valencia) FL, 98 (Valencia) WP WP WP Residues, mg/kg No. EBDC as CS ETU pe 5 pu c pe pe 0 pu 0.9. WP pe. pu pe 0. pu c pe: peel; pu: pulp; c: control sample. Table. Mancozeb residues (as CS ) in pome fruits from supervised trials in Australia, Austria, Belgium, Brazil, Hungary, Japan and The Netherlands. Underlined residues are from treatments according to GAP. CROP Country, year (Variety) Apples Australia, 99 (Hi-Early Red Delicious) Austria, 98 (Golden Delicious) Belgium, 99 (Jonagold) Belgium, 99 (Jonagold) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU WG WG WG WP WP Brazil, 989 WP 0. 4 Brazil, 989 WP AUE R. R&H/BA.8/99 R&H/BA.8/99 FPA FPA-89-00

19 mancozeb 589 CROP Country, year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU Hungary, Hungary, 989 WG Japan, 986 (Tsugaru) Japan, 986 (Starking) Netherlands, 984 (Golden Delicious) Netherlands, 984 (Golden Delicious) Netherlands, 985 (Golden Delicious) Netherlands, 985 (Golden Delicious) Netherlands, 986 (Golden Delicious) Netherlands, 98 (Golden Delicious) Netherlands, 98 (Golden Delicious) Netherlands, 988 (Golden Delicious) Netherlands, 988 (Golden Delicious) WP WP WP WP WP WP WP WP WP WG WP WP WG WP WP WG WP WG , , , , , () , , () , () 9 0., , , , , , , , , , , 0. 8 () 0. 0., < , < , 0. >6 0., 0.8 >6 0.45, 0.48 >6 0.4, <0.00 () 0.004, <0.00 <0.00 () <0.00 () <0.00 () 0.004, <0.00 () 0.0, <0.00 () 0.09, () <0.00, 0.00 () 0.06, 0.09 () <0.00, () 0.00, 0.0 <0.00 () <0.00 () <0.00 () <0.00 () <0.00 () <0.00 () 0.00, < () <0.00, 0.00 <0.00, <0.00 () 0.00, , , , <0.00, <0.00, <0.00 () 0.00, , 0.00 <0.00, , () 0.006, () R65.9 R.0 Saku6P--54 Saku6P--54 PH84 PH84 PH85 PH85 PH86 PH8 PH8 PH8845 PH884

20 590 mancozeb CROP Country, year (Variety) Netherlands, 989 (Golden Delicious) Netherlands, 990 (Jonagold) Netherlands, 990 (Golden Delicious) PEARS Australia, 99 (Beurre Bosc) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU >6 0.6, , WP , , <0.00 PH8959 WG WG WG WG Brazil, 990 WP Brazil, 990 WP Japan, 986 (Kosui) Japan, 986 (Hosui) WP WP fruit without stalk. 0., , <0.05, <0.05, <0.00 () <0.00 () <0.00 () <0.00 () PH904 PH9044 AUE /90 094/90 Saku6P-6-6 Saku6P-6-6 Table 5. Mancozeb residues (as CS ) in pome fruits from supervised trials in France. Underlined residues are from treatments according to GAP. CROP Year (Variety) APPLES Application EBDC residues, mg/kgas CS Form kg ai/ha kg ai/hl No. 989 (Golden Delicious) WP R. 989 (Golden Delicious) WP (Golden Delicious) WP (Golden Delicious) WP R R R. 989 (Golden Delicious) WP R. 989 (Golden Delicious) WP R. 990 (Golden Delicious) WP R9.4

21 mancozeb 59 CROP Year (Variety) Application EBDC residues, mg/kgas CS Form kg ai/ha kg ai/hl No. 990 (Golden Delicious) WP (Bertane) WP.0t (Golden Delicious) WP t t R8.50 <0.05 R8.6 6 <0.05 R (Golden Delicious) WP. 0. <0.05 R (Golden Delicious) WP (Golden Delicious) WP (Granny Smith) WP.0t t R R9.60 <0.05 R (Golden Delicious) WP R (Starkrimson) WP (Granny Smith) WP (Welspur, Melrose, Granny Smith) WP <0.05 R R c R (Golden Delicious) WP R (Granny Smith) WP 4 86 R80. PEARS 990 (Beurre-Hardy) y(Doyenné de Comice) (Williams) (Passe Crassone) c c c c 0. R8.6 R8.8 R8.4 R8.40 t: thiram whole fruit without stalk trials with apple varieties. 4 c: control sample. Table 6. Mancozeb residues (as CS ) in pome fruits from supervised trials in Germany. Underlined residues are from treatments according to GAP. CROP Year (Variety) Apples Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU 98 (Roter Boskoop) WP (Jonathon) WP (Cox's Orange) WP R68. R68. R68.

22 59 mancozeb CROP Year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU 98 (Gravenstein) WP (Cox's Orange) WP (Boskoop) WP (Idared) WG (Cox's Orange) WG (Idared) WG (Cox's Orange) (Idared) (Cox's Orange) WP (Idared) WP (Idared) WP (Gloster) WG s 0.59, s 4.0 s 0..4, s w (Cox's Orange) WG (Jonagold) WP (Golden) WG (Gloster) WG (Cox's Orange) WG PEAR R68.4 R65. R65. R65. R65. R65. R65. R65. R65.6 R65.6 R65.6 R80.8 R80.8 R80.9 R80.9 R80.9 R80.9

23 mancozeb 59 CROP Year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU 98 (Conference) WP (Charneu) WP (Charneu) WP (Charneu) WP (Conference) WP (Williams) WP WP < cm.5, cm.9 cm., cm <0. R68. R68. R68. R65. R65. R68.4 R65. s: sauce. w: washed fruit. cm: compote. Table. Mancozeb residues (as CS ) in pome fruits from supervised trials in Italy. Analyses were on whole fruit without stalk. Underlined residues are from treatments according to GAP. CROP Year (Variety) Application Form kg ai/ha kg ai/hl Residues, mg/kg No. EBDC as CS ETU Apples 989 (Double Red) WP R.5/6/ 989 (Double Red) WP (Double Red) WG (Double Red) (Double Red) WP (Double Red) WG (Rome Beauty) WP (Golden) WP (Golden) WP R.5/6/ R.5/6/ 9 0. R.5/6/ R.5/6/ R.5/6/ (Morgenduft) WP R (Morgenduft) WP (Morgenduft) WP (Morgenduft) WP (Jonathan) WP (Jonathan) WP R5.5 R5.5 R R R R R R5.5

24 594 mancozeb CROP Year (Variety) Application Form kg ai/ha kg ai/hl Residues, mg/kg No. EBDC as CS ETU 990 (Jonathan) WP (Jonathan) WP (Jonathan) WP R R R (Super Stark) WP R (Super Stark) WP (Super Stark) WP (Super Stark) WP (Hi Early Starking) WP R R R (Golden Granny) WP R (Badami) WP R (Neijpling Early) WP R (Acrynae) WP R (Cooper) WP R (Golden) WP (Cooper ) WP R (Perleberg) WP R (Starkrimson) WP (Golden) WP (Golden Stark) WP (Golden) WP (Double Red) WP R (Low Red) WP PEARS R5.5 R5.5 R5.5 R5.5 R5.5 R5.5 R (William) WP R (William) WP R5.5 trials with different formulations.

25 mancozeb 595 Table 8. Mancozeb residues (as CS ) in apples from supervised trials in the UK. Underlined residues are from treatments according to GAP. Year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU 989 (Bramley) WP (Cox) WP (Bramley) WP (Bramley) WP < <0.006 <0.006 < R.6 R.6 R.6 R (Bramley) WG R (Bramley) WG (Idared) (Golden) (Cox) (Red Delicious) WG WG WG WG R R (Bramley) WG R (Bramley) WG R (Cox) WG (Cox) WG (Bramley) WG. +.6 WG (Bramley) WG WG R R <0.05 <0.05 R < R R.6 nut-sized immature fruit. fruit without stalk. Table 9. Mancozeb residues (as CS ) in pome fruits from supervised trials in the USA (Loftus, 99. ETU 9-0). Underlined residues are from treatments according to GAP. CROP State, year (Variety) Application Residues, mg/kg

26 596 mancozeb Form kg ai/ha kg ai/hl No. EBDC as CS ETU APPLES MI, 990 (Paula Red) WP fb <0.005 ETU 9-0 MI, 990 (Paula Red) WP. 4 fb 96 <0.005 ETU 9-0 MI, 990 (Paula Red) WP <0.005 ETU 9-0 MI, 990 (Paula Red) WP. 0 <0.005 ETU 9-0 MI, 990 (Paula Red) WP < <0.005 c ETU 9-0 NY, 990 (Twenty Ounce) WP fb 6 <0.005 ETU 9-0 NY, 990 (Twenty Ounce) WP. 4 fb 6 <0.005 ETU 9-0 NY, 990 (Twenty Ounce) WP <0.005 ETU 9-0 NY, 990 (Twenty Ounce) WP. <0.005 ETU 9-0 NY, 990 (Twenty Ounce) WP ETU 9-0 OH, 990 (MacIntosh) WP.8 fb 0.0 <0.005 ETU 9-0 OH, 990 (MacIntosh) WP 5.4 fb <0.005 ETU 9-0 OH, 990 (MacIntosh) WP OH, 990 (MacIntosh) WP OH, 990 (MacIntosh) WP <0.005 ETU <0.005 ETU ETU 9-0 PA, 990 (Empire) WP fb 9 <0.005 ETU 9-0 PA, 990 (Empire) WP. 4 fb <0.005 ETU 9-0 PA, 990 (Empire) WP <0.005 ETU 9-0 PA, 990 (Empire) WP <0.005 ETU 9-0 PA, 990 (Empire) WP ETU 9-0 VA, 990 (Red Delicious) WP. fb ETU 9-0 VA, 990 (Red Delicious) WP. fb 0. <0.005 ETU 9-0 VA, 990 (Red Delicious) WP <0.005 ETU 9-0 VA, 990 (Red Delicious) WP c 0.0 <0.005 ETU 9-0 VA, 990 (Red Delicious) WP ETU 9-0 WA, 990 (Red Delicious) WP fb 58 <0.005 ETU 9-0 WA, 990 (Red Delicious) WP. 4 fb 58 <0.005 ETU 9-0 WA, 990 (Red Delicious) WP <0.005 ETU 9-0 WA, 990 (Red Delicious) WP <0.005 ETU 9-0 WA, 990 (Red Delicious) WP ETU 9-0 PEARS CA, 985 (Bartlett) WP

27 mancozeb 59 CROP State, year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU CA, 985 (Bartlett) WP PA, 985 (Bartlett) WP fb: final application at full bloom. c: control sample. Table 0. Mancozeb residues (as CS ) in stone fruits from supervised trials in Australia, Brazil and France. Underlined residues are from treatments according to GAP. CROP Country, year (Variety) Application Form kg ai/ha kg ai/hl No. Residues, mg/kg, EBDC as CS APRICOT Australia, 99 (Moorpark) Australia, 99 (Moorpark) PEACH Australia, 99 (Red Haven) WG WG WP WP WG WG Brazil, 989 WP Brazil, 989 WP PLUMS Brazil, 990 WP Brazil, 990 WP France, 990 (Ente 0) France, 990 (Ente 0) France, 990 (Mirabellier) WP c 0.08 AUI-9-04 AUI-9-04 AUE-9-0 0/90 0/90 0/90 0/90 R8.54/5 WP R8.56 WP R8.59

28 598 mancozeb c: control sample fruit without stone Table. Mancozeb residues (as CS ) in berry fruits from supervised trials in Australia, Brazil, Hungary, Japan, Portugal and Spain. Underlined residues are from treatments according to GAP. CROP Country, year (Variety) GRAPES Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU Australia, 990 (Rhine Reisling) Australia, 990 (Rhine Reisling) Australia, 990 (Rhine Reisling) WP WP 0. 4 WG WG WG WG Brazil, 990 WP.8 0 Brazil, 990 WP Hungary, Japan, 989 (Delaware) Japan, 989 (Delaware) Japan, 989 (Kyoh_) Japan, 989 (Kyoh_) Portugal, 99 (Cardinal) STRAWBERRIES Japan, 98 (Reik_) Japan, 98 (Reik_) WP WP WP WP WP WP WP /90 86/90 868/90 868/90/5 00/90 00/90 R65. SakuP-6-9 SakuP-6-9 SakuP-6-9 SakuP R80.??

29 mancozeb 599 CROP Country, year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU Spain, 985 (Cruz) WP R66./ Spain, 985 (Cruz) WP R66./ Spain, 986 (Douglas) WP R66./ sampled one hour before the final application whole cluster Table. Mancozeb residues (as CS ) in cranberries from supervised trials in the USA. Underlined residues are from treatments according to GAP. State, year (Variety) WA, 985 (McFarlin) WA, 985 (McFarlin) OR, 985 (McFarlin) NJ, 985 (Franklin) NJ, 985 (Early Black) NJ, 985 (Early Black) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU WP WP WP WP WP c WP c MA, 988 (Crowley) WP c: control sample. Table. Mancozeb residues (as CS ) in grapes from supervised trials in France. Underlined residues are from treatments according to GAP. Year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU 95 (Chardonnay + Pinot Meunier) WP w w w w R (Pinot Meunier) WP (Pinot Meunier + Chardonnay) 96 (Pinot Noir + Pinot Meunier) 96 (Chardonnay + Pinot Meunier) 988 (Carbernet + Merlot) 988 (Carbernet + Merlot) WP WP WP WP WP w w R w w w w w w w w w w w w R60.9 R60.9 R w <0.05 R8.8 8 w <0.05 R8.8

30 600 mancozeb Year (Variety) Application Residues, mg/kg Form kg ai/ha kg ai/hl No. EBDC as CS ETU 988 (Carbernet + Merlot) 988 (Carbernet + Merlot) 989 (Carbernet + Merlot) WP WP (Pinot Noir) WP w <0.05 R w <0.05 R9. 46 w <0.05 R w (Pinot) WP < (Carignan) WP (Gamay) WP w w <0.05. w < (Carignan) WP j < (Carignan) WP (Cabernet Sauvignon) WP w <0.05 R8.44 R8.5 R8.6/6 R9.5 R9.6 R R (Pinot Noir) WP R (Carignan) WP c 0. R (Pinot Meunier) WP R (Meunier) WP c 0. R (Auxerrois) WP R (Merlot) WP w (Ugni blanc) WP (Malbec) WP c (Syrah) WP (Cabernet Sauvignon) 990 WP (Grenache) WP (Merlot) (Carignan) WP (Sauvignon) WG R8. R R9. c 0. WP c.8 R9.6 R R9.50/5 0. R R R w R9.65