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    VAMIDOTHION           JMPR 1973

    IDENTITY

    Chemical name

         O,O-dimethyl S-[2-(1-methylcarboylethylthio)ethyl]
         phosphorothioate.

    Synonyms

         10 465 R.P., Kilval(R),  Trucidor(R).

    Structural formula

    CHEMICAL STRUCTURE 1


    Other information on identity and properties

    Physical state:     White crystalline solid (pure)
                        Amber waxy solid (technical)

    Melting point:      40°C (pure)

    Solubility:         Water - about 4 g/ml
                        Benzene, toluene, methyl ethyl ketone, ethyl
                        acetate, acetonitrile, methylene chloride,
                        anisole, cyclohexanone, chloroform - 1 g/ml
                        [xylene - 0.125 g/ml petroleum ether, cyclohexane
                        - insoluble

    Volatility:         Very low. Negligible loss under vacuum (2 mm Hg)
                        at 20°C.

    Stability:          The technical solid decomposes slowly at room
                        temperature but is stable in organic solvents
                        (e.g. cyclohexanone, methyl ethyl ketone).

                        Hydrolyzed by alkali

    Optical             Vamidothion consists of a mixture of optically
    isomerism:          active isomers. Their systemic activity as
                        pesticides is similar, but the D form shows higher
                        contact activity as an araricide.

    Formulation:        Water-miscible solution containing 400 g/l.

    EVALUATION FOR ACCEPTABLE DAILY INTAKE

    Biochemical aspects

    Biodegradation

         One NC-5 mouse was administered 30 mg 32P vamidothion orally.
    Urine collected over the following 24 hours contained 32P labelled
    phosphoric acid, 0-methyl phosphate, 0,0-dimethyl phosphate and an
    unknown compound.

         Rat liver homogenate incubated for two hours with 32P labelled
    vamidothion produced 0,0-dimethyl phosphate, phosphoric acid and an
    unknown compound which was possibly dimethyl phosphothionate.

         The same metabolites were produced by incubation of 32P labelled
    vamidothion with plant leaves. In addition desmethyl vamidothion was
    detected; this may not have been detected as a metabolite in animals
    because of the low activity of 32p incorporated into the vamidothion
    (Morikawa and Saito, 1969).

         The oxidation product, vamidothion sulfoxide, has been
    demonstrated to be formed in plants (Desmoras et al., 1961).

    Effects on enzymes

         Vamidothion inhibits cholinesterase in vitro and in vivo. A
    concentration of 40 mg/l caused 50% inhibition of enzyme activity of
    plasma. Four hours after guinea-pigs had received 40 mg vamidothion/kg
    orally, 81% inhibition of plasma and 20% inhibition of cellular enzyme
    occurred. With higher dosage levels the plasma cholinesterase level
    remained stationary but cellular enzyme activity decreased (Dubost et
    al., 1960).

    TOXICOLOGICAL STUDIES

    Special studies on the metabolites

         A summary of the results of acute toxicity studies on
    vamidothion sulfoxide is shown in Table 1.

         A test for neurotoxicity was carried out in the same manner as
    for vamidothion itself. Positive controls showed signs of paralysis in
    9-14 days while vamidothion sulfoxide was without effect (Anon.,
    1966b).

    TABLE 1. THE ACUTE TOXICITY OF VAMIDOTHION SULFOXIDE

                                                                         

    Species        Sex      Route    LD50     References
                                                                         

    Mouse                   Oral     80       Desmoras et al., 1961

    Rat            F        Oral     160      Desmoras et al., 1961
                                              Rivett and Corbett, 1966

    Guinea-pig              Oral     205      Desmoras et al., 1961

    Chicken        F        s.c.     60       Anon., 1966b

                                                                         


         A short-term study was carried out on groups of five male and
    five female rats which were fed diets containing 0, 5, 50, 100 and 200
    ppm vamidothion sulfoxide for three months. The degree of depression
    of cholinesterase activity was similar to that in animals receiving
    the same dosage levels of vamidothion. The 100 and 200 ppm dosage
    levels depressed cholinesterase levels to approximately 20% And 12%
    respectively of the control level. Cholinesterase activity returned to
    normal within four weeks when vamidothion sulfoxide was withdrawn from
    the diet. Histological examination of two male and two female rats
    from each group showed no abnormality attributable to ingestion of the
    test compound (Rivett and Corbett, 1966).

         A three generation reproduction study with each generation
    producing two litters, was carried out on groups of 20 male and 40
    female rats (generation Fo, test animals), 40 male and 80 female
    (generation Fo controls) or 10 male and 30 female (other generations).
    Animals were administered 0, 5, 15 or 45 ppm of vamidothion sulfoxide
    in the diet for four weeks before the first mating. The study included
    tests in which some female test animals were mated with untreated
    males and some untreated females were mated with treated male animals.
    A small number of females of the F1b and F2b generations were killed
    after the thirteenth day of pregnancy and the uterus examined for
    implantation sites, viable and resorbed embryos and macroscopically
    observable abnormalities. The F1a, F2a and F3a litters were killed
    at weaning and autopsied. Rats of the F1b and F2b litters not used to
    produce the next generation were killed at weaning and autopsied. The
    F3b litters were killed at weaning and the heart, kidneys and livers
    weighed and spleen, suprarenals, thyroid and (in the case of the
    highest dosage group) brain examined histologically. The results
    showed that the dosage levels of vamidothion sulfoxide used had no
    untoward effect on treated animals, in particular on fertility or
    reproductive activity of rats. There was no indication of teratogenic
    activity in this study (Ganter et al., 1969b).

    Special studies on neurotoxicity

         Groups of five white leghorn chickens were injected s.c. with 60
    and 120 mg vamidothion/kg (1X and 2X LD50 dose). Positive control
    groups received 20 and 40 mg di-isopropyl-fluorophosphoridono. All
    birds were treated with atropine and P2AM. No signs of neurotoxicity
    appeared in vamidothiontreated birds while positive control groups
    developed paralysis in 9-14 days (Anon., 1966b).

    Special studies on the pharmacological effects

         The motility of mice was unaffected by 10 mg vamidothion/kg
    orally and exploratory activity and conditioned reflexes were normal
    in rats treated orally with 30 mg/kg. No effect was found on
    neuromuscular transmission, respiratory rate, ECG or heart rate and
    the effects of i.v. adrenalin and i.v. acetylcholine were largely
    unchanged by treatment with vamidothion, Salivary excretion was
    increased, slightly and isolated intestine and uterus preparations
    were affected weakly by vamidothion (Julou et al., 1966).

         Mice were administered 100 mg vamidothion/kg orally (LD50 dose).
    Some also received atropine, pralidoxime or both. Ten to 20 mg
    atropine/kg i.p. provided 60-70% and 50 mg pralidoxime/kg i.p. 100%
    protection against vamidothion (Dubost et al., 1960; Anon., 1966a).

         Groups of 10 rats received 3 x LD50 dose (300mg/kg) of
    vamidothion orally. One group received 17.4 mg atropine/kg i.p. when
    signs of intoxication showed. Another received atropine plus 50 mg
    P2AM/kg i.p. All control animals died within 45 min., 7-10 animals
    with atropine died in 7-24 hours and three animals receiving atropine
    and P2AM died. All of the latter group appeared normal two hours after
    treatment while those on atropine alone appeared ill (Anon., 1966a).

    Special studies on reproduction

    Rat. A three-generation reproduction study, with each generation
    producing two litters, was carried out on groups of 20 male and 40
    female rats which were administered 5, 15 and 45 ppm vamidothion in

    the diet. The control group consisted of 40 males and 80 females.
    Animals of the Fo generation received diets for 11 weeks before being
    mated. The study included tests in which some female test animals were
    mated with untreated males and untreated females were mated with
    treated males. A small number of females of the F1b and F2b
    generations were killed after the thirteenth day of pregnancy and the
    uterus examined for implantation sites, viable and resorbed embryos
    and macroscopically apparent abnormalities. The F1a, F2a and F3a,
    litters were killed at weaning and autopsied. Animals of the F1b and
    F2b groups not used to produce the next generation were killed at
    weaning and autopsied. The F3b litters were killed at weaning and the
    heart, kidneys and liver weighed and the spleen, suprarenals, thyroid
    and (with the highest dose level only) the brain examined
    histologically. Haematological studies and examinations of bone marrow
    of one animal of each sex of each group were carried out. Because of a
    technical error some animals chosen as parents of the second and third
    generations may have been produced from untreated male parents; the
    proportion so produced is uncertain. All females were, however,
    treated with the correct diets. Results show that at the dosage levels
    used vamidothion had no untoward activity on rats, in particular on
    their fertility or reproductive functions, There was no indication
    that vamidothion is teratogenic (Ganter et al., 1969a).

    Acute toxicity

         The results of acute toxicity studies on vamidothion are
    summarized in Table 2.

         Administration of vamidothion in fatal doses produced signs
    typical of cholinesterase inhibitors.

         Groups of 20 mice were administered half the LD50 dose of
    vamidothion plus half the LD50 dose of demeton-methyl, parathion,
    phencapton, dimetboate, ethion, malathion, azinphos ethyl, mevinphos
    or phosphamidon and observed for five days. No significant
    potentiation was observed (Anon., 1966c).

    Short-term studies

    Rat. Groups of 10 male rats were administered 3 or 6 mg
    vamidothion/kg/day orally for one month. It was reported that body
    weight was unaffected, no animals died and no clinical signs of
    toxicity occurred. Haematological examination including examination of
    bone marrow and chemical analysis of urine and blood showed no
    abnormalities except for blood cholinesterase activity which was
    depressed by 50% (3 mg/kg/day) or 607 (6 mg/kg/day). Brain
    cholinesterase levels were not depressed. The weights and histological
    appearance of organs were unaffected by treatment (Dubost et al.,
    1960).

    TABLE 2. SUMMARY OF THE RESULTS OF STUDIES ON ACUTE TOXICITY
                                                                                   

    Species     Sex     Route     Purity       LD50        References
                                                                                   

    Mouse               Oral      p            43          Johnston and Rivett, 1966

    Mouse               Oral      p            34          Dubost et al., 1960

    Mouse       M+F     Oral      Tech.        64          Pasquet and Mazuret, 1972a

    Mouse               Oral      Tech.        40          Pak, 1970

    Mouse               s.c.      p            34          Johnston and Rivett, 1966

    Mouse               Dermal    p            1450        Johnston and Rivett, 1966

    Mouse               Dermal    Tech.        1060        Pasquet and Mazuret, 1972a

    Rat         M       Oral      p            100         Johnston and Rivett, 1966

    Rat         M       Oral      p            105         Dubost et al., 1960

    Rat         M+F     Oral      p            105         Pasquet and Ma.uret, 1972b

    Rat         F       Oral      p            77          Desmoras et al., 1961

    Rat         M+F     Oral      Tech.        168         Pasquet and Mazuret, 1972a

    Rat                 Oral      Tech.        103         Pak, 1970

    Rat         F       Oral      p            64          Johnston and Rivett, 1H6

    Rat         M       s.c.      p            48          Johnston and Rivett, 1966

    Rat         F       s.c.      p            35          Johnston and Rivett, 1966

    Guinea-pig          Oral      p            85          Dubost et al., 1960

    Rabbit              Oral      Tech.        160         Pak, 1970

    Rabbit              Dermal    p            1160        Quoted in Johnston and
                                                           Rivett, 1966

    Rabbit      M+F     Dermal    Tech.        3000        Pasquet and Mazuret, 1972a

    Dog         M+F     Oral      p            110         Julou and Pasquet, 1967
    Mouse               Oral      p            50          Desmoras and Fournel, 1961
    Mouse               Oral      l-isomer     68          Desmoras and Fournel, 1961
    Mouse               Oral      d-isomer     34          Desmoras and Fournel, 1961
                                                                                   
    M = male         F = female        P = pure

         Groups of five male and five female rats were fed on diets
    containing 0, 0.2, 1 and 5 ppm vamidothion for six weeks after which
    the test substance was withdrawn from the diet. Regular observation of
    plasma and erythrocyte cholinesterase activity showed that only in the
    plasma of female rats on the 5 ppm diet was enzyme activity
    consistently depressed to a significant extent. The enzyme level
    returned to normal within five weeks. Cholinesterase activity was not
    depressed significantly at lower dosage levels (Wheldon et al., 1969).

         Groups of five male and five female rats were fed on diets
    containing 0, 5 and 50 ppm vamidothion for three months. No ill effect
    was seen on growth or general health. Blood cholinesterase levels were
    reduced to approximately 75% and 25% respectively of the control level
    in the 5 and 50 ppm groups. Cholinesterase levels returned to normal
    within four weeks when vamidothion was withdrawn from the diet.
    Histopathological examination of two rats of each sex from the 50 ppm
    group showed no abnormalities related to ingestion of the compound
    (Rivett and Corbett, 1966).

         Groups of rats were administered, by gavage, doses of
    approximately 2, 5 or 10 mg vamidothion/kg daily for three months. At
    the end of the test serum acetylcholinesterase activity was decreased
    to 35%, 12% and 8%, respectively, of the normal value (Pak, 1970).

    Dog. Groups of three dogs were administered orally 0, 1 and 2
    mg/vamidothion/kg/day for one month. Two dogs received 8 mg/kg/day for
    one month. No effect was seen on growth except for one animal on the
    highest dose level which developed diarrhoea (cause unknown).
    Haematological indices and blood coagulation were normal. Slight
    differences between groups in urine urobilinogen, glucose and bile
    salts, serum protein, PSP clearance and behaviour could not be
    attributed to treatment. In particular no neurological abnormalities
    were seen although erythrocyte cholinesterase was severely depressed
    (100% inhibition at sixteenth day with 8 mg/kg dosage regime).   In
    six dogs receiving 1 and 2 mg/kg/day no abnormalities were found on
    gross and histopathologic examination. (Dubost et al., 1960).

         Groups of two male and two female beagle dogs were fed on diets
    containing 0, 0.2, 1 and 5 ppm vamidothion for five to six weeks.
    Animals on the lowest dosage level were then fed for a further four
    weeks on diet containing 20 ppm vamidothion, after which they were
    observed for four more weeks on normal diet. No clinical signs of
    abnormality were seen in any group. The plasma and erythrocyte
    cholinesterase levels were slightly depressed in dogs on the highest
    dosage. These levels returned to normal within two weeks of return to
    a normal diet. No abnormalities in the appearance or weight of organs
    were found in any group (Noel et al., 1969).

    Long-term studies

         No data are available.

    Observations in man

         Groups of 6-11 normal healthy volunteers of both sexes were
    administered 9.6 or 37.2 µg vamidothion/kg/day orally in aqueous
    solution on five days each week for three weeks. Other groups received
    78.8 or 122.8 µg vamidothion/kg/day in aqueous solution for five
    weeks. A control group was studied for 25 weeks. No clinical signs or
    symptoms were found which could be attributed to treatment. Plasma
    cholinesterase, estimated weekly, showed no consistent depression in
    any group but erythrocyte cholinesterase was depressed in three of six
    volunteers receiving 122.8 µg/kg/day. The no-effect level was
    considered to be 78.8 µg/kg/day, (calculated to be equivalent to 56.3
    µg/kg/day if vamidothion was administered every day without a break)
    (Noel et al., 1970).

         Serum and erythrocyte cholinesterase levels were determined
    periodically in workers who had been involved in the manufacture of
    vamidothion over a period of several months to a few years. Enzyme
    levels were also determined in experimentalists exposed several times
    a year to vamidothion over a seven-year period. The actual exposure is
    uncertain. Fluctuations in enzyme levels in both groups were within
    the limits of normal (Celice et al., 1966),

    Comments

         It has been shown that vamidothion is partly absorbed from the
    gastric intestinal tract and is excreted in urine. Several metabolic
    products have been found in urine; these ewe compounds are also
    produced by liver slices. One metabolite (desmethyl vamidothion) was
    shown to be produced by plants but has not yet been found as a
    metabolite in animals. Vamidothion sulfoxide has been examined
    toxicologically but the toxicity of other metabolites has not
    apparently been examined.

         Vamidothion depresses serum cholinesterase activity at lower
    concentrations than it depresses the activity of erythrocyte
    cholinesterase, except in dogs. Brain cholinesterase activity is less
    affected. The dosage level of vamidothion which is without effect in
    man is just over 50 µg/kg/day. The no-effect level with regard to
    cholinesterase depression was 1 ppm in the diet of rats and 5 ppm in
    the diet of dogs. These dietary levels are approximately equivalent to
    50 µg/kg/day in rats and 125 µg/kg/day in dogs.

         Studies showed that vamidothion had no adverse effects on
    reproduction. Short-term tests were carried out in only small numbers
    of dogs and rats and although no ill effects other than that on
    cholinesterase activity were detected, the observations were not
    sufficiently extensive to eliminate the possibility that the compound
    has other significant effects, No long-term tests have been reported.

    TOXICOLOGICAL EVALUATION

         It is not possible, on the information available, to estimate an
    ADI for vamidothion.

    RESIDUES IN FOOD AND THEIR EVALUATION

    Use pattern

         Vamidothion is a systemic organophosphorus aphicide and miticide.
    Its most important use is on apples and pears against the woolly apple
    aphid. It is also used on other pome fruits, sugar beet and brussels
    sprouts. and to a lesser extent on grapes, cereal crops, sugar cane
    and hops.

    Pre-harvest treatments

         The recommended uses are as follows:

    Orchard fruits. In France, Western Europe, Australia, New Zealand
    and South Africa, a single treatment at 40-50 g a.i./100 l. For
    low-volume application, a rate of 0.4-0.5 kg a.i./ha is used. In Great
    Britain an application at 20 g/100 l before flowering, and one or two
    treatments at 40 g/100 l after flowering are recommended for apple and
    pear; a single application at 40 g/100 l after flowering for plum and
    cherry.

    Grapes. A single treatment at 40-50 g/100 l during active sap
    movement. A second similar treatment if necessary.

    Citrus fruits. 60-80 g/100 l.

    Hops. In England, three applications at 700 g/ha, with a minimum
    pre-harvest interval of four weeks. In France, Belgium and Germany,
    one application at 50 g/100 l when the aphid first appears.

    Rice. Three applications at 50 g/100 l (600 g/ha).

    Cotton. 40-60 g/100 l high-volume application, repeated, if
    necessary.

    Post-harvest treatments

         None known.

    Other possible uses

         Trials against aphids of maize and sorghum have been successful.
    Aphids and red spider of strawberries, tomatoes and beans have been
    successfully controlled. A pre-harvest interval of six weeks is
    recommended.

         Aphids have been controlled in trials in France, Brazil and Japan
    by brushing tree trunks with vamidothion during active sap movement.

    Residues resulting from supervised trials

         Residue data are available from supervised trials in France,
    Germany, Switzerland and the United Kingdom (Rhône-Poulenc, 1966,
    1969; May and Baker Ltd. 1963), together with limited data on
    application to sugar cane in Trinidad (May and Baker Ltd, 1973). These
    data have been deposited with FAO and are summarized in Table 3.
    Residues of vamidothion are converted to the sulfoxide in or on the
    plant, and residues reported in the table refer to the sum of the
    parent compound and the sulfoxide.

         The combined residue is unusually persistent. The half-life on
    apples and pears is between 35 and 45 days, and more limited results
    on peaches, plums, grapes, cherries and straw berries indicate a
    similar persistence. Half-life periods on cereals and vegetables are
    generally between 6 and 20 days.

         Data from supervised trials in Japan (Tomizawa, 1973) show very
    low residues, usually below 0.02 ppm in a wide range of crops. As
    these data apparently refer only to the parent compound, they are not
    quoted in the Table.

    Fate of residues

    In plants. As mentioned above, the main biologically active product
    is the sulfoxide, and this is the main terminal residue. The sulfone
    is not found to any significant extent, but it has been detected as a
    metabolite in citrus leaves kept at a low temperature. (Results quoted
    by Tomizawa, 1973). The other main metabolites are demethyl
    vamidothion, phosphoric acid and diethyl phosphate (Morikawa and
    Saito, 1969).

    In animals. In experiments with 32B-vamidothion (Morikawa and
    Saito, 1969), 69% of the activity in the urine of dosed mice appeared
    as phosphoric acid and its mono and dimethyl esters. The remaining 31%
    was an unknown metabolite. The dimethyl compound was not detectable.
    In the same series of experiments, rat liver homogenate metabolized
    55% of the vamidothion with which it was incubated to the unknown
    metabolite, 31% to phosphoric acid and 14% to diethyl phosphate.

    Methods of residue analysis

         Residues normally consist essentially of a mixture of vamidothion
    and its sulfoxide. Three methods have been developed by the
    Rhône-Poulenc Laboratories to determine this mixture after suitable
    clean-up: gas chromatography after oxidation of both compounds to the
    sulfone, colorimetric determination of total phosphorus after
    mineralization, and bioassay (Rhône-Poulenc, 1972). The

    gas-chromatographic method should be suitable for regulatory purposes.
    The other two are non-specific but are suitable for determining
    residues arising from supervised trials: most of the data in Table 3
    were obtained by these methods, often by both of them. Identity can be
    confirmed, and the parent compound and sulfoxide separately determined
    semi-quantitatively if required, by TLC (Rhône-Poulenc, 1972).

    Determination by gas chromatography (Desmoras et al., 1972)
    The sample is blended with buffered methanol or acetone and the organic
    solvent evaporated. The extract is washed with petroleum ether, in
    which vamidothion and its sulfoxide are insoluble, and then extracted
    continuously with dichloromethane. (Vamidothion is readily extracted,
    but continuous extraction is needed for the sulfoxide.) An aliquot of
    the solution is evaporated to dryness and oxidized with potassium
    permanganate in aqueous acetone. The resulting sulfone is extracted
    with dichloromethane and transferred to benzene for determination by
    gas chromatography on DEGS (diethylene glycol succinate) stationary
    phase with electron capture detection. Recoveries are within a range
    of 80-110% and the limit of determination is about 0.05 ppm.

         The method described is more sensitive than methods in which
    thermionic (Ruzicka et al., 1967) or flame photometric (Mestres, 1973)
    detection is used. Separate determination of vamidothion and the
    sulfoxide by GLC without oxidation is unsatisfactory because of the
    large difference between their retention times. The two compounds can
    be differentiated if required by first extracting vamidothion by
    shaking with dichloromethane, then obtaining the sulfoxide by
    continuous extraction and oxidizing the residues in the two extracts
    to the sulfone separately.

    Total phosphorus determination. The residue is extracted, and
    cleaned-up as in the GLC method and the extract is evaporated to
    dryness. The residue is digested with nitric and sulfuric acids and
    phosphorus is determined colorimetrically as molybdenum blue. The
    limit of determination is about 0.1 ppm.

    Biological determination. The solvent is evaporated from the
    dichloromethane extract obtained as described above, and some of the
    co-extractives are removed by precipitation from acetone solution at
    -70°C. The acetone in the filtrate from this step is evaporated and
    replaced with water, and residues of vamidothion plus sulfoxide are
    determined by bio-assay with Daphnia pulex as the test organism. The
    procedure has been described in detail by Desmoras (1963).

    Thin-layer chromatography. Thin-layer chromatography, TLC, is useful
    as a confirmatory test of identity and to separate the parent compound
    from the sulfoxide. It is carried out on the cleaned-up
    dichloromethone extract, using silica gel which has been activated by
    heating at 120°C for at least one hour. Approximate Rf values of
    vamidothion, its sulfoxide and its sulfone on silica gel GF254
    (Merek), developed with various solvent systems, are listed in Table
    4. Separated spots can be detected by esterase inhibition or by
    spraying with iodoplatinate, palladium chloride or

    nitrobenzylpyridine. The enzyme inhibition method is the most
    sensitive, with detection limits of 30-50 ng for the three compounds.

         TLC of the dichloromethane extract does not satisfactorily
    indicate the ratio of vamidothion to sulfoxide in the original
    residue, because some vamidothion is converted to sulfoxide during the
    continuous extraction.

    Appraisal

         Vamidothion is an organophosphorus compound with pronounced
    systemic activity, effective against aphids and mites not resistant to
    organophosphorus compounds.

         It is applied as water-miscible solution to pome fruits, sugar
    beet, brussels sprouts and, to a lesser extent, cereal crops, grapes,
    sugar cane and hops. By far the most important use is on apples and
    pears against woolly apple aphid.

         Vamidothion is particularly persistent. Numerous studies have
    been carried out in France, England, Switzerland and Germany and these
    indicate the half-life in pome fruit to be between 35 and 45 days. The
    half-life on cereals and vegetables is generally between six and 20
    days.

         The main biologically active metabolite is the sulfoxide which
    has a higher systemic insecticidal activity than the parent compound.
    The sulfone is not found in plants to any significant extent.

         Residues consisting of a mixture of the sulfoxide and the parent
    compound, can be determined by bio-assay or estimation of total
    phosphorus. The recommended method, which should be suitable :Per
    regulatory purposes, is by gas chromatography with electron-capture
    detection after oxidation to the sulfone. The limit of determination
    is about 0.05 ppm. TLC can be used for confirmation of identity.

         The limited data available on sugar cane indicated residues of
    about 0.2 ppm soon after application, decreasing to below 0.05 ppm
    before harvest. As the available information on wheat and sunflower
    was restricted to the whole plant, it was not suitable for judging the
    probable residue level in the grain and seed.

    National tolerances

         In Switzerland a tolerance of 0.6 ppm has been established for
    residues arising from applications to fruit trees, except cherry, with
    the end of May as the last date of application.



        TABLE 3.  VAMIDOTHION RESIDUES IN CROPS
                                                                                                                                               
                                           Dosage rate,      Residue (ppm vamidothion + sulfoxide) after interval (days)
    Crop                     Country       a.i. g/100 l                                                                                        
                                           or kg/ha          0-2       5-11      13-18     20-30     34-39    41-49    52-69    72-95    >100
                                                                                                                                               

    Apple                    France        50 g/100 l        3.0       2.5       2.0       1.6       1.3      1.1
                                           50 g/100 l                                                                                    0.1
                                           2 x 50 g/100 l              1.7
                                           2 x 50 g/100 l                                                              0.3      0.3

                             Germany       60 g/100 l        0.7                 < 0.1     0.5                0.5      0.4
                                           1.0 kg/ha                                                 1.1               0.6      0.3
                                           1.8 kg                                                                               0.75     0.2
                                           2 x 1.8 kg/ha                                                                        0.7      0.2

                             Switzerland   50 g/100 l                  0.85                < 0.65    0.8
                                           50 g/100 l                                                                  0.5

                             England       40+80 g/100 l                                                      3.5*
                                                                                                              1.6*
                                                                                                              1.7*
                                                                                                              2.4*
                                           40+80 g/100 l                                             3.4

    Pear                     France        50 g/100 l                                                                                    0.1
                                           2 x 50 g/100 l                                                              0.2      0.2

                             England       40 g/100 l                                                1.5*                       0.6*
                                                                                                     1.9*                       >0.2*
                                           40+80 g/100 l                                                      2.1*
                                                                                                              1.8*
    Peach                    France        50 g/100 l                                                                           0.1
                                           2 x 50 g/100 l                                  0.4                0.3
    Cherry                   England       80 g/100 l                                                >0.4*
                                                                                                     >0.4*
                                                                                                     >0.4*

    Plum                     England       80 g/100 l                                                         1.9

    TABLE 3.  (Cont'd.)
                                                                                                                                               
                                           Dosage rate,      Residue (ppm vamidothion + sulfoxide) after interval (days)
    Crop                     Country       a.i. g/100 l                                                                                        
                                           or kg/ha          0-2       5-11      13-18     20-30     34-39    41-49    52-69    72-95    >100
                                                                                                                                               

    Grape                    France        50 g/100 l                                                                           0.2
                                           2 x 50 g/100 l              0.25                                   0.15

    Hop                      France        3 x 50 g/100 l                                  <0.1
    " (fresh and dry cones)                3 x 100 g/100 l                                 <0.1
    " (fresh cones)          England       25+40 g/100 l                                                               < 0.5

    Wheat (whole plant)      France        50 g/100 l        9         4.1       1.4       0.4                0.4
                                           50 g/100 l              approx. 10    4.2       1.9
    " (grain)                              50 g/100 l                                                         0.25
                                           50 g/100 l                                      0.1

    Sugar beat (leaves)      France        50 g/100 l                            1.1*
                                                                                 0.2*
      "    "  (root)                       50 g/100 l                                                                  0.2

    Sunflower (leaves)       France        75 g/100 l        60        23        19        10        7        5

    Strawberries             Scotland      50 g/100 l                                                                  0.6*
                                                                                                                       0.6*
                                                                                                                       0.6*
                                           50 g/100 l                                                                  0.3

    Broad beans              France        50 g/100 l        81        64        51        40        23       13
    (glasshouse,leaves)

    French beans             France        50 g/100 l        87        35        21        8.5
    (glasshouse, leaves)

    Sugar cane               Trinidad      0.9 kg/ha         0.2                 0.1
                                           0.9 kg/ha                                       0.2                < 0.05
      "    " (juice)                       0.9 kg/ha                                                          < 0.05
                                                                                                                                     
    * Separate crop treatments.
        
    TABLE 4.  Rf VALUES OF VAMIDOTHION, ITS SULFOXIDE AND ITS SULFONE
              ON SILICA GEL* IN SEVERAL SOLVENT SYSTEMS

                                                                                      
                                                              Approximate Rf
    Developing solvent                                                                
                                                 Vamidothion    Sulfoxide     Sulfone
                                                                                      

    Dichloromethane-methanol (90:10, v/v)        0.65           0.4           0.55

    Ethyl acetate-methanol (75:25, v/v)          0.65           0.5           0.65

    Acetonitrile-methanol (97:3 v/v)             0.5            0.1           0.65

    Acetone-dimethylformanide (99:1, v/v)        0.6            0.35          0.65
                                                                                      

    * Silica gel GF254 (Merck) activated at 120°C for one hour before use.
    

    RECOMMENDATION

         As no acceptable daily intake could be established no tolerances
    are recommended. Following officially acceptable use in various
    countries residues of vamidothion can occur in the following
    commodities up to the levels indicated. The guide-lines indicated
    below are unlikely to be exceeded as a result of the recommended use
    of vamidothion.

    Guide-line levels (based on a pre-harvest interval of six weeks)

         Apples and pears    2 ppm
         Brussels sprouts    1 ppm
         Sugar beet          0.5 ppm
         Grapes              0.5 ppm
         Hops                0.2 ppm

    FURTHER WORK OR INFORMATION

    Required (before an acceptable daily intake can be established)

    1.   Long-term studies in at least one animal species.

    2.   Adequate short-term studies in several species including a
         non-rodent species.

    3.   Studies to identify metabolites and investigate their toxicity.

    4.   Studies on the nature and level of residues in animal products
         from the feeding of residues at levels occurring on food wastes.

    5.   Information showing the fate of residues in the major crops in
         countries with different meteorological and growth conditions.


    REFERENCES

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    des Usine Chimiques, Rhône-Poulenc. Unpublished report

    Anon. (1966b) Vamidothion. Essai do neurotoxicité, submitted by
    Société des Usines Chimiques, Rhône-Poulenc. Unpublished report

    Anon. (1966e) Vamidothion. Etude de la potentialisation sur souris
    avec des insecticides comerciaux, submitted by Société dos Usines
    Chimiques, Rhône-Poulene. Unpublished report

    Celice, J., Fournel, J. and Koenig F. (1966) Evaluation des risques
    l'intoxication par le vamidothion (10.465 R.P.) au cours de sa
    fabrication et do son experimentation plein champ, submitted by
    Société dos Usines Chimiques, Rhône-Poulene. Unpublished report

    Desmoras, J. (1963) Biological determination of vamidothion in plants.
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    Desmoras, R. and Fournel, J. (1961) Insecticides.  Activités
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    Desmoras, R., Fournel, J. and Koenig F. (1961) Insecticides. Activités
    insecticides et toxicités comparées des 10.465 R.P. et 11.905 R.P.
    Submitted by Sociétés des Usines Chimiques, Rhône-Poulene. Unpublished
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    Desmoras, J., Laurent, M. and Buys, M. (1972) Unpublished report No.
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    Produit No. 10.463 R.P. Toxicité ague, tolerance locale, activités
    anticholinesterasique et antidotes, toxicité chronique chez le rat et
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    Ganter, P., Julou, L., Pasquet, J., Delesque, M. and Durel, J. (1969a) 
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    See Also:
       Toxicological Abbreviations
       Vamidothion (ICSC)
       Vamidothion (Pesticide residues in food: 1982 evaluations)
       Vamidothion (Pesticide residues in food: 1985 evaluations Part II Toxicology)
       Vamidothion (Pesticide residues in food: 1988 evaluations Part II Toxicology)