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    FAO Meeting Report No. PL/1965/10/2
    WHO/Food Add/28.65

    EVALUATION OF THE HAZARDS TO CONSUMERS RESULTING FROM THE USE OF
    FUMIGANTS IN THE PROTECTION OF FOOD

    The content of this document is the result of the deliberations of the
    Joint Meeting of the FAO Committee on Pesticides in Agriculture and
    the WHO Expert Committee on Pesticide Residues, which met 15-22 March
    19651

    Food and Agriculture Organization of the United Nations
    World Health Organization
    1965

             
    1 Report of the second joint meeting of the FAO Committee on
    Pesticides in Agriculture and the WHO Expert Committee on Pesticide
    Residues, FAO Meeting Report No. PL/1965/10; WHO/Food Add./26.65.

    CARBON DISULFIDE

    Compound

         Carbon disulfide

    Chemical name

         Carbon disulfide

    Synonym

         Carbon bisulfide

    Empirical formula

         CS2

    Structural formula

         S = C = S

    Relevant physical and chemical properties

    Physical state (atmospheric pressure, 20°C): liquid

    Boiling-point: 46°C

    Odour: sweetish when pure; impurities such as hydrogen sulfide give
    characteristic unpleasant odours

    Lowest concentration in air which is detectable by odour: undetectable
    by odour at toxic concentrations

    Flash point: 20°C (open cup)

    Flammability limits in air: 1.25 to 44% by volume

    Solubility:

        Water: 0.22 g/100 ml

        Organic solvents: infinitely soluble in alcohol, ether and benzine

    Specific gravity (liquid): 1.27

    Specific gravity (gas): 2.64

    Uses

         Carbon disulfide is sometimes used as a fumigant for grain,
    stored honeycombs and potatoes. It is often mixed with carbon
    tetrachloride or trichlorethylene.

    Residues

         See below.

    Effect of fumigant on treated crop

         Although the vapours of carbon disulfide have commonly been
    observed to disappear rapidly upon aeration of a fumigated foodstuff,
    there are no precise data on the rate of disappearance. Carbon
    disulfide is soluble in the lipid constituents and essential oils
    which may be present in some foodstuffs.

    BIOLOGICAL DATA

    Biochemical aspects

         Carbon disulfide has been recommended for use in tropical
    countries, inter alia, as an insecticidal fumigant for various
    vegetable foods, in particular legumes. It may persist in the form of
    residues because of its solubility in the lipid constituents and the
    essential oils. In this connexion it should be noted that a certain
    number of observations show that carbon disulfide may be absorbed
    through the digestive tract giving rise, if the doses are sufficiently
    high, to symptoms of poisoning of the same type as those caused by
    inhalation of the solvent (Zangger, 1930; Madlo and Zangger, 1930).

         Furthermore the possibility must be taken into consideration of
    the reaction of carbon disulfide with certain constituents of foods of
    vegetable origin. In this connexion its reactivity should be stressed
    with peptide and protein amino groups, as described in numerous papers
    (Chervenka and Wilcox, 1956; Leonis, 1948; Levy, 1950; Soucek and
    Madlo, 1953, 1954, 1955; Zahradnik, 1954, 1955).
    Dithiocarbamino-carboxylic derivatives are produced, and tend to form
    cyclic derivatives of 2-thio-5-thiazolidone:

    FIGURE 

         The existence of these reactions has been proved by
    chromatography of the amino acids and peptides in blood brought into
    contact, in vitro, with carbon disulfide labelled with 35S (Soucek
    et al., 1956).

         Various findings and, in particular, the increase in the thiol
    groups in the blood serum of animals or human beings exposed to carbon
    disulfide and especially chromatographic identification (Soucek and
    Madlo, 1955) and spectrophotometric measurements (Cohen et al., 1958;
    Cohen et al., 1959) show that these reactions occur in vivo.

         Their toxicological implications are important from various
    points of view:

    (1) They may occur over and above the solubility of the poison in
    lipid constituents and essential oils and thus affect the residues in
    plants, in certain cases.

    (2) The dithiocarbamino-carboxylic and thiazolidone derivatives (in
    their tautomeric form) have the power of forming complexes, thanks to
    their thiol groups, with polyvalent cations of great physiological
    importance, such as zinc and copper. Thus in rabbits subjected to
    poisoning with carbon disulfide, either by the cutaneous route (Cohen
    et al., 1958) or by inhalation (Cohen et al., 1959), increased
    excretion of zinc in the urine and faeces has been found to occur, as
    well as a corresponding fall in the blood level (serum and corpuscles)
    of this element. As concerns copper, a distinct fall in the content of
    the cerebral cortex and spinal cord was noted. The lack of zinc, and
    particularly the lack of copper in the central nervous system, may
    easily have serious pathological consequences, as revealed, moreover,
    by the degenerative lesions found at the histological level. The
    formation by fixation of carbon disulfide on peptides and proteins, of
    derivatives giving chelates with physiological polyvalent cations is
    one of the fundamental biochemical mechanisms in the toxicity of
    carbon disulfide (Cohen et al., 1959; Stokinger, 1963).

    (3) Dithiocarbamino-carboxylic derivatives can be decomposed by the
    cysteine desulfhydrylase in the liver of mammals, with liberation of
    hydrogen sulfide (Madlo and Soucek, 1957). This explains why carbon
    disulfide retained in the organism can subsequently be gradually
    excreted in the urine after partial metabolization into mineral
    sulfates, as has been demonstrated by the work of Strittmatter, Peters
    and McKee (Strittmatter et al., 1950), inter alia, on the mouse and
    the guinea-pig using carbon disulfide labelled with 35S.

         It must be carefully stressed, nevertheless, that these data
    concern the metabolism of carbon disultide in man and the higher
    mammals and that no research in this direction seems to have been
    carried out in the case of plants.

    Acute toxicity

                                                                     
    Animal      Route                  LD50 mg/kg      Reference
                                       body-weight
                                                                     

    Rabbit  Subcutaneous                 300          Lewin (1879)
    Rabbit  Inhalation (exposure      16 mg/litre     Negherbon (1959)
            for six hours)            dead in seven
                                      days
    Cat     Inhalation (exposure      23 mg/litre     Negherbon (1959)
            for three hours)
                                                                     

         Carbon disulfide emits highly toxic vapour, inhalation of which
    by laboratory animals and by man causes multiple symptoms showing
    attack on numerous phsyiological receptors, and especially on the
    central nervous system and the liver.

         Exposure of man to a concentration of 15 mg/litre during 50
    minutes to an hour may cause death; exposure during the same period to
    a concentration of the order of 3.5 mg/litre causes serious nervous
    disturbances (Flury and Zernik, 1931; Flury and Lehmann, 1938).

         Carbon disulfide is a cumulative poison. The maximum tolerable
    concentration in the air adopted by the United States Association of
    Government Hygienists is 20 ppm, or 60 mg/m3 (Anon, 1964). Some
    workers feel that this limit should be decreased to 10 ppm or 30
    mg/m3.

    Short-term studies

         Although much research has been carried out on the effects of
    repeated inhalation of carbon disulfide and although the results
    obtained, combined with observations on human subjects occupationally
    exposed to inhalation of the product, have made it possible to assess
    both qualitatively and quantitatively the toxicity of carbon disulfide
    when absorbed through the lungs and to suggest permissible limits
    under industrial conditions (10 to 20 ppm for repeated exposure over
    long periods), the same does not apply as concerns absorption per
    os. The few experiments recorded have been carried out on individual
    animals.

         Dog.    A dog weighing 13 kg was given daily for five months
    200 to 300 ml of water containing 0.5 g of carbon disulfide without
    any apparent symptoms (Sapelier, 1894).

    Long-term studies

    There is no information in regard to absorption per os.

    Comments on the experimental studies reported

         There are extremely few data on the short-term effects of carbon
    disulfide absorbed per os while data on long-term effects are
    completely lacking.

    Evaluation

         The very scanty data available do not make it possible to
    evaluate an acceptable daily intake for man.

    Further work required

         If the use of carbon disulfide for the fumigation of certain
    types of food proved to be essential, then research would have to be
    carried out:

    (1) on the nature and quantity of the residues present in the treated
    food;

    (2) on the long-term effects in at least two animal species of carbon
    disulfide and the products to which it may give rise by reaction with
    the protein constituents of food.

    REFERENCES

    Anon. (1964) Threshold limit values for 1964, Arch. environm.
    Hlth, 9, 545

    Cohen, A. E., Paulus, H. J., Keenan, R. G. & Scheel, L. D. (1958)
    Arch. industr. Hlth, 17, 164

    Cohen, A. E., Scheel, L. D., Kopp, J. F., Stockell, F. R., Keenan, R.
    G., Mountain, J. T. & Paulus, H. J. (1959) Amer. industr. Hyg. Ass.
    Quart., 20, 303

    Chervenka, H. & Wilcox, P. E. (1956) J. biol. Chem., 222, 21

    Flury, F. & Lehmann, K. B. (1938) Toxicologie und Hygiene der
    technischen Lösungsmitte, Springer, Berlin

    Flury, F. & Zernik, F. (1931) Schädliche gase, Springer, Berlin

    Leonis, J. (1948) C.R. Trav. Lab. Carlsberg fer. Chim., 26, 315

    Levy, A. L. (1950) J. chem. Soc., 404

    Lewin, -. (1897) Arch. Path. anat., 78, 113

    Madlo, Z. & Soucek, B. (1957) Bull. Soc. Chim. biol. (Paris), 39,
    989

    Madlo, Z. & Zangger, H. (1930) Schweiz med. Wschr., 60, 193

    Negherbon, W. O. (1959) Handbook of Toxicology, vol. 3, Saunders,
    Philadelphia

    Sapelier, E. (1894) Etude sur le sulfure de carbone (Thčse pour le
    Doctorat en médecine, Paris), cited by Lehman, K. B. (1894) Arch.
    Hyg. (Berl.), 20, 26

    Soucek, B. & Madlo, Z. (1953) Pracov. Lék., 5, 309

    Soucek, B. & Madlo, Z. (1954) Pracov. Lék., 6, 11

    Soucek, B. & Madlo, Z. (1955) Bull. Soc. Chim. biol. (Paris), 37,
    1373

    Soucek, B., Jensovsky, L., Pavelkova, E. & Zahradnik, R. (1956)
    Chemické listy, 50, 1651

    Soucek, B. & Madlo, Z. (1956) Arch. Gewerbepath. Gewerbehyg., 14,
    511

    Stokinger, H. E. (1963) Pharmacodynamie biochemical and toxicologic
    methods as bases for air quality standards, Report presented at the
    second symposium on the tolerable limits for toxic substances in
    industry

    Strittmatter, C. F., Peters, Th. & McKee, R. W. (1950) Arch.
    industr. Hyg., 1, 54

    Zahradnik, R. (1954) Chemické listy, 48, 11

    Zahradnik, R. (1955) Chemické listy, 49, 1002

    Zangger, H. (1930) Arch. Gewerbepath. Gewerbehyg., 1, 77
    


    See Also:
       Toxicological Abbreviations
       Carbon disulfide (EHC 10, 1979)
       Carbon disulfide (ICSC)
       Carbon disulfide (PIM 102)
       Carbon disulfide (FAO/PL:1967/M/11/1)
       Carbon disulfide (FAO/PL:1968/M/9/1)
       Carbon disulfide (WHO Pesticide Residues Series 1)
       Carbon Disulfide (CICADS 46, 2002)