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    INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY




    ENVIRONMENTAL HEALTH CRITERIA 15





    TIN AND ORGANOTIN COMPOUNDS

    A Preliminary Review





    This report contains the collective views of an international group of
    experts and does not necessarily represent the decisions or the stated
    policy of either the World Health Organization or the United Nations
    Environment Programme.

    Published under the joint sponsorship of the United Nations
    Environment Programme and the World Health Organization

    World Health Organization
    Geneva, 1980

    ISBN 92 4 154075 3

    (c) World Health Organization 1980

        Publications of the World Health Organization enjoy copyright
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    Universal Copyright Convention. For rights of reproduction or
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    should be made to the Office of Publications, World Health
    Organization, Geneva, Switzerland. The World Health Organization
    welcomes such applications.

        The designations employed and the presentation of the material in
    this publication do not imply the expression of any opinion whatsoever
    on the part of the Secretariat of the World Health Organization
    concerning the legal status of any country, territory, city or area or
    of its authorities, or concerning the delimitation of its frontiers or
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    CONTENTS

    TIN AND ORGANOTIN COMPOUNDS: A PRELIMINARY REVIEW

    1. SUMMARY AND RECOMMENDATIONS FOR FURTHER RESEARCH
         1.1. Chemistry and uses of tin compounds
               1.1.1. Inorganic tin
               1.1.2. Organotin compounds
         1.2. Analytical methods
         1.3. Environmental concentrations and exposures
               1.3.1. Environmental exposures
               1.3.2. Occupational exposure
         1.4. Metabolism
               1.4.1. Inorganic tin
               1.4.2. Organotin compounds
         1.5. Effects on experimental animals
               1.5.1. Inorganic tin
                       1.5.1.1   Local effects
                       1.5.1.2   Systemic effects
               1.5.2. Organotin compounds
                       1.5.2.1    Local effects
                       1.5.2.2    Systemic effects
         1.6. Effects in man
               1.6.1. Inorganic tin
               1.6.2. Organotin compounds
                       1.6.2.1   Local effects
                       1.6.2.2   Systemic effects
         1.7. Recommendations for further studies
               1.7.1. Analytical methods
               1.7.2. Environmental data
               1.7.3. Metabolism
               1.7.4. Effects

    2. CHEMISTRY AND ANALYTICAL METHODS
         2.1. Elemental tin
         2.2. Tin(II) compounds
         2.3. Tin(IV) compounds
         2.4. Organometallic compounds of tin
         2.5. Analytical methods
               2.5.1. Determination of inorganic tin
                       2.5.1.1   Atomic absorption spectrocopy
                       2.5.1.2   Emission spectroscopy
                       2.5.1.3   Neutron activation analysis
                       2.5.1.4   X-ray fluorescence
                       2.5.1.5   Miscellaneous analytical methods
               2.5.2. Determination of organotin compounds
                       2.5.2.1   Diorganotin compounds
                       2.5.2.2   Triorganotin compounds

    3. SOURCES OF ENVIRONMENTAL POLLUTION35
         3.1. Natural occurrence
         3.2. Industrial production
         3.3. Tin consumption
         3.4. Uses of tin
               3.4.1. Tin and inorganic tin compounds
               3.4.2. Organotin compounds
         3.5. Tin-containing waste

    4. ENVIRONMENTAL TRANSPORT AND TRANSFORMATIONS
         4.1. Transport and bioconcentration
         4.2. Environmental chemistry of tin
         4.3. Degradation of organometallic tin compounds

    5. ENVIRONMENTAL CONCENTRATIONS AND EXPOSURES
         5.1. Ambient air
         5.2. Soils and plants
         5.3. Water and marine organisms
         5.4. Food
         5.5. Organotin residues
         5.6. Working environment
         5.7. Estimate of effective exposure of man through environmental
               media

    6. METABOLISM
         6.1. Inorganic tin
               6.1.1. Absorption
               6.1.2. Distribution
                       6.1.2.1   Distribution in human tissues and
                                 biological fluids
               6.1.3. Excretion
               6.1.4. Biological half-time
         6.2. Organotin compounds
               6.2.1. Absorption
               6.2.2. Distribution
               6.2.3. Excretion
               6.2.4. Biotransformation

    7. EFFECTS ON ANIMALS
         7.1. Inorganic tin compounds
               7.1.1. Effects on the skin
               7.1.2. Respiratory system effects
               7.1.3. Effects on the gastrointestinal system
               7.1.4. Effects on the liver
               7.1.5. Effects on the kidney
               7.1.6. Effects on the blood-forming organs
               7.1.7. Central nervous system effects
               7.1.8. Effects on the reproductive system and the fetus
               7.1.9. Carcinogenicity and mutagenicity

               7.1.10. Other effects
               7.1.11. Effective doses and dose rates
                       7.1.11.1  Lethal doses
                       7.1.11.2  Minimum effective and no-observed effects
                                 doses
         7.2. Organotin compounds
               7.2.1. Effects on the skin and eyes
               7.2.2. Respiratory system effects
               7.2.3. Effects on the gastrointestinal system
               7.2.4. Effects on the liver and bile duct
               7.2.5. Effects on the kidney
               7.2.6. Effects on lymphatic tissue and immunological
                       effects
               7.2.7. Haematological effects
               7.2.8. Central nervous system effects
               7.2.9. Effects on reproduction and the fetus
               7.2.10. Carcinogenicity
               7.2.11. Effects on chromosomes
               7.2.12. Other effects
               7.2.13. Mechanisms of action
               7.2.14. Effective doses and dose rates
                       7.2.14.1  Lethal doses
                       7.2.14.2  Minimum effective and no-observed-effect
                                 doses

    8. EFFECTS ON MAN
         8.1. Inorganic tin compounds
               8.1.1. Acute poisoning
               8.1.2. Prolonged exposure
                       8.1.2.1   Effects of inhalation
                       8.1.2.2   Effects of ingestion
         8.2. Organotin compounds
               8.2.1. Local effects
               8.2.2. Systemic effects
                       8.2.2.1   Effects of dermal exposure
                       8.2.2.2   Effects of inhalation
                       8.2.2.3   Effects of ingestion
         8.3. Treatment of poisoning

    REFERENCES

    


    NOTE TO READERS OF THE CRITERIA DOCUMENTS

        While every effort has been made to present information in the
    criteria documents as accurately as possible without unduly delaying
    their publication, mistakes might have occurred and are likely to
    occur in the future. In the interest of all users of the environmental
    health criteria documents, readers are kindly requested to communicate
    any errors found to the Division of Environmental Health, World Health
    Organization, Geneva, Switzerland, in order that they may be included
    in corrigenda which will appear in subsequent volumes.

        In addition, experts in any particular field dealt with in the
    criteria documents are kindly requested to make available to the WHO
    Secretariat any important published information that may have
    inadvertently been omitted and which may change the evaluation of
    health risks from exposure to the environmental agent under
    examination, so that the information may be considered in the event of
    updating and re-evaluation of the conclusions contained in the
    criteria documents.

    WHO TASK GROUP ON ENVIRONMENTAL HEALTH ASPECTS OF TIN AND ORGANOTIN
    COMPOUNDS

     Members

    Professor R. Lauwerys, Unité de Toxicologie industrielle et médicale,
        Université catholique de Louvain, Bruxelles, Belgium
         (Rapporteur)

    Dr J. G. Noltes, Department of Organic and Organo-Element Chemistry,
        Institute for Organic Chemistry, Organization for Applied
        Scientific Research (TNO), Utrecht, Netherlands

    Professor M. Piscator, Department of Environmental Hygiene, The
        Karolinska Institute, Stockholm, Sweden

    Professor A.B. Roscin, Department of Occupational Hygiene, Central
        Institute for Advanced Medical Training, Moscow, USSR

    Dr M. Sharratt, Division of Environmental Health & Chemical Hazards,
        Department of Health & Social Security, London, England
         (Chairman)

    Professor M. Timar, State Institute of Occupational Health, Budapest,
        Hungary  (Vice-Chairman)

    Dr L. Cemisanska, Department of Occupational Toxicology, Centre of
        Hygiene, Sofia, Bulgaria

     Secretariat

    Dr L. Fishbein, National Centre for Toxicological Research, US Food &
        Drug Administration, Jefferson, AR, USA  (Temporary Adviser)

    Dr Y. Hasegawa, Control of Environmental Pollution and Hazards,
        Division of Environmental Health, WHO, Geneva, Switzerland

    Dr J. E. Korneev, Control of Environmental Pollution and Hazards,
        Division of Environmental Health, WHO, Geneva, Switzerland

    Dr A. Stiles, Division of Vector Biology and Control, WHO, Geneva,
        Switzerland

    Dr V. B. Vouk, Control of Environmental Pollution and Hazards,
        Division of Environmental Health, WHO, Geneva, Switzerland
         (Secretary)


        The following list of organotin compounds includes the trivial name of the compound used throughout the document, the Chemical Abstracts
    Service (CAS) name and number, the molecular formula, and alternative names,
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

     Monosubstituted compounds

    ethyltin trichloride           stannane, trichloroethyl-(9Cl) (8Cl)      1066-57-5     C2H5Cl3Sn        trichloroethylstannane;
                                                                                                            trichloroethyltin;
                                                                                                            ethyltrichlorostannane;
                                                                                                            ethyltrichlorotin
    ethyltin triiodide             stannane, ethyltriiodo- (9Cl) (8Cl)       3646-94-46    C2H5I3Sn         triiodoethyltin
    butyltin trichloride           stannane, butyltrichloro- (9Cl) (8Cl)     1118-46-3     C4H9Cl3Sn        monobutyltin trichloride;
                                                                                                            trichlorobutyltin;
                                                                                                            butyltrichlorostannane;
                                                                                                            butyltrichlorotin;
                                                                                                            trichlorobutyltin;
                                                                                                            trichlorobutylstannane;
                                                                                                            stannane, trichlorobutyl-
    butylstannoic acid             stannane, butylhydroxyoxo- (9Cl) (8Cl)    2273-43-0     C4H10O2Sn        1-butanestannoic acid;
                                                                                                            butyltin hydroxide
                                                                                                            oxide; butylstannoic acid (VAN)
    butylthiostannoic acid         stannane, butylmercaptooxo- (8Cl)         26410-42-4    C4H10O S Sn
    butyltin-S,S',S"-tris          acetic acid, 2,2',2"-                     25852-70-4    C34H66O6S3Sn     butyltin tris(isooctyl
                                                                                                            thioglycolate);
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Monosubstituted compounds cont'd.

    (isooctylmercaptoacetate)      ((butylstannylidyne)) tris (thio)                                        stannane, butyltris
                                   tris-, triisooctyl ester                                                 ((carboxymethyl) thio)-,
                                   (9Cl);                                                                   triisooctyl ester; butyltin
                                   acetic acid, ((butylstannylidyne)                                        tris(isooctyl thioglycollate);
                                   trithio) tri,-triisooctylester (8Cl)                                     monobutyltin tris 
                                                                                                            (isooctylthioglycolate);
                                                                                                            monobutyltin tris(isooctyltin
                                                                                                            thioglycolate); butyltin tris
                                                                                                            (isooctyl mercaptoacetate);
                                                                                                            triisooctyl(butylstannylidyne)
                                                                                                            trithio) triacetate;
                                                                                                            butylstannane tris(isooctyl
                                                                                                            mercaptoacetate)
    butyltin-S,S',S"-tris          8 oxa-3,5-dithia-4-                       26864-37-9    C34H66O6S3Sn     monobutyltin tris(2-ethylhexyl
    (2-ethyl                       stannatetradecanoic acid,                                                thioacetate), monobutyltin
    hexylmercaptoacetate)          4 butyl-10-ethyl-4-((2-((2-                                              tris(2-ethylhexyl thioglycolate)
                                   ethylhexyl)oxyl)-2-oxoethyl)
                                   thio)-7-oxo-, 2-ethylhexyl
                                   ester (9Cl); acetic acid,
                                   ((butylstannylidyne)
                                   trithio)tri-,tris(2-ethylhexyl)
                                   ester (8Cl)
    butyltin sulfide               distannathiane,                           15666-29-2    C8H18S3Sn2       butyl thiostannoic arthydride;
                                   dibutyldithioxo-(9Cl);                                                   monobutyltin sulfide
                                   distannthiane, 1,3-dibutyl-
                                   1,3-dithioxo- (8Cl)
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Monosubstituted compounds cont'd.

    octyltin trichloride           stannanne,                                3091-25-6     C8H17Cl3Sn       trichlorooctylstannane;
                                   trichlorooctyl-(9Cl) (8Cl)                                               octyltrichlorostannane;
                                                                                                            n-octyltin trichloride;
                                                                                                            n-octyltri-chlorostannane;
                                                                                                            mono-n-octyltin tri-chloride;
                                                                                                            trichloro-n-octylstannane

    octyltin tris(2-ethyl          8-oxa-3,5-dithia-4-                       27107-89-7    C38H74O6S3Sn
    hexylmercaptoacetate)          stannatetradecanoic acid,
                                   10-ethyl-4-((2-((2-ethylhexyl)oxy)
                                   -2-oxoethyl) thio)-4-octyl-7-oxo-,
                                   2-ethylhexylester (9Cl);
                                   acetic acid, ((octylstannylidyne)
                                   trithio)tri-, tris(2-ethylhexyl)
                                   ester (8Cl)

    cyclohexylstannoic acid        stannano, cyclohexylhydroxyoxo-           22771-18-2    C6H12O2Sn        cyclohexanestannoic acid
                                   (9Cl) (8Cl)

    Disubstituted compounds
    dimethyltin dichloride         stannane, dichlorodimethyl-               753-73-1      C2H6Cl2Sn        dichlorodimethylstannane;
                                   (9Cl) (8Cl)                                                              dichlorodimethyltin;
                                                                                                            dimethyldichlorostannane
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dimethyltin S,S'-bis           acetic acid, 2,2'-((dimethyl-             26636-01-1    C22H44O4S2Sn     TM 181; diisooctyl
    (isooctyl mercaptoacetate)     stannylene) bis (thio))bis-,                                             ((dimethylstannylene)
                                   diisooctyl ester (9Cl)                                                   dithio)diacetate;
                                                                                                            dimethylfin bis
                                                                                                            (isooctylthioglycolate);
                                                                                                            dimethyltin-S,S'-bis
                                                                                                            (iso-octylthyoglycolate);
                                                                                                            bis((((isooctyloxy)-
                                                                                                            carbonyl)methyl)thio)
                                                                                                            dimethylfin; T 40 (ester);
                                                                                                            TM 181S; Advastab TM 181S;
                                                                                                            Advastab TM 181 S
    diethyltin dichloride          stannane, dichlorodiethyl-                866-55-7      C4H10Cl2Sn       tin, dichlorodiethyl-;
                                                                                                            dichlorodiethyltin;
                                                                                                            diethyldichlorotin;
                                                                                                            dichlorodiethylstannane;
                                                                                                            diethyldichlorostannane

    diethyltin diiodide            stannanne, diethyldiiodo-                 2767-55-7     C4H10I2Sn        tin, diethyldiiodo-;
    diethyltin dioctanoate         stannane, diethylbis((1-oxo               2641-56-7     C20H40O4Sn       diethyldiiodostannane
                                   octyl)oxy) (9Cl);                                                        diethyltin dicaprylate
                                   stannane, diethylbis
                                   (octanoyloxy) (8Cl)
    dipropyltin dichloride         stannane, dichlorodipropyl-               867-36-7      C6H14Cl2Sn       dipropyltin chloride;
                                   (9Cl) (8Cl)                                                              dichlorodipropylstannane;
                                                                                                            di-n-propyltin dichloride
    diisopropryltin dichloride     stannane, dichlorobis                     38802-82-3    C6H14Cl2Sn
                                   (1-methylethyl)- (9Cl)
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dibutyltin dichloride          stannane, dibutyldichloro- (9Cl) (8Cl)    683-18-1      C8H18Cl2Sn       dichlorodibutyltin; dibutyltin 
                                                                                                            chloride;
                                                                                                            dichlorodibutylstannane;
                                                                                                            dibutyldichlorotin;
                                                                                                            di-n-butyltin dichlorlde;
                                                                                                            dibutyldi-chlorostannane
    dibutyltin oxide               stannane, dibutyloxo- (9Cl) (8Cl)         818-08-6      C8H18OSn         di-n-butyltin oxide; tin,
                                                                                                            dibutyloxo-;
                                                                                                            dibutylstannane oxide;
                                                                                                            dibutyloxotin;
                                                                                                            dibutyloxostannane
    dibutyltin diacetate           stannane, bis(acetyloxy)dibutyl- (9Cl)    1067-33-0     C12H24OSn        diacetoxydibutyltin;
                                                                                                            T 1[catalyst]; T 1 (VAN);
                                                                                                            Ba 2726
    dibutyltin dilaurate           stannane, dibutylbis                      77-58-7       C32H64O4Sn       Butynorate; DBTL; dibutylbis
                                   ((1-oxododecyl)oxy)-                                                     (lauroyloxy)-tin; Stabilizer
                                                                                                            D-22; tin dibutyl dilaurate;
                                                                                                            Stanclere DBTL; Davainex;
                                                                                                            TVS Tin Lau;
                                                                                                            dibutyltin didodecanoate;
                                                                                                            dibutylbis-(laurato)tin;
                                                                                                            Mark 1038; Tinostat; dibutyl-
                                                                                                            tin n-dodecanoate; Stavinor
                                                                                                            1200 SN; T 12 (catalyst);
                                                                                                            dibutylstannylene dilaurate;
                                                                                                            T 12 (VAN)
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dibutyltin maleate             1,3,2-dioxastannepin-4,7-dione,           78-04-6       C12H20O4Sn       dibutyl(maleoyldioxy)tin;
                                                                                                            Advastab DBTM;
                                   2,2'-dibutyl-(9Cl) (8Cl)                                                 Advastab T 290; Stavinor
                                                                                                            1300 SN; dibutyl-stannylene
                                                                                                            maleate; Advastab T 340;
                                                                                                            Nuodex V 1525; Irgastab T 290
    dibutyltin sulfide             stannane, dibutylthioxo-                  4253-22-9     C12H20O4Sn       tin dibutyl mercaptide
                                   (9Cl) (8Cl)
    dibutyltin di                  stannane, dibutylbis                      2781-10-4     C24H48O4Sn       dibutyltin bis
    (2-ethylhexoate)               ((2-ethyl-1-oxohexyl)oxy)- (9Cl)                                         (2-ethylhexanoate); dibutyltin
                                                                                                            bis(alpha-ethylhexanoate)

    dibutyltin dioctanoate         stannane, dibutyl-                        4731-77-5     C24H48O4Sn       dibutyltin dioctoate;
                                   bis((1-oxooctyl)oxy)- (9Cl);                                             dibutyltin dicaprylate;
                                   stannane, dibutyl                                                        dibutyltin octanoate
                                   bis(octanoyloxy)- (8Cl)
    dibutyltin di                  5,7,12-trioxa-6-stannahexa                15546-16-4    C24H40O8Sn       dibutyltin bis(monobutyl
    (butyl maleate)                deca-2,9-dienoic acid,6,6-dibutyl-                                       maleate); maleic acid
                                   4,8,11-trioxo, butyl ester,                                              dibutyltin salt (2:1)
                                   (Z,Z)- (9Cl) stannane, dibutylbis                                        diisobutyl ester; B5
                                   (3-carboxyacryloyl)oxy-,                                                 [stabilizer]; dibutyltin
                                   dibutyl ester,(Z,Z)-(8Cl)                                                bis(butyl maleate)
    dibutyltin di                  stannane, dibutylbis                      10584-97-1    C34H60O8Sn
    (nonylmaleate)                 ((3-carboxyacryloyl)oxy)
                                   -dinonyl ester, (z,z)-(8Cl)
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dibutyltin ß-mercapto          6H-1,3,2-oxathiastannin-6-one,            78-06-8       C11H22O2S Sn     Thermolite 35; Advastab T-306;
    propanoate                     2,2-dibutyldihydro-                                                      Mark 488; dibutyltin
                                                                                                            O,S'-mercaptopropionate,
                                                                                                            dibutyltin
                                                                                                            S,O-mercaptopropionate;
                                                                                                            dibutyltin ß-mercaptopropionate
    dibutyltin bis(lauryl          stannane, dibutylbis                      1185-81-5     C32H68S2Sn       dibutylbis(dodecylthio)tin;
    mercaptide)                    (dodecylthio)-(9Cl) (8Cl)                                                Mellite 39; dibutyltin
                                                                                                            bis(dodecylmercaptide); 
                                                                                                            bis-(dodecylthio)dibutyltin; 
                                                                                                            dibutylbis(dodecyl-thio)
                                                                                                            dibutyltin; dibutylbis 
                                                                                                            (dodecylthio)-stannane;
                                                                                                            Advastab TM 98; Mellite 139;
                                                                                                            Thermolite 20; dibutyltin
                                                                                                            S,S'-bis(dode-cylmercaptide)
    dibutyltin "laurate-           2-butenoic acid, 4,4'-                    73246-84-1    C32H64O4Sn       solution of dibutyltin dilaurate
    maleate"                       [(dibutylstannylene)bis(oxy)]                           C16H24O8Sn       and dibutyltin maleate;
                                   bis [4-oxo-, (Z,Z)- mixed with dibutyl                                   Thermolite 17
                                   bis [(1-oxododecyl)oxy] stannane (1-1)
                                   (9Cl)
    dibutyltin S,S'-bis            acetic acid, 2,2' (dibutyl                25168-24-5    C28H56O4S2Sn     dibutyltin bis(isooctyl
    (isooctylthioglycolate)        stannylene)bis(thio)bis-,                                                mercaptoacetate); dibutyltin
                                   diisooctyl ester (9Cl);                                                  S,S'-bis(isooctyl
                                   acetic acid, ((dibutylstannylene)                                        mercapto-acetate);
                                   dithio)di, diisooctyl ester (8Cl)                                        diisooctyl((dibutylstannylene)-
                                                                                                            dithio)diacetate;
                                                                                                            Thermolite 31; bis(iso-
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dibutyltin S,S'-bis                                                                                     octyioxycarbonylmethylthiolato)
    (isooctylthioglycolate)                                                                                 dibutyibis((((isooctyloxy)
    cont'd.                                                                                                 carbonyl)methyl)-thio)tin;
                                                                                                            BTS 70; T 101 (accelerator);
                                                                                                            Irgastab 17M; T 101
    dibutyltin S,S'-bis(2-         8-oxa-3,5-dithia-4-stannatetra            10584-98-2    C28H56O4S2Sn     dibutyltin bis(2-ethyihexyl
    ethylhexylmercaptoacetate)     decanoic acid 4,4-dibutyl-10-                                            thioglycolate); dibutyltin
                                   ethyl-7-oxo-2-ethylhexyl ester (9Cl);                                    S,S'-bis(2-ethylhexyl
                                   acetic acid, ((dibutylstannylene)                                        thio-glycolate)
                                   dithio)di-, bis(2-ethylhexyl)
                                   ester (9Cl)
    dipentyitin dichloride         stannane, dichlorodipentyl- (9Cl)         1118-42-9     C10H22Cl2Sn      dichlorodipentyltin
    dioctyltin dichloride          stannane, dichlorodioctyl- (9Cl) (8Cl)    3542-36-7     C16H34Cl2Sn      dichlorodioctyltin;
                                                                                                            dichlorodioctylstannane

    dioctyltin oxide               stannane, dioctyloxo- (9Cl) (8Cl)         870-08-6      C16H34O Sn       tin, dioctyloxo-; di-n-octyltin
                                                                                                            oxide; dioctyloxostannane

    dioctyltin acetate             stannane, bis(acetyloxy)dioctyl- (9Cl)    17586-94-6    C20H40O4Sn       dioctyldiacetoxytin

    dioctyltin dilnurate           stannane, dioctylbis                      3648-18-8     C40H30O4Sn       lauric acid, dioctyltin deriv;
                                   ((1-oxododecyl)oxy)-(9Cl);                                               dioctyl-dilauroyloxytin;
                                   stannane, bis(lauroyloxy)                                                dioctyltin didodecanoate
                                   dioctyl-(8Cl)
    dioctyltin maleate             1,3,2-dioxastannepin-4,7-dione,           16091-18-2    C20H36O4Sn       di-n-octyltin maleate;
                                   2,2-dioctyl- (9Cl);                                                      Thermolite 813; Estabex U 18;
                                                                                                            dioctylstannylene maleate;
                                                                                                            Mellite 825
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dioctyltin dibutylmaleate      5,7,12-trioxa-6-stannahexadeca-           29575-02-8    C32H36O8Sn       dioctyltinbis(butylmaleate)
                                   2,9-dienoic acid, 6,6-dioctyl-
                                   4,8,11-trioxo-, butyl ester,
                                   (Z,Z)-(9Cl);
                                   stannane, bis(3-carboxyacryloyl)
                                   oxy)dioctyl-, dibutyl ester (Z,Z)-
                                   (8Cl)
    dioctyltin-S,S'-(ethylene      1,3-dioxa-6,9-d ithia-2-stanna            56875-68-4    C22H42O4S2Sn     ethylenebisthioglycolate
    glycol-bis-mercaptoacetate)    cycloundecane-4,11-dione,2,2-                                            dioctyltin
                                   dioctyl-(9Cl)
    dioctyltin-S,S'-bis            acetic acid, 2,2'-                        26401-97-8    C36H72O4S2Sn     diisooctyl((dioctylstannylene)
    (isooctyl-mercaptoacetate)     ((dioctylstannylene)bis(thio)                                            dithio)-diacetate; dioctyltin
                                   bis-,diisooctyl ester (9Cl);                                             bis(isooctylmercapto-acetate);
                                   acetic acid, ((dioctylstannylene)                                        Thermalite 831; dioctyltin
                                   dithio)di-, diisooctyl ester (8Cl)                                       di(iso- octylthyoglycolate);
                                                                                                            di-n-octyltin bis(iso-
                                                                                                            octylmercaptoacetate), bis
                                                                                                            ((((isooctyloxy)-carbonyl)
                                                                                                            methyl)thio)dioctyltin; Mellite
                                                                                                            831C; Irsastab 17 MOK;
                                                                                                            dioctyltin bis
                                                                                                            (iso-octylthyoglycolate);
                                                                                                            dioctyltin bis 
                                                                                                            (diiso-octylthioglycolate)

    dioctyltin mercaptoacetate     1,3,2-oxathiastannolan-5-one,             15535-79-2    C18H36O2S Sn     dioctyltin S,O-mercaptoacetate
                                   2,2-dioctyl-(9Cl) (8Cl)
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dioctyltin ß-mercapto          6H-1,3,2-oxathiastannin-6-one,            3033-29-2     C19H38O2S Sn     dioctyltin
    propanoate                     dihydro-2,2-dioctyl- (9Cl) (8Cl)                                         S,O-3-mercaptopropionate;
                                                                                                            dioctyltin mercaptopropionate
    dioctyltin-S,S'-bis            8-oxa-3,5-dithia-4-stanna                 27107-88-6    C28H56O4S2Sn
    (butyl mercaptoacetate)        dodecanoic acid, 4,4-dioctyi-7-oxo-,
                                   butyl ester (9Cl)
                                   acetic acid, (((dioctylstannylene)
                                   dithio)di-, butyl ester (8Cl)
    dioctyltin-S,S'-bis(2-         8-oxa-3,5-dithia-4-stannatetra            15571-58-1    C36H72O4S2Sn     bis(2-ethylhexyl)
    ethylhexylmercaptoacetate)     decanoic acid, 10-ethyl-4,4-                                             (dioctylstannylene)
                                   dioctyl-7-oxo-, 2-ethylhexyl                                             dithio)diacetate; dioctyltin
                                   ester (9Cl);                                                             bis(2-ethyl-hexyl thioglycolate);
                                                                                                            bis(2-ethylhexylthyo-glycolato)
                                                                                                            dioctyltin; Advastab 17 MOK
                                   acetic acid, ((dioctylstannylene)
                                   dithio)di-, bis(2-ethylhexyl)
                                   ester (8Cl)
    dioctyltin-S,S'-bis            8-oxa-3,5-dithia-4-stannaeicosanoic       73246-85-2    C44H88O4S2Sn     dioctyltin bis
    (laurylmercaptoacetate)        acid, 4,4-dioctyl-7-oxo, dodecyl ester                                   (laurylthioglycolate)
                                   (9Cl)
    dioctyltin bis(2-              5,7,12-trioxa-6-stannaoctadeca-2,9-       10039-33-5    C40H72O8Sn       di-n-octyltin bis
    ethylhexylmaleate)             dienoic acid, 14-ethyl-6,6-                                              (2-ethylhexylmaleate)
                                   dioctyl-4,8,11-trioxo, 2-ethylhexyl
                                   ester, (Z,Z) (9Cl)

    dioctyltin bis(dodecyl         stannane, bis(dodecylthio)                22205-30-7    C40H84S2Sn       bis(dodecylthio)dioctyltin;
    mercaptide)                    dioctyl-(9Cl) (8Cl)                                                      dioctyltin bis(lauryl
                                                                                                            mercaptide); dioctyltin,
                                                                                                            dilauryl mercaptan salt
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    Disubstituted compounds cont'd.

    dioctyltin-S,S'-(1,4-          1,9-dioxa-4,6-dithia-5-                   69226-46-6    C24H46O4S2Sn
    butanediol-bis-mercapto        stannacyclotridecane-2,8-
    acetate)                       dione, 5,5-dioctyl- (9Cl)
    dioctyltin di(1,2-             1,3,8,11-tetraoxa-2-                      69226-45-5    C27H44O8Sn
    propyleneglycolmaleate)        stannacyclo-pentadeca-5,13-diene
                                   4,7,12,15-tetrone, 9-methyl-2,2-
                                   dioctyl-, (Z,Z)-(9Cl)
    dioctyltin bis(isobutyl        stannane, bis[(3-carboxy-                 15571-59-2    C32H56O8Sn       dioctyltin bis(isobutylmaleato)
    maleate)                       acryloyl)oxy]dioctyl-, diisobutyl                                        tin; 5,7,12-triox-6-stannapenta-
                                   ester, (Z,Z)- (9Cl)                                                      2,9-dienoic acid, 6,6-dioctyl-
                                                                                                            13-methyl-4,8,11-trioxo,
                                                                                                            1-methyl-propyl ester
    diphenyltin dichloride         stannane, dichlorodiphenyl- (9Cl) (8Cl)   1135-99-5     C12H10Cl2Sn      dichlorodiphenyltin;
                                                                                                            diphenylstannyl dichloride;
                                                                                                            diphenyldichlorotin;
                                                                                                            diphenyl-tin chloride;
                                                                                                            dichlorodiphenylstannane
    dicyclohexyltin oxide          stannane, dicyclohexyloxo-                22771-17-1    C12H22O Sn
                                   (9Cl) (8Cl)
    didodecyltin dibromide         stannane, dibromodidodecyl-               65264-08-6    C24H50Br2Sn      di-n-dodecyltin dibromide
                                   (9Cl)
    dioctadecyltin dibromide       stannane, dibromodioctadecyl-             65264-09-7    C36H74Br2Sn      di-n-octadecyltin dibromide
                                   (9Cl)
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    TRISUBSTITUTED COMPOUNDS
    triethyltin bromide            stannane, bromotriethyl- (9Cl) (8Cl)      2767-54-6     C6H15Br Sn
    triethyltin chloride           stannane, chlorotriehyl- (9Cl) (8Cl)      994-31-0      C6H15Cl Sn       chlorotriethyistannane;
                                                                                                            chlorotriethyltin;
                                                                                                            triethylstannyl chloride;
                                                                                                            triethylchloro-stannane;
                                                                                                            triethylchlorotin
    triethyltin iodide             stannane, triethyliodo-                   2943-86-4     C6H15I Sn        triethyliodostannane;
                                   (9Cl) (8Cl)                                                              triethylstannyl iodide;
                                                                                                            iodotriethylstannane
    triethyltin suifate            4,6-dioxa-5-thia-3,7-distannanonane,      57-52-3       C12H30O4S Sn2    triethylhydroxytin sulfate;
                                   3,3,7,7-tetraethyl- 5,5-dioxide (9Cl)                                    bis(triethyltin)
                                   stannane, triethylhydroxy-                                               sulfate
                                   sulfate (2:1) (8Cl)
    triethyltin acetate            stannane, (acetyloxy)                     1907-13-7     C8H18O2Sn        acetoxytriethylstannane
                                   triethyl-(9Cl);
                                   stannane, acetoxytriethyl-
                                   (8Cl)
    triethyltin hydroxide          stannane, triethylhydroxy-                994-32-1      C6H16O Sn        triethylstannanol;
                                   (9Cl) (8Cl)                                                              triethylstannol;
                                                                                                            triethyl-hydroxystannane;
                                                                                                            hydroxytriethylstannane
    trlethylstannylmethyl          stannane, triethyl(3-methoxy              17869-84-0    C11H22O2Sn
    (1-propynyl) formal            methoxy)-l-propynyl-
    triethylstannylphenyl          stannane, trlethyl(phenylethynyl)-        1015-27-6     C14H20Sn
    acetylene                      (9Cl) (8Cl)
    1-triethylstannyl-3-           silane, trimethyl((3-triethylstannyl)-    4628-88-0     C12H26O SiSn
    trimethylsiloxi-1-propyne      2-propynyl)oxy)-
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    TRISUBSTITUTED COMPOUNDS

    2-trichloro-1-(butine-         stannane, (1-(3-butinyloxy)               17869-91-9    C12H21C13O2Sn
    1'-oxide)-1-(triethyl          -2,2,2-trichloroethoxy)triethyl-
    stannyloxy)ethane

    trivinyltin chloride           stannane, chlorotriethenyl-               10008-90-9    C6H9Cl Sn        chlorotrivinyltin;
                                   (9Cl);                                                                   chlorotrivinylstannane
                                   stannane, chlorotrivinyl-
                                   (8Cl)
    tributyltin chloride           stannane, tributylchloro-                 1461-22-9     C12H27Cl Sn      tributylchlorotin;
                                   (9Cl) (8Cl)                                                              chlorotributylstannane;
                                                                                                            tributylstannyl chloride
    tributyltin fluoride           stannane, tributylfluoro-                 1983-10-4     C12H27F Sn       tributylfluorostannane;
                                   (9Cl) (8Cl)                                                              fluorotributyltin;
                                                                                                            tri-n-butylstannyl fluoride
    bis(tributyltin) oxide         hexabutyldistannoxane                     56-35-9       C24H54O2 Sn2     C-Sn-9; BioMeT TBTO; Bultinox;
                                   distannoxane, hexabutyl- (9Cl) (8Cl)                                     hexabutyl-distannoxane;
                                                                                                            oxybis(tributyitin); TBTO;
                                                                                                            6-oxa-5,7-distannaundecane,
                                                                                                            5,5,7,7-tetra-butyl-;
                                                                                                            Lastanox T; Vikol AF-25;
                                                                                                            Vikol LO-25; BioMeT 66;
                                                                                                            oxybis(tributylstannane);
                                                                                                            BioMeT SRM; Lastanox T20;
                                                                                                            bis(tri-butylstannyl)oxide;
                                                                                                            Lastanox Q; Lastanox
                                                                                                            F; Stannicide A; tributyltin
                                                                                                            oxide; Myko-lastanox F
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    TRISUBSTITUTED COMPOUNDS

    tributyltin acetate            stannane, (acetyloxy)tributyl- (9Cl);     56-36-0       C14H30O2Sn       acetoxytributyltin;
                                   stannane, acetoxytributyl- (8Cl)                                         tributylacetoxystannane;
                                                                                                            tri-n-butyltin acetate;
                                                                                                            acetoxytributyl-
    tributyltin linoleate          stannane, tributyl((1-oxo-9,12-           24124-25-2    C30H58O2Sn       stannane; tributylstannylacetate
                                   octadecad ienyl)oxy)-(Z,Z)-(9Cl);
                                   stannane, tributyl(linoleoyloxy)-
                                   (8Cl)
    tributyltin benzoate           stannane, (benzoyloxy)tributyl-           4342-36-3     C19H32O2Sn       tri-n-butyltin benzoate; tin,
                                   (9Cl) (8Cl)                                                              (benzoyloxy) tributyl-
    tributyltin salicylate         phenol, 2-[[(tributylstannyl)oxy]         4342-30-7     C19H32O3Sn       tin, tributyl(salicyloyloxy)-
                                   carbonyl]- (9Cl)
                                   stannane, tributyl(salicyloyloxy)-
                                   (8Cl)
    tributyltin methacrylate       stannane, tributyl((2-methyl-1-           2155-70-6     C16H32O2Sn       tributylstannyl methacrylate;
                                   oxo-2-propenyl)oxy)-(9Cl);                                               tributyl- (methacryloxy)stannane;
                                   stannane, tributyl(methacryloyloxy-                                      tin, tributyl-
                                   (8Cl)                                                                    methacrylate; (methacryloyloxy) 
                                                                                                            tributyl-stannane;
                                                                                                            tributylmethacryloyloxystannane
    tributyltin laurate            stannane, tributyl                        3090-36-6     C24H50O2Sn       tin, tributyl(lauroyloxy)-;
                                   ((1-oxo-dodecyl)oxy)-(9Cl)                                               tributyltin laurate;
                                   stannane, tributyl(lauroyloxy)- (8Cl)                                    tributyltin dodecanoate
    tributyltin oleate             stannane, tributyl((1-oxo-9-octa          3090-35-5     C30H60O2Sn       tin, tributyl(oleoyloxy)-;
                                   decenyl)oxy)-, (Z)-(9Cl);                                                N 5117 (Stauffer); N 5117
                                   stannane, tributyl(oleoyloxy)- (8Cl)
    trihexyltin acetate            stannane, (acetyloxy)trihexyl-            2897-46-3     C20H42O2Sn       tin, acetoxytrihexyl-;
                                   (9Cl);                                                                   acetoxytrihexyltin
                                   stannane, acetoxytrihexyl- (8Cl)
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    TRISUBSTITUTED COMPOUNDS

    tricyclohexyltin hydroxide     stannane, tricyclohexylhydroxy-           13121-70-5    C18H34O Sn       Plictran;
                                   (9Cl) (8Cl)                                                              tricyclohexylhydroxystannane;
                                                                                                            tricyclohexylhydroxytin;
                                                                                                            Plyctran; M 3180; Cyhexatin;
                                                                                                            hydroxytricyclohexylstannane;
                                                                                                            Dowco 213; tricyclohexylstannanol

    trioctyltin chloride           stannane, chlotrioctyl- (9Cl) (8Cl)       2587-76-0     C24H51ClSn       tin, chlorotrioctyl-;
                                                                                                            chlorotrioctyltin; tri-n-
                                                                                                            chlorotrioctylstannane
                                                                                                            octyltin chloride;
    triphenyltin chloride          stannane, chlorotriphenyl-                639-58-7      C18H15ClSn       LS 4442; GC 8993; General
                                   (9Cl) (8Cl)                                                              Chemicals 8993; TPTC; HOE 2872;
                                                                                                            Brestanoi; Fentin chloride;
                                                                                                            chlorotriphenyltin;
                                                                                                            chlorotri-phenylstannane;
                                                                                                            triphenylchlorostannane;
                                                                                                            triphenylchlorotin
    triphenyltin hydroxide         stannane, hydroxytriphenyl-               76-87-9       C18H16OSn        hydroxytriphenyttin; 
                                   (9Cl) (8Cl)                                                              hydroxytriphenyl-stannane;
                                                                                                            TPTH; triphenylstannanol; K 19
                                                                                                            (VAN); Tenhide; Fenolovo; Du-Ter
                                                                                                            Extra; Erithane; Vancide KS;
                                                                                                            Dowco 186; ENT 28009; Du-Ter;
                                                                                                            Fentin hydroxide
                                                                                                                                                

                                                      ORGANOTIN COMPOUNDS
                                                                                                                                                

    Name used in text              CAS Index name                            CAS number    Molecular             Synonyms
                                                                                           formula
                                                                                                                                                

    TRISUBSTITUTED COMPOUNDS

    triphenyltin acetate           stannane, (acetyloxy)triphenyl-           900-95-8      C20H18O2Sn       Brestan;
                                   (9Cl);                                                                   acetoxytriphenylstannane;
                                   stannane, acetyloxytriphenyl- (8Cl)                                      Batasan; Phentin acetate;
                                                                                                            Suzu; acetato-triphenylstannane;
                                                                                                            GC 6936; ENT 25208; Fentin
                                                                                                            acetate; Lirostanol; tin
                                                                                                            triphenyl acetate; TPTA;
                                                                                                            triphenylacetostannane;
                                                                                                            VP 19-40; Brestan 60; Liromatin
    p-bromophenoxy triethyltin     stannane, (p-bromophenoxy)                20961-09-5    C12H19BrOSn
                                   triethyl- (8Cl)

    TETRASUBSTITUTED COMPOUNDS
    tetrarnethyltin                stannane, tetramethyl- (9Cl) (8Cl)        594-27-4      C4H12Sn          tetramethylstannane
    tetraethyltin                  stannane, tetraethyl- (9Cl) (8Cl)         597-64-8      C8H20Sn          tetraethylstannane
    tetrabutyltin                  stannane, tetrabutyl- (9Cl) (8Cl)         1461-25-2     C16H36Sn         tetra-n-butyltin;
                                                                                                            tetrabutylstannane
    tetraisobutyltin               stannane, tetrakis(2-methylpropyl)-       3531-43-9     C16H36Sn         tetraisobutylstannane
                                   (9Cl)
                                   stannane, tetraisobutyl- (8Cl)
    tetraphenyltin                 stannane, tetraphenyl- (9Cl) (8Cl)        595-90-4      C24H20Sn         tetraphenylstannane
    tetraoctyltin                  stannane, tetraoctyl- (9Cl) (8Cl)         3590-84-9     C32H68Sn         tetra-n-octyltin;
                                                                                                            tetra-n-octylstannane
    stannous octanoate             octanoic acid, tin(2+) salt               1912-83-0     C8H16O2 1/2Sn    tin octanoate; stannous
                                   (9Cl) (8Cl)                                                              dioctanoate; tin(II)octanoate;
                                                                                                            stannous caprylate;
                                                                                                            stannous octcate
    tin (II) cyclopentadienyl      stannocene (9Cl)                          1294-75-3     C10H10Sn         tin, di-pi-cyclopentadienyl-
                                                                                                                                                
    

    TIN AND ORGANOTIN COMPOUNDS: A PRELIMINARY REVIEW

        This is the first volume in the UNEP/WHO Environmental Health
    Criteria series containing a preliminary review of environmental
    health aspects of a group of chemicals. Such reports are prepared in
    accordance with the second objective of the WHO Environmental Health
    Criteria Programme "to identify new or potential pollutants by
    preparing preliminary reviews on health effects of agents likely to be
    used in industry, agriculture, in the house, and elsewhere" (WHO,
    1976). Organometallic tin compounds are being used in increasing
    amounts for a variety of applications and the annual world production
    has risen from less than 50 tonnes in 1950 to about 25 000 tonnes in
    1975. One of the main applications is the use of dialkyland, to a much
    lesser extent, monoalkytin compounds in the stabilization of
    poly(vinyl chloride). Other applications include the use of
    tributyltin compounds as industrial biocides and surface disinfectants
    and the use of triphenyltin and tricylohexyltin compounds as
    agricultural fungicides and agricultural acaricides.

        Preliminary reviews differ from the criteria documents in that
    they do not contain a separate section on health risk evaluation and
    that the procedure for their preparation is simpler. Draft preliminary
    reviews are not submitted for comments to the national focal points
    for the WHO Environmental Health Criteria Programme. The first draft
    is reviewed by a Task Group of experts, and on the basis of their
    comments, a final draft is prepared and scientifically edited by the
    WHO Secretariat. However, individual members of the Task Group and
    other experts may be consulted during the scientific editing of the
    documents.

        The first draft of the present document was prepared by Dr L.
    Fishbein, National Center for Toxicological Research, Jefferson, AR,
    USA. Dr A. E. Martin, formerly Principal Medical Officer, Department
    of Health and Social Security, London, England, assisted the
    Secretariat in the preparation of a revised first draft, which was
    circulated to the members of the Task Group prior to the meeting. The
    Task Group on Environmental Health Aspects of Tin and Organotin
    Compounds met in Geneva from 10-14 March 1975 to review and revise
    this draft, and, on the basis of their comments, a final draft was
    prepared by the Secretariat. The Secretariat wishes to acknowledge the
    most valuable assistance in the final phases of preparation of the
    document of Dr Renate Kimbrough, Center for Disease Control, Atlanta,
    GA, USA, Professor Magnus Piscator, Department of Environmental
    Hygiene, Karolinska Institute, Stockholm, Sweden, Dr Robert J. Horton,

    US Environmental Protection Agency, Research Triangle Park, NC, and Dr
    Warren T. Piver, National Institute of Environmental Health Sciences,
    Research Triangle Park, NC, USA. The help is also gratefully
    acknowledged of Dr H. Nordman, Institute of Occupational Health,
    Helsinki, Finland, who assisted both in the preparation of the final
    draft and in the final scientific editing of the document and of
    Professor C. Schlatter and Dr R. Utzinger, Institué de Toxicologie,
    Ecole Fédérale Polytechnique et Université de ZÜrich, Dr. D. S. Valley
    Dr D. F. Walker, National Library of Medicine, Department of Health,
    Education and Welfare, USA, and Dr A. Stiles, Consultant, Department
    of Environmental Health, WHO, Geneva, who helped in compiling the list
    of organotin compounds.

        This document is based primarily on original publications listed
    in the reference section. However, several publications reviewing the
    health effects of inorganic and organotin compounds have also been
    used. These include reviews by Barnes & Stoner (1959), Browning
    (1969), FAO/WHO (1971), International Labour Office (1972), Kimbrough
    (1976), MacIntosh (1969), National Institute of Occupational Safety
    and Health (1976), and Piver (1973).

        Details of the WHO Environmental Health Criteria Programme,
    including definitions of some of the terms used in the documents, may
    be found in the general introduction to the Environmental Health
    Criteria Programme, published together with the environmental health
    criteria document on mercury (Environmental Health Criteria I M
    Mercury, Geneva, World Health Organization, 1976) and now available as
    a reprint.

    1.  SUMMARY AND RECOMMENDATIONS FOR FURTHER RESEARCH

    1.1  Chemistry and Uses of Tin Compounds

    1.1.1  Inorganic tin

        The annual world production of tin is around 225 000 tonnes, about
    70% of which is obtained from ores, the remaining 30% being recovered
    from scrap metal. Tin is mainly used in tinplated containers, but it
    is also extensively used in solders, in alloys such as bronzes,
    babbit, pewter, and type metal, and in more specialized alloys such as
    dental amalgams and the titanium alloys used in aircraft engineering.

        Inorganic tin compounds, in which the element may be present in
    the oxidation states of +2 or +4 are used in a variety of industrial
    processes for the strengthening of glass, as a base for colours, as
    catalysts, as stabilizers in perfumes and soaps, and as dental
    anticariogenic agents.

    1.1.2  Organotin compounds

        Organotin compounds are classified as R4Sn, R3SnX, R2SnX2, and
    RSnX3. In compounds of industrial importance, R is usually a butyl,
    octyl, or phenyl group and X, a chloride, fluoride, oxide, hydroxide,
    carboxylate, or thiloate. So far, monosubstituted organotin compounds
    (RSnX3) have had a very limited application, but they are used as
    stabilizers in poly(vinyl chloride) films. Disubstituted organotin
    compounds R2SnX2) are mainly used in the plastics industry,
    particularly as stabilizers in poly(vinyl chloride). They are also
    used as catalysts in the production of polyurethane foams and in the
    room-temperature vulcanization of silicones. Trisubstituted organotin
    compounds (R3SnX) have biocidal properties that are strongly
    influenced by the R-groups. The most important of these compounds are
    the tributyl-, triphenyl-, and tricyclohexyltin compounds, which are
    used as agricultural and general fungicides, bactericides,
    antihelminthics, miticides, herbicides, molluscicides, insecticides,
    nematocides, ovicides, rodent repellents, and antifoulants in boat
    paints. The tetrasubstituted organotin compounds (R4Sn) are mainly
    used as intermediates in the preparation of other organotin compounds.

    1.2  Analytical Methods

        A wide variety of analytical methods is available for the
    determination of tin at low concentrations.a However, these methods
    have rarely been compared with regard to their suitability for
    application to a particular problem and, on the basis of available
    information, it is not possible to recommend a specific analytical
    technique for a particular application.

        Inorganic tin in food and biological materials is usually
    determined by atomic absorption. Other spectroscopic methods have also
    been used with satisfactory accuracy and precision, including emission
    spectroscopy for air, water, and food samples and neutron activation
    analysis for geological samples.

        Many analytical methods have been used for the determination of
    organotin compounds. Atomic absorption and other spectroscopic methods
    combined with chromatography have been used for the estimation of
    diorganotin compounds. Pesticide residues have been determined by
    spectroscopic methods and gas-liquid or thin-layer chromatography.
    However, reliable methods have still to be developed for the
    quantitative extraction, separation, and determination of many
    individual tin species in mixtures containing both inorganic tin and
    organotin compounds that may occur in various media.

    1.3  Environmental Concentrations and Exposures

    1.3.1  Environmental exposures

        On the whole, contamination of the environment by tin is only
    slight. The levels of pollution arising from gases and fumes, waste
    slag, and liquid wastes from tin processing are low because of the
    high degree of recovery and reprocessing used in this industry.

        Concentrations of tin in air are often below the detection limits
    and, when detected, the levels are generally below 0.2-0.3 µg/m3,
    except in the vicinity of industrial sources of emission, where
    concentrations up to 5 µg/m3 may occur.

              

    a  Throughout the document the word concentration indicates mass
       concentration unless otherwise stated.

        Tin has not always been found in soils and plants; however, it is
    possible that in some cases, concentrations have been below the
    detection limits. Tin concentrations in soils are generally below
    200 mg/kg but in regions of tin-containing minerals, the levels may
    exceed 1000 mg/kg. The small amount of evidence available concerning
    the uptake of tin by crops suggests that soil concentrations do not
    markedly influence its uptake by plants.

        Tin has been detected only occasionally in river and municipal
    waters. Values exceeding 1 µg/litre are exceptional, although values
    as high as 30 µg/litre have been found in drinking water. Sea water
    concentrations are of the order of 3 µg/litre. Organotin compounds may
    enter water, for example, from antifouling paints on the bottoms of
    ships or from molluscicides, which, to be effective, should be present
    at concentrations of about 1 mg/litre.

        Food is the main source of tin for man. A diet composed
    principally of fresh meat, cereals, and vegetables, is likely to
    contain a mean tin concentration of about 1 mg/kg. Larger amounts of
    tin exceeding 100 mg/kg may be found in foods stored in plain cans
    and, occasionally, in foods stored in lacquered cans. Some foods such
    as asparagus, tomatoes, fruits, and their juices tend to contain high
    concentrations of tin if stored in unlaquered cans. Organotin
    compounds may be introduced into foods through the use of such
    compounds as pesticides and, to some extent, through migration of tin
    from poly(vinyl chloride) materials. However, the levels of organotin
    compounds in food are generally below 2 mg/kg.

        Experimental studies have provided evidence of the
    biotransformation of some triphenyl-, and tricyclohexyltin compounds.
    There are also limited data suggesting methylation of tin by organisms
    present in the environment. From the available information, it appears
    that bioconcentration of tin and organotin compounds of a magnitude
    that might endanger life or the environment is unlikely to occur.

        The estimated mean total daily intake of tin by man ranges from
    200 µg to 17 mg. A diet consisting of fresh foods probably provides
    about 1-4 mg/day. The likely daily intake from water is estimated to
    be less than 30 µg/day, and the daily amount entering the body from
    air, less than 1 µg.

    1.3.2  Occupational exposure

        Several technological operations associated with the processing of
    tin are known to cause excessive occupational inhalation exposure to
    tin oxide which may result in a benign pneumoconiosis termed
    stannosis, many cases of which have been reported in the past.

        Workers involved in the processing of di- and trisubstituted
    organotin compounds may be subject to excessive exposure from time to
    time. Workers spraying fields or treating plants with trialkyl- or
    triaryltin compounds may also run the risk of exposure to these
    compounds.

    1.4  Metabolism

    1.4.1  Inorganic tin

        The extent of absorption through the respiratory route has still
    to be assessed. The absorption of ingested inorganic tin is likely to
    be less than 5% although figures as high as 20% have been suggested.
    Gastrointestinal absorption is influenced by the oxidation state,
    tin(II) compounds being more readily absorbed than tin(IV) compounds.
    The anion complement may also influence the rate of absorption.

        Absorbed tin leaves the vascular system rapidly. Bone is the main
    site of deposition and the highest concentrations of tin are found in
    the lung, kidney, liver, and bone. Penetration of the blood-brain and
    placental barriers appears to be very slight. With the exception of
    the lungs, inorganic tin does not accumulate in organs with increasing
    age.

        Absorbed inorganic tin is mainly excreted in the urine. The
    fraction excreted with the bile varies with the type of compound and
    is probably below 15%.

    1.4.2  Organotin compounds

        In general, organotin compounds are more readily absorbed from the
    gut than inorganic tin compounds; allowance must be made, however, for
    the great variations found between different compounds and different
    species. As a rule, tin compounds with a short alkyl chain are more
    readily absorbed from the intestinal tract. The trialkyltin compounds
    are usually well absorbed through the skin. As far as distribution is
    concerned, the highest concentrations in rats, guineapigs, rabbits,
    and hamsters have mostly been detected in the liver. Trisubstituted
    organotin compounds have been found in the brain of various species
    but the form of tin present in the brain has not been satisfactorily
    identified.

        Many organotin compounds are transformed, to some extent, in the
    tissues. The dealkylation and dearylation of tetra-, tri-, and
    disubstituted organotin compounds seem to occur in the liver, but the
    dealkylation of diethyltin compounds appears to take place both in the
    gut and in tissues of other organs. The mode of excretion of organotin
    compounds largely depends on the type of the compound. For example,

    ethyltin trichloride seems to be mainly excreted with the urine, but
    diethyltin is eliminated with the faeces, urine, and the bile.
    Triethyltin is not only excreted with the urine, but, at least in
    lactating sheep, also with the milk. The route of excretion for many
    compounds is not known. The biological half-time of different
    organotin compounds varies and many compounds are slow to disappear
    from the organs. Usually the biological half-time seems to be longer
    in the brain than in other organs.

    1.5  Effects on Experimental Animals

        Although there is evidence that tin is essential for the normal
    growth of rats, no evidence exists that it is essential for other
    species including man.

    1.5.1  Inorganic tin

    1.5.1.1  Local effects

        Many of the reported effects of inorganic tin are localized
    because of its irritant properties. Vomiting and diarrhoea are typical
    signs that follow oral intake of foods with a high tin content. In
    cats, tin concentrations of 540 mg/litre or 1370 mg/litre in orange
    juice caused vomiting in 1/11 animals and 3/10 animals, respectively.
    However, these levels did not produce any effects in dogs. The only
    adverse effect produced in guineapigs by both short-term and prolonged
    exposure to 3 mg of tin tetrachloride per m3 of air was transient
    irritation of the nose and eyes, but these findings have not been
    corroborated. Application of 1% tin(II) chloride or 0.25% tin(II)
    fluoride to the abraded skin of rabbits caused intradermal pustule
    formation and epidermal destruction, but did not have any effect on
    intact skin.

    1.5.1.2  Systemic effects

        The major systemic effects of inorganic tin salts in animals
    include ataxia, twitching of the limbs, and fore-and hindleg weakness
    progressing to paralysis. In rats, growth retardation and decreased
    haemoglobin levels may follow administration of tin(II) chloride,
    orthophosphate, sulfate, oxalate, and tartrate at a dietary level of
    3 g/kg. However, administration of iron prevents the development of
    anaemia. Higher dietary levels of tin (10 g/kg) over several weeks may
    induce testicular degeneration, pancreatic atrophy, and a spongy state
    of the white matter of the brain. Doses of pentafluorostannite of
    100 mg/kg body weight may also affect growth, and a dose-related
    decrease in haemoglobin levels may be seen with doses exceeding
    100 mg/kg; no effect on growth was found at a dose of 20 mg/kg
    administered orally to rats. A single intravenous injection of
    pentafluorostannite at a concentration of 35 mg/kg body weight or
    tin(II) chloride dihydrate (SnCl2-2H20) at 44.4 mg/kg in rats

    produced extensive necrosis, mainly in the proximal tubules of the
    kidney. A subcutaneous dose of tin(II) chloride at a concentration of
    5.6 mg/kg body weight caused a 20-30 fold increase in the haem
    oxidation activity in the kidney; this effect was dose-related.
    Administration of tin(II) chloride at a concentration of 5 mg/litre,
    from weaning to natural death, did not affect longevity in mice or in
    male rats, but caused a decrease in longevity in female rats combined
    with an increased incidence of fatty degeneration of the liver. There
    is no conclusive evidence concerning the carcinogenicity or
    teratogenicity of inorganic tin.

    1.5.2  Organotin compounds

    1.5.2.1  Local effects

        Some butyltin compounds are known to produce gastrointestinal
    irritation; submucosal, subserosal, and intraluminar haemorrhages were
    seen in mice after a single oral dose of 4000 mg/kg body weight.
    Dibutyltin dichloride administered at a dose of 50 mg/kg body weight
    per day, for one week, produced gastroenteritis in rats.
    Gastroenteritis was also produced in rats by administration of
    tricyclhexyltin hydroxide (25 mg/kg body weight per day, for 19 days).

        Dermal application of dibutyltin dichloride (10 mg/kg body weight
    per day, for 12 days) caused severe local damage. Local irritation was
    produced in rats by applications to the shaved skin of
    bis(tributyltin) oxide in doses of 0.36-0.95 mg/kg; necrosis was
    produced at doses of 1.4-185 mg/kg. Triphenyltin acetate also
    irritated the skin of the rat, whereas triphenyltin hydroxide was
    reported not to irritate the skin of the rabbit but to be extremely
    irritating to the eyes.

    1.5.2.2  Systemic effects

        The systemic effects of monosubstituted, disubstituted, and
    tri-substituted organotin compounds differ. In general, mono- and
    di-organotin compounds are less toxic than triorganotin compounds. The
    toxicity of trialkyltin compounds decreases as the number of carbon
    atoms in the alkyl chain increases.

        Dibutyltin compounds can produce inflammatory changes in the bile
    duct. Single oral doses of dibutyltin dichloride at 50 mg/kg body
    weight produced this effect in rats, and higher doses produced more
    severe injury; necrotic changes were also produced in the liver of
    mice and rats. Bile duct injury in rats and rabbits was seen following
    dermal application of dibutyltin dichloride (10 mg/kg body weight).
    Dioctyltin compounds produced slight changes in the germinal centres
    of the spleen and steatosis of hepatocytes in mice at a single oral
    dose of 4000 mg/kg body weight. Pulmonary oedema may be seen in rats
    following intravenous administration of diethyl-, dipropyl-,

    diisopropyl-, and dipentyltin compounds. Dibutyltin compounds can slow
    down growth in rats. The no-observed-effect dietary level was reported
    to be 40 mg/kg for a 3 month feeding period and 20 mg/kg for 6 months.
    Recent studies showed that dioctyltin dichloride and dibutyltin
    dichloride administered at dietary levels of 50 and 150 mg/kg,
    respectively for 6 weeks, caused a dose-dependent atrophy of the
    thymus and thymus-dependent organs and suppression of the
    immunological response in rats, but not in mice and guineapigs.

        Some trialkyltin compounds produce a characteristic lesion in the
    central nervous system consisting of oedema throughout the white
    matter. Orally administered trimethyl- and triethyltin compounds are
    more potent in inducing this lesion than the higher homologues. The
    first changes in the rat brain were visible after 3 days of
    administration of triethyltin hydroxide at a dietary level of
    20 mg/kg. Maximum changes were found after 2 weeks. Typical signs of
    such intoxication included prostration and weakness of the progressing
    to flaccid paralysis. The effects disappeared when exposure ceased.

        Administration of triphenyltin compounds produced a reduction in
    weight and in food intake in many species. Lethargy was a typical
    symptom and histological changes in the liver and spleen were also
    seen. A decreased immunological response with a reduction in the
    number of leukocytes and of plasma cells in the lymph nodes of
    guineapigs has been reported. A 2-year study indicated a
    no-observed-effect level for triphenyltin acetate of 0.1 mg/kg body
    weight per day.

        A single intrarumenal dose of tricyclohexyltin hydroxide at
    50 mg/kg body weight produced central nervous depression and diarrhoea
    in sheep, whereas a dose of 15 mg/kg did not result in any adverse
    effects. At higher doses, pulmonary congestion, tracheal haemorrhage,
    enteritis, and eleotrocardiographic changes were seen.
    No-observed-effect doses for long-term intake in the rat and dog were
    given as 3 mg/kg body weight per day and 0.75 (mg/kg) per day,
    respectively.

        Tetraalkyltin compounds may produce muscular weakness, paralysis,
    respiratory failure, tremors, and hyperexcitability as acute effects
    in mice and dogs, while late effects are similar to those seen with
    triorganotin poisoning.

        There is no evidence that organotin compounds are carcinogenic or
    teratogenic. Reported effects of triphenyltin hydroxide on the testes
    and ovaries of rats require further confirmation.

        Information concerning the mechanism of the toxic action of
    organotin compounds is inadequate. Several dimethyl- and dioctyltin
    compounds inhibit the oxidation of keto-acids and block mitochondrial
    respiration. Trialkyltin compounds inhibit oxidative phosphorylation.

    1.6  Effects in Man

    1.6.1  Inorganic tin

        Inhalation of elemental tin does not produce any effects in man,
    whereas extended exposure to tin(IV) oxide dust and fumes can produce
    a benign pneumoconiosis termed stannosis. This condition develops
    after at least 3-5 years of exposure and is characterized by small
    dense shadows in the pulmonary X-ray picture without impairment of
    pulmonary function. Fibrosis is not seen. The generally-accepted
    maximum allowable concentration of tin(IV) oxide in the air of work
    rooms of 2 mg/m3 appears to give protection against this disorder.

        Symptoms that have been reported following ingestion of food with
    a high tin content include nausea, vomiting, diarrhoea, stomach
    cramps, fatigue, and headache. The lowest concentration of tin
    reported in association with such outbreaks was about 250 mg/litre in
    canned orange and apple juice. Five human volunteers did not
    experience any symptoms from the ingestion of fruit juices containing
    concentrations of 500-730 mg/litre but all had gastrointestinal
    disturbances at a level of 1370 mg/litre (corresponding to
    4.4-6.7 mg/kg body weight). Ingestion of 50 mg of tin through eating
    canned peaches that contained tin concentrations of about
    300-600 mg/kg caused acute symptoms in 2 out of 7 persons. The
    relative importance of, on one hand, the total amount of tin ingested
    and, on the other hand, the concentration of tin in relation to the
    development of symptoms has not been satisfactorily assessed.

    1.6.2  Organotin compounds

    1.6.2.1  Local effects

        Dibutyl- and tributyltin compounds produced skin irritation in
    workers 1-8 h after contact. Experimental application to the skin of
    volunteers showed that some compounds (e.g., dibutyltin dichloride and
    tributyltin chloride) produced this effect, whereas others such as
    dibutyltin maleate and tetrabutyltin did not. Di- and tributyltin
    compounds caused eye irritation after brief contact. A 20% solution of
    triphenyltin acetate produced irritation of the skin and the mucous
    membranes of the upper respiratory tract while tricyclohexyltin
    hydroxide was reported not to cause skin irritation at a concentration
    of 0.01 mg/kg body weight.

    1.6.2.2  Systemic effects

        The majority of accidental poisonings involving systemic effects
    have been due to occupational exposure to triphenyltin acetate.
    Systemic effects reported to have followed both dermal and inhalation
    exposure include general malaise, nausea, gastric pain, dryness of the
    mouth, vision disturbance, and shortness of breath. Hepatomegaly and
    elevated levels of liver transaminase activity have been found in some
    cases. Recovery has generally been complete but liver damage has been
    known to persist for up to 2 years.

        The hazard associated with the use of organotin compounds was
    unmasked by an episode of intoxication in 1954 involving over 200
    cases, 100 of which were fatal. The cause was the ingestion of an oral
    preparation containing diethyltin diiodide at 15 mg/capsule. It was
    suggested, however, that ethyltin triiodide, triethyltin iodide, and
    tetraethyltin were present as impurities. Predominant symptoms and
    signs included severe headache, nausea and vomiting, visual and
    psychological disturbances, and sometimes loss of consciousness. At
    autopsies and decompressive surgery, cerebral oedema of the white
    matter was found. In many cases, symptoms lasted for at least 4 years;
    follow-up information on the subjects involved is not available.

    1.7  Recommendations for Further Studies

    1.7.1  Analytical methods

        More information is needed on the specificity, precision, and
    accuracy of methods for the determination of inorganic tin compounds.
    Data concerning interlaboratory comparisons of the methods used are
    also lacking. In view of the variable results obtained in studies on
    the tin contents of various materials and tissues, the use of
    reference laboratories is recommended. Better methods are needed for
    the quantitative extraction and separation of the various organotin
    compounds present in environmental and biological samples. As
    organotin compounds used as pesticides or stabilizers occur in foods
    in minute amounts only, mare sensitive methods for their measurement
    are needed.

    1.7.2  Environmental data

        More information regarding bioconcentration is needed. The fate of
    organotin compounds entering water is largely unknown. The possibility
    of the methylation of tin by organisms present in the environment is
    of particular interest.

        A wide variety of results concerning the daily intake of tin has
    been reported. Although a certain range is to be expected, further
    investigations of the concentrations of tin in food and water, and of
    dietary intake are needed.

    1.7.3  Metabolism

        Information on the rate of absorption of tin from the
    gastrointestinal tract is insufficient and little is known about the
    absorption of various compounds through the respiratory tract which
    may be of importance in occupational exposure. Furthermore, there is a
    gap in information concerning the rate of absorption of organotin
    compounds through the skin.

        Many of the studies conducted on the distribution of tin in human
    tissues may be unreliable because of the analytical methods available
    at that time: thus, data on tissue contents should be obtained using
    as sensitive methods as possible with emphasis on the precision,
    specificity, and accuracy of the assays employed. Information on tin
    concentrations in newborn infants compared with adults is lacking, and
    data concerning tin concentrations in the tissues of occupationally-
    exposed persons compared with unexposed populations are not available.
    The increasing development and use of new organotin compounds will
    necessitate further studies on the metabolism of such compounds.

        At present, there is an obvious lack of information on the
    bio-transformation of several organotin compounds. Data concerning the
    accumulation and retention times of various compounds in animal
    tissues are also desirable. Finally, the route or routes of excretion
    of many organotin compounds are completely unknown.

    1.7.4 Effects

        Probably the most conspicuous lack of information concerns the
    mechanism of action of various organotin compounds. More information
    should be obtained on the carcinogenicity, teratogenicity, and
    mutagenicity of these compounds. Compounds used industrially should be
    studied with reference to possible allergenic properties. Recently
    reported results suggest that the effects of various organotin
    derivatives on the immune system should be studied in more detail.
    Moreover, properly conducted studies on the effects on the sex glands
    of different species using multigeneration studies seem urgent. The
    importance of longitudinal epidemiological studies on
    occupationally-exposed populations and the usefulness of information
    that may be obtained through follow-up studies of accidental
    intoxication should be emphasized.

    2. CHEMISTRY AND ANALYTICAL METHODS

        Tin can form a variety of both inorganic and organometallic
    compounds. These two classes of compounds have different chemical and
    physical properties which make them suitable for different
    applications in industry, agriculture and elsewhere. They also have
    different toxicities and require separate assessments of health risk.
    The inorganic chemistry of tin has been described in standard texts on
    inorganic chemistry such as those by Cotton & Wilkinson (1972, 1976)
    and Heslop & Jones (1976). Sources of information on new developments
    in the organometallic chemistry of tin include a review by van der
    Verk (1972) and a collection of papers presented at a symposium of the
    American Chemical Society (Zuckerman, 1976).

    2.1  Elemental Tin

        Tin (atomic number 50; relative atomic mass 118.70) is an element
    of group IVb of the periodic system, together with carbon, silicon,
    germanium, and lead. It exits in three allotropic modifications. At
    room temperature, the stable form is a metallic form called ß- or
    white tin. White tin is a silver-white, lustrous and soft metal with
    considerable ductility, and can be rolled into very thin "tin foil".
    Its density is 7.27, melting point 231.9°C, and boiling point 2507°C.
    At ordinary temperatures, it is stable in both air and water. Below
    13.3°C, the stable form of tin is the non-metallic grey tin
    (alpha-tin). Above 161°C, the stable modification is the so-called
    brittle tin, another metallic modification.

        Metallic tin is normally covered with a thin protective film of
    tin dioxide. Because tin is resistant to cold acids, a cohesive tin
    layer will protect iron from corrosion (tin plate). However, if the
    layer is damaged, the iron will rapidly corrode. Tin-plate used in the
    food industry should not contain lead, not only because lead is toxic,
    but also because its presence aids the corrosion of tin by dilute
    organic acids.

        Neutral aqueous salt solutions react slowly with metallic tin in
    the presence of oxygen but solutions containing nitrates, iron(II)
    chloride or sulfate, aluminium chloride or tin(IV) chloride dissolve
    elemental tin.

        Tin can form inorganic compounds in the oxidation state +2 (SnII,
    tin(II) compounds, or stannous compounds), and in the oxidation state
    +4 (SnIV, tin(IV) compounds, or stannic compounds). Because of their
    different physieochemical properties, it is useful to discuss the 2
    groups of compounds separately.

    2.2  Tin(II) Compounds

        Tin(II) compounds are generally more ionic than tin(IV) compounds.
    They are unstable in dilute aqueous solutions, are easily oxidized,
    and normally contain some SnIV; after some time, hydrolysis occurs
    with the formation of the hydrated tin(II) oxide ion [Sn3(OH)4]2+.

        Tin(II) chloride is readily soluble in small amounts of water. It
    is a fairly good reducing agent, and has many uses in industry,
    particularly as a mordant in dye printing. Aqueous solutions of
    tin(II) chloride become turbid on dilution because a basic salt is
    precipitated. The fluoride (SnF2) is slightly soluble in water. It is
    used in fluoride-containing toothpastes. In aqueous solutions,
    SnF3- is the major ion but other ions such as SnF+ and Sn3F5-
    are also present. Tin(II) sulfate is a good source of SnII. Its
    solubility decreases with temperature.

        Tin(II) oxide (SnO) is a stable, blue-black crystalline solid. It
    reacts with both mineral and organic acids, and dissolves in sodium
    hydroxide solutions forming stannites, which probably contain the
    SnO22- ion.

        Other tin(II) compounds that have practical applications are
    tin(II) acetate, tin(II) arsenate, tin(II) fluoroborate, tin(II)
    pyrophosphate, and several tin(II) salts or organic acids, such as
    tin(II) oxalate and tin(II)-2-ethylhexoate (tin(II)"octoate").

    2.3  Tin(IV) Compounds

        Tin in the oxidation state + 4 forms a large number of inorganic
    compounds as well as organometallic compounds, which are discussed in
    section 2.4. Some tin(IV) compounds, such as tin(IV) oxide (SnO2),
    have long been used in industry; Others, e.g., tin(IV) chloride
    (SnCl4), have found technological applications more recently. Also of
    practical importance are the stannates, compounds in which the tin
    atom is part of an anion. The structure of stannates can be
    represented by MnSn(OH)6, where M is a metal ion.

        The physical properties of tin tetrahalides, except those of
    SnF4, correspond to the properties of covalent halides of carbon and
    silicon. Tin(IV) chloride is a colourless liquid that fumes in moist
    air and becomes turbid because of hydrolysis when complex ions such as
    [SnCl3(OH)3]2- are formed. The addition of a limited amount, of
    water to tin(IV) chloride results in the formation of a crystalline
    hydrate, SnCl4.5H2O, the ionic character of which is probably due to
    the presence of a complex ion [Sn(H2O4]4+.

        Tin(IV) oxide occurs naturally as the mineral cassiterite. It has
    a very high melting point (1127°C) and has wide application in
    industry. The fusion of tin(IV) oxide with sodium or potassium
    hydroxide yields stannates.

        Other tin(IV) compounds that have found practical applications
    include tin(IV) sulfide, tin(IV) vanadate, and tin(IV) molybdate.

    2.4  Organometallic Compounds of Tin

        Organometallic tin compounds or organotin compounds have one or
    more carbon-tin covalent bonds that are responsible for the specific
    properties of such molecules. Essentially all organometallic tin
    compounds are of the SnIV type. The only well established compound
    with tin in the oxidation state + 2 is the tin(II)cyclopentadienyl,
    C10H10Sn. There are four series of organotin compounds depending on
    the number of carbon-tin bonds. These series are designated as mono-,
    di-, tri-, and tetraorganotin compounds with the general structure:

                        RnSn X4-n

    where   R   = an alkyl or aryl group
            Sn  = the central tin atom in the oxidation state +4
            X   = a singly charged anion or an anionic organic group.

        In the organotin compounds of practical importance, R is usually a
    butyl, octyl, or phenyl group and X is commonly chloride, fluoride,
    oxide, hydroxide, carboxylate, or thiolate.

        Monoorganotin compounds, RSnX3, are known but so far have found
    only limited application, for example, butyltin sulfide is used as a
    stabilizer in poly(vinyl chloride) (PVC) film.

        Diorganotin compounds, R2SnX2, are chemically reactive and most
    of their applications are based on this property. They are used. as
    stabilizers of PVC, as catalysts in the production of polyurethane
    foams, and in the cold-curing of silicon elastomers.

        Triorganotin compounds, R3SnX, are the most important class of
    organotin chemicals. They are biologically very active and are widely
    used as biocides. The chemical nature of the R group has a strong
    influence on the biological properties of these compounds. The
    X-group, on the other hand, influences their solubility and
    volatility. The two most important groups of triorganotin compounds
    are tributyltin and triphenyltin derivatives.

        Tetraalkyl- and tetraaryltin compounds are primarily used as
    intermediates in the preparation of other organotin compounds.
    Tetraalkyltin compounds are colourless and the compounds of lower
    molecular weight are liquids at room temperature. The tetraaryltin
    compounds are solids. Tetraorganotin compounds possess typical
    covalent bonds and are stable in the presence of air and water.
    Tetrabutyltin, Sn(C4H9)4 is a colourless oily liquid with a
    distinct odour. Tetraphenyltin, Sn(C6H5)4, is a white crystalline
    powder, soluble in organic solvents and insoluble in water.

        Since 1974, a new class of organotin compounds, called estertins,
    has been developed for use as stabilizers in poly(vinyl chloride).
    Their general structure is (R-O-CO-CH2-CH2)2SnX2 or
    R-O-CO-CH2-CH2SnX3 where X may be, for example,
    isooctylmercaptoacetate. They have a comparatively low volatility and
    ex,tractability (Lanigon & Weinberg, 1976).

        Solubility data for organotin compounds are incomplete. In
    general, their solubility in water at ambient temperatures is of the
    order of 5 to 50 mg/litre, but they are very soluble in many common
    organic solvents, such as alcohol, ethers, and halogenated
    hydrocarbons.

        Commercial products are usually pure chemicals since, for
    technological reasons, scrupulous care must be taken to avoid metal
    contamination during manufacture. The impurities are primarily solvent
    residues remaining from the product purification and separation
    processes.

        The carbon-tin bond is susceptible to nucleophilic and
    electrophilic attack, e.g., hydrolysis, solvolysis, acidic and basic
    attack, and halogenation. Water has little effect on symmetrical
    saturated organotin compounds. Dialkyltin compounds react
    spontaneously with moisture and air to form dialkyl hydrated oxides.
    Photochemical reactions of organotin compounds are mentioned in
    connexion with environmental transport and transformations (section
    4). The physicochemical properties of some organotin compounds have
    been listed by Weast (1976).

    2.5  Analytical Methods

    2.5.1  Determination of inorganic tin

    2.5.1.1  Atomic absorption spectroscopy

        Atomic absorption spectroscopy is the method most widely used for
    the detection of low concentrations of tin. In general, the lowest
    limit of detection is obtained with a fuel-rich, air-hydrogen flame,
    e.g., about 1-1.5 mg/kg compared with 2-2.5, and 4-5 mg/kg for
    air-ethylene and nitrous oxide-ethylene flames, respectively
    (Christian & Feldman, 1970). The detection limits at the 3 absorption
    lines, 2246.1, 2354.8, and 2863.3 nm do not differ much. Using some of
    the procedures mentioned later, the detection limit may be reduced to
    about 0.1-0.5 mg/kg.

        Several atomic absorption techniques, modified to suit specific
    purposes, have been reported. A detection limit of 0.5 µg/litre was
    obtained when a hydride generation technique using sodium borohydride
    and a flame-heated silica atomizing tube was used in the air-acetylene
    atomic absorption determination of tin in solution (Thompson &
    Thomerson, 1974). Capacho-Delgado & Manning (1966), using a high
    intensity hollow cathode lamp as the source, reported a detection
    limit of 0.1 mg/litre for water solutions of metallurgical samples,
    while Schallis & Kann (1968) determined tin in lubricating oils with a
    detection limit of about 0.5 mg/litre. Carbon filament atomic
    absorption spectroscopy was employed by Everett et al. (1974) to
    determine tin(II) chloride in aqueous and xylene solutions and tin
    octoate in oil solution.

        Atomic absorption spectroscopy has been used extensively for the
    determination of tin in foods (Allan, 1962; Amos & Willis, 1966;
    Capacho-Delgado & Manning, 1966; Christian & Feldman, 1970; Gatehouse
    & Willis, 1961) and particularly in canned foods, including fruit
    juice, fruits, and vegetables (Catala et al., 1971; Price & Roos,
    1969; Sato et al., 1973; Shiraishi et al., 1972; Woidich &
    Pfannhäuser, 1973). A detection limit of 0.5 mg/kg has been reported
    for the determination of tin in canned fruit juice using a nitrous
    oxide-acetylene flame (Price & Roos, 1969).

        Engberg (1973) compared atomic absorption with a
    spectrophotometric method using 2-(3,4,-dihydroxyphenyl)-3,5,7-
    trihydroxy-4H-1-benzopyran-4-one (quercetin) for the determination
    of tin in food. The methods gave similar results at concentrations of
    tin generally found in canned food, but at very low concentrations
    (e.g., organotin residues), the quercetin method was more suitable
    because of its lower detection limit (section 2.5.1.5).

        Atomic absorption spectroscopy has also been used for the
    determination of tin in biological samples (Pearlman et al., 1970).

    2.5.1.2  Emission spectroscopy

        Emission spectroscopy is a rapid and specific method that has
    frequently been used for the simultaneous determination of several
    elements. Unfortunately, this method is exacting, demanding highly
    qualified personnel, and the cost of the instrument is high. It has
    been used for the determination of tin in atmospheric samples
    (Hasegawa & Sugimae, 1971; Keenan & Byers, 1952; Laamanen et al.,
    1971, Lee et al., 1972; Schroll & Krachsberger, 1970; Sugimae, 1974;
    Tabor & Warren, 1958), tin in water (Ghafouri, 1970; Konovalov &
    Kolesnikova, 1969; Rittenhouse et al, 1969), and for tin in various
    foods including meats (Krylova & Balabuh, 1970), fruits, and
    vegetables (Chisaka et al., 1973). A sensitivity of 0.04 mg/kg fresh
    weight was reported by Tihonova & Zore (1968) for vegetables and
    berries. Several investigators have used emission spectroscopy for the
    determination of tin in biological samples (Avtandilov, 1967;
    Geldmacher-von Mallinckrodt & Pooth, 1969; Kas'yanenko & Kul'skaya,
    1969; Kehoe et al., 1940; Mulay et al., 1971; Saito & Endo, 1970
    Tipton et al., 1963).

    2.5.1.3  Neutron activation analysis

        Although the limit of detection of tin by neutron activation is
    comparatively high, the technique has been used to determine tin in
    air samples (Bogen, 1973; Tuttle et al., 1970). It is also the most
    commonly used method for the determination of tin in geological
    samples (soils, sediments, rocks, off) (Johansen & Steinnes, 1969;
    Obrusnik, 1969; Schramel et al, 1973). A neutron activation electron
    probe was used by Kurosaki & Fusayama (1973) for the estimation of tin
    in teeth. Disadvantages of neutron activation include the need for a
    nuclear reactor and the possibility of interference from formation of
    other isotopes.

    2.5.1.4  X-ray fluorescence

        X-ray fluorescence, a non-destructive method for the determination
    of tin, has been used in the analysis of air for elements ranging from
    titanium to caesium with a detection limit of 0.5 µg/m3 of air
    (Dittrich & Cothern, 1971) and for river water with a detection limit
    of 20-30 µg/litre for metals in the suspended or particulate form, and
    0.25-0.4 mg/litre for ionic metals (Blasius et al., 1972).

    2.5.1.5  Miscellaneous analytical methods

        Among the spectrophotometric methods reported, Kirk & Pocklington
    (1969) recommended the tin-quercetin method for the estimation of the
    tin contents of foods at concentrations ranging from 10 to over
    500 mg/kg. The smallest absolute amount of tin detectable with the
    quercetin method has been reported to be about 1 µg (Engberg, 1973).

    The pyrocatechol violet method