IPCS INCHEM Home


    IPCS INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY

    Health and Safety Guide No. 76





    1,3-DICHLOROPROPENE, 1,2-DICHLOROPROPANE AND MIXTURES
    HEALTH AND SAFETY GUIDE



    UNITED NATIONS ENVIRONMENT PROGRAMME

    INTERNATIONAL LABOUR ORGANISATION

    WORLD HEALTH ORGANIZATION



    WORLD HEALTH ORGANIZATION, GENEVA 1992


    This is a companion volume to Environmental Health Criteria
    146: Dichloropropene, Dichloropropane and mixtures

    Published by the World Health Organization for the International
    Programme on Chemical Safety (a collaborative programme of the
    United Nations Environment Programme, the International Labour
    Organisation, and the World Health Organization)

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

    WHO Library Cataloguing in Publication Data

    1,3-dichloropropene, 1,2-dichloropropane and
      mixtures : health and safety guide.

    (Health and safety guide ; no. 76)

    1.Allyl compounds - adverse effects 2.Allyl compounds - standards
    3.Hydrocarbons, Chlorinated - standards
    4.Hydrocarbons, Chlorinated - toxicity
    5.Propane - analogs & derivatives
    6.Propane - standards
    7.Propane - toxicity
    I.Series

    ISBN 92 4 151076 5          (NLM Classification: QV 633)
    ISSN 0259-7268

    The World Health Organization welcomes requests for permission to
    reproduce or translate its publications, in part or in full.
    Applications and enquiries should be addressed to the Office of
    Publications, World Health Organization, Geneva, Switzerland, which
    will be glad to provide the latest information on any changes made
    to the text, plans for new editions, and reprints and translations
    already available.

    (c) World Health Organization 1992

    Publications of the World Health Organization enjoy copyright
    protection in accordance with the provisions of Protocol 2 of the
    Universal Copyright Convention. All rights reserved.

    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 boundaries.

    The mention of specific companies or of certain manufacturers'
    products does not imply that they are endorsed or recommended by the
    World Health Organization in preference to others of a similar
    nature that are not mentioned. Errors and omissions excepted, the
    names of proprietary products are distinguished by initial capital
    letters.


    CONTENTS

    INTRODUCTION

    1. PRODUCT IDENTITY AND USES
         1.1. Identity
              1.1.1. 1,3-Dichloropropene
              1.1.2. 1,2-Dichloropropane
              1.1.3. Mixtures of 1,3-dichloropropene 
                        and 1,2-dichloropropane
         1.2. Physical and chemical properties
              1.2.1. 1,3-Dichloropropene
              1.2.2. 1,2-Dichloropropane
              1.2.3. "Mix D/D"
         1.3. Analytical methods
         1.4. Production and uses
              1.4.1. 1,3-Dichloropropene
              1.4.2. 1,2-Dichloropropane
              1.4.3. "Mix D/D"

    2. 1,3-DICHLOROPROPENE: SUMMARY AND EVALUATION, CONCLUSIONS
         AND RECOMMENDATIONS
         2.1. Summary and evaluation
              2.1.1. Environmental fate
              2.1.2. Kinetics and metabolism
              2.1.3. Effects on organisms in the environment
              2.1.4. Effects on experimental animals and
                         in vitro test systems
                        2.1.2.1   Mode of action
              2.1.5. Effects on human beings
         2.2. Conclusions
              2.2.1. General population
              2.2.2. Occupational exposure
              2.2.3. Environment
         2.3. Recommendations

    3. 1,2-DICHLOROPROPANE: SUMMARY AND EVALUATION CONCLUSIONS
         AND RECOMMENDATIONS
         3.1. Summary and evaluation
              3.1.1. Environmental fate and occurrence
              3.1.2. Kinetics and metabolism
              3.1.3. Effects on organisms in the environment
              3.1.4. Effects on experimental animals and  in vitro
                        test systems
              3.1.5. Effects on human beings
         3.2. Conclusions
              3.2.1. General population
              3.2.2. Occupational exposure
              3.2.3. Environment
         3.3. Recommendations

    4. "MIX D/D": SUMMARY AND EVALUATION, CONCLUSIONS AND RECOMMENDATIONS
         4.1. Summary and evaluation
              4.1.1. Environmental fate and occurrence
              4.1.2. Kinetics and metabolism
              4.1.3. Effects on organisms in the environment
              4.1.4. Effects on experimental animals and
                         in vitro test systems
              4.1.5. Effects on humans beings
         4.2. Conclusions
              4.2.1. General population
              4.2.2. Occupational exposure
              4.2.3. Environment
         4.3. Recommendations

    5. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY
         ACTION
         5.1. Human health hazards, prevention and protection,
              first aid
              5.1.1. Advice to physicians
                        5.1.1.1   Symptoms of poisoning
                        5.1.1.2   First aid
                        5.1.1.3   Medical advice
              5.1.2. Health surveillance advice
              5.1.3. Personal hygiene
         5.2. Explosion and fire hazards
         5.3. Storage
         5.4. Transport
         5.5. Spillage and disposal
              5.5.1. Spillage
              5.5.2. Disposal

    6. HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION

    7. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS
         7.1. Previous evaluations by international bodies
         7.2. Exposure limit values
         7.3. Specific restrictions
         7.4. Labelling, packaging, and transport
         7.5. Waste disposal

    BIBLIOGRAPHY
    

    INTRODUCTION

    The Environmental Health Criteria (EHC) documents produced by the
    International Programme on Chemical Safety include an assessment of
    the effects on the environment and on human health of exposure to a
    chemical or combinations of chemicals, or physical or biological
    agents.  They also provide guidelines for setting exposure limits.

    The purpose of a Health and Safety Guide is to facilitate the
    application of these guidelines in national chemical safety
    programmes. The first four sections of this Health and Safety Guide
    highlight the relevant technical information in the corresponding
    EHC.  Section 5 includes advice on preventive and protective
    measures and emergency action; health workers should be thoroughly 
    familiar with the medical information to ensure that they can act
    efficiently in an emergency.  The section on regulatory information
    has been extracted from the legal file of the International Register
    of Potentially Toxic Chemicals (IRPTC) and from other United Nations
    sources.

    The target readership includes occupational health services, those
    in ministries, governmental agencies, industry, and trade unions who
    are involved in the safe use of chemicals and the avoidance of
    environmental health hazards, and those wanting more information on
    this topic.  An attempt has been made to use only terms that will be
    familiar to the intended user.  However, sections 1 and 2 inevitably
    contain some technical terms.  A bibliography has been included for
    readers who require further background information.

    Revision of the information in this Guide will take place in due
    course, and the eventual aim is to use standardized terminology. 
    Comments on any difficulties encountered in using the Guide would be
    very helpful and should be addressed to:

    The Director
    International Programme on Chemical Safety
    World Health Organization
    1211 Geneva 27
    Switzerland

    1.  PRODUCT IDENTITY AND USES

    1.1  Identity

    1.1.1  1,3-Dichloropropene

         Chemical structure:

    CHEMICAL STRUCTURE 1

     cis- or (Z) 1,3-dichloropropene   trans- or (E)
    1,3-dichloropropene

    Chemical formula:            C3H4Cl2

    Relative molecular mass:     110.98

    Chemical name:               1,3-dichloropropene;
                                 dichloro-1,3-propene;
                                 1,3 dichloro-1-propene

    Common synonyms:             chloroallylchloride,
                                 1,3-dichloropropylene

    Trade name:                  Telone II(R)

    CAS registry number:         542-75-6

          cis-isomer:            10061-01-5

          trans-isomer:          10061-02-6

    RTECS registry number:       UC8310000

    Commercial 1,3-dichloropropene is a mixture of  cis- and
     trans-isomers and 92% pure. It may also be used in admixtures with
    1,2-dibromoethane (Dorlone(R)) or with 1,2-dichloropropane
    (D-D(R), soil fumigant; Nemex(R); Telone(R), and Vidden
    D(R)); 1% epichlorohydrin is added in certain countries as a
    stabilizer.

    Other names include: Dedisol C, Nematox II, D-D 95, Telone 2000
    (Hayes 1982; Worthing & Hance, 1991).

    1.1.2  1,2-Dichloropropane

    Chemical structure:

                             Cl
                             '
                        ClCH2CHCH3

    Chemical formula:            C3H6Cl2

    Relative molecular mass:     113.0

    Chemical name;               1,2-dichloropropane,
                                 dichloro-1,2-propane

    Common synonyms:             propylene dichloride

    CAS registry number:         78-87-5

    RTECS registry number:       TX9625000

    1.1.3  Mixtures of 1,3-dichloropropene and
         1,2-dichloropropane (in text abbreviated to "Mix D/D")

    "D-D" is the internationally registered trademark for a mixture of
    chlorinated hydrocarbons containing not less than 50%
    1,3-dichloropropene ( cis- and  trans-isomer), 20-35%
    1,2-dichloropropane, and 15-30% 3,3-dichloropropene,
    2,3-dichloropropene, and other related chlorinated hydrocarbons. It
    may also contain 1% epichlorohydrin as a stabilizer.

    CAS registry number:         8003-19-8

    Major trade names:           DD mixture, Nemafene, Nemax, Vidden-D.
                                 Other formulations on the market are
                                 Ditrapex (a mixture of
                                 1,2-dichloropropane,
                                 1,3-dichloropropene and
                                 methylisothiocyanate), Ditrapex CP
                                 (the same mixture as Ditrapex with the
                                 addition of chloropicrin).

    1.2  Physical and chemical properties

    1.2.1  1,3-Dichloropropene

    1,3-Dichloropropene is a white to amber coloured liquid with
    penetrating and irritating chloroform-like odour. The technical
    product is a 92% mixture of the  cis- and  trans-isomers. It is
    flammable; the vapour is heavier than air and may travel along the
    ground; distant ignition is possible. The substance decomposes in a
    flame or on a hot surface forming highly toxic (phosgene) and
    corrosive (hydrochloric acid) gases. It reacts with light metals,
    with the generation of heat. It reacts violently with strong
    oxidants, acids, and bases, causing a fire and explosion hazard.

    Table 1. Physical properties of 1,3-dichloropropene

                                                                      

    Boiling point (C)                 108
    Flash point (C)                   25
    Relative density (water=1)         1.22
    Relative vapour density (air=1)    3.8
    Vapour pressure (20 C)            3.7 kPa
    Explosive limits (vol. % in air)   5.3-14.5
    Relative molecular mass            111.0
    Log Pow                            1.4-2.0
    Solubility in water (20 C)        2.0 g/kg
    Miscible with:                     acetone, benzene, carbon
                                       tetrachloride, heptane, and
                                       methanol
    Conversion factor                  1 ppm=4.54 mg/m3 (at 25 C)
                                                                      

    1.2.2  1,2-Dichloropropane

    1,2-Dichloropropane is a colourless liquid with a characteristic
    odour. It is highly flammable; the vapour is heavier than air and
    may travel along the ground; distant ignition is possible. The
    substance decomposes in a flame or on a hot surface, forming highly
    toxic (phosgene) and corrosive (hydrochloric acid) gases. It reacts
    with light metals with the generation of heat. The liquid degreases
    the skin. It reacts violently with strong oxidants, acids, and
    bases, causing a fire and explosion hazard. It is corrosive to
    aluminium alloys.

    Table 2. Physical properties of 1,2-dichloropropane

                                                                      

    Boiling point (C)                 96
    Melting point (C)                 -100
    Flash point (C) (o.c.)            21
    Autoignition temperature (C)      557
    Relative density (water=1)         1.156
    Relative vapour density (air=1)    3.9
    Vapour pressure (20 C)            56 mbar
    Explosive limits (vol. % in air)   3.4-14.5
    Relative molecular mass            113.0
    Log Pow                            2.28
    Solubility in water (20 C)        2.7 g/kg
    Soluble in:                        ethanol and methyl ether
    Conversion factors                 1 ppm=4.66 mg/m3
                                       1 mg/m3=0.214 ppm
                                                                      

    1.2.3  "Mix D/D"

    "Mix D/D" is an amber liquid with a pungent odour. It is flammable;
    the vapour is heavier than air and may travel along the ground;
    distant ignition is possible. The mixture is stable up to 500 C but
    reacts with dilute organic bases, concentrated acids, halogens, and
    some metal salts. It is corrosive to some metals (e.g., aluminium,
    magnesium, and their alloys), and may remove lacquer from
    lacquer-lined containers. It is not corrosive to mild steel. The
    mixture decomposes in a flame or on a hot surface, forming highly
    toxic (phosgene) and corrosive (hydrochloric acid) gases. It
    degreases the skin.

    1.3  Analytical methods

    Current methods are based on gas chromatography (GC).

    In the case of crops, water, and soil, special care should be taken
    in the handling of samples, because of the high volatility of these
    substances.

    1.4  Production and uses

    1.4.1  1,3-Dichloropropene

    1,3-Dichloropropene was introduced in 1956, as a soil fumigant for
    the control of nematodes in vegetables, potatoes, and tobacco. It is
    used worldwide and manufactured in ten thousands of tonnes/annum.

    Table 3. Physical properties of "Mix D/D"

                                                                       

    Boiling point (C)                 59-115

    Flash point (C) (o.c.)            10

    Relative density (g/m3; 20 C)     1.17-1.22

    Vapour pressure (20 C)            4.6 kPa

    Solubility in water                2 g/kg

    Soluble in:                        hydrocarbon solvents, halogenated
                                       solvents, esters, ketones
                                                                       

    1.4.2  1,2-Dichloropropane

    1,2-Dichloropropane is a solvent for fats and oils and is used as a
    component of certain furniture finishes, dry cleaning fluids, and
    paint removers. It has also been used as an insecticidal fumigant on
    grain and soil and to control peach tree borers. Other uses are in
    gum processing, metal degreasing, oil processing, and organic
    chemical synthesis. It is a chemical intermediate for the production
    of tetrachloroethylene and carbon tetrachloride. It is a component
    of "Mix D/D".

    1.4.3  "Mix D/D"

    "Mix D/D" is a preplant nematocide effective against soil nematodes
    including root knot, meadow, sting and dagger, spiral and sugar beet
    nematodes. "Mix D/D" is usually applied by injection into the soil
    or through tractor-drawn hollow tines, to a depth of 15-20 cm at a
    rate of 150-400 litre/ha (occasionally to a maximum of 1000
    litre/ha), depending on the soil type and following crop. The soil
    surface is sealed by rolling. "Mix D/D" volatilizes and diffuses as
    a vapour, and, thus, its effectiveness depends on how readily this
    can occur. Because the components of "Mix D/D" are highly
    phytotoxic, it is essential that, after an application of 220
    litre/ha or more, a period of not less than 14 days should elapse
    before planting or sowing.

    2.  1,3-DICHLOROPROPENE: SUMMARY AND EVALUATION, CONCLUSIONS
        AND RECOMMENDATIONS

    2.1  Summary and evaluation

    2.1.1  Environmental fate

    In air, decomposition of 1,3-dichloropropene is mainly by reaction
    with free radicals and ozone. The half-lives for  cis- and
     trans-isomers for the reaction with free radicals are 12 and 7 h,
    respectively, and for the reaction with ozone, 52 and 12 days.
    Direct phototransformation seems to be insignificant, but may be
    enhanced in the presence of atmospheric particles.

    In water, 1,3-dichloropropene is likely to disappear rapidly,
    because of its relatively low water solubility and high volatility;
    reported half-lives are less than 5 h.

    The distribution of 1,3-dichloropropene in soil compartments is
    dependent on the vapour pressure, diffusion coefficient,
    temperature, and moisture content of the soil. The persistence of
    1,3-dichloropropene in soil is influenced by volatilization,
    chemical and biological transformation, photochemical
    transformation, and organism uptake. Volatilization and diffusion in
    the vapour phase are the most significant mechanisms for
    environmental dispersion and dilution.

    Transformation of 1,3-dichloropropene is initially by hydrolysis to
    3-chloroallyl alcohol and then by microbial transformation to
    3-chloro-acrolein and 3-chloroacrylic acid. In a laboratory study,
    the half-lives for the hydrolysis of  cis- and  trans-isomers of
    1,3-dichloropropene at 15 C and 29 C were 11.0 and 2.0 days,
    respectively, for the  cis-isomer and 13.0 and 2.0 days,
    respectively, for the  trans-isomer. For soil at pH 7 and a
    temperature of 25 C, the half-life for hydrolysis for both isomers
    was 4.6 days. Because of its relatively rapid disappearance from
    soil, residues are unlikely to accumulate when the fumigant is
    applied at the recommended rate and frequency.

    1,3-Dichloropropene is potentially mobile in soil, especially in
    open-textured, sandy soils with a low moisture content. Downward
    movement is enhanced by deep cultivation of soils with low porosity. 
    1,3-Dichloropropene has been detected in "upper ground water" (up to
    2 m below the surface), but not in deep ground water, which is more
    likely to be used for drinking-water.

    1,3-Dichloropropene can be taken up by crops. However, significant
    residues are unlikely to occur in edible crops, because these are
    not normally planted until most of the fumigant has dissipated.

    Bioaccumulation of 1,3-dichloropropene is unlikely, because of its
    relatively high water solubility (>1 g/kg), low log P octanol-water
    partition coefficient, and rapid elimination from mammals and other
    organisms.

    2.1.2  Kinetics and metabolism

    1,3-Dichloropropene administered orally to rodents is rapidly
    eliminated. The major route of elimination is in the urine where 81%
    of the  cis-isomer and 56% of the  trans-isomer are eliminated
    within 24 h of dosing. The half-life of elimination in the urine is
    5-6 h. Faecal elimination is minor. Expired CO2 accounts for 4 and
    24% of the elimination of the  cis- and  trans-isomers of
    1,3-dichloropropene, respectively. Tissue concentrations after oral
    administration are low; the highest residual concentrations are
    found in the stomach wall, followed by lower amounts in the kidneys,
    liver, and bladder.

    Unchanged 1,3-dichloropropene is not found in the urine. The  cis-
    and  trans-isomers are substrates for hepatic glutathione- S-alkyl
    transferase, forming mercapturic acids, which are excreted in the
    urine. The  trans-isomer is conjugated 4-5 times more slowly than
    the  cis-isomer. The principal urinary metabolite in rats and mice
    is  N-acetyl- S-(3-chloroprop-2-enyl)- L-cysteine, which can also
    be used for biological monitoring in man. A second, minor metabolic
    pathway has been identified for the  cis-isomer involving
    mono-oxygenation to  cis-1-dichloropropene oxide, which can also be
    conjugated with glutathione. The high proportion of the
     trans-isomer that occurs in expired air is a consequence of an
    alternative metabolic pathway to conjugation, which has a higher
    specificity for this isomer than for its  cis-counterpart.

    Inhalation exposure of rats to 1,3-dichloropropene did not lead to
    blood concentrations increasing proportionally with dose. At a dose
    of 408.6 mg/m3 (90 ppm), respiratory frequency and respiratory
    minute volume were decreased and saturation of metabolism occurred
    at 1362 mg/m3 (300 ppm).  Cis- and  trans-isomers were rapidly
    eliminated from the blood, the half-life of elimination being 3-6
    minutes at concentrations below 1362 mg/m3, but considerably
    longer (33-43 minutes) at higher concentrations.

    2.1.3  Effects on organisms in the environment

    The EC50 values for growth (96-h) for the freshwater algae
     Selenastrum capricornutum and the estuarine diatom  Skeletoneria
     costatum are 4.95 mg/litre and 1 mg/litre, respectively. The acute
    toxicity (96-h LC50) of 1,3-dichloropropene for fish is of the
    order of 1-7.9 mg/litre. In an embryo-larval test with Fathead
    minnow, the maximum no-observed-effect level (NOEL) was
    0.24 mg/litre. These data, and the fact that 1,3-dichloropropene is
    unlikely to persist in water, indicate that the hazard for fish lies
    in acute toxic effects, with little potential for additional effects
    resulting from long-term exposure.

    1,3-Dichloropropene at dose levels of 30-60 mg/kg can reduce the
    abundance of fungi and the rate of microbial enzyme activity, but
    the effect is not usually long lasting (<7 days) and does not occur
    in all soil types. In some studies, there was a significant increase
    in microbial numbers following application.

    1,3-Dichloropropene is phytotoxic. The toxicity of
    1,3-dichloropropene for honey bees is low. Using a dusting
    technique, the 48-h LD50 was 6.6 g/bee. Birds are relatively
    non-sensitive to 1,3-dichloropropene. An LC50 of >10 g/kg was
    reported for Mallard duck and Bobwhite quail.

    2.1.4  Effects on experimental animals and in vitro test 
        systems

    The acute oral toxicity of 1,3-dichloropropene for experimental
    animals is moderate to high. The LD50 values reported in rats range
    between 127 and 713 mg/kg body weight. The oral LD50 values in rats
    for the  cis- and  trans-isomers are 85 and 94 mg/kg body weight,
    respectively.

    Acute toxicity through dermal exposure is moderate. The reported
    dermal LD50 is 423 mg/kg body weight for the rat, and 504 mg/kg
    body weight for the rabbit. The dermal LD50 values for the  cis-
    and  trans-isomers are 1090 and 1575 mg/kg body weight,
    respectively.

    Inhalation exposure (4 h) to 1,3-dichloropropene in rats indicated a
    LC50 of 3310 mg/m3 (729 ppm); the LC50 for the  cis-isomer was
    3042-3514 mg/m3 (670-744 ppm), and that for the  trans-isomer,
    4880-5403 mg/m3 (1075-1190 ppm).

    Acute intoxication showed central nervous and respiratory system
    involvement.

    In rabbit skin and eye irritation tests, there were severe
    reactions, but recovery occurred in 14-21 days. The results of skin
    sensitization tests on guinea-pigs were positive.

    Several short-term inhalation toxicity studies have been conducted
    on mice, rats, guinea-pigs, rabbits, and dogs. In mice, the nasal
    mucosa and urinary bladder were the target organs. Degeneration of
    the olfactory epithelium and hyperplasia of the respiratory
    epithelium were observed. Moderate hyperplasia of the transitional
    epithelium in the urinary bladder was found. An NOEL of 136 mg/m3
    (30 ppm) was estimated for mice.

    Similar degenerative changes of the olfactory epithelium and
    hyperplasia were demonstrated in rats. The reported NOEL value for
    1,3-dichloropropene from a well-designed study was 45.4 mg/m3; an
    NOEL of 136 mg/m3 was reported for the  cis-isomer.

    A 90-day, oral study on rats indicated an NOEL of 3 mg/kg body
    weight. The only observed effect at the next higher dose level of
    10 mg/kg body weight was an increase in relative kidney weight in
    the male.

    In a 2-generation, 2-litter, inhalation reproduction study on rats,
    doses of up to 408.6 mg/m3 (90 ppm) did not show any adverse
    effects on the reproductive parameters examined. However, the
    highest dose level of 408.6 mg/m3 induced maternal toxicity as
    evidenced by decreased growth and histopathological changes in the
    nasal mucosa. An NOEL of 136.2 mg/m3 (30 ppm) was established for
    maternal toxicity.

    Inhalation teratogenicity studies on rats and rabbits did not
    indicate any teratogenic potential for 1,3-dichloropropene at
    exposure levels up to 1362 mg/m3 (300 ppm). In the rat, exposure
    to 1362 mg/m3 resulted in embryotoxicity (reduction in litter size
    and increase in resorption rates). Maternal toxicity in both rats
    and rabbits was observed at dose levels of 544.8 mg/m3 (120 ppm)
    or more.

    In most of the studies,  cis- and  trans-1,3-dichloropropene and
    the mixture were mutagenic in bacteria with, and without, metabolic
    activation. Pure 1,3-dichloropropene and pure
     cis-1,3-dichloropropene were negative in bacteria. Glutathione was
    shown to prevent the mutagenic activity of 1,3-dichloropropene in
    bacteria. Cis-1,3-dichloropropene was negative in a gene mutation
    assay with V79 Chinese hamster cells, as well as in the Chinese
    hamster ovary HPRT test.

     Cis- and  trans-1,3-dichloropropene induced unscheduled DNA
    synthesis in HeLa S3 cells. In rat hepatocytes, 1,3-dichloropropene
    did not elicit significant DNA repair. 1,3-Dichloropropene was
    positive in the  Bacillus subtilis strain H17 microsome recassay
    with metabolic activation.

    In Chinese hamster ovary cells,  cis- and
     trans-1,3-dichloropropene induced chromosome damage in the
    presence of metabolic activation but, in another study,
    1,3-dichloropropene was positive without metabolic activation.
     Cis-1,3-dichloropropene did not induce chromosomal damage in rat
    liver cells. 1,3-Dichloropropene induced sister chromatid exchange
    in Chinese hamster ovary cells with, and without, metabolic
    activation and in Chinese hamster V79 cells without metabolic
    activation.

    1,3-Dichloropropene was negative in a bone marrow micronucleus test
    on mice and in a sex-linked recessive lethal assay on  Drosophila
     melanogaster.

    Carcinogenicity studies were carried out on mice and rats. Technical
    1,3-dichloropropene (containing 1% epichlorhydrin) was administered
    by gavage for 2 years. In mice, a significant increase in epithelial
    hyperplasia and transitional cell carcinomas in the urinary bladder,
    an increase in lung tumours, a slight increase in tumours of the
    liver, and an increase in epithelial hyperplasia and squamous cell
    papillomas or carcinomas in the forestomach were found. In rats,
    there were increases in the incidences of neoplastic nodules in the
    liver and of squamous cell papillomas or carcinomas of the
    forestomach.

    Carcinogenicity studies were carried out on mice and rats exposed
    through inhalation to 1,3-dichloropropene (without epichlorohydrin)
    for 2 years. In mice, increased incidences of hyperplasia of the
    urinary bladder, of the forestomach, and of the nasal mucosa were
    observed. The only other response observed was an increase in the
    incidence of benign lung tumours. Some toxic changes in the
    olfactory mucosa of the nasal cavity were also seen in rats, but
    there was no increase in tumour incidence.

    Epichlorohydrin has been shown to produce forestomach tumours in a
    gavage study and nasal cavity tumours in an inhalation study on
    rats. But a carcinogenic effect in the urinary bladder cannot be
    excluded for 1,3-dichloropropene, administered orally in mice.

    2.1.2.1  Mode of action

    Given that the major metabolic route of elimination of
    1,3-dichloropropene is via conjugation with glutathione, it is to be
    expected that situations that affect tissue glutathione (non-protein
    sulfhydryl) concentrations may modify the effects of the compound.
    1,3-Dichloropropene itself depletes the glutathione content of a
    variety of tissues, especially those that are the initial points of
    entry into the body, i.e., predominantly the forestomach and liver
    following gavage administration and the nasal tissue after
    inhalation exposure. Decreases in nasal epithelium and forestomach
    glutathione occurred in mice after inhalation of 1,3-dichloropropene
    concentrations greater than 22.7 mg/m3 (5 ppm) and 113.5 mg/m3
    (25 ppm), respectively.

    The toxicity of 1,3-dichloropropene in animals occurs at exposures
    that deplete glutathione; prior reduction of tissue glutathione
    exacerbates 1,3-dichloropropene toxicity. Long-term inhalation of
    concentrations higher than 90.8 mg/m3 (60 ppm) causes degeneration
    of nasal tissue in rats.

    The protective role of glutathione is further highlighted by studies
    that demonstrate that covalent binding of 14C-1,3-dichloropropene
    to mouse forestomach increases as the non-protein sulfhydryl content
    decreases. Similarly, the genotoxicity of 1,3-dichloropropene and
    its minor oxidative (cytochrome P-450) metabolite
    (1,3-dichloropropene oxide) in  in vitro test systems is markedly
    ameliorated by glutathione.

    2.1.5  Effects on human beings

    The exposure of the general population through air, water, or food
    is unlikely.

    Studies have shown that occupational exposures are generally below
    4.54 mg/m3 (1 ppm), but higher levels have also been reported (up
    to 18.3 mg/m3 during filling or nozzle changing). Occupational
    exposure is likely to be through inhalation and via the skin.
    Irritation of the eyes and the upper respiratory mucosa appears
    promptly after exposure. Inhalation of air containing concentrations
    of > 6810 mg/m3 (> 1500 ppm) gave serious signs and symptoms of
    poisoning; at lower exposures, there was depression of the central
    nervous system and irritation of the respiratory system. Dermal
    exposure caused severe skin irritation.

    In a group of 1,3-dichloropropene applicators, some liver and kidney
    function changes were reported at the end of the application season.
    The cause-effect relationship, however, has been contested.

    Some poisoning incidents have occurred in which persons were
    hospitalized with signs and symptoms of irritation of the mucous
    membrane, chest discomfort, headache, nausea, vomiting, dizziness,
    and, occasionally, loss of consciousness and decreased libido. Three
    cases of haematological malignancies were attributed to earlier
    accidental overexposure to 1,3-dichloropropene, but the cause-effect
    relationship remains uncertain.

    The fertility status of workers employed in the production of
    chlorinated three-carbon compounds was compared with a control
    group. No indication of an association between decreased fertility
    and exposure was found.

    2.2  Conclusions

    2.2.1  General population

    Exposure of the general population to 1,3-dichloropropene is low or
    non-existent, and its risk for the general population is negligible.

    2.2.2  Occupational exposure

    Filling operations and field applications may lead to operator
    exposures exceeding the maximum allowable concentration, when
    appropriate safety precautions have not been taken.

    2.2.3  Environment

    Provided that 1,3-dichloropropene is used at the recommended rate,
    it is unlikely to attain levels of environmental significance and is
    unlikely to have adverse effects on populations of terrestrial or
    aquatic organisms.

    2.3  Recommendations

    *    Filling operations and field applications of
         1,3-dichloropropene should only be conducted with appropriate
         safety precautions, in order to avoid exposures exceeding the
         maximum allowable concentrations of 1,3-dichloropropene.

    *    Do not apply near drinking-water sources.

    3.  1,2-DICHLOROPROPANE: SUMMARY AND EVALUATION, CONCLUSIONS AND
        RECOMMENDATIONS

    3.1  Summary and evaluation

    3.1.1  Environmental fate and occurrence

    Concentrations of 1,2-dichloropropane in city air were determined to
    be 1.2 g/m3 (mean value), 0.021-0.040 g/m3, and
    0.0065-1.4 g/m3 in Philadelphia and Portland (USA), and in Japan,
    respectively. Decomposition in the atmosphere is slow; on the basis
    of reaction with hydroxyl radicals, the half-life of
    1,2-dichloropropane was >313 days. Phototransformation is likely to
    be the dominant process for the decomposition. Adsorption on to
    particulate matter is necessary for appreciable phototransformation.
    Volatilization is likely to be the major route of loss from water.

    In soil, the main routes of loss are volatilization and diffusion.
    1,2-Dichloropropane is persistent in soil. More than 98% of the
    1,2-dichloropropane applied to loam soil was recovered 12-20 weeks
    after treatment.

    Leaching of 1,2-dichloropropane occurs from soil and can contaminate
    upper and deeper ground water in areas where "Mix D/D" has been used
    as a soil fumigant. In well water and ground water in the USA,
    concentrations of up to 440 g/litre and 51 g/litre, respectively,
    have been found. In the Netherlands, concentrations of up to
    160 g/litre have been measured in well water and
    1,2-dichloropropane has been found to a depth of 13 m.

    1,2-Dichloropropane can be taken up by edible crops, but residues
    detected have been low (<0.01 mg/kg) and are unlikely to be
    biologically significant.

    Bioaccumulation of 1,2-dichloropropane is unlikely, because of its
    high water solubility (2.7 g/kg) and low log P octanol-water
    partition coefficient.

    3.1.2  Kinetics and metabolism

    1,2-Dichloropropane administered orally to rats is rapidly
    eliminated: 80-90% within 24 h. There are no major differences in
    kinetics or elimination between males and females. Urine is the
    major route of elimination, with up to half an oral dose being
    eliminated by this route within 24 h. Less than 10% is eliminated in
    the faeces. Approximately one-third is eliminated through expired
    air, both as carbon dioxide and as a mixture of volatile materials.
    Tissue concentrations are low, the highest concentration being found
    in the liver. Rapid elimination also occurs following inhalation
    exposure of rats; 55-65% of a dose is eliminated in the urine and
    16-23% in expired air. The half-life of elimination from blood is
    24-30 min.

    Unchanged 1,2-dichloropropane is not found in urine. Three major
    urinary metabolites have been identified. These metabolites result
    from oxidative and conjugation pathways that yield the
    mercapturates,  N-acetyl- S-(2-hydroxypropyl)- L-cysteine,
     N-acetyl- S-(2-oxypropyl)- L-cysteine, and
     N-acetyl- S-(1-carboxyethyl)- L-cysteine. 1,2-Dichloropropane
    can also be oxidized to lactate with resultant carbon dioxide or
    acetyl co-enzyme A production.

    Oral administration of 1,2-dichloropropane (2 ml/kg) to rats
    significantly depleted tissue glutathione content. There is a
    correlation between tissue glutathione loss and expression of
    toxicity in the liver, kidney, and red blood cells. Prior depletion
    of intracellular glutathione exacerbates 1,2-dichloropropane
    toxicity, whereas pretreatment with precursors for glutathione
    synthesis reduces the toxicity. These results demonstrate the
    protective effect of glutathione on 1,2-dichloropropane toxicity.

    3.1.3  Effects on organisms in the environment

    EC50 data for freshwater algae have not been calculated, because of
    difficulties with volatilization of the chemical from the test
    solution. The acute toxicity of 1,2-dichloropropane for aquatic
    invertebrates and fish is low to moderate; 48-h LC50 values for
    invertebrates range between 52 and > 100 mg/litre and 96-h LC50
    values for fish lie between 61 and 320 mg/litre. A short-term
    toxicity test on Fathead minnows demonstrated a maximum NOEL of
    82 mg/litre. A 32-day test on early life stage toxicity in the same
    species demonstrated that larval growth and survival were the most
    sensitive parameters. The estimated maximum acceptable toxicant
    concentration (MATC) was between 6 and 11 mg/litre. Growth
    inhibition has been noted in Sheephead minnows after exposure for 33
    days to a 1,2-dichloropropane concentration of 164 mg/litre.

    1,2-Dichloropropane is phytotoxic.

    Contact tests on 4 species of earthworm showed an LC50 of
    44-84 g/cm2 (mean values) of filter paper. In artificial soil, the
    LC50 values were 3880-5300 mg/kg soil (dry weight).

    3.1.4  Effects on experimental animals and  in vitro test
           systems

    The acute oral toxicity of 1,2-dichloropropane in experimental
    animals is low. The oral LD50 for the rat is 1.9 g/kg body weight,
    and the dermal LD50 in rabbits is 8.75 ml/kg body weight.

    Short-term, oral, toxicity studies of 1,2-dichloropropane in mice
    and rats showed growth inhibition, clinical toxic signs associated
    with central nervous system depression, and/or increased mortality,
    at dose levels of 250 mg/kg body weight per day or higher. In rats

    given 250 mg/kg per day for 10 days, there were changes in serum
    enzymes indicative of slight hepatotoxicity with a NOEL of 100 mg/kg
    per day.

    In a 13-week mouse inhalation study (highest dose 681 mg/m3
    (150 ppm)), no adverse effects were observed. In a similar study on
    rats exposed to 68.1, 227, or 681 mg/m3 (15, 50, or 150 ppm), a
    decrease in body weight and minimal damage to nasal tissues occurred
    in the 2 highest dose groups.

    In a 2-generation reproduction study, rats exposed to
    1,2-dichloropropane in the drinking-water at 0.024, 0.1, or 0.24%
    (equivalent to 33.6, 140, or 336 mg/kg body weight per day) resulted
    in lower maternal body weight gain and decreased water consumption
    at the mid- and high-dose levels. Neonatal body weights were lower
    at the high dose level. The NOAELs established for maternal and
    reproductive toxicity were 33.6 and 140 mg/kg body weight per day,
    respectively.

    The results of studies did not indicate any teratogenic activity of
    1,2-dichloropropane at oral dose levels up to 125 mg/kg body weight
    in the rat and 150 mg/kg body weight in the rabbit. However, at
    these dose levels, 1,2-dichloropropane was maternally toxic and
    fetotoxic, as evidenced by central nervous system-associated
    clinical signs, decreased maternal body weight gain, and delayed
    ossification of bones in the fetuses. The NOELs for the rat and
    rabbit are 30 and 50 mg/kg body weight per day, respectively.

    1,2-Dichloropropane was mutagenic in bacteria in most studies with,
    and without, metabolic activation, but very high dose levels were
    used, up to 10 mg/plate. In Chinese hamster ovary cells,
    1,2-dichloropropane caused chromosome aberrations and sister
    chromatid exchange; in Chinese hamster V79 cells, it increased the
    sister chromatid exchange. In an  in vitro system with human
    lymphocytes, the tritiated thymidine uptake and cell viability in
    cultures grown with, and without, rat liver metabolizing system,
    were similar to those in control cultures. A sex-linked recessive
    lethal test was negative in  Drosophila melanogaster. A dominant
    lethal test in rats over 14 weeks via drinking-water containing
    1,2-dichloropropane, followed by 2 weeks of mating, was negative.

    In a carcinogenicity study on mice administered 125 or 250 mg
    1,2-dichloropropane/kg body weight by gavage, a dose-related
    increase in the incidence of liver adenomas in the treated groups
    was higher than that in the concurrent control group, but was within
    the historical control range.

    In rats administered dose levels of 125 and 250 mg/kg body weight
    (females) and 62 and 125 mg/kg body weight (males), by gavage, 5
    days per week for 113 weeks, a slight increase in the incidence of
    mammary gland adenocarcinomas exceeding the historical range was
    observed in high-dose females.

    3.1.5  Effects on human beings

    Exposure of the general population to 1,2-dichloropropane via air
    and water is unlikely, except in areas where there is extensive use
    of 1,2-dichloropropane and "Mix D/D" in agriculture. Residues of
    1,2-dichloropropane in edible crops are generally below the limit of
    detection. In view of these low exposures to 1,2-dichloropropane,
    the risk to the general population is negligible.

    Several cases of acute poisoning have been reported through
    accidental or intentional (suicide) overexposure to
    1,2-dichloropropane. Effects are mainly on the central nervous
    system, liver, and kidney. Haemolytic anaemia and disseminated
    intravascular coagulation have also been reported. In one case,
    delirium progressed to irreversible shock, cardiac failure, and
    death.

    Occupational exposures can be via both skin and inhalation. Several
    cases of dermatitis and skin sensitization have been reported in
    workers using solvent mixtures containing 1,2-dichloropropane.

    3.2  Conclusions

    3.2.1  General population

    Exposure of the general population to 1,2-dichloropropane from air
    and food is low or non-existent. However, in certain areas, exposure
    may occur when ground water is contaminated.

    3.2.2  Occupational exposure

    With reasonable work practices, hygienic measures, and safety
    precautions, the use of 1,2-dichloroproprane is unlikely to present
    a risk to those occupationally exposed to it.

    3.2.3  Environment

    1,2-Dichloropropane is unlikely to attain levels of environmental
    significance, when used at the recommended rate. It is unlikely to
    have adverse effects on populations of terrestrial and aquatic
    organisms.

    3.3  Recommendations

    *    Appropriate safety precautions should be taken when handling
         1,2-dichloropropane, in order to avoid exposures exceeding the
         maximum allowable concentration.

    4.  "Mix D/D": SUMMARY AND EVALUATION, CONCLUSIONS AND
        RECOMMENDATIONS

    4.1  Summary and evaluation

    4.1.1  Environmental fate and occurrence

    The environmental transport, distribution, and fate of the major
    constituents of "Mix D/D" in air, water, and soil are described in
    sections 2.1.1 and 3.1.1 on 1,3-dichloropropene and on
    1,2-dichloropropane.

    There is a significant potential for "Mix D/D" derived
    1,2-dichloropropane to leach from the soil and contaminate well
    water and ground water. In a 68-m deep irrigation bore in Western
    Europe, mean 1,2-dichloropropane concentrations at different depths
    ranged between 0.8 and 8.5 g/litre and the maximum concentration
    recorded was 165 g/litre.

    Significant uptake of the constituents of "Mix D/D" by crops is
    unlikely. Bioaccumulation of the constituents of "Mix D/D" is also
    unlikely, because of their low log P octanol-water partition
    coefficient and relatively high water solubility.

    4.1.2  Kinetics and metabolism

    There have not been any metabolic studies on "Mix D/D". The two
    major components, 1,3-dichloropropene and 1,2-dichloropropane, are
    rapidly eliminated, primarily through the urine and, to a lesser
    extent, via expired air. The components of "Mix D/D" are metabolized
    by oxidative and conjunction pathways. The major urinary metabolites
    are mercapturic acids.

    4.1.3  Effects on organisms in the environment

    "Mix D/D" is moderately toxic for fish; 96-h LC50 values range
    between 1 and 6 mg/litre. The toxicity largely resides in the
    1,3-dichloropropene content of the "Mix D/D".

    When used at recommended application rates, the main effects of
    "Mix D/D" are a transient (<7 days) reduction in soil fungi and
    inhibition of the oxidation of ammonium to nitrate. "Mix D/D" is
    toxic to nitrifying bacteria, but soon after "Mix D/D" disappears
    from the soil, recolonization of bacteria takes place. In field
    trials, "Mix D/D" (applied at 600 litre/ha) killed soil
    invertebrates. Recolonization times ranged between 6 and 24 months.

    "Mix D/D" is highly phytotoxic.

    4.1.4  Effects on experimental animals and in vitro test systems

    The acute toxicity of "Mix D/D" is moderate to high for laboratory
    animals. The oral LD50 values in rats and mice range from 132 to
    300 mg/kg body weight. The dermal LD50 values for rats and rabbits
    are 779 and 2100 mg/kg body weight, respectively. The LC50 (4-h)
    for rats is approximately 1000 mg/kg. Acute exposure results in
    clinical signs associated with central nervous system depression.
    "Mix D/D" is a severe eye and skin irritant and a moderate dermal
    sensitizer.

    The available short-term toxicity studies on rats and dogs are not
    adequate to assess fully the toxicity potential of "Mix D/D",
    because the dose levels tested have been relatively low and have not
    demonstrated any biologically significant effects.

    Several short-term inhalation (whole-body) studies have been
    conducted on rats. "Mix D/D" at levels up to 145 mg/m3 did not
    cause any toxic effects. Toxic effects associated with central
    nervous system depression were evident at levels of 1362 mg/m3
    300 ppm) or more. Exposure to 443 mg/m3 for 10 weeks led to
    reduced body weight gain and increased absolute kidney weight.

    An oral teratogenicity study on rats was inadequate for the
    assessment of the teratogenic potential of "Mix D/D".

    In an inhalation study on male and female fertility in rats, no
    effects were found at dose levels up to 443 mg/m3 for 10 weeks.
    Complete evaluation of the reproductive effects of "Mix D/D" was not
    possible because of the inadequacy of the protocol designs.

    "Mix D/D" is mutagenic in  Salmonella typhimurium strains TA100 and
    TA1535, as well as  Escherichia coli WP2 HCR, without metabolic
    activation. It is negative in  Salmonella strains TA98, TA1537, and
    TA1538. In a long-term study on rats fed diets containing up to 120
    mg "Mix D/D" per kg (equivalent to 6 mg/kg body weight per day) for
    2 years, no toxic or carcinogenic effects were seen.

    4.1.5  Effects on humans beings

    As "Mix D/D" is no longer extensively used, exposure of the general
    population via air, water and food is therefore unlikely.

    The levels of exposure of drum-filling operators and field
    applicators were generally below 4.54 mg/m3 (1 ppm)
    1,3-dichloropropene when recommended procedures were used, otherwise
    levels of up to 36.32 mg/m3 (8 ppm) have been measured.

    One case of acute fatal poisoning has been reported following the
    accidental ingestion of "Mix D/D".

    Several cases of contact dermatitis and skin sensitization have been
    reported following exposure to "Mix D/D".

    4.2  Conclusions

    4.2.1  General population

    As "Mix D/D" is no longer extensively used, exposure of the general
    population to 1,3-dichloropropene from air, water, and food, is
    negligible, but, in certain areas, exposure to 1,2-dichloropropane
    may occur when ground water is contaminated.

    4.2.2  Occupational exposure

    Filling operations and field applications of "Mix D/D" can lead to
    operator exposures to 1,3-dichloropropene exceeding maximum
    allowable concentrations, especially under warm climatic conditions.

    4.2.3  Environment

    "Mix D/D" is unlikely to reach biologically significant levels in
    either the terrestrial or aquatic environment, when used at the
    recommended rate. Lasting adverse effects on organisms in the
    environment are unlikely to occur.

    4.3  Recommendations

    *    "Mix D/D" should not be used as a soil fumigant, because of
         potential leaching into ground water.

    5.  HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION

    5.1  Human health hazards, prevention and protection, first aid

    1,3-Dichloropropene and "Mix D/D" are volatile, severely irritant
    liquids that may cause skin burns. They are hazardous for humans and
    animals, if incorrectly or carelessly handled. The human health
    hazards associated with certain types of exposure to these
    substances, together with preventive and protective measures and
    first aid are listed in Table 4.

    According to the International Agency for Research on Cancer (IARC
    Monographs Vol. 41, 1986; and Suppl. 7, 1987), there is sufficient
    evidence for carcinogenicity to animals in the case of technical
    grade 1,3-dichloropropene containing 1% epichlorohydrin, after oral
    administration to experimental animals.

    1,2-Dichloropropane is less irritant than the above two substances.
    The human health hazards associated with certain types of exposure
    to 1,2-dichloropropane are listed in Table 5, together with
    preventive and protective measures and first aid.

    5.1.1  Advice to physicians

    5.1.1.1  Symptoms of poisoning

    Inhalation of the vapour of these substances causes irritation to
    the eyes, nose, and throat, cough, shortness of breath, and pain in
    the chest. At higher concentrations, inhalation will cause chemical
    pneumonitis and pulmonary oedema. Ingestion causes abdominal pain,
    diarrhoea, and vomiting. During vomiting, aspiration into the lungs
    may occur, resulting in chemical pneumonitis. The possibility of
    delayed systemic effects (among others: hepatic and renal effects)
    should not be overlooked.

    5.1.1.2  First aid

    If any of the above symptoms or signs occur, obtain medical
    attention immediately. If skin is contaminated, remove clothing and
    wash all affected parts with soap and water. If eyes are
    contaminated, flush with clean water for up to 15 minutes and obtain
    medical attention immediately. If swallowed, obtain medical
    attention immediately. DO NOT INDUCE VOMITING.


        Table 4.  1,3-Dichloropropene and "Mix D/D": human health hazards, preventive and protective measures, and first aid

                                                                                                                              
    Hazards/Symptoms                   Prevention and protection               First aid
                                                                                                                              

    SKIN: corrosive to the             Avoid contact, wear protective          Remove contaminated clothing immediately
    skin; sensitizer                   gloves and clothing, PVC or             and launder before reuse; wash skin with
                                       neoprene gloves, rubber boots           water and soap; destroy all contaminated
                                                                               leather goods

    EYES: severe primary               Wear face-shield or goggles             Flush eyes immediately with clean water for
    eye irritant                                                               15 minutes; obtain medical attention

    INHALATION: Severe primary         Wear appropriate respiratory            Remove victim to fresh air immediately;
    irritant to respiratory tract      protection                              keep at rest and warm; obtain medical
    mucosa; excessive inhalation                                               attention immediately; give artificial
    of vapour can cause pulmonary                                              respiration, if breathing has stopped
    oedema and delayed systemic
    effects

    INGESTION: Corrosive               Do not eat, drink, or smoke             Do not induce vomiting; give water
    to the digestive tract; nausea,    during work.                            to drink; obtain medical attention
    abdominal pain, diarrhoea                                                  immediately
                                                                                                                              

    Table 5.  1,2-Dichloropropane: human health hazards, preventive and protective measures, and first aid

                                                                                                                              
    Hazards/Symptoms                   Prevention and protection               First aid
                                                                                                                              

    SKIN: irritant                     Avoid contact, wear protective          Remove contaminated clothing and launder
                                       gloves and clothing, PVC or             before reuse; wash skin with plenty of
                                       neoprene gloves, rubber boots           water and soap

    EYES: irritant                     Wear face-shield or goggles             Flush eyes with clean water for 15 minutes;
                                                                               obtain medical attention

    INHALATION: irritant;              Wear appropriate respiratory            Remove victim to fresh air;
    anorexia, diarrhoea, drowsiness,   protection                              keep at rest and warm; obtain medical
    headache, (maybe delayed effect)                                           attention

    INGESTION: abdominal pain,         Do not eat, drink or smoke              Do not induce vomiting; give water
    vomiting, diarrhoea,               during work                             to drink; obtain medical attention
    drowsiness, headache
                                                                                                                              
    
    5.1.1.3  Medical advice

    Skin irritation and chemical burns should be treated
    symptomatically. In case of ingestion, carry out gastric lavage with
    care to prevent aspiration. Do not administer fatty substances, such
    as milk or oil. Check for any liver or kidney damage. In case of
    excessive inhalation, observe in hospital for 48 hours for signs of
    pulmonary oedema.

    There is no special antidote - treatment is symptomatic and
    supportive.

    5.1.2  Health surveillance advice

    In view of the skin-sensitizing properties of "Mix D/D" (and to a
    lesser extent of 1,3-dichloropropene) and their systemic toxicity
    (liver, kidney), medical surveillance may be advisable at the
    discretion of a medical adviser, taking into account the frequency
    and degree of exposure.

    5.1.3  Personal hygiene

    Prevent all contact with the skin, eyes, nose, and mouth.

    Wear goggles, cotton overalls, neoprene or polyethylene gloves, and
    rubber boots. Do not wear leather footwear.

    Do not suck or blow on/into obstructed injection pipes by mouth.

    In all situations where vapour concentrations in air do, or may,
    exceed maximum allowable concentrations (see section 7.2)
    appropriate respiratory protection must be used.

    Wash off any skin contamination with soap and water. If eyes are
    contaminated, flush immediately with clean water for up to 15
    minutes. Obtain medical attention.

    If clothes or overalls become contaminated, remove them without
    delay and thoroughly wash before reuse. Contaminated leather shoes
    should be discarded, since they cannot be decontaminated.

    Wash hands and exposed skin before eating, drinking, smoking, using
    the toilet, and after work.

    5.2  Explosion and fire hazards

    These substances are highly flammable and are not miscible with
    water. Vapour/air mixtures can be explosive. The vapours are heavier
    than air and may travel along the ground; distant ignition is
    possible. They can decompose in a flame or on a hot surface, forming
    toxic (e.g., phosgene) and corrosive (e.g., hydrochloric acid)

    gases. They react with light metals with the generation of heat.
    1,3-Dichloropropene and "Mix D/D" may react violently with strong
    oxidants.

    When dealing with fires or in situations where these substances are
    exposed to the atmosphere, self-contained breathing apparatus must
    be used. Fire service personnel should be advised that these
    chemicals and their mixtures are hazardous through skin contact and
    inhalation.

    Extinguish fires with alcohol-resistant foam or powder. The use of
    water spray should be confined to the cooling of unaffected stock,
    to avoid polluted run-off from the site.

    5.3  Storage

    These substances should be stored in locked, well-ventilated
    buildings. Do not expose to direct sunlight. Keep products out of
    reach of children and unauthorized personnel. Do not store near
    animal feed or food. Separate from bases, strong oxidants, and
    acids.

    5.4  Transport

    Comply with any local regulations regarding the movement of
    hazardous goods. Do not load with animal feed or food. Check that
    containers are sound and labels undamaged, before despatch.

    5.5  Spillage and disposal

    5.5.1  Spillage

    Stay upwind, avoid skin contamination and inhalation of vapour.

    Keep spectators away from leaking product and prevent all smoking or
    use of naked flames.

    When dealing with spillage, approved respiratory protective
    equipment must be used in addition to the protective clothing
    advised under personal hygiene (section 5.1.3).

    Absorb spillage with sawdust, sand, or earth, sweep up and place in
    a closeable, impervious container. Ensure that container is tightly
    closed and suitably labelled before transfer to a safe place for
    disposal.

    Prevent liquid from spreading and contaminating other cargo,
    vegetation, or waterways with a barrier of the most suitable
    material available, e.g., earth or sand.

    Empty any of the product remaining in the damaged/leaking container
    into a clean empty container, which should then be tightly closed
    and suitably labelled.

    5.5.2  Disposal

    Contaminated absorbents, containers, surplus product, etc., should
    be burnt in a proper incinerator at high temperatures, in a unit
    with effluent gas scrubbing. When no incinerator is available, bury
    in an approved dump, or in an area where there is no risk of
    contamination of surface or ground water. Punch holes and crush
    empty containers to prevent reuse. Comply with any local
    legislation.

    6.  HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION

    1,3-Dichloropropene and "Mix D/D" are moderately toxic for most
    forms of aquatic and terrestrial life. On direct application to
    water or soil they severely (but temporarily) disturb the local
    ecosystem.

    The toxicity of 1,2-dichloropropane is 1-2 orders of magnitude less.

    Avoid contamination of soil, water, and the atmosphere by proper
    methods of storage, transport, handling, and waste disposal. Avoid
    application near drinking-water sources.

    In case of spillage, use the methods advised in section 5.5.1.

    7.  CURRENT REGULATIONS, GUIDELINES, AND STANDARDS

    The information given in this section has been extracted from the
    International Register of Potentially Toxic Chemicals (IRPTC) legal
    file and other United Nations sources. A full reference to the
    original national document from which the information was extracted
    can be obtained from IRPTC.

    The reader should be aware that regulatory decisions about chemicals
    taken in a certain country can only be fully understood in the
    framework of the legislation of that country. Furthermore, the
    regulations and guidelines of all countries are subject to change
    and should always be verified with the appropriate regulatory
    authorities before application.

    7.1  Previous evaluations by international bodies

    The International Agency for Research on Cancer (IARC) evaluated
    technical grade 1,3-dichloropropene (containing 1% epichlorohydrin)
    in 1986 and 1987 and concluded that there is sufficient evidence for
    its carcinogenicity to animals and inadequate evidence for its
    carcinogenicity to humans (group 2B).

    The IPCS and the CEC have issued an International Chemical Safety
    Card on 1,2-dichloropropane (ICSC No. 0441).

    7.2  Exposure limit values

    Some exposure limit values for 1,3-dichloropropene and
    1,2-dichloropropane are given in Tables 6 and 7, respectively. For
    "Mix D/D", both tables apply.

    7.3  Specific restrictions

    1,3-Dichloropropene, 1,2-dichloropropane, and "Mix D/D" have been
    registered for use as pesticides (nematocides) in many countries; in
    each country specific uses are defined as well as limitations and
    precautions.


        Table 6. Exposure limit values for 1,3-dichloropropene

                                                                                                                              
    Medium    Specification     Country/            Exposure limit description                   Value          Effective
                                organization                                                                    date
                                                                                                                              

    AIR       Workplace         Germany             Maximum work-site concentration (MAK)        -              1991
                                                    Carcinogenic in animals, therefore
                                                    no MAK established

                                United Kingdom      Recommended limit (RECL)
                                                    - 8-h time-weighted average (TWA)            5 mg/m3 a      1985
                                                    - Short-term (10-min) exposure level (STEL)  50 mg/m3

                                USA (ACGIH)         Threshold limit value (TLV)
                                                    - Time-weighted average (TWA)                5 mg/m3 a      1986

                                USSR                Maximum allowable concentration (MAC)
                                                    - Ceiling value (CLV)                        5 mg/m3        1977

    AIR       Ambient           USSR                Maximum allowable concentration (MAC)
                                                    (average per day)                            0.01 mg/m3     1984
                                                    (1  1 day)                                  0.1 mg/m3

    FOOD      Plant             Germany             Maximum residue limit (MRL)
                                                    (all plant products)                         0.05 mg/kg     1989

    WATER     Surface           USSR                Maximum acceptable concentration             0.4 mg/litre   1983
                                                                                                                             

              

    a  Skin absorption

    Table 7. Exposure limit values for 1,2-dichloropropane

                                                                                                                             
    Medium    Specification     Country/            Exposure limit description                   Value          Effective
                                organization                                                                    date
                                                                                                                              

    AIR       Workplace         Brazil              Acceptable limit (AL)
                                                    - Time-weighted average (TWA)                275 mg/m3      1980

                                Germany             Maximum work-site concentration (MAK)
                                                    - Time-weighted average (TWA)                350 mg/m3      1991
                                                    - 30-min short-term exposure limit (STEL)    700 mg/m3

                                Hungary             Maximum allowable concentration (MAC)
                                                    - 8-h time-weighted average (TWA)            50 mg/m3       1988
                                                    - Short-term exposure level (30 min)         100 mg/m3      1988

                                USA/OSHA            Permissible exposure limit (PEL)
                                                    - Time-weighted average (TWA)                350g/m3        1974

                                USA (ACGIH)         Threshold limit value (TLV)
                                                    - Time-weighted average (TWA)                347 mg/m3      1990
                                                    - Short-term exposure limit (STEL)           508 mg/m3

                                USSR                Maximum allowable concentration (MAC)
                                                    - Ceiling value                              10 mg/m3       1976

    AIR       Ambient           USSR                Maximum allowable concentration (MAC)
                                                    (average per day)                            0.18 mg/m3     1984
                                                                                                                             
    

    7.4  Labelling, packaging, and transport

    The following applies to 1,3-dichloropropene, 1,2-dichloropropane,
    and "Mix D/D".

    The United Nations Committee of Experts on the Transport of
    Dangerous Goods classifies these compounds in:

         Hazard Class 3: flammable liquid;

         Packing Group II: a substance presenting medium danger.

    The label should be as follows:

    FIGURE 1

    The European Economic Community legislation requires labelling as a
    flammable and harmful substance using the symbols:

    FIGURE 2

    FIGURE 3

    The label must read:

          Highly flammable; harmful by inhalation; keep container in a
          well-ventilated place; keep away from sources of ignition - no
          smoking; do not empty into drains; take precautionary measures
          against static discharges; (it must be stated on the label
          whether the substance is a specific isomer or a mixture of
          isomers).

    7.5  Waste disposal

    In the USA, any non-domestic waste containing 1,3-dichloropropene or
    1,2-dichloropropane is considered a toxic waste, subject to
    handling, transport, storage, and disposal regulations and permit
    and notification requirements. An owner or operator of a hazardous
    waste incinerator must achieve 99.99% destruction and removal
    efficiency for these substances.

    BIBLIOGRAPHY

    CEC (1987) Legislation on dangerous substances - Classification and
    labelling in the European Communities. Vol. 1 & 2, Commission of the
    European Communities, London, Graham & Trotman Ltd.

    FAO (1985a) Guidelines for the packaging and storage of pesticides.
    Rome, Food and Agriculture Organization of the United Nations.

    FAO (1985b) Guidelines for the disposal of waste pesticides and
    pesticide containers on the farm. Rome, Food and Agriculture
    Organization of the United Nations.

    FAO (1985c) Guidelines on good labelling practice for pesticides.
    Rome, Food and Agriculture Organization of the United Nations.

    FAO (1986) International code of conduct on the distribution and use
    of pesticides. Rome, Food and Agriculture Organization of the United
    Nations.

    FAO/WHO (1986) Guide to Codex recommendations concerning pesticide
    residues. Part 8. Recommendations for methods of analysis of
    pesticide residues. 3rd ed. Rome, Codex Committee on Pesticide
    Residues.

    GIFAP (1982) Guidelines for the safe handling of pesticides during
    their formulation, packing, storage, and transport. Brussels,
    Groupement International des Associations Nationales des Fabricants
    de Produits Agrochimiques.

    GIFAP (1983) Guidelines for the safe and effective use of
    pesticides. Brussels, Groupement International des Associations
    Nationales des Fabricants de Produits Agrochimiques.

    GIFAP (1984) Guidelines for emergency measures in cases of pesticide
    poisoning. Brussels, Groupement International des Associations
    Nationales des Fabricants de Produits Agrochimiques.

    GIFAP (1987) Guidelines for the safe transport of pesticides.
    Brussels, Groupement International des Associations Nationales des
    Fabricants de Produits Agrochimiques.

    HAYES, W.J. Jr & LAWS, E.R. Jr (1991) Handbook of pesticide
    toxicology, 3 Vol. New York, Academic Press.

    IARC (1972-present) IARC Monographs on the evaluation of
    carcinogenic risk of chemicals to man. Lyon, International Agency
    for Research on Cancer.

    ILO (1991) Safety and health in the use of agro-chemicals - a guide.
    Geneva, International Labour Office.

    IRPTC (1985) IRPTC file on treatment and disposal methods for waste
    chemicals. Geneva, International Register for Potentially Toxic
    Chemicals, United Nations Environment Programme.

    IRPTC (1987) IRPTC legal file 1986. Geneva, International Register
    for Potentially Toxic Chemicals, United Nations Environment
    Programme.

    PLESTINA, R. (1984) Prevention, diagnosis, and treatment of
    insecticide poisoning. Geneva, World Health Organization
    (Unpublished document No. VBC/84.889).

    SAX, N.I. (1984) Dangerous properties of industrial materials. New
    York, Van Nostrand Reinhold Company, Inc.

    UNEP/IEO (1990) Storage of hazardous materials : a technical guide
    for safe warehousing of hazardous materials. Paris, United Nations
    Environment Programme - Industry and Environment Office, 80 pp.

    UNITED NATIONS (1989) Recommendations on the transport of dangerous
    goods. 6th ed. New York, United Nations.

    UNITED NATIONS (1989) Consolidated list of products whose
    consumption and/or sale have been banned, withdrawn, severely
    restricted or not approved by governments. 2nd ed. New York, United
    Nations, New York.

    US NIOSH/OSHA (1981) Occupational health guidelines for chemical
    hazards. 3 Vol., Washington DC, US Department of Health and Human
    Services, US Department of Labor (Publication No. DHHS (NIOSH)
    01-123).

    WHO (In preparation) EHC No. 146: 1,3-Dichloropropene,
    1,2-dichloropropane, and mixtures. Geneva, World Health
    Organization.

    WORTHING, C.R. & HANCE, R.J. (1991) The pesticide manual. 9th ed.
    Old Woking, United Kingdom, Unwin Brothers Ltd.


    See Also:
       Toxicological Abbreviations