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
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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:
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 µg/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 µg/m3 (mean value), 0.021-0.040 µg/m3, and
0.0065-1.4 µg/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 µg/litre and 51 µg/litre, respectively,
have been found. In the Netherlands, concentrations of up to
160 µg/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 µg/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 µg/litre and the maximum concentration
recorded was 165 µg/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:
The European Economic Community legislation requires labelling as a
flammable and harmful substance using the symbols:
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
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See Also:
Toxicological Abbreviations