CHLOROPICRIN
CASRN: 76-06-2
http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~AAAynaGIG:1
Human Health Effects:
Human Toxicity Excerpts:
Exposure to chloropicrin
produces more coughing than does phosgene and there is less delay in onset of
pulmonary edema. Late deaths may occur from secondary infections,
bronchopneumonia, or bronchiolitis obliterans.
VAPOR IS INTENSELY IRRITATING TO...EYES, MUCOUS MEMBRANE, & STOMACH. ...
INGESTION OF LIQ PRODUCES GASTROENTERITIS.
PRODUCES SEVERE SENSORY IRRITATION IN UPPER RESP PASSAGES. HAS STRONG
LACRIMATORY PROPERTIES, PRODUCES INCR SENSITIVITY AFTER FREQUENT EXPOSURES.
ORALLY, SEVERE NAUSEA, VOMITING, COLIC, DIARRHEA. POTENT SKIN IRRITANT...
AT CONCN OF 1 PPM IN AIR IT CAUSES...SMARTING PAIN IN EYES.
INHALATION MAY ALSO PRODUCE ANEMIA, WEAK & IRREGULAR HEART & RECURRENT
ASTHMATIC ATTACKS.
COMMON SYMPTOMS AMONG 5 CLINICAL CASES OCCURRING FROM TIME OF EXPOSURE TO
SEVERAL HR FOLLOWING INCL EXCESSIVE LACRIMATION, VERTIGO, FATIGUE &
HEADACHE. CHLOROPICRIN EXACERBATED ORTHOSTATIC
HYPOTENSION OF ALL PT.
A 73-YEAR-OLD MAN ACCIDENTALLY SPLASHED CHLOROPICRIN IN
HIS RIGHT EYE. EDEMA OF THE RIGHT EYELID AND CORNEA WAS SEVERE, AND THE OCULAR
CONJUNCTIVA BEGAN TO PARTIALLY LIQUIFY WITH A BULBAR ADHERENCE AT 2 DAYS AFTER
THE ACCIDENT.
... INDIVIDUALS INJURED BY INHALATION OF CHLOROPICRIN
BECOME MORE SUSCEPTIBLE, SO THAT CONCN OF THE GAS NOT PRODUCING SYMPTOMS IN
OTHERS CAUSE THEM DISTRESS.
RESPONSE TO VARIOUS CONCN OF TRICHLORONITROMETHANE--MAN.
2.0 MG/L (297.6 PPM) FOR 10 MIN WAS LETHAL; 0.8 MG/L (119.0 PPM) FOR 30 MIN WAS
LETHAL; 0.1 MG/L (15.0 PPM) FOR 1 MIN WAS INTOLERABLE; 0.050 MG/L (7.5 PPM) FOR
10 MIN WAS INTOLERABLE; 0.009 MG/L (1.3 PPM) WAS LOWEST IRRITANT CONCN; ODOR WAS
DETECTABLE AT 0.0073 MG/L (1.1 PPM); 0.002-0.025 MG/L (0.3-3.7 PPM) FOR 3-30 SEC
RESULTED IN CLOSING OF EYELIDS ACCORDING TO INDIVIDUAL SENSITIVITY. /FROM TABLE/
EFFECTS OF CHLOROPICRIN APPLICATION FOR SEVERAL YR IN
TOTTORI PREFECTURE, JAPAN, WERE SUFFERED FOR OVER 1 MO BY 3.9% OF 760
RESPONDENTS SURVEYED & WERE SEEN IN PEOPLE LIVING OVER 100 MILES AWAY FROM
APPLICATION SITE. THERE WAS A POSITIVE CORRELATION BETWEEN SYMPTOM OCCURRENCE
FROM CHLOROPICRIN APPLICATION & AGE OF INDIVIDUAL.
Chloropicrin is both a lacrimator and a lung irritant. It is intermediate
in toxicity between chlorine and phosgene. ... Whereas chlorine in fatal
concentrations produces more injury of the upper respiratory tract, trachea, and
larger bronchi than in the alveoli, and phosgene acts primarily on the alveoli, chloropicrin
produces more injury to medium and small bronchi than to the trachea and large
bronchi. The alveolar injury is less than with phosgene but pulmonary edema
occurs and is the most frequent cause of early deaths.
INGESTION MAY OCCUR DUE TO SWALLOWING OF SALIVA CONTAINING DISSOLVED CHLOROPICRIN...
Chloropicrin is intensely irritating to the eyes and has a tear gas-like
effect. Chloropicrin in concn of 0.3-0.37 ppm resulted
in painful irritation to the eyes in 3-30 sec. This response varies according to
individual susceptibility. A concn of 15 ppm could not be tolerated longer than
a minute even by individuals accustomed to chloropicrin.
Slightly higher levels cause lacrimation and vomiting, and finally bronchitis
and death through pulmonary edema. A level of 4 ppm for a few seconds renders a
man unfit for activity, and 15 ppm for the same duration resulted in respiratory
tract injury.
A man accidentally exposed to residual spray containing an undetermined chloropicrin
concn had a dry cough, and his nasal and pharyngeal mucosa were red and
edematous.
Due to the strong irritating properties of the chemical, exposure would produce
eye irritation, pulmonary irritation, and dermatitis. More serious exposures can
cause pulmonary edema, coma, hepatic necrosis, renal damage, and cardiac
necrosis ... .
One report of a home treated with chloropicrin produced
respiratory illness in the family and a pet dog ... The dog developed bronchitis
and pneumonia. The family members developed cough, sinus irritation, and
inflammation of the oropharynx. Chloropicrin concn
ranged up to 48 ppb in certain areas of the home.
Human toxicity following inhalation of chloropicrin can
be manifest by pulmonary irritation, mucous membrane irritation, and pulmonary
edema.
... Described findings in a worker exposed to an unknown concn of a mixture of
sulfuryl fluoride and 1% chloropicrin for 4 hr who
developed nausea, vomiting, abdominal pain, pleuritis with diffuse rhonchi, and
paresthesia of the right leg, all rapidly subsiding after pulmonary exposure.
The exact role of the sulfuryl fluoride was not known, but the cyanotic symptoms
are those expected of chloropicrin overexposure.
... Was first prepared in 1848, was well
known from industrial uses before it was employed as a combat gas in World War
I. In this connection, it was used partly because of its inherent toxicity. The
concentrations of chlorine, chloropicrin, and phosgene
that are lethal in 10 minutes are 5,600, 2,000, and 500 mg/cu m, respectively.
However, the main reason for using chloropicrin was its
irritating properties. It is adsorbed on charcoal, but it was not removed from
the air by certain World War I gas masks designed specifically for chlorine
and/or phosgene. The lacrimation, coughing, and vomiting produced by chloropicrin
could cause troops wearing such masks to remove them and thus expose themselves
to even greater danger, especially from phosgene.
... In Japan, some people who lived near where leaf tobacco was fumigated
complained of excessive lacrimation, cough, vertigo, headache, nausea, vomiting,
and fatigue at the time of exposure. In most instances symptoms lasted for
several hours to as much as 3 days after exposure. A few persons reported that
their difficulties lasted more than a month. Complaints were received from some
persons living over 100 meters away from the site of application.
Persistence of symptoms after substantial exposure is not unexpected. Persons
exposed to chloropicrin as a war gas often experienced
nausea, vomiting, and diarrhea lasting for weeks.
The soil of a portion (approximately 100 m x 130 m) of a large field was
fumigated with a mixture of methyl bromide and chloropicrin,
and the area was covered with plastic. One side of the treated area was
contiguous with a residential area. The application was made during daylight,
but there apparently was no difficulty until a light wind arose at about 9:00
p.m. Everyone who reported any symptoms reported eye irritation and this began
an average of 2.5 hours after each person noticed the odor. Nausea was reported
by 20 of those affected and coughing and sore throat by 11% each. Other symptons
reported by 3 to 6% of persons reporting any symptom included: vomiting,
dizziness, drowsiness, wheezing, blurred vision, skin irritation, headache, and
a bad taste in mouth. Three of the residents were treated as outpatients at a
local hospital. The attack rate among residents of the street nearest the
treated area was 53%. Again some persons were affected at a distance greater
than 100 m. Although the material applied was a mixture, the character and
timing of the effects indicated that chloropicrin was
the cause of symptons.
Human Toxicity Values:
RESPONSE TO VARIOUS CONCN OF TRICHLORONITROMETHANE--MAN.
2.0 MG/L (297.6 PPM) FOR 10 MIN WAS LETHAL; 0.8 MG/L (119.0 PPM) FOR 30 MIN WAS
LETHAL; 0.1 MG/L (15.0 PPM) FOR 1 MIN WAS INTOLERABLE; 0.050 MG/L (7.5 PPM) FOR
10 MIN WAS INTOLERABLE; 0.009 MG/L (1.3 PPM) WAS LOWEST IRRITANT CONCN. /FROM
TABLE/
Skin, Eye and Respiratory Irritations:
Chloropicrin is
intensely irritating to the eyes and has a tear gas-like effect. Chloropicrin
in concn of 0.3-0.37 ppm resulted in painful irritation to the eyes in 3-30 sec
... A level of 4 ppm for a few seconds renders a man unfit for activity, and 15
ppm for the same duration resulted in respiratory tract injury ... Chloropicrin
is also noted to be a potent skin irritant.
Medical Surveillance:
Initial Medical Examination: A complete
history and physical examination: The purpose is to detect pre-existing
conditions that might place the exposed employee at increased risk, and to
establish a baseline for future health monitoring. Examination of the
respiratory system should be stressed. The skin should be examined for evidence
of chronic disorders. ... Persons with pulmonary function may be at increased
risk from exposure. ... Medical examinations should be repeated on an annual
basis.
Probable Routes of Human Exposure:
Exposure to chloropicrin
would be primarily occupational via inhalation and dermal contact. Exposure is
most probable for applicators of the fumigant. The general public may be exposed
to chloropicrin in drinking water, especially
chlorinated drinking water. It is possible that people residing near where chloropicrin
is applied as a soil sterilant would also be exposed to this dense gas. Since chloropicrin
may be used as a war gas, people will be exposed to the gas during this type of
use. (SRC)
There were 4 reported cases of exposure to chloropicrin
in California in 1987 that was sufficient to cause injury, 1 systemic and 3 eye
related(1).
Minimum Fatal Dose Level:
5. 5= EXTREMELY TOXIC: PROBABLE ORAL LETHAL
DOSE (HUMAN) 5-50 MG/KG; BETWEEN 7 DROPS & 1 TEASPOONFUL FOR 70 KG PERSON
(150 LB).
Animal Toxicity Studies:
Non-Human Toxicity Excerpts:
RESPONSE TO VARIOUS CONCN ... DOGS TOLERATED
0.32 MG/L (48 PPM) FOR 15 MIN. DEATH AFTER 8 TO 12 DAYS IN CATS EXPOSED TO 0.32
MG/L (48 PPM) FOR 20 MIN. CATS SURVIVED 7 DAYS AFTER BEING EXPOSED TO 0.26 MG/L
(38 PPM) FOR 21 MIN. MICE TOLERATED 0.17 MG/L (25 PPM) FOR 15 MIN. /FROM TABLE/
RESPONSE TO VARIOUS CONCN ... DEATH IN 3 HR TO 1 DAY IN MICE EXPOSED TO 0.85
MG/L (125 PPM) FOR 15 MIN. DEATH USUALLY IN 1 DAY IN CATS EXPOSED TO 0.51 MG/L
(76 PPM) FOR 25 MIN. DEATH AFTER 10 DAYS IN MICE EXPOSED TO 0.34 MG/L (50 PPM)
FOR 15 MIN. /FROM TABLE/
RESPONSE TO VARIOUS CONCN ... DOGS EXPOSED TO 1.05 MG/L (155 PPM) FOR 12 MIN
BECAME ILL; @ 0.8-0.95 MG/L (117-140 PPM) FOR 30 MIN, DEATH OF 43% OF ANIMALS;
SURVIVAL OF REMAINDER. /FROM TABLE/
RELATIVELY FEW PESTICIDES ARE TOXIC TO EARTHWORMS. CHLOROPICRIN
IS ONE WHICH DOES KILL EARTHWORMS.
INHALATION OF CHLOROPICRIN AEROSOL (171 MG/CU M) FOR 4
HOURS PRODUCED 100% MORTALITY IN MICE. CHLOROPICRIN
AEROSOL LC50 WAS 66.0 MG/CU M AGAINST MICE AFTER 4 HOURS OF EXPOSURE. THE GAS
FORM OF CHLOROPICRIN WAS MORE TOXIC THAN THE AEROSOL.
PULMONARY EDEMA AND HARD BREATHING WERE OBSERVED.
CCl4, CS2, ethylene dichloride (ED), ethylene dibromide (EDB), chloropicrin,
ethylene dichloride-CCl4 mixture (3:1) (ED/CT), and CCl4-CS2 mixture were tested
against 1,3, and 5 week old adult Sitophilus oryzae. ...The relative performance
of the fumigants was: EDB> chloropicrin> CS2> CCl4-CS2 (4:1)> ED/CT
(3:1)> ED> CCl4. LD50 values for each fumigant decreased with an increase
in the age of animals. As the time of exposure period increased, the mortality
of the insects also increased for each fumigant.
Concentrations of 340 ppm of chloropicrin in air are
lethal to rats in 1 min. The major pathological manifestations are congestion,
hemorrhage, edema, and infiltration of the lung tissue in early stages of
inhalation. Chronic stages of inhalation produced marked necrosis of the kidney,
liver, and skeletal muscles.
Mice exposed @ 9 ppm showed a 50% decrease in respiratory rate. Lesions included
ulceration and necrosis of the respiratory epithelium and moderate damage to
lung tissue.
One report of a home treated with chloropicrin produced
respiratory illness in the family and a pet dog ... The dog developed bronchitis
and pneumonia. The family members developed cough, sinus irritation, and
inflammation of the oropharynx. Chloropicrin concn
ranged up to 48 ppb in certain areas of the home.
In animal studies, chloropicrin vapors produced
ulceration of the olfactory epithelium and necrosis of lung tissues ... .
The subchronic oral toxicity of chloropicrin was
studied in rats. Sprague Dawley rats were gavaged with 10, 20, 40, or 80 mg/kg chloropicrin
daily for 10 days or with 2, 8, or 32 mg/kg for 90 days. ... Exposure period
were necropsied. The In the 1O day study, two of ten males in the 80 mg/kg dose
group and six of 30 females in the 20, 40, and 80 mg/kg groups died. Mean body
weights were significantly decreased in 40 and 80 mg/kg males and 80 mg/kg
females. Thymus weights were significantly decreased by 80 mg/kg chloropicrin
in both male and female rats. The 80 mg/kg dose caused a significant increase in
white blood cell counts and decreases in erythrocyte counts and hemoglobin and
hematocrit values. The major histological changes were seen in the stomach.
These included forestomach inflammation, necrosis, acantholysis, hyperkeratosis,
and ulceration. These changes were caused by all doses, but their severity was
dose related. In the 90 day study, 60% of the males and 80% of the females in
the 32 mg/kg dose group died. These deaths were due to pulmonary complications,
probably caused by aspiration of chloropicrin into the
lungs. The 32 mg/kg dose caused a significant decrease in body weight in male
rats and decreased thymus weights in females. Hemoglobin and hematocrit values
were significantly decreased by the 32 mg/kg dose. Chronic inflammation,
acantholysis, and hyperkeratosis of the forestomach induced by 32 mg/kg chloropicrin
was the major histological finding. Chronic pulmonary inflammation and
congestion were seen in rats that died during the study. ... The stomach appears
to be the primary organ for chloropicrin oral toxicity.
The 8 mg/kg dose used in the 90 day study may be taken as the no observable
adverse effect level for chloropicrin.
Whole-body inhalation studies were conducted to assess the maternal and
developmental toxicity potential of chloropicrin (CP)
in CD VAF rats and New Zealand White rabbits. Exposures were on Days 6-15 (rats)
or 6-18 (rabbits) of gestation at target exposure levels of 0, 0.4, 1.2 and 2.0
(rabbit) or 3.5 ppm (rat) chloropicrin. In both
species, maternal toxicity was observed at 1.2 ppm and higher levels, and was
manifested in rats by mortality (3.5 ppm) and body weight gain reduction 11.2
and 3.5 ppm) and in rabbits by mortality, abortion, and body weight gain and
food consumption inhibition (at 1.2 and 2.0 ppm). In both species, developmental
toxicity was limited to reduced fetal body weight at the highest dose. No
selective developmental toxicity was observed in either species. Based on these
results, the maternal NOAEL was 0.4 ppm for both species whereas the
developmental NOAEL was 1.2 ppm.
Male Fischer 344 rats were exposed to chloropicin (CP) vapor for 4 hr by
whole-body, nose-only and dermal exposures. Each exposure was followed by a 14
day observaton period. The LC50 values for the whole-body and nose-only
exposures were 14.4 and 6.6 ppm, respectively. In the dermal exposure
experiment, no deaths occurred in the rats exposed to chloropicrin
vapor at a mean actual concentration of 25.0 ppm. In the whole body exposure
experiment, chloropicrin vapor produced a biphasic
toxic manifestation. The first phase lasted about 3 days after exposure, and the
second phase was between post-exposure days 6 and 14. Irritation and/or damage
to the respiratory tract was mainly o6served in both phases. Most deaths
occurred within 24 hr after exposure. The rest were caused by a high exposure
concentration, and the dead animals were found on post-exposure day 9. In the
nose-only exposure experiment, toxic effects were observed only in the first
phase and they were similar to those in the whole-body exposure experiment. All
deaths occurred within 24 hr after exposure. In the dermal exposure experiment,
no toxic effects were observed. Acute dermal toxicity of chloropicrin
vapor due to whole-body exposure was minimal compared to acute inhalation
toxicity, and restraint of experimental animals during the nose-only exposure
increased the acute inhalation toxicity of chloropicrin
vapor.
A preliminary in-vitro investigation of the genotoxic effects of grain fumigants
and pesticides was performed as a precursor to the human evaluation of pesticide
applicators. The parameters of this inquiry were chosen to simulate a single
in-vivo exposure to these toxicants. The ability of chloropicron to induce
sister chromatid exchanges and chromosomal aberrations in human lymphocyte cells
was examined. The results indicated dose related increases in sister chromatid
exchanges with chloropicrin. /It was/ concluded that an
evaluation of worker exposure to fumigants should be cumulative or seasonal as
opposed to a single exposure.
National Toxicology Program Studies:
A bioassay of technical grade chloropicrin
for possible carcinogenicity was conducted using Osborne-Mendel rats and B6C3F1
mice. Chloropicrin in corn oil was administered 5
days/wk by gavage, at either of two dosages, to groups of 50 male and 50 female
animals of each species. Time weighted avg dosages of 25 mg/kg/day for low dose
male rats and 20 mg/kg for low dose female rats were administered during wk 1
through 33, then administered cyclically (1 dose free wk followed by 4 wk
administration) from wk 34 through 78. Time weighted avg doses of 26 mg/kg/day
for high dose male rats and 22 mg/kg/day for high dose female rats were
administered from wk 1-17, wk 31-33, and cyclically (1 dose free wk followed by
4 wk of administration) during wk 34 through 78. Time weighted avg doses of 66
and 33 mg/kg/day, respectively for male and female mice were administered for 78
wk. These dosing regimens were followed by observation periods of 32 wk for rats
and 13 wk for mice. ... The bioassay of chloropicrin
using Osborne-Mendel rats did not permit an evaluation of the carcinogenicity
because of the short survival time of dosed animals. The bioassay of chloropicrin
using B6C3F1 mice did not /provide/ conclusive ... evidence for the
carcinogenicity of this cmpd. Levels of Evidence for Carcinogenicity: Male Rats:
Inadequate study; Female Rats: Inadequate study; Male Mice: Negative; Female
Mice: Negative.
Non-Human Toxicity Values:
LD43 Dog, inhalation: 117-140 ppm, 30 min;
tolerated 48 ppm, 15 min
Mouse, inhalation: death 50-125 ppm, 15 min; tolerated 25 ppm, 15 min
Cat, inhalation: survived 7 days; 38 ppm, 21 min
LD50 Mouse ip 25 mg/kg
LC50 MOUSE INHALATION 66.0 MG/CU M AFTER 4 HR OF EXPOSURE
Metabolism/Pharmacokinetics:
Metabolism/Metabolites:
A comparison was made of the products and
rates of heme oxidation by five alkyl halides in five environments: homogeneous
solution, p450 cam, phenobarbital induced p450 from rat liver and reduced rat
liver microsomes. The products stoichiometries and kinetics of the reduction of trichloronitromethane,
bromotrichloromethane, carbon-tetrachloride, ethylene-dibromide, and
1,2-dibromo-3-chloropropane by iron(II)-deuteroporphyrin-IX and rat liver
p450-PB and p450-cam were compared to the reactions of reduced liver microsomes.
In all cases the polyhalomethanes underwent quantitative reductive
hydrogenolysis. All p450 components converted the vicinal halides quantitatively
to the corresponding olefins. p450 exhibited no steric inhibition at all.
Absorption, Distribution & Excretion:
THE CHLORONITROPARAFFINS APPEAR NOT TO SHOW
APPRECIABLE PERCUTANEOUS ABSORPTION, AS JUDGED BY LACK OF APPARENT SYSTEMIC
EFFECTS ... . /CHLORONITROPARAFFINS/
THE RATE OF CHLOROPICRIN VAPOR AND LIQUID MOVEMENT UP
AND DOWN STANDING DOUGLAS-FIR HEARTWOOD SPECIMENS WAS GREATER IN MORE PERMEABLE
WOOD.
Interactions:
Intravenous injection with chloropicrin
at a dosage of 15 mg/kg killed all of 14 rabbits within 15 to 240 minutes;
clinical and autopsy findings were typical of acute pulmonary edema. Fifteen
rabbits injected subcutaneously with an antihistamine
(N-dimethylamino-2-propyl-1-thiodiphenylamine) at a rate of 20 mg/kg 30 to 40
minutes before intravenous chloropicrin at 15 mg/kg
survived without any sign of pulmonary edema.
Pharmacology:
Interactions:
Intravenous injection with chloropicrin
at a dosage of 15 mg/kg killed all of 14 rabbits within 15 to 240 minutes;
clinical and autopsy findings were typical of acute pulmonary edema. Fifteen
rabbits injected subcutaneously with an antihistamine
(N-dimethylamino-2-propyl-1-thiodiphenylamine) at a rate of 20 mg/kg 30 to 40
minutes before intravenous chloropicrin at 15 mg/kg
survived without any sign of pulmonary edema.
Minimum Fatal Dose Level:
5. 5= EXTREMELY TOXIC: PROBABLE ORAL LETHAL
DOSE (HUMAN) 5-50 MG/KG; BETWEEN 7 DROPS & 1 TEASPOONFUL FOR 70 KG PERSON
(150 LB).
Environmental Fate & Exposure:
Environmental Fate/Exposure Summary:
Chloropicrin may be
released to the environment, as emissions and in wastewater, resulting from its
manufacture, transport, disposal and use as a chemical intermediate, soil
sterilant, fumigant for cereals and grain, fungicide, rat extermination agent,
and war gas. Chloropicrin is formed in the chlorination
of drinking water and wastewater and may be released during these processes. If
applied to soil as would be the case in its use as a soil sterilant, chloropicrin
will both rapidly volatilize and leach. It should photolyze on the soils
surface. It may degrade in soil by chemical or biological processes. However
degradation rates are unknown. Chloropicrin has a high
Henry's Law Constant and if released in water would readily volatilize
(half-life in a model river and model lake are 4.3 hr and 5.2 days
respectively). It will photodegrade in the surface layers of water (half-life
about 3 days). Its rate of biodegradation in natural water is unknown, as is its
rate of other abiotic dechlorination reactions. Chloropicrin
would not be expected to adsorb to sediment or bioconcentrate in fish. If
released to the atmosphere, chloropicrin will photolyze
(half-life 20 days), producing phosgene and nitrosyl chloride. Being relatively
soluble in water, it may be washed out by rain. Exposure to chloropicrin
would be primarily occupational via inhalation and dermal contact, especially to
applicators of the fumigant. The general public may be exposed to chloropicrin
in drinking water, especially chlorinated drinking water. (SRC)
Probable Routes of Human Exposure:
Exposure to chloropicrin
would be primarily occupational via inhalation and dermal contact. Exposure is
most probable for applicators of the fumigant. The general public may be exposed
to chloropicrin in drinking water, especially
chlorinated drinking water. It is possible that people residing near where chloropicrin
is applied as a soil sterilant would also be exposed to this dense gas. Since chloropicrin
may be used as a war gas, people will be exposed to the gas during this type of
use. (SRC)
There were 4 reported cases of exposure to chloropicrin
in California in 1987 that was sufficient to cause injury, 1 systemic and 3 eye
related(1).
Artificial Pollution Sources:
Chloropicrin may be
released to the environment, as emissions and in wastewater resulting from its
manufacture, transport, disposal and use(SRC) as a chemical intermediate, soil
sterilant, fumigant for cereals and grain, fungicide, rat extermination agent,
and tear gas(1,2,7). Chloropicrin is formed in the
chlorination of natural water containing humic substances in the presence of
nitrites(2,6) which would explain its presence in drinking waters(SRC). The use
of ozone in water treatment to reduce trihalomethanes (especially ozonation
followed by chloramination), appears to increase the amount of chloropicrin
in the treated water. In two utilities studied, the concn of chloropicrin
in the treated water was 0.073 and 0.25 ppb using chlorine alone and 0.49 and
0.57 ppb when both ozone and chlorine treatment was used(4). In another study
chlorination of water from mesotrophic and eutrophic lakes produced 0.4 and 2
ppb of chloropicrin; with preozination these levels
increased to about 2 and 6 ppb, respectively(5). Chloropicrin
may be formed during the chlorination of industrial waste water. Studies show
that the chlorination of nonnitrogenous organic compounds (0.1 mmol/L) in the
presence of nitrites (0.1 mmol/L) can lead to chloropicrin
formation(2). Among these, phenolic compounds and 2- and 3-hydroxyphenol, in
particular, give the highest production rates. Choropicrin is also readily
formed from nitromethane during chlorination(3).
Environmental Fate:
TERRESTRIAL FATE: If applied to soil as would
be the case in its use as a soil sterilant(1), chloropicrin
will both rapidly volatilize and leach. It should photolyze on the soils
surface. It may degrade in soil by chemical or biological process. However
degradation rates are unknown(SRC).
AQUATIC FATE: Chloropicrin has a high Henry's Law
Constant, 2.05X10-3 atm-cu m/mol at 25 deg C(1), and would readily volatilize
from bodies of water into which it is released. Its half-life in a model river
and model lake are 4.3 hr and 5.2 day, respectively(2, SRC). It will
photodegrade in the surface layers of water (half-life about 3 days). Its rate
of biodegradation and other abiotic dechlorination reactions in natural water is
unknown, the latter may depend on the presence of specific catalytic agents. Chloropicrin
would not be expected to adsorb to sediment or bioconcentrate in fish(SRC).
ATMOSPHERIC FATE: If released to the atmosphere, chloropicrin
will photolyze (half-life 20 days), producing phosgene and nitrosyl
chloride(2,3). Chloropicrin's reaction with
photochemically-produced hydroxyl radicals is predicted to be very slow
(half-life 123 days)(4,SRC). Being relatively soluble in water, 1621 mg/L at 25
deg C and 2272 mg/L at 0 deg C(1), it may be washed out by rain(SRC).
Environmental Biodegradation:
The aerobic biodegradation rate and half-life
for chloropicrin at 20 deg C with an activate sludge
inoculum were 1.5/day and 0.46 days, respectively(2). Uninoculated controls were
tested. The biodegradation rate and half-life for chloropicrin
under anaerobic conditions was the same as under aerobic conditions, namely
1.5/day and 0.46 days(2). Several Pseudomonas sp. isolated from soil
dehalogenate chloropicrin(1). One strain of Pseudomonas
putida transformed chloropicrin to nitromethane in
three successive reductive dehalogenation steps in the course of about an
hour(1).
Environmental Abiotic Degradation:
Chloropicrin is
stable in neutral aqueous solution with no hydrolysis being detected after 10
days and a minimum half-life of 11 yrs(1). It photohydrolyzes rapidly in water
when exposed to light below 300 nm producing CO2, chloride and nitrate in the
presence of air(1). Its half-life in sunlight is about 3 days (1). However,
under ambient room light it is stable to photodegradation(1). While no
particular cases were found in the literature for chloropicrin,
dehalogenation reactions may be chemically, as well as biologically
catalyzed(4). Under simulated atmospheric conditions, the vapor photodegrades to
phosgene and nitrosyl chloride (half-life 20 days) with the nitrosyl chloride
further photolyzing to chlorine and nitric oxide(2). The photooxidation of chloropicrin
in the vapor to form phosgene has also been observed in the field(3). While chloropicrin
reacts with photochemically-produced hydroxyl radicals in the atmosphere, the
reaction is predicted to be slow, 1.3x10-13 cu cm/molecule-s(5). Assuming a
hydroxyl radical concn of 5X10+5 radicals/cu cm, the half-life of chloropicrin
in the atmosphere would be 123 days(SRC).
Environmental Bioconcentration:
Using the log Kow of 2.09(1), one would
estimate a BCF of 23 for chloropicrin using a
recommended regression equation(2). This would indicate that chloropicrin
will not bioconcentrate in aquatic organisms(SRC).
Soil Adsorption/Mobility:
The Freundlich adsorption constant Kf and
exponent 1/n were determined for chloropicrin in 3
organic soils, A, B, and C and Na-bentonite clay at 25 deg C(5). The Kf (ug/g-dry
soil/ug/g-water) values were (soil (organic carbon), Kf): A (6.8%), 5.9; B
(5.5%), 5.0; C (2.3%), 1.2; clay (0.2%), 560 and n was 1.2 for the organic soils
and 1.0 for the clay. Its adsorption on kaolinite was negligible(5). The Koc
value for the 4 soils is 81(5). The Koc for chloropicrin
is calculated from its water solubility to be 62(1). One investigator found that
chloropicrin is adsorbed more by mineral soil than by
muck which has a higher organic content(2), indicating that adsorption to
organic matter is not the principle mechanism for adsorption. Another
investigator's results suggested that the organic content of the soil is the
main factor determining absorptivity(5). This latter investigator found that
adsorption to different clays was very different(5). Chloropicrin
readily penetrates sandy soil and diffuses horizontally along the soil surface
when used as a soil fumigant in winter(3). An example of its ability to leach
into soil is the contamination of a well by chloropicrin
buried 35 m away(4).
The octanol water partition coefficient /was found to be/ 1.08X10+1 or log Kow=
2.38 for chloropicrin.
Volatilization from Water/Soil:
The Henry's Law constant for chloropicrin
is 2.05X10-3 atm-cu m/mol at 25 deg C(1). Using this value for the Henry's Law
constant, one can estimate a volatilization half-life for chloropicrin
of 4.3 hr in a model river 1 m deep flowing at 1 m/s with a wind speed of 3
m/s(3,SRC). Similarly, the volatilization half-life of chloropicrin
from a model lake 1 m deep, with a 0.05 m/s current and a 0.5 m/s wind is
estimated to be 5.2 days(2,SRC). Due to its high vapor pressure, 23.8 mm Hg at
25 deg C(2), high Henry's Law Constant, and low soil adsorptivity, chloropicrin
would volatilize rapidly from moist and dry soil and other surfaces(SRC).
The air water partition coefficient /was calculated as/ 8.4X10-2 for chloropicrin
Environmental Water Concentrations:
SURFACE WATER: Chloropicrin
in the ppb range is present in surface water with an organic content of about 10
mg/L total organic carbon(1). In two French treatment plants, prechlorinated
water from surface sources with 6-14 mg/L organic carbon contained <10 ng/L chloropicrin(1).
DRINKING WATER: Finished drinking water survey of 5 cities with varied sources
of raw water and types of contaminants: Cincinnati 3 ppb, Philadelphia 2 ppb,
Miami 0.4 ppb, Seattle and Ottuma, IA 0 ppb(1). In a survey of 14 treated
drinking water supplies of varied sources in England, chloropicrin
was detected in 3 supplies that were obtained from rivers(2). Among the 14
medium and large water treatment plants surveyed in Utah (serving >10,000
people), the mean, median, 25th percentile and 75th percentile concn of chloropicrin
was 0.37, 0.51, 0.47, and 0.55 ug/L, respectively(3). In a previous nationwide
survey of disinfectation byproducts in drinking water, the median concn of chloropicrin
was 0.1 ug/L(3).
GROUNDWATER: Chloropicrin was detected in 3 of the
16,561 wells sampled in California (1386 wells) and Florida (15,175 wells)
between 1990 and 1991 according to EPA's Pesticides in Ground Water Database(1).
The positive wells, all in Florida, contained chloropicrin
levels between 0.035 and 0.068 ppb. In wells 35 and 65 m from site where chloropicrin
was buried, 2.1 and 0.001 ppm respectively(2).
OTHER WATER: Swimming pool waters. 90% of 74 swimming pools in the Bonn area,
Germany, 0.4 ppm avg(1).
Effluent Concentrations:
In a comprehensive survey of wastewater from
4000 industrial and publicly owned treatment works (POTWs) sponsored by the
Effluent Guidelines Division of the U.S. EPA, chloropicrin
was identified in discharges of the following industrial category (positive
occurrences, median concn in ppb): organics and plastics (1; 77.8),
pharmaceuticals (1; 7.5), electoplating (1; 40.5)(1).
Atmospheric Concentrations:
Chloropicrin was
detected, but not quantified, in air at a grain farm in Japan(1).
Food Survey Values:
An FDA survey of over 500 foods for the
presence of fumigants resulted in 2 findings of chloropicrin
at an average concn of 17 ppb(1). Chloropicrin was
detected in food during FDA's regulatory monitoring program in FY83-86 in which
49,055 samples of domestic and imported raw agricultural commodities were
sampled(2). The number of residues found, although <2% of the total, and the
level of contamination was not reported.
Environmental Standards & Regulations:
FIFRA Requirements:
Classified for restricted use, limited to use
by or under the direct supervision of a certified applicator. FORMULATION: All
formulations greater than 2%. USE PATTERN: All uses. CLASSIFICATION: Restricted.
CRITERIA INFLUENCING RESTRICTION: Acute inhalation toxicity.
Classified for restricted use, limited to use by or under the direct supervision
of a certified applicator. FORMULATION: All formulations. USE PATTERN: Rodent
control. CLASSIFICATION: Restricted CRITERIA INFLUENCING RESTRICTION: Hazard to
non-target organisms.
Classified for restricted use, limited to use by or under the direct supervision
of a certified applicator. FORMULATION: All formulations 2% and less. USE
PATTERN: Outdoor uses (other than rodent control). CLASSIFICATION: Unclassified.
The insecticide chloropicrin is exempted from the
requirement of a tolerance for residues when used as a fumigant after harvest
for the following grains: barley, buckwheat, corn (including popcorn), oats,
rice, rye, grain sorghum, wheat.
As the federal pesticide law FIFRA directs, EPA is conducting a comprehensive
review of older pesticides to consider their health and environmental effects
and make decisions about their future use. Under this pesticide reregistration
program, EPA examines health and safety data for pesticide active ingredients
initially registered before November 1, 1984, and determines whether they are
eligible for reregistration. In addition, all pesticides must meet the new
safety standard of the Food Quality Protection Act of 1996. Chloropicrin
is found on List A, which contains most food use pesticides and consists of the
194 chemical cases (or 350 individual active ingredients) for which EPA issued
registration standards prior to FIFRA, as amended in 1988. Case No: 0040;
Pesticide type: Insecticide; Registration Standard Date: 09/28/82; Case Status:
OPP is reviewing data from the pesticide's producers regarding its human health
and/or environmental effects, or OPP is determining the pesticide's eligibility
for reregistration and developing the Reregistration Eligibility Decision (RED)
document.; Active ingredient (AI): Chloropicrin; Data
Call-in (DCI) Date(s): 09/28/90; AI Status: The producers of the pesticide has
made commitments to conduct the studies and pay the fees required for
reregistration, and are meeting those commitments in a timely manner.
State Drinking Water Guidelines:
(CA) CALIFORNIA 50 ug/l
(FL) FLORIDA 7.3 ug/l
Allowable Tolerances:
The insecticide chloropicrin
is exempted from the requirement of a tolerance for residues when used as a
fumigant after harvest for the following grains: barley, buckwheat, corn
(including popcorn), oats, rice, rye, grain sorghum, wheat.
Chemical/Physical Properties:
Molecular Formula:
C-Cl3-N-O2
Molecular Weight:
164.39
Color/Form:
SLIGHTLY OILY LIQUID
Faint yellow liquid.
Colorless liquid
Colorless to faint-yellow, oily liquid.
Odor:
Intensely irritating tear gas odor
Intensely irritating odor.
Boiling Point:
112 deg C @ 757 mm Hg
Melting Point:
-64 deg C (-69.2 deg C corr)
Corrosivity:
RELATIVELY INERT CHEMICALLY &
NON-CORROSIVE TO COPPER, BRASS & BRONZE BUT ATTACKS IRON, ZINC & OTHER
LIGHT METALS
Density/Specific Gravity:
1.6558 @ 20 DEG C/4 DEG C
Dissociation Constants:
2.7 pKa
Heat of Vaporization:
LATENT HEAT OF VAPORIZATION: 57.3 CAL/G
Octanol/Water Partition Coefficient:
log Kow of 2.09
Solubilities:
IN WATER: 0.2272 G/100 ML @ 0 DEG C, 0.1621
G/100 ML @ 25 DEG C
MISCIBLE WITH BENZENE, ABSOLUTE ALCOHOL, CARBON DISULFIDE; SOL IN ETHER
MISCIBLE WITH CARBON TETRACHLORIDE, ACETONE, METHYL ALCOHOL
MISCIBLE WITH ACETIC ACID
0.19 g/100 ml H2O at 20 deg C
Spectral Properties:
INDEX OF REFRACTION: 1.4611 @ 20 DEG C/D;
1.4596 @ 25 DEG C/D
MAX ABSORPTION (ALCOHOL): 276.5 NM (LOG E= 1.79)
IR: 11589 (Sadtler Research Laboratories Prism Collection)
MASS: 4235 (National Bureau of Standards EPA-NIH Mass Spectra Data Base,
NSRDS-NBS-63)
Surface Tension:
LIQUID SURFACE TENSION: 32.3 DYNES/CM @ 20 DEG
C; LIQUID-WATER INTERFACIAL TENSION: (EST) 30 DYNES/CM @ 20 DEG C
Vapor Density:
5.7 (AIR= 1); CONVERSION FACTORS: 1 MG/L=
148.8 PPM, 1 PPM= 6.72 MG/CU M
Vapor Pressure:
3.2 kPa (24 mm Hg) @ 25 deg C
Other Chemical/Physical Properties:
DIPOLE MOMENT IN HEPTANE OR BENZENE, 1.80
DEBYES
HEAVY LIQUID
DECOMP @ VERY HIGH TEMP
NOT DECOMPOSED BY WATER OR MINERAL ACIDS
Saturated vapor concn 170 g/cu m at 20 deg C; 286 g/ cu m at 30 deg C
RATIO OF SPECIFIC HEATS OF VAPOR (GAS): 1.0991.
5.7 MM HG @ 0 DEG C
Henry's Law constant = 2.05X10-3 atm-cu m/mol at 25 deg C
Chemical Safety & Handling:
DOT Emergency Guidelines:
Health: TOXIC, inhalation, ingestion, or skin
contact with material may cause severe injury or death. Contact with molten
substance may cause severe burns to skin and eyes. Avoid any skin contact.
Effects of contact or inhalation may be delayed. Fire may produce irritating,
corrosive and/or toxic gases. Runoff from fire control or dilution water may be
corrosive and/or toxic and cause pollution.
Fire or explosion: Non-combustible, substance itself does not burn but may
decompose upon heating to produce corrosive and/or toxic fumes. Some are
oxidizers and may ignite combustibles (wood, paper, oil, clothing, etc.).
Contact with metals may evolve flammable hydrogen gas. Containers may explode
when heated.
Public safety: CALL Emergency Response Telephone Number on Shipping Paper first.
If Shipping Paper not available or no answer, refer to appropriate telephone
number listed on the inside back cover. Isolate spill or leak area immediately
for at least 25 to 50 meters (80 to 160 feet) in all directions. Keep
unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate
enclosed areas.
Protective clothing: Wear positive pressure self-contained breathing apparatus (SCBA).
Wear chemical protective clothing which is specifically recommended by the
manufacturer. Structural firefighters' protective clothing is recommended for
fire situations ONLY, it is not effective in spill situations.
Evacuation: Spill: See the Table of Initial Isolation and Protective Action
Distances for highlighted substances. For non-highlighted substances, increase,
in the downwind direction, as necessary, the isolation distance shown under
"PUBLIC SAFETY". Fire: If tank, rail car or tank truck is involved in
a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider
initial evacuation for 800 meters (1/2 mile) in all directions.
Fire: Small fires: Dry chemical, CO2 or water spray. Large fires: Dry chemical,
CO2, alcohol-resistant foam or water spray. Move containers from fire area if
you can do it without risk. Dike fire control water for later disposal; do not
scatter the material. Fire involving tanks or car/trailer loads: Fight fire from
maximum distance or use unmanned hose holders or monitor nozzles. Do not get
water inside containers. Cool containers with flooding quantities of water until
well after fire is out. Withdraw immediately in case of rising sound from
venting safety devices or discoloration of tank. ALWAYS stay away from the ends
of tanks.
Spill or leak: ELIMINATE all ignition sources (no smoking, flares, sparks or
flames in immediate area). Do not touch damaged containers or spilled material
unless wearing appropriate protective clothing. Stop leak if you can do it
without risk. Prevent entry into waterways, sewers, basements or confined areas.
Absorb or cover with dry earth, sand or other non-combustible material and
transfer to containers. DO NOT GET WATER INSIDE CONTAINERS.
First aid: Move victim to fresh air. Call emergency medical care. Apply
artificial respiration if victim is not breathing. Do not use mouth-to-mouth
method if victim ingested or inhaled the substance; induce artificial
respiration with the aid of a pocket mask equipped with a one-way valve or other
proper respiratory medical device. Administer oxygen if breathing is difficult.
Remove and isolate contaminated clothing and shoes. In case of contact with
substance, immediately flush skin or eyes with running water for at least 20
minutes. For minor skin contact, avoid spreading material on unaffected skin.
Keep victim warm and quiet. Effects of exposure (inhalation, ingestion or skin
contact) to substance may be delayed. Ensure that medical personnel are aware of
the material(s) involved, and take precautions to protect themselves.
Initial Isolation and Protective Action Distances: Small Spills (from a small
package or small leak from a large package): First, ISOLATE in all Directions 95
meters (300 feet); then, PROTECT persons Downwind during DAY 0.5 kilometers (0.3
miles) and NIGHT 2.1 kilometers (1.3 miles). LARGE SPILLS (from a large package
or from many small packages): First, ISOLATE in all Directions 305 meters (1000
feet); then, PROTECT persons Downwind during DAY 1.8 kilometers (1.1 miles) and
NIGHT 7.7 kilometers (4.8 miles).
Odor Threshold:
Threshold odor concn: 1.1 ppm
Faint odor at 0.0073 mg/l
Skin, Eye and Respiratory Irritations:
Chloropicrin is
intensely irritating to the eyes and has a tear gas-like effect. Chloropicrin
in concn of 0.3-0.37 ppm resulted in painful irritation to the eyes in 3-30 sec
... A level of 4 ppm for a few seconds renders a man unfit for activity, and 15
ppm for the same duration resulted in respiratory tract injury ... Chloropicrin
is also noted to be a potent skin irritant.
Fire Potential:
Not flammable.
NFPA Hazard Classification:
Health: 4. 4= Materials that, on very short
exposure, could cause death or major residual injury, including those that are
too dangerous to be approached without specialized protective equipment. A few
whiffs of the vapor or gas can cause death, or contact with the vapor or liquid
may be fatal, if it penetrates the fire fighter's normal protective gear. The
normal full protective clothing and breathing apparatus available to the typical
fire fighter will not provide adequate protection against inhalation or skin
contact with these materials.
Flammability: 0. 0= This degree includes any material that will not burn.
Reactivity: 3. 3= This degree includes materials that, in themselves, are
capable of detonation, explosive decomposition, or explosive reaction, but
require a strong initiating source or heating under confinement. This includes
materials that are sensitive to thermal and mechanical shock at elevated
temperatures and pressures and materials that react explosively with water.
Fires involving these materials should be fought from a protected location.
Fire Fighting Procedures:
Stop discharge if possible. Cool exposed
containers with water.
Extinguish fire using agent suitable for surrounding fire. use dry chemical,
foam, carbon dioxide, or water spray. Water may be ineffective. Explosive
decomposition may occur under fire conditions. Fight fire from protected
location or maximum possible distance. Use water spray to keep fire-exposed
containers cool. Approach fire from upwind to avoid hazardous vapors and toxic
decomposition products.
If material involved in fire: Extinguish fire using agent suitable for type of
surrounding fire. (Material itself does not burn or burns with difficulty.) Use
water in flooding quantities as fog. Use foam, dry chemical, or carbon dioxide.
Explosive Limits & Potential:
Not combustible, but material under
confinement may explode when heated or with friction or contamination. Closed
containers may rupture violently when heated.
An insecticidal mixture in a rail tank exploded with great violence during pump
transfer operations, possibly owing to the pump running dry and overheating.
Both components of the mixture are explosive and the mixture was also found to
be shock and heat sensitive.
During addition of the nitrocompound in methanol to sodium methoxide solution,
the temperature must not be allowed to fall much below 50 deg C. If this happens
, excess nitro compound will accumulate and cause a violent and dangerous
exotherm.
Hazardous Reactivities & Incompatibilities:
Incompatible with strong oxidizers.
During destruction of chemical warfare ammunition, pierced shells containing chloropicrin
reacted violently with alcoholic sodium hydroxide.
Strong oxidizers [Note: The material may explode when heated under confinement.]
Other Hazardous Reaction:
Poisonous gases are produced in a fire.
Compound forms a powerful tear gas when heated.
Immediately Dangerous to Life or Health:
2 ppm
Protective Equipment & Clothing:
CHLOROPICRIN IS AMONG
CMPD WHOSE ODOR THRESHOLD DATA IN PRESENT LITERATURE ARE COMPARED WITH CURRENT
TLV DATA. RECOMMENDATIONS ARE GIVEN FOR USING CHEM CARTRIDGE RESPIRATORS FOR
CMPD WITH ODOR THRESHOLD VALUE SAME AS, 2-10 TIMES & GREATER THAN TLV.
Wear all-purpose canister mask, self-contained breathing apparatus and neoprene
gloves.
Wear appropriate personal protective clothing to prevent skin contact.
Wear appropriate eye protection to prevent eye contact.
Eyewash fountains should be provided in areas where there is any possibility
that workers could be exposed to the substance; this is irrespective of the
recommendation involving the wearing of eye protection.
Facilities for quickly drenching the body should be provided within the
immediate work area for emergency use where there is a possibility of exposure.
(Note: It is intended that these facilities provide a sufficient quantity or
flow of water to quickly remove the substance from any body areas likely to be
exposed. The actual determination of what constitutes an adequate quick drench
facility depends on the specific circumstances. In certain instances, a deluge
shower should be readily available, whereas in others, the availability of water
from a sink or hose could be considered adequate.)
Recommendations for respirator selection. Max concn for use: 2 ppm. Respirator
Class(es): Any supplied-air respirator operated in a continuous flow mode. Eye
protection needed. Any powered, air-purifying respirator with organic vapor
cartridge(s). Eye protection needed. Any chemical cartridge respirator with a
full facepiece and organic vapor cartridge(s). Any air-purifying, full-facepiece
respirator (gas mask) with a chin-style, front- or back-mounted organic vapor
canister. Any self-contained breathing apparatus with a full facepiece. Any
supplied-air respirator with a full facepiece.
Recommendations for respirator selection. Condition: Emergency or planned entry
into unknown concn or IDLH conditions: Respirator Class(es): Any self-contained
breathing apparatus that has a full facepiece and is operated in a
pressure-demand or other positive pressure mode. Any supplied-air respirator
with a full facepiece and operated in pressure-demand or other positive pressure
mode in combination with an auxiliary self-contained breathing apparatus
operated in pressure-demand or other positive pressure mode.
Recommendations for respirator selection. Condition: Escape from suddenly
occurring respiratory hazards: Respirator Class(es): Any air-purifying, full-facepiece
respirator (gas mask) with a chin-style, front- or back-mounted organic vapor
canister. Any appropriate escape-type, self-contained breathing apparatus.
Preventive Measures:
If material not involved in fire: Keep
material out of water sources and sewers. Use water spray to knock-down vapors.
Contact lenses should not be worn when working with this chemical.
SRP: The scientific literature for the use of contact lenses in industry is
conflicting. The benefit or detrimental effects of wearing contact lenses depend
not only upon the substance, but also on factors including the form of the
substance, characteristics and duration of the exposure, the uses of other eye
protection equipment, and the hygiene of the lenses. However, there may be
individual substances whose irritating or corrosive properties are such that the
wearing of contact lenses would be harmful to the eye. In those specific cases,
contact lenses should not be worn. In any event, the usual eye protection
equipment should be worn even when contact lenses are in place.
The worker should immediately wash the skin when it becomes contaminated.
Work clothing that becomes wet or significantly contaminated should be removed
and replaced.
Personnel protection: Avoid breathing vapors. Keep upwind. ... Avoid bodily
contact with the material. ... Do not handle broken packages unless wearing
appropriate personal protective equipment.
Evacuation: If material leaking (not on fire) consider evacuation from downwind
area based on amount of material spilled, location and weather conditions.
May be dangerous if it enters water intakes. Notify local health and wildlife
officials. Notify operators of nearby water intakes.
Stability/Shelf Life:
RELATIVELY STABLE
SLOWLY VOLATILIZED
Shipment Methods and Regulations:
No person may /transport,/ offer or accept a
hazardous material for transportation in commerce unless that person is
registered in conformance ... and the hazardous material is properly classed,
described, packaged, marked, labeled, and in condition for shipment as required
or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./
The International Air Transport Association (IATA) Dangerous Goods Regulations
are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618
and 619 and constitute a manual of industry carrier regulations to be followed
by all IATA Member airlines when transporting hazardous materials.
The International Maritime Dangerous Goods Code lays down basic principles for
transporting hazardous chemicals. Detailed recommendations for individual
substances and a number of recommendations for good practice are included in the
classes dealing with such substances. A general index of technical names has
also been compiled. This index should always be consulted when attempting to
locate the appropriate procedures to be used when shipping any substance or
article.
Storage Conditions:
Store in a cool, dry, well-ventilated
location. Separate from oxidizing materials. Outside or detached storage is
preferred.
STORAGE: DO NOT USE MAGNESIUM, ALUMINUM OR THEIR ALLOYS FOR HANDLING EQUIPMENT
OR CONTAINERS. BE SURE CONTAINER IS CLOSED COMPLETELY. STORE IN COOL,
WELL-VENTILATED PLACE. NOT FOR USE OR STORAGE IN OR AROUND HOME.
STORAGE: ...ATTACKS IRON...BUT FORMS PROTECTIVE COATING & HENCE CAN BE
STORED IN IRON OR GALVANIZED IRON.
STORAGE TEMP: AMBIENT. VENTING: PRESSURE-VACUUM.
Keep containers tightly closed, and store in a cool and dark place. Separate
from sources of ignition or heat.
Cleanup Methods:
After covering the spills with soda ash, mix
and spray with water. Scoop into bucket of water and leave it stand for two
hours. Neutralize with 6M-HCl and pass into the drain with sufficient water.
Releases may require isolation or evacuation. Stop or control the leak., if this
can be done without undue risk. Use water spray to cool and disperse vapors and
protect personnel. Absorb in noncombustible material for proper disposal.
Disposal Methods:
SRP: At the time of review, criteria for land
treatment or burial (sanitary landfill) disposal practices are subject to
significant revision. Prior to implementing land disposal of waste residue
(including waste sludge), consult with environmental regulatory agencies for
guidance on acceptable disposal practices.
The following scheme is proposed for treating effluents from the production of chloropicrin.
These wastewaters contain Ca(ClO)2 approx 2000 mg/l, chloropicrin
approx 80 mg/l, and picric acid approx 80 mg/l. The Ca(ClO)2 is first removed by
reduction with FeSO4 at 90-95 deg, and pH of 11-11.5. Complete removal is
achieved in 3 hours. The nitro compounds are then reduced to MeNH2 and
triaminophenol by heating the effluent from the first stage with FeSO4 and Fe
turnings at 90-95 deg. Reduction of the nitro compounds is approx 81% complete,
the residue containing compounds are not readily reduced. The MeNH2 vapor is
oxidized to MeOH in a reactor containing a soln of NaNO2 and HCl at 5-6 deg. The
reaction time is 2-2.5 hours. The MeOH and triaminophenol are then oxidized with
Ca(ClO)2, and the final treated effluent is clearified before discharge.
Chloropicrin reacts
readily with alcoholic sodium sulfite soln to produce methanetrisulfonic acid
(which is relatively non volatile and less harmful). This reaction has been
recommended for treating spills and cleaning equipment. Although not
specifically suggested as a decontamination procedure, the rapid reaction of chloropicrin
with ammonia to produce guanidine (LD50= 500) could be used for detoxication.
The Manufacturing Chemists Association suggest two procedures for disposal of chloropicrin:
1) Pour or sift over soda ash. Mix and wash slowly into large tank. 2) Adsorb on
vermiculite. Mix and shovel into paper boxes. Drop into incinerator with
afterburner and scrubber. Recommendable methods: Neutralization, &
incineration.
Occupational Exposure Standards:
OSHA Standards:
Permissible Exposure Limit: Table Z-1 8-hr
Time Weighted Avg: 0.1 ppm (0.7 mg/cu m).
Threshold Limit Values:
8 hr Time Weighted Avg (TWA) 0.1 ppm
Excursion Limit Recommendation: Excursions in worker exposure levels may exceed
three times the TLV-TWA for no more than a total of 30 min during a work day,
and under no circumstances should they exceed five times the TLV-TWA, provided
that the TLV-TWA is not exceeded.
A4. A4= Not classifiable as a human carcinogen.
NIOSH Recommendations:
Recommended Exposure Limit: 10 Hr
Time-Weighted Avg: 0.1 ppm (0.7 mg/cu m).
Immediately Dangerous to Life or Health:
2 ppm
Other Occupational Permissible Levels:
Emergency Response Planning Guidelines (ERPG):
ERPG(1) 0.1 ppm (no more than mild, transient effects) for up to 1 hr exposure;
ERPG(2) 0.3 ppm (without serious, adverse effects) for up to 1 hr exposure;
ERPG(3) 1.5 ppm (not life threatening) up to 1 hr exposure.
Manufacturing/Use Information:
Major Uses:
AS RODENTICIDE
TEAR GAS
IT MAY BE INJECTED IN SOIL IN COMBINATION WITH XYLENE, CARBON TETRACHLORIDE, OR
ETHYLENE DICHLORIDE TO HELP DISTRIBUTE GAS.
FUMIGANT FOR NON-DECIDUOUS FRUITS, TOMATOES, & TOBACCO
Disinfecting cereals and grains; in synthesis, esp in manuf of methyl violet;
fumigant; soil insecticide; war gas
Soil/space fumigant for nematodes, bacteria, fungi, insects and weeds. warning
agent. Warning agent for use with odorless fumigants (e.g. methyl bromide).
Methods of Manufacturing:
PREPN: BY ACTION OF HYPOCHLORITES & STEAM
ON CALCIUM PICRATE.
PREPN: FIRST PREPARED IN 1848 BY STENHOUSE FROM PICRIC ACID & BLEACH POWDER.
PREPN: ...NITRIFICATION OF CHLORINATED HYDROCARBONS.
Manuf from nitromethane and alkaline hypochlorite.
General Manufacturing Information:
IN FIELD BEANS (PHASEOLUS VULGARIS),
FUMIGATION WITH 400 KG/HA CHLOROPICRIN SIGNIFICANTLY
INCREASED SHOOT WEIGHT, ROOT WEIGHT, AND TOTAL NITROGEN UPTAKE THROUGHOUT THE
SEASON AND DECREASED THE INCIDENCE OF ROOT ROT.
Formulations/Preparations:
...COMMONLY USED IN MIXT WITH METHYL BROMIDE
OR WITH CHLORINATED C3 HYDROCARBONS. BROZONE (1.4% CHLOROPICRIN)
(DISCONTINUED BY DOW), DOWFUME MC-2 (2% CHLOROPICRIN),
DOWFUME MC-33 (33% CHLOROPICRIN)...TELONE C-17 (17% CHLOROPICRIN).
Ready-to-use concentrate.
Brom-O-Gas, Bromo-O-Sol, Terr-O-Gas, Bromocoop (with methyl bromide); Rootect
Oil (with DCIP)
Consumption Patterns:
FUMIGANT FOR NON-DECIDUOUS FRUITS, 44%;
TOMATOES, 14%; TOBACCO, 6%; POTATOES, 3%; OTHER FIELD CROPS-EG, COTTON, PEANUTS,
SUGAR BEETS, & DECIDUOUS FRUITS & NUTS, 8%; OTHER VEGETABLES, 5%; FLORAL
CROPS, LAWNS, TURF, & ORNAMENTALS, 11%; COMMODITIES, SPACE, & STRUCTURAL
PEST CONTROL, 3%; MISCELLANEOUS SOIL FUMIGATION, 5% (1982)
Laboratory Methods:
Analytic Laboratory Methods:
PRODUCT ANALYSIS: DETECTION: (A) PASS AIR
THROUGH SODIUM ETHYLATE SOLN & TEST FOR PRESENCE OF NITRITES. (B) PASS AIR
THROUGH 4% ALCOHOLIC SODIUM NITRATE SOLN, CHLORINE CONVERTED TO SODIUM CHLORIDE.
(C) ADD 1 DROP TO 5 ML 20% SODIUM SULFIDE, CLOSE TUBE & PUNGENT ODOR OF CHLOROPICRIN
DISAPPEARS.
A gas chromatographic (GC) procedure for determining fumigants in grains. ...
Fumigants were leached from grain samples ... using acetone-water (5+1). They
were then partitioned from the leachate with isooctane, yielding a dry, stable
extract that was analyzed by GC. Fortified sample recoveries ranged from
90-100%. Two GC columns were used, 20% OV-101 and 20% OV-225/20% OV-17 (2+1).
...AIR: COLLECT IN ISOPROPYL ALCOHOL, TREAT ALIQUOT WITH 4.5% SODIUM PEROXIDE,
NEUTRALIZE WITH HYDROCHLORIC ACID, REACT LIBERATED NITRITE WITH SULFANILIC ACID,
COUPLE WITH N-1-NAPHTHYLENETHYLENE DIAMINE & DETERMINE @ 540 NM(FEINSILVER
L, OBERST FW; ANAL CHEM (25) 820 (1953).
AIR CONTAINING CHLOROPICRIN WAS BUBBLED THROUGH PROPYL
ALCOHOL, SOLN... HYDROLYZED BY REFLUXING WITH NAOH. RESULTING NANO2 AFTER
ELIMINATING PROPYL ALCOHOL... DETERMINED AS NA SALT OF SULFANILAMIDOCHRYSOIDINE,
BY REACTION WITH SULFANILAMIDE & COUPLING WITH M-PHENYLENEDIAMINE. IOANID N
ET AL; FARMACIA (11) 349 (1963).
OVERVIEW & STATUS STUDY OF ANALYTICAL METHODS INCL COMBINATIONS OF GAS
CHROMATOGRAPHY, ION-SELECTIVE ELECTRODES & NEW DEVELOPMENTS IN SPECTROMETRY
& POLAROGRAPHY IN FUMIGANT RESEARCH.
EMSLC Method 551, Determination of Chlorination Disinfection Byproducts and
Chlorinated Solvents in Drinking Water by Liquid-Liquid Extraction and Gas
Chromatography with Electron-Capture Detection, capillary gas chromatography
with electron capture detection, method detection limit 0.012 ug/L
EMSLC Method 618, Determination of Volatile Pesticides in Municipal and
Industrial Wastewaters by Gas Chromatography, gas chromatography with electron
capture detection, method detection limit 0.08 ug/L
Sampling Procedures:
AIR WAS COLLECTED IN A TEDLAR BAG, AND CHLOROPICRIN
IN THE AIR WAS DETERMINED WITH AN ELECTRON CAPTURE DETECTOR.
Special References:
Special Reports:
Bioassay of Chloropicrin
for Possible Carcinogenicity (1978) Technical Rpt Series No. 65 DHEW Pub No. (NIH)
78-1315, U.S. Department of Health Education and Welfare, National Cancer
Institute, Bethesda, MD 20014
Synonyms and Identifiers:
Synonyms:
G 25
**PEER REVIEWED**
S 1
**PEER REVIEWED**
ACQUINITE
**PEER REVIEWED**
CHLOORPIKRINE (DUTCH)
**PEER REVIEWED**
CHLOROFORM, NITRO-
**PEER REVIEWED**
CHLOROPICRINE (FRENCH)
**PEER REVIEWED**
CHLOROPICRIN, LIQUID
(DOT)
**PEER REVIEWED**
CHLOR-O-PIC
**PEER REVIEWED**
CHLORPIKRIN (GERMAN)
**PEER REVIEWED**
CLOROPICRINA
(ITALIAN)
**PEER REVIEWED**
DOJYOPICRIN
**PEER REVIEWED**
DOLOCHLOR
**PEER REVIEWED**
LARVACIDE
**PEER REVIEWED**
LARVACIDE 100
**PEER REVIEWED**
METHANE, TRICHLORONITRO-
**PEER REVIEWED**
MICROLYSIN
**PEER REVIEWED**
NCI-C00533
**PEER REVIEWED**
NITROCHLOROFORM
**PEER REVIEWED**
NITROTRICHLOROMETHANE
**PEER REVIEWED**
OG 25
**PEER REVIEWED**
PIC-CLOR
**PEER REVIEWED**
PICFUME
**PEER REVIEWED**
PICRIDE
**PEER REVIEWED**
PROFUME A
**PEER REVIEWED**
PS
**PEER REVIEWED**
TRICHLOORNITROMETHAAN
(DUTCH)
**PEER REVIEWED**
TRICHLORNITROMETHAN
(GERMAN)
**PEER REVIEWED**
TRICHLORONITROMETHANE
**PEER REVIEWED**
TRI-CLOR
**PEER REVIEWED**
TRICLORO-NITRO-METANO (ITALIAN)
**PEER REVIEWED**
Formulations/Preparations:
...COMMONLY USED IN MIXT WITH METHYL BROMIDE
OR WITH CHLORINATED C3 HYDROCARBONS. BROZONE (1.4% CHLOROPICRIN)
(DISCONTINUED BY DOW), DOWFUME MC-2 (2% CHLOROPICRIN),
DOWFUME MC-33 (33% CHLOROPICRIN)...TELONE C-17 (17% CHLOROPICRIN).
Ready-to-use concentrate.
Brom-O-Gas, Bromo-O-Sol, Terr-O-Gas, Bromocoop (with methyl bromide); Rootect
Oil (with DCIP)
Shipping Name/ Number DOT/UN/NA/IMO:
UN 1580; Chloropicrin,
liquid
IMO 6.1; Chloropicrin,
liquid
Standard Transportation Number:
49 214 14; Chloropicrin,
liquid
RTECS Number:
NIOSH/PB6300000
Administrative Information:
Hazardous Substances Databank Number: 977
Last Revision Date: 20020513
Last Review Date: Reviewed by SRP on 9/14/1995
http://panna.igc.org/resources/gpc/gpc_...
Chloropicrin, a chlorinated chemical commonly used in tear gas and as a soil
fumigant, is highly toxic to the aquatic environment. In addition to acute
health effects, exposure to chloropicrin has been linked to recurrent asthma,
pulmonary edema, anaemia and irregular heartbeat. Other chronic, long-term
effects may include respiratory, eye, skin, heart, gastro-intestinal and musculo-skeletal
problems. Occupational exposure to the chemical is also thought to cause
rhabdomyolosis, a potentially fatal condition marked by the degeneration of
skeletal muscles.
http://www.alternatives2toxics.org/tric.htm
Chloropicrin, a tear gas is added as a warning agent but it may not be effective
for that purpose. Methyl bromide and chloropicrin are each restricted use
chemicals which can only be applied by licensed applicators and require a
special permit in advance of application.
http://www.unec.net/health_effects.htm
Pending Study. Fumigant; soil insecticide; war gas
http://ace.orst.edu/info/extoxnet/pips/chloropi.htm
Acute Toxicity: Undiluted
chloropicrin is highly toxic by ingestion or direct contact with the skin or
eyes. According to the American Conference of Governmental Industrial Hygienists
(261), airborne exposure to 0.3-0.37 ppm (2-2.5 mg/meters cubed) for 3-30
seconds results in eye irritation. This response is reported to be highly
variable among individuals and tearing (lachrymation) may occur at airborne
exposures of 0.15-0.3 ppm (1-2 mg/meters cubed) (261). Inhalation exposure to 4
ppm (26 mg/meters cubed) for a few seconds may cause some degree of
incapacitation (261) and an exposure of a few seconds to 15 ppm (100 mg/meters
cubed) can cause injury to the respiratory track. Exposure to concentrations
above 15 ppm can result in lacrimation, vomiting, and if allowed to continue for
a minute or longer, can cause pulmonary edema and possibly death (261). The
American Industrial Hygiene Association Emergency Response Planning Guideline
for one hour exposure to chloropicrin is 3 ppm (20 mg/meters cubed)(262). Animal
studies established that the 4-hour inhalation LC50 for chloropicrin vapor in
rats is 11.9 ppm (79.7 mg/meters cubed)(293) and the respiratory irritation
potential threshold (RD50) in mice is 7.98 ppm (53.5 mg/meters cubed)(293). The
FIFRA Toxicity Classification for chloropicrin acute effects is Category I and
the signal word for that classification is "Danger."
Signs and Symptoms of Poisoning: Undiluted chloropicrin is severely and immediately irritating to the upper respiratory tract, eyes and skin upon direct contact. Exposure to airborne concentrations of chloropicrin exceeding 0.15 ppm (1 mg/meters cubed) can cause tearing and eye irritation which is reversible upon termination of exposure. Prolonged inhalation exposures at airborne concentrations above 1 ppm may cause symptoms of respiratory system damage including irritation of the airways, shortness of breath and/or tightness in chest and difficulty in breathing. Inhalation exposure to very high levels, even if brief, can lead to pulmonary edema, unconsciousness and even death.
Chronic Toxicity/Subchronic Effects: Studies with male and female CD rats and CD-1 mice exposed to chloropicrin vapor in whole body inhalation chambers at concentrations of 0.3, 1.0, or 3.0 ppm for six hours per day, five days per week for thirteen weeks (263) and male Fisher 344 rats exposed to chloropicrin (264) indicated that respiratory tissue is the target for chloropicrin inhalation toxicity. Portal-of-entry effects occurred in the upper respiratory tissue of animals inhaling chloropicrin vapor for 90 days at concentrations at or above 0.1 ppm (0.67 mg/meters cubed).
Reproductive Effects: A study utilizing chloropicrin vapor administered by whole body inhalation for six hours per day, seven days per week to male and female CD rats at concentrations of 0.5, 1.0, or 1.5 ppm through two generations of animals indicated that reproduction fitness is not adversely affected by chloropicrin inhalation even at systemically toxic levels (265). The No Observable Adverse Effect Level (NOAEL) was 1.0 ppm for systemic toxicity and greater than 1.5 ppm for developmental toxicity and reproductive parameters.Teratogenic Effects: In a study with sexually mature virgin female Sprague-Dawley rats exposed by whole body inhalation to chloropicrin vapor for six hours per day for days 6-15 of gestation, there were no treatment-related fetal malformations (266). The incidence of developmental variations in the mid- and high-dose groups increased over the control group and was statistically significant in the high-dose group. The NOAEL for maternal toxicity was 0.4 ppm and the NOAEL for fetal toxicity was 1.2 ppm indicating that the developing fetus is not a target tissue for chloropicrin.The developmental toxicity of chloro-picrin in sexually mature virgin female New Zealand White SPF rabbits was evaluated by whole body exposure/inhalation to chloropicrin vapor for six hours per day for days 7-20 of gestation (267). There were no treatment related fetal malformations reported, the incidence of developmental variations in the mid- and high-dose groups was increased over the control group and was considered to be treatment related but was not dose related nor was it statistically significant. The NOAEL for maternal toxicity was 0.4 ppm and the NOAEL for fetal toxicity was 1.2 ppm indicating that the developing fetus is not a target tissue.
Mutagenic Effects: Chloropicrin has been evaluated in several in vitro genetic toxicity test systems (268, 271). Bacterial cell testing for gene mutation produced some evidence of genetic toxicity in one of five tester strains in the presence of an exogenous metabolic activation system but testing in higher order cells (mammalian cells) did not confirm the potential for chloropicrin to produce gene mutation. Chloropicrin did not cause damage to mammalian cell DNA. In vitro testing of mammalian cell chromosomes for damage (breaks, exchange figures, fragments, etc.) produced evidence suggestive of a clastogenic effect but the data were equivocal.
Carcinogenic Effects: Six long-term bioassays have been performed to evaluate the potential of chloropicrin to cause chronic and/or carcinogenic effects by inhalation, oral, and gavage dosing (272, 276). Chronic toxicity was limited to inflammatory and other degenerative changes associated with chronic wound healing at the portal-of-entry and at associated tissues (i.e. rodent forestomach following life-long oral dosing). No neoplastic or tumorigenic response was produced by chloropicrin in any species tested by the three routes of exposure.
Organ Toxicity: Target organs for chloropicrin toxicity include eyes, skin, respiratory tract and tissue associated with portal-of-entry into the body.http://www.ilo.org/public/english/protection/safework/cis...
Inhalation and/or Ingestion: Abdominal pain. Cough. Diarrhoea.
Dizziness. Headache. Nausea. Sore throat. Vomiting. Weakness. Symptoms may be
delayed (see Notes).
Skin: Redness. Pain.
Eyes: Redness. Pain. Blurred vision.
CHEMICAL DANGERS:
May explode on heating and on shock. The substance decomposes on heating and
under influence of light producing toxic fumes including hydrogen chloride and
nitrogen oxides. Reacts violently with alcoholic sodium hydroxide, sodium
methoxide, propargyl bromide, aniline+heat.
ROUTES OF EXPOSURE:
The substance can be absorbed into the body by inhalation of its vapour and by
ingestion.
INHALATION RISK:
A harmful contamination of the air can be reached very quickly on evaporation of
this substance at 20°C.
EFFECTS OF SHORT-TERM EXPOSURE:
Tear drawing. The substance irritates strongly the eyes, the skin and the
respiratory tract. Inhalation of vapor may cause lung oedema (see Notes).
Exposure above the OEL may result in death. The effects may be delayed. Medical
observation is indicated.
Depending on the degree of exposure,
periodic medical examination is indicated. The symptoms of lung oedema often do
not become manifest until a few hours have passed and they are aggravated by
physical effort. Rest and medical observation is therefore essential. Immediate
administration of an appropriate spray, by a doctor or a person authorized by
him/her, should be considered. The odour warning when the exposure limit value
is exceeded is insufficient.
http://www.osha-slc.gov/dts/chemicalsampling/...
SYNONYM(s): Nitrotrichloromethane; Trichloronitromethane; Nitrochloroform
SYMPTOM(s): Eye irritation, lacrimation;
coughing, pulmonary edema; nausea, vomiting; skin irritation
HEALTH EFFECTS: Irritation-Eye, Nose, Throat, Skin---Marked (HE14) Acute
lung damage/edema (HE11)
ORGAN: Respiratory system, skin, eyes