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SECTION 1. CHEMICAL IDENTIFICATION

CHEMINFO Record Number: 528
CCOHS Chemical Name: Chloropicrin

Synonyms:
Nitrochloroform
Nitrotrichloromethane
Trichloronitromethane

Chemical Name French: Chloropicrine
CAS Registry Number: 76-06-2
UN/NA Number(s): 1580
RTECS Number(s): PB6300000
EU EINECS/ELINCS Number: 200-930-9
Chemical Family: Halogenated aliphatic nitro compound / halogenated nitroparaffin / chlorinated mononitroparaffin / halonitroalkane / trihalonitroalkane / nitrohaloform / chloronitroalkane / trichloronitroalkane
Molecular Formula: C-Cl3-N-O2
Structural Formula: Cl3-C-NO2

SECTION 2. DESCRIPTION

Appearance and Odour:
A colourless, slightly oily liquid with an intense and penetrating odour.(21) Lachrymator (vapour irritates the eyes and causes tears).(15)

Odour Threshold:
1.1 ppm (threshold concentration) (7,9)

Warning Properties:
POOR - odour threshold is above the TLV

Composition/Purity:
When used as a pesticide, this material is often only a small percentage of the formulation. The overall physical, chemical and toxic characteristics of the product may depend on other ingredients such as solvents. Consult your Material Safety Data Sheet, other relevant CHEMINFO records and your manufacturer/supplier for additional information.

Uses and Occurrences:
Chloropicrin is used in chemical synthesis, especially in the manufacture of methyl violet, also used as a pesticide for insect and rodent control, as a fungicide for fruits and vegetables, as a fumigant for stored grains, cereals and fruits and as a sterilizing agent. Used, in the past, as a chemical warfare agent.


SECTION 3. HAZARDS IDENTIFICATION

EMERGENCY OVERVIEW:
Colourless, slightly oily liquid with an intense and penetrating odour. Lachrymator. Will not burn. Can decompose at high temperatures forming toxic gases, such as phosgene, hydrogen chloride and nitrogen oxides. Unstable. Can decompose upon exposure to light forming toxic gases such as phosgene, chlorine, nitrosyl chloride and nitrogen oxides. Closed containers may rupture and explode if heated. DANGEROUSLY REACTIVE. May become self-reactive at temperatures above 150 deg C or if exceeds critical volume. VERY TOXIC. May be fatal if inhaled, or swallowed. CORROSIVE to the eyes, skin and respiratory tract. May cause lung injury--effects may be delayed.



POTENTIAL HEALTH EFFECTS

Effects of Short-Term (Acute) Exposure

Inhalation:
Chloropicrin is a very severe irritant when inhaled and may cause corrosive damage to the lungs and airways. Symptoms include severe irritation of the respiratory tract and mucous membranes, coughing, difficult breathing, dizziness, fatigue, headache, stomach pain, decreased blood pressure, nausea, vomiting and diarrhea.(5,10,15) Severe lung damage (congestion, hemorrhage) leading to pulmonary edema (a life-threatening accumulation of fluid in the lungs) and airways damage (lesions in the nose, throat and bronchi) may occur.(5,15) Pulmonary edema can be delayed so that the effects develop several hours after the exposure and are aggravated by physical exertion.(10) Death can occur due to the lung damage if exposure is severe. Secondary infections of the lungs can lead to death, days or weeks after the exposure.(1,5) Exposure to low concentrations (15 ppm for 1 minute or 7.5 ppm for 10 minutes) is intolerable.(1) A 10-minute exposure to 298 ppm and a 30-minute exposure to 119 ppm are lethal.(1) Individuals previously injured by chloropicrin may become more susceptible so that they are more affected by subsequent exposures to lower concentrations.(5)

Skin Contact:
No human information is available, but animal studies have shown that chloropicrin is corrosive.(3) Skin contact with the liquid would probably cause severe skin damage. Permanent scarring may result.

Eye Contact:
Chloropicrin is corrosive. The vapour can cause tearing and severely irritate the eyes. Concentrations of approximately 0.3 ppm resulted in painful irritation to the eyes in 3-30 seconds. This response varies according to individual susceptibility.(1,21) A concentration of 1-3 ppm can cause irritation and tears.(9,13) In one case, a man severely damaged his right eye when he accidently splashed liquid chloropicrin into it.(14)

Ingestion:
No human information is available, but based on animal data and because of its corrosive nature, ingestion of small amounts of chloropicrin would be painful, and possibly cause nausea, gastroenteritis, and even death. Ingestion is not a typical route of occupational exposure.

Effects of Long-Term (Chronic) Exposure

No human information is available. One animal study found high death rates in rats and mice given low oral doses for up to 78 weeks.(4)

Carcinogenicity:

No human information is available. Animal data is inconclusive.

The International Agency for Research on Cancer (IARC) has not evaluated the carcinogenicity of this chemical.

The American Conference of Governmental Industrial Hygienists (ACGIH) has designated this chemical as not classifiable as a human carcinogen (A4).

The US National Toxicology Program (NTP) has not listed this chemical in its report on carcinogens.

Teratogenicity and Embryotoxicity:
No human or animal information is available.

Reproductive Toxicity:
No human or animal information is available.

Mutagenicity:
No human or animal in vivo information is available. Chloropicrin significantly induced sister chromatid exchanges in cultured human lymphocytes, with and without metabolic activation. It did not induce chromosomal aberrations.(22)

Toxicologically Synergistic Materials:
No information is available

Potential for Accumulation:
No specific information is available. In general, related chemicals are rapidly metabolized and excreted.


SECTION 4. FIRST AID MEASURES

Inhalation:
Take proper precautions to ensure your own safety before attempting rescue (e.g. wear appropriate protective equipment, use the buddy system). Remove source of contamination or move victim to fresh air. If breathing is difficult, oxygen may be beneficial if administered by trained personnel, preferably on a doctor's advice. DO NOT allow victim to move about unnecessarily. Symptoms of pulmonary edema can be delayed up to 48 hours after exposure. Immediately transport victim to an emergency care facility.

Skin Contact:
Avoid direct contact. Wear chemical protective clothing, if necessary. Quickly and gently, blot or brush away excess chemical. Remove contaminated clothing, shoes and leather goods (e.g. watchbands, belts). Flush contaminated area with lukewarm, gently flowing water for at least 20- 30 minutes, by the clock. If irritation persists, repeat flushing. DO NOT INTERRUPT FLUSHING. If necessary, keep emergency vehicle waiting. Transport victim to an emergency care facility immediately. Discard contaminated clothing, shoes and leather goods.

Eye Contact:
Avoid direct contact. Wear chemical protective gloves, if necessary. Quickly and gently blot or brush away excess chemical. Immediately flush the contaminated eye(s) with lukewarm, gently flowing water for at least 20-30 minutes, by the clock, while holding the eyelid(s) open. Neutral saline solution may be used as soon as it is available. DO NOT INTERRUPT FLUSHING. If necessary, keep emergency vehicle waiting. Take care not to rinse contaminated water into the unaffected eye or onto the face. If irritation persists, repeat flushing. Quickly transport victim to an emergency care facility.

Ingestion:
NEVER give anything by mouth if victim is rapidly losing consciousness, is unconscious or is convulsing. Have victim rinse mouth thoroughly with water. DO NOT INDUCE VOMITING. Have victim drink 240 to 300 mL (8 to 10 oz.) of water to dilute material in stomach. If milk is available, it may be administered AFTER the water has been given. If vomiting occurs naturally, have victim rinse mouth and repeat administration of water. Quickly transport victim to an emergency facility.

First Aid Comments:
Provide general supportive measures (comfort, warmth, rest).
Consult a doctor and/or the nearest Poison Control Centre for all exposures except under minor instances of inhalation or skin contact.
Some recommendations in the above sections may be considered medical acts in some jurisdictions. These recommendations should be reviewed with a doctor and appropriate delegation of authority obtained, as required.
All first aid procedures should be periodically reviewed by a doctor familiar with the material and its conditions of use in the workplace.



SECTION 5. FIRE FIGHTING MEASURES

Flash Point:
Not applicable. Will not burn.

Lower Flammable (Explosive) Limit (LFL/LEL):
Not applicable

Upper Flammable (Explosive) Limit (UFL/UEL):
Not applicable

Autoignition (Ignition) Temperature:
Not applicable

Sensitivity to Mechanical Impact:
Normally stable. Although there are no case reports of dangerous reactions, tests have indicated that there is a "critical volume", above which sufficient shock may cause detonation. Accordingly, chloropicrin is now shipped in special containers not exceeding 700 kg (1500 lb) and special 180 kg (400 lb) drums.(11,18)

Sensitivity to Static Charge:
Insufficient information

Combustion and Thermal Decomposition Products:
When exposed to heat or flame, can decompose to highly toxic gases such as phosgene, hydrogen chloride, nitrosyl chloride, and nitrogen oxides

Fire Hazard Summary:
Vapour or liquid can cause death if it penetrates the firefighter's normal protective gear. During a fire, irritating/toxic phosgene, hydrogen chloride, nitrosyl chloride and nitrogen oxides may be generated. Sensitive to thermal and mechanical shock at elevated temperatures and pressures. Exposure to heat may promote violent decomposition. Closed containers may rupture violently when heated.

Extinguishing Media:
Will not burn. Use extinguishing media suitable for surrounding fire. Use dry chemical, foam, carbon dioxide,or water spray. Water may be ineffective.(24)

Fire Fighting Instructions:
Chloropicrin is not combustible. However, explosive decomposition may occur under fire conditions. Use extreme caution since heat may rupture containers. If possible, isolate materials not yet involved in the fire and protect personnel. Move containers from fire area if this can be done without risk. Use extinguishing media suitable for the surrounding fire. Fight fire from a protected, explosion-resistant location or maximum possible distance. Approach fire from upwind to avoid hazardous vapours and toxic decomposition products. If fire occurs in the vicinity of chloropicrin, use unmanned monitors and hoseholders to keep cooling streams of water on fire-exposed tanks or drums until well after the fire is out. Stay away from ends of tanks. Withdraw immediately in case of rising sound from venting safety device or any discolouration of tank due to fire. In an advanced or massive fire, the area should be evacuated; use unmanned hoseholders or monitor nozzles. If this is not possible, withdraw from fire area and allow the fire to burn. Do not attempt to fight the fire.
Tanks or drums should not be approached directly after they have been involved in a fire or heated by exposure, until they have completely cooled down. Clean-up or salvage operations should not be attempted until the chloropicrin is cooled.
Do not enter without wearing specialized protective equipment, suitable for the situation. Firefighter's normal protective clothing (Bunker Gear) will not provide adequate protection. A full-body encapsulating chemical resistant suit with positive pressure self-contained breathing apparatus (MSHA/NIOSH approved or equivalent) may be necessary.



NATIONAL FIRE PROTECTION ASSOCIATION (NFPA) HAZARD IDENTIFICATION

NFPA - Health: 4 - Very short exposure could cause death or major residual injury.
NFPA - Flammability: 0 - Will not burn under typical fire conditions.
NFPA - Instability: 3 - Capable of detonation or explosive decomposition or explosive reaction, but requires a strong initiating source or must be heated under confinement before initiation, or reacts explosively with water.

SECTION 9. PHYSICAL AND CHEMICAL PROPERTIES

Molecular Weight: 164.4

Conversion Factor:
1 ppm = 6.71 mg/m3; 1 mg/m3 = 0.15 ppm at 25 deg C (calculated)

Physical State: Liquid
Melting Point: -69 deg C (-92 deg F) (9); - 64 deg C (-83 deg F) (7,9,21)
Boiling Point: 112 deg C (234 deg F) (1,7)
Relative Density (Specific Gravity): 1.65 at 20 deg C (water = 1) (7,21)
Solubility in Water: Slightly soluble (162 mg/100 mL) at 25 deg C (14)
Solubility in Other Liquids: Soluble in all proportions in benzene, absolute alcohol, carbon disulfide, carbon tetrachloride, acetone, methyl alcohol and acetic acid. Soluble in ether.(9,14)
Coefficient of Oil/Water Distribution (Partition Coefficient): Log P(oct) = 2.44 (6); Log P (olive oil) = 2.43 at 20 deg C (9)
pH Value: 2.3 (0.01 M solution) (calculated)
Vapour Density: 5.7 (air = 1)
Vapour Pressure: 2.25 kPa (16.9 mm Hg) at 20 deg C (1,7); 2.67 kPa (20 mm Hg) at 20 deg C (21)
Saturation Vapour Concentration: Approximately 22200-26300 ppm (2.22-2.63%) at 20 deg C (calculated)
Evaporation Rate: Not available
Critical Temperature: Not available

Other Physical Properties:
ACIDITY: Strong acid; pKa = 2.7 (14)
LIQUID SURFACE TENSION: 32.3 dynes/cm at 20 deg C (9,14)


SECTION 10. STABILITY AND REACTIVITY

Stability:
Unstable. Upon exposure to light, chloropicrin decomposes to toxic gases such as phosgene, nitrosyl chloride, chlorine and nitrogen oxides.(23) When heated above 150 deg C, it decomposes to form phosgene and nitrosyl chloride.(9) Sensitive to shock under certain conditions.(11,18)

Hazardous Polymerization:
Unlikely to occur

Incompatibility - Materials to Avoid:

NOTE: Chemical reactions that could result in a hazardous situation (e.g. generation of flammable or toxic chemicals, fire or detonation) are listed here. Many of these reactions can be done safely if specific control measures (e.g. cooling of the reaction) are in place. Although not intended to be complete, an overview of important reactions involving common chemicals is provided to assist in the development of safe work practices.


REDUCING AGENTS, COMBUSTIBLE MATERIALS - May react violently.(1)

ALKALI (e.g. sodium) AND ALKALINE EARTH METALS (e.g. magnesium) - React violently, with risk of fire and explosion.(10)

SODIUM HYDROXIDE - Has reacted violently with alcoholic sodium hydroxide.(11)

SODIUM METHOXIDE - When mixing with sodium methoxide, in methanol, the temperature must not fall below 50 deg C (122 deg F) or a violent and dangerous exothermic reaction may occur.(11)

ANILINE - Reaction with excess aniline at 145 deg C (293 deg F) is violent.(11)

METAL POWDER - Reacts violently, with risk of fire and explosion.(10)

3-BROMOPROPYNE - Components of mixture of chloropicrin and 3-bromopropyne are both explosive and the mixture is shock and heat sensitive.(11,24)

Hazardous Decomposition Products:
Phosgene, nitrosyl chloride, chlorine and nitrogen oxides can be formed upon exposure to light.(23)

Conditions to Avoid:
Open flames, heat, temperatures above 150 deg C, light, particularly ultraviolet light.

Corrosivity to Metals:
Chloropicrin is corrosive to metals (e.g. iron, zinc). However, it is not a strong enough corrosive material to prevent the use of metal for containers.(9)


SECTION 11. TOXICOLOGICAL INFORMATION

LC50 (rat): 12.75 ppm (4-hour exposure); cited as 25.5 ppm (171 mg/m3) (1-hour exposure) (3)
LC50 (mouse): 66 mg/m3 (9.8 ppm) (aerosol) (4- hour exposure) (19, unconfirmed)

LD50 (oral, rat): 250 mg/kg (2)
LD50 (oral, rat): 37.5 mg/kg (3)

LD50 (dermal, rabbit): 100 mg/kg (3)

Eye Irritation:

The vapour caused irritation and tearing in the eyes of dogs and guinea pigs.(15,16)

Skin Irritation:

Caused corrosive tissue damage in rabbits.(3)

Effects of Short-Term (Acute) Exposure:

Inhalation:
Chloropicrin is a lachrymator, severe respiratory irritant and causes respiratory tract damage.(15,16,17). In animal studies, it has caused irritation of the eyes and mucous membranes of the mouth and nose. In some cases, the respiratory passages became clogged and the nasal passages almost completely closed. The effects seen in inhalation studies included closed eyes, increased tearing, nasal secretions, salivation, sneezing, gasping for breath, nausea, vomiting and, at higher concentrations, unconsciousness, convulsions and death. Respiration is usually affected early, being somewhat rapid during the early part of the exposure and becoming laboured and painful at the end.(15,16) A concentration of 7.98 ppm of 6 hours/day for 5 days caused a 50% reduction in the respiratory rate (RD50) of mice.(17) Pulmonary edema (a life-threatening accumulation of fluid in the lungs) and emphysema were found in animals that died.(15) Secondary effects included bronchitis, a weak irregular heart beat and inflammation of the stomach. It may also cause acute inflammation of the kidneys.(15) For mice, cats and dogs, exposures of 25 to 48 ppm (depending on species) were tolerated for 15 minutes, while exposures of 48 ppm to 117-140 ppm for 15 to 30 minutes were fatal.(1)

Effects of Long-Term (Chronic) Exposure:

Ingestion:
A high death rate was seen in a 78 week study with rats given oral doses of about 20-26 mg/kg/day and in mice given oral doses of about 33 or 66 mg/kg/day.(4)

Carcinogenicity:
No statistically significant increase in tumour incidence was seen when mice were given relatively high oral doses for 78 weeks. In the same study, rats were also given oral doses of chloropicrin. However, the results were inconclusive due to a large number of early deaths.(4)


SECTION 16. OTHER INFORMATION

Selected Bibliography:
(1) Patty's industrial hygiene and toxicology. 3rd rev. ed. Vol. 2C. John Wiley & Sons, 1982. p. 4163-4166. 4202, 4204-4208
(2) RTECS record for methane, trichloronitro-. Last updated: 9704
(3) Toxicological and skin corrosion testing of selected hazardous materials. (Report no: DOT/MTB/OHMO-76/2) U.S. Department of Transportation, April 1976
(4) Bioassay of chloropicrin for possible carcinogenicity. National Cancer Institute Technical Report Series no. 65. U.S. Department of Health, Education, and Welfare, 1978
(5) Okada, E., et al. A study of chloropicrin intoxication. Journal of the Japanese Society of Internal Medicine. Vol. 59, no. 11 (1970). p. 1214-1221 (English translation)
(6) Leo, A., et al. Partition coefficients and their uses. Chemical Reviews. Vol. 71, no. 6 (Dec. 1971). p. 525-616
(7) Verschueren, K. Handbook of environmental data on organic chemicals. 2nd ed. Van Nostrand Reinhold, 1983. p. 383-384
(8) Forsberg, K., et al. Quick selection guide to chemical protective clothing. 4th ed. Van Nostrand Reinhold, 2002
(9) Macy, R. Constants and physiological action of chemical warfare agents. Edgewood Arsenal, U.S. Army, September 15, 1941
(10) Chemical safety sheets : working safely with hazardous chemicals. Kluwer Academic Publishers, 1991. p. 218
(11) Bretherick, L. Bretherick's handbook of reactive chemical hazards. 4rd ed. Butterworths, 1990. p. 120-121
(12) NIOSH pocket guide to chemical hazards. NIOSH, June 1994. p. 66-67
(13) Grant, W.M. Toxicology of the eye. 3rd ed. Charles C. Thomas, 1986. p. 215
(14) HSDB record for chloropicrin. Date of last update: 9501
(15) Underhill, F.P. The lethal war gases. Yale University Press, 1920. p. 1-21
(16) Teramoto, M. Changes in the mucosa of the upper respiratory tract by inhalation of toxic gases. Nagoya Journal of Medical Science. Vol. 7 (1933). p. 69-74 (English translation - NIOSHTIC Control Number: 00103194)
(17) Buckley, L.A., et al. Respiratory tract lesions induced by sensory irritants at the RD50 concentration. Toxicology and Applied Pharmacology. Vol. 74, no. 3 (July 1984). p. 417-429
(18) Concentrates: Technology. Chemical and Engineering News. Vol. 50, no. 38 (Sept. 18, 1972). p. 13
(19) Igaku, S. Inhalation toxicity of phosgene and trichloronitromethane (chloropicrin). Japanese Journal of Industrial Health. Vol. 15 (1973). p. 406-407
(20) Haworth, S., et al. Salmonella mutagenicity test results for 250 chemicals. Environmental Mutagenesis. Vol. 5, supplement 1 (1983). p. 3- 142
(21) Documentation of the threshold limit values and biological exposure indices. 6th ed. Vol. 1. ACGIH, 1991. p. 299-300
(22) Garry, V.F., et al. Preparation for human study of pesticide applicators: sister chromatid exchanges and chromosome aberrations in cultured human lymphocytes exposed to selected fumigants. Teratogenesis, Carcinogenesis, and Mutagenesis. Vol. 10, no. 1 (1990). p. 21-29
(23) Moureau, H., et al. Organic chemistry: the photochemical transformation of chloropicrin into phosgene and the characterization of these two compounds. Comptes Rendus Hebdomadaires des Seances. Academie des Sciences. Vol. 228 (1949). p. 1954-1956 (English translation - NIOSHTIC Control Number: 00052720)
(24) Fire protection guide to hazardous materials. 13th ed. Edited by A.B. Spencer, et al. National Fire Protection Association, 2002. NFPA 49; NFPA 491
(25) Emergency response planning guidelines. AIHA Journal. Vol. 56, no. 3 (1995). p. 297
(26) European Economic Community. Commission Directive 93/72/EEC. September 1, 1993
(27) Emergency response planning guidelines. AIHA Journal. Vol. 56, no. 3, 1995. p. 297
(28) Occupational Safety and Health Administration (OSHA). Chloropicrin. In: OSHA Analytical Methods Manual. Revision Date: Oct. 31, 2001. Available at: <www.osha-slc.gov/dts/sltc/methods/toc.html>

Information on chemicals reviewed in the CHEMINFO database is drawn from a number of publicly available sources. A list of general references used to compile CHEMINFO records is available in the database Help.


Review/Preparation Date: 1995-06-29

Revision Indicators:
EU number 1995-10-01
EU risk 1995-10-01
EU safety 1995-10-01
Respiratory guidelines 1995-10-01
Sampling 1996-04-01
EU class 1996-04-01
TDG 1996-04-01
TLV-TWA 1996-09-01
TLV comments 1996-09-01
US transport 1998-03-01
Resistance of materials 1998-06-01
Bibliography 1998-06-01
Acute exposure (ingestion) 2000-08-01
First aid (ingestion) 2000-08-01
ERPG 2001-03-01
TDG 2002-05-27
Bibliography 2003-04-15
Extinguishing media 2003-04-15
PEL-TWA final 2003-11-06
PEL transitional comments 2003-11-06
Resistance of materials for PPE 2004-03-29
Bibliography 2005-03-15
Passive Sampling Devices 2005-03-15
Sampling/analysis 2005-03-15



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