Chloropicrin

H302: Harmful if swallowed [Warning Acute toxicity, oral]

H315: Causes skin irritation [Warning Skin corrosion/irritation]

H319: Causes serious eye irritation [Warning Serious eye damage/eye irritation]

H330: Fatal if inhaled [Danger Acute toxicity, inhalation]

H335: May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation]

P260, P261, P264, P264+P265, P270, P271, P280, P284, P301+P317, P302+P352, P304+P340, P305+P351+P338, P316, P319, P320, P321, P330, P332+P317, P337+P317, P362+P364, P403+P233, P405, and P501 (click each P-code to see the statement)

H302 (98.3%): Harmful if swallowed [Warning Acute toxicity, oral]

H315 (100%): Causes skin irritation [Warning Skin corrosion/irritation]

H319 (100%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]

H330 (100%): Fatal if inhaled [Danger Acute toxicity, inhalation]

H335 (100%): May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation]

Aggregated GHS information provided per 60 reports by companies from 6 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Information may vary between notifications depending on impurities, additives, and other factors. The percentage value in parenthesis indicates the notified classification ratio from companies that provide hazard codes. Only hazard codes with percentage values above 10% are shown. For more detailed information, please visit ECHA C&L website.

H301: Toxic if swallowed [Danger Acute toxicity, oral]

H314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H318: Causes serious eye damage [Danger Serious eye damage/eye irritation]

H370: Causes damage to organs [Danger Specific target organ toxicity, single exposure]

H372: Causes damage to organs through prolonged or repeated exposure [Danger Specific target organ toxicity, repeated exposure]

H400: Very toxic to aquatic life [Warning Hazardous to the aquatic environment, acute hazard]

H410: Very toxic to aquatic life with long lasting effects [Warning Hazardous to the aquatic environment, long-term hazard]

P260, P264, P264+P265, P270, P271, P273, P280, P284, P301+P316, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P308+P316, P316, P317, P319, P320, P321, P330, P363, P391, P403+P233, P405, and P501 (click each P-code to see the statement)

H373: May causes damage to organs through prolonged or repeated exposure [Warning Specific target organ toxicity, repeated exposure]

P260, P264, P264+P265, P270, P271, P280, P284, P301+P316, P302+P352, P304+P340, P305+P354+P338, P308+P316, P316, P317, P319, P320, P321, P330, P332+P317, P362+P364, P403+P233, P405, and P501 (click each P-code to see the statement)

Fresh air, rest. Half-upright position. Refer for medical attention.

Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Give one or two glasses of water to drink. Refer for medical attention .

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop.

SKIN: IMMEDIATELY flood affected skin with water while removing and isolating all contaminated clothing. Gently wash all affected skin areas thoroughly with soap and water. If symptoms such as redness or irritation develop, IMMEDIATELY call a physician and be prepared to transport the victim to a hospital for treatment.

INHALATION: IMMEDIATELY leave the contaminated area; take deep breaths of fresh air. If symptoms (such as wheezing, coughing, shortness of breath, or burning in the mouth, throat, or chest) develop, call a physician and be prepared to transport the victim to a hospital. Provide proper respiratory protection to rescuers entering an unknown atmosphere. Whenever possible, Self-Contained Breathing Apparatus (SCBA) should be used; if not available, use a level of protection greater than or equal to that advised under Protective Clothing.

INGESTION: DO NOT INDUCE VOMITING. If the victim is conscious and not convulsing, give 1 or 2 glasses of water to dilute the chemical and IMMEDIATELY call a hospital or poison control center. Be prepared to transport the victim to a hospital if advised by a physician. If the victim is convulsing or unconscious, do not give anything by mouth, ensure that the victim's airway is open and lay the victim on his/her side with the head lower than the body. DO NOT INDUCE VOMITING. IMMEDIATELY transport the victim to a hospital. (NTP, 1992)

General First Aid:

· Call 911 or emergency medical service.

· Ensure that medical personnel are aware of the material(s) involved, take precautions to protect themselves and avoid contamination.

· Move victim to fresh air if it can be done safely.

· Administer oxygen if breathing is difficult.

· If victim is not breathing:

-- DO NOT perform mouth-to-mouth resuscitation; the victim may have ingested or inhaled the substance.

-- If equipped and pulse detected, wash face and mouth, then give artificial respiration using a proper respiratory medical device (bag-valve mask, pocket mask equipped with a one-way valve or other device).

-- If no pulse detected or no respiratory medical device available, provide continuous compressions. Conduct a pulse check every two minutes or monitor for any signs of spontaneous respirations.

· Remove and isolate contaminated clothing and shoes.

· For minor skin contact, avoid spreading material on unaffected skin.

· In case of contact with substance, remove immediately by flushing skin or eyes with running water for at least 20 minutes.

· For severe burns, immediate medical attention is required.

· Effects of exposure (inhalation, ingestion, or skin contact) to substance may be delayed.

· Keep victim calm and warm.

· Keep victim under observation.

· For further assistance, contact your local Poison Control Center.

· Note: Basic Life Support (BLS) and Advanced Life Support (ALS) should be done by trained professionals.

Specific First Aid:

· For corrosives, in case of contact, immediately flush skin or eyes with running water for at least 30 minutes. Additional flushing may be required.

In Canada, an Emergency Response Assistance Plan (ERAP) may be required for this product. Please consult the shipping paper and/or the "ERAP" section.

(General first aid procedures)

Eye: Irrigate immediately - If this chemical contacts the eyes, immediately wash (irrigate) the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately.

Skin: Soap wash immediately - If this chemical contacts the skin, immediately wash the contaminated skin with soap and water. If this chemical penetrates the clothing, immediately remove the clothing, wash the skin with soap and water, and get medical attention promptly.

Breathing: Respiratory support

Swallow: Medical attention immediately - If this chemical has been swallowed, get medical attention immediately.

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]:

SMALL FIRE: Dry chemical, CO2 or water spray.

LARGE FIRE: Dry chemical, CO2, alcohol-resistant foam or water spray. If it can be done safely, move undamaged containers away from the area around the fire. Dike runoff from fire control for later disposal.

FIRE INVOLVING TANKS, RAIL TANK CARS OR HIGHWAY TANKS: Fight fire from maximum distance or use unmanned master stream devices 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 tanks in direct contact with flames. (ERG, 2024)

In case of fire in the surroundings, use appropriate extinguishing media.

- Chloropicrin (PS) is non-combustible.

- The agent itself does not burn, but it may decompose upon heating to produce corrosive and/or toxic fumes.

- Explosive decomposition may occur under fire conditions.

- Fire may produce irritating, corrosive, and/or toxic gases.

- The agent may be an oxidant, and it may ignite combustibles (wood, paper, oil, clothing, etc.).

- For small fires, use dry chemical, carbon dioxide, or water spray.

- For large fires, use dry chemical, carbon dioxide, alcohol-resistant foam, or water spray. Move containers from the fire area if it is possible to do so without risk to personnel. Dike fire control water for later disposal; do not scatter the material.

- For fire involving tanks or car/trailer loads, fight the 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 the fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tanks. Always stay away from tanks engulfed in fire.

- Run-off from fire control or dilution water may be corrosive and/or toxic, and it may cause pollution.

- If the situation allows, control and properly dispose of run-off (effluent).

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.

If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Use "alcohol" foam, dry chemical or carbon dioxide. Extinguish fire using agent suitable for type of fire. /Chloropicrin (Toxic liquids, flammable, organic, NOS)/

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· Keep unauthorized personnel away.

· Stay upwind, uphill and/or upstream.

· Ventilate closed spaces before entering, but only if properly trained and equipped.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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.

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]:

IMMEDIATE PRECAUTIONARY MEASURE: Isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.

SPILL: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1580 datasheet.

FIRE: If tank, rail tank car or highway tank 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. (ERG, 2024)

Immediate precautionary measure

· Isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.

· For highlighted materials: see Table 1 - Initial Isolation and Protective Action Distances.

· For non-highlighted materials: increase the immediate precautionary measure distance, in the downwind direction, as necessary.

· If tank, rail tank car or highway tank 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.

Small spill:

- ISOLATE in all directions: 60 m (200 ft)

Large spill:

- ISOLATE in all directions: 200 m (600 ft)

- PROTECT people from downwind during DAY time: 0.5 km (0.4 mi)

- PROTECT people from downwind during NIGHT time: 1.2 km (0.8 mi)

- PROTECT people from downwind during DAY time: 2.4 km (1.5 mi)

- PROTECT people from downwind during NIGHT time: 3.7 km (2.3 mi)

- ISOLATE in all directions: 30 m (100 ft)

- ISOLATE in all directions: 300 m (1000 ft)

- PROTECT people from downwind during DAY time: 0.1 km (0.1 mi)

- PROTECT people from downwind during NIGHT time: 0.6 km (0.4 mi)

- PROTECT people from downwind during DAY time: 2.1 km (1.3 mi)

- PROTECT people from downwind during NIGHT time: 5.9 km (3.7 mi)

Evacuate danger area! Consult an expert! Personal protection: chemical protection suit including self-contained breathing apparatus. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations.

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.

Environmental considerations: Land spill: Dig a pit, pond, lagoon, holding area to contain liquid or solid material. /SRP: If time permits, pits, ponds, lagoons, soak holes, or holding areas should be sealed with an impermeable flexible membrane liner./ /Chloropicrin (Toxic liquids, flammable, organic, NOS)/

Environmental considerations: Water spill: Use natural barriers or oil spill control booms to limit spill travel. Use natural deep water pockets, excavated lagoons, or sand bag barriers to trap material at bottom. Remove trapped material with suction hoses. /Chloropicrin (Toxic liquids, flammable, organic, NOS)/

Environmental considerations: Air spill: Apply water spray or mist to knock down vapors. Vapor knockdown water is corrosive or toxic and should be diked for containment. /Chloropicrin (Toxic liquids, flammable, organic, NOS)/

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational exposure or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal, aquatic, and plant life; and conformance with environmental and public health regulations.

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.

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]:

ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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. (ERG, 2024)

Separated from food and feedstuffs. See Chemical Dangers. Cooled. Keep in the dark. Ventilation along the floor.

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.

· Wear positive pressure self-contained breathing apparatus (SCBA).

· Wear chemical protective clothing that is specifically recommended by the manufacturer when there is NO RISK OF FIRE.

· Structural firefighters' protective clothing provides thermal protection but only limited chemical protection.

TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].

7.0 [ppm]

0.1 [ppm]

AEGL 1: Notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling and are transient and reversible upon cessation of exposure (Unit: ppm)

AEGL 2: Irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape (Unit: ppm)

AEGL 3: Life-threatening health effects or death (Unit: ppm)

AEGLs Status: Interim

0.050 [ppm]

0.15 [ppm]

1.4 [ppm]

0.1 ppm (0.7 mg/m³)

TWA 0.1 ppm (0.7 mg/m3)

2 ppm (NIOSH, 2024)

2.0 [ppm]

Excerpts from Documentation for IDLHs: Other human data: It has been reported that 4 ppm for a few seconds renders a worker unfit for activity and that a 10­minute exposure to 7.5 ppm is intolerable [Flury and Zernik 1931].

See: 76062

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; Not classifiable as a human carcinogen.

0.1 ppm as TWA; A4 (not classifiable as a human carcinogen).

0.68 mg/m

Small Fire

· Dry chemical, CO2 or water spray.

Large Fire

· Dry chemical, CO2, alcohol-resistant foam or water spray.

· If it can be done safely, move undamaged containers away from the area around the fire.

· Dike runoff from fire control for later disposal.

Fire Involving Tanks, Rail Tank Cars or Highway Tanks

· Fight fire from maximum distance or use unmanned master stream devices 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 tanks in direct contact with flames.

ERPG-1: 0.075 ppm - one hour exposure limit: 1 = mild transient health effects or objectionable odor [AIHA]

ERPG-2: 0.15 ppm - one hour exposure limit: 2 = impaired ability to take protective action [AIHA]

ERPG-3: 1.5 ppm - one hour exposure limit: 3 = life threatening health effects [AIHA]

/The Chemical Weapons Convention (CWC) is an international treaty which bans the development, production, stockpiling, and transfer or use of chemical weapons. The Convention mandates the destruction and prohibition of chemical weapons and related facilities and provides for restrictions on international trade in toxic chemicals and precursors./ The Convention's monitoring and verification measures involve submission of declarations regarding ... /Schedule 1, 2, and 3 chemicals/ and inspections by the Organization for the Prohibition of Chemical Weapons of the facilities where these chemicals are produced. ... Schedule 3 chemicals ... /may/ have been stockpiled or used as weapons, but ... are produced /and used/ in large quantities for purposes not prohibited by the Convention (2). Chloropicrin is listed in the CWC Annex on Chemicals under Schedule 3 (1).

Chloropicrin appears as a slightly oily colorless to yellow liquid with a strong irritating odor. Noncombustible. Denser than water. Vapors are poisonous by inhalation and irritate eyes, nose, and throat.

Colorless to faint-yellow, oily liquid with an intensely irritating odor. [pesticide] [NIOSH]

SLIGHTLY OILY COLOURLESS LIQUID WITH PUNGENT ODOUR.

Colorless to faint-yellow, oily liquid with an intensely irritating odor.

Colorless to faint-yellow, oily liquid with an intensely irritating odor. [pesticide]

Colorless to faintly yellow oily liquid.

Slightly oily liquid

Faint yellow liquid.

Colorless liquid

Colorless to faint-yellow, oily liquid.

Intensely irritating tear gas odor

Intensely irritating odor.

Pepper-like

234 °F at 760 mmHg (NTP, 1992)

112 °C at 757 mm Hg

112 °C @760 [mm Hg]

-92.6 °F (NTP, 1992)

-64 °C (-69.2 °C corr)

1 to 5 mg/mL at 72 °F (NTP, 1992)

Miscible with most organic solvents, e.g. acetone, benzene, ethanol, methanol, carbon disulfide, diethyl ether, carbon tetrachloride

Miscible with absolute alcohol; soluble in ether

Miscible with acetic acid

0.19 g/100 ml H2O at 20 °C

For more Solubility (Complete) data for CHLOROPICRIN (6 total), please visit the HSDB record page.

Solubility in water, g/100ml at 25 °C: 0.162

1.64 at 77 °F (USCG, 1999) - Denser than water; will sink

1.6448 at 20 °C/4 °C; 1.6483 at 25 °C/4 °C

Relative density (water = 1): 1.7

1.6558 @ 20°C

5.7 (NTP, 1992) - Heavier than air; will sink (Relative to Air)

5.7 (air = 1)

Relative vapor density (air = 1): 5.7

16.9 mmHg at 68 °F ; 40 mmHg at 92.8 °F (NTP, 1992)

24.0 [mmHg]

3.2 kPa (24 mm Hg) at 25 °C

Vapor pressure, kPa at 20 °C: 2.7

7.5 [mm Hg] @4.4000000000000004 °C

log Kow = 2.09

Henry's Law constant = 2.05X10-3 atm-cu m/mol at 25 °C

Relatively Stable

Slightly soluble in water. Slowly decomposes in water.

Halogenated Organic Compounds

Nitro, Nitroso, Nitrate, and Nitrite Compounds, Organic

Explosive

CHLOROPICRIN is a powerful irritant affecting all body surfaces, more toxic then chlorine. It can be shocked into detonation. When heated to decomposition, it emits highly toxic fumes of chlorine gas and nitrogen oxides [Sax, 9th ed., 1996, p. 821]. It produces a violent reaction with aniline [Jackson, K. E., Chem. Rev., 1934, 14, p. 269] or strong bases in the presence of alcohols (alkoxides) [Ramsey, B. G., et al., J. Am. Chem. Soc., 1966, 88, p. 3059]. An insecticidal mixture of the nitrocompound and 3-bromopropyne exploded violently, initiated by an overheated pump during a railcar transfer operation, [BCISC Quart. Safety Summ., 1968, 39, 12].

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.]

Violent reaction with aniline plus heat, alcoholic sodium hydroxide, sodium methoxide, and propargyl bromide.

For more Hazardous Reactivities and Incompatibilities (Complete) data for CHLOROPICRIN (7 total), please visit the HSDB record page.

Chloropicrin

Volatile Organic Compound (VOC)

Smith, C.D. and Nowell, L.H., 2024. Health-Based Screening Levels for evaluating water-quality data (3rd ed.). DOI:10.5066/F71C1TWP

A4; Not classifiable as a human carcinogen.

TR-065: Bioassay of Chloropicrin for Possible Carcinogenicity (CASRN 76-06-2) (1978 )

01/18/78

Inadequate Experiment

No Evidence

No indication of carcinogenicity to humans (not listed by IARC).

The substance can be absorbed into the body by inhalation of its vapour and by ingestion.

inhalation, ingestion, skin and/or eye contact

Chloropicrin (PS) can be absorbed systemically through inhalation, ingestion, and the skin. It is severely irritating to the lungs, eyes, and skin.

Abdominal pain. Cough. Diarrhoea. Dizziness. Headache. Nausea. Sore throat. Vomiting. Weakness. Symptoms may be delayed.

Redness. Pain.

Redness. Pain. Blurred vision.

See Inhalation.

irritation eyes, skin, respiratory system; lacrimation (discharge of tears); cough, pulmonary edema; nausea, vomiting

- Intense painful irritation, tear production (lacrimation), and eye damage.

- Burns in the mouth, esophagus, and stomach; stomach pain; sore throat; nausea and vomiting (emesis); difficulty breathing or shortness of breath (dyspnea); headache; dizziness; and bluish discoloration of the skin (cyanosis).

- Adverse health effects due to mild to moderate exposure:- Severe irritation leading to coughing, choking, difficulty breathing or shortness of breath (dyspnea).

- Feeling of tightness in the chest and chest wall pain.

- Pulmonary edema, possibly resulting in death (more likely in severe exposure).

- Nausea, vomiting (emesis), and diarrhea.

- Headache.

- Dizziness, orthostatic hypotension, anxiety, lethargy, and fatigue.

- Bluish discoloration of the skin (cyanosis) is possible due to methemoglobinemia.

- Adverse health effects due to severe exposure:- Profound inflammation of the lower respiratory tract, with potentially fatal accumulation of fluid in the lungs (pulmonary edema).

- Severe skin irritation, possibly resulting in blisters, difficulty breathing or shortness of breath (dyspnea), headache, and bluish discoloration of the skin (cyanosis).

Eyes, skin, respiratory system

Occupational hepatotoxin - Secondary hepatotoxins: the potential for toxic effect in the occupational setting is based on cases of poisoning by human ingestion or animal experimentation.

Dermatotoxin - Skin burns.

Lacrimator (Lachrymator) - A substance that irritates the eyes and induces the flow of tears.

Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.

ACGIH Carcinogen - Not Classifiable.

LC50 (rat) = 14.4 ppm/4 hr

Human lethality data for chloropicrin are limited to ...earlier reports noting that exposure to 2.00 mg chloropicrin/L (300 ppm) for 10 minutes or 20 0.80 mg/L (120 ppm) for 30 minutes was lethal...

LD50 Rat oral 250 mg/kg

LD50 Rat oral 37.5 mg/kg /From table/

LC50 Rat (Fischer 344, male) inhalation 14.4 ppm/4 hr /Whole-body exposure/

LC50 Rat (Fischer 344, male) inhalation 6.6 ppm/4 hr /Nose-only exposure/

EC50; Species: Daphnia pulex (Water flea, first instar larvae); Conditions: freshwater, static; Concentration: 63 ug/L for 48 hr (95% confidence interval: 47-86 ug/L); Effect: intoxication, immobilization /96.5% purity/

LC50; Species: Lepomis macrochirus (Bluegill, juvenile); Conditions: freshwater, static; Concentration: 105 ug/L for 96 hr (95% confidence interval: 92-119 ug/L)

LC50; Species: Oncorhynchus mykiss (Rainbow trout, juvenile); Conditions: freshwater, static; Concentration: 16.5 ug/L for 96 hr (95% confidence interval: 14.2-19 ug/L)

/OTHER TERRESTRIAL SPECIES/ Relatively few pesticides are toxic to earthworms. Chloropicrin is one which does kill earthworms.

2.00e+00

8.20e+00

4.20e-01

1.80e+00

8.30e-01

8.0E+01(G)

2.50e-04

4.00e-04

Volatile

6.17e+02

5.90e+00

2.50e+01

1.30e+00

5.30e+00

2.50e+00

8.0E+01 (G)

Chloropicrin's production and use in chemical synthesis and as a grain and cereal disinfectant may result in its release to the environment through various waste streams. Its use as a fumigant and soil insecticide will result in its direct release to the environment. During World War I, it was employed as both a lacrimator and as a lethal chemical; its toxicity makes for a poor riot control agent. Chloropicrin is a disinfection byproduct formed upon the addition of chlorine to water containing organic matter. If released to air, a vapor pressure of 23.8 mm Hg at 25 °C indicates chloropicrin will exist solely as a vapor in the atmosphere. Vapor-phase chloropicrin will be degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 123 days. Chloropicrin absorbs UV light in the 280 to 390 nm range and therefore may be susceptible to direct photolysis. If released to soil, chloropicrin is expected to have high mobility based upon a Koc of 81. Volatilization from moist soil surfaces is expected to be an important fate process based upon a Henry's Law constant of 2.05X10-3 atm-cu m/mole. Chloropicrin may volatilize from dry soil surfaces based upon its vapor pressure. Half-lives in soil ranging from 0.2 to 4.5 days at 20 °C suggests that biodegradation is an important environmental fate process in soil. If released into water, chloropicrin is not expected to adsorb to suspended solids and sediment based upon the Koc. A half-life of 0.5 days in activated sludge suggests that biodegradation may be an important environmental fate process in water. Volatilization from water surfaces is expected to be an important fate process based upon this compound's estimated Henry's Law constant. Estimated volatilization half-lives for a model river and model lake are 4 hours and 5 days, respectively. An estimated BCF of 8 suggests the potential for bioconcentration in aquatic organisms is low. Chloropicrin is stable to hydrolysis in neutral aqueous solution. Occupational exposure to chloropicrin may occur through inhalation and dermal contact with this compound at workplaces where chloropicrin is produced or used. Monitoring data indicate that the general population may be exposed to chloropicrin via inhalation of ambient air following adjacent agricultural applications and ingestion of drinking water. (SRC)

Chloropicrin's production and use in chemical synthesis and as a grain and cereal disinfectant(1) may result in its release to the environment through various waste streams(SRC). Its use as a fumigant and soil insecticide(1) will result in its direct release to the environment(SRC). During World War I, it was employed as both a lacrimator and as a lethal chemical; its toxicity makes for a poor riot control agent(2). Chloropicrin is a disinfection byproduct formed upon the addition of chlorine to water containing organic matter(3).

TERRESTRIAL FATE: Based on a classification scheme(1), a Koc value of 81(2) indicates that chloropicrin is expected to have high mobility in soil(SRC). Volatilization of chloropicrin from moist soil surfaces is expected to be an important fate process(SRC) given a Henry's Law constant of 2.05X10-3 atm-cu m/mole(2). Chloropicrin is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 23.8 mm Hg(3). Half-lives in soil ranging from 0.2 to 4.5 days at 20 °C(4) suggests that biodegradation is an important environmental fate process in soil(SRC).

AQUATIC FATE: Based on a classification scheme(1), a Koc value of 81(SRC), determined from a structure estimation method(2), indicates that chloropicrin is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon a Henry's Law constant of 2.05X10-3 atm-cu m/mole(2). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 4 hours and 5 days, respectively(SRC). According to a classification scheme(4), an estimated BCF of 8(SRC), from its log Kow of 2.09(5) and a regression-derived equation(6), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Chloropicrin photohydrolyzes rapidly in water when exposed to light below 300 nm producing CO2, chloride and nitrate in the presence of air; its half-life in sunlight is about 3 days(7). However, under ambient room light chloropicrin is stable to photodegradation(7). The photooxidation of vapor-phase chloropicrin to form phosgene has also been observed in the field(8). A half-life of 0.5 days in activated sludge(9) suggests that biodegradation may be an important environmental fate process in water(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), chloropicrin, which has a vapor pressure of 24 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase chloropicrin is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 120 days(SRC), calculated from its rate constant of 1.3X10-13 cu cm/molecule-sec at 25 °C(SRC), that was derived using a structure estimation method(3). Chloropicrin absorbs UV light in the 280 to 390 nm range(4) and therefore may be susceptible to direct photolysis(SRC).

AEROBIC: The aerobic biodegradation rate and half-life for chloropicrin at 20 °C with an activated sludge inoculum were 1.5/day and 0.46 days, respectively(1). Chloropicrin degradation was studied in three soils, Arlington sandy loam (0.92% organic matter, pH 7.2), Carsitas loamy sand (0.22% organic matter, pH 8.0), and Waukegen silt loam (3.1% organic matter, pH 5.5), at a test compound concentration of 50 mg/kg(2). Degradation rates at 20 °C were 0.45 d-1, 0.16 d-1, and 3.25 d-1, respectively, corresponding to half-lives of 1.5, 4.3 and 0.2 days, respectively(2). Degradation rates at 30 °C were 0.62 d-1, 0.49 d-1, and 8.37 d-1, respectively, and at 40 °C were 1.78 d-1, 0.95 d-1, and 13.99 d-1, respectively, showing that degradation accelerates as soil temperature increases(2). Several Pseudomonas sp. isolated from soil dehalogenate chloropicrin(3). One strain of Pseudomonas putida transformed chloropicrin to nitromethane in three successive reductive dehalogenation steps in the course of about an hour(3).

ANAEROBIC: The anaerobic biodegradation rate and half-life for chloropicrin at 20 °C with an activated sludge inoculum were 1.5/day and 0.46 days, respectively(1).

The rate constant for the vapor-phase reaction of chloropicrin with photochemically-produced hydroxyl radicals has been estimated as 1.3X10-13 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 120 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). Chloropicrin is stable in neutral aqueous solution with no hydrolysis being detected after 10 days and a minimum half-life of 11 yrs(2). At 25 °C hydrolysis half-life has been extrapolated to 5X10+6 years(1). At a concentration of 65X10-4 M/L and in contact with 0.5 g parrot feather plant in a 2.5 mL vial, chloropicrin degraded with a half-life of less than 20 hours, attributed to enzymatic dehalogenation(6). The compound photohydrolyzes rapidly in water when exposed to light below 300 nm producing CO2, chloride and nitrate in the presence of air, with a half-life in sunlight of about 3 days(2). However, under ambient room light chloropicrin is stable to photodegradation(2). While no particular cases where found in the literature, dehalogenation reactions may be chemically, as well as biologically catalyzed(3). 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(4). The photooxidation of chloropicrin in the vapor phase to form phosgene has also been observed in the field(5). Chloropicrin absorbs UV light in the 280 to 390 nm range(7) and therefore may be susceptible to direct photolysis(SRC). In environmental chamber studies it was shown to greatly enhance rates of NO oxidation and O3 formation(7).

An aqueous solution of chloropicrin at a concentration of 15 mM was degraded in the presence of zero-valent iron (1.8 g Fe(0)/L buffer) at a rate of 2.75 1/hr(1). Batch experiments employed 123-mL serum bottles prepared in an anaerobic chamber. The two major products identified were dichloronitromethane and methylamine. Hydrogenolysis accounted for 60.7% of degradation with alpha-elimination accounting for 39.3% loss; hydrolysis was negligible(1).

An estimated BCF of 8 was calculated in fish for chloropicrin(SRC), using a log Kow of 2.09(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC).

The Koc value in 4 soils has been reported as 81(1). According to a classification scheme(2), this Koc value suggests that chloropicrin is expected to have high mobility in soil. 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 °C(1). 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; exponent n was 1.2 for the organic soils and 1.0 for the clay. Its adsorption on Na-bentonite was higher than on kaolinite, which was negligible(1).

Chloropicrin is adsorbed more by mineral soil than by muck which has a higher organic content(1), indicating that adsorption to organic matter may not be the principle mechanism for adsorption. Also, chloropicrin adsorption was shown to increase with decreasing temperature(1). Chloropicrin readily penetrates sandy soil and diffuses horizontally along the soil surface when used as a soil fumigant in winter(2). An example of its ability to leach into soil is the contamination of a well by chloropicrin buried 35 meters away(3).

The Henry's Law constant for chloropicrin is 2.05X10-3 atm-cu m/mole(1). This Henry's Law constant indicates that chloropicrin is expected to volatilize from water surfaces(2). Based on this Henry's Law constant, the volatilization half-life from a model river (1 m deep, flowing 1 m/sec, wind velocity of 3 m/sec)(2) is estimated as 4 hours(SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(2) is estimated as 5 days(SRC). Chloropicrin's Henry's Law constant indicates that volatilization from moist soil surfaces may occur(SRC). Chloropicrin is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 24 mm Hg(3). Volatilization of chloropicrin following application to Arlington sandy loam soil columns (0.92% organic matter, pH 7.2) was 82% within 15 days(4).

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). Chloropicrin was not detected in 34 wells sampled in 2 California counties, collected from July 1, 1994 through June 30, 1995(3).

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 disinfection byproducts in drinking water, the median concn of chloropicrin was 0.1 ug/L(3). Chloropicrin concentration in finished water from 35 US water treatment facilities ranged from not detected (detection limit not specified) to 0.59 ug/L, median of 0.12 ug/L(4). It was reported at a concentration range of 0.1 to 2.5 ug/L in 73% of finished water samples collection from 53 Canadian water treatment facilities(4). The compound was identified in finished drinking water that had been treated by ozone and combinations of ozone with chlorine and chloramine(5). Ozonations were carried out at a plant that treats Mississippi River Water in Jefferson Parish, LA. Treatments occurred in four rounds on January 1994 (total organic carbon 2.7 mg/L; temperature 7.8 °C; pH 7.4; alkalinity 102 mg/L), August 1994 (total organic carbon 2.6 mg/L; temperature 28.5 °C; pH 7.6; alkalinity 110 mg/L), May 1995 (total organic carbon 3.7 mg/L; temperature 18.5 °C; pH 7.5; alkalinity 112 mg/L), and September 1996 (total organic carbon 3.0 mg/L; temperature 28.5 °C; pH 7.9; alkalinity 140 mg/L)(5). Chloropicrin was detected not quantified in the May 1995 and September 1996 treatment rounds(5).

SURFACE WATER: Chloropicrin was present in the ug/L range in surface waters at Dunkerque and Cholet, in the north and west of France, respectively, which contained an organic content of about 10 mg/L total organic carbon(1). In two French treatment plants, pre-chlorinated water from these surface sources contained <10 ng/L chloropicrin(1).

RAIN/SNOW/FOG: Chloropicrin was not detected in snow samples from Sweden and Poland sampled in January and March 1996 and from December 1996 through February 1997(1).

In a comprehensive survey of wastewater from 4,000 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 concentration in ppb): organics and plastics (1; 77.8), pharmaceuticals (1; 7.5), electroplating (1; 40.5)(1). Chloropicrin has been identified as a volatile formed in the bleaching of hardwood (birch) and softwood pulp (pine, spruce) with carbon dioxide(2).

Chloropicrin is formed in the chlorination of natural water containing humic substances in the presence of nitrites(1,5) 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(3). In another study chlorination of water from mesotrophic and eutrophic lakes produced 0.4 and 2 ppb of chloropicrin; with preozonation these levels increased to about 2 and 6 ppb, respectively(4). 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(1). 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(2).

URBAN/SUBURBAN: A mean concentration of <0.0085 ug/cu m chloropicrin was reported in urban communities in California, over the years 1996-1999(1).

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational exposure or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal, aquatic, and plant life; and conformance with environmental and public health regulations.

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.

If ... THERE IS NO FIRE, go directly to the Table of Initial Isolation and Protective Action Distances /(see table below)/ ... to obtain initial isolation and protective action distances. IF THERE IS A FIRE, or IF A FIRE IS INVOLVED, go directly to the appropriate guide /(see guide(s) below)/ and use the evacuation information shown under PUBLIC SAFETY.

Table: Table of Initial Isolation and Protective Action Distances for Chloropicrin [Table#2621]

/GUIDE 154: SUBSTANCES - TOXIC AND/OR CORROSIVE (NON-COMBUSTIBLE)/ 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.

/GUIDE 154: SUBSTANCES - TOXIC AND/OR CORROSIVE (NON-COMBUSTIBLE)/ 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.

/GUIDE 154: SUBSTANCES - TOXIC AND/OR CORROSIVE (NON-COMBUSTIBLE)/ Public Safety: CALL Emergency Response Telephone Number ... . As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas.

For more DOT Emergency Guidelines (Complete) data for CHLOROPICRIN (9 total), please visit the HSDB record page.

1583 154(mixture, n.o.s.)

UN 1580; Chloropicrin

IMO 6.1; Chloropicrin

49 214 14; Chloropicrin, liquid

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.

Poison Inhalation Hazard

Unbreakable packaging. Put breakable packaging into closed unbreakable container. Do not transport with food and feedstuffs.

Symbol: T+; R: 22-26-36/37/38; S: (1/2)-36/37-38-45

UN Hazard Class: 6.1; UN Pack Group: I