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Mustard Gas Safety: Distilled Muster – Blister

DISTILLED MUSTARD (HD)

SECTION I – GENERAL INFORMATION

DATE: 22 September 1988
REVISED: 28 February 1996

MANUFACTURER’S ADDRESS:

U.S. ARMY CHEMICAL BIOLOGICAL DEFENSE COMMAND
EDGEWOOD RESEARCH DEVELOPMENT,
AND ENGINEERING CENTER (ERDEC)
ATTN: SCBRD-ODR-S
ABERDEEN PROVING GROUND, MD 20101-5423

Emergency telephone #’ s: 0700-1630 EST: 410-671-4411/4414
After: 1630 EST: 410- 278-5201, Ask for Staff Duty Officer

CAS REGISTRY NUMBERS: 505-60-2, 39472-40-7, 68157-62-0

CHEMICAL NAME:

Bis-(2-chloroethyl)sulfide

TRADE NAMES AND SYNONYMS:

Sulfide, bis (2-chloroethyl)
Bis(beta-chloroethyl)sulfide
1,1′-thiobis(2-chloroethane)
1-chloro-2(beta-chloroethylthio)ethane
Beta, beta’-dichlorodiethyl sulfide
2,2’dichlorodiethyl sulfide
Di-2-chloroethyl sulfide
Beta, beta’-dichloroethyl sulfide
2,2′-dichloroethyl sulfide
H; HD; HS
Iprit
Kampstoff “Lost”; Lost
Mustard Gas
S-Lost; S-yperite; Schewefel-lost
Senfgas
Sulfur mustard; Sulphur mustard gas
Yellow Cross Liquid
Yperite
Y

CHEMICAL FAMILY: Chlorinated sulfur compound

FORMULA/CHEMICAL STRUCTURE:
C4H8Cl2S

NFPA 704 HAZARD SIGNAL:

Health – 4
Flammability – 1
Reactivity – 1
Special – 0

SECTION II – HAZARDOUS INGREDIENTS

INGREDIENTS NAME FORMULA PERCENTAGE BY WEIGHT AIRBORNE EXPOSURE LIMIT (AEL)
Sulfur MustardC4H8Cl2S1000.003 mg/m3

SECTION III – PHYSICAL DATA

BOILING POINT: 422 F 217 C

VAPOR PRESSURE (mm Hg):

0.072 mm Hg @ 20 C
0.11 mm Hg @ 25 C

VAPOR DENSITY (AIR=1): 5.5

SOLUBILITY IN WATER: Negligible. Soluble in fats and oils, gasoline, kerosene, acetone, carbon tetrachloride, alcohol, tetrachloroethane, ethylbenzoate, and ether. Miscible with the organophosphorus nerve agents.

SPECIFIC GRAVITY (H2O=1): 1.27 @ 20 C

FREEZING POINT: 14.45 C

LIQUID DENSITY (g/cc):

1.268 @ 25 C
1.27 @ 20 C

PERCENTAGE VOLATILE BY VOLUME:

610 mg/m3 @ 20 C
920 mg/m3 @ 25 C

APPEARANCE AND ODOR: Normally amber to black colored liquid with garlic or a horseradish odor. Water clear if pure. The odor threshold for HD is 0.6 mg/m3 (.0006 mg/L).

SECTION IV – FIRE AND EXPLOSION DATA

FLASHPOINT : 105 C (Can be ignited by large explosive charges)

FLAMMABILITY LIMITS (% by volume): Unknown

EXTINGUISHING MEDIA: Water, fog, foam, CO2. Avoid use of extinguishing methods that will cause splashing or spreading of HD.

SPECIAL FIRE FIGHTING PROCEDURES: All persons not engaged in extinguishing the fire should be immediately evacuated from the area. Fires involving HD should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations. Respiratory protection is required. Positive pressure, full face piece, NIOSH-approved self-contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief or chemical accident/incident (CAI) operations officer. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes they will wear appropriate levels of protective clothing (See Section VIII).

Do not breathe fumes. Skin contact with agents must be avoided at all times. Although the fire may destroy most of the agent, care must still be taken to assure the agent or contaminated liquids do not further contaminate other areas or sewers. Contact with the agent liquid or vapor can be fatal.

SECTION V – HEALTH HAZARD DATA

AIRBORNE EXPOSURE LIMIT (AEL): The AEL for HD is 0.003 mg/m3 as found in “AR 40-173, Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Mustard Agents H, HD, HT.” To date, the Occupational Safety and Health Administration (OSHA) has not promulgated a permissible exposure concentration for HD.

EFFECTS OF OVEREXPOSURE: HD is a vesicant (causing blisters) and alkylating agent producing cytotoxic action on the hematopoietic (blood-forming) tissues which are especially sensitive. The rate of detoxification of HD in the body is very slow and repeated exposures produce a cumulative effect. HD has been found to be a human carcinogen by the International Agency for Research on Cancer (IARC).

Median doses of HD in man are:
LD50 (skin) = 100 mg/kg ICt50 (skin) = 2000 mg-min/m3 at 70 – 80 F (humid environment)= 1000 mg-min/m3 at 90 F (dry environment)

ICt50 (eyes) = 200 mg-min/m3

ICt50 (inhalation) = 1500 mg-min/m3 (Ct unchanged with time)

LD50 (oral) = 0.7 mg/kg

Maximum safe Ct for skin and eyes are 5 and 2 mg-min/m3, respectively.

ACUTE PHYSIOLOGICAL ACTION OF HD IS CLASSIFIED AS LOCAL AND SYSTEMIC.

LOCAL ACTIONS: HD effects both the eyes and the skin. SKIN damage occurs after percutaneous absorption. Being lipid soluble, HD can be absorbed into all organs. Skin penetration is rapid without skin irritation. Swelling (blisters) and reddening (erythema) of the skin occurs after a latency period of 4-24 hours following the exposure, depending on degree of exposure and individual sensitivity. The skin healing process is very slow. Tender skin, mucous membrane and perspiration-covered skin are more sensitive to the effects of HD. HD’s effect on the skin, however, is less than on the eyes. Local action on the eyes produces severe necrotic damage and loss of eyesight Exposure of eyes to HD vapor or aerosol produces lacrimation, photophobia, and inflammation of the conjunctiva and cornea.

SYSTEMIC ACTIONS: Occurs primarily through inhalation and ingestion. The HD vapor or aerosol is less toxic to the skin or eyes than the liquid form. When inhaled, the upper respiratory tract (nose, throat, tracheae) is inflamed after a few hours latency period, accompanied by sneezing, coughing, and bronchitis, loss of appetite, diarrhea, fever, and apathy. Exposure to nearly lethal doses of HD can produce injury to bone marrow, lymph nodes, and spleen as showed by a drop in white blood cell count, thus resulting in increased susceptibility to local and systemic infections. Ingestion of HD will produce severe stomach pains, vomiting, and bloody stools after a 15-20 minute latency period.

CHRONIC EXPOSURE : HD can cause sensitization, chronic lung impairment, (cough, shortness of breath, chest pain), cancer of the mouth, throat, respiratory tract and skin, and leukemia. It may also cause birth defects.

EMERGENCY AND FIRST AID PROCEDURES:

INHALATION: Hold breath until respiratory protective mask is donned. Remove from the source IMMEDIATELY. If breathing is difficult, administer oxygen. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exits. Seek medical attention IMMEDIATELY.

EYE CONTACT: Speed in decontaminating the eyes is absolutely essential. Remove the person from the liquid source, flush the eyes immediately with water for at least 15 minutes by tilting the head to the side, pulling the eyelids apart with the fingers and pouring water slowly into the eyes. Do not cover eyes with bandages but, if necessary, protect eyes by means of dark or opaque goggles. Transfer the patient to a medical facility IMMEDIATELY.

SKIN CONTACT: Don respiratory protective mask. Remove the victim from agent sources immediately. Immediately wash skin and clothes with 5% solution of sodium hypochlorite or liquid household bleach within one minute. Cut and remove contaminated clothing, flush contaminated skin area again with 5% sodium hypochlorite solution, then wash contaminated skin area with soap and water. Seek medical attention IMMEDIATELY.

INGESTION: Do not induce vomiting. Give victim milk to drink. Seek medical attention IMMEDIATELY.

SECTION VI – REACTIVITY DATA

STABILITY: Stable at ambient temperatures. Decomposition temperature is 149 C to 177 C. Mustard is a persistent agent depending on pH and moisture, and has been known to remain active for up to three years in soil.

INCOMPATIBILITY: Rapidly corrosive to brass @ 65 C. Will corrode steel at a rate of .0001 in. of steel per month @ 65 C.

HAZARDOUS DECOMPOSITION: Mustard will hydrolyze to form HCl and thiodiglycol.

HAZARDOUS POLYMERIZATION: Does not occur.

SECTION VII – SPILL, LEAK, AND DISPOSAL PROCEDURES

STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If spills or leaks occur, only personnel in full protective clothing will remain in the area (See Section VIII). In case of personnel contamination See Section V for emergency and first aid instructions.

RECOMMENDED FIELD PROCEDURES: The HD should be contained using vermiculite, diatomaceous earth, clay or fine sand and neutralized as soon as possible using copious amounts of 5.25% sodium hypochlorite solution. Scoop up all material and clothing and place in a approved DOT container. Cover the contents of the container with decontaminating solution as above. The exterior of the container will be decontaminated and labeled according with EPA and DOT regulations. All leaking containers will be over packed with vermiculite placed between the interior and exterior containers. Decontaminate and label in accordance with EPA and DOT regulations. Dispose of the material in accordance with waste disposal methods provided below. Dispose of the decontaminate according to Federal, state and local regulations. Conduct general area monitoring with an approved monitor to confirm that the atmospheric concentrations do not exceed the airborne exposure limits (See Sections II and VIII).

If 5.25 % sodium hypochlorite solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Calcium Hypochlorite, contamination Solution No. 2 (DS2), and Super Tropical Bleach Slurry (STB).

WARNING: Pure, undiluted calcium hypochlorite will burn on contact with liquid HD.

RECOMMENDED LABORATORY PROCEDURES: A minimum of 65 grams of decon solution per gram of HD is allowed to agitate for a minimum of one hour. Agitation is not necessary following the first hour if a single phase is obtained. At the end of 24 hours, the resulting solution will be adjusted to a pH between 10 and 11. Test for presence of active chlorine by use of acidic potassium iodide solution to give free iodine color. Place 3 ml of the decontaminate in a test tube. Add several crystals of potassium iodine and swirl to dissolve. Add 3 ml of 50 wt.% sulfuric acid:water and swirl. IMMEDIATE iodine color shows the presence of active chlorine. If negative, add additional 5.25% sodium hypochlorite solution to the decontamination solution, wait two hours, then test again for active chlorine. Continue procedure until positive chlorine is given by solution. A 10 wt.% calcium hypochlorite (HTH) mixture may be substituted for sodium hypochlorite.

Use 65 grams of decon per gram of HD and continue the test as described for sodium hypochlorite. Scoop up all material and clothing and place in a approved DOT container. Cover the contents of the container with decontaminating solution as above. The exterior of the container will be decontaminated and labeled according with EPA and DOT regulations. All leaking containers will be over packed with vermiculite placed between the interior and exterior containers. Decontaminate and label in accordance with EPA and DOT regulations. Dispose of the material in accordance with waste disposal methods provided below. Dispose of the decontaminate according to Federal, state and local regulations. Conduct general area monitoring with an approved monitor to confirm that the atmospheric concentrations do not exceed the airborne exposure limits (See Section VIII).

NOTE: Surfaces contaminated with HD, then rinse and decontaminated may evolve sufficient HD vapor to produce a physiological response. HD on laboratory glassware may be oxidized by its vigorous reaction with concentrated nitric acid.

WASTE DISPOSAL METHOD: Open pit burning or burying of HD or items containing or contaminated with HD in any quantity is prohibited. Decontamination of waste or excess material will be accomplished according to the procedures outlined above can be destroyed by incineration in EPA approved incinerators according to appropriate provisions of Federal, State and local Resource Conservation Recovery Act (RCRA) regulations.

NOTE: Some states define decontaminated surety material as a RCRA hazardous waste.

SECTION VIII – SPECIAL PROTECTION INFORMATION

RESPIRATORY PROTECTION:

CONCENTRATIONRESPIRATORY PROTECTIVE EQUIPMENT.

< 0.003 mg/m3A full face piece, chemical canister, air purifying protective mask will be on hand for escape. (The M9-, M17-, or M40-series masks are acceptable for this purpose. Other masks certified as equivalent may be used)

> 0.003 mg/m3A NIOSH/MSHA approved pressure demand full face piece SCBA suitable for use in high agent concentrations with protective ensemble. (See DA PAM 385-61 for examples).

VENTILATION:

Local Exhaust: Mandatory. Must be filtered or scrubbed. Air emissions will meet local, state and federal regulations.

Special: Chemical laboratory hoods will have an average inward face velocity of 100 linear feet per minute (lfpm) +/- 10% with the velocity at any point not deviating from the average face velocity by more than 20%. Existing laboratory hoods will have an inward face velocity of 150 lfpm +/- 20%. Laboratory hoods will be located such that cross drafts do not exceed 20% of the inward face velocity. A visual performance test using smoke producing devices will be performed in assessing the ability of the hood to contain agent HD.

Other: Recirculation of exhaust air from agent areas is prohibited. No connection between agent area and other areas through the ventilation system are permitted. Emergency backup power is necessary. Hoods should be tested semiannually or after modification or maintenance operations. Operations should be performed 20 centimeters inside hoods.

PROTECTIVE GLOVES: Butyl Rubber Gloves M3 and M4 Norton, Chemical Protective Glove Set

EYE PROTECTION: As a minimum, chemical goggles will be worn. For splash hazards use goggles and face shield.

OTHER PROTECTIVE EQUIPMENT: For laboratory operations, wear lab coats, gloves and have mask readily accessible. In addition, daily clean smocks, foot covers, and head covers will be required when handling contaminated lab animals.

MONITORING: Available monitoring equipment for agent HD is the M8/M9 detector paper, blue band tube, M256/M256A1 kits, bubbler, Depot Area Air Monitoring System (DAMMS), Automated Continuous Air Monitoring System (ACAMS),CAM- M1, Hydrogen Flame Photometric Emission Detector (HYFED), the Miniature Chemical Agent Monitor (MINICAM), and Real Time Analytical Platform (RTAP).

Real-time, low-level monitors (with alarm) are required for HD operations. In their absence, an Immediately Dangerous to Life and Health (IDLH) atmosphere must be presumed. Laboratory operations conducted in appropriately maintained and alarmed engineering controls require only periodic low-level monitoring.

SECTION IX – SPECIAL PRECAUTIONS

PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: When handling agents, the buddy system will be incorporated. No smoking, eating, or drinking in areas containing agents is permitted. Containers should be periodically inspected for leaks, (either visually or using a detector kit). Stringent control over all personnel practices must be exercised. Decontaminating equipment will be conveniently placed. Exits must be designed to permit rapid evacuation. Chemical showers, eyewash stations, and personal cleanliness facilities must be provided. Wash hands before meals and shower thoroughly with special attention given to hair, face, neck, and hands using plenty of soap and water before leaving at the end of the work day .

OTHER PRECAUTIONS: HD should be stored in containers made of glass for Research, Development, Test and Evaluation (RDTE) quantities or one-ton steel containers for large quantities. Agent will be double-contained in liquid and vapor tight containers when in storage.

For additional information see “AR 385-61, The Army Toxic Chemical Agent Safety Program,” “DA PAM 385-61, Toxic Chemical Agent Safety Standards,” and “AR 40-173, Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to HD Agents H, HD, and HT.”

SECTION X – TRANSPORTATION DATA

FORBIDDEN FOR TRANSPORT OTHER THAN VIA MILITARY (TECHNICAL ESCORT UNIT) TRANSPORT ACCORDING TO 49 CFR 172

PROPER SHIPPING NAME: Poisonous liquids, n.o.s.

DOT HAZARD CLASS: 6.1, Packing Group I, Hazard Zone B

DOT LABEL: Poison

DOT MARKING: Poisonous liquids, n.o.s. Bis-(2-chloroethyl) sulfide UN 2810, Inhalation Hazard

DOT PLACARD: POISON

EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See Sections IV, VII and VIII.

PRECAUTIONS TO BE TAKEN IN TRANSPORTATION: Motor vehicles will be placarded regardless of quantity. Drivers shall be given full information regarding shipment and conditions in case of an emergency. AR 50-6 deals specifically with the shipment of chemical agents. Shipment of agents will be escorted in accordance with AR 740-32.

While the Edgewood Research Development, and Engineering Center, Department of the Army believes that the data contained herein are actual and the opinions expressed are those of the experts regarding the results of the tests conducted, the data are not to be taken as a warranty or representation for which the Department of the Army or Edgewood Research Development, and Engineering Center assume legal responsibility. They are offered solely for your consideration, investigation, and verification. Any use of these data and information must be determined by the user to be in accordance with applicable Federal, State, and local laws and regulations.

ADDENDUM A

ADDITIONAL INFORMATION FOR THICKENED HD

TRADE NAME AND SYNONYMS: Thickened HD, THD

HAZARDOUS INGREDIENTS: K125 (acryloid copolymer, 5%) is used to thicken HD. K125 is not known to be hazardous except in a finely-divided, powder form.

PHYSICAL DATA: Essentially the same as HD except for viscosity. The viscosity of HD is between 1000 and 1200 centistoke @ 25 C.

FIRE AND EXPLOSION DATA: Same as HD.

HEALTH HAZARD DATA: Same as HD except for skin contact. For skin contact, don respiratory protective mask and remove contaminated clothing IMMEDIATELY. IMMEDIATELY scrape the HD from the skin surface, then wash the contaminated surface with acetone. Seek medical attention IMMEDIATELY.

SPILL, LEAK, AND DISPOSAL PROCEDURES: If spills or leaks of HD occur, follow the same procedures as those for HD, but dissolve THD in acetone before introducing any decontaminating solution. Containment of THD is generally not necessary. Spilled THD can be carefully scraped off the contaminated surface and placed in a fully removable head drum with a high density, polyethylene lining. THD can then be decontaminated, after it has been dissolved in acetone, using the same procedures used for HD. Contaminated surfaces should be treated with acetone, then decontaminated using the same procedures as those used for HD.

NOTE: Surfaces contaminated with THD or HD and then rinse- decontaminated may evolve sufficient HD vapor to produce a physiological response.

SPECIAL PROTECTION INFORMATION: Same as HD.

SPECIAL PRECAUTIONS: Same as HD with the following addition. Handling THD requires careful observation of the “stringers” (elastic, threadlike attachments) formed when the agents are transferred or dispensed. These stringers must be broken cleanly before moving the contaminating device or dispensing device to another location, or unwanted contamination of a working surface will result.

TRANSPORTATION DATA: Same as HD.