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Material Safety Data Sheet -- Lethal Nerve Agents Sulfur Mustards (HD and THD)

Section I: General Information
Section II: Composition
Section III: Physical Data
Section IV: Fire and Explosion Data
Section V: Health Hazard Data
Section VI: Reactivity Data
Section VII: Spill, Leak and Disposal Procedures
Section VIII: Special Protection Information
Section IX: Special Precautions
Section X: Transportation Data
Addendum A: Additional Information for Thickened HD


Section I: General Information

MANUFACTURER'S NAME: Department of the Army

MANUFACTURER'S ADDRESS:

U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423

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

CHEMICAL NAME AND SYNONYMS:

TRADE NAME AND SYNONYMS:

CHEMICAL FAMILY: chlorinated sulfur compound

FORMULA: C4(H8)C12(S)

NFPA 704 SIGNAL:

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Section II: Composition

INGREDIENTS     FORMULA       PERCENTAGE     AIRBORNE
NAME                          BY WEIGHT      EXPOSURE LIMIT (AEL)

Sulfur Mustard  C4(H8)C12(S)        100      0.003 mg/m3 (8 hr-TWA)

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Section III: Physical Data

BOILING POINT DEG F (DEG C): 422 DEG F. (217 DEG C)

VAPOR PRESSURE (mm Hg): 0.072 mm Hg @ 20 DEG C (0.11 mm Hg @ 25 DEG C)

VAPOR DENSITY (AIR=1): 5.5

SOLUBILITY IN WATER: Negligible. Soluble in acetone, CH3(C1), tetrachloroethane, ethylbenzoate, and ether.

SPECIFIC GRAVITY (H20=1): 1.27 @ 20 DEG C

VOLATILITY: 610 mg/m3 @ 20 DEG C; 920 mg/m3 @ 25 DEG C

APPEARANCE AND ODOR: Water clear if pure. Normally pale yellow to black. Slight garlic type odor. The odor threshold for HD is 0.0006 mg/m3

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Section IV: Fire and Explosion Data

FLASHPOINT (METHOD USED): 105 DEG C (ignited by large explosive charges)

FLAMMABILITY LIMITS (% by volume): Unknown

EXTINGUISING MEDIA: Water, fog, foam, CO2. Avoid using extinguishing methods that will splash or spread mustard.

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 facepiece, NIOSH-approved self contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief of chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).

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Section V: Health Hazard Data

AIRBORNE EXPOSURE LIMIT (REL): The AEL for HD is 0.003 mg/m3 as proposed in the USAEHA Technical Guide No. 173, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Mustard Agents H, HD and HT." No individual should be intentionally exposed to any direct skin or eye contact.

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:

Maimum 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:

EMERGENCY AND FIRST AID PROCEDURES:

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Section VI: Reactivity Data

STABILITY: Stable at ambient temperatures. Decomposition temperature is 149 DEG C to 177 DEG 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: Conditions to avoid. Rapidly corrosive to brass @ 65 DEG C. Will corrode steel at a rate of .0001 in. of steel per month @ 65 DEG C.

HAZARDOUS DECOMPOSITION PRODUCTS: Mustard will hydrolize to form HCI and thiodiglycol.

HAZARDOUS POLYMERIZATION: Will not occur.

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Section VII: Spill, Leak and Disposal Procedures

STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: Only personnel in full protective clothing (see Section 8) will remain in area where mustard is spilled.

RECOMMENDED FIELD PROCEDURES:

The mustard should be contained using vermiculite, diatomaceious earth, clay or fine sand and neutralized as soon as possible using copious amounts of 5.25 percent Sodium Hypochlorite solution.

Scoop all material and place in an approved DOT container. Cover the contents of the drum with decontaminating solution as above. The exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of the material used to decontaminate exterior of drum IAW Federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).

If 5.25 percent Sodium Hypochlorite solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Calcium Hypochlorite Decontamination Solution No. 2 (DS2), and Super Tropical Bleach Slurry (STB). WARNING: Pure, undiluted Calcium Hypochlorite (HTH) will burn on contact with liquid blister agent.

RECOMMENDED LABORATORY PROCEDURES:

A minimum of 65 grams of decon 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 shall 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 percent Sulfuric Acid water and swirl. IMMEDIATE Iodine color indicates the presence of active chlorine. If negative, add additional 5.25 percent 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 percent 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 place in approved DOT containers. Cover the contents of the drum with decontaminating solution as above. The exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of the material used to decontaminate exterior of drum IAW federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limits (see Section 8).

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

WASTE DISPOSAL METHOD:

All decontaminated material should be collected, contained and chemically decontaminated or thermally decomposed in an EPA approved incinerator, which will filter or scrub toxic by-products from effluent air before discharge to the atmosphere. Any contaminated protective clothing should be decontaminated using HTH or bleach and analyzed to assure it is free of detectable contamination (3X) level. The clothing should then be sealed in plastic bags inside properly labeled drums and held for shipment back to the DA issue point. Decontamination of waste or excess material shall be accomplished in accordance with the procedures outlined above with the following exception:

HD on laboratory glassware may be oxidized by its vigorous reaction with concentrated nitric acid.

Open pit burning or burying of HD or items containing or contaminated with HD in any quantity is prohibited.

NOTE: Some states define decontaminated surety material as a RCRA Hazardous Waste.

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Section VIII: Special Protection Informaton

RESPIRATORY PROTECTION:


Concentration mg/m3      Respiratory Protection/Emsemble Required

Less than or equal to 0.003   Protective mask not required provided that: 
as an 8-hr TWA             (a)               Continuous real-time monitoring (with alarm
                                             capability is conducted in the work area at the 0.003
                                             mg/m3 level of detection.
                           (b)               M9, M17 or M40 mask is available and donned if
                                             ceiling concentrations exceed 0.003 mg/m3.
                           (c)               Exposure has been limited to the extent practicable
                                             by engineering controls (remote operations,
                                             ventilation, and process isolation) or work
                                             practices.

                         If these conditions are not met then the following applies:

                           Full facepiece, chemical canister, air purifying
                           respirators.  (The M9, M17 or M40 series or other
                           certified equivalent masks are acceptable for this
                           purpose in conjunction with the M3 toxicological agent
                           protective (TAP) suit for dermal protection.)

Greater than 0.003 as an   The Demilitarization Protective Ensemble (DPE), 30 mil, 
8 hr TWA                 may be used with prior approval from the AMC Field
                         Safety Activity.  Use time for the 30 mil DPE must be
                         restricted to two hours or less.

NOTE: When 30 mil DPE is not available the M9 or M40 series mask with Level A protective ensemble including impregnated innerwear can be used. However, use time shall be restricted to the extent operationally feasible, and may not exceed one hour.

As an additional precaution, the cuffs of the sleeves and the legs of the M3 suit shall be taped to the gloves and boots respectively to reduce aspiration.

VENTILATION:

Local Exhaust: Mandatory. Must be filtered or scrubbed.

Special: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (lfpm) plus or minus 10% with the velocity at any point not deviating from the average face velocity by more than 20%. Laboratory hoods shall be located such that cross- drafts do not exceed 20% of the inward face velocity. A visual performance test utilizing smoke-producing devices shall 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 areas and other areas through ventilation system is permitted. Emergency backup power is necessary. Hoods should be tested semi-annually or after modificaton or maintenance operations. Operations should be performed 20 cm inside hoods.

PROTECTIVE GLOVES: MANDATORY. Butyl toxicological agent protective gloves (M3, M4, gloveset).

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

OTHER PROTECTIVE EQUIPMENT:

Full protective clothing will consist of the m3 butyl rubber suit with hood, M2A1 butyl boots, M3 gloves, impregnated underwear, M9 series mask and coveralls (if desired), or the Demilitarization Protective Ensemble (DPE). For general lab work. gloves and lab coat shall be worn with M9 or M17 mask readily available.

In addition, when handling contaminated lab animals, a daily clean smock, foot covers, and head covers are required.

MONITORING: Available monitoring equipment for agent HD is the M8/M9 Detector paper, blue bank tube, M256/M256A1 kits, bubbler. Depot Area Air Monitoring System (DAMMS), Automated Continuous Air Monitoring System (ACMS), CAM-M1, Hydrogen Flame Photometric Emission Detector (HYFED), and the Minature Chemical Agent Monitor (MINICAM).

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Section IX: Special Precautions

PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING:

During handling, the "buddy" (two-man) system will be used. Containers should be periodically inspected for leaks either visually or using a detector kit, and prior to transfering the containers from storage to work areas. Stringent control over all personnel handling HD must be exercised. Chemical showers, eyewash stations, and personal cleanliness facilities must be provided. Each worker will wash their hands before meals and shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the workday. No smoking, eating, or drinking is permitted at the work site.

Decontaminating equipment shall be conveniently located. Exits must be designed to permit rapid evacuation. 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 shall be double-contained in liquid-tight containers when in storage.

OTHER PRECAUTIONS: For additional information, see AMC-R 385-131, "Safety Regulations for Chemical Agents H, HD, HT, GB, and VX" and USAEHA Technical Guide No. 173, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Mustard Agents H, HD, and HT."

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Section X: Transportation Data

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

DOT HAZARD CLASSIFICATION: Poison A

DOT LABEL: Poison gas

DOT MARKING: Poisonous liquid, n.o.s. (Sulfide, bis 2-chloroethyl) NA 1955

DOT PLACARD: POISON GAS

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

PRECAUTIONS TO BE TAKEN IN TRANSPORTATION:

Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency. AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.

While the Chemical Research Development and Engineering Center, Department of the Army believes that the data contained herein are factual and the opinions expressed are those of qualified 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 Chemical Research Development Engineering Center assumes 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.

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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 HV is between 1000 and 1200 centistokes @ 25 DEG 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 HV 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 HV occur, follow the same procedures as those for HD, but dissolve the THD in acetone prior to introducing any decontaminating solution. Containment of THD is generally not necessary. Spilled THD can be carefuly scraped off the contamininated surface and placed in a fully removable head drum with a high density, polyethylene lining. The 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 mustard vapor to produce a physiological response.

SPECIAL PROTECTION INFORMATION: Same as HD.

SPECIAL PRECAUTIONS: Same as HD with the following addition. Handling the THD requires careful observation of the "stringers" (elastic, thread-like 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.

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