APPENDIX B-9Distilled Mustard
HD
Standard NATO agreement (STANAG) code: HD
Chemical name: bis (2-chloroethyl) sulfide Common name: distilled mustard [1] Formula: C1(CH2)2S(CH2)2C1
Family: casualty agent
Type: blister agent (mustard)
An amber brown liquid with an odor similar to that of burning garlic, the odor becoming more pronounced with impurities in the solution. Creates a lowlaying colorless vapor around the splashed liquid.
History Distilled mustard (HD) was known as early as the late 1880s as a by-product of the dye industry whose toxic effects might be of use in both treating minor tumors and in killing warehouse pests.
Originally investigated by the British and rejected as not being lethal enough, it was first used against them. At 10 PM on the evening of July 12th, 1917 the British 15th and 55th infantry divisions came under an artillery barrage in their positions near Ypres, France. Mixed in with high explosives was a significant quantity of distilled mustard. Other than a stench "like garlic" of "like mustard" (which is how the compound gets its name) there was little nuisance beyond eye irritation like diluted phosgene. Many troops did not bother to put their gas masks on. By the following afternoon the British field hospitals were clogged and on the next evening the first deaths began.
Distilled mustard, the first of the major blister agents, became the chemical compound by which all others have been judged since.
According to a British army study, the Foulkes Papers, 16-1/2% of all encountered casualties in the last eighteen months of that war were due to chemicals, mainly distilled mustard. In 1920 about 19,000 British veterans drew permanent disability, mainly from mustard. A 1927 Porton Down study of HD victims found pre-cardiac conditions common, and typical conjunctivitis, laryngitis, bronchitis, and reoccurring skin burns. A Porton Down study of 1929 of 29 severe cases showed fibrosis, respiratory and spinal TB, persistent laryngitis, anemia, conjunctivitis, aphonia, and pulmonary fibrosis. By 1930, 80% of known survivors suffered chronic bronchitis. After the first world war, limited production continued in Great Britain and France. Production began in Italy and the Soviet Union by 1925, and in Japan in 1928.
HD was allegedly used against the Afghans by the British in 1919. It was known to be used against Moroccans by the French and Spanish in 1925, against Ethiopians by the Italians after 1935, and by the Japanese against China after 1934 and ending by 1944. The late 1920s through the 1930s were a time a chemical warfare experimentation as the older agents were adapted to fit new methods and tactics of war. New munitions, especially those for aerial sprays and bombs, were developed. It was assumed that chemicals would be used in the the "next war" to the same extent they had been used in 1915-1918. As German rearmament beginning in 1934 started a general trend, chemical munitions plants were upgraded.
Great Britain built new facilities such as those at Sutton Oak-St Helens, Lancashire. France opened a HD and CG plant at Clancy. The USSR built new HD-L-CG plants at Brandyuzhsky, Kuibyshev, and Karaganda. Germany built plants at Munster, Wunsdorf, and List.
The U.S. reluctantly reopened Pine Bluff Arsenal (in production by 1942) and built new facilities such as Rocky Mountain Arsenal (near Denver) and opened the Dugway, Utah, Proving Grounds for the express purpose of testing chemical agents. Casualty agent use in the second world war, outside of China through 1943-1944, was virtually non-existent. The only known incident in the west occurred in Bari harbor on the Italian Adriatic.
An American merchantman, the S.S. John Harvey, carried the bulk of U.S. chemical munitions for the Mediterranean area, in the form of 2000 M47A1 aerial bombs, containing a total of about 100 tons of HD. The S.S. John Harvey's cargo was known only to SHAFE in London and a few junior Army Ordinance officers on board. On 7:30 PM, July 2nd, 1943, the John Harvey was sunk in a German air raid. Her cargo of HD had all been made by the quick-but-dirty Levinstein process. Thus it had hydrogen and ethane gas impurities in the HD mix. The John Harvey blew up and flooded the harbor. By the following morning it was Ypres all over again, except nobody knew why the massive blistering was happening, especially among sailors soaked in oil and some smelly stuff from the harbor waters. About 630 serious military cases occurred and over a thousand Italian civilians died within a few days. Allegations of the use of distilled mustard surface from time to time. Yemen and Afghanistan are often mentioned in this regard, as are Laos and Cambodia. Allegations they remain. New chemical and biological technologies have produced whole new variations and nobody's bragging about what they may or may not be doing.
A known area of occasional distilled mustard use is in the Iran-Iraq war which began in 1979. When Iraq was pushed back to its starting point by the early 1980s, it is alleged to have begun the use of chemical agents as an effective weapon against Iranian human wave attacks consisting of untrained volunteer levies begging for death and receiving it in spades.
Structure Distilled mustard has a simple structure, consisting of two ethyl (C2H5) groups bound together around an atom of sulphur. The outer two hydrogen bonds along the central axis have been replaced by chlorine bonds.
The old Levinstein process consisted of treating ethylene with sulphur chloride.
Pathology Both distilled mustard and its vapors create an extreme hazard. The greater the absorbed dose of either the greater the damage. Vapors of this agent will cause temporary blindness and inflammation of the entire respiratory tract. Further heavy vapor exposure will make the blindness permanent and will strip the bronchial tubes of their mucus membrane lining. Any concentration will cause a severe choking effect. Distilled mustard liquid is corrosive to human tissue both locally and systematic. Local effects include immediate inflammation of the tissues around the eyes and pronounced reddening of exposed skin. If not decontaminated, reddened skin will ulcerate into waterish boils within four to six hours. These blisters, if crudely broken, will reblister. Systemic effects from prolonged exposure may include internal inflammation and blistering (ulceration) of the throat and lungs, resulting in what is termed "dry land drowning," in which the windpipe clogs from bottom to top. Ingestion will cause nausea and vomiting within the same time frame. Absorption into the blood, results in white blood cell destruction. Long term exposures may promote bone marrow destruction and subsequent damage to the immune system. Currently listed by NIOSH/RTECS as being mutagenic in all mammals in solution concentrations above 750 m/liter. Field behavior Distilled mustard is among the most commonly listed military casualty agents. It is used to deny terrain and to contaminate equipment and stores.
The delayed effects of distilled mustard necessitate constant chemical survey and monitoring. The human body slowly detoxifies this agent, so prolonged toxic exposures may slowly build up without initial warning symptoms. The vapors are heavier than air and may persist as long as one month in winter weather. They will seek lower elevations in open terrain and substructures, tunnels, and conduits in man-made terrain. With a flash point of 105°C (221°F) distilled mustard, and particularly its vapors, may explode if exposed to fire or munitions detonations.
Decontamination must be immediate and thorough when this agent is discovered. Exposed personnel should receive immediate personal decontamination and medical examination.
Slightly soluble in cold water, although volatile in steam. Soluble in most organic solvents.
Specific data median lethal dosage (LCt50)
(Inhalation) 1500 mg-min/m3 or 23cppm/10 molar.
(Skin absorption) 10,000 mg-min/m3 or 34 mg/kg.
median incapacitating dosage (ICt50)
(Eye injury) 200 mg-min/m3.
(Skin absorption) 2000 mg-min/m3.
eye toxicity Very susceptible to low concentrations (see above). Damage is accumulative to tissue and blood vessels, causing blindness or permanent impairment if untreated. skin toxicity Less susceptible to concentrations, but accumulative and irritating. Severe blistering is possible and permanent damage to skin tissues may result even from delayed treatment. HD dissolved in sweat is of great danger to areas of skin like the face, underarms, knees, elbows, and crotch! rate of action Delayed. Major pathological symptoms commonly do not appear until at least four hours after exposure. However, due to the accumulative effect of this compound, symptoms may manifest perhaps a week or more after a series of incremental exposures. Effects from ingestion and eye exposure may be more immediate.
protection required Protective mask/respirator, with full protective overclothing under all conditions. rate of detoxification Very low natural detoxification in the body makes the dosages (and effects) accumulative. decontaminantStrong bleach solutions and caustic soda (sodium hypochlorite) for personnel and terrain. For the decontamination of buildings and substructures live steam may also be used. Under combat conditions fire may be used as a field expedient decontaminant, mindful of an explosive hazard.
vapor density 5.4 times heavier than air.
vapor pressure 0.072 mm Hg at 20°C (68°F).
liquid density 1.27 g/cc.
persistency Heavily splashed liquid may last several days in temperate climates. May last up to a month under winter conditions.
volatility (Solid) 75 mg/m3 at 0°C (32°F), (liquid) 610 mg/m3 at 20°C (68°F), 2680 mg/m3 at 40°C (104°F).
latent heat of vaporization 94 calories per gram
melting point 14.45°C (58.1°F).
boiling point 217°C (422. 6°F) with decomposition.
decomposition point Begins at 149°C (300°F).
flash point 105°C (221°F).
rate of hydrolysisHydrolyses within 17 minutes in distilled water at 25°C (77°F) and two hours in salt water at the same temperature.
hydrolysis productsHydrochloric acid and thiodiglycol.
stability in storage Stable in steel or aluminum canisters.
actions on metals or other materialsLittle corrosive property when pure. Electrostatic properties in electrical equipment.
molecular weight 159.08
Warning The above specific data refer to distilled mustard in its traditional form of a pure chemical.
Microencapsulation techniques could make this into a highly persistent poison presenting a profoundly greater hazard. _______________
Notes:1. During WWI HD was variously known as HS (Britain), das Lost (Germany), and Yprite (France). International codes became standardized by convention after 1919-1920.