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Mustard gas

Mustard gas or sulfur mustard is any of the several chemical compounds that contain the chemical structure S(CH2CH2Cl)2. In the wider sense, compounds with the substituent S(CH2CH2X)2 and N(CH2CH2X)3 are known as sulfur mustards and nitrogen mustards, respectively, where X = Cl or Br. Such compounds are potent alkylating agents, which can interfere with several biological processes. Also known as mustard agents, this family of compounds are infamous cytotoxins and blister agents with a long history of use as chemical weapons. The name mustard gas is technically incorrect: the substances, when dispersed, are often not gases but a fine mist of liquid droplets.[4] Sulfur mustards are viscous liquids at room temperature and have an odor resembling mustard plants, garlic, or horseradish, hence the name.[4] When pure, they are colorless, but when used in impure forms, such as in warfare, they are usually yellow-brown. Mustard gases form blisters on exposed skin and in the lungs, often resulting in prolonged illness ending in death. The typical mustard gas is the organosulfur compound bis(2-chloroethyl) sulfide.[5]

Mustard gas
Names
Preferred IUPAC name
1-Chloro-2-[(2-chloroethyl)sulfanyl]ethane
Other names
Bis(2-chloroethyl) sulfide
HD
Iprit
Schwefel-LOST
Lost
Sulfur mustard
Senfgas
Yellow cross liquid
Yperite
Distilled mustard
Mustard T- mixture
1,1'-thiobis[2-chloroethane]
Dichlorodiethyl sulfide
Identifiers
  • 505-60-2 Y
3D model (JSmol)
  • Interactive image
1733595
ChEBI
  • CHEBI:25434 Y
ChEMBL
  • ChEMBL455341 Y
ChemSpider
  • 21106142 Y
ECHA InfoCard 100.209.973
EC Number
  • 684-527-7
324535
KEGG
  • C19164 Y
  • 10461
UNII
  • T8KEC9FH9P Y
  • DTXSID0037100
  • InChI=1S/C4H8Cl2S/c5-1-3-7-4-2-6/h1-4H2 Y
    Key: QKSKPIVNLNLAAV-UHFFFAOYSA-N Y
  • InChI=1/C4H8Cl2S/c5-1-3-7-4-2-6/h1-4H2
    Key: QKSKPIVNLNLAAV-UHFFFAOYAK
  • ClCCSCCCl
Properties
C4H8Cl2S
Molar mass 159.07 g·mol−1
Appearance Colorless if pure. Normally ranges from pale yellow to dark brown. Slight garlic or horseradish type odor.[1]
Density 1.27 g/mL, liquid
Melting point 14.45 °C (58.01 °F; 287.60 K)
Boiling point 217 °C (423 °F; 490 K) begins to decompose at 217 °C (423 °F) and boils at 218 °C (424 °F)
7.6 mg/L at 20°C[2]
Solubility Alcohols, ethers, hydrocarbons, lipids, THF
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Flammable, toxic, vesicant, carcinogenic, mutagenic
GHS labelling:[3]
Danger
H300, H310, H315, H319, H330, H335
P260, P261, P262, P264, P270, P271, P280, P284, P301+P310, P302+P350, P302+P352, P304+P340, P305+P351+P338, P310, P312, P320, P321, P322, P330, P332+P313, P337+P313, P361, P362, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
Health 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
4
1
1
Flash point 105 °C (221 °F; 378 K)
Safety data sheet (SDS) External MSDS
Related compounds
Related compounds
Nitrogen mustard, Bis(chloroethyl) ether, Chloromethyl methyl sulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)

History as chemical weapons edit

Sulfur mustard is a type of chemical warfare agent. As a chemical weapon, mustard gas was first used in World War I, and has been used in several armed conflicts since then, including the Iran–Iraq War, resulting in more than 100,000 casualties.[6][7] Today, sulfur-based and nitrogen-based mustard agents are regulated under Schedule 1 of the 1993 Chemical Weapons Convention, as substances with few uses other than in chemical warfare (though since then, mustard gas has been found to be useful in cancer chemotherapy[8]). Mustard agents can be deployed by means of artillery shells, aerial bombs, rockets, or by spraying from aircraft.

Mechanism of cellular toxicity edit

 
Mustard gas alkylating an amino group via conversion to a sulfonium ion (2-chloroethylthiiranium)

Sulfur mustards readily eliminate chloride ions by intramolecular nucleophilic substitution to form cyclic sulfonium ions. These very reactive intermediates tend to permanently alkylate nucleotides in DNA strands, which can prevent cellular division, leading to programmed cell death.[2] Alternatively, if cell death is not immediate, the damaged DNA can lead to the development of cancer.[2] Oxidative stress would be another pathology involved in mustard gas toxicity.

In the wider sense, compounds with the structural element BC2H4X, where X is any leaving group and B is a Lewis base, are known as mustards.[citation needed] Such compounds can form cyclic "onium" ions (sulfonium, ammonium, etc.) that are good alkylating agents. Other such compounds are bis(2-haloethyl)ethers (oxygen mustards), the (2-haloethyl)amines (nitrogen mustards), and sesquimustard, which has two α-chloroethyl thioether groups (ClC2H4S−) connected by an ethylene bridge (−C2H4−).[citation needed] These compounds have a similar ability to alkylate DNA, but their physical properties vary.

Physiological effects edit

 
Soldier with moderate mustard agent burns sustained during World War I showing characteristic bullae on the neck, armpit, and hands

Mustard gases react with DNA, which interferes with cellular division and can lead to mutations.[2]

Mustard gases are extremely toxic and have powerful blistering effects on victims. Their alkylating capabilities make them strongly carcinogenic and mutagenic. Furthermore, they are highly lipophilic, which accelerates their absorption into the body.[2] Because people exposed to mustard agents rarely suffer immediate symptoms, and contaminated areas may appear completely normal, victims can unknowingly receive high doses. Within 24 hours of exposure, they experience intense itching and skin irritation. If this irritation goes untreated, blisters filled with yellow fluid (pus) can form wherever the agent contacted the skin. These are chemical burns and are very debilitating. Mustard gases easily penetrate clothing fabrics such as wool or cotton, so it is not only exposed skin that gets burned. If the victim's eyes were exposed, then they become sore, starting with conjunctivitis (also known as pink eye), after which the eyelids swell, resulting in temporary blindness. Extreme ocular exposure to mustard gas vapors may result in corneal ulceration, anterior chamber scarring, and neovascularization.[9][10][11][12] In these severe and infrequent cases, corneal transplantation has been used as a treatment option.[13] Miosis, when the pupil constricts more than usual, may also occur, which is probably the result of the cholinomimetic activity of mustard.[14] At very high concentrations, if inhaled, mustard agents cause bleeding and blistering within the respiratory system, damaging mucous membranes and causing pulmonary edema. Depending on the level of contamination, mustard agent burns can vary between first and second degree burns, though they can also be every bit as severe, disfiguring, and dangerous as third degree burns.[15] Burns that are severe (i.e. covering more than 50% of the victim's skin) are often fatal, with death occurring after only days or weeks. Mild or moderate exposure to mustard gases is unlikely to kill, though victims still require lengthy periods of medical treatment and convalescence before recovery is complete.

Mustard gases' carcinogenic and mutagenic effects mean that victims, even if they fully recover, have an increased risk of developing cancer later in life. In a study of patients 25 years after wartime exposure to chemical weaponry, c-DNA microarray profiling indicated that 122 genes were significantly mutated in the lungs and airways of mustard gas victims. Those genes all correspond to functions commonly affected by mustard gas exposure, including apoptosis, inflammation, and stress responses.[16] The long-term ocular complications include burning, tearing, itching, photophobia, presbyopia, pain, and foreign-body sensations.[17][18]

 
Typical appearance of bullae on an arm caused by vesicant burns

Mustard gases' blistering effects can be neutralized by oxidation or chlorination, using household bleach (sodium hypochlorite), or by nucleophilic attack using decontamination solutions such as "DS2" (2% NaOH, 70% diethylenetriamine, 28% 2-methoxyethanol). After initial decontamination of the victim's wounds is complete, medical treatment is similar to that required by any conventional burn. The degree of pain and discomfort suffered by the victim is also comparable. Mustard agent burns do not heal quickly, and (as with other types of burns) present a risk of sepsis caused by pathogens such as Staphylococcus aureus and Pseudomonas aeruginosa. The mechanisms behind mustard gas's effect on endothelial cells are still being studied, but recent studies have shown that high levels of exposure can induce high rates of both necrosis and apoptosis. In vitro tests have shown that at low concentrations of mustard gas, where apoptosis is the predominant result of exposure, pretreatment with 50 mM N-acetyl-L-cysteine (NAC) was able to decrease the rate of apoptosis. NAC protects actin filaments from reorganization by mustard gas, demonstrating that actin filaments play a large role in the severe burns observed in victims.[19]

A British nurse treating soldiers with mustard agent burns during World War I commented:[20]

They cannot be bandaged or touched. We cover them with a tent of propped-up sheets. Gas burns must be agonizing because usually the other cases do not complain, even with the worst wounds, but gas cases are invariably beyond endurance and they cannot help crying out.

Formulations edit

 
Lewisite (top row) and mustard gas (bottom row) test with concentrations from 0.01% to 0.06%

In its history, various types and mixtures of mustard gas have been employed. These include:

  • H – Also known as HS ("Hun Stuff") or Levinstein mustard. This is named after the inventor of the "quick but dirty" Levinstein Process for manufacture,[21][22] reacting dry ethylene with disulfur dichloride under controlled conditions. Undistilled mustard gas contains 20–30% impurities, which means it does not store as well as HD. Also, as it decomposes, it increases in vapor pressure, making the munition it is contained in likely to split, especially along a seam, releasing the agent to the atmosphere.[1]
  • HD – Codenamed Pyro by the British, and Distilled Mustard by the US.[1] Distilled mustard of 95% or higher purity. The term "mustard gas" usually refers to this variety of mustard.
  • HT – Codenamed Runcol by the British, and Mustard T- mixture by the US.[1] A mixture of 60% HD mustard and 40% O-Mustard, a related vesicant with lower freezing point, lower volatility and similar vesicant characteristics.
  • HL – A blend of distilled mustard (HD) and lewisite (L), originally intended for use in winter conditions due to its lower freezing point compared to the pure substances. The lewisite component of HL was used as a form of antifreeze.[23]
  • HQ – A blend of distilled mustard (HD) and sesquimustard (Q) (Gates and Moore 1946).
  • Yellow Cross – any of several blends containing sulfur mustard and sometimes arsine agents, along with solvents and other additives.

Commonly-stockpiled mustard agents (class) edit

Chemical Code Trivial name CAS number PubChem Structure
Bis(2-chloroethyl) sulfide H, HD Mustard 505-60-2 CID 10461 from PubChem  
1,2-Bis(2-chloroethylsulfanyl) ethane Q Sesquimustard 3563-36-8 CID 19092 from PubChem  
2-Chloroethyl ethyl sulfide Half mustard 693-07-2 CID 12733 from PubChem  
Bis(2-(2-chloroethylsulfanyl)ethyl) ether T O-Mustard 63918-89-8 CID 45452 from PubChem  
2-Chloroethyl chloromethyl sulfide 2625-76-5  
Bis(2-chloroethylsulfanyl) methane HK 63869-13-6  
1,3-Bis(2-chloroethylsulfanyl) propane 63905-10-2  
1,4-Bis(2-chloroethylsulfanyl) butane 142868-93-7  
1,5-Bis(2-chloroethylsulfanyl) pentane 142868-94-8  
Bis((2-chloroethylsulfanyl)methyl) ether 63918-90-1  

History edit

Development edit

Mustard gases were possibly developed as early as 1822 by César-Mansuète Despretz (1798–1863).[24] Despretz described the reaction of sulfur dichloride and ethylene but never made mention of any irritating properties of the reaction product. In 1854, another French chemist, Alfred Riche (1829–1908), repeated this procedure, also without describing any adverse physiological properties. In 1860, the British scientist Frederick Guthrie synthesized and characterized the mustard agent compound and noted its irritating properties, especially in tasting.[25] Also in 1860, chemist Albert Niemann, known as a pioneer in cocaine chemistry, repeated the reaction, and recorded blister-forming properties. In 1886, Viktor Meyer published a paper describing a synthesis that produced good yields. He combined 2-chloroethanol with aqueous potassium sulfide, and then treated the resulting thiodiglycol with phosphorus trichloride. The purity of this compound was much higher and consequently the adverse health effects upon exposure were much more severe. These symptoms presented themselves in his assistant, and in order to rule out the possibility that his assistant was suffering from a mental illness (psychosomatic symptoms), Meyer had this compound tested on laboratory rabbits, most of which died. In 1913, the English chemist Hans Thacher Clarke (known for the Eschweiler-Clarke reaction) replaced the phosphorus trichloride with hydrochloric acid in Meyer's formulation while working with Emil Fischer in Berlin. Clarke was hospitalized for two months for burns after one of his flasks broke. According to Meyer, Fischer's report on this accident to the German Chemical Society sent the German Empire on the road to chemical weapons.[26]

Mustard gas can have the effect of turning a patient's skin different colors, including shades of red, orange, pink, and in unusual cases, blue. The German Empire during World War I relied on the Meyer-Clarke method because 2-chloroethanol was readily available from the German dye industry of that time.

Use edit

 
Pallets of 155 mm artillery shells containing "HD" (distilled mustard gas agent) at the Pueblo Chemical Depot. The distinctive color-coding scheme on each shell is visible

Mustard gas was first used in World War I by the German army against British and Canadian soldiers near Ypres, Belgium, "on the night of July 12, 1917."[27] Later also against the French Second Army. Yperite is "a name used by the French, because the compound was first used at Ypres."[28] The Allies did not use mustard gas until November 1917 at Cambrai, France, after the armies had captured a stockpile of German mustard shells. It took the British more than a year to develop their own mustard agent weapon, with production of the chemicals centred on Avonmouth Docks (the only option available to the British was the Despretz–Niemann–Guthrie process).[29][30] This was used first in September 1918 during the breaking of the Hindenburg Line.

Mustard gas was originally assigned the name LOST, after the scientists Wilhelm Lommel and Wilhelm Steinkopf, who developed a method of large-scale production for the Imperial German Army in 1916.[31]

Mustard gas was dispersed as an aerosol in a mixture with other chemicals, giving it a yellow-brown color. Mustard agent has also been dispersed in such munitions as aerial bombs, land mines, mortar rounds, artillery shells, and rockets.[1] Exposure to mustard agent was lethal in about 1% of cases. Its effectiveness was as an incapacitating agent. The early countermeasures against mustard agent were relatively ineffective, since a soldier wearing a gas mask was not protected against absorbing it through his skin and being blistered. A common countermeasure was using a urine-soaked mask or facecloth to prevent or reduce injury, a readily available remedy attested by soldiers in documentaries (e.g. They Shall Not Grow Old in 2018) and others (such as forward aid nurses) interviewed between 1947 and 1981 by the British Broadcasting Corporation for various World War One history programs; however, the effectiveness of this measure is unclear.

Mustard gas can remain in the ground for weeks, and it continues to cause ill effects. If mustard agent contaminates one's clothing and equipment while cold, then other people with whom they share an enclosed space could become poisoned as contaminated items warm up enough material to become an airborne toxic agent. An example of this was depicted in a British and Canadian documentary about life in the trenches, particularly once the "sousterrain" (subways and berthing areas underground) were completed in Belgium and France. Towards the end of World War I, mustard agent was used in high concentrations as an area-denial weapon that forced troops to abandon heavily contaminated areas.

 
US Army World War II gas identification poster, c. 1941–1945

Since World War I, mustard gas has been used in several wars and other conflicts, usually against people who cannot retaliate in kind:[32]

The use of toxic gases or other chemicals, including mustard gas, during warfare is known as chemical warfare, and this kind of warfare was prohibited by the Geneva Protocol of 1925, and also by the later Chemical Weapons Convention of 1993. The latter agreement also prohibits the development, production, stockpiling, and sale of such weapons.

In September 2012, a US official stated that the rebel militant group ISIS was manufacturing and using mustard gas in Syria and Iraq, which was allegedly confirmed by the group's head of chemical weapons development, Sleiman Daoud al-Afari, who has since been captured.[48][49]

Development of the first chemotherapy drug edit

As early as 1919 it was known that mustard agent was a suppressor of hematopoiesis.[50] In addition, autopsies performed on 75 soldiers who had died of mustard agent during World War I were done by researchers from the University of Pennsylvania who reported decreased counts of white blood cells.[40] This led the American Office of Scientific Research and Development (OSRD) to finance the biology and chemistry departments at Yale University to conduct research on the use of chemical warfare during World War II.[40][51]

As a part of this effort, the group investigated nitrogen mustard as a therapy for Hodgkin's lymphoma and other types of lymphoma and leukemia, and this compound was tried out on its first human patient in December 1942. The results of this study were not published until 1946, when they were declassified.[51] In a parallel track, after the air raid on Bari in December 1943, the doctors of the U.S. Army noted that white blood cell counts were reduced in their patients. Some years after World War II was over, the incident in Bari and the work of the Yale University group with nitrogen mustard converged, and this prompted a search for other similar chemical compounds. Due to its use in previous studies, the nitrogen mustard called "HN2" became the first cancer chemotherapy drug, chlormethine (also known as mechlorethamine, mustine) to be used. Chlormethine and other mustard gas molecules are still used to this day as an chemotherapy agent albeit they have largely been replaced with more safe chemotherapy drugs like cisplatin and carboplatin.[52]

Disposal edit

In the United States, storage and incineration of mustard gas and other chemical weapons were carried out by the U.S. Army Chemical Materials Agency.[53] Disposal projects at the two remaining American chemical weapons sites were carried out near Richmond, Kentucky, and Pueblo, Colorado. Although not yet declassified,[specify] toxicology specialists who dealt with the accidental puncturing of World War I gas stockpiles add that Air Force bases in Colorado have been made available to assist veterans of the 2003 American war with Iraq in which many Marines were exposed to gas as caches of up to 25,000 lb (11,000 kg).[citation needed] The United Nations definition of a weapon of mass destruction for mustard gas is 30,000 lb (14,000 kg), typically the Marines and other coalition allies discovered caches of 25,000 pounds (11,000 kg) located across a road from 5,000 pounds (2,300 kg) caches as multiple memoirs attest[citation needed]. These were discovered by the assistance of host country allies, or through leaks affecting personnel in an area with a weapon and gas cache called an ASP.[citation needed]

New detection techniques are being developed in order to detect the presence of mustard gas and its metabolites. The technology is portable and detects small quantities of the hazardous waste and its oxidized products, which are notorious for harming unsuspecting civilians. The immunochromatographic assay would eliminate the need for expensive, time-consuming lab tests and enable easy-to-read tests to protect civilians from sulfur-mustard dumping sites.[54]

In 1946, 10,000 drums of mustard gas (2,800 tonnes) stored at the production facility of Stormont Chemicals in Cornwall, Ontario, Canada, were loaded onto 187 boxcars for the 900 miles (1,400 km) journey to be buried at sea on board a 400 foot (120 m) long barge 40 miles (64 km) south of Sable Island, southeast of Halifax, at a depth of 600 fathoms (1,100 m). The dump location is 42 degrees, 50 minutes north by 60 degrees, 12 minutes west.[55]

A large British stockpile of old mustard agent that had been made and stored since World War I at M. S. Factory, Valley near Rhydymwyn in Flintshire, Wales, was destroyed in 1958.[56]

Most of the mustard gas found in Germany after World War II was dumped into the Baltic Sea. Between 1966 and 2002, fishermen have found about 700 chemical weapons in the region of Bornholm, most of which contain mustard gas. One of the more frequently dumped weapons was "Sprühbüchse 37" (SprüBü37, Spray Can 37, 1937 being the year of its fielding with the German Army). These weapons contain mustard gas mixed with a thickener, which gives it a tar-like viscosity. When the content of the SprüBü37 comes in contact with water, only the mustard gas in the outer layers of the lumps of viscous mustard hydrolyzes, leaving behind amber-colored residues that still contain most of the active mustard gas. On mechanically breaking these lumps (e.g., with the drag board of a fishing net or by the human hand) the enclosed mustard gas is still as active as it had been at the time the weapon was dumped. These lumps, when washed ashore, can be mistaken for amber, which can lead to severe health problems. Artillery shells containing mustard gas and other toxic ammunition from World War I (as well as conventional explosives) can still be found in France and Belgium. These were formerly disposed of by explosion undersea, but since the current environmental regulations prohibit this, the French government is building an automated factory to dispose of the accumulation of chemical shells.

In 1972, the U.S. Congress banned the practice of disposing of chemical weapons into the ocean by the United States. 29,000 tons of nerve and mustard agents had already been dumped into the ocean off the United States by the U.S. Army. According to a report created in 1998 by William Brankowitz, a deputy project manager in the U.S. Army Chemical Materials Agency, the army created at least 26 chemical weapons dumping sites in the ocean offshore from at least 11 states on both the East Coast and the West Coast (in Operation CHASE, Operation Geranium, etc.). In addition, due to poor recordkeeping, about one-half of the sites have only their rough locations known.[57]

In June 1997, India declared its stock of chemical weapons of 1,044 tonnes (1,151 short tons) of mustard gas.[58][59] By the end of 2006, India had destroyed more than 75 percent of its chemical weapons/material stockpile and was granted extension for destroying the remaining stocks by April 2009 and was expected to achieve 100 percent destruction within that time frame.[58] India informed the United Nations in May 2009 that it had destroyed its stockpile of chemical weapons in compliance with the international Chemical Weapons Convention. With this India has become the third country after South Korea and Albania to do so.[60][61] This was cross-checked by inspectors of the United Nations.

Producing or stockpiling mustard gas is prohibited by the Chemical Weapons Convention. When the convention entered force in 1997, the parties declared worldwide stockpiles of 17,440 tonnes of mustard gas. As of December 2015, 86% of these stockpiles had been destroyed.[62]

A significant portion of the United States' mustard agent stockpile was stored at the Edgewood Area of Aberdeen Proving Ground in Maryland. Approximately 1,621 tons of mustard agents were stored in one-ton containers on the base under heavy guard. A chemical neutralization plant was built on the proving ground and neutralized the last of this stockpile in February 2005. This stockpile had priority because of the potential for quick reduction of risk to the community. The nearest schools were fitted with overpressurization machinery to protect the students and faculty in the event of a catastrophic explosion and fire at the site. These projects, as well as planning, equipment, and training assistance, were provided to the surrounding community as a part of the Chemical Stockpile Emergency Preparedness Program (CSEPP), a joint program of the Army and the Federal Emergency Management Agency (FEMA).[63] Unexploded shells containing mustard gases and other chemical agents are still present in several test ranges in proximity to schools in the Edgewood area, but the smaller amounts of poison gas (4 to 14 pounds (1.8 to 6.4 kg)) present considerably lower risks. These remnants are being detected and excavated systematically for disposal. The U.S. Army Chemical Materials Agency oversaw disposal of several other chemical weapons stockpiles located across the United States in compliance with international chemical weapons treaties. These include the complete incineration of the chemical weapons stockpiled in Alabama, Arkansas, Indiana, and Oregon. Earlier, this agency had also completed destruction of the chemical weapons stockpile located on Johnston Atoll located south of Hawaii in the Pacific Ocean.[64] The largest mustard agent stockpile, at approximately 6,200 short tons, was stored at the Deseret Chemical Depot in northern Utah. The incineration of this stockpile began in 2006. In May 2011, the last of the mustard agents in the stockpile were incinerated at the Deseret Chemical Depot, and the last artillery shells containing mustard gas were incinerated in January 2012.

In 2008, many empty aerial bombs that contained mustard gas were found in an excavation at the Marrangaroo Army Base just west of Sydney, Australia.[65][66] In 2009, a mining survey near Chinchilla, Queensland, uncovered 144 105-millimeter howitzer shells, some containing "Mustard H", that had been buried by the U.S. Army during World War II.[66][67]

In 2014, a collection of 200 bombs was found near the Flemish villages of Passendale and Moorslede. The majority of the bombs were filled with mustard agents. The bombs were left over from the German army and were meant to be used in the Battle of Passchendaele in World War I. It was the largest collection of chemical weapons ever found in Belgium.[68]

A large amount of chemical weapons, including mustard gas, was found in a neighborhood of Washington, D.C. The cleanup was completed in 2021.[69]

Post-war accidental exposure edit

In 2002, an archaeologist at the Presidio Trust archaeology lab in San Francisco was exposed to mustard gas, which had been dug up at the Presidio of San Francisco, a former military base.[70]

In 2010, a clamming boat pulled up some old artillery shells of World War I from the Atlantic Ocean south of Long Island, New York. Multiple fishermen suffered from blistering and respiratory irritation severe enough to require hospitalization.[71]

WWII-era tests on men edit

 
Mustard gas test subjects enter gas chamber, Edgewood Arsenal, March 1945

From 1943 to 1944, mustard agent experiments were performed on Australian service volunteers in tropical Queensland, Australia, by British Army and American experimenters, resulting in some severe injuries. One test site, the Brook Islands National Park, was chosen to simulate Pacific islands held by the Imperial Japanese Army.[72][73]

The United States tested sulfur mustards and other chemical agents including nitrogen mustards and lewisite on up to 60,000 servicemen during and after WWII. The experiments were classified secret and as with Agent Orange, claims for medical care and compensation were routinely denied, even after the WWII-era tests were declassified in 1993. The Department of Veterans Affairs stated that it would contact 4,000 surviving test subjects but failed to do so, eventually only contacting 600. Skin cancer, severe eczema, leukemia, and chronic breathing problems plagued the test subjects, some of whom were as young as 19 at the time of the tests, until their deaths, but even those who had previously filed claims with the VA went without compensation.[74]

 
Arms of four test subjects after exposure to nitrogen mustard and lewisite agents.

African-American servicemen were tested alongside white men in separate trials to determine whether their skin color would afford them a degree of immunity to the agents, and Nisei servicemen, some of whom had joined after their release from Japanese American Internment Camps were tested to determine susceptibility of Japanese military personnel to these agents. These tests also included Puerto-Rican subjects.[75]

Detection in biological fluids edit

Concentrations of thiodiglycol in urine have been used to confirm a diagnosis of chemical poisoning in hospitalized victims. The presence in urine of 1,1'-sulfonylbismethylthioethane (SBMTE), a conjugation product with glutathione, is considered a more specific marker, since this metabolite is not found in specimens from unexposed persons. In one case, intact mustard gas was detected in postmortem fluids and tissues of a man who died one week post-exposure.[76]

See also edit

References edit

Notes

  1. ^ a b c d e FM 3–8 Chemical Reference handbook, US Army, 1967
  2. ^ a b c d e Mustard agents: description, physical and chemical properties, mechanism of action, symptoms, antidotes and methods of treatment. Organisation for the Prohibition of Chemical Weapons. Accessed June 8, 2010.
  3. ^ "Pubchem".
  4. ^ a b "Mustard Gas" (PDF). ChemMatters. American Chemical Society.
  5. ^ "What is a Chemical Weapon?". OPCW. Retrieved 2023-09-15.
  6. ^ Salouti, Ramin; Ghazavi, Roghayeh; Rajabi, Sattar; Zare, Mohammad; Talebnejad, Mohammadreza; Abtahi, Mohammad Bagher; Parvizi, Maryam; Madani, Sedigheh; Asadi-Amoli, Fahimeh; Mirsharif, Ensieh-Sadat; Gharebaghi, Reza (2020). "Sulfur Mustard and Immunology; Trends of 20 Years Research in the Web of Science Core Collection: A Scientometric Review". Iranian Journal of Public Health. 49 (7): 1202–1210. doi:10.18502/ijph.v49i7.3573. ISSN 2251-6085. PMC 7548481. PMID 33083286.
  7. ^ Watson, A. P.; Griffin, G. D. (1992). "Toxicity of vesicant agents scheduled for destruction by the Chemical Stockpile Disposal Program". Environmental Health Perspectives. 98: 259–280. doi:10.1289/ehp.9298259. ISSN 0091-6765. PMC 1519623. PMID 1486858.
  8. ^ Smith, Susan L. (27 February 2017). "War! What is it good for? Mustard gas medicine". CMAJ. 189 (8): E321–E322. doi:10.1503/cmaj.161032. PMC 5325736. PMID 28246228.
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Further reading edit

  • Cook, Tim. "‘Against God-Inspired Conscience’: The Perception of Gas Warfare as a Weapon of Mass Destruction, 1915–1939." War & Society 18.1 (2000): 47-69.
  • Dorsey, M. Girard. Holding Their Breath: How the Allies Confronted the Threat of Chemical Warfare in World War II (Cornell UP, 2023) online.
  • Duchovic, Ronald J., and Joel A. Vilensky. "Mustard gas: its pre-World War I history." Journal of chemical education 84.6 (2007): 944. online
  • Feister, Alan J. Medical defense against mustard gas: toxic mechanisms and pharmacological implications (1991). online
  • Fitzgerald, Gerard J. "Chemical warfare and medical response during World War I." American journal of public health 98.4 (2008): 611-625. online
  • * Freemantle, M. (2012). Gas! GAS! Quick, boys! How Chemistry Changed the First World War. The History Press. ISBN 978-0-7524-6601-9.
  • Geraci, Matthew J. "Mustard gas: imminent danger or eminent threat?." Annals of Pharmacotherapy 42.2 (2008): 237-246. online
  • Ghabili, Kamyar, et al. "Mustard gas toxicity: the acute and chronic pathological effects." Journal of applied toxicology 30.7 (2010): 627-643. online
  • Jones, Edgar. "Terror weapons: The British experience of gas and its treatment in the First World War." War in History 21.3 (2014): 355-375. online
  • MacPherson, W. G.; Herringham, W. P.; Elliott, T. R.; Balfour, A. (1923). Medical Services: Diseases of the War: Including the Medical Aspects of Aviation and Gas Warfare and Gas Poisoning in Tanks and Mines. History of the Great War Based on Official Documents by Direction of the Historical Section of the Committee of Imperial Defence. Vol. II. London: HMSO. OCLC 769752656. Retrieved 19 October 2014.
  • Padley, Anthony Paul. "Gas: the greatest terror of the Great War." Anaesthesia and intensive care 44.1_suppl (2016): 24-30. online
  • Rall, David P., and Constance M. Pechura, eds. Veterans at risk: The health effects of mustard gas and lewisite (1993). online
  • Richter, Donald (1994). Chemical Soldiers. Leo Cooper. ISBN 0850523885.
  • Schummer, Joachim. "Ethics of chemical weapons research: Poison gas in World War One." Ethics of Chemistry: From Poison Gas to Climate Engineering (2021) pp. 55-83. online
  • Smith, Susan I. Toxic Exposures: Mustard Gas and the Health Consequences of World War II in the United States (Rutgers University Press, 2017) online book review
  • Wattana, Monica, and Tareg Bey. "Mustard gas or sulfur mustard: an old chemical agent as a new terrorist threat." Prehospital and disaster medicine 24.1 (2009): 19-29. online

External links edit

  • Mustard gas (Sulphur Mustard) (IARC Summary & Evaluation, Supplement7, 1987). Inchem.org (1998-02-09). Retrieved on 2011-05-29.
  • Institute of Medicine (1993). "History and Analysis of Mustard Agent and Lewisite Research Programs in the United States". Veterans at Risk: The Health Effects of Mustard Gas and Lewisite. National Academies Press. ISBN 978-0-309-04832-3.
  • . cdc.gov. Archived from the original on 2006-08-09.
  • . NTI: Nuclear Threat Initiative. Archived from the original on 2016-01-02. Retrieved 2015-11-06.
  • Includes many references to scientific literature
  • Detailed information on physical effects and suggested treatments
  • Iyriboz Y (2004). "A Recent Exposure to Mustard Gas in the United States: Clinical Findings of a Cohort (n = 247) 6 Years After Exposure". MedGenMed. 6 (4): 4. PMC 1480580. PMID 15775831. Shows photographs taken in 1996 showing people with mustard gas burns.
  • (Caution: contains graphic images)
  • A research center studying mustard gas, includes with many early references on mustard gas.
  • Clayton, William; Howard, Alfred John; Thomson, David (25 May 1946). "Treatment of Mustard Gas Burns". British Medical Journal. 1 (4455): 797–799. doi:10.1136/bmj.1.4455.797. PMC 2058956. PMID 20786722.
  • Nightmare in Bari
  • surgical treatment of mustard gas burns
  • Rhydymwyn Valley History Society
  • The advent of mustard gas in 1917, Simon Jones
  • Measures to protect against mustard gas, 1917-1918, Simon Jones

mustard, sulfur, mustard, several, chemical, compounds, that, contain, chemical, structure, ch2ch2cl, wider, sense, compounds, with, substituent, ch2ch2x, ch2ch2x, known, sulfur, mustards, nitrogen, mustards, respectively, where, such, compounds, potent, alkyl. Mustard gas or sulfur mustard is any of the several chemical compounds that contain the chemical structure S CH2CH2Cl 2 In the wider sense compounds with the substituent S CH2CH2X 2 and N CH2CH2X 3 are known as sulfur mustards and nitrogen mustards respectively where X Cl or Br Such compounds are potent alkylating agents which can interfere with several biological processes Also known as mustard agents this family of compounds are infamous cytotoxins and blister agents with a long history of use as chemical weapons The name mustard gas is technically incorrect the substances when dispersed are often not gases but a fine mist of liquid droplets 4 Sulfur mustards are viscous liquids at room temperature and have an odor resembling mustard plants garlic or horseradish hence the name 4 When pure they are colorless but when used in impure forms such as in warfare they are usually yellow brown Mustard gases form blisters on exposed skin and in the lungs often resulting in prolonged illness ending in death The typical mustard gas is the organosulfur compound bis 2 chloroethyl sulfide 5 Mustard gas Names Preferred IUPAC name 1 Chloro 2 2 chloroethyl sulfanyl ethane Other names Bis 2 chloroethyl sulfideHD IpritSchwefel LOSTLostSulfur mustardSenfgasYellow cross liquidYperiteDistilled mustardMustard T mixture1 1 thiobis 2 chloroethane Dichlorodiethyl sulfide Identifiers CAS Number 505 60 2 Y 3D model JSmol Interactive image Beilstein Reference 1733595 ChEBI CHEBI 25434 Y ChEMBL ChEMBL455341 Y ChemSpider 21106142 Y ECHA InfoCard 100 209 973 EC Number 684 527 7 Gmelin Reference 324535 KEGG C19164 Y PubChem CID 10461 UNII T8KEC9FH9P Y CompTox Dashboard EPA DTXSID0037100 InChI InChI 1S C4H8Cl2S c5 1 3 7 4 2 6 h1 4H2 YKey QKSKPIVNLNLAAV UHFFFAOYSA N YInChI 1 C4H8Cl2S c5 1 3 7 4 2 6 h1 4H2Key QKSKPIVNLNLAAV UHFFFAOYAK SMILES ClCCSCCCl Properties Chemical formula C 4H 8Cl 2S Molar mass 159 07 g mol 1 Appearance Colorless if pure Normally ranges from pale yellow to dark brown Slight garlic or horseradish type odor 1 Density 1 27 g mL liquid Melting point 14 45 C 58 01 F 287 60 K Boiling point 217 C 423 F 490 K begins to decompose at 217 C 423 F and boils at 218 C 424 F Solubility in water 7 6 mg L at 20 C 2 Solubility Alcohols ethers hydrocarbons lipids THF Hazards Occupational safety and health OHS OSH Main hazards Flammable toxic vesicant carcinogenic mutagenic GHS labelling 3 Pictograms Signal word Danger Hazard statements H300 H310 H315 H319 H330 H335 Precautionary statements P260 P261 P262 P264 P270 P271 P280 P284 P301 P310 P302 P350 P302 P352 P304 P340 P305 P351 P338 P310 P312 P320 P321 P322 P330 P332 P313 P337 P313 P361 P362 P363 P403 P233 P405 P501 NFPA 704 fire diamond 411 Flash point 105 C 221 F 378 K Safety data sheet SDS External MSDS Related compounds Related compounds Nitrogen mustard Bis chloroethyl ether Chloromethyl methyl sulfide Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Contents 1 History as chemical weapons 2 Mechanism of cellular toxicity 3 Physiological effects 4 Formulations 5 Commonly stockpiled mustard agents class 6 History 6 1 Development 6 2 Use 6 2 1 Development of the first chemotherapy drug 6 2 2 Disposal 6 2 3 Post war accidental exposure 6 3 WWII era tests on men 6 4 Detection in biological fluids 7 See also 8 References 9 Further reading 10 External linksHistory as chemical weapons editSulfur mustard is a type of chemical warfare agent As a chemical weapon mustard gas was first used in World War I and has been used in several armed conflicts since then including the Iran Iraq War resulting in more than 100 000 casualties 6 7 Today sulfur based and nitrogen based mustard agents are regulated under Schedule 1 of the 1993 Chemical Weapons Convention as substances with few uses other than in chemical warfare though since then mustard gas has been found to be useful in cancer chemotherapy 8 Mustard agents can be deployed by means of artillery shells aerial bombs rockets or by spraying from aircraft Mechanism of cellular toxicity edit nbsp Mustard gas alkylating an amino group via conversion to a sulfonium ion 2 chloroethylthiiranium Sulfur mustards readily eliminate chloride ions by intramolecular nucleophilic substitution to form cyclic sulfonium ions These very reactive intermediates tend to permanently alkylate nucleotides in DNA strands which can prevent cellular division leading to programmed cell death 2 Alternatively if cell death is not immediate the damaged DNA can lead to the development of cancer 2 Oxidative stress would be another pathology involved in mustard gas toxicity In the wider sense compounds with the structural element BC2H4X where X is any leaving group and B is a Lewis base are known as mustards citation needed Such compounds can form cyclic onium ions sulfonium ammonium etc that are good alkylating agents Other such compounds are bis 2 haloethyl ethers oxygen mustards the 2 haloethyl amines nitrogen mustards and sesquimustard which has two a chloroethyl thioether groups ClC2H4S connected by an ethylene bridge C2H4 citation needed These compounds have a similar ability to alkylate DNA but their physical properties vary Physiological effects edit nbsp Soldier with moderate mustard agent burns sustained during World War I showing characteristic bullae on the neck armpit and hands Mustard gases react with DNA which interferes with cellular division and can lead to mutations 2 Mustard gases are extremely toxic and have powerful blistering effects on victims Their alkylating capabilities make them strongly carcinogenic and mutagenic Furthermore they are highly lipophilic which accelerates their absorption into the body 2 Because people exposed to mustard agents rarely suffer immediate symptoms and contaminated areas may appear completely normal victims can unknowingly receive high doses Within 24 hours of exposure they experience intense itching and skin irritation If this irritation goes untreated blisters filled with yellow fluid pus can form wherever the agent contacted the skin These are chemical burns and are very debilitating Mustard gases easily penetrate clothing fabrics such as wool or cotton so it is not only exposed skin that gets burned If the victim s eyes were exposed then they become sore starting with conjunctivitis also known as pink eye after which the eyelids swell resulting in temporary blindness Extreme ocular exposure to mustard gas vapors may result in corneal ulceration anterior chamber scarring and neovascularization 9 10 11 12 In these severe and infrequent cases corneal transplantation has been used as a treatment option 13 Miosis when the pupil constricts more than usual may also occur which is probably the result of the cholinomimetic activity of mustard 14 At very high concentrations if inhaled mustard agents cause bleeding and blistering within the respiratory system damaging mucous membranes and causing pulmonary edema Depending on the level of contamination mustard agent burns can vary between first and second degree burns though they can also be every bit as severe disfiguring and dangerous as third degree burns 15 Burns that are severe i e covering more than 50 of the victim s skin are often fatal with death occurring after only days or weeks Mild or moderate exposure to mustard gases is unlikely to kill though victims still require lengthy periods of medical treatment and convalescence before recovery is complete Mustard gases carcinogenic and mutagenic effects mean that victims even if they fully recover have an increased risk of developing cancer later in life In a study of patients 25 years after wartime exposure to chemical weaponry c DNA microarray profiling indicated that 122 genes were significantly mutated in the lungs and airways of mustard gas victims Those genes all correspond to functions commonly affected by mustard gas exposure including apoptosis inflammation and stress responses 16 The long term ocular complications include burning tearing itching photophobia presbyopia pain and foreign body sensations 17 18 nbsp Typical appearance of bullae on an arm caused by vesicant burns Mustard gases blistering effects can be neutralized by oxidation or chlorination using household bleach sodium hypochlorite or by nucleophilic attack using decontamination solutions such as DS2 2 NaOH 70 diethylenetriamine 28 2 methoxyethanol After initial decontamination of the victim s wounds is complete medical treatment is similar to that required by any conventional burn The degree of pain and discomfort suffered by the victim is also comparable Mustard agent burns do not heal quickly and as with other types of burns present a risk of sepsis caused by pathogens such as Staphylococcus aureus and Pseudomonas aeruginosa The mechanisms behind mustard gas s effect on endothelial cells are still being studied but recent studies have shown that high levels of exposure can induce high rates of both necrosis and apoptosis In vitro tests have shown that at low concentrations of mustard gas where apoptosis is the predominant result of exposure pretreatment with 50 mM N acetyl L cysteine NAC was able to decrease the rate of apoptosis NAC protects actin filaments from reorganization by mustard gas demonstrating that actin filaments play a large role in the severe burns observed in victims 19 A British nurse treating soldiers with mustard agent burns during World War I commented 20 They cannot be bandaged or touched We cover them with a tent of propped up sheets Gas burns must be agonizing because usually the other cases do not complain even with the worst wounds but gas cases are invariably beyond endurance and they cannot help crying out Formulations edit nbsp Lewisite top row and mustard gas bottom row test with concentrations from 0 01 to 0 06 In its history various types and mixtures of mustard gas have been employed These include H Also known as HS Hun Stuff or Levinstein mustard This is named after the inventor of the quick but dirty Levinstein Process for manufacture 21 22 reacting dry ethylene with disulfur dichloride under controlled conditions Undistilled mustard gas contains 20 30 impurities which means it does not store as well as HD Also as it decomposes it increases in vapor pressure making the munition it is contained in likely to split especially along a seam releasing the agent to the atmosphere 1 HD Codenamed Pyro by the British and Distilled Mustard by the US 1 Distilled mustard of 95 or higher purity The term mustard gas usually refers to this variety of mustard HT Codenamed Runcol by the British and Mustard T mixture by the US 1 A mixture of 60 HD mustard and 40 O Mustard a related vesicant with lower freezing point lower volatility and similar vesicant characteristics HL A blend of distilled mustard HD and lewisite L originally intended for use in winter conditions due to its lower freezing point compared to the pure substances The lewisite component of HL was used as a form of antifreeze 23 HQ A blend of distilled mustard HD and sesquimustard Q Gates and Moore 1946 Yellow Cross any of several blends containing sulfur mustard and sometimes arsine agents along with solvents and other additives Commonly stockpiled mustard agents class editChemical Code Trivial name CAS number PubChem Structure Bis 2 chloroethyl sulfide H HD Mustard 505 60 2 CID 10461 from PubChem nbsp 1 2 Bis 2 chloroethylsulfanyl ethane Q Sesquimustard 3563 36 8 CID 19092 from PubChem nbsp 2 Chloroethyl ethyl sulfide Half mustard 693 07 2 CID 12733 from PubChem nbsp Bis 2 2 chloroethylsulfanyl ethyl ether T O Mustard 63918 89 8 CID 45452 from PubChem nbsp 2 Chloroethyl chloromethyl sulfide 2625 76 5 nbsp Bis 2 chloroethylsulfanyl methane HK 63869 13 6 nbsp 1 3 Bis 2 chloroethylsulfanyl propane 63905 10 2 nbsp 1 4 Bis 2 chloroethylsulfanyl butane 142868 93 7 nbsp 1 5 Bis 2 chloroethylsulfanyl pentane 142868 94 8 nbsp Bis 2 chloroethylsulfanyl methyl ether 63918 90 1 nbsp History editDevelopment edit Mustard gases were possibly developed as early as 1822 by Cesar Mansuete Despretz 1798 1863 24 Despretz described the reaction of sulfur dichloride and ethylene but never made mention of any irritating properties of the reaction product In 1854 another French chemist Alfred Riche 1829 1908 repeated this procedure also without describing any adverse physiological properties In 1860 the British scientist Frederick Guthrie synthesized and characterized the mustard agent compound and noted its irritating properties especially in tasting 25 Also in 1860 chemist Albert Niemann known as a pioneer in cocaine chemistry repeated the reaction and recorded blister forming properties In 1886 Viktor Meyer published a paper describing a synthesis that produced good yields He combined 2 chloroethanol with aqueous potassium sulfide and then treated the resulting thiodiglycol with phosphorus trichloride The purity of this compound was much higher and consequently the adverse health effects upon exposure were much more severe These symptoms presented themselves in his assistant and in order to rule out the possibility that his assistant was suffering from a mental illness psychosomatic symptoms Meyer had this compound tested on laboratory rabbits most of which died In 1913 the English chemist Hans Thacher Clarke known for the Eschweiler Clarke reaction replaced the phosphorus trichloride with hydrochloric acid in Meyer s formulation while working with Emil Fischer in Berlin Clarke was hospitalized for two months for burns after one of his flasks broke According to Meyer Fischer s report on this accident to the German Chemical Society sent the German Empire on the road to chemical weapons 26 Mustard gas can have the effect of turning a patient s skin different colors including shades of red orange pink and in unusual cases blue The German Empire during World War I relied on the Meyer Clarke method because 2 chloroethanol was readily available from the German dye industry of that time Use edit nbsp Pallets of 155 mm artillery shells containing HD distilled mustard gas agent at the Pueblo Chemical Depot The distinctive color coding scheme on each shell is visible Mustard gas was first used in World War I by the German army against British and Canadian soldiers near Ypres Belgium on the night of July 12 1917 27 Later also against the French Second Army Yperite is a name used by the French because the compound was first used at Ypres 28 The Allies did not use mustard gas until November 1917 at Cambrai France after the armies had captured a stockpile of German mustard shells It took the British more than a year to develop their own mustard agent weapon with production of the chemicals centred on Avonmouth Docks the only option available to the British was the Despretz Niemann Guthrie process 29 30 This was used first in September 1918 during the breaking of the Hindenburg Line Mustard gas was originally assigned the name LOST after the scientists Wilhelm Lommel and Wilhelm Steinkopf who developed a method of large scale production for the Imperial German Army in 1916 31 Mustard gas was dispersed as an aerosol in a mixture with other chemicals giving it a yellow brown color Mustard agent has also been dispersed in such munitions as aerial bombs land mines mortar rounds artillery shells and rockets 1 Exposure to mustard agent was lethal in about 1 of cases Its effectiveness was as an incapacitating agent The early countermeasures against mustard agent were relatively ineffective since a soldier wearing a gas mask was not protected against absorbing it through his skin and being blistered A common countermeasure was using a urine soaked mask or facecloth to prevent or reduce injury a readily available remedy attested by soldiers in documentaries e g They Shall Not Grow Old in 2018 and others such as forward aid nurses interviewed between 1947 and 1981 by the British Broadcasting Corporation for various World War One history programs however the effectiveness of this measure is unclear Mustard gas can remain in the ground for weeks and it continues to cause ill effects If mustard agent contaminates one s clothing and equipment while cold then other people with whom they share an enclosed space could become poisoned as contaminated items warm up enough material to become an airborne toxic agent An example of this was depicted in a British and Canadian documentary about life in the trenches particularly once the sousterrain subways and berthing areas underground were completed in Belgium and France Towards the end of World War I mustard agent was used in high concentrations as an area denial weapon that forced troops to abandon heavily contaminated areas nbsp US Army World War II gas identification poster c 1941 1945 Since World War I mustard gas has been used in several wars and other conflicts usually against people who cannot retaliate in kind 32 United Kingdom against the Red Army in 1919 33 Alleged British use in Mesopotamia in 1920 34 Spain against the Rifian resistance in Morocco during the Rif War of 1921 27 see also Spanish use of chemical weapons in the Rif War 32 35 Italy in Libya in 1930 32 The Soviet Union in Xinjiang Republic of China during the Soviet Invasion of Xinjiang against the 36th Division National Revolutionary Army in 1934 and also in the Xinjiang War 1937 in 1936 37 33 35 Italy against Abyssinia now Ethiopia in 1935 1936 32 The Japanese Empire against China in 1937 1945 33 The US military conducted experiments with chemical weapons like lewisite and mustard gas on Japanese American Puerto Rican and African Americans in the US military in World War II to see how non white races would react to being mustard gassed with Rollin Edwards describing it as It felt like you were on fire Guys started screaming and hollering and trying to break out And then some of the guys fainted And finally they opened the door and let us out and the guys were just they were in bad shape and It took all the skin off your hands Your hands just rotted 36 After WWII stockpiled mustard gas was dumped by the British in the sea near Port Elizabeth South Africa resulting in many cases of burns among trawler crews 37 The United States Government tested effectiveness on US Naval recruits in a laboratory setting at The Great Lakes Naval Base June 3 1945 38 The 2 December 1943 air raid on Bari destroyed an Allied stockpile of mustard gas on the SS John Harvey 39 killing 83 and hospitalizing 628 40 Egypt against North Yemen in 1963 1967 32 Iraq against Kurds in the town of Halabja during the Halabja chemical attack in 1988 33 41 Iraq against Iranians in 1983 1988 42 Possibly in Sudan against insurgents in the civil war in 1995 and 1997 32 In the Iraq War abandoned stockpiles of mustard gas shells were destroyed in the open air 43 and were used against Coalition forces in roadside bombs 44 By ISIS forces against Kurdish forces in Iraq in August 2015 45 By ISIS against another rebel group in the town of Mare in 2015 46 According to Syrian state media by ISIS against the Syrian Army during the battle in Deir ez Zor in 2016 47 The use of toxic gases or other chemicals including mustard gas during warfare is known as chemical warfare and this kind of warfare was prohibited by the Geneva Protocol of 1925 and also by the later Chemical Weapons Convention of 1993 The latter agreement also prohibits the development production stockpiling and sale of such weapons In September 2012 a US official stated that the rebel militant group ISIS was manufacturing and using mustard gas in Syria and Iraq which was allegedly confirmed by the group s head of chemical weapons development Sleiman Daoud al Afari who has since been captured 48 49 Development of the first chemotherapy drug edit As early as 1919 it was known that mustard agent was a suppressor of hematopoiesis 50 In addition autopsies performed on 75 soldiers who had died of mustard agent during World War I were done by researchers from the University of Pennsylvania who reported decreased counts of white blood cells 40 This led the American Office of Scientific Research and Development OSRD to finance the biology and chemistry departments at Yale University to conduct research on the use of chemical warfare during World War II 40 51 As a part of this effort the group investigated nitrogen mustard as a therapy for Hodgkin s lymphoma and other types of lymphoma and leukemia and this compound was tried out on its first human patient in December 1942 The results of this study were not published until 1946 when they were declassified 51 In a parallel track after the air raid on Bari in December 1943 the doctors of the U S Army noted that white blood cell counts were reduced in their patients Some years after World War II was over the incident in Bari and the work of the Yale University group with nitrogen mustard converged and this prompted a search for other similar chemical compounds Due to its use in previous studies the nitrogen mustard called HN2 became the first cancer chemotherapy drug chlormethine also known as mechlorethamine mustine to be used Chlormethine and other mustard gas molecules are still used to this day as an chemotherapy agent albeit they have largely been replaced with more safe chemotherapy drugs like cisplatin and carboplatin 52 Disposal edit This section needs to be updated Please help update this article to reflect recent events or newly available information February 2022 In the United States storage and incineration of mustard gas and other chemical weapons were carried out by the U S Army Chemical Materials Agency 53 Disposal projects at the two remaining American chemical weapons sites were carried out near Richmond Kentucky and Pueblo Colorado Although not yet declassified specify toxicology specialists who dealt with the accidental puncturing of World War I gas stockpiles add that Air Force bases in Colorado have been made available to assist veterans of the 2003 American war with Iraq in which many Marines were exposed to gas as caches of up to 25 000 lb 11 000 kg citation needed The United Nations definition of a weapon of mass destruction for mustard gas is 30 000 lb 14 000 kg typically the Marines and other coalition allies discovered caches of 25 000 pounds 11 000 kg located across a road from 5 000 pounds 2 300 kg caches as multiple memoirs attest citation needed These were discovered by the assistance of host country allies or through leaks affecting personnel in an area with a weapon and gas cache called an ASP citation needed New detection techniques are being developed in order to detect the presence of mustard gas and its metabolites The technology is portable and detects small quantities of the hazardous waste and its oxidized products which are notorious for harming unsuspecting civilians The immunochromatographic assay would eliminate the need for expensive time consuming lab tests and enable easy to read tests to protect civilians from sulfur mustard dumping sites 54 In 1946 10 000 drums of mustard gas 2 800 tonnes stored at the production facility of Stormont Chemicals in Cornwall Ontario Canada were loaded onto 187 boxcars for the 900 miles 1 400 km journey to be buried at sea on board a 400 foot 120 m long barge 40 miles 64 km south of Sable Island southeast of Halifax at a depth of 600 fathoms 1 100 m The dump location is 42 degrees 50 minutes north by 60 degrees 12 minutes west 55 A large British stockpile of old mustard agent that had been made and stored since World War I at M S Factory Valley near Rhydymwyn in Flintshire Wales was destroyed in 1958 56 Most of the mustard gas found in Germany after World War II was dumped into the Baltic Sea Between 1966 and 2002 fishermen have found about 700 chemical weapons in the region of Bornholm most of which contain mustard gas One of the more frequently dumped weapons was Spruhbuchse 37 SpruBu37 Spray Can 37 1937 being the year of its fielding with the German Army These weapons contain mustard gas mixed with a thickener which gives it a tar like viscosity When the content of the SpruBu37 comes in contact with water only the mustard gas in the outer layers of the lumps of viscous mustard hydrolyzes leaving behind amber colored residues that still contain most of the active mustard gas On mechanically breaking these lumps e g with the drag board of a fishing net or by the human hand the enclosed mustard gas is still as active as it had been at the time the weapon was dumped These lumps when washed ashore can be mistaken for amber which can lead to severe health problems Artillery shells containing mustard gas and other toxic ammunition from World War I as well as conventional explosives can still be found in France and Belgium These were formerly disposed of by explosion undersea but since the current environmental regulations prohibit this the French government is building an automated factory to dispose of the accumulation of chemical shells In 1972 the U S Congress banned the practice of disposing of chemical weapons into the ocean by the United States 29 000 tons of nerve and mustard agents had already been dumped into the ocean off the United States by the U S Army According to a report created in 1998 by William Brankowitz a deputy project manager in the U S Army Chemical Materials Agency the army created at least 26 chemical weapons dumping sites in the ocean offshore from at least 11 states on both the East Coast and the West Coast in Operation CHASE Operation Geranium etc In addition due to poor recordkeeping about one half of the sites have only their rough locations known 57 In June 1997 India declared its stock of chemical weapons of 1 044 tonnes 1 151 short tons of mustard gas 58 59 By the end of 2006 India had destroyed more than 75 percent of its chemical weapons material stockpile and was granted extension for destroying the remaining stocks by April 2009 and was expected to achieve 100 percent destruction within that time frame 58 India informed the United Nations in May 2009 that it had destroyed its stockpile of chemical weapons in compliance with the international Chemical Weapons Convention With this India has become the third country after South Korea and Albania to do so 60 61 This was cross checked by inspectors of the United Nations Producing or stockpiling mustard gas is prohibited by the Chemical Weapons Convention When the convention entered force in 1997 the parties declared worldwide stockpiles of 17 440 tonnes of mustard gas As of December 2015 86 of these stockpiles had been destroyed 62 A significant portion of the United States mustard agent stockpile was stored at the Edgewood Area of Aberdeen Proving Ground in Maryland Approximately 1 621 tons of mustard agents were stored in one ton containers on the base under heavy guard A chemical neutralization plant was built on the proving ground and neutralized the last of this stockpile in February 2005 This stockpile had priority because of the potential for quick reduction of risk to the community The nearest schools were fitted with overpressurization machinery to protect the students and faculty in the event of a catastrophic explosion and fire at the site These projects as well as planning equipment and training assistance were provided to the surrounding community as a part of the Chemical Stockpile Emergency Preparedness Program CSEPP a joint program of the Army and the Federal Emergency Management Agency FEMA 63 Unexploded shells containing mustard gases and other chemical agents are still present in several test ranges in proximity to schools in the Edgewood area but the smaller amounts of poison gas 4 to 14 pounds 1 8 to 6 4 kg present considerably lower risks These remnants are being detected and excavated systematically for disposal The U S Army Chemical Materials Agency oversaw disposal of several other chemical weapons stockpiles located across the United States in compliance with international chemical weapons treaties These include the complete incineration of the chemical weapons stockpiled in Alabama Arkansas Indiana and Oregon Earlier this agency had also completed destruction of the chemical weapons stockpile located on Johnston Atoll located south of Hawaii in the Pacific Ocean 64 The largest mustard agent stockpile at approximately 6 200 short tons was stored at the Deseret Chemical Depot in northern Utah The incineration of this stockpile began in 2006 In May 2011 the last of the mustard agents in the stockpile were incinerated at the Deseret Chemical Depot and the last artillery shells containing mustard gas were incinerated in January 2012 In 2008 many empty aerial bombs that contained mustard gas were found in an excavation at the Marrangaroo Army Base just west of Sydney Australia 65 66 In 2009 a mining survey near Chinchilla Queensland uncovered 144 105 millimeter howitzer shells some containing Mustard H that had been buried by the U S Army during World War II 66 67 In 2014 a collection of 200 bombs was found near the Flemish villages of Passendale and Moorslede The majority of the bombs were filled with mustard agents The bombs were left over from the German army and were meant to be used in the Battle of Passchendaele in World War I It was the largest collection of chemical weapons ever found in Belgium 68 A large amount of chemical weapons including mustard gas was found in a neighborhood of Washington D C The cleanup was completed in 2021 69 Post war accidental exposure edit In 2002 an archaeologist at the Presidio Trust archaeology lab in San Francisco was exposed to mustard gas which had been dug up at the Presidio of San Francisco a former military base 70 In 2010 a clamming boat pulled up some old artillery shells of World War I from the Atlantic Ocean south of Long Island New York Multiple fishermen suffered from blistering and respiratory irritation severe enough to require hospitalization 71 WWII era tests on men edit nbsp Mustard gas test subjects enter gas chamber Edgewood Arsenal March 1945 From 1943 to 1944 mustard agent experiments were performed on Australian service volunteers in tropical Queensland Australia by British Army and American experimenters resulting in some severe injuries One test site the Brook Islands National Park was chosen to simulate Pacific islands held by the Imperial Japanese Army 72 73 The United States tested sulfur mustards and other chemical agents including nitrogen mustards and lewisite on up to 60 000 servicemen during and after WWII The experiments were classified secret and as with Agent Orange claims for medical care and compensation were routinely denied even after the WWII era tests were declassified in 1993 The Department of Veterans Affairs stated that it would contact 4 000 surviving test subjects but failed to do so eventually only contacting 600 Skin cancer severe eczema leukemia and chronic breathing problems plagued the test subjects some of whom were as young as 19 at the time of the tests until their deaths but even those who had previously filed claims with the VA went without compensation 74 nbsp Arms of four test subjects after exposure to nitrogen mustard and lewisite agents African American servicemen were tested alongside white men in separate trials to determine whether their skin color would afford them a degree of immunity to the agents and Nisei servicemen some of whom had joined after their release from Japanese American Internment Camps were tested to determine susceptibility of Japanese military personnel to these agents These tests also included Puerto Rican subjects 75 Detection in biological fluids edit Concentrations of thiodiglycol in urine have been used to confirm a diagnosis of chemical poisoning in hospitalized victims The presence in urine of 1 1 sulfonylbismethylthioethane SBMTE a conjugation product with glutathione is considered a more specific marker since this metabolite is not found in specimens from unexposed persons In one case intact mustard gas was detected in postmortem fluids and tissues of a man who died one week post exposure 76 See also editBis chloromethyl ether Chlorine gas Keen as Mustard Phosgene oxime Poison gas in World War I Rawalpindi experiments Selenium mustardReferences editNotes a b c d e FM 3 8 Chemical Reference handbook US Army 1967 a b c d e Mustard agents description physical and chemical properties mechanism of action symptoms antidotes and methods of treatment Organisation for the Prohibition of Chemical Weapons Accessed June 8 2010 Pubchem a b Mustard Gas PDF ChemMatters American Chemical Society What is a Chemical Weapon OPCW Retrieved 2023 09 15 Salouti Ramin Ghazavi Roghayeh Rajabi Sattar Zare Mohammad Talebnejad Mohammadreza Abtahi Mohammad Bagher Parvizi Maryam Madani Sedigheh Asadi Amoli Fahimeh Mirsharif Ensieh Sadat Gharebaghi Reza 2020 Sulfur Mustard and 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for the Prohibition of Chemical Weapons 30 November 2016 Annex 3 Report of the OPCW on the Implementation of the Convention on the Prohibition of the Development Production Stockpiling and Use of Chemical Weapons and on Their Destruction in 2015 Report p 42 Retrieved 8 March 2017 CSEPP Background Information US Federal Emergency Management Agency FEMA 2 May 2006 Archived from the original on 27 May 2006 Milestones in U S Chemical Weapons Storage and Destruction fact sheet US Chemical Materials Agency Archived from the original on 15 September 2012 Retrieved 15 January 2012 Ashworth L 7 August 2008 Base s phantom war reveals its secrets Fairfax Digital Archived from the original on 5 December 2008 a b Chemical Warfare in Australia Mustardgas org Retrieved on 29 May 2011 Cumming Stuart 11 November 2009 Weapons await UN inspection Toowoomba Chronicle Farmer discovers 200 bombs Dutch 5 March 2014 Cleanup Complete At WWI Chemical Weapons Dump In D C s Spring Valley DCist Archived from the original on 2022 02 07 Retrieved 2022 02 07 Sullivan Kathleen 2002 10 22 Vial found in Presidio may be mustard gas Army experts expected to identify substance sfgate com Wickett Shana Beth Daley 2010 06 08 Fishing crewman exposed to mustard gas from shell The Boston Globe Archived from the original on June 9 2010 Goodwin Bridget 1998 Keen as mustard Britain s horrific chemical warfare experiments in Australia St Lucia University of Queensland Press ISBN 978 0 7022 2941 1 Brook Island Trials of Mustard Gas during WW2 Home st net au Retrieved on 2011 05 29 Dickerson Caitlin 2015 06 23 The VA s Broken Promise To Thousands Of Vets Exposed To Mustard Gas NPR Retrieved 2019 05 03 the Department of Veterans Affairs made two promises to locate about 4 000 men who were used in the most extreme tests and to compensate those who had permanent injuries Dickerson Caitlin 2015 06 22 Secret World War II Chemical Experiments Tested Troops By Race NPR Retrieved 2019 05 03 And it wasn t just African Americans Japanese Americans were used so scientists could explore how mustard gas and other chemicals might affect Japanese troops Puerto Rican soldiers were also singled out R Baselt Disposition of Toxic Drugs and Chemicals in Man 10th edition Biomedical Publications Seal Beach CA 2014 pp 1892 1894 Further reading editCook Tim Against God Inspired Conscience The Perception of Gas Warfare as a Weapon of Mass Destruction 1915 1939 War amp Society 18 1 2000 47 69 Dorsey M Girard Holding Their Breath How the Allies Confronted the Threat of Chemical Warfare in World War II Cornell UP 2023 online Duchovic Ronald J and Joel A Vilensky Mustard gas its pre World War I history Journal of chemical education 84 6 2007 944 online Feister Alan J Medical defense against mustard gas toxic mechanisms and pharmacological implications 1991 online Fitzgerald Gerard J Chemical warfare and medical response during World War I American journal of public health 98 4 2008 611 625 online Freemantle M 2012 Gas GAS Quick boys How Chemistry Changed the First World War The History Press ISBN 978 0 7524 6601 9 Geraci Matthew J Mustard gas imminent danger or eminent threat Annals of Pharmacotherapy 42 2 2008 237 246 online Ghabili Kamyar et al Mustard gas toxicity the acute and chronic pathological effects Journal of applied toxicology 30 7 2010 627 643 online Jones Edgar Terror weapons The British experience of gas and its treatment in the First World War War in History 21 3 2014 355 375 online MacPherson W G Herringham W P Elliott T R Balfour A 1923 Medical Services Diseases of the War Including the Medical Aspects of Aviation and Gas Warfare and Gas Poisoning in Tanks and Mines History of the Great War Based on Official Documents by Direction of the Historical Section of the Committee of Imperial Defence Vol II London HMSO OCLC 769752656 Retrieved 19 October 2014 Padley Anthony Paul Gas the greatest terror of the Great War Anaesthesia and intensive care 44 1 suppl 2016 24 30 online Rall David P and Constance M Pechura eds Veterans at risk The health effects of mustard gas and lewisite 1993 online Richter Donald 1994 Chemical Soldiers Leo Cooper ISBN 0850523885 Schummer Joachim Ethics of chemical weapons research Poison gas in World War One Ethics of Chemistry From Poison Gas to Climate Engineering 2021 pp 55 83 online Smith Susan I Toxic Exposures Mustard Gas and the Health Consequences of World War II in the United States Rutgers University Press 2017 online book review Wattana Monica and Tareg Bey Mustard gas or sulfur mustard an old chemical agent as a new terrorist threat Prehospital and disaster medicine 24 1 2009 19 29 onlineExternal links editMustard gas Sulphur Mustard IARC Summary amp Evaluation Supplement7 1987 Inchem org 1998 02 09 Retrieved on 2011 05 29 Institute of Medicine 1993 History and Analysis of Mustard Agent and Lewisite Research Programs in the United States Veterans at Risk The Health Effects of Mustard Gas and Lewisite National Academies Press ISBN 978 0 309 04832 3 CDC Facts About Sulfur Mustard cdc gov Archived from the original on 2006 08 09 NATO Presses New Libyan Leaders to Eliminate Mustard Agent Global Security Newswire NTI NTI Nuclear Threat Initiative Archived from the original on 2016 01 02 Retrieved 2015 11 06 nbsp Wikimedia Commons has media related to Sulfur mustard Textbook of Military Medicine Intensive overview of mustard gas Includes many references to scientific literature Detailed information on physical effects and suggested treatments Iyriboz Y 2004 A Recent Exposure to Mustard Gas in the United States Clinical Findings of a Cohort n 247 6 Years After Exposure MedGenMed 6 4 4 PMC 1480580 PMID 15775831 Shows photographs taken in 1996 showing people with mustard gas burns An overview of the sulfur and nitrogen mustard agents Caution contains graphic images Questions and Answers for Mustard Gas UMDNJ Rutgers University CounterACT Research Center of Excellence A research center studying mustard gas includes searchable reference library with many early references on mustard gas Clayton William Howard Alfred John Thomson David 25 May 1946 Treatment of Mustard Gas Burns British Medical Journal 1 4455 797 799 doi 10 1136 bmj 1 4455 797 PMC 2058956 PMID 20786722 Nightmare in Bari surgical treatment of mustard gas burns UK Ministry of Defence Report on disposal of weapons at sea and incidents arising Rhydymwyn Valley History Society The advent of mustard gas in 1917 Simon Jones Measures to protect against mustard gas 1917 1918 Simon Jones Retrieved from https en wikipedia org w index php title Mustard gas amp oldid 1219937059, wikipedia, wiki, book, books, library,

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