chemical warfare agents

introduction
history
WWI
after WWI
WWII
after WWII
existing arsenal
Chemical Weapons Convention
dumping
environmental recovery
toxic chemical agents
mustard agents >>>
arsenic agents
organophosphate nerve agents
Baltic
conclusions
references

introduction

In this group there are poisons used by the army in order to kill, or permanently injure the enemy. Usage of such substances is prohibited, while manufacturing and storage restricted by international agreements. However, these restrictions do not apply to waste created during weapons production. Residues and byproducts are usually placed under the water (seas, lakes) or buried in the ground. It is estimated that the global inventory of combat poisons released into the environment would show more than one million tonnes. Due to the extremely hazardous and diversified properties of these waste, there is a lack of organized manner in which neutralization could takes place and storage locations are kept confidential. The largest quantity of such waste belong to the following groups:

• sulfur mustard agents
• arsenic agents
• organophosphates nerve agents 

Ways of localization and neutralization of chemical weapons are strongly related to types and configurations of this armament. The chemical toxins used to eliminate the enemy manpower shall be designed in such way that:

• they possess ability to be scattered in toxic doses within the area occupied by the enemy.
• they are able to sustain their toxic properties over a long period of time for effective shock purposes.
• they are able to cause death or inability to function.
• they can be relatively easy neutralized, destroyed or dispersed by chemical disinfectants available to those who spread toxins; reason for this being - to clean up environment fast and effectively after adversary has been eliminated or withdrew from the area.

There are several patterns for application of chemical weapons. Each pattern requires different preparations of poisons.

• strategic or land covering use of chemicals

Attacker prepares chemical toxins capable to affect targets located at the considerable distance. Distance must be large enough, so attacker remains without any exposure to the poison he spread. Poisons are carried by missile warheads, artillery shells and air bombs. The main objective is to create chaos within enemy’s territory, therefore typically, the density of the dispersed poisons is minimal. Panic among unprepared people (civilians or military personnel) ensues. This in turn disorganizes and disrupts emergency response services.

Defender strengthens its line of defense, preparing and mounting chemical landmines firewalls. Such firewalls are in some cases ready to release even larger quantities of poisons. The task is to complete elimination or at least exhaustion of the opponents‘ troops and tactical military units. This of course is expected by the striker, therefore he tries to overpower enemy’s capacity by using more chemical warfare. Resulting vicious circle leads to premeditated planning and escalating use of new extremely strong toxic chemicals, possessing long term environmental stability, persistence and resistance to neutralization.

• tactical use of chemical weapons

Strategic as well as tactical use of chemical weapons, requires long distance transportation of deadly cargo. This distance may vary and has to be determined by the user in order to not expose its own military forces. Small area can be successfully attacked by aircrafts used for pesticides spraying. Task is complicated - relatively small amount of toxins should cause massive destruction of enemy troops, but at the same time, the same chemicals should become quickly harmless and easy to neutralize by the troops overtaking the battleground.

• use of chemical weapons in chambers and contained spaces

In order to exterminate large groups of people, poison must be highly effective, easy to spray and able to react quickly with water during neutralization.. This ensures minimal exposure for operators who damp poison into the gas chambers; they do not have to be concerned about traces of left-over deadly compounds. Terrorists plan use of poisons in contained spaces in order to kill or incapacitate maximum number of people with minimum amount of substance. However, additionally, such actions are designed to disorganize response of emergency teams as well; therefore selected poisons, would have rather long lasting chemical stability in this case.

All the above, points to a little-known extra environmental problems. The multitude of ways how poisons can be utilized and applied, requires that producers must constantly modify toxic physicochemical properties of the active substances. Containers, unexploded bombs, mines and shells found in the environment must be analyzed not only for their main deadly content, but for additional components and by-products created during the chemical syntheses. Ultimately it is necessary to identify all components that have been used during the synthesis of particular poison. It is worth to observe , that in most of cases manufacturers of chemical poisons were not under any obligation to ordering party, to care and pay attention for environmental wellbeing. Consequently additional components and reagents selected for synthetic processes belonged to non-degradable organic toxins.

Efforts to eliminate poisons from the combat environment get often complicated, because the presence of still not detonated explosives. Abandoned, useless armament remaining after the conflict, contains unexploded devices equipped with active igniters. Shells slowly corrode and poisonous substances sometimes penetrate explosives, what is the cause of chemical instability inside the shells. Therefore, the risk assessment for cleaning work must be extremely detailed. Possibilities of toxic shock as well as potential risk of direct explosion are extremely high. All this has to be taken under consideration before special forces decide to remove or dig out abandoned weapons.

Without the doubt, neutralization of chemical weapons belong to the most dangerous and most expensive duties. This one fact alone is just enough to keep information (or at least to try) about the existence of such waste as a secret. It is not that difficult task - responsible institutions usually belong to military structures, where long tradition of maintaining the secrecy of possessing chemical weapons is widely approved and accepted. This type of weapons were always the most closely protected resources of any army. It would be highly inappropriate, should public and civilians recognize and perceive top military officials as treacherous poisoners.

history

World War I

World War I clearly demonstrated the deadly and destructive nature of chemicals in modern warfare. Both sides in the war experimented with novel forms of warfare, including chemical weapons. It is little wonder this war is known as the ‘‘chemist’s war’’. Initially, the French used gas grenades (though with little effect) and were followed by the Germans who used shells filled with tear gas. Germans appreciated application of chemical warfare for two reasons: the shortage of artillery shells and the ability to defeat the distant enemy's trench system. Germans released chlorine in April 1915 at Ypres, Belgium.

It did not take long for the British and French forces to respond in the same manner to the German offensive. In the fall of 1915 British introduced a modified mortar that could send gas-filled shells of chlorine or phosgene, the two agents of choice at that time.

Both chlorine and phosgene caused extreme respiratory problems to exposed soldiers. As the danger of chlorine and phosgene became diminished by the advent of gas masks, the Germans turned to dichlorethyl sulfide (mustard agent) against the British at Ypres.

As opposed to the gases, mustard (called Yperite) sticks persistently to the ground and contact avoidance is extremely difficult. It is worth noting that after almost 100 years, there have been no effective treatments for Yperite removal while research still continues.

By the end of the WWI, some 124,200 tons of chemical warfare agents (chlorine, phosgene, mustard, etc.) had been released, causing at least 1.3 million casualties of which more than 90,000 were fatal. Efficacy of Yperite was clearly evident: 1 ton of classic explosives caused 4.9 casualties; 1 ton of ammunition containing gases caused 11.5 casualties; and 1 ton of Yperite caused 36.4 casualties.

In this military conflict and subsequent wars in which chemical agents were used, neither systematic attempt was made to accurately describe the epidemiology of the exposures, nor were any accurate data established to follow the health of exposed population after the acute exposure. Concern regarding potential long-term effects of these exposures continued to be an issue. In 1975 a longitudinal follow-up study of the mortality experience of three samples of World War I veterans was conducted to determine if a single exposure to mustard gas with respiratory injury was associated with increased risk of lung cancer in later life. The risk of death from lung cancer among men gassed, relative to that for the controls was estimated as 1.3, with 95% confidence level.

Nearly 66 million artillery shells containing chemical weapons were fired during World War I. At least 40 different poisonous compounds were deployed. Now, nearly a century later, hundreds of World War I shells are being recovered annually from the European battlefields, mostly in Belgium and France. When the farmers find grenades, they call sappers to collect them. And so it goes on, generation after generation. The soil continues to produce grenades, buttons, buckles, knives, skulls, bottles, rifles, sometimes even a whole tank. The Great War seems to never end.

after World War I

Year 1922 saw the establishment of the Washington Treaty, signed by the United States, Japan, France, Italy and Britain. The Treaty prohibited the use of chemicals during the military conflicts. In 1925 the Geneva Protocol (signed by 16 major nations) prohibited use of asphyxiating toxic gases and bacteriological methods of warfare. This Protocol has become a cornerstone of chemical arms’ control since then. However it neither forbids the stockpiling nor the research on chemical weapons. At that time debate was initiated on the merits of treaties with nations balancing the military needs versus the potential irrational concept of chemical warfare. Terrible events of World War I convinced some groups of people and nations, that humanity had learned a lesson from the cruel nature of chemical warfare. Others prudently went to develop improved systems against chemical attacks. Many professional military officers were unconvinced that future wars would be fought without chemical warfare. They introduced policy of equipping armies with new types of gas masks, training on artificially contaminated lands was undertaken again.

Chemical agents were used to subdue rioters and suppress rebellions. In early 1920s the British used bombs containing chemical agents to suppress uprisings in Mesopotamia (modern-day Iraq). The Soviet Union used chemical agents to quell the Tambov rebellion in 1921, and France and Spain used mustard gas bombs to subdue the Berber rebellion during the 1920s. Italy and Japan used mustard in small regional conflicts. Lewisite and mustard gas were applied in Ethiopia, China and South-East Asia. Each conflict ended up as a success for poisoners. As a result, contemporary theory arrived, that chemicals are viable alternative to traditional combat.

In 1936, Gerhard Schrader, a German chemist working on the development of insecticides for IG Farben, developed a highly toxic organophosphate (OP) compound which he named ‘‘tabun’’. Between 1934 and 1944, Schrader’s team synthesized approximately 2,000 different OPs including two well-known OP compounds: parathion and paraoxon. As early as in 1935, the Nazi government insisted that Schrader focus on OP insecticides as a potential CWAs. Schrader cooperated manufacturing series of nerve - paralyzing gas compounds like sarin, tabun, soman. Production reached large industry scale. Germans were also the greatest producer of nitrogen mustard making about 2,000 tons of it.

World War II

At the onset of World War II, the Allies and the Germans anticipated return of chemical agents and their deployed on the battlefields. This expectation resulted in intensified research and development of new agents, delivery systems, and methods of protection. The Allied forces were unaware that at the beginning of the war that Germans had possessed new nerve agent called tabun. “Fortunately” the blitzkrieg tactic of advancing German armies offered very little opportunity to use chemical agents. Nevertheless, Germans produced and stockpiled large amounts of nerve agents throughout the war. Other chemical agents that had been produced during and following World War I were still being ready to use as well.

Germans did not use toxic agents on the battlefields, but instead, were killing prisoners in concentration camps. First they applied carbon monoxide, followed by the more ‘‘effective’’ hydrogen cyanide (insecticide Zyklon B, manufactured by IG Farben). Millions died in camps. Toxic gases helped to finish up the last standing defenders during the 1943 Warsaw Ghetto Uprising. Experiments were conducted on camps' prisoners, trialing mustard gas, phosgene and certain biological agents.

In the pre-war years Germans erected several manufacturing sites in USSR; production of gases was carried out in Chapayevsk, Stalingrad (Volgograd), Dzerzhinsk, Berezniki and Stalinogorsk (Novomoskovsk) - 110,000 tons of first generation toxic chemicals were produced between 1940-1945 and most of them were yperite, lewisite, and irritating agents. By the end of the war, chemical munitions had been charged with imported yperite in Kirovo-Chepetsk facilities. During the prewar years, manufacturing sites in Kemerovo, Yaroslavl, Moscow and few other, attempted to plan and start production of yperite. Large-scale industrial production of TC was organized in the Volga basin, although numerous attempts to expand the localizations are known. Chemical weapons were produced mostly along the shores of deep unpolluted rivers: Volga, Oka and Kama. Clean water was needed for production needs, as well as for waste dumping.

after World War II

At the end of WWII, many Allied nations seized the chemical weapons from Germans. The captured chemicals, total around of 300, 000 tons, were dumped into the seas. This would prevent any attempts by Germans to release it again.

It is known that Russians captured stockpiles of 12,000 tons of tabun, 600 tons of sarin, and an unknown amount of soman in Dyhenfurt (now city of Brzeg Dolny), few kilometers north of Breslau (Wrocław). Presumably, the factory was dismantled and along with it's deadly load, transported back to the Soviet Union. Soviets, apparently, were getting ready for the next world conflict, prioritizing CW's R&D. The Soviets began consecutive production of sarin gas in 1958-59, soman in 1967, and VX gas in 1972. During the most intensive production activities, 60,000 scientists and engineers were employed. Numbers of auxiliary personnel went of course much higher.

For example, city of Shikhany was secretly divided into two centers after World War II, one of them civilian, another military. The military site alone housed 12,000-15,000 civilians and 60,000 military personnel, most of them engaged in production of military agents. Stockpile of toxic compounds in 1980s reached tens of thousands of tons. There is a strong evidence that Egypt used Soviet-supplied chemicals during the 1967 counterinsurgency war in Yemen. Iraq used blistering and nerve agents in its war with Iran and against the Kurds during the ’80s. However, there is no clear evidence whether these agents came directly from USSR or were manufactured with the help of Soviets.

By the early 1950s, production of sarin had been initiated in the USA. At nearly the same time, Ranajit Ghosh, a chemist at the British Imperial Chemical Industries plant, developed a new organophosphate extremely toxic compound as a potential insecticide. The compound was sent to researchers in Porton Down, England, synthesized and developed as a first of a new class of nerve agents called ‘‘V’’. Agents ‘‘V’’ have a second letter designation: VE, VG, VM, and VX. Of these agents, VX is the most commonly produced. The ‘‘V’’ agents are generally much more toxic than the sarin ‘‘G’’ agents. In a deal brokered between the British and US governments, the British traded the VX technology for USA thermonuclear weapons technology. The USA produced and stockpiled large quantities of VX.

At the same time, Americans became interested in developing CWs capable of incapacitating humans instead of killing. Mescaline and its derivatives were studied but without practical output. Five years later, a new project for K-agents was established. Psychotropic drugs like LSD-25 and tetrahydrocannabinol were studied. However none of these agents were found to be of military importance. The first and only incapacitant was BZ, developed in 1962; however, its stocks destroyed in 1992 as declared by the US delegation during the Conference on Disarmament in Geneva.

existing arsenal

The existing world's arsenal of chemical weapons consists of two categories:

• - ready to use bulk storage of chemical warfare (CW) agents in military magazines and holding tanks as well as acumulated ammunitions containing toxic agents, and
• - buried chemical material, binary chemical weapons, recovered undetonated munition, former facilities for chemical weapons production, and other miscellaneous chemical warfare materials.

The stockpile of unitary chemical warfare agents and ammunition

Egypt: First country in the Middle East to obtain training, chemical weapons as well as indoctrination. It employed phosgene and mustard agents against Yemeni Royalist forces in the mid-1960s. Some reports claim, Egypt used an organophosphate nerve agents in addition.

Israel: Developed its own offensive weapons program - research facility is located in the Negev desert.

Syria: It began developing chemical weapons in the 1970s. Syria received first chemical weapons from Egypt in the 1970s, and started production in 1980. It allegedly has a 500-kilogram aerial bombs, and chemical warheads for Scud-B missiles. There are two chemical munitions storage depots: at Khna Abu Shamat and Furqlus. Centre D'Etude et Recherche Scientifique, near Damascus, was the primary research facility. Factory of new chemical-weapons is located near the city of Aleppo.

Iran: Initiated a chemical weapons program in response to Iraq's use of mustard gas against Iranian troops in 1980s. At end of this war, Iran possessed ammunition containing mustard and phosgene. in addition to artillery shells and bombs filled with chemical agents as well as ballistic surface-to-surface missiles equipped with chemical agent filled warheads.

Iraq: Used chemical weapons repeatedly during the Iraq-Iran war. Later attacked Kurdish villagers in the North part of the country, dropping bombs containing mustard and nerve gas. Since the end of Gulf War UN had destroyed more than 480 tons of chemical agents and 1800 tons of production ingredients.

Libya: Obtained its first chemical agents from Iran, using them against Chad in 1987. Opened its own production facility (100 tons/year capacity of blistering and paralyzing gases) in Rabta in 1988. Second facility is being under construction in an underground location at Tarhunah.

Saudi Arabia: obtained 50 CSS-2 ballistic missiles from China. These highly inaccurate missiles are thought to be suitable only for delivering chemical agents.

North Korea: Has been developing its own , probably largest in the region, program since 1960s. Can produce "large quantities" of blister, and nerve paralyzing gases.

South Korea: Has the chemical infrastructure and technical capability to produce chemical agents, has a chemical weapons usage program.

India: Has CW stocks and its usage program.

Pakistan: Has artillery projectiles and rockets able to carry chemicals.

China: Has a mature chemical warfare capability, including ballistic missiles.

Taiwan: Established an aggressive high-priority CW program to develop both offensive and defensive capabilities. This has yield full ability to be operational in 1989.

Burma: Its program and military equipment (similar to Pakistan), under development since 1983, may still be active.

Vietnam: this country was ready of deploying, or already had chemical agents. Also it captured large stocks of tear gases left behind by Americans.

Yugoslavia: The former Yugoslavia had a CW production capability. Produced Sarin, sulphur mustard, BZ (a psychochemical incapacitant), and irritants CS and CN as well as necessary armament to drop them. The Bosnians produced crude chemical weapons during the 1992-1995 war.

Romania: Has research and production facilities (including cheaper method for synthesizing Sarin), and chemical weapons stockpiles and storage facilities.

Czech Republic, Slovakia and Poland: WW II found Germans concentrating production and chemical weapons arsenal there. During the Warsaw Pact membership all three countries participated in the preparation for the invasion of NATO countries, using strategy involving CW. They had factories for poison paralyzing gas production, related chemical weapons, and extensive network of warehouses for storage. After regaining independence, and prior to the CWC, these countries supposed to get rid of chemicals and production facilities. However, officially, details of this process are unknown.

Bulgaria: Has stockpile of chemical munitions of Soviet origin.

France: Has stockpile of chemical weapons, including aerosol bombs.

USA: Has the second largest arsenal of chemical weapons in the world, consisting of ~31,000 tons of toxic chemicals, and 3.6 million grenades. The chemical weapons contain about 12,000 tons of agents, and 19,000 tons are in bulk storage. As of 23 September 2007, the United States has destroyed only 47.9% of its original stockpile.

Russia: declares its stockpile in 1993. It is ~40,000 toxic and poisonous agents in storage tanks. It is 30,000 tons of phosphoric organic agents (Sarin, Soman, VX), the remaining 10,000 tons are 7,000 tons of Lewisite, 1,500 tons of mixed mustard gas and Lewisite, and 1,500 tons of mustard gas. Riddance operation of this deadly tonnage was divided by Convention deadline into three stages. In the first stage, 400 tons, or 1% of Russia’s stockpiles, had been destroyed by April 29, 2003. In the second stage, 8,000 tons, or 20% of Russia’s stockpiles, have been destroyed by April 29, 2007. No data exists on remaining 80%.

The non-stockpile material

Here information is hard to collect and scarce. All the materials recovered from underground in the US, contains hundreds of tons. A considerable amount of money will be required for the destruction of all former facilities for chemical weapons production, particularly factories constructed or used after January 1, 1946. Abandoned chemical weapons do represent a huge safety risk. Between 1985 and 1995 Dutch fishermen reported more than 350 places where chemical weapons were dumped into the Baltic Sea. Fishing nets caught deadly cargo, some of it resulting in serious burns. In China during World War II, the Japanese left 678,729 units of chemical weapons. Recent negotiations resulted in Japan's agreement to collect and destroy these weapons.

The most persistent agents - sulfur mustards - can and will remain dangerous for decades. Recovery of ammunitions from WWI still continues. In France, annual collection amounts to about 30-50 tons along the old front line, in Belgium to 17 tons (circa 1,500 items). Conservative estimation predicts tonnage of useless chemical weapons at total of roughly 500,000 tons, to be neutralized and destroyed. Traditional munitions must be taken apart and separated from the chemical agents. The cost of munitions' disassembly can outrun 10-20 times the cost of toxins' neutralization. The US choose high-temperature incineration and chemical neutralization as its preferred destruction technique, though scale of these processes is limited.

Chemical Weapons Convention

As of September 2008, 184 countries have ratified or acceded to the CWC. This Convention prohibits production, storage and employment of CWs. The Technical Secretariat (TS) of the Organization for the Prohibition of Chemical Weapons (OPCW) is located in Hague. It admits declarations from countries that signed the CWC and at the same time carries out onsite inspections of military and civilian chemical facilities in relevant locations. Licensed international inspectors, or teams, have permits for inspection of any sites where illicit activities are suspected. The CWC requires every party to destroy all chemical weapons it owns or possesses, or chemicals that are located in any place under party's jurisdiction.

The Convention requires that chemical weapons be destroyed in ‘an essentially irreversible way in order to render it non-toxic and unsuitable for conversion to any chemical weapons in the future’. No quantitative minimum threshold of destruction efficiency has apparently been agreed. But it would seem that 99.99 per cent is the minimum acceptable level of destruction efficiency for which there is consensus among delegations. 

Under the CWC, the direct costs of verification are borne by the inspected State Party under the general principle that ‘the possessor pays’. Costs not incurred as a direct result of an inspection are covered by the OPCW as a whole. In the case of abandoned CW, the Abandoning State Party (ASP) pays for the direct costs of international verification. In cases where there is no State Party or Territorial State Party (the State Party which has had ACW left on its territory), the direct costs of international verification would probably have to be borne by the all OPCW States Parties according to the UN scale of assessment (some of the costs could perhaps be offset by the establishment of a special fund). Such a situation may exist in cases where CWs have been dumped in the high seas.

Underwater dumping has been carried out throughout the world on a very large scale; much of the details on where and how it was carried out remain uncertain and will probably will not change. An important principle reflected in the provisions of the CWC is the proper allocation of rights and responsibilities of the States Parties. However, determining who is responsible for the destruction of dumped CW is potentially problematic. In the case of the Baltic Sea, most of the ammunitions (conventional and chemical) appear to be of German origin. Fact though remains, these weapons were not under the jurisdiction or control of Germany when they were dumped. Having this in mind, it would not be reasonable to place too many financial and administrative burdens on those states in the region that might wish to participate in the recovery or remediation of dumped CW. Any such activity should be carried out in a reasoned and balanced manner. Nor should any state be compelled to participate in such operations.

dumping

Dumping was carried out on a global scale. As WW II ended, armies of more than a dozen countries kept unloading its chemical weapon stockpiles. There are more than 100 sea dumping sites used between 1945 - 1970. 46,000 tons were dumped in the Baltic areas known as the Gotland Deep, Bornholm Deep, and the Little Belt. The Continental Committee on Dumping obliged US with 93,995 tons, France with 9,250 tons, Britain with 122,508 tons, and Russia with 70,500 tons: all this, found and collected on German territories. The US dumped 40,000 tones: nine ships in the Skagerrak Strait and two more in the North Sea at depth of 650 to 1,180 meters. Between 1945 and 1949, the British dumped 34 shiploads carrying 127,000 tons of chemicals (containing 40,000 tons of mustard gas) and conventional weapons in the Norwegian Trench at 700 meters depth. The Russians dumped 30,000 tons in the Gotland and Bornholm Islands area of 2,000 square kilometers in size. Furthermore, the US is additionally responsible for 60 sea dumpings totaling about 100,000 tons of chemical weapons filled with toxic materials: in the Gulf of Mexico, off the coast of New Jersey, California, Florida, and South Carolina, and near India, Italy, Norway, Denmark, Japan, and Australia.

The following known US Army dumps (sinking) of captured German chemical warfare agents include:

1945 July 1: An estimated 1,349 tons of unidentified chemical munitions,were sunk on "Sperrbrecher" under 2,100 feet of water in the North Sea. On the same day, a ship called T65 filled with 1,526 tons of captured chemical munitions was sunk under 2,100 feet of water, .
1945 Dec. : The Army dumped 11,000 tons of nerve gas, 4,000 tons of mustard gas and 66,000 tons of either mustard gas or phosgene gas. Water depth is unknown.
1946 July 2: About 671 tons of unidentified chemical weapons on "UJ305" were sunk under 2,100 feet of water.
1946 Aug 30: "James Otis"was scuttled. It contained an estimated 3,653 tons of unidentified chemical warfare agents. The load rests under 2,100 feet of water.
1947 June 6: An estimated 4,000 tons of unidentified chemical munitions were loaded on "James Swell"and sunk under 2,300 feet of water.
1947 June 30: 3,000 tons of unidentified chemical munitions were sunk on "James Harrod" under 2,200 feet of water.
1947 June 30: 1,000 tons of unidentified chemical munitions were sunk on "George Hawley" under the depth of 2,200 feet of water.
1947 July 18: About 6,000 tons of unidentified chemical munitions were sunk loaded on "Nesbit" at the depth of 1,900 feet of water.
1948 July 24: Between Scotland and Norway, ship "Philip Heiniken" was sunk with 2,000 tons of unidentified German chemical munitions at the depth of 3,400 feet of water.
1948 Aug. 24: Ship "Marey" loaded with estimated 2,500 tons of unidentified German chemical munitions, was scuttled landing at the bottom under 3,900 feet of water.
 

The US Army and the British dumped an estimated 170,000 tons of captured German mustard and nerve gas in the Skagerrak area of the North Sea, a relatively narrow strait that separates Norway and Denmark. Much of the chemical ordnance was sunk in 33 German ships, part of Operation Davy Jones Locker.

- After World War II, the US Army dumped an unknown quantity of phosgene and hydrogen cyanide bombs near the west coast resort island of Ischia. The material was loaded at Italian ports under Army control and dumping occurred from Oct. 21 to Dec. 15, 1945.
- Over two weeks in April 1946, the Army disposed a load of U.S.-made mustard gas and Lewisite bombs near Ischia. The number of bombs and exact location where, have never been determined. The bombs were shipped for disposal from Auera, Italy.
- An unknown number of 100-pound mustard filled bombs were dumped in the Mediterranean Sea off Italy after World War II.
- A barge, sailing from La Serpe to Manfredonia loaded with 100-pound mustard gas bombs, either sank or listed enough to dislodge some of its load close to Adriatic Sea east coast. A few weeks later, some of the bombs were recovered, the barge reloaded and the shipment thrown overboard again at another unknown location.
- Near the end of WW II, somewhere near Naples, the Army dumped 13,000 mustard gas mortar rounds and artillery shells, as well as 438 55-gallon drums of mustard agent. The Army doesn't know exactly where that dump zone is.
- 1,700 mustard gas bombs were dumped by US Army in the Mediterranean Sea somewhere off St. Raphael (French Riviera) during the time of July to October 1946. It’s unclear whether they were of U.S. or French manufacture.
- In 1943, unknown quantities of mustard gas bombs were thrown over the side of an unidentified ship at the depth of mere 250 feet of water near the coast of Karachi.
- From May 10 to 12, 1945, 16,000 mustard gas bombs were dumped around the coasts of India, Pakistan or Bangladesh. Bombs were stored at Ondal Advance Chemical Park in India during the World War II. Involved in dumping were ships USS "George B. Porter" and USS "O.B. Martin". The ships were under orders to dump their loads at least 60 miles offshore at the depth of at least 5,000 feet of water. Dumping location is unknown.
- The US Army recorded other dumpsites in the Bay of Bengal in May 1945, but it is unclear whether it is just one site or more . Thrown overboard were 9,000 100-pound mustard gas bombs; 2,400 500-pound phosgene gas bombs; 8,700 1000-pound phosgene bombs; and 2,500 1,000-pound cyanogen chloride bombs; 608 55-gallon drums of mustard agent; 2,600 1-ton containers of mustard agent and 883 1-ton containers of Lewisite.
- An unknown number of 100-pound mustard gas bombs were dumped in Manila Bay from the USS "Tilly" in December 1941. The bombs had been stored at Fort William McKinley in the Philippines and dumped by order of the Army's Ordnance Department. The exact location is unknown. They haven't been found to this day, to the Army's knowledge. The average depth of Manila Bay is just a 55 feet.
- About 500 kg of white phosphorous shells of unknown caliber were dumped together with six 1-ton containers of chlorine in Mariveles Bay in 1942. Japan invaded the country at the close of 1941, so the Weapons might have been dumped to keep invading Japanese from capturing it. Mariveles Bay, at the southern tip of Bataan, is also shallow and has long been dredged for oysters.
- The U.S. ship "Robert Lesley" unloaded an unknown number of leaking mustard gas bombs near Asuncion (Philippines) in October 1945.

As in Germany, captured Japanese chemical ammunition was dumped off its coast after World War II. On top of it, The US Army sent several shipments from U.S. West Coast bases for disposal near Japanese coast. The Japanese government designated eight areas as a chemical sea dumps, that either the Japanese or U.S. military use. During the last 50 years, at least 52 people have been injured just at one dumpsite. Known U.S. dumpsites contain:
- 3,200 tons of unspecified chemical agents, probably part of a captured Japanese stockpile, off the Japanese coast.
- On March 06, 1946, one 150-pound chlorine cylinder was dumped near the Japanese coast from S.S. "Eugene Skinner" en route from Washington state to Yokohama.
- More than 1 million Japanese chemical smoke candles and 191,000 cans of mustard gas imitation were dumped at sea by US Army permission in 1946.
- Between May 8 to Nov. 30, 1946 Americans dumped at least 3,200 tons of presumably captured mustard and Lewisite warfare agents at the sea bottom.
- The Army emptied its chemical weapon depot near Brisbane in 1945 and dumped it all 20 miles off the island of Cape Moreton at the depth of 600 feet of water. Over a three-month span, thrown overboard were at least 8,000 tons of mustard gas containers, 8,000 tons of Lewisite containers, 8,000 tons of artillery shells filled with unidentified chemical warfare agents and 6,400 tons of unidentified toxic “projectiles." Australian government indicates this area on nautical charts as hazardous for shipping traffic.
-In September 1945, more than 4200 tons of "toxic artillery ammunition'' were taken from Guadalcanal. S.S. "Louis A. Sengteller"dumped all this somewhere near Noumea, New Caledonia.

During the 1950s, the US conducted an ambitious nerve gas program, manufacturing what would eventually total 400,000 M-55 rockets, each capable of delivering a 5 kg of Sarin. Many of those rockets had manufacturing defects, specifically unstable and self igniting propulsion fuel. For this reason in 1967 and 1968, 51,180 nerve gas rockets were dropped 240 km off the coast of New York State at the depth of about 2000 meters, and off the coast of Florida.

environmental clean up and recovery of CW

High safety precautions must be applied during recovery and handling of the old chemical munitions from the land. Over the period of decades, the munitions bodies have corroded, the agents and explosives inside might have been partially degraded or decomposed and the condition of fuses and ignition charges are unpredictable.

Sank chemical munitions present an additional element of unpredictability. This is because the potential impact that seawater might have on these old munitions, is still not clearly understood, particularly impact on decomposition of CW agents and the associated explosive material as well as dynamics of these processes. From a practical point of view, it may be desirable to distinguish the following possibilities:

(a) the chemical munitions shell's body is not damaged;
(b) the shell's body is partly corroded and its content , agent or/and explosive is partially in contact with sea water;
(c) the shell is completely corroded and its content flooded with sea water.

Next step involves inspection of fuses, ignition sytems and charges. Theirs possible conditions may be as follow:

(a) degraded/decomposed over the years,
(b) in contact with the chemical warfare agent, and reacted, depredated or decomposed as a result of this,
(c) remaining still active or
(d) partially reacted with the shell's body.

Taking into account the chemical warfare agents present in the munitions being dumped after WWII into the Baltic Sea (these have been mainly S-mustard, arsine-oil, phosgene/diphosgene, Clark I and Clark I, Adamsite, chloroacetophenone , tabun and N-mustard, and small amounts of lewisite), there is a priority need to examine the properties of these agents. Their behavior, decomposition and degradation will depend on local water conditions surrounding particular toxins. Specifically we may list here:

(a) temperature,
(b) pH-value,
(c) salinity,
(d) pressure,
(e) current velocity and
(f) chemical composition and corrosive activity of water.

As for chemical agents, there are additional factors to be considered such as:

(a) solubility,
(b) content of impurities,
(c) stability and
(d) reactivity.

It should also be noted that the CWC allows for multiple solutions for recovery and destruction of sea-dumped CW. The first ten years of the CWC have shown that the approach applied for sea-dumped CW has not been practical. No major recovery operations have been performed. If there was real need to conduct such recovery operations on sea-dumped CW in the future, the concerned states should clarify all necessary aspects before starting the recovery and destruction operations, including technical approach, cost and legal aspects. Dumped CW have rested in the sea for many decades. Having hands on them again, will increase the potential dangers and threats. The longer the dumped materials remain at the bottom, the greater the deterioration. Without having the resources available to destroy immediately recovered sea-dumped CW materials immediately, a state should not perform such recovery operations. Storage of the recovered material is not a practical solution because it creates more threats to human and environmental safety. A fundamental difficulty is whether doing ‘nothing’ is preferable to doing ‘something’. In majority cases public opinion will always support some type of action to be taken. However public pressure cannot be taken seriously without ability to instant and complete destruction of sea-dumped CW right on the spot.

toxic chemical agents

a. Classification.
A toxic chemical agent is any chemical which, through its chemical action on life processes, can cause death, temporary incapacitation, or permanent harm to humans or animals. Chemical agents are further divided into chemical warfare (CW) agents and military chemical compounds. The terms “persistent” and “non-persistent” do not classify the agents technically. They describe lengths of time for chemical agents remaining active in the particular area.

(1) CW Agents.
The CW agents are toxic chemicals and their precursors prohibited under the CWC. These agents include choking, nerve, blood, blister, and incapacitating agents. Their physiological actions are as follows:

(a) Choking Agents.
Choking agents cause damage to the lungs, irritation to the eyes and the respiratory tract, and pulmonary edema (“dry-land drowning”).
(b) Nerve Agents.
Nerve agents affect and deactivate cholinesterase (ChE) enzymes. This inhibition permits acetylcholine (ACh), which transmits many nerve impulses, to accumulate excessively in various sites of action. The body’s muscles and glands become over-stimulated due to excessive amounts of ACh. At sufficient doses, this can lead to inability to sustain breathing.
(c) Blood Agents.
The blood transports these agents to all body tissues. Hydrogen cyanide (AC) and cyanogen chloride (CK) are cellular poisons, and they disrupt the oxidative processes used by the cells. Arsine (SA) is different. It causes hemolysis of the red blood cells. The central nervous system (CNS) is especially vulnerable to lack of oxygen. Respiratory tract and cardiovascular system collapse. In the case of SA poisoning, the proximal cause of death is myocardial failure.
(d) Blister Agents (Vesicants).
Blister agents are noted for producing reddening and blistering of the skin, but the eyes and respiratory tract are more sensitive than the skin. Eye exposure results in reddening of the eyes and temporary/permanent blindness. Inhaled mustard damages mucous membranes and the respiratory tract.
(e) Incapacitating Agents.
Incapacitation leads to inability to perform any military task effectively. An incapacitating agent is an agent that produces temporary physiological or mental effects rendering such conditions.

(2) Military Chemical Compounds.
Military chemical compounds are less toxic and include respiratory chemical irritant agents, RCAs, smoke releasing and incendiary materials. They belong to CW agents but some of them may not be officially classified. Their physiological actions are as follows:

(a) RCAs (Lachrymators)
produce rapid irritation of humans sensory and disabling physical effects that disappear within a short time following exposure. They are rather local irritants that, in very low concentrations, act primarily on the eyes, causing intense pain and tearing. At high concentrations they irritate the respiratory tract and the skin. They sometimes cause nausea and vomiting.
(b) Respiratory Irritant Agents.
These agents were previously called vomiting agents. Their primary action is irritation of the respiratory tract. In addition, these agents cause lacrimation (tearing), irritation of the eyes, uncontrollable coughing, sneezing, nausea, and a general feeling of bodily discomfort. Usually symptoms disappear in 20 minutes to 2 hours, leaving no residual injury.

b. Duration of Effectiveness.
Several factors determine how long chemical agent remains effective. These include, (but are not limited to): the method of dissemination, weather and terrain conditions, and the physical and chemical properties of the agent.

(1) Method of Dissemination.
Chemical agents are usually disseminated in the form of vapors (gases), aerosols, or liquids. When a chemical agent is disseminated as a vapor from a bursting munitions, initially the cloud expands, grows cooler and heavier, and tends hang above the ground retaining its form. Aerosols are finely divided liquid and/or solid substances suspended in the atmosphere. Liquid can be absorbed (soaked into) and adsorbed (adhered to) by surfaces. Then evaporation may follow causing a vapor hazard.

(2) Weather and Terrain Conditions.
Most important weather factors include temperature, temperature gradient, wind speed, relative humidity, and precipitation. Important terrain conditions include vegetation, soil, and terrain topology.

(3) Physical Properties.
Some of the important physical properties are vapor density, vapor pressure (VP), volatility, freezing point (FP), and melting point (MP). Vapor density determines if the agent is lighter or heavier than air. This consequently determines whether the agent will drop down to the lowest areas or float away and dissipate in the atmosphere. Vapor pressure is used to determine the volatility of an agent. The volatility affects vapor concentration. It also affects the time during particular agent remains hazardous after dissemination. The boiling and freezing points influence operational use and the means of disseminating selected agents.

(4) Chemical Properties.
The chemical properties of an agent include its stability and reactivity with water and other substances.

c. Potency and Physiological Actions.

Damaging health effects of chemical agents include: toxicity, route of exposure (ROE), dosage, exposure duration, minute volume (MV), temperature, end point, physiological stressors, rate of detoxification (ROD), and rate of action (ROA). Note that not all factors are applicable at the same time during the exposure. For example, MV is not applicable to a percutaneous liquid exposure. Dosage is given assuming 70-kilogram (kg) male with air’s MV of 15 liters per minute (L/min). Approximations for women and children require additional toxicological data. Emphasis is placed on acute toxic effects. Acute toxic effects are those occurring between initial and lasting to a few days toxic exposure. Thus the provided acute toxic effects are not applicable to the general population.

d. CWC Chemicals.

There are, by conservative estimates, 25,000 or more chemicals that are subject to the CWC regulation. Chemicals covered under the CWC are divided into three categories as follows:

(1) Schedule 1 chemicals that have little or no use in industrial and agricultural industries. They pose a high risk by virtue of their high potential for use in activities prohibited under the CWC.
(2) Schedule 2 chemicals may be useful in the production of chemical weapons; however, they also have legitimate uses in other industrial areas. They pose a significant risk to the object and purpose of the CWC.
(3) Schedule 3 chemicals have legitimate use in industrial areas and pose a risk to the object and purpose of the CWC.

e. Dual-Use Precursors.
Precursors for CW agents also have civil uses in industrial and agricultural industries.

f. CW Agents and Other Military Chemical Compounds.

g. Agent Mixtures.
Mixing chemical agents with each other or with other selected materials can alter the characteristics and effectiveness of the particular agents or mixture. Mixtures may attain lower freezing point and increased effectiveness over a wider range of temperatures. The addition of thickeners or thinners to agents will increase or decrease it’s persistency: for example, Soman (GD) mixed with thickeners will gain persistency; RCAs mixed with thinners will decrease persistency. In addition to changing the physical properties, mixing agents together will create special problems through their physiological effects. Mixing will produce difficulty in identification. Unpredictable, immediate and delayed effects, simultaneous hazardous contact with vapor and liquid may occur. Some mixtures make it difficult to maintain the protective masks‘ fittings and tightness. Mixing some agents can also boost up their toxicity, either due to synergy effect or by speeding absorption through the skin.

mustard agents (yperites)

Large volume production of this group of poisons is dated from the time of the First World War. Sulfur mustard was produced by all countries involved in World War II. After this war, unused stocks of Yperites were disposed by sinking in the sea or buried in the ground. It is estimated that USSR "neutralized" by this way more than 100,000 tons of Yperites sealed in containers, in mines, bombs and missiles. The same “methods“ have been employed by United States, Britain, Japan and France. Due to the remarkable stability of mustard gases in the aquatic environment, Yperites will retain its toxic potential for the next tens and hundreds of years.

Contact with mustards is a threat to all living creatures. Mustards were tried as a therapy for fast growing tumors, however it was quickly discovered that these attempts result in an even more forms of cancer and death of patients. Trials have been abandoned. Mustards belong to external agents that cause mutation and exogenous damage of DNA cells, similar to damages by X-rays and gamma rays. For this reason, mustards are used in genetic engineering to create a stochastic cell mutations. Presence of mustards in the environment may play a similar role and lead to the emergence of previously unknown strains of bacteria and viruses.

Distilled mustard and purified agent H is called HD. Distilled sulphur mustard is an oily liquid, colourless and odourless in its pure form. If it contains small quantities of impurities, it is yellowish and having a characteristic odour resembling oil of mustard, hence the name mustard gas. During WWI and WWII, other types of mustard agents were used in munitions, like agent Q and agent T shown in figure.

Munition grade HQ is a mixture of 75% HD and 25% agent Q, whereas HT contains typically 60% HD and 40% agent T. Later on, mainly distilled agent H has been used.

Hydrolysis of sulphur mustard

When solved in freshwater, HD easily hydrolyses with a half-life of 4-8 min at 25 °C, giving thiodiglycol (TDG) as the main product. The first step in the hydrolysis process is a neighbouring group nucleophilic attack of the sulphide to form a sulphonium ion intermediate. The sulphonium ion then reacts quickly with water to form 2-chloroethyl 2-hydroxyethyl sulfide (hemimustard).

The hemimustard can react in the same way, eventually leading to TDG.

Two other common degradation products of HD are the cyclic sulphur compounds 1,4-thioxane and 1,4-dithiane. 1,4-Thioxane is formed from an internal displacement of the hemimustard sulphonium ion.

The formation of 1,4-dithiane occurs from degradation of sesquimustard (Q). Q can form a 6-ring sulphonium chloride through an internal reaction, which forms 1,4-dithiane upon attack by the chloride ion.

Q can be formed from degradation of HD, or be present as an impurity. In addition, Q can be present as an additive in what is known as munition grade HQ.

In addition to the compounds discussed above, HD can form a variety of degradation products, both cyclic and open longer chain compounds. A range of intermediate sulphonium ions can react with water, with other HD molecules, or through internal reactions. Furthermore, both HD and many of the hydrolysis products can be oxidized to sulphoxides or sulphones. One example is soil samples taken from a Kurdish village in Iraq in 1988. HD and 22 different degradation products were found in the soil. Chunk of old munition grade mustard that was retrieved from the Baltic Sea dumping site, revealed 16 new different degradation or contaminating compounds. Likewise, analyses of abandoned munition grade mustards in China showed traces of HD and 27 new related compounds of degradation.

Sulphur mustard has low aquatic solubility, and chunks of HD can stay intact at the sea bead for several decades after the artillery shell corroded. Accidents have been reported both in the Baltic Sea and along the coast of China, involving fishermen who caught mustard agent with their nets; large tonnage of abandoned chemical weapons have been left there during Japanese retreat in the closing stages of WWII. It has been estimated that abandoned CWA in China have caused 2,000 casualties or fatalities since the end of the war. Examples of such incidents are construction workers digging beneath city streets or riverboat workers who scooped up CWA from the water during dredging operations. Many of the casualties are associated with mustard agents or with mixtures of mustard agents and lewisites.

Toxicity of sulphur mustard

As HD appears as an oily liquid at room temperature, the name mustard gas is somewhat misleading. However, the vapour pressure and toxicity above even the small liquid amount are sufficient to become dangerous. Skin, eyes and the respiratory system are the principal target of HD. Skin effects caused by HD vapour depend on ambient temperature and moisture as well as length of exposure. Blisters generally appear 18-24 hours after exposure, and they often contain large volumes of fluid. Erythema appears within 2-4 hours and causes extreme itching, which diminishes as the blisters appear. Eye exposure causes intense irritation with watering, conjunctival swelling and erythema. Inhalation of HD causes damages to the respiratory system, vomiting and diarrhea. HD is classified as a human carcinogen by the International Agency for Research on Cancer. Two examples of injuries caused by HD exposure are shown in figure. The left picture shows an Iranian soldier exposed to HD in the Iran-Iraq war. He was treated for mustard agent burns in a Swedish hospital. The other picture shows a Baltic fisherman, exposed to HD from old ammunition brought up from the water by a fishing net.

Number of individuals work for organizations created due to existence of Chemical Weapons Convention. They clean and decontaminate storage depots, demilitarization facilities, or research laboratories; consequently they face potential risks of inadvertent exposure to many agents. To a much lesser degree, this risk is also shared by the general population in communities surrounding areas where chemical agents are stored, transported, or processed for disposal. The most likely route of exposure to sulfur mustard is by skin or eye contact, or by inhalation of the aerosol or vapor.

CDC has released exposure limits (AELs) for sulfur mustard in the air - for example:
- 0.003 mg/m³ for an 8-hr/day, 5 day/wk work intensity;
- 0.0001 mg/m³ for the general population, assuming 24 hr/day, 7 days/wk continuous exposure.

If HD is not found by sampling, the next step would be to search for its most common degradation products, like TDG. However, this compound is used in the manufacture of several commercial products including pulp and paper, paints, coatings and furniture. Thus, traces of TDG in the environment could originate from there. Therefore, several of the common degradation products should be identified to give a reliable and trustworthy verification for the presence of HD.

arsenic agents

These compounds and their organic derivatives were produced as well; the quantities assessed to be not less than Yperites. Only small amounts of these poisons were used during the wars. Inventories, unfortunately, have not been liquidated properly and they still endanger the environment. Chemicals from this group react easier with moisture, and final products of hydrolysis are inorganic arsenic compounds. Consequently, arsenic compounds located on the seabed, systematically contribute to increase of the concentration of toxic substances. Even small doses of arsenic can cause genetic changes. Sea food collected from the contaminated areas poses a health risk and should be eliminated from the commercial market. Losses in the ecosystem may be even far more serious. Expansions of the “death zones” around sunk chemical weapons represent the difficulties for marine organisms in adapting to abnormally elevated concentrations of arsenic.

Lewisite

In pure form, lewisite is colorless and odorless, usually occurs as a brown oily liquid with a distinct geranium-like odor. There is an odor threshold of 14–23 mg/m³ for lewisite. There are three types of Lewisite - they differ in toxicity and necrotic strength. The light burning of the skin changes into the blisters quite fast. At the dose of 0,2 mg/cm² cherry red blisters appear after several hours. Then the blisters burst after 2 -3 hours leaving vast open wounds. Dermal or intravenous exposure to lewisite leads to local skin edema and pulmonary edema due to increased capillary permeability. The increased capillary permeability results in blood plasma loss and resultant physiological responses collectively referred to as ‘‘lewisite shock’’.

It has been hypothesized that functional changes in the lungs, kidneys, respiratory tract, cardiovascular, and lymphatic systems may be caused by a disturbance of osmotic equilibrium. Fatalities following dermal exposure to lewisite may be due to blood plasma loss resulting from extensive capillary damage. An oral dose of as little as 2 ml (equivalent to 37.6 mg/kg) may be fatal within several hours. Attacked organs include liver, gall bladder, urinary bladder, lung, and kidneys; this possibly due to Lewisite interactions with proteins’ thiol groups. Arsenic interactis with enzymes’ sulfhydryl groups, this in turn may cause inhibition of the enzyme. In summary, these thiol interactions result in energy depletion of the cell, leading to cell death.

Information regarding the atmospheric degradation of lewisite, is limited. Some the photo-degradation may take place and accelerate when hydrolysis occurs in the gas phase. Lewisite is not readily soluble in water; 0.5 g/L. Hydrolysis of lewisite occurs rapidly yielding lewisite oxide and hydrogen chloride. It is a complex reaction and includes several reversible stages. Under acidic conditions, lewisite initially undergoes rapid and reversible conversion to dihydroxy arsine, 2-chlorovinyl arsine oxide and two equivalents of hydrogen chloride. The completion of the reaction requires several hours. Hydrolysis of 2-chlorovinyl arsine oxide is slower, resulting in lewisite oxide and polymerized lewisite oxide; both not soluble in water. In a basic solution, the trans-lewisite isomer is cleaved by the hydroxyl ion to give acetylene and sodium arsenite; this reaction may occur even at low temperatures.

Contacting water, the toxic trivalent arsenic of lewisite oxide is converted to the less toxic pentavalent arsenic. Lewisite in soil may rapidly volatilize or may be converted to lewisite oxide due to moisture in the soil. The low water solubility suggests long term persistence in the moist soil. Both: lewisite and lewisite oxide slowly oxidize to 2-chlorovinylarsonic acid. Microbial degradation in soil includes epoxidation, dehydrohalogenation and reductive dehalogenation. Due to the epoxy bond incorporated into arsine group, toxic metabolites may result. Additionally, residual hydrolysis may result in arsenic compounds. Lewisite is not likely to bioaccumulate. However its degradation products may bioaccumulate. Presence of arsenic tolerating bacteria can be used as a pollutants identification method.

Clark I (diphenylochloroarsine), Clark II (diphenylocyanoarsine) and Adamsite belong to the toxic irritants.

Clark I

Clark I seriously irritates eye mucous membranes as well as respiratory tract. The irritation symptoms are following: tears, cough, sneezing, pain in the lungs and difficulty in breathing with a tendency to choke. First symptoms appear at the concentration 10-4 mg/dm³ . High concentration around 2 mg/dm³ may prove to be deadly due to the permanent respiratory tract irritation effect.

Clark II

Toxic activation of Clark II in the human body is similar, if not stronger, to that of Clark I. First symptoms show at 10-5 mg/dm³ ; the primary paralysis occurs at concentration higher than of 5x10^-4 mg/dm³.

Adamsite

Adamsite is the third toxic agent from the sternity group. Adamsite aerosol strongly irritates respiratory tract and eye mucous membranes. The irritation symptoms are as follows: immediate excessive saliva production, and after a short period of time the pain in the lungs causes respiration obstruction. The threshold concentration of adamsite is felt at 2x10^-4 mg/dm³

organophosphate nerve agents

The most lethal chemicals produced by the industry belong to organophosphates. Production of these poisons started during the World War II and peaked most probably at 50,000 tons. This is a quantity sufficient to kill more than once the entire population of humanity. Currently, stocks of organophosphate poisons are to be destroyed under the disarmament programs. However, organophosphates and other chemical waste remain in a large number of unreported dumping and burial sites used by the military.

Organophosphates undergo rapid degradation in the environment, but its hydrolysis products are toxic as well. Organophosphates belong to group of neurotoxin, which means that they are able to block the nervous system of every living organism. Few milligrams of such may result in human's death within minutes. The smallest doses are capable to inflict partial paralysis, which also represents health risk. The best-known, observed cases of severe health disorders were reported after the Gulf War. Gulf War Syndrome affected tens of thousands of veterans. They suffered after accidental exposures during demolition of organophosphates stockpiles. A number of incurable neurological and cancerous disorders attribute to the symptoms of this syndrome. 

Nerve agents are more toxic than other CW agents. They may cause effects within seconds and death within minutes. The nerve agents are all liquids, not gases per se. They can be rapidly absorbed through any body surface and can penetrate ordinary clothing. They are divided into the G agents and V agents. The V agents have high boiling points, low volatility, and resultant high persistency in the environment. V agents are primarily hazardous at direct contact, but they are at least twice as potent as GB, and even a minute amount of airborne material is extremely hazardous. Nerve agents are cumulative poisons. Repeated exposure to low concentrations may produce intoxication symptoms.

a. Physiological Effect.

Both: the G and V agents have the same physiological action on humans. Normally, the enzyme acetyl cholinesterase (AChE) binds and hydrolyzes the acetylcholine neurotransmitter ACh at the receptor sites. This allows for opening the reception points of the neuron. Upon exposure, the nerve agents bind to AChE, making it unable to bind with ACh. As a result, ACh is not hydrolyzed. The accumulation of ACh causes hyperactivity of the body organs stimulated by cholinergic neurons. Individuals poisoned by nerve agents may experience symptoms in the following order:

• Miosis, runny nose, and chest tightness.
• Dim vision and headache.
• Nausea, vomiting, and cramps.
• Drooling, excessive sweating, drowsiness, and confusion.
• Difficulty breathing, twitching, and dizziness.
• Convulsions and coma.

b. Miosis.

When airborne vapor comes in contact with the eyes, miosis occurs as a result of a direct local effect of the nerve agent on the eyes and can occur prior to any inhibition of ChE in the blood. This type of exposure is frequently accompanied by tightness of the chest and/or rhinorhea. In cases of nerve agent exposure not involving vapor contact with the eyes, miosis is one of the last effects to occur before death.

Tabun (GA).
GA was the first of the nerve agents developed by the Germans. GA creates primarily an inhalation hazard.

Sarin (GB).
Pure GB is a odorless and colorless liquid , volatile at room temperature. Unlike many other agents, for which clothing affords some protection, clothing may enhance the potency of GB liquid on the skin. It is hypothesized that clothing fibers absorbs Sarin’s vapors, thereby increasing its effective dose directed towards the skin.

Soman (GD)
Pure Soman liquid is colorless, very toxic and does not mix with water. Liquid will enter the body through the skin, vapors by breathing. Lethal dose require a few milligrams.

O-ethyl methyl phosphonothiolate (VX)
Pure VX is a colorless and odorless liquid, significantly less volatile than the other agents. However it vaporizes at room temperature to some extent and is extremely potent when getting in contact with the skin.

Toxicology

Exposure to acutely toxic concentrations of nerve agents can result in excessive bronchial, salivary, ocular and intestinal secretions, sweating, miosis, bronchospasm, intestinal hypermotility, bradycardia, muscle fasciculations, twitching, weakness, paralysis, loss of consciousness, convulsions, depression of the central respiratory drive, and death.

Nerve agents disturb functioning of ant cholinesterase. Depending on this disturbance , exposure can be characterized as muscarinic, nicotinic, or central nervous system (CNS). Muscarinic effects occur in the parasympathetic system and, depending on the amount absorbed, can be manifested as conjunctival congestion, miosis, ciliary spasm, nasal discharge, increased bronchial secretion, bronchoconstriction, anorexia, emesis, abdominal cramps, sweating, diarrhea, salivation, bradycardia, and hypotension. Nicotinic effects are those that occur in somatic (skeletal/motor) and sympathetic systems, and can be expressed as muscle fasciculations and paralysis. CNS reacts by confusion, reflex loss, anxiety, slurred speech, irritability, forgetfulness, depression, impaired judgment, fatigue, insomnia, depression of central respiratory control, and death.

For mild toxicity in humans (miosis, rhinorrhea), recent multi-service (Army, Marine Corps, Navy, and Air Force) guidance for VX agent-specific exposure estimates maximum EC_t50 = 0.10 mg/m³ for 2–360 min exposure. For severe effects in humans (i.e. muscular weakness, tremors, breathing difficulty, convulsions, paralysis) , estimation calls for EC_t50 = 10mg/m³ for 2–360 min exposures.

Ecotoxicology

Minimal effects observed at low concentrations in human subjects include miosis, a feeling of ‘‘tightness’’ in the chest, rhinorrhea, and dyspnea. A continuing area of public concern regarding nerve agent exposure is the possibility of chronic neurological effects, particularly delayed neuropathy. Neuropathic effects have been observed following high levels of occupational exposure to the lipophilic agricultural pesticides. Exposure to some OP anticholinesterase compounds results in delayed neurotoxic effects (ataxia, distal neuropathy, paralysis), which are collectively described as organophosphate-ester induced delayed neuropathy (OPIDN).

OPIDN is characterized mostly by partial paralysis and paresthesia of legs, due to. noncholinergic, proteolytic mechanism involving cytoskeletal proteins found in neurofilaments. The resulting proteolysis, accompanied by perturbed ionic gradients, cellular edema, and myelin debris, can generate neuropathy. Symptoms develop usually after several weeks (that is why the word “delayed”). Recuperation is very slow (years) and in majority cases not complete. Described are diversified dysfunctions of central nervous system as well. Other various dysfunctions of the central nervous system have been observed, for which no common term exists.

Sometimes such symptoms are referred to chronic neurotoxicity of organophosphorus pesticides in food poisoning (organophosphorus ester – induced chronic neurotoxicity, in short: OPICN). OPICN is characterized by variety of disorders, especially affecting emotions (emotional lability, depression, irritability), memory functioning and ability to concentrate. Here we encounter similarity to symptoms of posttraumatic stress disorder (PTSD). Symptoms last many years and mechanism remains unknown. However it seems that OPICN manifests itself after interaction of organophosphate poisons with the AChE.

Credible short-term organophosphate nerve agent exposure limits have been derived. These limits are designed to aid state and local government agencies in developing emergency response plans in the event of accidental or deliberate atmospheric release of the agents. These short-term values serve as a guideline for health protection agencies and monitoring-detecting institutions responsible for quick and timely alarms warning exposed cities and conglomeration of people. Acute Exposure Guideline Levels (AEGL) are vapor exposure guideline values for numerous hazardous compounds (primarily toxic industrial compounds) that have been published by the National Academy Press. AEGL helps to assess maximum time of evacuation from endangered area. For each hazardous compound, guideline levels are developed for vapor exposure durations of 10 and 30 min, 1 h, 4 h, and 8 h as well as for three gradations of toxic effect severity. AEGLs are expressed in units of mg/m³ :

AEGL-1 concentrations are the mildest effect category while AEGL-3 concentrations represent the most severe effect category. The point above the AEGL-3 concentration for any given human exposure duration is not identified in the AEGL assessment protocol. Typically, the AEGL concentration established for any given effect level is often 50% less than the known experimental concentration at which such toxicological effects occur. For example in case of AEGL-1, values was demonstrated for each of the nerve agents, where observed human thresholds for reversible effects occur at air concentrations greater than AEGL-1 levels.

The AEGL values was recognized by the Chemical Stockpile Emergency Preparedness Program (CSEPP). FEMA and Army representatives adopted final nerve agent AEGL concentrations to replace previous agent toxicity criteria for emergency response decision making. As of February 2003, standing CSEPP policy guidance for each of the communities hosting agent demilitarization facilities in the US recommends application of AEGL-2 concentrations as the protective action level for evacuation or shelter-in-place. AEGL-1 concentrations has been adopted as a threshold for alarm.

Baltic Sea

Issue of buried chemical weapons has been a taboo for a long time under the strict political privacy of USSR. After the collapse of the Soviet Union it appeared in mass media. In the beginning of 1990s for the first time Moscow declared that the presence of chemical weapons in the Baltic Sea endangered approximately 30 million people, and that it would be imperative to react quickly to prevent ecological disaster. After the Baltic States regained their independence, environment protection in each of them became one of the top priorities. In the beginning of 1990s, the Baltic States requested that Russia showed the location of the buried munitions. However, Russia, as for today, has not submitted any information about the location or types of mines referring to political privacy of the matter.

Lack of financial resources to carry out mine-clearing operations and lack of information about the location of mines were and still are the main obstacles to implement mine-clearing operations in the Baltic Sea. As stressed by experts, successful mine-clearing operations would be only possible in close cooperation with international organizations, particularly including NATO. Small Baltic countries with limited resources are unable to carry out any operations on their own. Between 1995 and 2000, 19 mine-clearing operations supported by NATO were conducted. Finland, Denmark and Sweden were especially helpful to the Baltic States in this regard. Nevertheless, due to lack of information about the location of mines and the lack of finances, further operations were hampered.

On November 26, 2005, the Baltic Assembly adopted a Resolution on dangers connected with construction of the gas pipeline across floor of the Baltic Sea. The Baltic Assembly expressed opinion that during the construction and exploitation of this gas pipeline, any kind of dangers, especially those arising from the chemical weapons dumped in the Baltic Sea after World War II, should be eliminated. This should be achieved by international cooperation, they concluded. The parliaments of the Baltic Sea states, the Baltic Council of Ministers and international organizations have been informed to focus their attention and ensure that the assessment of all environmental impacts of the construction of the planned gas pipeline is carried out in accordance with the Convention on Environmental Impact Assessment in a Transboundary Context, the Convention on the Protection of the Marine Environment of the Baltic Sea Area, as well as the valid legal acts of the European Union.

conclusions

At the end of the Cold War, both sides withdrew the whole stock of strategic weapons from the Central Europe. Officially, this included only quantity of nuclear weapons. Russians reported reduction of 17,000 of nuclear warheads from the former Warsaw Pact countries. Meanwhile, nothing is known about the number of remaining chemical and biological loads. Military authorities in Germany and in Poland claim frequently, that their territories contain unknown number of chemical compounds that have to be dealt with. This is not a separate case. For example U.S. authorities has not revealed the number of abandoned chemical cargoes at locations in foreign territories. After many interventions by Chinese authorities, Japan have finally acknowledged, its army left behind more than 2 million units of chemical weapons resting on the occupied territories.

While the responsible former policy-makers "movie into the historical dimension", repercussions of their hasty decisions persist. Earlier attempts managed to eliminate chemical weapons from the arsenals, however science and general public pays now more and strongly justified attention to large presence of unused, toxic stockpiles of related wastes, and how to get rid of it. Attention shifted to all chemical residues and by-products. Particular importance is assigned to carcinogenic risk arising from the properties of such forgotten waste. Only since not long time ago, it has been learned that presence and release of carcinogens to the environment can cause deadly changes in the population of microorganisms. For example: strains of bacteria, viruses and fungi have co-existed with humans and animals since millions of years. Under the influence of gigantic doses of carcinogens, these organisms may transpose into malignant, and able to cause new epidemics of unknown diseases among humans.