Explosives and breakdown products

In addition to the detonation danger, many ordinary explosives and breakdown products are toxic. Dinitrotoluene (DNT), for example, is carcinogenic. The Agency for Toxic Substances and Disease Registry (ATSDR) has a... 

Provides detailed instructions for planning the environmental remediation of military ranges and ordnance dumpsites, and includes lists of explosives, chemical warfare materials, and breakdown products that the soil and groundwater must be tested for. 

During World War I and World War II, most workers who routinely handled tetryl powder and pellets in munitions factories developed a distinct yellow staining of the skin. Many workers also developed skin rashes. These workers were exposed to high concentrations of tetryl dust in the air and by direct contact with the explosives. There are no medical tests to show if you have been specifically exposed to tetryl. However, if the breakdown products of tetryl found in the urine of animals exposed to tetryl were also present in the urine of exposed humans, these breakdown products could be used to indicate exposure to tetryl or similar substances. The symptoms caused by exposure to tetryl can also occur for many other reasons therefore, they cannot be used as proof of tetryl exposure. Refer to Chapters 2 and 6 for more information. 

Flash and Fire Point. Flash point is the temperature at which the volatile products are evolved at such a rate that they are capable of being ignited but not supporting combustion. At the fire point, the accumulated breakdown products are capable of supporting a flame on their own. A crude cottonseed oil with a fatty acid content of 1.8% was found to have a flash point of 560°F or 293.3°C. Solvent-extracted oils can have a low flash point because of a solvent residue. A flash point analysis would identify this crude oil deficiency to prevent an accidental fire or explosion in an atmosphere that was not explosion proof. Crude vegetable oil shipments received with a flash point below 250°F are rejectable by most trading rules. Figure 1 shows the relationship between free fatty acid content, smoke, flash, and fire points of processed cottonseed and peanut oils. 

Major MA et al., Bioconcentration, Bioaccumulation and Biomagnification of Common Nitroaromatic and Nitramine Explosives and Their Metabolites and Environmental Breakdown Products, Final Technical Report, Toxicology Study No. 87-MA-4677-01, Health Effects Research Program, Directorate of Toxicology, U.S. Army Center for Health Promotion and Preventative Medicine, Aberdeen Proving Ground, MD, 2002. 

A relatively broad variety of aquatic toxicity studies exists for nitro-substituted phenol, toluene, and benzene explosives and related compounds, but very little toxicological information is available for tetryl, cyclic nitramines, and the other energetic compounds discussed in this chapter. Several explosives, such as tetryl, are no longer manufactured and are, therefore, of diminishing environmental concern, although their persistence and the nature, stability, and toxicity of their breakdown products is not understood in sufficient detail and should be further investigated. A variety of other energetic compounds, for example, perchlorates, are used in military operations, and due to environmental concerns with their release, additional studies on their fate and effects in aquatic systems are recommended. 

Sediments spiked with the explosives TNT, TNB, picric acid, tetryl, and the TNT breakdown products 2-ADNT and 2,4-DANT promoted significant invertebrate mortality in laboratory exposures. Exposure to 2,6-DNT in sandy and fine-grained sediments did not result in significant lethality in the only sediment toxicity study with that compound. Limited available toxicity data suggests that amphipods are more sensitive to TNT and its transformation products than the other invertebrates investigated, and that TNT and its major breakdown products 2-ADNT and 2,4-DANT are lethal at similar concentrations in sediment exposures. 

Although many other explosives and explosives-related compounds exist, only the data for 2,4,6-trinitrotoluene (TNT) and its breakdown products, the cyclic nit-ramines (RDX and HMX), tetryl, trinitrobenzene, and nitroglycerin will be reviewed in this chapter. Two dinitrotoluene isomers are also included, as they are still used as explosives in addition to being side-products of TNT synthesis. 

Cyclonile (RDX, Irinilrolrimelhylenelriamine [CAS 121-82-4)) Dermal and Inhalation exposures affect the CNS with symptoms ol confusion. headache, nausea, vomiting, convulsions, and coma. Does not have nitrate-llke toxicity. 0.5 mg/m , S Crystalline solid. Vapor pressure Is negligible at 20°C (68°F). Thermal-breakdown products include oxides of nitrogen. Explosive. 

DInItrobenzene May stain tissues yellow upon direct contact. Vapors are Irritating to respiratory tract. Potent inducer of methemoglobinemia (see p 261). Chronic exposures may result in anemia and liver damage. Injuries testes In test animals. Very well absorbed through the skin. 0.15 ppm, S 50 mg/m 3 1 4 Pale yellow crystals. Explosive detonated by heat or shock. Vapor pressure is much less than 1 mm Hg at 20°C (68°F). Thermal-breakdown products include oxides of nitrogen. 

Nitrotoluene (o-, m-, /)-nitrotoluene [CAS 99-08-1]) Weak inducer of methemoglobinemia (see p 261), By analogy to structurally similar compounds, dermal absorption is likely, 2 ppm, S 200 ppm 3 1 1 Ortho ani mem, yellow liquid or solid. Para, yellow solid. All isomers have a weak, aromatic odor. Vapor pressure is approximately 0.15 mm Hg at 20°C (SS F). Thermal-breakdown products include oxides of nitrogen. Intermediate in synthesis of dye-stuffs and explosives. 

Many of the explosives compounds from decades ago are still present in the soil and groundwater. As of 1997, the Army noted over 80 sites with groundwater contaminated with explosive wastes. Dinifrotoluene (DNT), trinitrotoluene (TNT), high melting explosive (HMX), and royal Dutch (or demolition) explosive (RDX) are typical examples. Breakdown products and isomers from the list in Section 4.2.3 are also found. 

Soil gas surveys can be done rapidly and easily and can cover a wide area. One new type uses a Cortex shoelace with absorbent pellets inside (called the Goresorber). The shoelace is inserted into the ground with a two-foot push tube. (Clearance with a metal detector is recommended.) The lace is withdrawn in a day or so and the pellets analyzed for CWM or explosive breakdown products. A geographic information systems (CIS) computer printout is made extrapolating areas of increased concentrations. This method can be used to locate all manner of landfills or contaminated soils. Similarly, soil samples can hint at burial sites. Where most soil samples are clean but some reveal CWM or explosive breakdown products, this may present evidence of a nearby burial site. 

Now, the District of Columbia asserts that the emphasized statement quoted above is a mistake. The District maintains that trinitrotoluene (TNT) and tetryl are explosives and further, that Adamsite, chloroacetophenone, and phenyldichloroarsine were found in the original samples. These are all listed as chemical warfare agents in FM 3-9, Potential Military Chemical/ Biological Agents and Compounds (1990). Finally, numerous Lewisite and mustard breakdown products are identified in the sampling report. 

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