Contamination, white phosphorus

This paper describes the development of a system and facilities for safe, efficient, and accurate filling of white phosphorus (UP) munitions. This new development replaces dip-fill operations used by the U.S. Army for over thirty years, a production method that was hazardous to operating personnel and generated unacceptable quantities of phosphorus contaminated water and gas. The new development, Volumetric Filling, is relatively pollution free and exceeds the U.S. Army s standards for filling of white phosphorus munitions. 

The method, described relatively early, for the preparation of phosphine using the reaction of hot concentrated alkalies, such as NaOH, KOH or Ca(OH)2, on white phosphorus can also be used for the laboratory preparation. This method also produces a steady stream of phosphine, which, however, may be contaminated by up to 90% hydrogen and traces of P2H4 >>3.8s.ioi-io6) phine formed from the thermal decomposition of phosphorous or hypophos-phorous acids or their salts is similarly contaminated with hydrogen. In cases where hydrogen interfers, the phosphine can be purified by condensation and distillation. 

Existing Information on Health Effects of White Phosphorus 2-5 Existing Information on Health Effects of White Phosphorus Smoke 5-1 Frequency of NPL Sites with White Phosphorus Contamination... 

White phosphorus enters the environment when industries make it or use it to make other chemicals and when the military uses it as ammunition. It also enters the environment from spills during storage and transport. Because of the discharge of waste water, white phosphorus is likely to be found in the water and bottom deposits of rivers and lakes near facilities that make or use it. It may also be found at sites where the military uses phosphorus-containing ammunition during training exercises. Rainwater washout of these sites may contaminate nearby waterways and their bottom deposits. Hazardous waste sites that contain white phosphorus are also potential sources of exposure to people. However, because white phosphorus reacts very quickly with oxygen in the air, it may not be found far away from sources of contamination. 

White Phosphorus. Anemia (marked decrease in red blood cells or hemoglobin) and leukopenia (very low levels of white blood cells or leukocytes) were observed in workers chronically exposed to airborne white phosphorus (Ward 1928). Because the workers handled white phosphorus contaminated rags, it is possible that exposure occurred via oral and dermal routes also. No information on exposure levels was provided. In another occupational exposure study, no alterations in hemoglobin or total or differential leukocyte levels were observed (Hughes et al. 1962). 

WP/F is manufactured in the Pine Bluff Arsenal in Pine Bluff, Arkansas. Molten white phosphorus stored under water is loaded in munitions shells either by the dip-fill or dry-fill methods (Berkowitz et al. 1981). In the dip-fill method, the shell canisters containing the felt wedges are passed through tubs of molten phosphorus under water. In the dry fill method, molten phosphorus is added directly to the canister under an inert atmosphere. The latter method greatly reduces phosphorus waste (phossy water) and environmental contamination (Spanggord et al. 1983). 

Reliable monitoring data for the levels of white phosphorus in contaminated media at hazardous waste sites are needed so that the information obtained on levels of white phosphorus in the environment can be used in combination with the known body burden of white phosphorus to assess the potential risk of adverse health effects in populations living in the vicinity of hazardous waste sites. 

Racine CH, Walsh ME, Collins CM, et al. 1992b. Remedial investigation report White phosphorus contamination of salt marsh sediments at Eagle River Flats, Alaska. Cold Regions Research and Engineering Lab, Hanover, NH. NTIS/AD-A250 515/4. 

Richardson SM, Weston RF. 1992. White phosphorus contamination of wetlands Effects and options for restoration. In Proceedings of the Federal Environmental Restoration 92,... 

Walsh ME. 1995. Analytical method for white phosphorus in water. Bulletin of Environmental Contamination and Toxicology 54(3) 432-439. 

Walsh ME, Taylor S. 1993. Analytical method for white phosphorus residues in munitions-contaminated sediments. Analytica Chimica Acta 282(N1) 55-61. 

Crystalline [([18]crown-6)K][P(CN)2] is the preferred material for further reactions. In the P4-disproportionation reaction, crown ether potassium polyphosphides are formed as the second product. Their composition and solubility depend on the stoichiometry used. The intense red color of the solution in early stages of the reaction is caused by an intermediate high concentration of soluble polyphosphides. The final equilibrium concentration of these phosphides can contaminate and color the isolated dicyanophosphide. To avoid this contamination, the remaining soluble polyphosphides are converted to insoluble ones by an excess of white phosphorus. 

Investigation of those overexposed to screening smokes should include, at least, chest radiograph, pulmonary function tests, arterial oxygen tension measurement, blood clinical chemistry, sputum culture, ophthalmic examination with slit-lamp biomicroscopy, and possibly measurement of intraocular pressure. If available, CT scan may be used to assess the severity of lung injury (Hsu et al., 2005). With some smokes, notably white phosphorus, there may be skin contamination with severe irritation and penetrating bums the management of white phosphoms skin burns is discussed in detail in Section VI.A.2. 

The determination of oral LD50 values of red phosphoms gave inconsistent values. The presence of white phosphorus as a contaminant can produce high toxicity. 

White phosphorus can build up slightly in the bodies of fish that live in contaminated lakes or streams. 

Eating contaminated fish or game birds from sites containing white phosphorus. 

Touching soil contaminated with white phosphorus. 

Skin and eyes. Remove contaminated clothing and wash exposed areas with soap and water. Irrigate exposed eyes with copious tepid water or saline. Covering exposed areas may help prevent spontaneous combustion of yellow/white phosphorus. 

Ronald E Bellamy and Russ Zajtchuk, eds.. Textbook of Military Medicine, Part I, Vol. 5, Conventional Warfare Ballistic, Blast and Burn Injuries (Washington, DC Walter Reed Army Medical Center 1990) p. 49. Copper sulfate is no longer recommended for treating wounds contaminated with white phosphorus. Ibid, p. 340. 

The use of white phosphorus was eventually banned by international agreement, because of the terrible industrial diseases it caused. Breathing air that was contaminated with phosphorus vapour could eventually lead to tooth decay that ate it.s way down to the jaw bonp (known as phossy Jaw ). Because matches were first made by hand in the homes of the poor, the disease exacted a fearful toll among early workers. 

Five and twenty-three hundredths grams of germanium(IV) oxide (0.05 mol) is dissolved in 15 ml. of a concentrated aqueous solution of hydrofluoric acid (47 %). A platinum evaporating dish or a polyethylene plastic beaker is used to keep silicon contamination to a minimum. A solution of 10.5 g. of barium chloride (0.05 mol) in 50 ml. of water is added. Barium hexafluorogermanate forms as a white, granular precipitate, which is filtered and washed free of chloride. The product is dried by heating to 300° in vacuo and is stored in a desiccator over phosphorus(V) oxide. The yield is 15.24 g. (94%). 

Phosphorus(III) isocyanate boils at 169.3° (760 mm.), and melts at — 2.0°.1 Upon standing for 2-3 days polymerization occurs to yield a white material of m.p. 80-95°. The rate of polymerization is retarded by the presence of contaminants and serves as an indication of product purity. Distillation of the polymer melt results in nearly quantitative yields of the monomer. 

The reaction starts without warming. Phosphorus (V) fluoride contaminated with AsFg accumulates as a white solid in the trap. After completion of the conversion the crude PFg is purified fractionation. 

When phosphorus is burned in air the product is the highly hygroscopic white solid P4O10 (commonly called phosphorus pentoxide, P2O5) this is the P(V) oxide. In a limited supply of air the P(III) oxide, P40g (called phosphorus trioxide) contaminated with unreacted phosphorus is obtained. The oxides both react with water to form acids ... 

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