Pyrotechnics toxicity

The regulation Hsts 137 toxic and reactive substances and a threshold quantity for each. The regulation also appHes to flammable Hquids and gases in quantities of 10,000 lb or more (>4.5 metric tons), except hydrocarbon fuels and Hquids stored in unpressuri2ed, ambient temperature tanks, as weU as to the manufacture of any quantities of explosives (see Exlosives and propellants) and pyrotechnics (qv). 

Distances for storage of explosives Explosive and Toxic LLazard Materials page 370 (MeidI, 1970) Safe Handling Requirements during Explosive, Propellant and Pyrotechnic Manufacture (HSE, SIR 31)... 

New process technologies (Ref 53) such as jet mills (Fig 2) and co-precipitation (Ref 97) may allow safe compounding of sensitive or toxic formulations. New analytical tools such as neutron radiography (Ref 92) afford improved non-destructive testing of devices. X-ray fluorescence (Ref 93) and neutron activation (Ref 94) provide quantitative analysis of pyrotechnic compns and their trace contaminants... 

Karlsson N, Cassel G, Fangmark I, et al. 1986. A comparative study of the acute inhalation toxicity of smoke from Ti02-hexaehloroethane and Zn-hexachloroethane pyrotechnic mixtures. Arch Toxicol 59 160-166. 

The OSHA PSM Standard lists 131 distinct chemicals with toxic or reactive properties.40 It includes 25 chemicals with an NFPA rating of 3 and 13 chemicals with an NFPA rating of 4. PSM applies to processes that involve listed chemicals at or above threshold quantities and to processes with flammable liquids or gases onsite in one location, in quantities of 10,000 pounds or more. Companies that manufacture explosives and pyrotechnics are also required to comply with the standard. 

Volatilization of oil A pyrotechnic reaction produces the heat needed to vaporize high molecular weight hydrocarbons. The subsequent condensation of this oil in air creates a white smoke cloud. The toxicity of this smoke is probably the least of all the materials discussed here. 

Phosphorus is available in two forms, white (or yellow) and red. White phosphorus appears to be molecular, with a formula of P,. It is a waxy solid with a melting point of 44°C, and ignites spontaneously on exposure to air. It must be kept cool and is usually stored under water. It is highly toxic in both the solid and vapor form and causes burns on contact with the skin. Its use in pyrotechnics is limited to incendiary and white smoke compositions. The white smoke consists of the combustion product, primarily phosphoric acid (H 3PO,). 

The molecules creating the colored smoke must be of low toxicity (including low carcinogenicity). Further, they must readily sublime without decomposition at the temperature of the pyrotechnic reaction to yield a dense smoke of good color quality [3]. 

G1 Is generally considered to be moderately toxic, and more toxic than CS. It is used In much the same way as CS—sprayed in a liquid carrier, as a micropulverlzed powder, or In pyrotechnical grenades. 

Lead oxide is highly toxic as a dust. Use with adequate ventilation, and keep away from food and food products Refs 1) Gmelin, Syst Nr. 47, Teil C, Lfg 1 (1969), 122ff la) EngDesHdbk, Properties of Materials Used In Pyrotechnic Compositions , AM CP 706-187 (Oct 1963), 166-68 2)... 

Some of the important properties which are considered when choosing the ingredients for pyrotechnic formulations are density, hygroscopicity, melting and boiling points and decomposition temperatures, oxygen content of oxidizers, thermal conductivity of fuels and containers, nature of combustion products and toxicity etc. 

Some pyrotechnic formulations Ti/KDN/NC and Ti/CsDN/NC were formulated and tested for combustion velocity, sensitivity to impact, friction and electrostatic discharge etc. The data show that both formulations are extremely sensitive to impact (the sensitivity being in the range of pure HMX and PETN ). Further, it is also seen that the Ti/KDN/NC formulation is less sensitive [145] than Ti/ CsDN/NC. On the contrary, the formulations show a moderate sensitivity to friction and electrostatic discharge. The evaluation of such systems as components in ignition formulations appear to be very promising as this may allow replacement of the heavy metal primary explosives which are toxic in nature. 

Krone, U. (1990) A non-toxic pyrotechnic screening smoke for training purposes. Proc. 15th Inti. Pyrotech. Sem.,... 

Vincennite. Poisonous mixt used by the Fr in WWI in chemical shells. It consisted of hydrogen cyanide 50, As trichloride 30, Sn tetrachloride 15, and chloroform 5%. There was difficulty in obtaining toxic concns in field use because of the extreme volatility of the hydrocyanic acid Ref J. Bebie, Explosives, Military Pyrotechnics and Chemical Warfare Agents , Macmillan Co, NY (1943), 160... 

Ammonium Carbonate,(Nil 4)2C03 mw 96.09, col cryst plates si toxic (Ref 12,p 275). See also Spec MIL-A- 13938. DeMent (Ref 14) used this compd in smoke producing compns and Stevenson (Ref 11) used it to vaporize diphenylchloroarsine other smokes Barium Carbonate, BaC03 mw 197.37, wh powd, mp 1740 at 90atm, bp dec, d 4.43 this compd is poisonous when ingested (Ref 12,pp 331-2). It is used in expl mixts in pyrotechnics. (See also Spec JAN- B- 624)... 

Charcoal, A black amorphous substance a form of carbon derived from the incomplete combustion of animal or vegetable matter (Ref 2). When a pure form of charcoal is desired, it is derived from sugar. Its method of prepn by calcination of sugar heated to ca 800° is described in Ref 3 This method is considered superior to the treatment of sugar with coned HjSO. Toxicity, fire Sc expl hazards of charcoal are discussed in Ref.4 Charcoal is used in various chem processes, as a decolorizing Sc filtering medium, as absorbent, in pharmaceutical prepns Sc plastics and as a component of propellants, BkPdr, pyrotechnics Sc of other expls(Refs 1 5). Charcoals used by the US Armed Forces must comply with die applicable specifications (Ref 6)... 

Copper chromates have been used as mordants in dying and in some pyrotechnic compns. For example a blue light rifle signal light compn developed at PicArsn(Ref 5) contained Cu(II) chromate 25, K perchlorate 65 Cu resinate 10% it burned at the rate 3.5in/min developing CP 485/sq in Refs l)Mellor 11(1931), 260 2)Ullmann 5 (1954), 588 3)Sax(l957), 5l6(Toxicity fire hazard of basic salt) 4)CondChemDict(l961), 30l(Prepn props of basic salt) 5)G.J. 

Pb chromate is a powerful oxidizing agent which sometimes causes explns when in contact with org material. For example, Daniel (Ref 1) reported cases where org objects(such as paper lamp shades) covered with Pb chromate paint ignited spontaneously or even exploded. Toxicity fire hazards are discussed in Ref 10 Uses Pb chromate has been used as a yel pigment in paints and as a component of pyrotechnic compns of delay compns in fuzes(Refs 7,9 12). It was also used in pyrotechnic smokes(Ref 4a,p 122) and in some older types expls, such as Cornil and Halakite. Hale(Ref 3) proposed the following delay compn for fuzes ... 

See under COPPER AND ITS SALTS Lead Dlchromate, PbCr207, mw 423.23 brick red or brn-red,amorph or cryst pdr mp( ) decomp by w sol in ale or alkalies(Ref 5) can be prepd by treating Pb chromate with a coned soln of chromic acid or by other methods (Ref 1). It is a powerful oxidizer and reacts vigorously when heated with reducing materials when heated to decompn, it emits highly,toxic fumes of lead(Ref 4) can probably be used for the same purposes as PbCrO, namely in pyrotechnics... 

The most studied kinds of explosives are nitroaromatic explosives and their metabolites. Therefore, the emphasis of this review is on properties of nitroaromatic explosives, rather than propellants, pyrotechnics, or munitions, and their interactions with soils. Nitroaromatic explosives are toxic, and their environmental transformation products, including arylamines, arylhydroxyl-amines, and condensed products such azoxy- and azo-compounds, are equally or more toxic than the parent nitroaromatic [3]. Aromatic amines and hydroxylamines are implicated as carcinogenic intermediates as a result of nitrenium ions formed by enzymatic oxidation [4], Aromatic nitro compounds... 

R. Hagel, and K. Redecker, Sintox—A New, Non-Toxic Primer Composition by Dynamit Nobel AG, Propellants, Explosives, Pyrotechnics 11 (1986) 184. 

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