Drugs and Poisons in Humans - A Handbook of Practical Analysis (Part 9)

Introduction:The chemical warfare agents well known count only about 30 kinds of compounds, such as sarin, soman, tabun, VX, mustard gas, lewisite and others. When unknown toxic substances should be analyzed upon the occurrence of chemical terrorism, much more kinds of poisons and related compounds become the objects of analysis. In the Chemical Weapons Convention (CWC)a, 120 thousand compoundsb, including typical chemical warfare agents, their related compounds, precursors and decomposition products, are being listed to be controlled. In the CWC, the on-site inspection and chemical analysis to be made by the Organisation for the Prohibition of Chemical Weapons (OPCW)...
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Drugs and Poisons in Humans - A Handbook of Practical Analysis (Part 9) 9I.9 Analysis of chemical warfare agents and their related compounds By Shigeyuki HanaokaIntroductionThe chemical warfare agents well known count only about 30 kinds of compounds, such assarin, soman, tabun, VX, mustard gas, lewisite and others. When unknown toxic substancesshould be analyzed upon the occurrence of chemical terrorism, much more kinds of poisonsand related compounds become the objects of analysis. In the Chemical Weapons Convention(CWC)a, 120 thousand compoundsb, including typical chemical warfare agents, their relatedcompounds, precursors and decomposition products, are being listed to be controlled. In theCWC, the on-site inspection and chemical analysis to be made by the Organisation for theProhibition of Chemical Weapons (OPCW) are also being defined to verify the presence of achemical agent; the latter itself or their related compounds should be analyzed rapidly and ac-curately. The analytical methods can be also applied to other poisons and drugs. In this chapter, various analytical methods of chemical warfare agents and related com-pounds based on the verification defined in the CWC [1] are presented. The classification of chemical agents is shown in > Table 9.1. The scheduled chemicalsdefined in the CWC are listed in > Table 9.2; the chemical agents not listed in the scheduledchemicals of CWC, such as riot control agents and others, are shown in > Table 9.3.⊡ Table 9.1Classification of representative chemical agentsNerve agents G agents : sarin (GB), soman (GD), tabun (GA), V agents : VXBlister agents sulfur mustard (HD), nitrogen mustard (HN), lewisite (L)Incapacitant 3-quinuclidinyl benzilate (BZ)Emetics (sternutators) adamsite (DM), diphenylchloroarsine (DA), diphenylcyanoarsine (DC)Lacrimators 2-chlorobenzylidenemalononitrile (CS), 2-chloroacetophenone (CN)Suffocating agents phosgene (CG), PFIB, chloropicrinBlood agents cyanogen chloride (CK), hydrogen cyanide (AC)© Springer-Verlag Berlin Heidelberg 200570 Analysis of chemical warfare agents and their related compounds ⊡ Table 9.2 Scheduled chemicals listed by the Chemical Weapons Convention (CWC) Schedule 1 A. Toxic chemicals 1. O-alkyl ( C10, incl. cycloalkyl) alkyl ( C3)-phosphonofluoridates, e.g. sarin, soman 2. O- alkyl ( C10, incl. cycloalkyl)-N, N-dialkyl ( C3)phosphoramidocyanidates, e.g. tabun (GA) 3. O-alkyl (H or C10, incl. cycloalkyl)-S-dialkyl ( C3)-aminoethyl alkyl ( C3)- phosphonothiolates and corresponding alkylated or protonated salts, e.g. VX, VE, VM, VMM, VP, VS 4. sulfur mustards (9 chemicals), e.g. mustard gas (yperite), sesquimustard,O-mustard 5. lewisites (3 chemicals), e.g. 2- chlorovinyldichloroarsine (lewisite 1) 6. nitrogen mustards (3 chemicals), e.g. bis(2- chloroethyl)ethylamine (HN1) 7. saxitoxin 8. ricin B. Precursors 9. alkyl ( C3)phosphonyldifluorides 10. O-alkyl (H or C10, incl. cycloalkyl)-O-2-dialkyl ( C3)aminoethylalkyl ( C3) phosphonites and corresponding alkylated or protonated salts 11. chlorosarin 12. chlorosoman Schedule 2 A. Toxic chemicals 1. amiton 2. PFIB 3. BZ B. Precursors 4. chemicals, except for those listed in Schedule 1, containing a phosphorus atom to which is bonded one methyl, ethyl or propyl group but not further carbon atoms, e.g. methylphosphonyl dichloride, dimethyl methylphosphonate 5. N, N-dialkyl ( C3) phosphoramidic dihalides 6. dialkyl ( C3)-N,N-dialkyl ( C3)- phosphoramidates 7. arsenic trichloride 8. benzilic acid 9. quinuclidin-3-ol 10. N,N-dialkyl ( C3)aminoethyl-2-chlorides and corresponding protonated salts 11. N,N-dialkyl ( C3)aminoethane-2-ols and corresponding protonated salts (exemptions: N,N-dimethyl and N,N-diethylaminoethanol and corresponding protonated salts 12. N,N- dialkyl ( C3)aminoethane-2-thiols and corresponding protonated salts 13. thiodiglycol 14. pinacolyl alcohol Analysis of chemical warfare agents and their related compounds 71⊡ Table 9.2 (Continued)Schedule 3A. Toxic chemicals 1. phosgene 2. cyanogen chloride 3. hydrogen cyanideB. Precursors 4. chloropicrin 5. phosphorus oxychloride 6. phosphorus trichloride 7. phosphorus pentachloride 8. trimethyl phosphite 9. triethyl phosphite10. dimethyl phosphite11. diethyl phosphite12. sulfur monochloride13. sulfur dichloride14. thionyl chloride15. ethyldiethanolamine16. methyldiethanolamine17. triethanolamineMustard mixtures : mustard HT (60% H+ 40% T), HS ( H+ 15% carbon tetrachloride), HQ (75% H+ 25% Q), HL (50%H+ 50% L).⊡ Table 9.3Other chemical agents not included in the list of CWC (including riot control agents)Blister agents methyldichloroarsine (MD), ethyldichloroarsine (ED), phenyldichloroarsine (PD/PFIFFIKUS), phosgene oxime (CX), arsine oil*Emetics (sternutators) diphenylchloroarsine (Clark I/DA), diphenylcyanoarsine (Clark II/DC), 10-chloro-5,10-dihydrophenarsazine (adamsite/DM)Lacrimators α-bromobenzyl cyanide (CA), 2-chloroacetophenone (CN), 2-chloroben zylidenemalononitrile (CS), dibenzo-1,4-oxazepine (CR), benzyl bromide, cyanobenzyl bromide, methylbenzyl bromide, bromoethyl acetate, iodoethyl acetate, vanillylamine pelargonateSuffocating agents diphosgene, triph ...