Medical Aspects of Chemical Warfare (2008) - The Black Vault

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Medical Diagnosticsurine samples. The blood assay for both bound and freeCVAA will potentially provide a longer opportunityfor retrospective confirmation of exposure (based onone animal study), but also indicates a substantialdecrease (90%) in concentration levels observed overa 10-day period.CYANIDEBackgroundCyanide is an important industrial chemical that hasmany uses. It is produced in large quantities across theworld and people are exposed to cyanide in a varietyof ways. Many plants, including cassava roots, limabeans, and bamboo shoots, contain small amountsof cyanogenic glycosides. 131–133 Polymers that containcarbon and nitrogen release cyanide when burned.For example, large amounts of cyanide can be releasedduring house and forest fires and from tobacco smoke(100–1600 parts per million [ppm]). 131 Some drugs alsocontain cyanide or have active ingredients that areconverted to cyanide in the body, including sodiumnitroprusside, which is given for the critical care ofhypertension. 131 Synonyms for hydrogen cyanide(HCN) include prussic acid, formic anamminide, andfromonitrile. Deaths due to cyanide intoxication areusually due to the inhalation of HCN or the ingestionof cyanide salts. The signs of cyanide poisoning includeheadache, nausea, vomiting, tachypnoea, dyspnoea to131, 134–137convulsion, unconsciousness, and death.Cyanide in the Human BodyCyanide, the CN- ion, exists as HCN in the body atphysiological pH. The mechanism of cyanide toxicityis believed to be the inactivation of iron III (ferric)enzymes in the body. The inhibition of cytochromeoxidase, which disrupts mitochondrial oxidativephosphorylation, is thought to be the most importantmechanism for cyanide toxicity. 131, 138–141 Cyanide alsobinds to the hemoglobin in erythrocytes. 142 The bindingof cyanide to iron III enzymes and proteins isreversible. 140,141At low concentrations, 93% to 99% of total cyanideis bound to methemaglobin (metHb) in the erythocytes.131 The metHb is the deoxygenated iron III formof hemoglobin. Cyanide has a very high affinity tometHb and a low affinity to the oxygenated form ofhemoglobin. Usually less than 1% of the total hemoglobinis in the metHb form, so at increased concentrationsof cyanide in the blood, a larger amount isfound in the serum. In tissue, cyanide binds to theheme group in mitochondrial cytochrome oxidaseand inhibits electron transport. 140,141 All tissues are affectedby this enzymatic inhibition, but especially thosethat require high amounts of oxygen and adenosine5’-triphosphate. Other proteins and enzymes are alsoaffected by cyanide, such as superoxide dismutase andxanthine oxidase, and may also contribute to cyanide’stoxic effects. 131Cyanide’s metabolism in the body is very rapid andcan occur at 0.017 mg/min/kg. 131 The most commonform of metabolism is the conversion to thiocyanate(SCN - ), which is then excreted via the kidneys. 143,144 Themitochondrial enzyme rhodanese (thiosulfate sulfurtransferase) is thought to be the main catalyst for theformation of SCN - , but β-mercaptopyruvate-cyanidetransferase can transform cyanide to SCN - through adifferent route. 141,145 The conversion to SCN - is thoughtto be limited by the amount of thiosulfate. Cysteine,cystine, GSH, and β-mercaptopyruvic acid can also besulfur sources. 131, 141,145 The reaction with cystine is alsoan important pathway leading to 15% of the total cyanidedose excreted in the urine as 2-iminothiozoline-4-carboxylic acid. 144 Other elimination pathways are theexhalation of HCN and oxidation to cyanate and reactionswith vitamin B 12to form cyanocobalamin. 146Analytical MethodsSeveral matrices have been used to assess cyanideexposure. Whole blood is the most common, but measurementshave been made in serum, plasma, saliva,tissues, gastric aspirate, and urine.Whole BloodWhole blood has been the matrix of choice, thus far,to determine cyanide exposure in humans. However,there are problems associated with cyanide and SCN -measurements in blood. Sample collection, storage,and preparation are very important. Different levelsof cyanide have been found in samples collected fromdifferent vessels (venous, arterial, and ventricular).Different whole blood samples can contain differentamounts of metHb, which has a high affinity to cyanide.Also, free HCN may be more important becauseit is the form that reacts with cytochrome oxidase andcauses the most significant adverse health effects. 131Storage of the whole blood is also critical but not wellunderstood. Some studies have shown an increase incyanide of up to 40% upon storage of whole blood for1 week and a 14% increase after 1 day at 4°C, whileothers have shown a decrease of 20% to 30% within 1731
Medical Aspects of Chemical WarfareTable 22-13Analytical Methods for Determining Cyanide in Biological Samples 1PercentSample Matrix Preparation Method Analysis Method LOD RecoveryBlood Separation in MDC; derivatization Spectrophotometry 0.1 ppm nR 2Blood Separation in MDC; derivatization Spectrofluorometry (total CN) 0.025 ppm nR 3Plasma deproteination with TCA; Spectrophotometry (SCN-CN ~ 0.07 ppm 96 (SCN) 4derivatizationdetermination)Erythrocyte Sample purged; absorption of Spectrophotometry (SCN-CN NR 93–97 5suspension HCN in NaOH; oxidation of SCN determination)Blood cells Centrifugation to separate cells; HPLC-fluorescence detection 0.002 ppm 83 6extraction; derivatizationBlood acidification headspace GC-NPD ~ 0.03 ppm nR 7Blood acidification; derivatization Headspace GC-ECD 0.1 ppm nR 8Blood Separation in MDC; color Spectrophotometry ~ 0.07 ppm nR 9developmentBlood incubation of acidified sample GC-NPD 0.001 ppm nR 10Blood Separation in MDC; absorption in Spectrophotometric (free CN) 0.4 ppm ~ 80 11methemoglobinBlood acidification GC-NPD 0.014 ppm 86–99 12Blood microdiffusion, derivatization Isotope dilution LC-MS 5 ppb n/A 13Blood and liver Sample digestion; treatment with Specific ion electrode (total CN) 0.005 ppm 100–109 14lead acetate; absorption withnaOHBlood and urine Separation in MDC; derivatization Spectrofluorometric 0.008 ppm 66–83(blood)76–82(urine) 15Urine dilution; derivatization Spectrophotometry (SCN-CN ~ 0.07 ppm 88 (SCN) 16determination)Saliva derivatization hplc-UV (SCN) 2 ng (on instrument) 95–99 17Serum, urine, saliva Extraction of buffered sample Flame AAS (SCN) 0.004 ppm 96–102 18with isoamyl acetateSerum addition of acetonitrile; Spectrophotometry (SCN) 0.3 ppm 94 19centrifugation; separationUrine, saliva Basify; derivatization; extraction; GC-ECD (SCN) ~ 0.033 83–106 20back extractionUrine, saliva Dilution; filtration ion chromatography-UV (SCN) 0.02 95–101 21Urine ion chromatography; acidification; Spectrophotometry (SCN) ~ 0.145 ppm NR 22derivatization(lowest reported)Urine dilution; solid phase extraction Suppressed ion chromato- ~ 0.011 ppm nR 23graphy with conductivitydetectionUrine (2-aminothio- Cation exchange; reduction; Suppressed ion chromato- ~ 0.03 ppm nR 24zoline-4-carboxylic derivatization graphy with fluorescenceacid)detectionUrine (2-aminothio- Solid phase extraction and Isotope dilution GC-MS 25 ppb n/A 25zoline-4-carboxylic derivatizationacid)732(Table 22-13 continues)
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The Coat of Arms1818Medical Departm
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Textbooks of Military MedicinePubli
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MEDICAL ASPECTS o fCHEMICAL WARFARE
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ContentsContributorsForeword by The
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ContributorsMICHAEL ADLER, PhDResea
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DONALD M. MAXWELL, MSResearch Chemi
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ForewordThe US military has been co
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PrefaceA significant concern for th
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PrologueThe original edition of Med
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xxii
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Medical Aspects of Chemical Warfare
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Nerve AgentsChapter 5NERVE AGENTSFR
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Nerve AgentsAbout 10,000 to 30,000
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Nerve Agentsphorofluoridate (DFP) w
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Nerve AgentsFig. 5-2. This schemati
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Nerve AgentsExhibit 5-1 continuedis
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Nerve Agentsactivity but only 15% t
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Nerve AgentsTABLE 5-3CHEMICAL, PHYS
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Nerve AgentsTABLE 5-4EFFECTS OF EXP
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Nerve Agentsaffecting the other eye
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Nerve Agentsmay cause severe rhinor
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Nerve Agentsof jerks and tremor.Cen
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Nerve Agentsand they were decreased
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Nerve Agentsnerve agent toxicity on
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Nerve Agentspatient. Decontaminatio
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Nerve AgentsFig. 5-5. The Mark I ki
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Nerve Agentsadministered intramuscu
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Nerve Agentsthat hydroxamine reacti
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Nerve AgentsOral administration may
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Nerve AgentsTABLE 5-7RECOMMENDED TH
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Nerve Agentsimpairment such as whee
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Nerve Agentssuboptimal, manner. The
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Nerve Agentsthan those who did not.
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Nerve Agentssible for binding nerve
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Nerve Agentsfor comparison was not
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Nerve AgentsTABLE 5-11EFFECTS OF PY
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Nerve Agentstivity of smooth muscle
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Nerve Agents38. Grob D, Lilienthal
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Nerve Agents77. McDonough JH, Shih
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Nerve Agents117. McLeod CG Jr, Sing
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Nerve Agents154. Tryphonas l, Veino
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Nerve Agents193. Funckes AJ. Treatm
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Nerve Agents235. Suzuki T, Morita H
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Nerve Agents274. Pellegrini JE, Bak
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PROCESSMedical Aspects of Chemical
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Triage of Chemical CasualtiesChapte
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Triage of Chemical Casualtiesreceiv
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Triage of Chemical Casualtiescatego
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Triage of Chemical CasualtiesIn a f
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Triage of Chemical Casualtiesnose)
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Triage of Chemical CasualtiesWith n
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Triage of Chemical Casualties14. Sa
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Decontamination of Chemical Casualt
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