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

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Medical DiagnosticsTable 22-13 continuedAAS: atomic absorption spectrometryATC: 2-amino-thiazoline-4-carboxylic acidCN: cyanideECD: electron capture detectionGC: gas chromatographyGC-MSD: gas chromatography-mass selective detectionHCN: hydrogen cyanideHPLC: high-performance liquid chromatographyLC: liquid chromatographyLOD: limit of detectionMDC: microdiffusion cellNaOH: sodium hydroxideNPD: nitrogen phosphorus detectionNR: not reportedppb: parts per billionppm: parts per millionSCN: thiocyanateTCA: trichloroacetic acidUV: ultraviolet absorbance detectionData sources: (1) US Department of Health and Human Services, Public Health Services, Agency for Toxic Substances and Disease Registry.Toxicological profile for cyanide. Atlanta, Ga: USDHHS; 1997. (2) Morgan RL, Way JL. Fluorometric determination of cyanide in biologicalfluids with pyrudixal. J Anal Toxicol. 1980;4:78–81. (3) Ganjeloo A, Isom GE, Morgan RL, Way JL. Fluorometric determination of cyanidein biological fluids with p-benzoquinone. 1980;55:103–107. (4) Pettigrew AR, Fell GS. Simplified colorimetric determination of thiocyanatein biological fluid, and its application to investigation of the toxic amblypias. Clin Chem. 1972;18:996–1000. (5) McMillan DE, SvobodaAC 4th. The role of erythrocytes in cyanide detoxification. J Pharmacol Exp Ther. 1982;221:37–42. (6) Sano A, Takimoto N, Takitani S. Highperformanceliquid chromatographic determination of cyanide in human red blood cells by pre-column fluorescence derivitization. J Chromatogr.1992;582:131–135. (7) Levin BC, Rechani PR, Gruman JL, et al. Analysis of carboxyhemoglobin and cyanide in blood of victims of theDuPont Plaza Hotel fire in Puerto Rico. J Forensic Sci. 1990;35:151–168. (8) Odoul M, Fouillet B, Nouri B, Chambon R, Chambon P. Specificdetermination of cyanide in blood by headspace gas chromatography. J Anal Toxicol.1994;18:205–207. (9) Laforge M, Buneaux F, Houeto P,Bourgeios F, Bourdon R, Levillain P, et al. A rapid spectrophotometric blood cyanide determination applicable to emergency toxicology. JAnal Toxicol.1994;18:173–175. (10) Seto Y, Tsunoda N, Ohta H, et al.Determination of blood cyanide by headspace gas chromatography withnitrogen phosphorus detection and using a megabore capillary column. Analytica Chimica Acta.1993;276:247–259. (11) Tomoda A, HashimotoK. The determination of cyanide in water and biological tissues by methemoglobin. J Hazardous Materials. 1991;28:241–249. (12) Calafat AM,Stanfill SB. Rapid quantitation of cyanide in whole blood by automated headspace gas chromatography. J Chromatography B Analyt TechnolBiomed Life Sci. 2002;772:131–137. (13) Tracqui A, Raul JS, Geraut A, Berthelon L, Ludes B. Determination of blood cyanide by HPLC-MS.J Anal Toxicol. 2002;26:144–148. (14) Egekeze JO, Oehme FW. Direct potentiometric method for the determination of cyanide in biologicalmaterials. J Anal Toxicol. 1979;3:119–124. (15) Sano A, Takezawa M, Takitani S. Spectrofluorometric determination of cyanide in blood andurine with naphthalene-2,3-dialdehyde and taurine. Anal Chim Acta. 1989;225:351–358. (16) Pettigrew AR, Fell GS. Simplified colorimetricdetermination of thiocyanate in biological fluid, and its application to investigation of the toxic amblyopias. Clin Chem. 1972;18:996–1000.(17) Liu X, Yun Z. High-performance liquid chromatographic determination of thiocyanate anions by derivatization with pentafluorobenzylbromide. J Chromatogr A. 1993;653:348–353. (18) Chattaraj S, Das AK. Indirect determination of thiocyanate in biological fluids using atomicabsorption spectrometry. Spectrochica. 1992;47:675–680. (19) Li HZ, Bai G, Sun RM, Du LK. Determination of thiocyanate metabolite of sodiumnitroprusside in serum by spectrophotometry. Yao Xue Xue Bao. 1993:28:854–858. (20) Chen SH, Wu SM, Kou HS, Wu HL. Electron-capturegas chromatographic determination of cyanide, iodide, nitrite, sulfide and thiocyanate anions by phase-transfer-catalyzed derivatizationwith pentafluorobenzyl bromide. J Anal Toxicol. 1994;18:81–85. (21) Michigami Y, Fujii K, Ueda K, Yamamoto Y. Determination of thiocyanatein human saliva and urine by ion chromatography. Analyst. 1992;117:1855–1858. (22) Tominaga MY, Midio AF. Modified methodfor the determination of thiocyanate in urine by ion-exchange chromatography and spectrophotometry. Rev Farm Bioquim Univ Sao Paulo.1991;27:100–105. (23) Miura Y, Koh T. Determination of thiocyanate in human urine samples by suppressed ion chromatography. Anal Sci7. 1991;(Suppl Proc Int Congr Anal Sci, 1991, Pt 1):167–170. (24) Lundquist P, Kagedal B, Nilsson L, Rosling H. Analysis of the cyanide metabolite2-aminothiazoline-4-carboxylic acid in urine by high-performance liquid chromatography. Anal Biochem. 1995;228:27–34. (25) LogueBA, Kirschten NP, Petrovics I, Moser MA, Rockwood GA, Baskin SI. Determination of the cyanide metabolite 2-aminothiazole-4-carboxylicacid in urine and plasma by gas chromatography-mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci. 2005;819:237–244.day at 4°C and continued decreases over 2 weeks. Adecrease in cyanide levels was seen when whole bloodwas stored at 2°C. Results from storage at – 20°C hasbeen disputed, with some studies showing up to 3.5times the original cyanide levels and others showing nochange. 147 These differences appear to be independentof the original cyanide concentrations. 148Prior to detection, cyanide must first be separatedfrom hemoglobin. This separation is most often donewith sulfuric acid and followed by microdiffusion in aConway cell, although there have been some problemsassociated with the Conway cell. Other methods useacid to release the cyanide followed by a variety oftechniques. Most of these methods are colorimetricand rely on the König reaction to produce a dye thatis quantified using spectrophotometry. Cyanide andSCN - both react and must be separated using microdiffusionor distillation. Additionally, most of thesemethods are time consuming and lack specificity orsensitivity. Detection limits using this approach are733
Medical Aspects of Chemical Warfaregenerally in the high parts-per-billion range. Therehave also been assays developed that acidify thesolution and then sample the head space for HCNfollowed by GC with a nitrogen-phosphorus detectoror derivatization followed by GC with an electroncapture detector. Detection limits by nitrogen-phosphorusdetection and electron capture detector havebeen in the high parts-per-billion range. Cyanide hasbeen measured in RBCs by high-performance LC afterderivatization with fluorescence detection.Urine, Saliva, and Serum or PlasmaMethods to detect cyanide exposure in human urine,saliva, and either serum or plasma have concentratedon SCN - . These methods include derivatization withhigh-performance LC with ultraviolet detection, derivatizationwith spectrophotometric detection, or GCwith electron capture detection. Some urine methodshave measured the urinary metabolite 2-aminothiozoline-4-carboxylicacid.Reference Range ValuesReference range values for cyanide in variousmatrices tend to vary greatly depending on thestudy and on the method of analysis. Thus, a referencerange needs to be established for any method.In some of the studies, the range of blood cyanidelevels in normal populations is less than 150 partsper billion and urinary SCN - less than 1.0 mg/mL. 131Smokers have much higher cyanide levels thannonsmokers; in some smokers blood cyanide levelsas high as 500 ng/mL have been reported, whichis 50 times higher than that typically reported fornonsmokers (Table 22-13). 131PHOSGENEBackgroundPhosgene, also known as carbonyl chloride, wasused extensively in World War I and caused moredeaths than any other agent. 149 It is now a widely usedindustrial chemical. In 2002 the global production ofphosgene was estimated to be over 5 million metrictons, 150 most of which is consumed at the productionsite. 151 The first synthesis of phosgene was performedin 1812 by exposing a mixture of chlorine and carbonmonoxide (CO) to sunlight. 152 During World War Iphosgene was produced in bulk by the reaction ofchlorine and CO in the presence of activated carboncatalyst. 152 Phosgene is generally produced in thesame way today but with higher efficiency because ofnewer high-surface–area catalysts. 153 Phosgene is animportant intermediate in many industrial products,including insecticides, isocyanates, plastics, dyes, andresins. 150 Additionally, phosgene is formed duringthe combustion of chlorinated hydrocarbons duringfires, 154 and by the photooxidation of chlorinated solventsin the atmosphere. 155At room temperature (20°C) phosgene is a fumingliquid with a vapor pressure of 1180 mm Hg and boilingpoint of 7.6°C. The gas is heavier than air, witha relative density ratio of 4.39 at 20°C. This densityallows phosgene gas to collect in low-lying areas.Phosgene’s odor is somewhat sweet and resembles thatof fresh cut grass or hay. At higher concentrations theodor becomes pungent or burning and causes rapidolfactory fatigue. 156Exposure to phosgene gas causes irritation to theeyes, nose, throat, and respiratory tract. Higher phosgenegas exposures can lead to pulmonary edema anddeath. Exposure to liquid phosgene by direct skin oreye contact is rare but is thought to produce localizedsevere burns. 156 Inhalation is the most toxic exposureroute for phosgene and the route thought to havecaused most of the injuries and deaths during WorldWar I. A patient who has inhaled phosgene requiresadvanced treatment techniques.Phosgene is also a powerful acylating agent thatreacts with nucleophiles such as amines, sulfides, orhydroxyls. Phosgene’s toxicity was originally thoughtto be due to HCl generation during the reaction ofphosgene with moisture in the body. Later, acylationreactions were found to be responsible for a majorityof phosgene’s toxic effects. Phosgene is greater than800 times more toxic than HCl. Free amines protectagainst phosgene poisoning but not against the toxiceffects of HCl, phosgene inhibits coenzyme I and HCldoes not, and chemically similar compounds (suchas ketene) that do not have chlorine to generate HClhave similar toxicity to phosgene. 157 Furthermore,phosgene’s rate of reaction with free amines has beenfound to be much higher than its rate of reaction withwater. In a solution of aniline in water, phosgene reactsalmost exclusively with the aniline. 152Most of the data on health effects from phosgene arefrom inhalation exposures. The regulatory thresholdlimit value (8-hour, time-weighted average) for phosgenehas been established by the National Institute forOccupational Safety and Health, an institute withinthe Centers for Disease Control and Prevention, as 0.1ppm 158 ; the 60-minute and 24-hour emergency exposurelimits are 0.2 ppm and 0.02 ppm, respectively. 155734
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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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