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

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Cyanide PoisoningTable 11-2 continuedSpectrochemical Absorption or LuminescenceHCN Human blood (whole) Fluorometric 2,000 52 ~ 17 min 17HCN Equine blood Spectrophotometry following trapping 74 2 ~ 16 h 18of HCN gasHCN Human blood (whole) Spectrophotometry 1,000 27 ~ 45 min 19SCN − Human blood serum, Flame atomic absorption spectrometry; 69 4 ~ 20 min 20urine, salivacalibration*This table is meant to give a general overview of analytical methods in this area and their detection limits. It is not meant to be all-inclusive.The 2004 US Department of Health and Human Services Agency for Toxic Substances and Disease Registry toxicology profile for cyanidealso includes biological analytical methods not mentioned above and environmental analytical methods, including the US EnvironmentalProtection Agency and National Institute for Occupational Safety and Health standard methods. 21† Conversion of units; figures are multiplied by the molecular weight of HCN, 27 g/mol.EC: electron capture; GC: gas chromatography; GCMS: gas chromatography mass spectrometry; HCN: hydrogen cyanide; HPLC: highperformanceliquid chromatography; IC: ion chromatography; LC: liquid chromatography; LCMS: liquid chromatography mass spectrometry;NPD: nitrogen phosphorous detector; RDE: rotating disk electrode; SPME: solid phase microextraction; SCN − : thiocyanate; UV:ultravioletData sources: (1) Dumas P, Gingras G, LeBlanc A. Isotope dilution-mass spectrometry determination of blood cyanide by headspace gaschromatography. J Anal Toxicol. 2005;29:71–75. (2) Calafat AM, Stanfill SB. Rapid quantitation of cyanide in whole blood by automatedheadspace gas chromatography. J Chromatogr B Analyt Technol Biomed Life Sci. 2002; 772:131–137. (3) Ishii A, Seno H, Watanabe-Suzuki K,Suzuki O, Kumazawa T. Determination of cyanide in whole blood by capillary gas chromatography with cryogenic oven trapping. AnalChem. 1998;70:4873–4876. (4) Tracqui A, Raul JS, Geraut A, Berthelon L, Ludes B. Determination of blood cyanide by HPLC-MS. J Anal Toxicol.2002;26:144–148. (5) Meiser H, Hagedorn HW, Schultz R. Development of a method for determination of cyanide concentrations in serumand rumen fluid of cattle. Am J Vet Res. 2000;61:658–664. (6) Kage S, Nagata T, Kudo K. Determination of cyanide and thiocyanate in bloodby gas chromatography and gas chromatography-mass spectrometry. J Chromatogr B Biomed Appl. 1996;675:27–32. (7) Logue BA, KirschtenNP, Petrikovics I, Moser MA, Rockwood GA, Baskin SI. Determination of the cyanide metabolite 2-aminothiazoline-4-carboxylic acid inurine and plasma by gas chromatography-mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci. 2005;819:237–244. (8) WestleyAM, Westley J. Voltammetric determination of cyanide and thiocyanate in small biological samples. Anal Biochem. 1989;181:190–194. (9)Ganjali MR, Yousefi M, Javanbakht MJ, et al. Determination of SCN − in urine and saliva of smokers and non-smokers by SCN(-)- selectivepolymeric membrane containing a nickel(II)-azamacrocycle complex coated on a graphite electrode. Anal Sci. 2002;18:887–892. (10)Felscher D, Wulfmeyer M. A new specific method to detect cyanide in body fluids, especially whole blood, by fluorimetry. J Anal Toxicol.1998;22:363–366. (11) Chinaka S, Takayama N, Michigami Y, Ueda K. Simultaneous determination of cyanide and thiocyanate in blood byion chromatography with fluorescence and ultraviolet detection. J Chromatogr B Biomed Sci Appl. 1998;713:353–359. (12) Connolly D, BarronL, Paull B. Determination of urinary thiocyanate and nitrate using fast ion-interaction chromatography. J Chromatogr B Analyt TechnolBiomed Life Sci. 2002;767:175–180. (13) Casella IG, Guascito MR, De Benedetto GE. Electrooxidation of thiocyanate on the copper-modifiedgold electrode and its amperometric determination by ion chromatography. Analyst. 1998;123:1359–1363. (14) Chen SH, Yang ZY, Wu HL,Kou HS, Lin SJ. Determination of thiocyanate anion by high-performance liquid chromatography with fluorimetric detection. J Anal Toxicol.1996;20:38–42. (15) Lundquist P, Kagedal B, Nilsson L. An improved method for determination of thiocyanate in plasma and urine. Eur J ClinChem Clin Biochem. 1995;33:343–349. (16) Lundquist P, Kagedal B, Nilsson L, Rosling H. Analysis of the cyanide metabolite 2-aminothiazoline-4-carboxylic acid in urine by high-performance liquid chromatography. Anal Biochem. 1995;228:27–34. (17) Groff WA, Stemler FW, KaminskisA, Froehlich HL, Johnson RP. Plasma free cyanide and blood total cyanide: a rapid completely automated microdistillation assay. J ToxicolClin Toxicol. 1985;23:133–163. (18) Hughes C, Lehner F, Dirikolu L, et al. A simple and highly sensitive spectrophotometric method for thedetermination of cyanide in equine blood. Toxicol Mech Methods. 2003;13:1–10. (19) Lundquist P, Sörbo B. Rapid determination of toxic cyanideconcentrations in blood. Clin Chem. 1989;35:617–619. (20) Chattaraj S, Das AK. Indirect determination of thiocyanate in biological fluidsusing atomic absorption spectrometry. Spectrochica Acta. 1992;47:675–680. (21) Toxicological Profile for Cyanide. Atlanta, Ga: US Departmentlow temperature, and preserving agents arecommon procedures used to prevent loss ofcyanide. Rubber stoppers have been shown toadsorb or dissolve HCN when in contact withthe gas, so use of rubber stoppers to seal vialsshould be avoided. 95 Storing samples at lowtemperatures to slow chemical reactions hasbeen tested, and temperature studies for biologicalsamples containing cyanide have beenperformed. However, there are many temperaturediscrepancies in the literature. 69,81,83,96,97The temperature study performed by Lundquistet al resulted in the following fourdeterminations 82 : (1) cyanide in whole bloodis reasonably stable at −20°C, and this stabilitydecreased at the higher temperatures of 4°Cand room temperature; (2) the addition ofsilver ions (silver sulfate) immediately after379
Medical Aspects of Chemical Warfarecollection appeared to stabilize cyanide atthe higher temperatures; (3) the addition ofthe silver sulfate immediately after collectionincreased storage time of biological samples at4°C for at least 2 weeks; and (4) the addition ofsilver sulfate also appeared to quench the reactionof cyanide and bovine serum albumin toform iminothiazolidine and cysteine residuesin blood plasma. Forming other stable cyanidecomplexes, for example, by adding sodiumnitrite to form methemoglobin or by addinghydroxocobalamin, has also been performedsuccessfully. 87,98• Cyanide may form during storage. Artifactualformation of cyanide may also occur inbiological samples depending on storage conditions.91,97,99–101 It has been suggested that oxyhemoglobin,100 thiocyanate oxidase, 91,101 andgranulocytes (white blood cells) 99 may oxidizethiocyanate to cyanide and that these reactionsare dependent on the temperature and pH ofthe sample. Lundquist’s temperature dependenceanalysis was found to be different fromearlier studies 69,96,97 and his use of silver ionsmay also improve thiocyanate stability. 82 Microorganismsare also responsible for cyanideproduction, 101 and low temperature storagehelps to eliminate their growth.These considerations, common to all the analyticalmethods, are a major source for the vast discrepanciesin cyanide and cyanide metabolite levels reported fromcasualties. Because of the detoxification processes andcyanide’s physical and nucleophilic properties, directanalysis of cyanide is not normally done with urineor saliva samples, although traces have been found inurine, saliva, and expired air. The cyanide metabolitesthiocyanate and ATCA may be determined in urine,saliva, and blood plasma. Correlation of their concentrationsto cyanide exposure have been examined. 96,102–104,150–153Advantages to measuring thiocyanate are thatappreciable concentrations may be found immediatelyafter exposure, and that it is considered to be morestable than cyanide. However, the true concentrationmay also be difficult to determine because of itsconversion back to cyanide during storage. 153 ATCAis stable in biological samples for months at freezingand ambient temperatures. 154 Based on determinationof pK avalues (carboxylic acid: 2.03; amine: 8.48) andnuclear magnetic resonance studies, 154 ATCA formsa bipolar ion in solution and is therefore not volatile.It has been suggested that ATCA has lower initialconcentrations than thiocyanate, but its stability andapplicability to sensitive analytical techniques mayprove more beneficial. Disadvantages for both ATCAand thiocyanate, as with cyanide, include naturallyoccurring background levels that are different for eachperson, making it difficult to quantify low-level cyanideexposure without establishing baseline levels foran individual prior to exposure. 96,155 In addition, cyanidedistribution and concentrations in organs differdepending on the route of administration and primatespecies type. Organ cyanide concentrations have alsobeen used for blood cyanide intoxication levels inforensic cases; however, the postmortem productionand transformation of cyanide must be considered ininterpreting the results. 85,86,92,156–159The analytical determination of cyanide is not aneasy task because of its volatility, nucleophilic properties,and lack of color. Although numerous methodshave been developed, each must be used with precautionsbecause of interferences and instrumentationcapabilities. However, all the methods have helped insome way or another to provide insight into the detectionof cyanide in biological fluids. When selecting ananalytical method, several factors in addition to thedetection limit and length of time needed (Table 11-2)must be considered:• Does the method include consideration ofpreserving cyanide and its metabolites duringstorage?• Does the method include correct storage ofstock solutions 95 or use fresh preparationsdaily?• Does the method include consideration oftypical interferences found in blood?• Does the method test for cyanide with andwithout clinically used antidotes present?• Does the method include analysis procedures(eg, pH, heating, and acidification) that couldresult in the loss of cyanide? Are rubber stoppersor septums used?• Are the chemicals used in the determinationtoxic or carcinogenic?• Is the method precise, accurate, inexpensive,and practical?The literature displays a great deal of inconsistencyin reporting on how cyanide or thiocyanate analyticalmethods faired during storage, the validation of themethod in the presence of antidotes, and timing ofsample collection. Several authors strongly emphasizethe importance of collection and storage of cyanidecontaminatedbiological samples. 82,87,105–109,158–160 Becauseno simple, fast, lightweight, sensitive, and accuratemethods are currently available for detection of cyanidein biological fluids, none are appropriate for diagnostic380
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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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Page 351 and 352: Medical Aspects of Chemical Warfare
Page 375 and 376: 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 Casualtiesentran
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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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• Analyze using GC-MS with methan
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Abbreviations and AcronymsAbBreviat
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Abbreviations and AcronymsPADPRP: p
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