MMSL 2015, 84(3):128-139 | DOI: 10.31482/mmsl.2015.014
IRRITANT COMPOUNDS: MILITARY RESPIRATORY IRRITANTS. PART I. LACRIMATORSReview article
- 1 Department of Radiology and Toxicology, Faculty of Health and Social Studies, University of South Bohemia, Ceske Budejovice, Czech Republic
- 2 Center of Advanced Studies, Faculty of Military Health Sciences, University of Defence, Hradec Kralove, Czech Republic
- 3 Biomedical Research Centre, University Hospital; Hradec Kralove, Czech Republic
World War I was a conflict where chemical warfare was first used on a massive scale. The earliest chemical attack occurred on the Western Front in October 1914 in Neuve Chapelle, but its effects were so minimal that the Allies learned about it only after the war from German documents. The attack in the Bolimow area, carried out by the Germans against the Russian army with artillery shells containing gas T (xylyl and benzyl bromides), was therefore the first attack on a massive scale recorded on the victim side. The attack, which occurred after it, made it possible to obtain some tactical success, but without a strategic breakthrough. Some of the later German attacks on the Eastern Front where chlorine was used proved to be more effective, but despite many victims there was not any major strategic success achieved. The Russians did not take attempts to use chemical weapons in the World War I.
Keywords: respiratory irritants; irritant gases; chemical warfare agents; riot control agents; World War I
Received: September 29, 2014; Revised: May 24, 2015; Published: September 4, 2015 Show citation
References
- Aghabiklooei A, Zamani N, Shiva H, Rezaei N. Inhalational exposure to dimethyl sulfate vapor followed by reactive airway dysfunction syndrome. Indian J Occup Environ Med. 2010, 14(3), 104-106.
Go to original source...
Go to PubMed...
- Alarie Y, Schaper M, Nielsen GD, Abraham MH. Structure-activity relationships of volatile organic chemicals as sensory irritants. Arch. Toxicol. 1998, 72 (3), 125-140.
Go to original source...
Go to PubMed...
- Andreas M, Armbruster U, Atia H. Recent developments in dehydration of glycerol toward acrolein over heteropolyacids. Eur J Lipid Sci Technol. 2012, 114 (1), 10-23.
Go to original source...
- Bajgar J, Fusek J, Kassa J, Kuča K, Jun D. Global impact of chemical warfare agents used before and after 1945. In: Gupta RC. (ed.). Handbook of Toxicology of Chemical Warfare Agents. Elsevier, 2009. ISBN 978-0-12-374484-5
- Blain PG. Tear gases and irritant incapacitants. 1-chloroacetophenone, 2-chlorobenzylidene malononitrile and dibenz[b,f]-1,4-oxazepine. Toxicol Rev. 2003, 22(2), 103-110.
Go to PubMed...
- Boa AN, Jenkins PR. o-Nitrobenzyl Bromide. e-EROS Encyclopedia of Reagents for Organic Synthesis. Published Online: 15 APR 2001. DOI: 10.1002/047084289X.rn033.
- Brondeau MT, Bonnet P, Guenier JP, Simon P, de Ceaurriz J. Adrenal-dependent leucopenia after short-term exposure to various airborne irritants in rats. J Appl Toxicol. 1990, 10(2), 83-86.
Go to original source...
Go to PubMed...
- Budavari S. (ed.). The Merck Index - An Encyclopedia of Chemicals, Drugs, and Biologicals. Whitehouse Station, NJ: Merck and Co., Inc., 1996., p. 1725.
- Cardillo P, Girelli A. Thermal stability of nitrobenzyl halogenides. J Chem Engin Data. 1984, 29 (3), 348-351.
Go to original source...
- Casse F, Groten J, Feron V. Changes in the nasal epithelium of rats exposed by inhalation to mixtures of formaldehyde, acetaldehyde, and acrolein. Fundam Appl Toxicol, 1996, 29, 208-218.
Go to original source...
Go to PubMed...
- Catch JR, Elliot DF, Hey DH, Jones ERH. Halogenated ketones. Part I. The bromination of acetone and methyl ethyl ketone. J Chem Soc. 1948; 272-275.
Go to original source...
- ChemSink. http://www.chemsink.com/compound/10103469/
- Chen WP, Yang XY, Hegeman AD, Gray WM, Cohen JD. Microscale analysis of amino acids using gas chromatography-mass spectrometry after methyl chloroformate derivatization. J Chromatogr B Analyt Technol Biomed Life Sci. 2010, 878(24), 2199-2208.
Go to original source...
Go to PubMed...
- Clayton GD, Clayton EF (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982.
- Cozzi PG, Mignogna A, Vicennati P. Dimethylzinc-mediated, oxidatively promoted Reformatsky reaction of ethyl iodoacetate with aldehydes and ketones. Advanced Synthesis Catalysis 2008, 350(7-8), 975-978.
Go to original source...
- Dawson DA, Mooneyham T, Jeyaratnam J, Schultz TW, Pöch G. Mixture toxicity of S(N)2-reactive soft electrophiles: 2-evaluation of mix-tures containing ethyl α-halogenated acetates. Arch Environ Contam Toxicol. 2011, 61(4), 547-557.
Go to original source...
Go to PubMed...
- De Ceaurriz J, Desiles JP, Bonnet P, Marignac B, Muller J, Guenier JP. Concentration-dependent behavioral changes in mice following short-term inhalation exposure to various industrial solvents. Toxicol Appl Pharmacol. 1983, 67(3), 383-389.
Go to original source...
Go to PubMed...
- Deichmann WB. Toxicology of Drugs and Chemicals. New York, Academic Press, Inc., 1969, p. 169.
- Dreisbach RH. Handbook of Poisoning. 12th ed. Norwalk, CT: Appleton and Lange, 1987., p. 205.
- Dudek BR, Short RD, Brown MA, Roloff MV. Structure-activity relationship of a series of sensory irritants. J Toxicol Environment Hlth. 1992, 37(4), 11-18.
Go to original source...
Go to PubMed...
- Ellenhorn MJ, D.G. Barceloux. Medical Toxicology - Diagnosis and Treatment of Human Poisoning. New York, NY: Elsevier Science Publishing Co., Inc. 1988., p. 35
- Hamilton A, Hardy HL. Industrial Toxicology. 3rd ed. Acton, Mass.: Publishing Sciences Group, Inc., 1974., p. 314.
- Fall M, Haddouk H, Morin JP, Forster R. Mutagenicity of benzyl chloride in the Salmonella/microsome mutagenesis assay depends on exposure conditions. Mutat Res. 2007, 633(1), 13-20.
Go to original source...
Go to PubMed...
- Faroon O, Roney N, Taylor J, Ashizawa A, Lumpkin MH, Plewak DJ. Acrolein health effects. Toxicol Ind Health. 2008, 24(7), 447-490.
Go to original source...
Go to PubMed...
- Feron V, Kruysse A, Immel H. 1978. Repeated exposure to acrolein vapour: subacute studies in hamsters, rats, and rabbits. Toxicology, 1978, 9,47-57.
Go to original source...
Go to PubMed...
- Geering EJ. Process for preparing methyl chlorosulfates. US Patent 4649209 A, 1987.
- Ghilarducci DP, Tjeerdema RS. Fate and effects of acrolein. Rev Environ Contam Toxicol. 1995, 144, 95-146.
Go to original source...
Go to PubMed...
- Grant WM. Toxicology of the Eye. 2nd ed. Springfield, Illinois, Charles C. Thomas Publisher, 1974., p. 203.
- Grant WM. Toxicology of the Eye. 3rd ed. Springfield, IL: Charles C. Thomas Publisher, 1986.
- Hawley GG. The Condensed Chemical Dictionary. 9th ed. New York: Van Nostrand Reinhold Co., 1977., p. 932.
- Hemminki K, Falck K, Linnainmaa K. Reactivity, SCE induction and mutagenicity of benzyl chloride derivatives. J Appl Toxicol. 1983, 3(4), 203-207.
Go to original source...
Go to PubMed...
- Ho TL, Fieser M, Fieser L. Dichloromethyl chloroformate. Fieser and Fieser's Reagents for Organic Synthesis. John Wiley & Sons, Inc. 2007, On-line 2006.
Go to original source...
- IARC, 1999. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Man. Geneva: World Health Organization, International Agency for Research on Cancer, 1972-PRESENT. (Multivolume work). Available at: http://monographs.iarc.fr/index.php p. 71 584 (1999).
- ICRC 2010. International Committee of the Red Cross, Incapacitating Chemical Agents: Implication for International Laws, held in Montreux, Switzerland, 24 to 26 March 2010; 2010.
- ICRC 2012. Expert meeting entitled: Incapacitating Chemical Agents: Law Enforcement, Human Rights Law and Policy Perspectives, Montreux, Switzerland, from 24 to 26 April 2012.
- Ip M, Wong KL, Wong KF, So SY. Lung injury in dimethyl sulfate poisoning. J Occup Med. 1989, 31(2), 141-143.
- Ivanov VA. Brief comment on publication "First chemical mass attack in history of wars, Bolimow, January 31, 1915". Przegl Epidemiol. 2013, 67(1), 92.
Go to PubMed...
- Jackson KE, Jackson MA. Lachrymators. Chem Rev. 1935, 16(2), 195-242.
Go to original source...
- Jackson KE. Sternutators. Chem Rev. 1935, 17(2), 251-292.
Go to original source...
- Kawai A, Goto S, Matsumoto Y, Matsushita H. Mutagenicity of aliphatic and aromatic nitro compounds. Sangyo Igaku. 1987, 29(1), 34-55.
Go to original source...
Go to PubMed...
- Kinoshita M, Kawaguchi S, Higuchi E, Ichikawa Y, Oizumi K. [A case of dimethyl sulfate intoxication manifested by persistent dyspnea]. Nihon Kyobu Shikkan Gakkai Zasshi. 1992, 30(5), 959-963. Japanese.
Go to PubMed...
- Klaus A, Andres S, Palavinskas R, Berg K, Appel KE, Lampen A. Toxicology and risk assessment of acrolein in food. Mol Nutr Food Res. 2011, 55, 1277-1290.
- Kuča K, Pohanka M. Chemical warfare agents. Mol Clin Environ Toxicol, 2010, 543-558.
Go to original source...
- Larsen JP. Chemical Warfare, Terrorism, and National Defense. ARMY WAR COLL CARLISLE BARRACKS PA, 2001.
- Lide DR. (ed.). CRC Handbook of Chemistry and Physics. 79th ed. Boca Raton, FL: CRC Press Inc., 1998-1999.
- Lide DR, Milne GWA. Handbook of Data on Common Organic compounds. Volume 1. CRC Press, 1995, p. 2796.
- Lijinsky W. Chronic bioassay of benzyl chloride in F344 (C57BL/6J X BALB/C) F1 mice. J Natl. Cancer Inst. 1986, 76(6), 1231-1236.
Go to PubMed...
- Lewis RJ (ed). Hawley's Condensed Chemical Dictionary. 13th ed. NY, NY: John Wiley and Sons 1997; p. 1189.
- Lewis RJ (ed). Hawley's Condensed Chemical Dictionary 15th Edition. John Wiley & Sons, Inc. New York, NY 2007., p. 182.
- Lewis RJ ((ed). Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3. New York NY: Van Nostrand Reinhold, 1996a., p. 1524.
- Lewis RJ. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3. New York, NY: Van Nostrand Reinhold, 1996b, p. 3163.
- Lide DR. (ed.). CRC Handbook of Chemistry and Physics. 79th ed. Boca Raton, FL: CRC Press Inc., 1998-1999.
- Lucas SV; GC/MS Analysis of Organics in Drinking Water Concentrates and Advanced Waste Treatment Concentrates: Vol 1. Columbus, OH: USEPA-600/1-84-020A 1984. p. 321.
- Mackworth JF. The inhibition of thiol enzymes by lachrymators. Biochem J. 1948, 42(1), 82.
Go to original source...
Go to PubMed...
- TOXNET. Toxicology Data Network. Available from http://chem.sis.nlm.nih.gov/chemidplus/rn/623-48-3
- Marhold JV. Thiofosgen. Sborník Výsledků toxixologického vyšetreni látek a přípravků. Institut pro ýychovu vedoucich pracovniků chemického průmyslu Praha, Czechoslovakia, 1972; p. 13.
- Lyon JP, Jenkins LJ, Jones RA, Coon RA, Siegel J. Repeated and continuous exposure of laboratory animals to acrolein. Toxicol Appl Pharmacol. 1970, 17, 726-732.
Go to original source...
Go to PubMed...
- Marrs TT, Maynard RL, Sidell F. Chemical Warfare Agents: Toxicology and Treatment. Joh Wiley and Sons, 2007, p. 750.
Go to original source...
- Merrick BA, Smallwood CL, Meier JR, McKean DL, Kaylor WH, Condie LW. Chemical reactivity, cytotoxicity, and mutagenicity of chloropropanones. Toxicol Appl Pharmacol. 1987, 91(1), 46-54.
Go to original source...
Go to PubMed...
- Mirzayans R, Meredith J, Waters R. DNA damage and its repair in cultured human alveolar tumor cells treated with benzyl chloride, 4-chloromethylbiphenyl or 4 hydroxymethylbiphenyl. Mutat Res. 1982, 100(1-4), 203-206.
Go to original source...
Go to PubMed...
- Mudiam MK, Jain R, Varshney M, Ch R, Chauhan A, Goyal SK, Khan HA, Murthy RC. In matrix derivatization of trichloroethylene metabolites in human plasma with methyl chloroformate and their determination by solid-phase microextraction-gas chromatography-electron capture detector. J Chromatogr B Analyt Technol Biomed Life Sci. 2013, 925, 63-69.
Go to original source...
Go to PubMed...
- Olajos EJ, Stopford W. Riot Control Agents. CRC Press, Bocca Raton 2004, pp.353. ISBN 0415299020
Go to original source...
- O'Neil MJ (ed). The Merck Index - An Encyclopedia of Chemicals, Drugs, and Biologicals. Whitehouse Station, NJ: Merck and Co., Inc., 2006.
- Owens EA, Bruschi N, Tawney JG, Henary M. A microwave-assisted and environmentally benign approach to the syntheis of near-infrared fluorescent pentamethine cyanine dyes. Dyes Pigments. 2015, 113(1), 27-37.
Go to original source...
- Patočka J et al., Military Toxicology. Grada Publishing, Prague, 2004. p. 178.
- Patocka J, Kuca K. Irritant compounds: respiratory irritant gases. Milit Med Sci Lett. 2014, 83(2), 73-82.
- Patočka J, Měrka V. L'humanité a peur du chlore depuis 90 ans déjà. Rev Int Serv Sante Armees. 2005, 78(2), 128-131.
- Patty F. (ed.). Industrial Hygiene and Toxicology: Volume II: Toxicology. 2nd ed. New York: Interscience Publishers, 1963., p. 1928.
- Philippin C, Gilgen A, Grandjean E. Toxicological and physiological investigation on acroleine inhalation in the mouse. [Article in French] Int Arch Arbeitsmed. 1970, 26(4), 281-305.
Go to original source...
Go to PubMed...
- Potter W. Chloroacetophenone. OSHA Stopgap Method. Salt Lake City, UT: U.S. Department of Labor, OSHA Analytical Laboratory, Solvents Branch, 1982.
- Prager JC. Environmental Contaminant Reference Databook Volume 2. New York, NY: Van Nostrand Reinhold, 1996. p. 1021.
- Robinson JP. Problem of Chemical and Biological Warfare: A Study of Historical, Technical, Military, Legal, and Political Aspects of CBW. Vol 1. The Rise of CB Weapons. New York, NY: SIPRI/Humanities Press; 1971.
- Romano JA, Lukey BJ, Salem H (Eds.). Chemical Warfare Agents. Chemistry, Pharmacology, Toxicology, and Therapeutics. Boca Raton, CRC Tyalor & Francis, 2007. p. 723.
Go to original source...
- Royer J, Gainet F. Ocular effects of tear gases containing ethyl bromacetate. [Article in French] Bull Soc Ophtalmol Fr. 1973, 73(12), 1165-1171.
Go to PubMed...
- Sargent EV, Kirk GD, Hite M. Hazard evaluation of monochloroacetone. Am Ind Hyg Assoc J. 1986, 47(7), 375-378.
Go to original source...
Go to PubMed...
- Sax NI, Lewis RJ, Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van Nostrand Reinhold Co., 1987., p. 764.
- Schep LJ, Slaughter RJ, McBride DI. Riot control agents: the tear gases CN, CS and OC - a medical review. J R Army Med Corps. 2013 Dec 30. doi: 10.1136/jramc-2013-000165.
Go to original source...
Go to PubMed...
- Schettgen T, Broding HC, Angerer J, Drexler H. Dimethyl sulphate; a hidden problem in occupational medicine. Occup Environ Med. 2004, 61(1), 73-75.
- Schuckmann F. Symptomatics of methyl chloroformate intoxication. [Article in Germany]. Zentralbl Arbeitsmed Arbeitsschutz. 1972, 22(3), 74-76.
- Searle CE. (ed.). Chemical Carcinogens. ACS Monograph 173. Washington, DC: American Chemical Society, 1976., p. 160.
- Sharma S. Thiophosgene in Organic Synthesis. Synthesis. 1978, (11), 803-820.
Go to original source...
- Shimizu M, Yano E. Mutagenicity of mono-nitrobenzene derivatives in the Ames test and Rec assay. Mutat Res. 1986, 170(1-2), 11-22.
Go to original source...
Go to PubMed...
- Skog E. Anaesthetic and haemolytic action of lower aliphatic aldehydes and their effect on respiration and blood pressure. Acta Pharmacol Toxicol (Copenh). 1952, 8(3), 275-289.
Go to original source...
Go to PubMed...
- Středa L, Patočka J. Incapacitating chemicals - Risk to the purpose and objectives of the Chemical Weapons Convention? Kontakt, 2014, 16(1): e57-e63.
Go to original source...
- Szinicz L. History of chemical and biological warfare agents. Toxicology. 2005, 214(3), 167-181.
Go to original source...
Go to PubMed...
- Tuorinsky SD (ed.). Medical Aspects of Chemical Warfare, 2nd edition, Tuorinsky SD. (Ed), Office of the Surgeon General, TMM Publications, Washington, DC 2008. p. 339.
- Van Duuren BL, Goldschmidt BM, Katz C, Seidman I, Paul JS. Carcinogenic activity of alkylating agents. J Nat Cancer Inst. 1974, 53(3), 695-700.
Go to original source...
Go to PubMed...
- VERIFIN 1011. Technical Workshop on Incapacitating Agents, held in Spiez, Switzerland, 8 and 9 September 2011; 2011.
- Vernot EH, MacEwen JD, Haun CC, Kinkead ER. Acute toxicity and skin corrosion data for some organic and inorganic compounds and aqueous solutions. Toxicol Appl Pharmacol. 1977, 42(2), 417-423.
Go to original source...
Go to PubMed...
- Wang YJ, Zheng XL, He Y, Zhang D, Wang BD. [Research on determination of total volatile organic sulfur compounds in the atmosphere]. Huan Jing Ke Xue. 2011, 32(12), 3617-3622. Chinese.
Go to PubMed...
- Wu J, Chen ZS, Kang ZH, Ye LM, Yang L. [Nasopharyngeal manifestations and outcomes of acute dimethyl sulfate poisoning]. Zhonghua Lao Dong Wei Sheng Zhi Ye Bing Za Zhi. 2007, 25(2), 115-116. Chinese.
Go to PubMed...
- Yadav UC, Ramana KV, Srivastava SK. Aldose reductase regulates acrolein-induced cytotoxicity in human small airway epithelial cells. Free Radic Biol Med. 2013, 65, 15-25.
Go to original source...
Go to PubMed...
- Yasuko, K, Fzjimoto S, Katoph M, Kikuchi Y, Kada T. Mutagenicity of benzotrichloride and related compounds. Mutat Res. 1978, 58, 143-150.
Go to original source...
Go to PubMed...
- Zeigler E, Anderson B, Haworth S, Lawlor T, Mortelmans K. Salmonella mutagenicity tests. V. Results from the testing of 311 chemicals. Environ Mil Mutagen. 1992, 19(Suppl. 21), 2-141.
Go to original source...
Go to PubMed...
- Zheng J, Pritts WA, Zhang S, Wittenberger S. Determination of low ppm levels of dimethyl sulfate in an aqueous soluble API intermediate using liquid-liquid extraction and GC-MS. J Pharm Biomed Anal. 2009, 50(5), 1054-1059.
Go to original source...
Go to PubMed...