1、Chemical Defense MedicineKai Xiao(肖凯),Ph D,ProfessorChapter 1IntroductionWhat are Chemical Agents?Chemical warfare agents mean“chemicals(whether gaseous,liquid,or solid)with high toxicity are used in wars to kill and wound people,animals or plants on a large scale”.Substance that is intended for use
2、 in military operations to kill,seriously injure or incapacitate people because of its physiological effects.Excluded from this definition are riot control agents,herbicides,smoke,and flame.NATO HANDBOOK They are briefly called“chemical agents”.防化医学(chemical defense medicine)是军事医学的重要组成部分，核心是军事毒理学(mi
3、litary toxicology)化学战剂中毒的毒理学和预防、诊断及救治 战剂对食物、水源染毒的侦检、消毒等卫生学 中毒伤员的洗消等防化卫生勤务保障 防防 化化 医医 学学1.Why bother learning this course?1.1 历史上的化学战与现存的威胁历史上的化学战与现存的威胁 Chemical warfare will not become history1.1.1 古代的化学战古代的化学战最早的记录可追溯到黄帝与蚩尤大战。公元前2000年以前，古印度用毒沥青和硫磺来使得守卫者窒息死亡，从而削弱城市的防卫。春秋公羊传：庄公17年（公元前677年），齐军占领遂地，“遂人
4、共以药投其所饮水中，多杀之”。“迁延之役”：襄公14年（公元前559年），晋国联合鲁、郑等诸侯国，大举攻秦，当联军要渡过秦国泾河时，“秦人毒泾上流，师人多死”。北魏文帝时（公元452-471）济阴王讨伐库莫奚，“乃为毒酒，贼既逼，弃营而走。贼至竟饮，毒作。王以轻骑纵击，俘获万计”。诸葛亮:化学战的高手，incendiary agents or flame materials 423 BC,伯罗奔尼撒半岛战争中斯巴达攻陷雅典，使用了煤、硫磺、沥青 等燃烧的毒烟.Greek fire(公元 700年)15和16世纪:Venice 使用毒剂加入炮弹或进行投毒.The birth of modern
5、inorganic chemistry during the late 18th and early 19th centuries and the flowering of organic chemistry in Germany during the late 19th and early 20th centuries generated a renewed interest in chemicals as military weapons.1.1.2 现代的化学战现代的化学战The first large-scale use of chemical agents was in WWI by
6、 Germany,near Ypres,Belgium,in the afternoon of 15 April,1915.Fritz Haber(哈伯哈伯,18681934)Winner of 1918 Nobel Prize in chemistry for the synthesis of ammonia from its elements.Regarded as the father of modern chemical warfare as he organized and directed the first large scale release of chlorine gas
7、at Ypres.6,000 钢瓶钢瓶,168t Cl2 Smoke wall 50 feet high,4 miles long,Lasting 5 min 15,000 poisoned800 killed5,000 capturedWind:2 m/sThe large-scale chemical attack in WWI conducted by GermanyAlthough this attack caused probably no more than 800 deaths,it was psychologically devastating to the 15,000 Al
8、lied troops,who promptly retreated.The Germans,however,were unprepared to take advantage of this victory,and chlorine and its successors were doomed to play a tactical,rather than a strategic role,during the war.Chemical agents are most heavily used in WWI:45 kinds of agents used a total of 1,130,00
9、0 tons used a total of 1,300,000 casualties claimedWWI chemical war casualties(Total 1,300,000)countriescasualties%fatalGermany200,0004.5France190,0004.2Britain189,0004.2US 73,0002.0Russia475,00011.8Kurds 5,000100?nameFirst usetypeXylyl bromide 1914Lachrymatory,toxic Chlorine 1915Corrosive.Lung Irri
10、tant Phosgene 1915pulmonary,toxic Benzyl bromide 1915Lachrymatory Chloromethyl chloroformate 1915Irritant-Eyes,skin,lungs Trichloromethyl chloroformate 1916Severe irritant,causes burns Chloropicrin 1916Irritant,lachrymatory,toxic Stannic chloride 1916Severe irritant,causes burns Ethyl iodoacetate 19
11、16Lachrymatory,toxic Bromoacetone 1916Lachrymatory,irritant Bromomethyl ethyl ketone 1916Lachrymatory,irritantAcrolein 1916Lachrymatory,toxic Hydrogen cyanide(Prussic acid)1916Toxic,Chemical Asphyxiant Hydrogen sulfide1916Irritant,toxic Diphenylchloroarsine1917Irritant/Sternutatory a-Chlorotoluene(B
12、enzyl chloride)1917Irritant,lachrymatory Mustard gas1917Vesicant,lung irritant Bis(chloromethyl)ether1918Irritant,can blur vision Ethyldichloroarsine 1918Vesicant N-Ethylcarbazole 1918Irritant Gases used in WWISo,World War I was called the Chemists war-ushered in the beginning of the modern era of c
13、hemical warfare.The German side:Fritz Harber(and several future Nobel laureates),chlorine,maskThe French counterpart:Victor Grignard(phosgene,detection of mustard)World War (19391945)：二战时欧洲战场上并未使用毒剂。但日军在我国13个省78个地区使用毒剂1600多次二十多万人伤亡。德国法西斯在奥斯威辛集中营使用氢氰酸杀害了250多万犹太人.朝鲜战争(19501953)：美军使用7种毒剂百余次，1951年5月6日美军
14、光气炸弹使1379人中毒，死亡480人.也门内战(19631967)：埃及介入也门内战，使用VX、光气等毒剂炸弹40多次，造成1400多人死亡，900多人严重中毒.越南战争(19621970)：美国使用CS 7000吨，植物杀伤剂 12万吨，用毒700余次，使130多万人中毒，对农业生产造成严重危害.越南侵略柬埔寨、老挝：1981.9.14在柬埔寨、老挝使用第三代化学战剂“黄雨”，造成2万多人死亡.苏军入侵阿富汗：1979年使用梭曼，1986年8月在赫拉特省使用新型全氟毒剂炸弹，受害者出现头晕、呕吐等失能症状，持续时间2天，严重者肺水肿死亡.两伊战争(19801988)：伊拉克使用化学武器24
15、0多次，造成伊朗5万多人死亡。伊朗于1987年4月首次使用芥子气报复伊拉克的化学袭击.海湾战争中化学武器的威慑作用.叙利亚化武疑云:2012-2013.Vietnam victims from defoliants2013年8月21日在叙利亚大马士革东部郊区Ghouta的发生化学武器攻击事件，造成包括几百名儿童在内的一千多人死亡，引起国际社会的强烈关注和谴责Debate concerning the ethics of chemical warfare has been enduring since its birth.The two typical ideas:1.Inhumane and
16、against the rules of warfare2.Chemistry should be used to lessen the sufferings of combatants1.1.3 Ethic debate1812,the British admiralty rejected a request to use burning,sulfur-laden ships as a prelude to marine landings in France as,against the rules of warfare.Forty-two years later,the British W
17、ar Office similarly condemned Sir Lyon Playfairs proposal to use cyanide-filled shells to break the siege of Sebastopol during the Crimean War,arguing that to use cyanide was inhumane and as bad as poisoning the enemys water supply.Sir Lyon retorted,Theres no sense to this objection.It is considered
18、 a legitimate mode of warfare to fill shells with molten metal that scatters upon the enemy and produces the most frightful modes of death.Why a poisonous vapor that would kill men without suffering is to be considered illegitimate is incomprehensible to me.However,no doubt in time chemistry will be
19、 used to lessen the sufferings of combatants.Upon these ethic debate,Convention on the Prohibition of Chemical Weapons development,production,stockpiling and use of chemical weapons and on their Destruction(Chemical Weapons Convention,CWC,化学武器公约)has come a long way before it enters into force.www.op
20、cw.org1.2 Convention1.Each State Party to this Convention undertakes never under any circumstances:a)To develop,produce,otherwise acquire,stockpile or retain chemical weapons,or transfer,directly or indirectly,chemical weapons to anyone;b)To use chemical weapons;c)To engage in any military preparati
21、ons to use chemical weapons;d)To assist,encourage or induce,in any way,anyone to engage in any activity prohibited to a State Party under this Convention.2.Each State Party undertakes to destroy chemical weapons it owns or possesses,or that are located in any place under its jurisdiction or control,
22、in accordance with the provisions of this Convention.GENERAL OBLIGATIONS 3.Each State Party undertakes to destroy all chemical weapons it abandoned on the territory of another State Party,in accordance with the provisions of this Convention.4.Each State Party undertakes to destroy any chemical weapo
23、ns production facilities it owns or possesses,or that are located in any place under its jurisdiction or control,in accordance with the provisions of this Convention.5.Each State Party undertakes not to use riot control agents as a method of warfare.Schedule 1 Have few,if any,legitimate uses.These m
24、ay only be produced or used for research,medical,pharmaceutical or protective purposes(nerve agents,ricin,).Any production over 100 g must be notified to the OPCW,a stockpile of no more than one tonne.Schedule 2 Have no large-scale industrial uses,but may have legitimate small-scale uses(dimethyl me
25、thylphosphonate and thiodiglycol).Schedule 3 Have legitimate large-scale industrial uses(phosgene,HCN and chloropicrin).The OPCW must be notified of,and may inspect,any plant producing more than 30 tonnes per year.Chemicals that are toxic enough to be used as chemical weapons,or that may be used to
26、manufacture such chemicals,are divided into three groups:宣布本国有无化学武器及遗留遗弃在他国的化学武器、生产设施和其他包括实验室、试验场；接受专门设立的联合国官方机构OPCW核查；销毁遗留在他国的化学武器;控暴剂（刺激剂）不能用于战争中。中国印记中国印记：日本遗弃在华化学武器得以妥善解决 公约把可能用作化学武器或可能用于生产化学武器的有毒化学品和前体分列在三个附表里.附表1：曾经用作过化学武器并且/或者没有或几乎没有和平用途的化学品，对公约构成最直接的威胁。附表2：主要是附表1化学品的前体，大部分有某种工业用途。附表3：有大量商业化生产
27、的化学品，但曾用作过化学战剂并且也可以作为附表1或附表2化学品的前体。*特定有机化学品的生产设施 1675,The Strasbourg Agreement,the first international agreement limiting the use of CW(poison bullets).1874,The Brussels Convention on the Law and Customs of War,prohibited the employment of poison or poisoned weapons,and the use of arms,projectiles o
28、r material to cause unnecessary suffering.1899,Conference in The Hague leaded to an agreement prohibiting the use of projectiles filled with poison gas.1915,First large-scale use of chemical agents in WWI.The road to Convention(painstaking)Hague Declarations of 1899 and 1907 Did Not Prevent Use of C
29、hemical Weapons in World War ITear Gas in 1914Chlorine and Phosgene in 1915Mustard in 1917Cl21925,The Geneva Protocol concluded.This treaty bans the use of both bacteriological and chemical weapons but is not enough to stop countries from producing,using and stockpiling chemical weapons thereafter.(
30、USA and Japan rejected)1972,in Geneva,Biological and Toxin Weapons Convention concluded,but no verification mechanism;and committed to continue negotiations on CW as well.1984-1989,Iraq used chemical weapons against Iran and its own Kurdish citizens in the town of Halabja.1992,The negotiators in Gen
31、eva agreed on the text of the Chemical Weapons Convention.Chemical Weapons After World War I1919 in Russia1923-1926in Morocco1937-1945in Manchuria1925 Geneva Protocol(allowed reservations)1935-1940 in AbyssiniaCWC negotiations1972-19921997 CWC entry into force(possessor states declare stockpiles)198
32、3-1988,Iran-Iraq War2013in Syria1963-1975Vietnam War1994-1995Aum Shinrikyo(Tokyo subway)1963-1967in Yemen19192013BWC 1972NPT1968 公约于1993.1.13 在巴黎47届联大开放供签署。1997.4.29，公约生效并成为具有约束力的国际法，当时的缔约国有87个。中国 1996.12.30日批准，1997.4.25递交申请.我国政府和人民一贯主张禁止使用大规模杀伤性武器，恪守公约.(the Organization for the Prohibition of Chemi
33、cal Weapons,OPCW)2016The CWC:an international regime with 191 member states,covering above 98%of the worlds population,98%of its landmass,and 99%of its chemical industry.Green:membersYellow:signed yet not ratifiedRed:neither signed nor acceded www.opcw.orgSignatory States which have not yet ratified
34、 the Chemical Weapons Convention:No.StateSignature1Israel13/01/1993States that have neither signed nor acceded to the Chemical Weapons Convention：No.State1Angola2Democratic Peoples Republic of Korea3Egypt4South Sudan63,956(90%)of the worlds declared stockpile of 72,525 metric tonnes of chemical agen
35、t have been verifiably destroyed.(As at 31/05/2015)4.97(57.32%)of the 8.67 million chemical munitions and containers covered by the CWC have been verifiably destroyed.(As at 31/05/2015)They are supposed to be destroyed by 2007,then extended to 2012.国家宣布数（附表1,吨）销毁数（吨）销毁百分比阿尔巴尼亚1515100%利比亚26.34526.345
36、100%韩国601601100%印度10441044100%美国*27,77224,923.70290%俄罗斯39,97533,763.68488.48%叙利亚1,328.0411301.48098%拥有化学武器国家销毁进展（指附表拥有化学武器国家销毁进展（指附表1中的化学毒剂，截止中的化学毒剂，截止2015.5.31）*美国附表2与3中的化学武器已经销毁完毕；叙利亚的化武数量中包括附表2中的化学武器1998年禁化武组织首批指定实验室(中国、美国、芬兰、荷兰、瑞士、瑞典、韩国）2006开始参加禁化武组织指定实验室水平测试，2007年9月成为禁化武组织指定实验室 苏联和东欧等社会主义国家解体，使
37、西方失去了化学军备竞赛对手；对付第三世界的化学武器扩散、恐怖活动反而成了美国政府的主要考虑；第三世界通过海湾战争也认识到化学武器并非真正的“穷人的原子弹”。签约原因及背景公约并未彻底消除化学武器的威胁化学武器要多年才能全部销毁，这些年世界风云如何变幻还很难说；光气、HCN这些双用途毒剂是工业原料不可能销毁；目前公开承认有化学武器的只有7个缔约国（某一缔约国、阿尔巴尼亚、印度、利比亚、俄罗斯联邦、美国、叙利亚）。公约允许进行化学防护准备缔约国有权从事防护手段的研究、发展、生产、获取、转让和使用，并准许为此目的而保留1吨以下毒剂。1.3 World security is not guarante
38、edCurrent threats1.3.1 Limitation of the Convention 局部冲突中“隐蔽的化学战”是主要作战形式 非战争使用(东京地铁)化工企业在战争中遭袭击(不使用化学武器的化学战)伊拉克战争最终虽未使用化学武器，但化学战效应贯穿了战争的全过程未来高技术局部战争的缩影不能忽视和低估化学战的威胁USA（1996年公布的资料）犹他州武库 1138488件武器 13616吨糜烂/神经性毒剂阿肯色州武库 123093件武器 3850吨芥子气/神经性毒剂科罗拉多州武库 78万件武器 2611吨芥子气；俄勒冈州武库 22万件武器 3717吨芥子气/神经性毒剂亚拉巴马州武库
39、 66万件武器 2253吨芥子气/神经性毒剂马里兰州武库 1818件武器 1624吨芥子气印第安纳州武库 1690件武器 1629吨VX夏威夷州武库 29万件武器 1134吨芥子气/神经性毒剂肯塔基州武库 101764件武器 523吨芥子气/神经性毒剂RussiaNerve agents(Vx,sarin,soman)et al.32000 tonnes;Blister agents(mustard gas,lewisite and their mixture)8000 tonnes;Super lethal agents as A-230,A-232 and 33,binary chemci
40、al agents have not been included in the Convention.The biggest and most advanced chemical arsenal in the world:Taiwan化学障碍-运用化学地雷，通过炮兵、航空兵发射和投掷化学雷、弹，形成染毒地区不完全统计：日本第二次世界大战期间生产了518万枚化学弹药，日本战败后，分别遗弃在我国的安徽、河北、黑龙江、江苏、吉林、辽宁、陕西、浙江和内蒙古等18个确切地点和6个可疑地点，未处理的仍有200万枚化学弹药。Abandoned CW in China by Japan 1991年河北石家庄发
41、现的毒气弹2001年到现在，齐齐哈尔市已发现炮弹近千枚，其中毒气弹28枚。长沙等处也发现毒气弹哈尔巴岭8.4 事件Chemical accidentsHappen UnexpectedlyScatter rapidlyHard to prevent and rescueCause environmental pollution India Bopaer,methyl isocyanate(MIC)leakage in 1984,320,000 poisoned,80,000 severely poisoned,3,150 killed directly,50,000 blindness,1,5
42、00,000 affected)Shangrao(上饶),Jiangxi,Chemical accident in 1991 609 poisoned,39 killed2005,3月29日，江苏淮安，氯气泄露，死 29人，住院350,10000 转移 The emerging new agents and potential agents,esp.those between traditional chemical agents and biological agentsNew challenges and threatsbotulinum toxin A(BTXA,肉毒毒素A)*SEB(S
43、taphyloccucal enterotoxin B,葡萄球肠毒素SEB)Mycotoxin(真菌毒素)Aflatoxin(黄曲霉毒素)*Ricin(derived from Ricinus communis,蓖麻毒素)*weaponizedmarine toxins can also be used as potential agents:Saxitoxin(石房蛤毒素,STX)Tetradotoxin(河豚毒素,TTX)Palytoxin(岩沙海葵毒素,PTX)Maitotoxin(刺尾鱼毒素,MTX)TTXpufferlike fishesPalythoa tuberculosa(pr
44、oduce PTX)PTXGambierdiscus toxicus(岗比毒甲藻),a kind of dinoflagellattesSurgeon fishMTX1994.6.27，Matsumoto City sarin attack.1995.3.20，Tokyo subway sarin attack.VX and equipment for phosgene and HCN release were found in the Tokyo subway after the sarin attack on 3.20.1999,nerve agents threats during Wo
45、rld Expo in Yunnan Province,China.Chemical terrorismBio-chemical agents attack in terrorism has become a realityRobbery of gambling house using HCN in Ruichang,Jiangxi Province,7 died,including 2 robbers.US anthrax panic in 2001 after“9.11”.2007-2008,suicide bombers driving trucks rigged with tanks
46、of chlorine gas in Iraq.Ricin was also used as a terrorism tool thereafter.Incapacitating technology.2.Classification of Chemical Agents神经性毒剂(nerve agents)sarin、soman、tabun、VX 糜烂性毒剂(blister agents,vesicants)mustard gas、lewisite 全身中毒性毒剂(systemic agents,cyanides)HCN(hydrocyanic acid)、ClCN(cyanogens ch
47、loride)失能性毒剂(incapacitating agents)BZ、LSD 窒息性毒剂(choking agents,pulmonary agents)phosgene、diphosgene 其它刺激剂(irritant agents,riotcontrol agents)CN、DM、CS、CR 植物杀伤剂(anti-plant agents)2,4-D、2,4,5-T 持久性分类暂时性毒剂(non-persistent agents)sarin、phosgene、HCN 等；持久性毒剂(persistent agents)mustard gas、VX 等；半持久性毒剂(semi-pe
48、rsistent agents)soman、tabun、diphosgene 等。中等挥发度毒剂3.Chemical weaponsprimary chemical weaponspoison-arrow frogsStrychnos nux-vomica(马钱子)chemical agentsweaponizationModern chemical weapons3.1 Chemical weapon arsenals72爆炸型化学武器施放时利用弹体中的炸药爆炸的能量将毒剂分散为战斗状态；多用于杀伤性、迟滞性袭击。73热分散型化学武器施放时利用弹体中助燃剂产生的热能固体毒剂加热蒸发成毒烟；多
49、半用于扰乱性袭击。74布洒型化学武器施放时利用压力将毒剂从容器中喷出，在空气阻力撞击下使毒剂分散成战斗状态；多使用于杀伤及迟滞性袭击。Soviet chemical weapons canisters from a stockpile in Albania An American MC-1 gas bombThe principle for the use of binary weapons二元化学武器二元化学武器 The principle for the use of binary weapons M687型型155毫米二元沙林炮弹毫米二元沙林炮弹 3.2 Characteristics
50、of the effects of chemical weapons 毒性杀伤 作用时间长 局限影响大 中毒途径多 杀伤范围广 3.3 Hazard forms of chemical agentsThe agents can present a hazard on the field in the following forms:vapor aerosol airborne particles liquid 初生云再生云液滴2023-5-223.4 Factors that affect the use of chemical agents2023-5-2282在5m/s以内才能缓慢刮向敌方
