TECHNICAL MANUAL FOR THE SENIOR GAS OFFICER OF t CIVILIAN DEFENSE PREPARED) UNDER THE DIRECTION OF THE MEDICAL DIVISION OF THE OFFICE OF CIVILIAN DEFENSE WASHINGTON, D.C, AND TEE NATIONAL INSTITUTE OF HEALTH DIVISION OF PUBLIC HEALTH METHODS CINCINNATI, OHIO COLLEGE OF MEDICINE UNIVHRSZCY OF C2&CIKNATI JULY, 19^ 4-0998 PI of 150-NCBIJ-.COS-I'/P THIS MANUAL HAS BEEN EREPAHED "by THE FACULTY OF THE COLLEGE OF MEDICINE UNIVERSITY OF CINCINNATI , and THE STAFF OF THE OFFICE OF STREAM POLLUTION INVESTIGATION U.S. PUBLIC HEALTH SERVICE, CINCINNATI, OHIO The authors are grateful for the cooperation of The Chemical Warfare Service and The National Research Council. The opinions expressed in this manual are those of the Individual authors and do not represent the official opinion of any of the agencies con- cerned. 4-0998-P3-BU-C0S-WP INDEX 1, Senior Gas Officer 2. General Chemistry - Properties of Chemical Warfare Agents 5. Methods for Detection of Chemical Warfare Gases h. Methods for Detection for Chemical Warfare Agents in Water and Treatment of Contaminated Water Supplies 5. Detection and Analysis of Arsenic in Water Conta- minated with Chemical Warfare Agents 6. Detection of War Gases in Foods 7. Food and Poison Gases 8. Medical Aspects of Some Systemic Poisons 9. General Toxicology of War Gases 10. Prevention and First Aid Treatment of Chemical Casualties 11. The Chemistry and Methods of Decontamination 12. Decontamination Procedures 13• O.C.D, Bulletins h~ 0098- -WP GENERAL CHEMISTRY: PROPERTIES OF CHEMICAL WARFARE AGENTS Milan A, Logan, Ph.D.,. Bio-Chemistry Department 1. Requisites of Chemical Warfare Agents - A, Toxicity B, Availability C, Ease of manufacture D. Storage E. Transport F. Dissemination II. Classification according to physiological effects - A. Lung irritants B. Vesicants C. Lacrimators D. Stemutators (irritant smokes) E. Systemic poisons F. Sceenlng smokes G. Incendiaries III, Relation of Physical Properties to Tactical Employment - A. Gases 1. Volatility - depends on the vapor pressure at a given temperature. Casualty agents and harassing agents, relation to volatility and toxicity. 2. Persistency - depends chiefly on the density. Relation of density to molecular weight. 3* Factors influencing dissemination - a. Cooling effect on evaporation b. Influence of air currents (1) Lateral spread (2) Drag effect - relation to terrain (5) Vertical rise - convection currents 3. Smokes Lateral spread and drag effect similar to gases. Effect of heat from explosion and sunJs rays on the vertical rise. IV. Properties of Individual Chemical Agents: chlorine, phosgene, chlorpicrin, mustard, Lewisite, Brombenzylcyanide, ethyldichlorarsine, adamsite, chloracet ophenone, diphenylchloraraIne. Relation of chemical and physical properties to persistency, means of detection, and decontamination. ii-0096-I P -NODU-COSrWP MEMORANDUM OH TEE PHYSICAL AND CHEMICAL PROPERTIES- OF CHEMICAL WARFARE AGENTS*,* C. C e Ruchhoft-and Stuart Schott The term war gas is defined as any chemical agent, solid, liquid or gas, used in warfare for its toxic or irritant action. There is a large number of compounds possessing suitable physiological properties, but certain other properties limit the gases actually suitable for mili- tary use to less than two dozen, The important properties required of a war gas may be listed as follows: (l) Its toxicity should be high, i.e., only a low concentration must be required to produce i+s poisonous effects. (2) It must be easily manufactured, and the raw materials necessary in its manufacture must be cheap and available in large quantities. (5) The gas must oe stable enough so that it will not break down on storage or on explosion of the gas shell in which it is fired. (4) It should be persistent, i.e., remain effective around its point of release for some time. (5) It should be sufficiently noncorrosive toward metals to permit loading and subsequent storage of gas-filled shells. Besides the above properties, the gas should be insidious, i.e, give no dis- comfort on first exposure, and it should penetrate monks, protec- tive clothing and other means of gas defense. Considering all of those properties, it is easy to understand that out of JOOO cam- pounds investigated prior to 1913 for possible use as war gases, only 25 to 50 were used in actual combat and only about 6 sur- vived to the end of the last war. Several systems have been devised for classifying the war gases on the basis of physical, chemical, tactical and physi©pathological prop- erties. The physiopathological properties are used in the following classification: 1. Vesicants (Blister Gases) - These include the substances whose characteristic action is to produce blisters on the skin. They exhibit considerable variation in physical and chemical characteristics, the dichlorarsines being in general, less persistent and Jess stable than mustard gas. These include: dichlordiethyl sulfide (mustard gas), B-chlorvinyldichlorarslne (Lowlsite), ethyl and methyl dichlorar-sine. (*) From the National Institute of Health, Division of Public Health Methods. Cincinnati Laboratory, if) For a more complete discussion of the elementary principles of military chemistry and chemical agents, the reader is referred to War Department Technical Manual TM 5"215, April 21, 19^-2. 1 4-0098-P7-BTJ-C0S-HP 2. Lung Insurants (Toxic suffocants) - These include those gases which act on the respiratory tract. In general, the members of this group are either true gases or volatile, low boiling liquids. They are nonpersistent. These include: chlorine, phosgene, diphosgene, chloro- plcrln. As chlorine belongs to the bow and arrow age of chemical warfare, it will be given no more consideration here. 3. Eye Irrit ant a (Lachrymators) - These include those gases having lachrymatory power. They are, for the most part, heavy, oily and rela- tively high "boiling liquids which in the- crude state are dark colored owing to decomposition. They are mostly insoluble in water and are very corrosive to metals. Chloracetophenone is a white solid and does not corrode metals. The vapors possess a characteristic "but not unpleasant odor. These include xylyl and "benzyl bromides, bromacetone, ethyl lodoacetate, brombenzylcyanlde, chioracotophenone. Nose Irritants or irritant smokes - Under ordinary conditions these are crystalline solids with negligible vapor pressures. Chemically they are aromatic arsenic derivatives, practically insoluble in water but readily hydrolyzed by alkalies'and oxidized by oxidizing agents. These include: diphenyl chlorarsine, diphenylcyanarsine, diphenylamine chlorarsine (Adamsite), The foregoing classification has defects in that certain gases act differently in changing concentredions and that the biological action of these substances is very complex. General Properties The Important general properties include vapor pressure, volatility and persistence. Vapor Pressure - the tendency of all substances to pass into the vapor form causes a certain pressure, called Vapor pressure, to be exerted by the vapor produced. The vapor pressure is dependent on the temperature and is usually expressed in mm. of mercury at a specified temperature. This pressure is of special interest for war gases, as the usual toxic substances, in order to be effective, must exert a high enough Taper pressure to supply enough gas to the atmosphere to produce significant phyeiopathological results. This is of importance for the lachrymators, the vesicants and the lung injurants. In the case of the nose irritants (irritant smokes) the vapor pressure is of minor value as these substances are used in the form of aerosols (colloidal sus- pensions in the air). Vapor pressure is a principal factor in the persistence of a gas, that is, the time during which it remains effective at the point of re- lease, the higher the vapor pressure, the less the persistence. The nonpersistent gases (high vapor pressure) vaporize rapidly when released to form a very concentrated and hence highly toxic cloud, which, however, drifts away with the wind and becomes more or less quickly di- luted with the atmosphere. On the other hand, the persistent (low vapor pressure) gases when released, contaminate the surrounding ground, ii— 0996- P8-BU- c os -wp etc., with liquid which evaporates slowly and continues to give off dangerous vapors for a comparatively long time. It is the persistent. gases that make decontamination procedures necessary. -r. This distinction has an important bearing on the manner in which the gases are used. Both nonpersistent and persistent gases can be used ino. • shells and bombs; only the nonpersistent can be released as clouds from- • cylinders and only the persistent as spray from aircraft. The matter of gas identification is affected by the type of gas. With nonpersistent gases, if the gas officer is not on hand immediately when the concentration is very high, the gas will be dispersed by the time he arrives. With persistent gases on the other hand, owing to their lowered vapor pressure, the concentration in the air will never be high, but evidence of ground contandration will be encountered for hours or even days afterward under favorable conditions. The volatility is defined as the weight of the substance contained in a given volume of saturated air at a certain temperature. Our chemi- cal warfare service expresses volatility in ounces per 1000 cubic feet of air, which is nearly equivalent to mg. per liter. Neglecting changes in pressure, a simple formula for the volatility is; Tt : M.W'.x.m * I6 (t *275) in which z the volatility at temperature t MW : the molecular weight of the agent VPt " the vapor pressure of the agent at temperature t t s temperature in degrees Centigrade. The volatility is one of the most important factors in selecting and eval- uating a war gas. In the field it is impossible to reach saturation for the agent. Consequently volatilities as given for the agents in Table 1 my not be obtained. A comparison of the volatilities and the lethal concentrations given in Table 1 indicates which agents might be used ef- fectively for producing casualties. ' ' . 5 ' Vapor Density affects persistence to some.extent, the lighter gases having a greater tendency to rise and be dispersed whereas the heavier gases tend to hug the ground. The war gases mentioned here vary in vapor density from 2.5 for chlorine to for ethyliodoacetate. Freezing Point is not Important except Stir mustard gas (l4,4 G) and for brombenzylcyanlde (25.5°C). These gases are usually fluted with 15-20$ of carbon tetrachloride or chlorobenzene to lover the freezing point. if-Q919- BU-COS-WP In connection with freezing point, reference should he made to the” war ’’gases" which are really solids (chloracetophenone, m.p. 58° C and arsenical nose irritants m.p, from 52° to 195° C). The latter sub- stances, in particular, have very low vapor pressures and would he useless as war gases except for the fact that they can he dispersed hy heat, etc., in form of a "smoke" or particulate cloud, consisting of very small particles (about 10to 10~5 mm, diameter) suspended in the atmosphere and capable of exerting an irritant action on the nose and throat. The action is similar with chloracetophenone, although its vapor alone will cause irritation. These clouds are classified as nonpersistent since they are rapidly dissipated by the wind as are the true nonpersistent gases. Special type of bombs and thermogenerators have been devised for their employ- ment in warfare. They were originally designed as "mask breakers," the particles not being absorbed by activated charcoal as are vapors but necessitating the use of special filters. This aspect is of Importance in their detection; they cannot be satisfactorily sampled by the usual technique of absorption in solvents, but require a suitable filter. At the same time they are effective in exceedingly low concentrations and are nonpersistent so that the prospect of obtaining an analyzable sample is usually remote. Stability - Of the chemical properties, reaction with water is of prime importance, particularly the persistence under wet conditions. Most of the gases are relatively insoluble in water; some, such as chloro- picrin, are practically unaffected by it; others, like mustard gas, are slowly hydrolyzed; while still others, e.g,, phosgene and lewisite, are rapidly decomposed. This means that lewisite would be relatively in- effective in rainy weather and the persistence of mustard gas would be considerably reduced. From the tactical viewpoint, the stability of gases to heat and ex- plosion and their action on metals are of importance. From the standpoint of defense the behavior toward neutralizing agents such as alkalies and oxidizing agents is of importance. Physical and Chemical Properties 1. Lung Injurants (a) Phosgene (C.G.) (Carbonyl Chloride; C0C12). At ordinary temperature phosgene is a.colorless gas with a characteristic odor de- scribed as that of moldy hay. It was first used in war by Germans in December, 1915, and remained the principal war gas throughout the first world war. It condenses on cooling, below 8G°C to.va colorless liquid if pure; to a pale yellow or orange if the technical product* The gas is approxi- mately three and a half times as heavy as air. However, due to its high vapor pressure (low boiling point) it is a very nonpersistent gas. h-O998-PIO-BU-COS-WP Phosgene is readily soluble in many organic solvents, benzene, toluene, xylene, fats and oils, inorganic halides such as those of arsenic and sulfur. Phosgene is very soluble in water but is hydrolyzed with extreme rapidity to carbon dioxide and hydrochloric acid. Like all acid chlorides, phosgene is very reactive, reacting readily with alkalies, alcohols, phenols .and amines. The reaction with phenols and amine was utilized in the old type PH gas helmet which was impregnated with sodium phenate and hexamlnc. Phosgene is noncorrosive toward metals when dry but extremely corrosive when moist. (b) Diphosgene (Trichlormethyl chloroformate; ClCOOCCl^), known to the French as Surpalite and to the Germans as Perstoff, was one of the principal lethal gases used in the last war and was used in shells. Diphosgene boils at 128° C and has a specific gravity of 1,65 at 15° C. Its vapor density is 6.9 and its vapor pressure at 20° C is 10.5 mm., so that it is still a nonpersistent gas although it is more persistent than chlorine or phosgene. The vapor has an odor similar to that of phosgene although more pungent. With heat it decomposes to form two molecules of phosgene and reacts with water and amines as if consisting of two molecules of phosgene. When dry it is noncorrosive to metals. (c) Chloropicrin, (P.S.) (Trlchloronitromethane, CCl^NOg), known as ’’Slop1' to the Germans, as Aquinite to the French and sometimes as vomiting gas to the British, wa,s first used by. Pussians in hand grenades dissolved in 50$ sulfuryl chloride in 1916 and was later employed by the Allies as a constituent of their penetrating ITC mixture (QOp chloropicrin plus 20fo stannic chloride). Chloropicrin in the pure state is a slightly oily, colorless, refractive liquid with a characteristic odor. The crude product is yellow due to impurities. It boils at 112° at ordinary pressure and has a density of 1.66. Its vapor density is 5.69 vapor pressure 18.3 mm, at 20° C, so that it is relatively nonpersistent. The vapor has a sweetish odor and distinct lachrymatory properties. It is relatively insoluble in water but soluble in organic solvents. It is fairly stable, not being hydrolyzed by water nor affected by ordinary acids or alkalies. Alcoholic sodium hydroxide gradually decomposes it, as do also sodium sulfite and alkaline polysulfides. It is partially dissociated on heat- ing into nitrosyl chloride and phosgene and may explode on rapid heat- ing, When moist it is corrosive toward metals, but produces only a superficial stain which forms a protective layer. 2. Lachrymators Xylyl Bromide (German T-staff) (CH^-CgH^-GHg-Br). A crude mixture of c-, m- and p-xylyl bromides bromination of xylene used extensively as a lachrymatory shell-filling by the Germans. It was used for the first time as a war gas in January, 1915; (Sartori), but its use was abandoned toward the end of the war because of the ease with which it was dealt by ordinary carbon filters and of the incon- venience caused by its attack on iron containers. The mixture is a black liquid, density l.k and B.P, 210-222° C. It is persistent (vapor pressure about 0,07 mm, at 20° C), and its heavy vapors when diluted h -0998 - Pll-BU- COS-WP have an odor resembling lilacs or elder blossoms or leaves, hence the British wartime name of Elder-gas, It is insoluble in and slowly de- composed by water- but is readily hydrolyzed by alkalies. Benzyl bromide (CgHh Clip Br) (B.P, 200° C, D., l.khj vapor density is 9.8), called "cyclite" by French, First used by the Germans in March, 1915* but only for a short time due to the cost and scarcity of the raw material, toluene. Later it was completely abandoned, being superseded by other substances with greater irritant power. Bromacetone COCHp Sr), obtained by bromination of acetone, was used by the Germans as B-Stoff, and by the French, in 80/20 admixture with chloracetone as Martonite, Pure bromacetone is a colorless liquid with a pungent odor (BP. 156° C, D 3 1.6, vapor density = It is relatively volatile (vapor pressure at 20° = 9 mm,) and toxic concen- trations of its vapors may be met in the field. The liquid is slightly soluble in water, very soluble in organic solvents. It is not very stable, tending to polymerize to a resin under the influence of light and heat, although this action may be delayed for several months by addition of a stabilizer such as magnesium oxide. It attacks iron but not lead. Ethyl iodoacetate (English K.BrK,) used solely by the British, especially in mixtures with 10f> chloropicrin. It is a colorless dense liquid boiling at 179° C and having a density of 1.8, vapor pressure mm. at 20° C and a, vapor density of Thus it is a relatively persistent substance. It is insoluble in, and stable to water and is only slowly hydrolyzed by hot aqueous alkali. It reacts with alcoholic alkali and sodium thiosulfate and is decomposed by hot nitric acid. It is corrosive to metals. Brombenzylcyanide (C.A.) (CgHpjCHBr-CN) was experimentally tried out towards the end of the war and according to American post-war experiments it is one of the most efficient war gases because of its high lachrymatory power. When pure it consists of yellowish-white crystals which slowly turn red on decomposition. It has a M.P, of 25,5° C, B0P. 0,0“ 1.52, vapor density 3 6,8, vapor pressure 3 0.012 mm. at 20° C, The liquid is accordingly very persistent. It is insoluble in water, but dissolves easily in many organic solvents. It is highly resistant to chemical and atmospheric agencies. Water and humidity decompose it only very slowly. Cold sodium hydroxide acts similarly, but it is hydrolyzed by alcoholic alkali in the cold. It has the undesirable property of vigorously attack- ing all the common metals except lead and in doing so its lachrymatory properties are destroyed. Containers holding this compound must be lined with glass, lead or rubber. Another limitation is its low stability to the shock of the bursting projectile. It can only be employed in bombs with a comparatively small bursting charge. Chloracetophenone (CN) (C^H^COCI^Cl). This compound, because of its lachrymatory properties, was tested during the last war at Edgewood Arsenal. It is a white crystalline solid, m.p, 58° C, B.P, vapor pressure 0,0198 mm, at 25° C, with a pleasant aromatic odor re- sembling that of apple blossoms. As a chemical warfare agent it is dispersed by heat in the form of a nonpersistent particulate cloud. lj._ 0998-P12-BU-C0S-WP It is practically insoluble in water (about 0,3$. at ordinary temperature) but soluble in most organic solvents. The solubility of Chloracetophenone in readily volatile solvents may be utilized in diffusing it into the air. For this purpose benzene is the best solvent, carbon tetrachloride also being occasionally employed. When a solution in one of these solvents is sprayed into the air the solvent evaporates rapidly, leaving the chloracetophenone dispersed in a fine state of subdivision, (It is very effective when distilled into the air by the heat of a burning composition, e,g., a mixture of CN with small-grained smokeless powder). It is a stable compound, unaffected by boiling . water, but the chlorine is readily removed by alkaline hydrolysis. It does not attack iron and is insensitive to heat and detonation. Nose irritants (irritant smokes) The action of these compounds, of an aromatic arsenical nature, is provoked by finely divided solid particles which on liberation in the air form true smokes and are known as the toxic smokes. They were intended as "mask breakers” but were not very successful in this respect because their use in modified high explosive shells did not give a good particulate cloud. When released as a cloud from smoke candles they are very effective. Under ordinary conditions they are crystalline solids with negligible vapor pressure. Diphenylchlorarsine (D.S.) (CgHfOgAsCl) German ’’Clark I." The crude material is a dark brown liquid which gradually turns into a semisolid viscous mass. The pure material forms colorless crystals melting at C, B.P. 333°j vapor pressure 0,0009 mm. at 20°. It is only slightly soluble in water but soluble in some organic solvents. Water hydrolyzes it very slowly and aqueous and alcoholic alkali react rapidly. It is insensitive to heat and detonation and does not corrode iron or steel. DiphenyIcyanarsine (CDA) AsCN) German Clark II - Employed as war gas toward the end of the last war (May, 1918) both alone and mixed with diphenylchlorarsine. It forms colorless prisms with an odor of mixed garlic and bitter almonds. M.P, 55° C, sparingly soluble in water but dissolves in some organic solvents. Its properties are similar to that of the chlor derivative, being employed in the same manner but effective at a* lower concentration. Diphenylamihechlorarsine (D.M.) (KH(CgHi|.)2:AaCl) also called "phenarsazine chloride” and "Adamsite,11 In the crude state is a crystalline solid, the pure product being a yellow, odorless solid, M,P, 195° It is practically insoluble in water and sparingly soluble in common organic solvents. Phenarsazine chloride, unlike the chlor and cyano arsine mentioned above, is slowly hydrolyzed by water. It is readily hydrolyzed by alkalies, and oxidized by oxidizing agents. Iron, steel, bronze and copper are corroded by this compound. Vesicants Mustard gas is the chief member of this group, and was the only one used to any extent during the last war, although the potentialities of lewisite and other diohlorarsines were "being investigated at the end k -0998- PX3 -BU- C OS - WP of the last war,. These compoundsMW;.b.QRslderable variation in physical and chemical properties,; the* friin general, less persistent and less stable than_ mustardvrobThey 'all:possess the common characteristic of .being-able all' living tissues which they contact. •, r.-1 .•••.: M v .' :- Mustard gas (H.S.) (2,2* diciilorodiethyl sulf Me, S(Ci^CE^d)2* known to the French as ,!Yperite" and, to the Germans"as "Senfgas" or "Lost.” First employed by the Germans in July, 1917. Ir the pure state, mustard gas is a colorless oily liquid having a faint leek-like odor, B=1.28, B.P. 217,50 C, M.P. M.’MC, In the crude state it is brown and has an odor reminiscent of mustard. The vapor pressure is 0.115 mm. at 20° and its vapor density so that it is very persistent, especially on terrain covered with bush.es and shrubs„ The technical product containing 15~20$ of carbon tetrachloride or chlorobenzene is a brown or black oil, (freezing point about 5Q 0) having a characteristic odor described as resembling that of mustard, garlic or horseradish. It is sparingly soluble in water (about at ordinary' temperatures) in which It sinks. It is slowly hydrolysed to give harmless water soluble products. * 2 n20 > S(CH2CH20E)2 * 2 HC1 thiodiglycol The following values have been determined for the hydrolysis of mustard gas. 1..; .•:* r-v V i vv - Time (Minutes) Per cent hydrolyzed com- pared to that dissolved 10 50 r 20 . - to"" 50 ' . 79" , ko av- 50 85 6o 85 The velocity is influenced by time of contact, temperature, water-mustard .gas ratio, quantities of acid, alkali and hydrolysis products present and the degree of dispersion in water. In the presence of a large excess of water the above conversion is quantitative. Dry chloride of lime reacts with, mustard gas acting as an oxidant and chlorinating agent. A very violent reaction, with evolution of heat, flame and white vapors, takes place, Numerous compounds are formed, carbon dioxide, hydrochloric acid, chloral and chlorinated sub- stances which are not defined. By the action of chloride of lime mixed with water, the action is less violent and this type of mixture is em- ployed for decontamination of objects contaminated with mustard gas. This action of the bleaching powder depends on its available chlorine and the bleach should contain at least 15$ active chlorine. j+-0993-P1^-3U-C0S-WP The pure liquid does not attack metals under ordinary conditions but the technical product usually contains free hydrochloric acid and has a marked corrosive action on iron and steel. Lewisite (M-l) (Betachlorovinyl dichiorarsine, Cl-CH * CHAsClg) was developed as a war gas by the Americans during the last , war but was never used in the field. It has been termed the "Dew of Death," and is claimed to embody the aggressive qualities of the asphyxiants, the irritant characteristics of the tear and nose irritant gases and the universal action on all tissues of the blister gases. When pure, lewisite is a colorless liquid (B,P. 190°> with de- composition) , M.P, about 0° C, vapor pressure 0,4 mm. at 20° (less per- sistent than mustard), The vapor of the pure compound has an irritant action on the eyes and nose. The liquid tends to/ turn blue-black in the light. The technical product, which is usually black, has an intolerable geranium-like odor, perceptible in great dilution. Lewisite is sparingly soluble in water about 0.0yf>, but readily soluble in organic solvents. It is rapidly hydrolyzed by water or even a damp atmosphere at ordinary temperatures. Cl-CH»CH-As-(?| ♦ HgO \ 2HC1 ♦ Cl-CH=CHAs=0 chlorvinyl arsenious oxide Chlorvinylarsenious oxide is somewhat vesicant for direct contact but is much less dangerous than lewisite because it is nonvolatile, and sparingly soluble in water and other solvents. This hydrolysis is notably increased by an increase in temperature. Alkalies (except ammonia) completely decompose the molecule into acetylene and sodium arsenite: Cl CH * CH-AsClg ♦ 6Na0H~d Na,AsO* * 5 NaCl ♦ CgHg -1- 5 HgO When a 1% NaOH solution is employed at temperatures below 57° C, this decomposition takes place quantitatively, and only in the case of beta chlorvlnyldichlorarsine, Lewisite is very reactive, being readily oxidized (hydrogen peroxide) and chlorinated; the two chlorine atoms are replaceable by treat- ment with potassium iodide, hydrogen sulfide, etc. It does not attack steel appreciably and when stored in projectiles causes only a slight superficial rusting of the metal walls. Ethyl dlchlorarsine (ED) (CgH^AsClg) This compound was employed in March, 1918, hy the Germans, being considered suitable for replacing mustard gas in offensive operations because of its immediate vesicant effect and its nonpersistent character. It is a mobile liquid, fruity odor in dilution, (odor can be detected when concentration is 0,5 mgm, (cu, m. of air), B.P, lp6° C vapor density 6, vapor pressure at 21,5° C is 2,29 mm. It is readily soluble in organic solvents and dissolves to the extent of 0.1in water. U-0996-P15-BU-C0S-WP Water rapidly hydrolyzes ethyl dichlorarsine: * 2H£)0 ♦ 2HC1 The compound also reacts with sodium iodide to give the iodo derivative, with hydrogen sulfide to give the sulfide and is decomposed readily by bleaching powder which is used in decontamination. When dry it does not attack iron but it corrodes brass strongly. Methyl dichlorarsine (MD) is a mobile colorless liquid ■which does not fume in the air. 13.P. 132-35° C, vapor density 5.5, vapor pressure 10,8 at 25° C, Its properties are similar to those of the ethyl derivative. 4-0996-Pl6-BU-COS-WP PROPERTY VESICANTS LUNG INJURANT LACRIMATORS Common Name Mustard Lewisite Ethyl- dichlor- arsine Phosgene Chlorpicrin Brombenzyl- cyanide Chlor- aceto- phenone Chemical Name Diehlor ethyl- sulfide B”chlor- vinyl Di- ehl or arsine tf n Carbonyl- chloride Trichlor- nitromethane 11 11 n it Symbol (U. S.) ns M-l ED CG PS CA ON Melting Point i3°c. 57°F. -l8.2°C. 0°F. -50°c. -22°F, -ll8°C. -190°E. -69.2°c. -92.4°F. 25 °c. 77°F. 59°C. 138°f. Boiling Point 21?°C. 190°C. 37)+°E. 156^0. 512°F. 8.20c. 1120c. 251.50F. 225°c. 2d7°C. d76°F. Yapor Density (Air = 1) 5.5 7.1 6.5 5.5 5.6 6.6 5.2 Yapor Pressure (mm. Hg, at 20°C.) 0.065 0.595 5.0 1180 18.5 0.0112 0.015 Volatility (Oz. per 1000 cu, ft.) 0.625 *K5 10Q kk20 165 0.15 0,106 Lethal Concentration (Oz. per 1000 cu. ft.) 0.15 0,12 3.0 ml 0,50 nute Exposure 0.50 2.0 3.5 0.85 P er s i s t ency, summer 1 - 7 days 1-7' days 1-6 hrs, 5 - 10 min. 1 - k lirs. 5-7 days 10 min. Persistency, winter Several weeks 1 week 2-12 hrs. 20 min. to 2 hours 1/2 - 7 days Several weeks 10 min. Solvents for Oils PS Ethanol CClij. HS - PS Oils Ethanol Ethyl chloride ■ Cl PS CHCl*, CG Cl, CS2 C6n6 c2f^oh CgIL-Cl, CHGI3, PS, CG CHCI3, PS Ethylene dichlorid__ chior- acetone ii-0998-Pl 7 -BU-COS -WF PROPERTIES OB CHEMICAL WARFARE AGENTS TABLE 1 PROPERTY IRRITANT SMOKES SCREENING SMOKES ■ - - . . Common name Adamsite Diphenyl- chlorarsine Diphenyl- cyanoarsine EC Mixture Titanium tetrachloride Sulfur trioxide solu- tion Chemical Name Diphenyl- amine chlor- arsine >» u » « Hexachlor- ethane •> Zn * ZnO It ft SO5 Chior-' Sulfonic Acid Symbol (u, S.) • DM DA CDA EC FM FS Melting Point ■195°C. 387°?.' 115°iV 31.5°C. 91°F. l84oc. 3o3°F. -250c. -9°F. Below -30°C. -22°F. Boiling Point •tio°c. 770°F. 5S3°C. 720OF. 550°C. 662°F, 185°c. 565°F. 156°C. 277°F. — Vapor Density (Air = 1) — — — Negligible — — Vapor Pressure (ttm. Eg. at 20°C.) Negligible 0.0005 0.0001 0.22 8.32 — Volatility (Os. per 1000 cu, ft,) It ft 0.0007 0.0015 - 2,85 8.64 — Lethal Concentration (Oz. per 10CG cu. ft.) 3.0 j 1,5 .10 Minute Ext 1.0 )osure Smoke Harmless ■ — — — Persistency, summer 10 min. 10 min. 10 min. Only while burning 10 min. While container is operating Persistency, winter 10 min. 10 min,■ 10 min. It tt 10 min. " " Solvents for Furfural acetone Acetone CHCl^, PS Organic Solvents Alcohol and Ether for hexachlor- ethane Ethylene dichloride — ' Strong Sulfuric acid PROPERTIES OF CHEMICAL WARFARE AGENTS, TABLE 1 (Continued) L-C998-Pl8-BU-C0S-WP Agent Tactical Classes - C.WjS J Physiological Classification Casualty Harassing Screening Incendiary Vesicant Lung Injurant Lacrimator Irritant* Mustard Highly persistent Gas! ; HS J J Gas \ D Lewisite Persistent | M-l j I Gas i : M-l'} i Gas I |JL Ethyl di- Moderately El) j ; ed ; D ; i i chlorarsine Persistent i Gas i ! Gas 5 i i Phosgene Eon-persistent l GG 1 1 Gas t 1 ro; > r -.. Chlorpicrin Moderately Persistenr • PS 1 I Gas ; PS Gas D • I • » __j Brom "benzyl CA m cyanide Highly persistent Gas j. m, Chloraceto Eon-persistent CE | phenone Gas 1 i CE Solution ft IT 11 CES | Gas ! ■ Adamsite It ft tt DM ! > G-as J ■S Sulfur trioxide solution | FS 1 Smoke EG Mixture Eon-persistent ! HC i Smoke - . "White Phosphorus tt tt tt i wp : ; Smoke; j VP 1 Smoke ,r WP ! ; Smoke ; Thermit ■■ L Smoke f I = Immediate Action D = Delayed Action ID = Immediate to Delayed Action TACTICAL AND PHYSIOLOGICAL CLASSIFICATION OF COMM CHEMICAL WARFARE AGENTS U-0998-P19-BU-cos-WP TASta 2 Legend: [ Primary Classification i i Secondary Classification * Other than lacrimators MEMORANDUM ON METHODS FOR THE DETECTION OF CHEMICAL WARFARE GASES* By Assistant Chemist Stuart Schott and Principal Chemist C. C. Ruchhoft The detection of the presence of war gases along with the iden- tification of the gas plays a very important role in defense. In case of gas attack it is vital to know quickly the nature of the gas used and the extent of the areas affected and for this reason the methods for de- tection of gases must possess the following properties: 1. Results should be accurate and readily obtainable. (a) The tests should be of a simple nature requiring no complex manipulation. (b) The equipment necessary should be simple and preferably usable in the field. '(c) The test should be sensitive so that small traces of the gases may be identified.• 2. The method should be reasonably specific, i.e. give a typical result for only one gas. The British field kit contains simple apparatus for the detection of mustard gas and equipment for taking contaminated samples of material for subsequent examination, also detector paper for delineation of con- taminated areas and means for sampling vapors and particulate clouds. They consider mustard gas the principal subject for their work and depend on subjective methods for the others in the field, or on subsequent laboratory examination. In the case of non-persistent gases and particulate clouds, little action is possible unless the gas officer is present at the time of re- lease; otherwise by the time of arrival the gas is too dilute for iden- tification. With bombs containing the less volatile but still non- persistent lung irritants, such as diphoagene and chloropicrin, it will usually be possible to detect the gas in the earth surrounding the bomb crater for hours afterward. Of the persistent gases, the persistent lachrymators are identified by lachrymation. As mentioned above, the persistent vesicants, on the other hand, particularly mustard gas, are the main reason for the Gas Identification Service in Britain. Rapid detection of the blister gases is essential to avoid spreading of contamination from the gas bomb and to enable prompt decontamination measures to be started. * From Division of Public Health Methods, National Institute of Health. 0998-P20-BU-C0S-WP Two general methods of gas detection are available and used, these being the subjective and objective. Subjective tests Include smell, appearance and physiological action. Objective tests include physical and chemical methods. For speedy recognition in the field the subjective tests are very rapid and are normally of great value. The objective tests are, however, very useful for actual identification and for confirmation of the sub- jective tests. SUBJECTIVE METHOD 1. SMELL - Many of the war gases have definite odors that can be detected in relatively harmless concentrations, Crude mustard gas can be detected by smell in a concentration of 1 in 20,000,000 (approx. 0,55 mg. per cu. m. of air), and the geranium-like odor of lewisite can be detected in even greater dilutions. The sense of smell has certain limitations. It is liable to be erratic, subject to personal idiosyncrasy and individual variation in different Individuals, and from time to time in the same individual. In spite of the objections noted in the preceding paragraph, the sense of smell is very useful and can be developed by practice with odor kits. These are a collection of samples of war gases suitably contained (usually absorbed on activated carbon in a bottle) by which one may thoroughly acquaint himself with the characteristic odors of certain war gases. Certain rules should be followed in making odor tests: (1) Don't inhale deeply. (2) Smell only once; repeated smelling dulls perception. (5) First smell and then thlnfe the ability to recall smells can be acquired by practice. (4) After smelling breathe out strongly through the nose several times. *•(5) Don’t smoke while smelling; smoking dulls the sense of smell. *Even slight traces of phosgene affects the taste nerves so that tobacco smoke acquires a flat, metallic taste and becomes disagreeable and repugnant. Hydrocyanic acid and hydrogen sulfide have the same re- action to a lesser degree. (6) Lame each odor perception. A gas is odorless only when no odor is evident. In the event of an unfamiliar Smell, it is important that the description of the odor be accurate and comprehensive. it-COOP,-pen _PTT-nnc;_tjp Smell tests in the field should be made downwind —.when wearing a respirator by turning the back of the head to the wind and Inserting the fingers between the facepiece.and the cheek and sniffing gently. The tendency of gases and vapors to rise as they drift downward should also be borne in mind and care taken to make smell tests close to the ground when endeavoring to locate the source of contamination. SIGHT The sense of sight is of importance in the recognition of persistent gases. Certain cases of non-persistent gases may be mentioned; e.g., a concentrated cloud of chlorine has the characteristic yellow green color of this element unless there is much moisture in the atmosphere, when it appears whitish owing to condensation. Phosgene and diphosgene similarly give whitish clouds under damp conditions but are invisible when dry; particulate arsenic "smokes’* are white and opaque if sufficiently concentrated. A white cloud does not always indicate poison gas; it may be screening smoke or smoke arising from use of incendiary or other bombs. In general, the non-persistent gases will have been dissipated before the gas officers arrive, leaving a certain amount of residual evidence in the form of rotted clothing and bleached vegetation, or corroded metals, particularly copper and copper alloys (notably with the lung irritants in damp weather). The size of the bomb crater may in- dicate gas, as craters produced by high explosive bombs are usually considerably deeper and more extensive than those from gas bombs. With the persistent gases on the other hand, and mustard gas in particular, sight may or may not afford a reliable Indication according to circumstances, but contamination of grounds and building with the liquid gas will invariably occur and afford visual evidence. Contamination by crude mustard gas, which has a black color, is somewhat easier to detect than that of the pure pale yellow product, although the stains have the same appearance other than their color. On dry porous surfaces the liquid is rapidly absorbed, leaving a dark oily stain. On dry roads and dry earth it also appears as a dark oily patch, while on wet surfaces it spreads and gives a slight iridescent effect. It remains as liquid drops and splashes on painted surfaces for a con- siderable time although it eventually softens and dissolves in the film. It does not penetrate into metals, glazed tiles and other impermeable materials and also remains in droplet form pn green foliage and grass for some time, eventually penetrating and damaging vegetation. In water, the bulk settles to the bottom, but a thin and somewhat iridescent film usually remains on the surface for some time. The indications above noted are applicable to the immediate vicinity of the bomb crater. Lighter contamination further away and resulting from aerial spray takes the form of very small pinpoint droplets and is harder to see. ' The crude hlister gases are similar in appearance to the persistent lachrymators ("both dark colored oils) and the tvo may he confused. Periodic smelling tests should he made to avoid this confusion. PHYSIOLOGICAL EFFECTS Physiological action forms a valuable adjunct in the identification of some gases. Lachrymators are readily recognized by their immediate irritant effects on the eyes even in low concentrations (l in 20-30 million). Similarly the nose irritants give rise to their characteristic, though slightly delayed, irritation of the nose, throat and chest even in low concentrations. With those smokes which are practically odorless in such dilutions, physiological detection becomes the only practicable field method. Of the lung irritants, chloropicrin has lachrymatory effects in relatively low concentrations and like chlorine is intolerable to breathe in concentrations which are relatively harmless. With phosgene and dlphosgene, on the other hand, the irritant effects are far less marked, and concentrations which are just detectable by smell and slight irritation of the breathing passages are not intolerable to breathe, but may lead to serious results if breathed for any length of time. Further, the intensity of physiological effects afford little indication of the con- centration present. To wait for physiological indications in the case of such gases is inviting disaster. Similar remarks apply especially to mustard gas, which has a characteristic delayed action and produces no immediately recognizable symptoms. The arsenical vesicants, lewisite, etc., have an immediate irritant effect on the nose and eyes which can serve as a warning in- dication. The use of test animals is of value in certain circumstances but has obvious limitations and is not suitable for general war application. OBJECTIVE METHODS The majority of these methods fall to fulfill'the four essential requirements of simplicity, rapidity, specificity and sensitivity. PHYSICAL AND PEYSIGO - CHEMICAL METHODS On the physical side, various methods depending on altered physical properties (refractive index, rate of diffusion, electrical conductivity, etc.) have been suggested but all these methods are non-specific, merely indicating the presence of impurity in the air. Moreover, the apparatus is cumbersome. The proposed physico-chemical methods meet similar objections. Spectrographic work is specific and sensitive hut is not suitable for field work. The Beilstein flame test is useful for detecting halogens but is not specific. U-0998-P23-BU-C0S-WP For assisting ifi delineation of areas contaminated with vesicants, indicators have teen devised known as "Detectors, Ground", consisting of paper or other material painted with special yellow colored paint which turns red in ccntact with the liquid gas* Several objections arise, namely, that the paint is not specific for blister gases, a positive reaction is only given by liquid con- tamination, and a coloration is not always easily perceptible in case of the crude gases. A similar type of detector is valuable in cases of air- plane spray of persistent gases. CHEMICAL METHODS Chemical methods depend on the formation of insoluble or highly colored compounds by reaction of the gases with a particular agent. As many gases contain a hydrolyzable halogen, the simplest, but least specific, is the test for free acidity by means of a pad. impreg- nated with methyl red pressed into contact with the suspected materials, or bubbling the suspected air through a neutral unbuffered water containing brom thymol blue indicator. The S.D.C. portable pH kit containing a spot plate and the necessary indicators is very use- ful for detecting free acidity. This method holds only for those gases readily hydrolyzable and is affected by any extraneous gases present in the atmosphere in the case of the air sampling test. In the same way and subject to the same limitations, the gases may be passed through alcoholic silver nitrate and the presence of readily hydrolyzable halogen containing war gases detected. The ideal chemical method is one depending on the color change of an Impregnated paper. For certain industrial gases this method is fea- sible, but for the majority of war gases paper tests either are not available or are not sufficiently sensitive or specific. The Chemical Warfare Service has at present a very satisfactory detector set which will detect vesicants in the liquid state and is also specific for mustard gas in the vapor state. The Chemical Warfare Service is working to perfect and expand the set so that it will be more sensitive to vapor and so that it will show the presence of new suspected German gases. Another device which has recently been developed contains finely divided charcoal deposited in the mesh of a fine copper screen. If the presence of a war gas is sus- pected the screen is waved in the air and then placed in a hot flame. Part of the gas is absorbed on the charcoal and subsequently decomposed in the flame. Since many of the chemical warfare agents contain halogens a green flame on the screen indicates the presence of such a gas. In' the absence of such detectors one must resort to passing the suspected air through a suitable solvent or absorbent (a filter in case of the particulate clouds) and applying the reaction to the latter. This general method, despite obvious defects, is of value in gas identification as it enables the gas to be stored up in an artificially concentrated condition and if re- quired, taken away to the laboratory for identification. 1+-0998-P24-BU-C0S-WP Chemical methods can give accurate and definite information, but few of these'pan be described as rapid and simple and their application in the field may be questionable on account of the amount of apparatus and reagents involved. Collection of Samples Guided by subjective indications as to the general type of gas the samples collected may be: 1, Air samples of non-persistent gases taken with an activated carbon tube using the hand pump.* « 2. Samples of particulate clouds taken with a cotton wool filter using the hand pump. 5. Samples of material contaminated with persistent and semi- persistent gases - earth, plaster, drops absorbed on filter paper, etc. Examination of the Samples In the subsequent chemical examination of such samples to establish or confirm the identity of the gas present, the following general pro- cedure should be employed. 1. Non-persistent gases and particulate clouds Samples of these will normally not be available, but if taken the examination should be along the following lines; (a) Filter - Either examine as a whole for arsenic; or if a reasonable amount of particulate matter has been collected, extract with hot alcohol, and either examine the extract for suspected compounds or evaporate the extract and examine the residue for m.p., elements, or specific compounds. (b) Charcoal - The carbon granules may be examined for the elements. The gas absorbed on granules may be hydrolyzed by alcoholic potash and filtered and the filtrate examined for halides, nitrites and other products of hydrolysis. 2, Persistent and semi-persistent gases The sample bottles should be opened in a hood and the examination carried out for: (a) Persistent lachrymators. If the gas appears to he a lachrymator from its subjective properties, a portion of the sample should be extracted with alcohol. The filtered alcohol extract may be hydrolyzed by warming * Diagrams indicating common simple gas sampling devices are given in the appendix. E-0998-P25-BU-C0S-WP with alcoholic potassium hydroxide and the resultant solution examined for the lachrymators. Certain tests should be made on the unhydrolyzed alcoholic extract as noted under "Chemical Methods". (b) Other gases — If the presence of other gases is indicated or suspected, the bottle should be fitted with a two hole rubber stopper carrying two glass tubes. By means of this arrangement air is aspirated over the sample. The effluent air stream may be passed through alcoholic potash, and this solution after acidification tested for halides and cyanides, nitrite and arsenlte. The results of these preliminary experiments may be confirmed by aspirating the effluent air successively through reagents (one at a time) giving characteristic tests for certain gases; e.g., the aniline reaction for diphosgene, the gold chloride and iodeplatinate test for mustard, the acetylene test for lewisite, etc. The air flow analysis described in the preceding paragraph is in general the simplest, safest .and most satisfactory method for examining samples of contaminated materials. With this method, using reaction bubblers of simple type, the air should be aspirated relatively slowly (up to about 500 cc. per minute) and if the sample is only lightly contaminated it is best to surround the sample bottle with warm water to increase the volatility of the gas. The influent air should be purified by passage through an activated carbon tube and a calcium chloride tube; as far as possible all Joints should be glass to glass to avoid absorption of gases such as phosgene, chlorpicrin and mustard gas by rubber connections. Within limits the sensitivity of these reactions can be artificially increased and the time taken for analysis reduced by use of higher rates of flow with bubblers that break up the Influent air stream to some extent. A rough indication of the degree of contamination is obtained from the intensity of the reaction obtained* ’/ VESICANTS Mustard Gas - (HS) dichlordiethyl-sulfide /[C1CH2CE2)2S7 Yablich’s Reagent This reagent was suggested by the Chemical Warfare Service and •was especially employed by the Americans in the last war. When air containing mustard is passed through a solution of selenious : acid in dilute sulfuric acid and the reagent then heated for 10 minutes at 85° C. a yellow precipitate of metallic selenium is produced. If the amount of dichloroethyl sulfide present is small; a reddish orange sus- pension appears. The reagent is prepared by dissolving 1 gm. SeOg in 100 mi of a solution containing equal parts by weight of sulfuric acid and water. 4-0998-P26-BU-C0S-WP Although many war gases give a negative reaction with this reagent, all of the arsine derivatives give as positive a result as mustard. A similar reaction is also given by carbon monoxide and hydrogen sulfide. Sensitivity — 5 mgm mustard per cubic meter of air. Grignard's Reagent This reagent, which is fairly specific for mustard, was proposed by Grignard in 1918 but was kept secret until 1921. Detection is based on the following double decomposition: S(C2H4C1)2 4- 2HI 3(02%!)2 -f- 2HC1 The dichloroethyl sulfide is converted to diiodo-ethyl sulfide which separates as yellow crystals. PREPARATION OF REAGENT Sodium Iodide 2 gm. 7*5$ copper sulfate solution J+0 drops 35$ gum arable solution 2 ml. Water 200 ml. The copper sulfate is added to catalyze the reaction while the gum arabic causes the diiodo-ethyl sulfide to separate in the colloidal form. For the detection of mustard, the air under examination is passed through the above reagent and in the presence of mustard a yellow precipitate appears. 100 mgm of mustard may be detected in 1 cu. meter of air in 4 minutes. The British say that 0.025 mgm / ml. solution may be detected. ■ It was found that while the aliphatic arsines and phenylcarbylamines produce a similar turbidity at high concentrations (t$) other substances such as mono-, di-, and trlchloromethyl chloroformates, chloropicrin, benzyl bromide, acrolein, the aromatic arsines, thiodiglycol, etc., do not react. Schroter*s Method This is based on the property of mustard gas forming additive compounds with gold and palladium chlorides. On treating with mustard an aqueous solution containing 0.1$ gold chloride or 0.05$ palladium chloride a turbidity of colloidal type quickly forms, and if the quantity of the sulfide is large, yellowish- red oily droplets are produced. This reaction may be carried out on filter; paper. In this case a reddish brown stain is formed with a 10$ gold chloride solution and a yellow stain with a 0.2$ palladium chloride solution. 0998-P27 -BU-C0S-WP These reagents are supposedly specific for mustard gas and are not influenced by the presence of any other war gas, nor by the hydrolysis products of mustard. ■ The sensitivity with gold chloride is of the order of 10 mgm. mustard gas per cu. m. of air. The British give the sensitivity as 0.075 mgm.per ml. solution. An apparatus has been designed for detecting presence of mustard in a sample of air by this reaction. The air is drawn by means of a small pump through a glass tube containing silica gel, to which are added after a certain number of strokes of the pump, several drops of gold chloride solution. A little more air is drawn through the tube and then a few drops of hydrogen peroxide are added. In the presence of mustard a yellow ring forms. Sensitivity; 12 mgm. of mustard per cubic meter of air. lodoplatinate Test This test depends on the reduction of platinic chloride to platinous chloride with the liberation of free iodine. The mustard gas vapor is removed from the contaminated sample by passage through glass wool moistened with 5$ acetic acid, followed by addition of several drops of the lodoplatinate reagent to the glass wool followed by two drops of the starch reagent. On shaking the sampling tube a blue color appears if mustard gas is present or rose-red if absent. Preparation of the reagent 1. lodoplatinate 1 ml. 5$ platinic chloride and 5,5 ml, 5$ sodium iodide diluted to 180 ml, with water. 2. Starch. 1 gm. soluble or arrowroot starch rubbed to a smooth paste with cold water and the paste added to 200 ml. boiling water. Allow to cool and add 2 drops of toluene as preservative. Keep stoppered. The sensitivity of the above test is 0.005 mgm.of mustard gas. It is reasonably specific; phosgene, dlphosgene, chloropicrin, brombenzyl- cyanide, ethyl lodoacetate vapors give no reaction while the arsenical vesicants do not interfere unless present in exceptionally high con- centrations, when they tend to decolorize the reagent (sulfur dioxide has a similar decolorizing action). Chlorine and nitrous fumes, of course, give a positive test, and the detection should be carried out by aspirating air through the contaminated sample, in order to eliminate interference from such gases. Beta naphthol test The suspected gas is passed through a freshly prepared solution of beta naphthol in aqreous-alcoholic alkali. If mustard gas is present the corresponding dj-beta naphthyl ether (m.p. 135° C.) is slowly precipitated as a white turbidity (accelerated on warming). S(CHpCHoCl)P 4- £Ci nH7ONa > S(CHoCHP0- GlOHv)2 + 2NaCl Preparation of the Eeagent 1. 10$ alcoholic solution of betanaphthol 2, Approx. h/lO sodium hydroxide. Add 100 ml. of the alkali solution to 1 ml. of the naphthol solution. The mixture turns brown on keeping so that the two solutions should be mixed just before using. The sensitivity of the above test is given as 0.01-0.06 mgm. of mustard gas. Lewisite (M-l), chlorvinyldichlorarsine, Cl-CH CHAsClp 1. Lewisite is rapidly hydrolyzed by water with the production of hydrochloric acid and chlorvinylarsenious oxide. The hydrolyzed solution will therefore give the reactions for acid., chloride and arsenic. 2. When lewisite is decomposed by alkali, acetylene is formed which may be detected with cuprous chloride paper. Pass the gas through 1 ml 15/i NaOH. Acetylene can be recognized by suspending a of cuprous chloride paper above the alkali. A red stain on the test paper indicates that acetylene was formed and that lewisite was present. Sensitivity; 0.02-0.05 mgm/ml. solution. PREPARATION 0E CUPROUS CHLORIDE PAPER 1 gm. cupric sulfate (or preferably nitrate) dissolved in small quantity of water, add 1* ml.cone, ammonium hydroxide and 3 gms. hydro- xy lamine hydrochloride, shake until mixture is colorless. Make up to 50 ml. If the reagent is covered with mineral oil or a piece of copper wire is added it,will retain its activity. Filter paper may be saturated in this solution and used at once as stated above. EthyIdichlorars ine (ED), and Mcthyldlchlorars ine (MD) CH-AsGlp* U-0998-P29-BU-C0S-WP Hydrogen Sulfide Test Aspirate the suspected, gas through small amount.-of water. Add a few drops of hydrogen sulfide water; an opalescence or turbidity of the arsine sulfide is obtained if the amount of primary arsine exceeds 0.02-0.05 mgm/ml. solution. If the turbidity redissolves on addition of more hydrogen sulfide water, lewisite is present. Sensitivity: 0.02- 0.05 mgm. primary arsine. Mercurous Nitrate Test This test is less sensitive than the hydrogen sulfide test but is of greater value for differentiating between lewisite and the other alkyl dichlorarsines. The test is based on the reaction of the arsines with a solution of mercurous nitrate acidified with nitric acid. With lewisite a white precipitate is obtained; with ethyl dichlorarsine a white precipitate slowly changing to grey (reduction to metallic mercury) and with methyl dichlorarsine an immediate grey precipitate is formed. Sensitivity: 1 mgm. methyl, ethyl or chlorvinyldichlorarslne. Gutzelt Test for Arsenic This test depends on the reaction of arsine with mercuric chloride or bromide paper to give a yellow-brown stain. This reaction is carried out in a small bottle where hydrogen is generated by means of zinc and hydrochloric acid in presence of the sample, the gases pass out through sand moistened with lead acetate to absorb any hydrogen sulfide which would interfere. The gases then pass across the mercuric chloride test paper. A yellow or yellow-brown stain indicates arsine. A blank should be run on the reagents by reacting zinc and HC1 in the generator in the absence of the sample. The paper should show no stain. The details are as follows: Use a 2 oz. wide mouth bottle as generator. The bottle is equipped with a one-hole rubber stopper carrying a gla.ss tube 1 cm. in diameter and 6-7 cm. long, with one end narrowed down to facilitate its insertion in rubber stopper. Place a small wad cf glass wool in the constricted bottom end of the tube and add 3,5 - 4 gm. 50 mesh clean, sand. Moisten the sand with 10$ lead acetate solution and remove the excess with light suction. Connect the top of this tube by means of a rubber stopper with a narrow glass tube about 5 mm. in internal diameter, and 10-12 cm. long and place in this a strip of mercuric bromide (or chloride-5% aqueous) paper. These strips are made by cutting filter paper (similar to Whatman No. 40) into strips about 2,5 mm. wide and about 12 cm. long. Soak the strips for 1 hour or longer in fresh 5-6)0 solution of mercuric bromide in alcohol. Pry and use within two days. Store in well stoppered blackened tube, preferably containing PpOc;; as papers are sensitive to light and moisture. To make a test fot arsenic add 5 co cone. HCl (arsenic free) and 2-h gm granulated zinc (arsenic free) to the bottle, stopper and let stand for 2 minutes, if no darkening of test paper occurs the blank on the reagents is satisfactory. Insert the sample, stopper the bottle again and let stand. If arsenic is present in con- siderab3.e amount in the sample the test paper will begin to change color after several minutes. U-O998-P5O-BU-0OS-WP ' This method can be applied directly to the nose irritants, which are aerosols. The cotton filter used to collect the sample is extracted with alcohol and the alcohol extract used in the Gutzeit test. For the substances which are diffused in the air as vapors it is necessary that the sample be collected on silica gel. The silica'gel with the absorbed gas is boiled for 1 hour with 10 ml and 1 ml cooled, 5° ml HgO added and the sample evaporated to fumes. After cooling the sample is washed into a Gutzeit generator. CHLORINE (Cl) 0-Tolldlne Paper 0-tolidine (0.1 gm) is dissolved in 100 ml. 10f> hydrochloric acid. Filter paper moistened with this solution gives a yellow-orange color in the of chlorine. (2) Potassium Bromide-Fluorescein Paper 0,2 gm. fluorescein., 50 gm. of potassium bromide; 2 gm. potassium hydroxide and 2 gm. sodium carbonate are dissolved in 100 ml. water. Filter paper moistened with this solution and dried changes color from yellow ,to red in presence of chlorine. Phosgene (CG-) Carbonyl chloride; C1C0C1; and Diphosgene; Trichlormethylchlorformate ClCOOCCl* (l) Dimethylaminobenzaldehyde - diphenylamine paper ■ '5 gm, of the substituted benzaldehyde and 5 gm. diphenylamine are dissolved in 100 ml, alcohol. Filter paper is soaked in this reagent and then allowed to dry in a dark place. Test papers should be kept in closed container preferably filled with carbon dioxide and protected from the light. By exposing these papers, (originally white or pale straw yellow) to an atmosphere containing phosgene an orange yellow coloration is -produced in a few seconds, the intensity of the color varying with the concentration of phosgene. This change of color is also observed in the presence of chlorine and hydrochloric acid. It is possible to detect phosgene at a concentration of 4 mgm, per cu. meter of air. The British say 1 part phosgene is detectable per 1 million parts air. To remove traces of chlorine and hydrochloric acid is testing, draw the air first through a guard tube containing pumice impregnated with sodium thiosulfate before it comes in contact with the test paper. •' (2) Nitrosodimethylaminophenol Paper Two solutions are prepared in xylene; (a) 0,1 gm. 1j3)6 nitrosodimethylaminophenol in 50 ml. xylene. (b) 0.25 gm. m-diethyl aminophenol in 90 ml. xylene. I.-O998-P5I-BU-COS-WP 5 ml. solution "a" are mixed with. 2 ml, solution ”h” and strips of filter paper immersed in' the mixture and allowed to dry. The paper should he dampened with 50jo alcohol just before use as the dry paper does not give the test. In'the presence of phosgene the color changes from white to green. These papers are specific for phosgene and are more sensitive than the dimethyl amino henzaldehyde papers. Sensitivity is 0,8 mgm. per cu. meter of air. The two solutions should not he kept mixed for more than *+ days. (5) Aniline Reagent By passing the suspected gas through a saturated solution of aniline diphenylurea is formed which precipitates. By saturating the test reagent with diphenylurea the reaction is made more sensitive. 5 gm. of aniline are dissolved in 100 ml, of water end the mixture saturated with diphenylurea and then filtered to remove excess. On passing air containing phosgene or diphcsgene through this reagent a white turbidity of diphenylurea is obtained (mp. C.). This reaction will detect 0.2 mgm of phosgene and can he applied quantitatively hy weighing the precipitate after washing and then drying at 7P° C. By passing 5 liters of gas mixture (velocity 200 ml,/minute) it is possible to detect 1|0 mam ■phos.Rene ner cu. meter of air. CHLOROPICRIN (PS), CCl^NOo The detection of chloropicrin is most simply carried out hy direct sensory perception, None of the chemical methods are as sensitive as odor perception. (1) Nitrite Test This reaction depends on the formation of nitrite when chloropicrin is hydrolyzed with sodium ethylate. C Cl N02 ♦ C(0CoIL)if ♦ 3UaCl + M0? The presence of nitrite is demonstrated, hy the Griess-Illosvay reagent (sulfanilic acid and naphthylamine), Dissolve a drop of the poison gas freed from nitrous fumes in or aspirate the gas into 5 cc, of alcohol. Add a small piece of Qjo sodium amalgam. After a few minutes decant the solution from the mercury. Acidify with acetic acid adding the acid drop hy drop and then add 1-2 ml. of the Griess sulfanilic acid and naplithylamine reagent. After 10 minutes heat on the water hath. If much nitrous acid is present the red coloration will form in the cold. k-0998-Pd2-BU-C0S-WP Reagents (a) Qjo Sodium Amalgam Weigh out 8 gm, of sodium metal which is clean. Place 92 gm, clean dry mercury in a mortar. Cut the sodium metal in small pieces, and after cutting each small piece dry quickly with filter paper and use a stirring rod with a sharp point on which to impale the sodium, and plunge under the surface of the mercury. Goggles should be worn and face should be averted when placing the sodium in the mercury. Hold each piece under the surface until evidence of reaction occurs. The amalgam will become stiff after most of the sodium is added and the sodium should be moved around under the surface to stir the amalgam. When all the sodium is added and while still hot pour the amalgam onto a piece of asbestos board. When cool enough to handle break up the layer of amalgam and place in a tightly stoppered bottle. Griess-Illosvay Reagents (a) Dissolve 1 gram of sulfanilic acid in hot water; cool and dilute to 100 ml, (b) Boil 0.5 .gm, of alpha-naphthylamine hydrochloride with 100 ml. of water kept at constant volume for 10 minutes. Decolorize with activated charcoal if necessary. (a) 1 gm, sulfanilic acid is dissolved in hot water containing ml, glacial acetic acid and made up to J00 ml, with water, (b) 0.2 gm, alpha-naphthylanine is dissolved in water containing ml* glacial acetic acid and made up to 550 ml, with water. or For the test 1 ml, of each solution is used. The reagent is very sensitive and a blank test should be run simultaneously on the reagents. Sensitivity --6 mgm per cu, meter of air. The presence of nitrite is practically specific as an indication of the presence of chloropicrin for other chemical agents containing nitro groups are seldom used. It should be mentioned, however, that the develop- ment of vapor phase nitration of aliphatic hydrocarbons has made simple aliphatic nitro compounds easily available, Chloropicrin can already be made easily by the use of these compounds. Hitro compounds other than chloropicrin, being easily available, may find use in the present war. Dimethylaniline Test Expose the test paper which is white in color to the atmosphere to be tested or if the concentration is low wave gently in the suspected atmosphere. This paper changes from white to yellow or maroon in the presence of chloropicrin. 4-0998- P25 -BU-C OS-WP Preparation of dimethylaniline test papers Soak strips of filter paper in a 5-1Of> solution of dimethylaniline in benzene. Chlorine, bromine and nitrous gases also give a color with this reagent but of a different shade. The color change takes place only with strong concentrations of chloropicrin and preferably in contact with the liquid gas. Carbylamine, thymol and sodium sulfide tests also are available for detection of chloropicrin and the combustion method is preferable for quantitative determination. DETECTION OF NOSE IRRITANTS The main irritants considered here., diphenyl chlorarsine, diphenyl- cyanarsine and diphenylamine chlorarsine (Adamsite) are all used in the form of particulate clouds which means they will not be absorbed by pass- ing through reagents. It is necessary to use filters to catch the small particles, and then to test the filter for arsenic or if a reasonable amount of particulate matter has been collected to extract the filter with hot alcohol, evaporate the extract on a water bath and examine the residue for the elements, m.p. etc., or to use the alcoholic extract to test for the various nose irritants. Either the residue or the alcoholic extract may be used for detecting the presence of arsenic by the Gutzeit method. In the case of particulate clouds the presence of one of the arsenicals will be indicated by the presence of arsenic in the deposit on the filter. To determine whether or not the smoke consists of chloracetophenone, a lachrymalor used in the form of a non-persistent particulate cloud, a portion of the extract is treated with iodine-starch solution and sodium bicarbonate. If the arsenical smokes are present the blue color will disappear due to the reduction of free iodine to iodide by the trivalent arsenic of the arsenicals which is oxidized to the valence of five. Diphenylchlorarsine AsCl (l) To an alcoholic extract of the deposit on the filter is added an equal volume' of 9% alcohol saturated with hydrogen sulfide and the mixture is cooled in ice water,■ Diphenylarsenious sulfide is precipitated (m.p. 6?° C.). 2(CgE-3)2 AsCl 4 E2S > As] 2 S + 2HC1 (2) To 5 cc of an alcoholic extract of the filter add drops of % alcoholic potassium hydroxide and warm. Diphenylarsenious oxide (m.p, 92° C) is precipitated. As-Cl ♦ 2K0H—3>2KC1 ♦ 20 i^0998-P5^-BU-COS-WP DiphenyIcyanars ine (CDA) AsCil (1) Hydrogen cyanide test Alcoholic extract (5 ml) is hydrolyzed with 5alcoholic po- tassium hydroxide. After cooling, acidify the solution with dilute sulfuric acid. Have a piece of benzidine-copper acetate paper suspended in the vapor while warming the tube, A blue color appears in the presence of cyanide. Reagent Benzidine Copper Acetate Paper (a) 2-5 gm. pure benzidine acetate heated to 80° C. in 100 ml, distilled water for 10-15 with constant shaking. When cold filter by suction; the filtrate contains approximately 19o benzidine acetate. (b) 5 gm, copper acetate Cu2 H20 are dissolved in 100 ml. distilled water. Immediately before use 25 ml. of the benzidine acetate solution and 2 ml, of the copper acetate are mixed and stirred well. The test papers are dipped in the solution, allowed to drain and then dried until just moist. The mixed solution does not keep nor do the papers; they must be used immediately after preparation. (2) A more specific test for cyanides is the Prussian Blue test. After hydrolyzing add a crystal of ferrous sulfate and heat for a minute. Then acidify with hydrochloric acid. A Prussian Blue color indicates cyanide. Diphenylamine chlorarsine (DM) (Adaiaalte) HN( AsCl (l) The alcoholic extract is evaporated to dryness hy gentle heat. A drop of concentrated sulfuric acid is added to the residue. An intense red color, changing to blue green on addition of a drop of nitric acid indicates diphenylamine, an impurity usually found in industrial adamsite. (2) The alcoholic extract is evaporated to dryness. 5 ml. of a mlsture of equal parts of 10fo silver nitrate solution and glacial acetic acid are added. An intense yellow color is produced on standing for 10 minutes in the presence of Adamsite. If diphenylamine is present a dirty green color forms which gradually changes to Mack. LACHRYMAT0RS Brom-acetone Br Ci^COCH^ (1) Sodium Hi troprusside test The vapor is passed through 0*5 N. alcoholic potassium hydroxide, which decomposes the bromacetone to potassium bromide and hydroxy acetone. This ketone is identified by the addition of a few drops of a 1$ sodium 1^0998-P3>BU-COS-WP nltroprusside solution which forms a red color with the acetone derivative. The color of the acetone derivative is intensified by addition of acetic acid. (2) Indigo Test The gas is passed into sodium hydroxide solution and a few drops of an alcoholic solution of o-nitrobenzaldehyde added. The latter reacts with the acetone derivative to form indigo which is recognized by its purple color. This test is not as sensitive as the nitrbprusside test. An alcoholic extract may be used for the above tests. Ethyl Iodoacetate ICI^COOCgH^ (l) Glycollic Acid Test The gas is aspirated into 0.5 N. alcoholic potassium hydroxide. The solution is acidified and a portion is tested for iodide with silver nitrate giving a yellow precipitate of silver iodide if the gas is present. To the remainder of the solution is added a crystal of guiacol and a few drops of concentrated sulfuric acid. A violet color indicates the presence of glycollic acid formed by hydrolysis of ethyl iodoacetate: ♦ 2K0H—>KL ♦ HOCHgCOOK ♦ C^OH Glycollic acid (K salt) An alcoholic extract of the gas may be used for this test. Chloroacetophenone (CN) (C^H^COCHoCl) Chloroacetophenone has adequate warning properties in very low concentrations and this irritant action may be used as a means of detec- tion. Since it is used in the form of a non-persistent particulate cloud it is doubtful whether any sample will be obtained. An alcoholic extract should be used whenever possible. (l) Benzoic acid test Treat 1 ml. of the alcoholic extract with 5 nil hot alkaline permanganate solution (6 and 1 gm, NaOH dissolved in water and diluted to 100 ml.). Acidify with sulfuric acid and extract with ether. The residue upon evaporation of the ether is dissolved in water and tested with a drop of ferric chloride solution. A buff colored pre- cipitate indicates benzoic acid. (Benzyl bromide gives similar result). (2) Hydrogen Sulfide Test If the alcoholic extract contains sufficient gas the following test may be applied. Add 20f> aqueous-alcoholic (50:50) sodium sulfide and warm, if necessary, to effect reaction; cool and dilute with water. 4-0998-P36-BU-COS-WP 2 CgHrCOCEgCl ♦ Na2S > - C0-CE2)2 S ♦ 2NaCl The sulfide precipitate, diphenacyl sulfide has a m.p, of 77° C, Benzyl Bromide CgH^CHgBr The alkaline permanganate test applied to benzyl bromide gives the same result as for chloracetophenone. However, upon treatment of this gas or its alcoholic extract with alcoholic silver acetate, silver bromide and not silver chloride is precipitated. Xylyl Bromide The principal method for distinguishing Xylyl bromide depends on the invariable presence of the ortho Isomers which upon oxidation with alkaline permanganate yield phthalic acid. *-r C 00H LJcooh This can then be treated to form fluorescein which is identified by its green fluorescent solution. Treat 1 ml of the alcoholic extract with 5 Jd of hot alkaline per- manganate solution. Acidify with sulfuric acid and extract the phthalic acid with ether. Evaporate the ether extract to dryness. Add 5 ml con- centrated sulfuric acid and. a small amount (.025 gm) of resorcinol. Heat in a paraffin bath or very carefully over free flame (at l60° - 170° C) for about 10 minutes. Cool and pour into water. Add sodium hydroxide solution to make alkaline. Green fluorescence appears if xylyl bromide was present in the original extract. Brombenzylcyanlde (CA) CE CNBr This compound is such a powerful lachrymator and has such adequate warning properties that these in themselves serve as a means of de- tection, (1) By use of an alcoholic extract of the sample of aspirating the gas through 10“j silver nitrate solution and then boiling, a reduction of the silver nitrate occurs to metallic silver. The brombenzyl cyanide is converted to benzaldehyde which can be recognized by its characteristic odor. (2) An alcohol extract of the gas is treated with 0.5 N. alcoholic potash. On boiling the mixture ammonia is evolved. If the solution is cooled and acidified, a yellow precipitate of diphenyl maleic anhydride which melts at I560 C is obtained.. H H H - 6 - ON + KOI! —C5H5 - C - C - GjClIrj Br • CN Gil 0 H H C6H9 - C - Cv - 9 - G - ♦ HpO |j J.)+2NH^ ON CN " CgEt - C - CX 6 4 - 0998- P>7 -BU- G OS - WP Monochiormethyl Chlorfoimate GlCOOCHgCl The gas is aspirated through water where it is hydrolyzed to formaldehyde. On addition of a drop of a 1:jo phenol solution and then a layer of cone, sulfuric acid carefully run in; a red zone is formed at the interface between the sulfuric acid and water layers. This reaction is not given by dlphosgene (trichdxrmethylchloroformate) or by dichlor- methyl chloroformate. Hydrocyanic acid, hydrogen cyanide, HON (l) Benzidine and copper acetate test The benzidine and copper acetate test is one of the most sensitive and widely used tests for the detection of hydrogen cyanide in air. It depends upon the production of a blue color with moist freshly prepared benzidine and copper acetate test paper (within 5 to 50 seconds) in the presence of an atmosphere containing hydrogen cyanide. Procedure Place a freshly prepared test paper into a holder and attach to a hand exhausting pump which has a barrel capacity of approximately 125 ml. Make a preliminary test of-the atmosphere by making eight slow and steady strokes with the pump. Remove the paper and compare with the stains on standard charts.* In this way an estimate may be made of any concentration between 1 part in 3.0,000 and 1 part in 20,000 of air by volume. The latter is the maximum concentration that can be inhaled for 1 hour without serious disturbance. If the stain indicates a concentra- tion greater than 1 part in 20,000 a fresh paper is placed in the holder and further tests are made with 1, 2, 5 or 5 strokes of the pump; or if a concentration of less than 1 in 100,000 is indicated a rough estimate of the concentration may be obtained by repeating the test with a greater number of strokes. Comparison of the stains should be made in diffused daylight or with the aid of a daylight lamp. Reagents (1) Benzidine acetate solution. Heat two to three grams of pure henzidine acetate in 100 ml. of water for 10 to 15 minutes at 80° 0, with constant stirring. When cold filter the mixture by suction. The filtrate will contain about one percent benzidine acetate, (2) Copper acetate solution - Dissolve three grams of acetate, Cu 0 in 100 ml. of water. Immediately before the test is made mix 25 ml. of the benzidine acetate solutions with 2 ml. of copper acetate solution and stir well. The-mixed reagent will not keep more than 15 minutes. *Dept, of Sci. Ind. Research Brit, Leaflet No. 2-(1958) U-O998-P58-BU-COS-WP The test papers may he prepared from extra thick white filter paper cut into strips 2 inches wide. Immerse them in the mixed reagent for 1 minute, drain and allow to dry in a warm atmosphere. Cut off one inch at the top and bottom of the strip and discard. Cut the remainder of the strip into 3 inch lengths. 'The papers must he used'■'immediatedly. (2) The Methyl Orange-Mercuric Chloride Test.* This test which is not as sensitive as the first mentioned depends on the change in color produced in a methyl orange-mercuric chloride paper hy hydrocyanic acid. The color changes from orange to pink. These papers may he prepared in advance at a convenient place and under condi- tions of 70 to 75 per cent relative humidity will keep in a tightly stoppered hottle for as long as 30 days. , Procedure L The test is made hy carrying the paper in a small vial to the /place to he tested and exposing the paper to the atmosphere for two (minutes. A definite pink color at the end of this time indicates a [dangerous concentration of hydrogen cyanide gas in the air unless the 1humidity is great enough to accelerate the reaction. The test can also he made hy clipping the paper to a line carrying a small lead weight or casting plug, casting the paper with a casting rod and reel into the area to he tested and withdrawing the paper for examination after two minutes. Chlorine, hydrochloric acid or any compound hydrolyzing to give acid in a moist atmosphere will affect the color of the methyl orange-mercuric chloride test papers. The following table shpws the relationship of the hydrogen cyanide concentration, color of test paper and time of test. Methyl Orange-Mercuric Chloride Test Grains HCN per 1000 cubic feet Duration of Test in Minutes 0.5 1 1.5 2 5 6.7 slight pink at edge faint pink definite pink red red 5.35* no change slight pink at edge faint pink definite pink red 1,68 no change no change bright orange j . i.„, faint pink faint pink *Sherrard O. C., U. S, Public Health Service Eeprint No. 122h (1928) *This was the minimum lethal dose for exposure of white rats for 12 hours in a gas tight compartment. 4-0996-F'59-BU-C0S-WP Methyl Orange-Mercuric Chloride Test. (Continued) Grams HCN per 1000 cubic feet Duration of Test in Minutes 0.5 1 1.5 /' 2 3 0.84 no change no change no change slight pink very faint pink 0.42 no change no change no change no change no change Reagents (1) Mercuric chloride solution: - Dissolve 5 grams of mercuric chloride in 250 ml, of distilled water. (2) Methyl orange solution: - Dissolve 0,60 g, of methyl orange in 25O ml. of distilled water. Mix 10 ml. of mercuric chloride solution with 5 ml. of methyl orange solution and add 1 ml. of glycerine. Sheets of filter paper are immersed in this solution and hung up to dry in air which is free from any trace of acid. When dry cut the filter paper into strips i inch wide and preserve them in glass tubes protected from the light, (3) Additional methods which can he used for quantitative estimation of hydrocyanic acid in the laboratory include the thiocyanate method and the well known Liebig silver nitrate method. For a description of these procedures see M.B, Jacobs', ’’Analytical Chemistry of Industrial Poisons, Hazards and Solvents”, Interscience Publishers, 19^1, 1+-0998-P1+0-BIJ-C0S-WP Odor Other immediate effects Threshold Threshold of Claes Agent Symbol Character mg. per cu. meter Nature % action mg. per cu. meter CQ -p Mustard ES Garlic, horseradish 0.3 None — O Lewisite M-l Geraniums 1 Nose and throat irritation 2 cq ® Ethyl- 0.8 ' > di chiorarsine- ED Fruity, pungent irritant. Nose and eye irritation 1.5 -p Phosgene CG Musty hay, cut corn, silage 5-10 Thin white cloud produced coughing, tightness in chest .... IQ-15 3 ,cj Chlorpicrin PS Sweetish, fly-paper, like 8 Lacrimation, vomiting 15-20 pi H licorice cq Brombenzyl- Sour fruit, (irritates be- - 1 -- , - ' , V '. . ■ 1 O -P cyanide CA fore odor is noticed) 0.2 Lacrimation, nose irritation .2 Chlor- Lacrimation .3 * o acetophenone CN Locust or apple blossoms Skin irritation 2 ON Solution CHS Sweetish t» ii -p CQ Adamsite DM Odor from burning smokeless — Canary yellow smoke, headache, o.i cd (D •p u •P o fc 1 powder vomiting Diphenyl- H chi orarsine DA Aromatic, irritant 0,5 Sneezing, headache, vomiting 0.1 HC Mixture EG Smoky, camphor like -- Dense smoke, slight suffocat- !? CQ •H ing feeling -- in HCISO^ FS Acid (strong) ... i ■ Dense smoke, eye irritation, — 3 Ai 2HC1 ♦ (CEpOHCBpJoS Thiodiglycol The thiodlglycol formed is soluble in water and is non-toxic. The rate of hydrolysis depends upon the quantity of gas present, the temperature and the alkalinity of the water. Boiling destroys mustard in 15 to 3° minutes but 2 or 5 days are required if storage at ordinary temperature is used. The armed services of our country consider water containing 50° p.p.m. or more of mustard as impossible to treat for drinking purposes. With less than 500 p.p.m, the water may be treated if the following procedures can be employed. Treatment with unusually large doses of activated carbon followed by coagulation with the common coagulants and settling. The settled water is then filtered and chlorinated be- yond the break-point. However, if the filtered water has a 5-minute chlorine demand of more than 5 p.p.m. the water:is still unsatisfactory and must be retreated. For small doses of mustard (50 p.p.m. or less) the hydrolysis reaction will be sufficiently complete after one hour to permit use of the water from intermediate reservoir levels. Where other sources of water are available finished water reservoirs should be pumped to waste if contaminated with mustard gas to any extent. Water contamination by lewisite, ethyl dichlorarsine. of methyl- ', dichlorarsine would also give trouble. Lewisite is the least soluble of these gases but all of them are rapidly hydrolyzed. The chlorvinyl, ethyl and methyl arsenious oxide hydrolysis products are all sufficiently soluble to be dangerous in a water supply. These soluble arsenious oxides cannot be removed by ordinary water purification processes. Consequently, the extent of the contamination should be determined by complete sampling and careful analytical procedures for arsenioals. If the arsenic content does not exceed 1 to 5 p.p.m. the water would be 53 5-bu-cos-wp safe to use for period a varying from one day for the higher concentra- tion to one week for £he lover concentration. If larger quantities of arsenic are found, or' if other non-contaminated supplies are available, the water should be pumped to waste. These suggested limits for arsenic under emergency conditions are very much higher than the arsenic limit in the latest Public Health Service Drinking Water Standard(2) (Arsenic not to exceed 0.1 p,p,m,), The Public Health Service limit applies to waters which may be used continuously, while the limits suggested here apply under emergency conditions to supplies that are to be used only for periods of one week or less. Methods for detection of arsenic are given later in this memorandum. The last of the gases in group h which is likely to give trouble in water is Chlorcjilcrin is slowly soluble to the extent of 1700 p.p.m, is very stable and is not hydrolyzed by water. If a water supply was heavily contaminated with it most of the chloropicrin would settle to the bottom of the reservoir after which it would slowly go into solution. Ordinary water treatment processes are ineffective in its removal. Once the chloropicrin is dissolved in the water ex- cessive doses of activated carbon could not be relied upon to remove it. It can best be detected by its characteristic sweetish odor in concen- trations down to as little as 5 p.p.m, in water. Its odor and taste are easily noticeable at 10 to 20 p.p.m. A con- centration of p.p.m. gives a burning sensation to the tongue within a few seconds, and might be considered beyond the limit of potability. A water containing 80 p.p.m. or more will produce lacrimation. The odor and taste indications of chloropicrin in a water can be confirmed by the nitrite test after boiling a small sample of the water with alcoholic potassium iodide to decompose the gas. It is suggested that 20 p.p.m. be taken as the upper limit of potability for chloropicrin, Waters con- taining quantities of 100 p.p.m, or more might be made potable by aera- tion for several hours or by storage in open reservoirs for 1 or 2 days. Additional experimental work is needed to determine more exactly the upper limit of safety for chloropicrin and possible treatment procedures for its removal. The lung injurant, phosgene, is soluble to the extent of 1000 p.p.m, in water and is rapidly hydrolyzed to HC1 and COg. Consequently, no toxicity is produced with phosgene contamination after hydrolysis has been completed. If the pH of the water is lowered to the extent that it is unpleasant to the taste this can be easily adjusted with lime. The lacrimators, brombenzyl cyanide and chloracetophenone have been put in Group 5, for which additional information is required. These agents are considered insoluble and stable by all authorities. Con- sequently, they would be largely removed from raw waters by complete water purification processes. The extent to which they could be per- mitted in treated waters remains to be determined. The irritant smokes Including adamsite, diphenylchiorarsine and diphenylcyanarsine are either insoluble and stable or very slightly soluble and slowly hydrolyzed. These arsenical agents would, therefore. ij-0998-Pij-b-BU-COS-WP produce a turbid water .which could be purified by the complete water treatment processes. If contamination with these agents is suspected in clear water reservoirs,'samples of■the water should be examined for chlorine demand and arsenic,, and the limits, for arsenic already suggested for lewisite should not be exceeded. If additional water supplies are easily available, contaminated reservoirs should be pumped to waste even if they contain arsenic.-in concentrations within the above limits. The screening smokes do not produce toxic products and need give little concern. Although adjustment of the pH may be necessary with heavy contamination of these agents, no other treatment will be required. While titanium hydroxide will be formed by the hydrolysis of titanium tetrachloride (FM) there is ho evidence that this material is toxic. Titanium salts have, in fact, been suggested for use as coagulants in water purification. The possibility of the introduction of cyanide by saboteurs or by ..hydrogen cyanide bombs, should not be overlooked. Simple tests for scyanide in water are available and should be made if cyanide contami- t'nation is suspected, 1 ini shed waters she rid be pumped to waste if cyanide is found. In raw waters the cyanide can be removed by treatment i of the neutral or alkaline water with ferrous and ferric salts, followed by the standard water purification processes. This treatment would pre- cipitate the cyanide as Prussian blue, most of which would then be re- moved by coagulation and filtration. As long as an excess of iron salts were used any blue color coming through the filter would be non- toxic. DETECTION OF CONTAMINATION BY CHEMICAL WARFARE AGENTS An examination of Table 6 indicates that all of the troublesome chemical warfare agents with the exception of chlorpicrin hydrolyze with the production of acid; most of them contain arsenic and all of them increase the organic constituents of the water which would increase its oxygen consumed and chlorine demand values. Procedures to determine changes in the following criteria may be emplo3red to detect contamina- tion: (1) Odor and appearance, including turbidity, (2) pH, (b) Alkalinity, Chloride content, (5) The oxygon consumed value, (6) The chlorine demand, (7) Presence of arsenic. In devising ary plan of action, it should be remembered that scientific pert nnel my not be on hand at all waterworks and the plan of detection should be arranged so that the tests will be as simple as possible to enable persons with the minimum of training to carry them out. The above simple criteria will probably suffice to indicate to an alert observer whether or not a gas warfare contaminant is present. The interpretation of the tests will be easier if a complete record of these criteria is kept from day to day. Most of these methods are capable of giving rapid results and are, therefore, as important as tests for any specific material. In cases of attack with the vesicant gases, the same precautions must be observed by the waterworks personnel as by any other person in an area gassed with persistent vesicants. If the banks or the walls of the reservoir have been sprayed with these gases, protective clothing and gas masks will have to be worn even to sample the area to avoid injuries. Unless this protection is available the work of detection should be left to the Gas Officer. The detection of war gases and decontamination of any areas in the waterworks property which may be affected should be one of the first, if not the first job to be under- taken after a gas attack. Following this or simultaneously, if possible, the rapid tests for contamination of the water should be made to deter- mine the extent of contamination, so that an immediate decision can be reached regarding the cutting off of the flow of water from a finished water reservoir or the initiation of emergency purification procedures. Although most of the rapid tests given above are familiar to waterworks men, a. short discussion of their applicability here may be helpful to some. (l) Odor and appearance can be used to detect and identify some of the gases in contaminated water. The odor of mustard (HG) and lewisite (M-l) can be detected in many waters contaminated with p.p.m. or more of these gases. In concentrations of 100 p.p.m. these gases cannot be detected. As already stated, chlorpicrin can be detected in concentrations as low as 5 p.p.m. by odor. Most of the war gases are heavier than water and if dropped into a reservoir will sink to the bottom, but may leave a thin film on the surface of the water or they may give an insoluble hydrolysis product which may be detected. The white chlorovinylarsenious oxide is formed immediately upon contact of 1+-0998-PU8-BU-C0S-WP lewisite with water and rapidly settles to the bottom. Crude mustard looks like dirty crank.case oil and this gas leaves a .surface film which may remain for 2^-M3. hours, Solid particles on the water surface may he chloracetophenone (CBf) or one of the irritant smokes (DM, DA, CDA). These gases are considered stable and insoluble and may he de- tected hy increases in the turbidity. " (2) pH. An unusual"lowering of the pH will indicate an acid hydrolysis product. Most waterworks laboratories- are equipped with some apparatus to make'these determinations which may he electromatric .-or colorimetric. The S.D.C, colorimetric pH kit, as an example, is portable and simple to use. Its use may he taught to one with little training in a short time. Among the gases which lower the pH hy hydrolysis with the formation of a halogen acid are; mustard, lewisite, phosgene, diphosgene, ethyl dichiorarsine, methyl dichlorarsine, diphenylchlorarsine and possibly hromhenzyl cyanide. (3) Alkalinity. The alkalinity of the water is also lowered hy hydrolysis of the above gases. This determination should he made hy titrating 50 or 100 ml. of the sample with ,02N standard sulfuric acid using methyl orange as an indicator(5). The effect of mustard and lewisite on the pH and alkalinity of Cincinnati tap water is illustrated in the following table: Approximate Concentration of Gas in Tap Water P.P.m. Mustard (HS)* r~ Lewisite (M-l) PH Alkalinity P.P.m, Acidity P.P.m. pH Alkalinity P.P.m. Acidity P.P.m, 0 7.6 38 -- 7.8 58 10 7.2 3k — 7.3 3k — 50 5.5' 7 -- 6.2 15 — 100 21 3.3 — 10 500 2.k 256 2.8 -- 200 (*0 Chloride content. An increase in the chloride content may he detected hy titrating the sample with standard silver nitrate solu- tion using potassium chromate as an indicator (*0, or hy precipitating (*) The mustard was allowed to react for one hour with, frequent shaking "before the tests were made. The water temperature was 27°c. - 4-0998-P49-BU-C0S-WP the "chloride as the silver ’ salt and completing the determination ; "‘; gravimotrically. Ah example of the chloride increase found by volu- metric titration when Cincinnati tap water was contaminated with mustard and lewisite is given below: Approx. Quantity of Gas Added p.p.m. Mustard (HS)* Lewisite (M-l) p. p. m, Chioride p.p.m. Chloride Found Theoretical , Found Theoretical 0 18 18 18 18 10 25 22 23 21.k : 50 ko. 3 55 35.1 100 6? 62.7 52.2 500 25^ 2kl 168 189 (*) The mustard gas was allowed to react with the water for hours before the chloride was determined. (5), The oxygen consumed value is a chemical measure of the organic matter present in the water. It depends upon the oxidation of organic matter by a definite amount of standard potassium permanganate solution when heated with a sample of water in a boiling water bath for 50' minutes. The permanganate remaining after digestion is determined with standard ammonium oxalate solution and the permanganate absorbed is a measure of the oxygen consumed. As war gases are organic compounds they will be oxidized in the course of the oxygen consumed determination, leading to an increase of the oxygen consumed value above the normal value for the water. Other oxidizing agents such as potassium dichromate have been used for determining oxygen consumed, and dichromate possesses a slight advantage in oxidizing the organic matter more completely. It is suggested, however, that the permanganate’procedure as given in Standard Methods be followed for this work,. , Although the-oxygen consumbed value is non-specific it would be advisable to set a standard which should not be exceeded for potable waters. As the oxygen consumed values of most drinking waters are 1 p.p.m, or less, higher values will indicate organic contamination. An increase in the oxygen consumed value of’ 2 or 5 parts should bo looked on with suspicion. If the O.C. is increased 5 p.p.m. or more, the water should not be used unless it has been proven, that, this increase was not caused by gaS" co'ntamination or, by sewage pollution. ' The following modified procedure for O.C, has been proposed for rapid field use. To 50 ml. samples of the water 1,5 ml. of exactly 0.0125N potassium permanganate and 5 ml. of 25 per cent sulfuric acid if-0998-P50-BU-C0S-WP solution are added. This solution is then placed in a boiling water hath for exactly 10 minutes. At the end of this period of digestion, the presence or absence of color is determined. If the solution is still colored, the water may he considered as satisfactory providing all the other criteria give no evidence of contamination. Samples which are colorless when removed from the hath should he considered as non-potahle regardless of the results of other tests. (6). Chlorine Demand, Most of the war gases react with chlorine and may he detected by routine determinations of chlorine demand. Chlorine demand is considered one of the most important methods of de- tecting gas contamination in water. The chlorine demand of the water may he defined as the quantity in parts per million of chlorine required to he added as clilorlne water to produce a trace (0,1 p.p.m.) of residual chlorine after 5 minutes contact. The residual cnlorine should ordinarily he determined by the ortho-tolidin However, if the water to he tested contains more than 0.3 p.p.m, of Fe, 0,01 p.p.m, of manganic Mn and/or 0,3 p.p.m. of nitrite U, one of the modified procedures or the starch iodide procedure must he used.. It should he understood, however, that the starch iodide-thiosulfate titration is not as sensitive for traces of residual chlorine and should not he used unless difficulties are encountered in the ortho-tod.idin procedure, RFAGEHTS 1. Ortho-tolldin solution. Dissolve 1 g. of ortho-tolldin in 1 liter of hydrochloric acid (180 ml. HC1 op.gr, 1,18 to 1.19 diluted to 1 liter). It is sometimes easier to dissolve the ortho-tolldin by grind- ing in 130 ml. of strong acid and then diluting to 1 liter with distilled water. 2. Chlorine water. By passing chlorine gas through distilled water a solution is made which contains slightly more than 1 g, of chlorine per liter. This solution is not stable and must he standardized each time it is used. A chloramine T solution containing 1000 p.p.m. of available chlorine may he used if desired. Standard!zation. To 100 ml, of distilled water add 1 - 2 g. of IQ. crystals, shake until dissolved, add 5 ml. of chlorine water, 1 ml, of concentrated HC1 and allow five minutes for liberation of the iodine. Then titrate with 11/3+0 sodium thiosulfate using starch solution as an indicator. One ml. of sodium thiosulfate is equivalent to 0,886 mg. of chlorine, and mg, Clo per ml. soln = ml. sodium thiosulfate X 0.886 t 5, Procedure To a 250 ml, sample add the standard chlorine water (or chloramine T) 0.5 ml. at a time with gentle stirring until a spot plate test using 1 drop of ortho-tolldine solution and 0,25 ml. of sample gives a yellow color. If chloramine T is used one or two minutes will he required for the color to develop in each spot plate test. Call this the immediate 4-0998-P51-BU-COS-WP chlorine demand. On the basis of the immediate chlorine demand, take a new sample of smaller size if more convenient and add the proportionate total amount of chlorine solution added in the immediate determination plus 0,1 to 0,2 ml. in addition. Stir gently and in exactly five minutes test a portion of the sample for residual chlorine according to the standard method (7). Repeat this procedure until 0.1 p.p.m, residual chlorine is obtained after 5 minutes contact. When 250 ml. of sample are used, the p.p.m. chlorine demand = ml, of C±2 soln. X mg, of Gig per ml. X If more than 0 1 p.p.m, of residual chlorine is found after 5 minutes contact, an approximate value of the defined chlorine demand (if 25 0 ml. of sample were , sod) is equal to ml, of Clp soln. X mg, of Gig per ml, X plus 0.1 minus the residual chlorine found in p.p.m. The chlorine demand may he used as a standard of potability, lor this purpose, standard chlorine water may be used directly on the sample or if chloramine T is used the pH of the sample should be adjusted to 5 or less with a few drops of 6w sulfuric acrid. Using this procedure, the chlorine demand of a potable water should not exceed 5,0 p.p.m. The only interfering'sub- stance for this test is hydrogen sulfide. If the odor indicates hydrogen sulfide, it may be removed by aerating the acidified water sample for a few minutes before the chlorine demand test is made. A chlorine demand obtained in a clear water may indicate contamina- tion by mustard, lewisite, ethyldichiorarsine or methyldlchlorarsine. For the determination of these contaminants no adjustment of the pH is necessary. A chlorine demand in turbid waters may indicate diphenyl- chlor arsine (DA), diphe ayIcyanoar s ine (CDA), or adamsite (DM), along with the above gases. The chlorine demand obtained with chlorine water on samples of Cincinnati tap water contaminated with 100 p.p.m, of mustard (HS) was 513 p.p.m. and with 500 p.p.m. of lewisite (M-l) was 203 p.p.m. A pro- cedure has been suggested for determining the chlorine demand at several pH values with chloramine T and interpreting the differences obtained in terms of mustard and possibly other gases. This procedure needs further study for confirmation. (7) Arsenic. If members of Group 2 (the irritant smokes), lewisite ethyldichiorarsine mid methyldlchlorarsine of group or arsenates and arsenides of gr up 6 are suspected, tests for arsenic should be made. A separate memorandum on the Quantitative detection of arsenic in water by the standard Gutzeit method is attached hereto. Before the quantitative tests are carried out, one of the rapid qualitative tests may be made to determine whether the sample is heavily contaminated. It is suggested that on any sample which has a high chlorine demand, a Reinsch test, a hydrogen sulfide test or the molybdenum blue test be made. The Reinsch'test should be made as follows: To 100 ml. of sample on which the chlorine demand has been satisfied, add 16 ml. of cone. HC1 (analytical reagent). Then add a l/2 inch square of freshly -0998-P52-BU-COS-WP cleaned sheet copper*, cover the beaker with a watch glass and boil the liquid gently for 15 minutes. If arsenic is present, the surface of the copper will be darkened particularly at the edges. The same reaction is given by antimony and bismuth and some other metals. A water con- taining 500 p.p.m, of lewisite will completely blacken the copper in this test and a noticeable blackening will be obtained in concentrations down to about 20 p.p.m, of lewisite. For the hydrogen sulfide test, take 20 ml. of the tost solution and add 10 ml. of a freshly prepared, clear HgS solution. If any of the arsenical vesicants are present in a concentration of about 20 p.p.m, or more, a white opalesenee will be obtained by the formation of the arsine sulfide. The Molybdenum Blue Direct Colorimetric Test for Arsenic In the presence of the very small amounts of silicates and phosphates that are found in most water supplies, this test can be applied directly. The test is more sensitive than either of the other rapid tests for arsenic and can easily be adapted for use in the field. To detect arsenic con- tamination by vesicant or other arsenical gases the water sample should be oxidized with the permanganate solution used for the oxygen consumed determination with a sufficient excess to give a. slight pink color to assure the complete oxidation of the arsenic. This also applied to in- organic arsenites. Reagents - same as given on page 7 of the following arsenic memorandum,* Procedure To 20 ml. or more of sample in a Kessler tube add 5 drops of con- centrated sulphuric acid, and add standard permanganate solution for the 0.0. determination (0.*!- g. per liter) a drop or two at a time un- til the first indication of permanganate remains. Dilute to 100 ml. with distilled water and proceed as directed following line if, page 8, of the arsenic memorandum. A blue color developing within 10 to minutes indicates arsenic. If a quantitative estimation is desired, arsenic standards should be prepared and treated simultaneously as directed on page 8 of the above memorandum. (*) The copper may "be cleaned in a few cc of nitric acid and then washed in tap water followed by distilled water. (*) If desired, a stannous chloride solution may he used in place of the hydrazine sulfate. The stannous chloride stock solution contains g. of C.P, SnClg in 100 ml. of cone. HC1, Prepare a diluting HC1 solution hy diluting ml. of cone. HC1 to one liter. For the dilute stannous chloride, add 10 ml. of stock stannous chloride to 150 ml, of diluting HC1. One half ml. of dilute stannous chloride solution is substituted for the hydrazine sulfate in the procedure. 1+-0998-P55-BU-COS-WP Cyanides Because of the slight possibility of the Introduction of hydrogen cyanide in water supplies by bombs or saboteurs, water works personnel should familiarize themselves with methods for detecting cyanides in water. Hydrogen cyanide in quantities up to 6 p.p.m, in a water supply would probably cause no difficulty. The average single fatal dose of cyanide by mouth for adults is c)0 mgs. or more. There are a number of simple tests for the determination of cyanides in water. Among these are the pruosian blue test, the benzidine-copper acetate test, the silver nitrate test, the phenolpthalin test, the gug. guaiac-copper sulfate test and the ferric thiocyanate test. The methods to be described are the modified Schonbein-Sunberg gum guaiac test as a rapid qualitative test and the Fasken ferric thiocyanate procedure as a more sensitive quanti- tative method. Modified Schonbein-Sunberg Test(9) Reagents; (1) Alcoholic gum guaiac - 0,3. g, of powdered gum guaiac is dissolved in 50 Ml. of 9% ethyl alcohol. This reagent will keep about one week, (2) Copper sulfate solution. Dissolve 1.0 g. of copper sulfate in 1 liter of distilled water and add 0.2 ml. of cone. (C.P.) (5) Cyanide reagent - Mix 10 ml, of solution #1 with 5 ml. of solution #2, This reagent must be freshly prepared, every two or three days. Strips of filter paper about 1 cm. by 10 cm. to be moistened in solution #3 when the test is made. Procedure Add 100 ml. of sample to be tested to an Srlenmeyer flask and acidify "by adding cone, HC1 one drop at a time until the water is acid to litmus. Insert a stopper carrying a thermometer in the flask and adjust so that the thermometer is immersed in the liquid. Heat the flask over a small flame until the liquid attains a temperature of 70°C, Dip a strip of the filter paper into the cyanide reagent (solution //y), immediately remove the stopper and thermometer from the flask and in- sert the test filter paper inside the flask so as to test the air above the liquid. If cyanide is present, the reagent moistened test paper should become blue within a few seconds. Steam interferes somewhat with the development of the color so the contents of the flask should not be heated to boiling. If the first test is negative, replace the stopper and thermometer; keep the contents of the flask at 70° C, for about 5 minutes and repeat the test again, A negative test indicates that cyanide is not present in toxic quantities. Ferric Thiocyanate Method^0) Reagents; (l) Yellow ammonium sulfide. Ordinary laboratory reagent. k-0998-P.5^-BU-C0S-WP (2) A 10 per cent sodium hydroxide solution. Dissolve 10 grams of C.P, sodium hydroxide in distilled water and make up to 100 ml. (5) A 5 per cent hydrochloric acid. Dilute concentrated C.P. hydrochloric acid with distilled water to 5 per cent HC1 by weight. A 10 per cent ferric chloride solution. Dissolve 10 grams of C.P, ferric chloride, FeGl-6Hp0, in distilled water and made up to 100 ml. (5) Stock solution of potassium thoicyanate. Dissolve k grams of C.P, potassium f.iocyanate in 1000 ml. of distilled water. Determine the exact strength of the solution by titration with N/l0 silver nitrate and dilute with distilled water so that 1.0 ml. contains 1,0 mg, of CN, (l ml. N/lO silver nitrate « 2,6 mg, CN), (6) Diluted standard solution of potassium thiocyanate. Dilute 10 ml. of stock solution of potassium thiocyanate (reagent 5) with distilled water to 100 ml. One ml, of this solution is equivalent to 0,1 mg. CN. Procedure Five hundred ml. of the water is acidified with 0.5 grams of tartaric acid, distilled, and 50 ml, of distillate collected. The whole distillate or an aliquot containing less than 2 mg, CN is placed in an evaporating dish and 0,2 ml. of 10 per cent sodium hydroxide and 0.5 ml. yellow ammonium sulfide added. The mixture is evaporated just to dryness on the water hath. If the yellow color should fade at any time during the evaporation, a further drop or two of yellow ammonium sulfide is added. The residue is taken up with 10 ml. distilled water, 1.0 ml. of 5 per cent hydrochloric acid added, and the mixture heated just to boiling. It is then allowed to stand for some hours for the sulfur to coagulate, after which it is filtered and washed, into a 50 ml, Nessler tube till about h-0 ml. have passed through. A series of standard tubes is prepared containing from 0.2 ml, to 20 ml. dilute standard potassium thiocyanate solution, corresponding to from 0,02 mg, to 2 mg, cyanide, each of which is diluted to about *1-0 ml. and acidified with 1.0 ml. of 5 per cent hydrochloric acid. Now 1 ml. 10 per cent ferric chloride solution is added to each of the tubes and the volume adjusted to 50 ml. After mix- ing the colors are matched immediately. If the amount of cyanide is above 0,1 mg. the test may be simplified by making fewer standards and. comparing with the nearest in a colorimeter. While the color given by 0.01 mg. cyanide in 50 ml, is quite perceptible immediately after adding the ferric solution, it fades 7 ither rapidly and comparison must be made at once. Hence this method is not recommended for amounts less than 0.05 mg, ON or 0.1 p.p.m. in the original water. Chemical Detection of Chloropicrin in a Water Supply. None of the common water tests already described, will give any indication of chloropicrin in water. Hence, if contamination with chloropicrin is suspected, though the odor is not recognized, a chemical J+-O998-P55-BU-COS-WP confirmatory test should be made, Bolling a water sample with alcoholic potassium iodide decomposes the chloropicrin according to the follow- ing reaction: cci^no2 ♦. kia —ci)+ ♦ 3kci ♦ km)2 The nitrite formed can then be detected with the ordinary nitrite re- agents used in the water laboratory. Procedure To two ml. of the contaminated water sample in a test tube add 5 ml. of % alcoholic potassium iodide and heat to boiling. Cool and add 1 ml, of sulfanilic acid reagent and 1 ml, of alpha-napthylamine acetate reagent (reference 2, page k6), If the original water is nitrite free this procedure will detect chloropicrin to a concentra- tion of about 3 p.p.m. 4-0998-P36-BU-G0S-WP REFERENCES. (1) Leitch, James L. Memorandum Report 31. General Factors in the Contamination of Water Supply Systems ty Chemical Agents and Other Toxic Compounds, MD (EA), December 29, 1941. (2) Drinking Water Standards, U.S. Public Health Service. (Soon to be published). (3) Standard Methods of Water Analysis, Eighth Edition, American Public Health Association, pg, 64 (1956), (4) Ibid. pg. 54 (1936). (5) Ibid. pg. 136 (1936). (6) Ibid. pg. 20, 166, 228-232 (1956). (7) Ibid. pg. 164 (1936). (8) Fasken, J. E. Jour*. American Water Works Assn., 32, 487 (1940). (9) Harger, R. N., Forney, Robert B. and Farr, Fred Jr. Simple Procedures for the Detection of Certain Chemical Contami- nants in Drinking Water, Unpublished Memorandum (1942), 4-0998-P57-BU-C0S-WP TABLE 9 • CLASSIFICATION OF CHEMICAL AGENTS UPON BASIS OF TOXICITY TO WATER Group 1 Agents which probably will produce a non-toxic water, though it may be non-potable.' Thermit, crude oil FS Mixture HC Mixture Titanium tetrachloride FM Carbon Monoxide Group 2 Agents producing a turbid water which is non- toxic after removal of the turbidity. Adams ite Diphenylchiorarsine Diphenylcyanoarsine (/^A Group 5 Agents present in fairly high concen- \ trations which would produce a non-toxic water. Phosgene Group k Agents likely to cause trouble in a water supply unless extra precautions are taken. Chloropicrin PS Mustard HS Lewisite M-l Ethyldichiorarsine ED 'roup 5 Agents requiring additional data for definite classification. Brombenzylcyanide GA Chloracetophenone CN CN Solution CNS Group 6 Compounds only likely to be used for deliberate c ont aminat i on. Arsenates, Arsenites Cyanides Heavy metal salts Alkaloids and toxins Pathogenic Bacteria J+-0998-P58-BU-C0S-WP TABU' 6 CHEMICAL BLM7TQB OF "AGENTS TO WATER Agent Solubility mg, per liter at 20° C. Behavior Products of Hydrolysis Treatment Required (5) Mustard ns r “Boo Slowly hy- HC1 and thloglycolj Treatment for re- drolyzsd W (non-toxic) j moval difficult. m Lewisite M-l 500 Bap idly HC1 and ClG^HAsO May be used for pe ■g hydrolyzed (toxic, sparingly iod of week or les o soluble) if 10 p.p.m, are •H CQ present. 0 > Ethyldi chlor- Very n t« HOI and CoHr.As0 With higher concen arsine ED soluble (toxic, soluble) trations pump to waste 1 Chioropicrin PS 1700 Stable - - h P °rg Phosgene CC 1000 BapicLly HOI and CO2 Neutralization if ft hydrolyzed pH indicates it, otherwise no treat ment Brombenzyl- Probably ooagulati 1 •H rs cyanide CA Insoluble Stable _ - and filtration is Th O o -p all that would be a g Chloracoto - required. p he none ON . t 11 - - Adamsite DM Insoluble Stable - - 'S CQ Diphenyl- I Very Slowly KOI and Coagulation and. -P & o chlorarsine DA slightly hydrolyzed (PhoAs)o0 filtration h t, soluble H Diphe nylcyano- arsine GDA Insoluble Stable HC Mixture - _ slowly Neutralization wit bn hydrolyzed or lime, if & CD pH indicates it, fl 0 M o SO* in Very Rapid re- HoSOg and otherwise no treat 0 Jh 1 HCISO3 FS soluble action HC1 ment required. V CO Titanium Tetra- chloride FM Soluble Hydrolyzed HC1 and Ti(0H)k o Hydrocyanic Very Slowly Ammonium formate Ferrous, ferric ■g § acid soluble decomposed and brown poly- salt treatment fol 0 .p CQ •H meric products lowed by coagula- m l>a o Ph tion and filtra- ■ CQ tion. (1) Eighty-five (85) per cent of solute hydrolyzed within one hour. (2) Best treatment involves use of high doses of activated carton followed by co- agulation and filtration followed by chlorination to beyond the break-point. If chlorine demand of treated water is over 5 p.p.m. water is unsatisfactory. For small doses (50 p.p.m. or less) of mustard, wait one hour and then take water from intermediate level for purification. Water containing l)00 p.p.m. or more is not satisfactory for treatment. (5) Standard disinfection practice with chlorine should be understood to follow all water treatment suggestions. U-0998-P59-BU-C0S-WP REPORT OH CONTAMINATED WATER EXAMINATION Threshold odor limit found for chloroplcrin in water was p.p.m. Results on Contaminated Cincinnati Tap Water Sample i Control i i Tap j Unknown Water ! #1 r- Unknown #2 Unknown #5 II J Unknown Odor if any i i Hone i j 1 i 1 ! pH 7.6 to 7.8: i . ... .1 j - Chlorine Demand (5 minute contact) r r j Less tha.i! 1 p.p.m. | L J ' • Less than 1 p.p.m. Arsenic Hone found i ■ - - ..... Hone found Gas Suspected i 1 j • . i . . On basis of above tests is water potable ? j ' i Yes 1 i . 1 1 : i Name_ 60-BU-C0S-WP LABORATORY PROBLEMS Detection of Gas Contamination in Water (1) Determine threshold odor limit on Chloropicrln series and record on report sheet. Then analyze the following water samples as suggested. Unknown #1 This sample contains h-00 p.p.m, of an arsenical. Notice absence of odor. Determine pH and check arsenic by Reinch test. This sample has a high demand. Unknown #2 Determine pH and chlorine demand and arsenic by molybdenum blue method. Unknown 7^3 Determine pH and chlorine demand and arsenic by molybdenum blue method. Unknown Determine the odor and pH, If odor is recognized record contaminant, 4-0998-p6i-bu-cos-wp MEMORANDUM ON THE DETECTION AND ANALYSIS OF ARSENIC IN WATER CONTAMINATED WITH CHEMICAL WARFARE AGENT’S By C. C, Ruchhoft and Stuart Schott National Institute of Health Division of Public Health Methods Cincinnati, Ohio Some of the arsenical compounds which may be used in chemical warfare ahd contaminate water supplies include the following; Chemical War-* Name Formula fare Symbol 1. Methyldichlorarsine CILAsCl0 3 MD 2. Ethyldi chlorars ine C H AsClp 2 3 d ED 3- Phenyldichlorarsine CAErAsCl0 6 5 2 k. Diphenylchlorarsine (c6n5)&A3Ci DA 5- Lewis it e-Chlorovinyldichlorarsine C1CII;CHAsC12 M-l 6. Diphenylaminocyanoarsine NH(C JI, ) AsCN.l 6 k 2 * 7. D i phenylc yanoar sine (C.H ) AsCN 6 5X2 CDA 8. Adamsite-Phenarsazine Chloride MH(C6H,+ )2AeCl DM The first five of these compounds are hydrolyzed in water to form the corresponding arsenious oxides. These reactions are illustrated in the following equations: (2) C H AsCl ♦ HOH CJBLAsO * 2HC1 2 5 2 2 5 (5) C1CH:CHAsC12 * HOH CICH:CHAsO t 2HC1 Although some of these arsenicals hydrolyze in water, it ia necessary to break down the hydrolysis product before the arsenic can be detected quantitatively by most methods of analysis. However, with arsenicals in solution and hydrolyzed the bromate method can be used to titrate arsenic directly (page 11) without any preliminary preparation of the sample. With contamination by methyldichloraimine, ethvldi-'hlorarslne and Lewisite and in the practical absence of phosphate and silica the molybdenum blue method can be used directly after the water sample is oxidized with permanganate in a slightly acid solution. With contamina- tion by arsenics]s which are less soluble and more stable, such as k-0998'-P62-BU-COS-WP DiphenylaminOcyanOarsine and Adamsite, the sample must be prepared for analysis by digestion. Hence, it is advisable to digest all water samples suspected of being contaminated with arsenicals and after digestion apply the or alternate tests as described hereafter. Preparation of Sample ~by Digestion. 1, Reagents Sulfuric Acid - C.P. Analytical Reagent, Nitric Acid - C.P. Analytical Reagent, 2. Procedure To a 300 ml, water sample in an 300 ml. KJAldahl flask add 10 ml. of C,?. sulfuric acid, one ml, of C.P. nitric acid and a small piece of ignited pumice. Mix by shaking and digest under a hood until fumes of sulfuric acid are given off. After cooling 30 ml, of distilled water are added and the digestion is continued until sulfuric acid fumes are again obtained. Cool and add 10 ml. of water and transfer to a 50 ml. or 100 ml, volumetric flask, Rinse the KJeldahl flask with water and add to the volumetric flask, making the sample up to 50 ml. or 100 ml. Proceed to the analysis by one of the following procedures. The Gutzeit Official AQAC Method (19*+Q Edition). Reagents (a) Stannous chloride solution. Dissolve to gm, of As - free SnGlg.SHgO in HC1 and make up 100 ml. with same strength acid. (b) Zinc. Use 20-30 mesh, As - free granulated zinc which needs no preliminary treatment, (c) Ammonium oxalate solution - saturated. (d) Potassium iodide solution - Dissolve 13 gm. KI in HgO and dilute to 100 ml. (e) Sand. Clean 30 mesh (through 30 - but not mesh) white sea sand by washing successively with hot 10 per cent Na0H solution, hot concentrated MO3, and hot distilled HgO, Dry the clean sand, (f) Mercuric bromide paper. Use commercial arsenic papers cut from paper of uniform weight and texture into strips exactly 2.3 mm. wide and about 12 cm. long. (Uniformity in width and texture of paper ,are of great importance in this comparison method. Irregular texture produces irregular impregnation, with consequent inaccurate results), To sensitize, soak strips one hour or longer in 3 -6 per cent (optimum 5 per cent) solution of filtered HgBrg in alcohol, according 4-0998-P63-BU-C0S-WP to quantity character and. activity of zinc used, (Attenuated, unsatis- factory stains, due to over-rapid evolution of arsine can he shortened and intensified hy increasing concentration of HgBi’2 and vice versa). If the strips are in sheets cut off two sides before soaking and leave strips attached at ends. After sensitization remove strips and dry in- dividual ones on glass rods and groups by waving in the air. Place strips when nearly dry between clean sheets of paper and subject them to pressure long enough, to take out bends and curls. Store in dry dark place. (Aging of paper usually results in markedly fainter and longer stains. Desirable typos of stains result from use of impregnated strips not over two days old), When ready to use, cut individual strip-s off squarely half inch from one end and insert this end in the narrow tube of the apparatus. Handle sheets by the paper attached to either end and cut in half Just before use. Strips must be clean and free from any contamination. (g) Standard arsenic solution. Dissolve 1 gm. As£0x in 25 ml, 20 per cent NaOH. Saturate solution with CO2 and dilute to 1 liter with recently boiled distilled water. One (1) ml. of this solution con- tains 1 mg, ASpO--. Dilute ij-0 ml, of this solution to 1 liter. Make 50 ml, of the diluted solution to 1 liter and use to prepare standard stains. A solution containing ,001 mg, AD2OV, may also be prepared. Prepare fresh dilute solution at frequent intervals. Apparatus. (a) Generators and absorption tubes. Use 2 oz. wide-mouthed bottles of uniform capacity and design as generators and fit each by means of perforated stoppers with a glass tube 1 cm. in diameter and 6-7 cm, long, with an additional constricted end to facilitate connection. Place small wad of glass wool in constricted bottom end of tube and add 3.9 - gm. of the 50-mesh cleaned sand, taking care to have the same quantity in each tube. Moisten sand with 10 per cent Pb acetate solution and remove excess by light suction. Clean sand when necessary by treatment (do not remove sand from tube) with followed by H2O rinse and suction. Treat with Pb acetate solution. If sand has dried through disuse, clean and remoisten it as directed. Connect tube by means of rubber stoppers with narrow glass tube 2.6 - 2,7 mm. in internal diameter and 10 - 12 cm, long, and intro- duce the clean end of the strip of HgBr2 paper. (A 5 mm. bore allows the paper to curl, which results in an uneven stain and poor end-point). Clean and dry tube before inserting bromide paper. (An ordinary pipe cleaner may be used), Water Bath, Use any constant temperature water bath. If no water bath is available, use any flat bottomed container of suitable depth and capacity. (A deep water bath is suggested to insure uniform conditions during evolution and absorption of arsine). Determinations. Determine the acid by titration in a definite aliquot of the digested sample solution. Place aliquot containing O.Ol mg. - 0.05 mg. i|..099S-P6^-BU-COS-WP AsgO* (.020 - ,025 mg, is optimum) and not larger than 3>0 ml, in Gutzeit generator. If arsenic in aliquot taken is outside limits specified, re- peat with proper aliquot. On the basis of the acidity titration neutral- ize the sulfuric acid in the aliquot with a 20 per cent solution of sodium hydroxide, cool and add exactly 9 ml, of concentrated HC1. Cool when necessary and add ml, KI reagent and h drops of the SnClg. Pre- pare standards corresponding to o>01, 0,02 and 0.03 mg, from reagent (g). Since standards must contain same kind and amouhts of acid as samples, add 5 ml., of HC1, and as H SO, has been neutralized, add an equivalent quantity As - free tb standards. Mix and allow to stand 30 minutes at not less than 2p° or 5 minutes at 90°. Dilute with H20 to ml. Prepare generator as directed under 2 and center strip of paper carefully in narrow tube. According to activity of zinc, add 2-5 gm. granulated zinc adding same quantity to each generator. Immerse the apparatus within 1 inch of top of narrow tube in water bath (constant temperature of 20° - 25°) allow evolution to proceed 1,5 hours. Compare strips or prepare graph from standard strips. Molybdenum Hue Method.* (Alternate) Reagents. 1. Standard Arsenlous 0::lde Solution. Dissolve 0,32*11 gm. of arsenic tricxide, in 23 ml. 10 per cent sodium hydroxide solu- tion, make slightly acid with sulfuric acid (1:6) and dilute with water to 1 liter, 2, Ammonium. Molybdate Solution. Dissolve 25 gm. ammonium molybdate in 300 ml. water. Dilute 75 ml. of concentrated sulfuric acid to 200 ml. with water and add. to the ammonium molybdate solution. 3a Sodium Hyposulfite solution. Two (2) gm. sodium hyposul- fite dissolved in water and. diluted to 100 ml. Hydrazine sulfate solution, half saturated. Shake excess hydrazine sulfate with 50 ml. water until no more dissolves, filter and dilute filtrate with equal volume of water. Follow the method for digesting and preparing the sample heretofore described, for the official Gutzeit method. A Gutzeit generator is prepared in the usual way, but instead of the tube containing the mercuric bromide paper, attach another tube leading the generated gases to a trapping device containing 3 ml, of sodium hypobromite solution (3 ml-, bromine water plus 1 ml. 0.5 N NaOH solution) as shown in the accompanying figure. It is better to have 2 trapping devices in series, the second need contain only water. Treat the arsenic test solution in the same way as in the Gutzeit method. (*) For a complete discussion of this method see Colorimetric Micro- determination of Arsenic by Jacobs and Naylor, Ind. & Eng. Chom., Anal, Ed., Yol. No. % p. kk2 (19^2 1I-0998-P65-BU-C0S-WP Allow the generation of arsine to proceed as directed under the Gutzeit method. After generation is complete, transfer the contents of the traps to a graduated colorimeter' tube, Nessler tube or volumetric flask. Wash the trap with 6 two ill. portions of water using an aspira- tor to blow the wash solution out of the bead traps. Add 5 drops of concentrated sulfuric acid and stir. Add 1 ml, of ammonium molybdate solution and shake. Add 1 ml. of a half saturated solution of hydra- zine sulfate or 1 ml. sodium hyposulfite solution. The hyposulfite solution must be prepared at least 2Jl hours in advance and should not be used until then. Freshly prepared hyposulfite solution causes a turbidity which can be removed by filtration but the method works be s' when the reagent is prepared as directed, or with hydrazine sulfate. Make to volume. Allow to stand for 0.5 hour for full devel- opement of the blue color. Compare with standards treated in a similar •• . way at the same time. The standards are prepared from the stock arsenic solution. Add 3 ml, of hypobromite solution to the aliquot selected for the standard or standards, dilute to 17 ml., add 5 drops concentrated sulfuric acid, stir, add 1 ml, of molybdate solution, stir, add 1 cc0 of half-saturated hydrazine solution, stir and make up to same volume as test solution. To develop the proper quality of color in the test solution and to inhibit the development of color in the blank, it is necessary to add the proper amount of acid. If the final dilution is less than 20 - 25 ml., add less sulfuric acid; if the final dilution is greater than the aforementioned volume add more sulfuric acid. (Note: The Chaney Method (jour. Ind, Eng. Chem., Anal. Sd., Volume 3.2, p, 691 is a modification of the molybdenum blue method which re- quires a special glass digester and still. Where this equipment is available the procedure is permissible). BROMATE METHOD - ALTERNATE (Tentative Method, AOAC., Ed.), Applicable to the determination of arsenic in plants and food products where a sample of convenient size for .digestion will yield at least 0.321+ mg. Asg0^. Reagents. 1. Ammonlim oxalate - urea solution. To a saturated solution of ammonium ox:.late ,add 50 gm. urea per liter. 2. Hydrazine sulfate - sodium bromide reagent. Dissolve 20 gm. hydrazine sulfate and 20 gm. sodium, bromide in 1 liter dilute hydro- chloric acid (1 pt, HC1 ; k pts. water). 3. Sodium, chloride - commercial salt, uniodized. b-0998-P66-BU-C0S-WP k. Standard potassium bromate solution. Dissolve 0.1823 gm. KBrOr in water and dilute to 1 liter. Standardize by titration against standard solution, making the titration at about 90° and in the presence of lt)0 m3.. Ho0 and 25 ml, HOI in order to simulate conditions under which the samples will be titrated. One (l) ml, KBrO solution should be equivalent to 1 ml. ASg0_, solution, 5_. Standard AsgO-solution. Dissolve 0,3241 gm, Aso in 25 ml. 10 per cent N&0H, make slightly acid with HgSOp (diluted with 6 parts of water) and dilute to 1 liter with water. Distilling apparatus. The distillation apparatus consists of an 800 ml. Kjeldahl flask, a distilling tube and a 500 m3., Erlenmeyer flask as a receiver. To prepare the distilling tube bend 10 - 15 mm, glass tubing to an acute angle of about 70°. Draw the longer aim, which is about 15 - 20 inches long down to an orifice of approximately 3 mm.. Fit the shorter arm (about k inches; with a one-hole rubber stopper to fit the Kjeldahl flask. The stopper is to be previously boiled for 15 minutes in 10 per cent HaOH solution and then in HC1 for 15 minutes in order to remove sulfur compounds which might be distilled and react with the bromate solution. Preparation of Sample. Introduce 500 ml. water sample containing 0 mg. or more of into an 800 m3., flask. Proceed with acid digestion as follows; Add 20 m3., or (rarely) if material is difficult to digest, ,25 ml. at the beginning of digestion. After digestion is complete add 50 ml. HgO and 25 ml, ammonium oxalate-urea solution and boil until white SO fumes extend into the neck of the flask to decompose the oxalates^and urea completely (volatile intermediate products may distil and react with the hrornate). If the heat available is insufficient to decompose these substances, it is preferable to evaporate to fumes after the addition of water alone. Hydrazine sulfate will destroy small amounts of nitrogen oxides. isolation. Add 25 ml, water to the digested solution in the Kjeldahl flask and cool to room temperature. Place 100 ml. water in Erlenmeyer flask and set up apparatus so that the long arm is well under the surface of the water in the Erlenmeyer flask. Add 20 gm, had and 25 ml. hydrazine sulfate-sodium “bromide solution, to the KJeldahl flask and connect the distilling tube. Heat the flask over a. small well protected flame and distil into the water in the Erlenmeyer flask, (Pleating is not intended to “bring about boiling but to bring about evolution of HC1 gas which carries over with it. Absorption of the HC1 gas by the water causes J1-O998-P67 -BU-C0S-WP ■ a rise in temperature which indicates progress of distillation). Adjust the flame so that the temperature of the distillate solution will rise to 9°° in 9 - 11 minutes, and then disconnect' the distillation apparatus. (The residual mixture in the flask should be not less than 55 ml,). If distillation proceeds further or larger quantity of sulfuric, acid is used than that specified in digestion, sulfur dioxide is distilled which is titrated as arsenic). Determination. 1 Titrate the distillate at once with the hromate standard solution using 5 drops methyl orange indicator (0,5 gm. M.O. per liter water). (Single drops of the indicator not exceeding three may be added during the course of the titration). Toward the end of the titration add the bromate very slowly and with constant agitation to avoid local excess. The end point is reached when a single drop of bromate just destroys the final tinge of red color. Use an Erlenmeyer flask containing dis- tilled water alone as a reference. (The end point must not be overrun as the action of the indicator is not reversible and back titration is not reliable. At the proper end point the red color produced by 2 additional drops of methyl orange indicator should persist for at least 1 minute). Correct the results for the volume of bromate used in blank run. For this purpose digest 5 gm. sucrose with the same quantity of reagents and use the regular distillation procedure. (Blank titration should not exceed 0.7 ml. The method is accurate down to the variations in the blank which should not exceed 0.1 ml. when reagents from the same lot are used). Should the blank titration be high or variable, test the individual reagents for purity by a bromate titration. Test the sulfuric acid by bringing 20 ml, to a boil, cool, dilute with HoO to 100 ml., add a little HC1 and titrate while hot. It probably will furnish most of the blank. Select rubber stoppers carefully as these are often the source of unsatisfactory blanks. 6l Ii.-0998-p68-bu-cos-wp KEFEREMCES, The War Gases, Chemistry and Analysis. Mario Sartori, D. Van Nos brand Co., New York. 19^0, The Detection and Identification of War Gases. Ministry of Home Security, Air Raid Precautions Department, Chem. Publishing Co., Brooklyn, 19^0, Analytical Chemistry of Industrial Poisons, Hazards and Solvents, M. B, Jacobs. Interscience Publishers, New York, 19*5-1, The Rapid Detection of Arsenic in Foodstuffs Contaminated with Lewisite. W. J. Stainsby and A. M. Taylor. Analyst 66, 253 (19*5-1). Official and Tentative Methods of Analysis of the Associa- tion of Official Agricultural Chemists. Washington, 19*5-0, Colorimetric Microdetermination of Arsenic. M. B, 0‘acobs and Jack Nagler. Ind. & Eng. Chem., Anal, Ed., Vol. Ik, No. 5, pp. (19^2). APPARATUS FOR THE molybdenum P) ■ i-;' . D U Lr .method.. TRAP With 3MM.GLASS BEADS CONNECTTO SECOND TRAP RUBBEROR#3 GROUND GLASS JO r SAND WET WITH LEAD ACETATE STAND CUTZEIT gener atok 70-BU-COS-WP GU T2LJT • T gonltatou .GLASS TULL ,2.6 0,7 MNO IN LIAM. :: 10 -12 CAA. LOmG GLASS TULL 1 C M. D(A M. b-7 CM.LONG 2 02. V/JDS MOO'/rJ .GOTTIS • I-0998-P71-BU-C0S-WP CHEMICAL WARFARE BIBLIOGRAPHY General Prentis, A.M, "Chemicals in War", McGraw-Hill, New York (1937). Sartori, M. and Morrison, L. W, "The War Gases", D-Van Kostrand Co. Inc. Hew York (19*+0). Jacobs, M, B, "War Gases". Interscience Publishers, Inc. New York (19^2). Jacobs, M, B. "Analytical Chemistry of Industrial Poisons, Hazards and Solvents", Interscience Publishers, Inc, New York (19^1). . U, S. War Department Technical Manual TM 3-215 "Military Chemistry and Chemical Agents". (19^2). Chemical Warfare School Pamphlet No, 6, "Chemical Warfare Miscellany". pages, Edgewood Arsenal, Md. (19^0), Chemical Warfare Service, "Chemical Warfare and the Chemical Warfare Service", Chemical Warfare School, Edgewood Arsenal, Md. United States Navy, "Service Chemicals", (19^2). Identification and Detection Ministry of Home Security, "The Detection and Identification of War Gases". Chemical Publishing Co, (19^0), Studinger, J. "A Short System of Analysis for the Detection of Materials Used in Chemical Warfare". Mitt Lebenam Hyg., 27, pg. 8-20 (1936}. Hoogeveon, A, P, J, "The Detection of Small Quantities of War Gases". Chemistry and Industry, 59, lf% 500-56. (Aug. 3, 19^0). Hickey, F. C. and Hanley, J, J. "War Gas Identification Sets". Jour, of Chemical Education, 19, pg. (Aug. 19^2). Bradley, T. F. "Chemical Detection of War Gases for Civilian Defense", Chemical & Engineering Hews, 20, pg. 893-896.(July 25, l$h2) Jf-0998 -P72-BU-COS-WP Schott, Stuart and Ruchhoft, C. C. "Method for the Detec- tion of Chemical Warfare Gases". Unpublished Memorandum, U.. S. Public Health Service, Stream Pollution Investigations, Cincinnati, Ohio (19^2), Chemical Warfare School Pamphlet Ho. U-, "Instructions for Using Gas Identification Sets", (19^2), Defense and Protection U. S. War Department, Basic Field Manual, FM 21-^0, "Defense Against Chemical Attack". (19^0). U. S, Office of Civilian Defense, "Protection Against Gas". (19^1). U. S, Havy Passive Defense Handbook Ho. 7> "Passive Defense of Haval Shore Activities Against Chemical Warfare". Bureau of Yards and Docks, Havy Dept. (July, 19^2), Tanner, H. G, "The Construction of an Emergency Civilian Gas Mask", Jour, of Chemical Education, 19, PS. 522-326. (July, i9te). Chemical Warfare School Pamphlet Ho, 2, "Training Guide Chemical Warfare". Edgewood Arsenal. (July, 19^2) U, S. War Department, TM 3-505. "Use of Smokes and Lachrymators in Training". (19^0). Chemical Warfare School Pamphlet Ho. 3. "Study Guide- Incendiaries". Edgewood Arsenal. (April, 19^2). U. S. War Department, TM 3-205, "The Gas Mask", (October 19^1). Standard School Lectures, "Civilian Protection". U.S. Office of Civilian Defense, Washington, D.C. (19^2). De c ont aminat i on Air Raid Precautions Handbook Ho, k. "Decontamination of Materials". H, M. Stationery Office, London, (1939). Air Raid Precautions Handbook Ho, k~At "Decontamination of Clothing". H. M. Stationery Office, London. (1939). (Chemical Publishing Company, Hew York, 19^1). L-0998-P75-BU-COS-WP Chemical Warfare School Pamphlet No. 12. "Decontamination". Edgewood Arsenal, Md. (1942), U. S, Office of Civilian Defense. "A Handbook for Decon- tamination Squads", (1941), Physical and Chemical Properties, Jackson, K. E, "Chloropicrin". Chemical Reviews, 14, 251 (1954). Jackson, K. E. "Mustard Gas". Ibid., 15, (193P. Jackson, K. E. and Jackson, M. A. "Lewisite and Other Ar- seni cals". Ibid., 16, (1955). Jackson, K, E. and Jackson, M. A. "Lachrymators". Ibid., 16, 195 (1935). Jackson, K. E. "Smokes". Ibid., 25, .67 (1939). Chemical Warfare Agents and Water Supplies. Leitch, James L. Memorandum Report No. 51. "General Factors in the Contamination of Water Supply Systems by Chemical Agents and Other Toxic Compounds". U, S. War Department (MD) EA, December 29, 1941. Zeitzev, S, "Protection of Water Supplies from Chemical In- fection", Vestnik Protivovogdushnoi Oborony, Part 7, pg. 20-24 (1957). Hess, Seth G. "Water Supply, Sewerage, and Public Health Problems Created by Aerial Bombing", (Ps.per presented at the National Conference on Aerial Bombing held.in New York City, Feb. 16-24, 1942, under auspices of the U. S. Office of Civilian Defense). Medical Division Sanitary Engineering Bulletin No. 1. "Protection and Maintenance of Public Water Supplies under War Conditions". U. S. Office of Civilian Defense. (1942) Harger, R, N., Forney, Robert B. and Farr, Fred Jr. "Procedures for the Detection of Certain Chemical Contaminants in Drink- ing Water". Unpublished Memorandum, Indiana State Board of Health, (1942). 4-0998-P74-BU-C0S-WP Ruchhoft, G. C. and Schott, Stuart. "Methods for Detection of Chemical. Warfare Agents in Water arid Treatment of Con- taminated Water Supplies", Unpublished Memorandum, U. S, Public Health Service, Stream Pollution Investigations Station, Cincinnati, Ohio (19^2), ------ "Detection and Determination of Toxic Substances in a Water Supply". Unpublished Memorandum, Bureau of Water Works and Supply, Los Angeles, California, (19^2). Goudy, Fay F. "Wartime Protection of Water Supplies". Amer. Jour, of Public Health, 3b, (19^1). Ruchhoft, C. C. and Schott, Stuart, "Detection and Analysis of Arsenic in Water Contaminated with Chemical Warfare Agents", Unpublished Memorandum, U. S. Public Health Service, Cin- cinnati, Ohio. (19^2). Chemical Warfare Agents and Food "Food and its protection Against Poison Gas". H. M. Stationery Office, London. Page, A. B. P. "Damage to Foodstuffs in Chemical Warfare". Jour, Hoy. San. Inst., 6.1, 105 (19^b). Wood, Robert, "Foodstuffs and Gas Contamination". Jour. Roy. San. Inst., 6l, l6o (19^1), Stainsby, W. J. and Taylor, A. McM. "The Rapid Determination of Arsenic in Foodstuff Contaminated with Lewisite". The Analyst, 66, p. 235-239.? (June, 19^1). Stainsby, W. J, and Taylor, A. McM. "The Detection of War Gases in Foodstuffs", The Analyst, 66, p. (Feb. 19^1). Vettier, Georges. "The Protection of Foodstuffs from War Gases". Thesis to the Faculty of Medicine of Paris (1957). Schoofs, F. "Contamination of Foodstuffs with Volatile Toxic Substances", The Analyst, 6k, 905-905 (Dec. 1939), Nisbet, B. R. "Food in Wartime". The Municipal Journal and Local Government Administrator, 99, P. 1266-1267 (Oct. 19^0). h-Q998-P75-BU-cos-wp Easskd, A. "Action of Mustard on Food". Tierartzl Rundshau 151 (1939). (C. A. 53, 55*ll6) Vastagh Gabor, Per. Ungar. pharm, Ges. 16, 19-1 (19*4-0). C. A. 5*+, hlCp. Perotti, Luigi. "The Utilization of Food Products Impregnated with Toxic Gases". Rev. liyg, med. prey, 6l, 79 (1959). (C. A. 53, 5958^). Fuchs, A, W. "Milk Control, in the Defense Program". Unpublished Memorandum, States Relations Division, U. S0 Public Health Service, Washington, D.C. (19*+2). Mimeographed Training Manuals "Chemical Warfare and Training of Gas Officers in Civilian Areas", Committee on Decontamination, Alameda (California) County Council of Defense, (19*4-2). "Course cn Chemical Decontamination Problems". Mass. State College, Mass, Dept, of Public Health, Mass. Committee o?i Public Safety in Cooperation with U. S. Office of Education. (l9J4-2). "Technical Manual for the Senior Gas Officer of Civilian De- fense" . Medical Division, Office of Civilian Defense, Washington, D. C. College of Medicine, University of Cincinnati (Ohio), (July, 19*4-2). "Technical Notes and Data on Civilian Protection Against Gas", The Pesearch Staff of the Champion Paper and Fibre Co., Hamilton, Ohio. (Sept. 19*4-2). 69 1+-0998-P76-BU-C0S-WP THE DETECTION OF WAR GASES, III. FOODS By Karl Bambach Kettering Laboratory of Applied Physiology, College of medicine, University of Cincinnati, Cincinnati, Ohio General Considerations I, Cases where tests need not bo miade for pres once of gas in foods, A, Properly packaged foods in containers impervious to gas, as described in previous discussion$ outside only of containers need be decontaminated, B, Some foods should bo destroyed without analysis, as milk in open vessels, or in bottles with cardboard caps which have been splashed with liquid gasj or vegetables or eggs which have been splashed, II. Types of contamination A, By liquid spray or splashing, or by arsenical smokes, B, By exposure to a gaseous atmosphere5 foods in this class may be rendered partially or completely usable, while those in class A can seldom bo usv,d, flhero mustard gas or lewisite has been used, butter, fats, cheese, and meats should receive special attention, and should be considered as always belonging to class A, III. Subjective examination A, Note appearance, odor, color, presence of visible stains on foods, B. Note location of food with respect to visible signs of area of gassing. C, If chemical smokes have been used, examine the surface layers of the food microscopically for the presence of appropriate solid particles, D. Apply cautious palatability tests only in the absence of all positive indications of contamination, E, Micro mustard gas or lewisite is the suspected contaminant chemical examination should always bo carried out, F. The possibility of mixed gases should always bo kept in mind. 1 k -0993-P? 7 -31J- COS -HP G, Growing crops contaminated by mustard gas or lewisite show scorching and bleaching; in the case of the former gas, the fresh growth on the plants after they have recovered will be wholesome. Lewisite and other arsenicalsy however, complicate the problem because of the residual arsenic; the plants should not be used until after the arsenic content has dropped to safe limits. IV, Sampling for chemical analysis A. For initial identification of gas, use grossly contaminated exposed surface layers of food, or actual droplets or splashes of the liquid gas, absorbed on filter paper or cotton, B. To determine usability of the food, tests should be made on large samples of foodstuffs (approximating that eaten in a •meal). 1, Take sample by cutting thin slices from suspected portions and placing them in clean, dry jar, fitted vith a screw cap, 2, Separate samples should bo taken from the surface and from interior portions of the food, using different sample jars, 3, The knife or other utensil must be cleaned between each cut, using a bleaching powder-water paste; all bleaching powder must be removed from the knife before touching the food, C. Proper precautions should be taken to prevent exposure of the analyst to the gas. V, Chemical analysis A, Air-flow analysis; apparatus consists of a large container fitted with a stopper carrying glass inlet and outlet tubes, with a supply of air purified by passage through granular activated charcoal and anhydrous calcium chloride. The con- tainer is kept at a temperature of about 37° C, by a water bath. Aspiration of air is carried out at the rate of 0,1 to 0,5 liter per minute, for 10 to 15 minutes, into 10 ml. of absorbent liquid. The first aspiration is made into water, then a second aspiration into alcoholic potassium hydroxide is carried out. The liquids are examined according to the follow- ing Qualitative Analysis Procedure, Parts I and II. B. A fresh portion of the sample is extracted with hot absolute alcohol; the extract is then examined according to the Qualitative Analysis Procedure, Part III. h-0998-P78-BU-C03-WP Rapid “Sorting: Testw The alcoholic potassium hydroxide solution through which air from the sample was passed in the air-flow analysis (second aspiration in V-A above) can, if desired, be put through a rapid “sorting test" which may shorten the analytical procedure. After acidification (nitric acid) test separate portions for halides and cyanide (precipitation with silver nitrate), nitrite (red color with Criess-Ilosvay reagent), and arsenitc (Gutzeit test). If definite positive indications are given by one or more of these tests, it may be possible to proceed directly to the Confirmatory Tests (p, 6), However, the following complete Qualitative Analysis Procedure is recommended for use whenever time permits. Classification of the War Gases The war gases may bo grouped according to the elements prosent, ignoring carbon, oxygen, and hydrogen. The standard tests for the par- ticular elements involved may bo applied in order to aid identification of a gas, I. Halogen only - Chlorine, phosgene, diphosgenc, benzyl and xylyl bromides, bromoacetonc, chloroacetophenone, ethyl iodoacstate. II. (a) Sulfur only - Hydrogen sulfide, dimethyl sulfate, / (b) Sulfur and Halogun - Mustard gas, thiophosgeno, mercaptan, sulfuryl chloride, III. (a) Nitrogen only - Hydrocyanic acid. (b) Nitrogen and Halogen - Ghloropicrin, bromobenzyl cyanide, phenyl carbylaraine chloride, cyanogen halides. IV. (a) Arsenic only - Arsine. (b) Arsenic and Halogen - Lewisite, Diethyl and ethyl dichlo- roarsines, diphenyl chloroarsinos, arsenic trichloride, V. Arsenic, Halogen, and/or Nitrogen - Diphenyl cyanoarsino, diphenylamine chloroarsine. Qualitative Analysis Procedure I, Aspiration into water A, The aqueous solution contains a precipitate - indicates presence of SiClg, diphenyl urea (from phenyl carbylamine chloride) or sulfur (from perchloromethyl mercaptan), B, After filtration (if necessary) test a portion of the filtrate with silver nitrate, acidified with nitric acid, 1, Precipitate - indicates presence of diphosgene, mustard gas, lewisite, or other readily hydrolyzable gases. 2, No precipitate - absence of gases covered in this section (I), 4-0998-P79-BU-C0S-WP except for those in C-4-b and C-6 below; test for them, then proceed to next section (ll), C. If a precipitate occurred in B, tost separate portions of the original filtrate as follows; 1, Add a few drops of hydrogen sulfide water (a) Turbidity - indicates presence of alkyl chloroarsines (b) Turbidity, which dissolves in excess - indicates presence of lewisite (c) Sulfur precipitate - indicates presence of cyanogen chloride or bromide (d) Oily suspension of phenyl isothiocyanate - indicates presence of phenyl carbylamine chloride 2. Add a drop of 1% phenol solution and run in carefully'a layer of concentrated sulfuric acid; a red zone at the interface (due ■ to formaldehyde) indr cates the presence of chloromethyl chloro- formato or a halogen-substituted methyl other. 3. Add'sodium hydroxide solution and warm; test the air above the liquid with moistened litmus paper for ammonia; a positive test indicates the presence of cyanogen halide, 4. Add barium chloride solution acidified with hydrochloric acid (a) White precipitate of b.rium sulfate; this sample also gave a positive test with silver nitrate above - indicates the presence of chlorosulfonic acid or ester, or sulfuryl chloridc, (b) White precipitate of barium sulfate; this sample did not give a positive tost with silver nitrate above - indicates the presence of sulfur trioxide or dimethyl sulfate, 5. Add lead acetate solution; a black precipitate of lead sulfide indicates the presence of thiophosgene or.pcrchloromothyl mercaptan, 6. Garry out the standard Gutzeit test for arsenic; a positive test greater than the reagent blank, indicates presence’of arsenic trichloride, lewisite, or othyldichloroarsine. II. Aspiration into alcoholic potassium hydroxide solution (10-204) Warm end then cool the solution| acidify where necessary and test separate portions as described under I above, then test other portions as follows; U-0998-P80-BU-C0S-WP A. Acifidy with nitric acid and add silver nitrate solution; a yellow precipitate of silver bromide indicates the presence of bromine- containing lachrymatory, as bro.nobenzyl cyanide, B, Acidify with acetic acid and test with Gricss-Ilosvay nitrite reagent (see below for details); a red color, deeper than the reagent blank, indicates the presence of chloropicrin, Grioss-Ilosvay Reagents (l) Dissolve 1 g, of sulfanilic acid in hot water containing 14.7 ml, of glacial acetic acid and dilute to 300 ml, with water. (2) Dissolve 0,2 g. of a-naphthylamino in water containing 14.7 ml, of glacial acetic acid and dilute to 350 ml, with water. Use equal parts of each solution; about 2 ml, of the mixture is sufficient for the test. III, Tests for persistent lachrymators Macerate the sample; extract it with hot absolute alcohol for several minutes, then filter and the filtrate. Aid .alcoholic potassium hydroxide to the filtrat., anu warm it, Ah intense rod color accompanied by the formation of resinous products, indicates the presence of chloro- or bromoacetone. Filter, if necessary, and test Separate portions of the filtrate as follows; A, Acidify with nitric acid end add silver nitrate solution; a white precipitate of silver chloride indicates the presence of diphosgone, mustard gas, loadsite, or other ra.adiiy hydrolyzed gases. B, Boil a portion of the filtrate and test the air above the liquid with moistened litmus paper for ammonia; a positive test indicates the presence of bromobenzyl cyanide or cyanogen halide, C, Evaporate the alcohol at a low head and treat the residue with hot alkaline potassium permanganate solution. Acidify the solution with dilute sulfuric acid and extract it with ether. Allow the ethereal extract to evaporate spontaneously, 1, Dissolve one portion of trie residue in water and add a drop of ferric chloride solution; a buff-colored precipitate, due to benzoic acid, indicates the presence of benzyl bromide, broraobenzyl cyanide, or chloroacetophenone, 2, Add concentrated sulfuric acid containing a little resorcinol to another portion of the residue; a greenish-red color, which shows a decided green fluorescence in alkali, indicates the presence of xylyl bromide, This color is caused by fluo- rescein, formed by the phthalic acid resulting from the oxidation of xylyl bromide. •;'v V- D, Acidify with acetic acid and divide the solution into two parts-, 1. Tost ono portion with silver nitrate solution for bromide or iodide, 4-0998-P81-BU-COS-WP 2. Add a crystal of gualacol and a few drops of concentrated sul- furic acid to tho other portion. A violet color, due to glycollic acid, indicates the of ethyl iodoacetato or ethyl bromoacotatc| this should also b„> confirmed in test 1 just above, Regardless of whether lewisite or other arsenicals arc detected after aspiration according to tho qualitative analysis procedure, tho arsenic content of the food itself should always be determined if con- tamination with a war gas is suspected. This arsenic determination can be adequately done by the Gutzeit method as described in the Methods of Analysis of the Association of Official Agricultural Chemists, Fifth Edition, p, 390 (1940), Concentrations of arsenic significantly greater than those normally expected in the type of food investigated may have resulted from hydrolysis of the arsenical war gases| if the hydrolysis is sufficiently complete, those gases would probably not be detected in the above qualitative analysis scheme. Decisions regarding the usability of the food must therefore be based not only on the subjective examination and the results of the qualitative analysis, but on the concentration of arsenic in the food itself. If contamination with hydrogen cyunide is suspected, a test should be carried out by aspiration of the air through benzidine copper acetate paper, a blue color indicates tho presence of cyanide. Benzidine copper acetate paper: Two to three g, of pure benzidine acetate are heated to 80° C, in 100 ml. of distilled water for 10-13 minutes, with constant shaking. The filtered solution is mixed with ono-twolfth its volume of cupric acetate solution (3 g./lOO ml.) immediately before tho tost| the test paper is dipped into this mixture, allowed to drain, and dried until only just moist. Confirmatory Tests Tho prosonce of any gas indicated by positive results in the Qualitative Analysis Procedure should always be confirmed by one of tho following tests, These confirmatory tests can bo carried out on test solutions or on filter papers impregnated with a reagent through which air from the preceding air-flow analysis can be drawn. A convenient holder for the test papers consists of t .o glass tubes with ground ends, which are fitted tightly into wooden blocks connected by a steel spring. The tension of this spring holds the ground glass ends together, with the tost paper being inserted between then. Phosgene and Diplio agones Five grams of p-dimethyl::minobonzaldehydo and 5 g. of diphenylamine are dissolved in 100 ml. of alcohol. Filter paper moistened with this reagent gives a yellow or orange color in the presence of phosgene or diphosgene. Chlorine or hydrochloric acid must first bo removed from the air used for the test by a guard tube containing sodium thiosulfate and sodium iodide. 4-0998-P82-BU-C0S-WP Mustard Gas; The gas is. aspirated into a 1% solution of B-naphthol in 0,1 N aqueous-alcoholic (30s50) alkali, A white turbidity, forming after 10-13 minutes or on warming (due to the di-B-naphthyl other) indicates the presence of mustard gas, A characteristic and sensitive test consists of -passing the air through one or two drops of 0,1$ .gold chloride solution; a yellow colloidal turbidity is formed if mustard gas is present. Lewisite and Primary Dichloroarsiness The air is aspirated into a small quantity of water and two or three drops of hydrogen sulfide water are added. An opalescence or turbidity indicates a primary dichloroarsine; if the turbidity is soluble in excess, lewisite is present. A specific, although not very sensitive, reaction of lewisite consists of treatment of a small drop of the liquid with cold 13$ sodium hydroxide. Acetylene which is liberated can be detected by a red stain on ammoniacal cuprous chloride paper, while the reaction liquid will contain arsenite (detected by the Gutzeit test) and chloride (detected by silver nitrate). Cyanogen Chloride or Bromide: The air is asrlratod through a paper soaked in saturated sodium sulfide solution and used moist. One drop of con- centrated hydrochloric acid followed by a few drops of 1$ ferric chloride solution are "spotted” on; a red color indicates the presence of cyanogen halide. Phenyl Garbylamine Chloride; The air is aspirated into water and the solution is boiled, A white precipitate of diphenyl urea indicates the presence of phenyl carbylamine chloride, Ohioromethyl Ohioroformates Use the test given in the Qualitative Analysis Proccdure, Ohiorosulfonic Acid or Aster, or Sulfuryl Chloride: Aspirate the air into hot water; the presence of both free hydrochloric and sulfuric acids (acid solution, barium chloride tost, silver nitrate test) characterizes these gases. Dimethyl Sulfate; Boil the contaminated sample with water under a reflux condenser for one hour and then distil. If the first portion of the dis- tillate contains methyl alcohol (tost according to U. 3. Pharmacopoeia XI, p. 335, methanol test in whisky) together with a positive sulfate tost in the Qualitative Analysis Procedure, dimethyl sulfate is present. Perchipromethyl Mercaptan: Aspirate the air into hot water; the evolution of carbon dioxide, and the presence of hydrogen sulfide (lead acetate test) and hydrochloric acid (silver nitrate tost) with the precipitation,of sulfur on boiling, indicates that pcrchlororaethyl mer- captan is present. 4-0998-P83-BU- COS-WP Thiopho.sgonc; Aspirate the air into water| tho presence of hydrogen sul- fide (lead acetate test) and hydrochloric acid (silver nitrate test) indicates that thiophosgonc is present, Bromobenzyl Cyanide; (l) The liquid gas gives a deep reel color with con- centrated sulfuric acid., (2) The air is aspirated into 10$ silver nitrate solution and the mixture is boiled. Reduction of the silver nitrate (with a precipitate) and the formation of bonzaldehydo, which can be detected by its ' characteristic odor, indicates the presence of bromobenzyl cyanide, Chloropierin; The air is aspirated through filter paper which has boon impregnated with a 10$ solution of dimethylaniline in benzone and dried, A yellow or maroon color indicates tile presence of chloropicrin. Benzyl Bromide; Aspirate tho air directly into hot alkaline potassium permanganate solution and treat the mixture as described in the Qualitative Analysis Procedure. Chloroacotophoneno; If the alcoholic extract in Part III of the Qualitative Analysis Procedure contains an appreciable amount of gas, 20$ aqueous-alcoholic (50s30) sodium sulfide is added, the mixture is warmed, cooled, and diluted with water, Tho chlorine is removed' from tho compound by this treatment and the corresponding sulfide (m,p. 77° C.) is precipitated, Xylyl Bromide; Use the test,given in the Qualitative Analysis Procedure, Ethyl lodoacctate or Ethyl Bronoacutate; Aspirate the air directly into warm alcoholic potassium hydroxide solution and apply the tost described in the Qualitative Analysis Procedure, Possible Interferences Certain substances often present in foods can give tests which may .bo mistaken for some of tho gases lists.. above, For instance, hydrogen sulfide, present in eggs, may not indicate foreign gas contamination. Benzoic acid or sodium benzoate is often used as a pros rvative in pre- pared foods| it would bv extracted in Section III of the Qualitative Analysis Procedure and give the test for benzyl bromide or bromobenzyl cyanide. Other interfering substances must be considered by the analyst before making a positive report. Clocnin? of Apparatus Scrupulous attention must bo paid to tho cleaning of all analytical apparatus aid sample containers in order to prevent tap contamination of one sample from yinother, A paste of bleaching powder, as indicated in tho sampling directicns, is useful in cleaning any apparatus, Treat.lent with hot alcoholic potassium hydroxide destroys or removes most gases, concentrated nitric acid removes mustard pas efficiently, while rubber or k-0998-P8k-BU-C0S-UP metallic apparatus m-.y be treated by Immersion in boiling water for 30 minutes. The usual dichromate-sulfuric acid cleaning solution should be used on glassware after the other decontaminating solutions are employed. References The Detection and Hen t ification of War Gases, Ministry of Hone Security, A.R.P. Dept, (Great Britain), Chemical Publishing Co., Inc,, New York, Nan York (194-0). The Detection of her Gases in Foodstuffs, Chemical Defense Research Division of the Ministry of Supply (Groat Britain), Analyst, 66, 4-4- (194-1). Damage to Foodstuffs in Chemical Warfare, A.B.P. Pago, Journal of the Royal Sanitary Inst,, 6l, 160 (1941). The Detection of Snail Quantities of War Gases (Dijkstra1s Method), A.P.J. Hoogeveen, Chen. & Ind,, 59. 550 (1940). Gas Identification, George Lev/i, Chon. & Ind,, .60, 374 (1941). Foodstuffs and Gas Contamination, Robert Woods, Jour, of the Royal Sanitary Inst,, 6l, 160 (1941). - 0 998 - P85 -NOBU“COS*'WP FOOD AND POISON GAS5S By J, Cholak Kettering Laboratory of Applied Physiology College of Medicine, University of Cincinnati, Cincinnati, Ohio In considering the possibility of contamination of.foodstuffs by poison gas, it is important to boar in mind thats (a) Poison gases are highly penetrative. (b) Foodstuffs are often highly absorbent, particularly moist and fatty foods. (c) Wrappings and packing materials may bo absorbent and may permit the passage of poison gas. (d) Gas con ponctrato wherever air cam enter (gas masks excepted) (e) Any material which soaks up oil or water will absorb -and eventually permit the passage of gas. (f) Vontilaabion may bo helpful, but aJLso provides a means of en- trance for the gas. It is not necessary to discard all affected foodstuffs, however, after exposure to poison gas0 Whether or not food can bo salvaged depends on the type of the chemical agent, the degree of exposure, the kind of food, the manner in which it is packaged, and the way it has been protected. All war gases contaminate food either by going into solution in the water or fat present in the food, or by being adsorbed on the solid surfo.ee. In either case chemical, actions may occur which will result in some decomposition of the chemical. If hydrolysis takes place, the absorbed substance loses its original properties o.nd, generally speaking, becomes innocuous. Mo such beneficial action occurs in the case of lewisite and the other arsenical gases, however5 with these agents, even though the original property of chemical is destroyed, danger of poisoning remains because of the presence of arsenic. Moreover, the action of hydrolysis is slow and therefore food may remain contaminated for a. considerable period, depending on the degree of initial exposure. Many of the decomposition products resulting from hydrolysis may bo unpleasant but not toxic and their only action is to render food unpala- table. A comparable action does not occur when the gas is absorbed by fat, and such food once contaminated must bo considered as unfit for human use. Poison gases may bo divided into the following categories, for the purposes of our study; Non-arsenical non-persistent gases; arsenical non-persistent gases; persistent lachryraators; non-arsenical vesicant gases; arsenical vesicant gases; smokes. Of the non-persistent gases, the one most likely to bo employed in modem warfare is phosgene. It is not considered a dangerous gas so far as contamination of foodstuffs is A-0998-P87-BU-C0S-W? concerned because, although absorbed to some extent - mainly in the outer layers of the food - its principal effect is on the palatability of the food. Foods contaminated by this and certain other non-persistent gases (including hydrogen cyanide) can ofton be rendered fit for consumption simply by airing them for a day or two, This is best done by spreading out the contaminated food so that a current of circulating air can carry away the residual gas. Much more dangerous are the persistent gasos, particularly the vesicants. The latter are heavy, oily liquids, dangerous in themselves as well as in the vapors they give off. The danger lies in the fact that the bursting bomb, or the spiw.y from an airplane, produces an immediate vapor cloud and also distributes droplets over a wide Those droplets, particularly of mustard gas and lewisite, contaminate everything on which they fall and continue to give off harmful vapors until removed by approp- riate decontamination procedures. In addition some gases, like lewisite, contain arsenic and there is therefore the additional hazard of arsenical poisoning. (a) Non-arsenical non-persi;:.tent :;":.ees Theso will not affect foods appreciably, Temporary offocts will pass off after the gas cloud disperses and the food will bo unharmed. Some slight deterioration map- occur with prolonged exposure to a relatively high concentration of a gas of the phosgene type but it should be runomberod that the palatability is mor e likely to bo imparied then the goner el whole- somonoss of the article of diet. The affects of phosgeno on certain foods and the treatment advised are given in the following table: Effect of Phosgene on Fends Food Effects Dangerous Treatment Flour Makes poor loaf, becomes sour ana unpalatable No Air for 4,8 hr. Mix alth 5 parts of undamaged flour to improve baking quality Broad Unpalatable (outer layers) No Air after cutting away outer layer Cereals Negligible No Air 48 hours Moat and fish Surf see may show discoloration No Improved by airing and cooking Milk Affects taste No Boml Choose, butter, fats Bleaches surface No Remove affected part which may bo used for cooking Fresh fruits Almost none No Wash, air, and peel off skin and outer layer Dried fruits Slight loss of taste No Nash, air and cook 4-0998-188-BIT-COS-WT Food Effects Dangerous Treatment Fresh Sometimes slight- No Wash, air, and cook vogotobies ly bleached Tea, coffee Bitter No None is effective; blend with undamaged stock '(b) Arsenical non-persistent gases These are usually the stornutator gases end it is considered im- probable that they would significantly affect foods, since they are readily dispelled. Airing is said to be the appropriate treatment. In addition, chemical analysis should be carried out to discover any arsenic con- tamination which may occur on prolonged exposure in en enclosed space. If there is any possibility of contamination with arsenic, the food should not be eaten until passed on by competent exports, (c) Persistent lachrymators It is thought unlikely that these gases will be used on civilian populations. However, they render foods unpalatable, Airing is the only treatment that is likely to be of value, and this will prove ineffective if much gas has been absorbed, (d) Non-arsenical vesicant gases Gases of this class, which includes mustard gas, may prove harmful to food, particularly with prolonged exposure to high concentrations of vapor. All foods contaminated with the liquid form must be viewed with suspicion. Fatty foods (milk, cream, butter, cheese, fatty meats, eggs, etc,) contaminated either by vapor or by liquid will almost certainly be highly dangerous and should be destroyed. Slight contamination with mustard gas vapor may affect palatability but, except for fatty foods, the materials should be edible after 4-8 hours’ airing end cooking. Effect of Exposure of Uncovered Foods to Low Concentration of Mustard Gas Vapor Food Effects Dangerous Treatment All typos (except fatty materials) None except occasional slight loss of palatability No Airing, Discard surface layers (icon meat) Fatty food (milk, Rapid absorp- croam, cheese, but- tion of poison ter, margarine, fats, oils, fatty'meats, fatty fish) Probably None effective A-0998-P89-BU-C0S-WP The subjective detection of mustard gas in dry foods is rather difficult since they rarely shovi marked changes. Moist foods,'however, will show brown spots or other surface changes. Cucumbers are particularly sensitive. In green peppers, green beans, peas, pears, gooseberries, apple and oranges the spots do not appear for 24 hours, and it takes throe days for the spots to develop in beets and radishes. Studios on the impregnation of food with mustard gas have shown that dry foods treated with 0,1 cc, of the agent remained poisonous for 20 days when kept at 12° C,, and for 6-B days at 20° G, Flour moderately contaminated may remain poisonous for 1 month at 16° C, (While in general increased temperatures arc beneficial in increasing the rsabe of aeration and removal of vapors, heat is not always permissible or readily available,) (e) Arsenical vesicant gases Lewisite belongs in this class. Food which has come in contact with these gases, whether vapor or liquid, should not be eaten because of the great danger of arsenical poisoning. The salvaging of foods exposed to this gas depends on the degree of contamination and the suitability of such food for consumption should bo passed on only by qualified exports Lifter a thorough chemical examination,. In case exposure has been to vapors only, it may be possible to salvage some of the food by dis- carding the outer layers before airing, but none of the food should be eaten until a chemical analysis shows that the concentration, of arsenic is within safe limits. In case of contamination with the liquid, decon- tamination will probably bo impossible. (f) Sjaofeoa Protection against solid chemicals, "smokes”, is not difficult, /toils they penetrate all ordinary fabrics and cracks, most wrappings will be impervious to them. The clouds are easily dispersed and in still air they settle to a much greater extent on horizontal than on vertical sur- faces, Prolonged airing of contaminated foods is suggested. Protection Against Contamination V/ith Gas The following table summarizes the data on the protective value of various coverings for foodstuffs, given in the pamphlet issued by the British Ministry of Foods Protective Value of Coverings for Foodstuffs Protection Against Protection Against Liquid Material Poison or Vapor Poison Gas Sealed metal Complete . Complete Metal, tight cover Fairly good Good L-0998-P90-BU-GOS-WP Material P ro t c c tion Against Poison or Vapor Protection Against Liquid Poison Gas Glass bottles, etc, with sealed top of similar material Complete Complete Bottles, jars, etc, with grease-proof paper seals Fairly good Fair Sealed wooden barrels Complete Complete■ Waxed cartons Good Good Cellophane Good Good Paper cartons Good Fairly good Metal foils Good Good Wooden boxes Good Poor Co.rdboard boxes Good Poor Paper bags, etc. Poor None Textiles, sacks, etc. None Nine Some protection against gas is also afforded by the proper stacking of packaged goods. Closely stacked piles aro not readily penetrated oven by vapor| therefore if penetration does occur, the packages in tho middle of such stacks will be only slightly contaminated, principally on the surface. In removing the contaminant the stack naturally should be broken down in order to permit tho ready circulation of air over every item in the pile, \ . Wood absorbs liquid and therefore protects poorly against liquid poison gas. Increased protection against vapor is provided by lining boxes with a grease-proof paper. If such material or cellophane is un- available, ordinary paper nay be made partially gas-proof by covering the surface with paste. Textiles generally aro useless in thorns-Ives, but are valuable as screens to prevent liquid from splashing onto the piled material. They also absorb vapor and liquid and will therefore offer some protection when used as a secondary cover over an impervious inner covering of paper. Water Sup-olios Trio of foots of the war gases on water supplies and tho treatment advised are considorod in tho section on "Water and Chemical Warfare," k -0998-P91 -BIT- COS-WP Growing Crops . Growing crops arc likely to bo contaminated by a chance bomb or spray intended for another objactive0 Scorching and bleaching of vegetation wguld 'occur in the iinniodiatc vicinity of the bonb explosion - or wherever 'spray was liberated by low-flying aircraft. The effect, however, ‘would bo transient since exposure to weather will,.in tine, remove all traces of the poison and the vegatatien..judli-recover. The recovery period for nori-arson- ical gases is said to be about one week. Arsenical gases of the lewisite type are much more damaging because of the toxic effect of the arsenic and a much longer period will bo required for the recovery of vegetation when the contamination is severe, f Foodstuffs on Farms Special measures for the protection of food supplies on farms do not appear to be necessary. None of the modem war gases, except the arsenical gases, are likely to affect stacks of hay, untlireshed grain, or other farm stocks to an extent that carnet bo remedied by airing or natural weathering* Protective coverings, tarpaulins, canvass, or sacking provide useful protection by soaking up liquid, thus reducing direct contamination. The question of effects on livestock is a more serious matter. Animals may have to be slaughtered if they show evidences of poisoning, particularly from the persistent vesicant gases. Warehouse Goods, etc. Common sonso in storage will prevent much damage to foods. Foods stored in cold rooms are reasonably safe from gas provided closures are fairly air-tight and precautions have boon taken to prevent the entrance of contaminated air through the ventilating, system. Food in packages may bo protected by covering it with oil-painted tarpaulins0. Danger of serious contamination by gas splashes may also be decreased by the use of canvas or sacking covers. It is good practice to avoid storing goods in the cellar or on the top floor. Retail Stores, Hotels, etc. Goods should be kept in original packages as long as possible. As in warehouses, tarpaulins, canvas, or sacking covers are useful in pre- venting contamination from splashes of gas. Gold storage chambers should bo air-tight, in order to give complete protection. Displays of goods in window's or shelves, otc, should bo kept to a minimum. Foodstuffs in tho Homo Foods in air-tight containers (sealed tins and bottles) are com- pletely protected against gas. If there is any question as to the.con- tainer, it may bo wrapped in cellophane as an additional protection. In order to protect the outside of-containers from contamination, as many as possible should bo stored in inside cupboards, wooden, or cardboard boxos. 4-0998-P92-BU-C0S-WP Flour, rice, sugar, and similar non-perishable foods should bo stored in tin or glass containers with tight covers, and additional protection nay bo provided by swapping with cellophane or waxed paper. Bread should be kept in tins with well-fitting lids, , Perishable foods, meat, fish, eggs, milk, and butter should be reasonably safe in the ordinary' kitchen refrigerator, provided the doors and cracks have boon made reasonably air-ti lit. MJ^ccnanoous Cigarettes and other tobacco products are sources of danger in the event of the use of poison gases. The general methods used to protect foodstuffs against gas contamination will bo effective with tobacco pro- ducts but opened packages of cigarette, smoking or chewing tobacco, or cigars had best be disposed of in the event >f known or possible exposure to poison gas. The trivial cost of most of those materials, as well as the unlikelihood that individuals will have largo supplies on their persons or in their homes, make it inadvisable to salvage the few affected items by lengthy aeration methods. The identification of gas-contaminated neats is a rather difficult procedure. In the event of tme release to the public of such meats by unscrupulous dealers, the only means of determining the degree of con- tamination will be by chemical methods, especially if surface stains and changes have been cut away. In case of doubt, a chemical determination for arsenic should be made, in addition to other tests, in order to make certain that any arsenic present is within permissible limits. One European authority considers solid food toxic if 10G sq, cm, of surface contain 0,05 mg, arsenic soluble in organic solvents. Doc jntc.iminc.tion The inexperienced individual should not attempt decontamination or solve.pc of food stocks. The sources of danper aro many and these can bo avoided only by carefully trained personnel provided with adequate decontamination equipnont, In all cases the suitability of food for consumption is a matter of .export opinion after careful examination. Food suspected of having been in contact with poison pas should not bo oaten until it has been chemically tested, and salvage should be left to the proper local authorities, When- ever there is any suspicion of food contanination, this sir uld b.. brought immediately to the attention of the authorities. Rjforcnccs Food and its protection against poison pas — British Ministry of Food, published by His Majesties Stationer Office, London, Pape, A, 3. Da.rape to Foodstuffs in Chemical Warfare, J, Roy, Son. Inst. 61, 155 (19a) 1f-0998-P9J-BU-CCS-l)P Wood, Robert, Foodstuffs and Gas Contamination, J, Roy, San, Inst, 6l, 160 (1941) Hasskc, A., Action of Mustard Gas on Food, Tiorartzl Rundsh.au (1939) 131 (C.A. 21, 33416) Vastagh Gabor, Bor, ungar. pham, Gog, 16, 191 (1940) (C.A, 2k, 41635) Perotti, Luigi, The utilization of food products impregnated with toxic gases, Rev. hyg, mod, prov. 6l, 75 (1939) (C. A, 21, 593B^) Jacobs, Morris 3., War Their Identification and Decontamination, Interscionco Publishers, Inc., Now York, York, 1942 4-0998-P94-BU-C0S-WP MEDICAL ASPECTS OF SOME SYSTEMIC POISONS By Robert A . Echoa, M. D, Kettering Laboratory of Applied Physiology, College of Medicine, University of Cincinnati, Cincinnati, Ohio Toxic elements or radicals cause injury according to manner of carriage into tissues, i.e,, nature of compound in which they are present, thereby establishing solubility, locus of absorption and distribution, manner of breakdown in body and mode of excretion. No necessarily uniform effect. Example; arsenic in various forms and combinations, with varied symptomatic and pathologic picture. Arsenic I, Common arsenic compounds A, Arsenic trioxido - lethal dose approx. 2.7 mg As/Kg, orally B, Mapharsen (Trivalent) G. Tryparsamide (P entavalcnt) II, Arsine A, Toxicity 1. Slight symptoms after several hours 30 p.p.m, 2. Dangerous - 1 hour . 50 p.p.m, 3. Fatal - half hour 250 p.p.m, B, Mode of Action 1. Combination with Hb ) 2. Oxidation to arsenicus acid) 3. Hemolysis - extensive ) mechanism questionable 4, Anemia in few hours ') 5. Circulatory failure C, Symptoms and signs 1. Vertigo, headache, nausea, vomiting, epigastric pain 2. Hemoglobinuria, hematuria, anuria 3. Jaundice 4. Circulatory failure, pulmonary edema 1+-0998-P95-BU-C0S-WP D, Diagnosis - History of exposure, clinical picture, quantitative analysis E, Treatment - Supportive - transfusion? III. Lewisite A. Sat. Vapor at 40° C « £ 15,6 mg/L (364 arsenic) B, Toxicity 1, Lethal cone, in air 0,048 mg/L or l/325 of sat, vapor at 40° C - c- (3000 p.p.n, or) "^-r (1000 p.p.m. As) 2, Cutaneous - 0,02 cc/sq. cm, - Total dose man 1,4 cc 0,95 g. As? (Vodder) 0,334 mg/L in form of vapor, or 21,000 p.p.m, causes vesicant action 0. Mode of Action 1, Cutaneous vesicant - mechanism? 2, Pulmonary irritant - mechanism? 3, Systemic poison (arsenic) by cutaneous absorption D. Diagnosis - History, clinical picture, quantitative analysis E. Treatment (Skin contact) 1, Wash off with solvent 2, Hydrolyse with NaOH or better IlgOp 3, Excise lesions to remove arsenic (12 to 24 hours) Hydrocyanic acid and other cyanides Use of cyanides in some form anticipated, because of speed of action of GW radical - minutes to few hours, because of high toxicity, because of experimental work done over a period of years in foreign laboratories, I. Hydrocyanic acid A, Toxicity HCN ~ fatal short exposure at 3000 p,p,m, - dangerous 150 p.p.rn, - lethal dose about 50 mg 4-0998-P96-BU-C0S-WP B. Mode of entry gas HCN - inhalation and cutaneous absorption C. Toxic mediansirn Suppresses oxidation, by paralyzing cellular oxidases in all probability (combines with iron) i.e., cellular asphyxia in presence of adequate oxygen in blood, D. Symptoms Initial stimulation of respiration (unimportant clinically be- cause fleeting warmth and alight burning of skin in contact with gas (through clothing) in presence of 5000 to S000 p.p.m. in air, (no effect in concentrations of 1600 to 2000 p.p.m, in air) with gas mask protection. Weakness and perhaps headache Nausea and vomiting Dyspnoea with chest constriction .Unconsciousness (All symptoms may be lacking in high concentrations, unconscious- ness occurring in as little as 30 seconds in 6000 to 6000 p.p.m.) E. Diagnosis Odor of bitter almonds on breath History of exposure May be no cyanosis but often present after respiratory failure Low differential Op content of arterial and venous blood By exclusion of CO, respiratory irritants (no appreciable irritation of upper resp, tract), arsine (hemolysis) P.M, diagnosis by cyanmethemoglobin (difficult) F. Treatment Artificial respiration in fresh air Artificial respiration with Op or Op and G0p mixture Warmth As long as heart is beating recovery need not be despaired of I(.-0998-P97 -BU-COS-vp Specific treatment dependent upon two principles 1, ON converted to thiocyanate in body, and so excreted in essentially harmless form. Sulphur compounds, therefore, indicated, especially thiosulphate. 2, CM combines with methemoglobin to form relatively non-toxic compound. Therefore, Hb should be converted to met Hb, to combine with CM and diminish its toxic action. Hence use of methylene blue and nitrites and oxidizing agents found especially effective. Other principles have been investigated 3, Heavy metal salts like iron combine with CM to fora complex, non-toxic or loss toxic compounds. Unfortunately the heavy metal compounds are toxic in themselves, and therefore, suf- ficient dosages cannot be used without the risk of heavy metal poisoning. The observations of Chen (Am. J. Med, Sc. 1602767, (1931)), and his associates on dogs have resulted in the use of sodium nitrite and sodium thiosulphate, giving the one after the other (never together), with amyl nitrite used when needed as a stop- gap until sodium nitrite can be prepared and given. The sodium nitrite works promptly, the thiosulphate slowly, but this is apparently a synergistic effect of the two. Treatment advised Pearls of amyl nitrite at first NaNOp 0.3 to 0.5 gm in 10-15 cc HpO Na thiosulphate 25 gm in 50 cc KpO administered over period of 10 to 15 minutes Adrenalin or Coraminc to support cardiac action, if needed. Repeat half dosages of above after 2 hours or as needed for maintenance Keep under observation 2L to 13 hours G, Sequcllae Essentially those of asphyxial sequollae Some tendency to persistent weakness for weeks or months Caso reports show speech defect (slow fatigued tongue) , loss of memory, inability to sustain attention f -0993- P 98 -BIJ -COS- WP II, Other cyanide compounds A. Toxicity NaCN 6 mg/Kg subcutaneously in dogs (Chon ot al) B. Mode of entry 1, Salts - by ingestion in food or water 2, Organic compound - by inhalation or skin absorption Hydrogen Siufide and Carbon Monoxide Mode of Action H2S C.N.S, poison with paralysis of rosp. center. Death from asphyxia - No combination with Hb except post mortem - Green yellow color CO - Firm union with Hb displacing Op with 300 times Op combining power % Hb 00 = E22.3C 300 Pop +■ (Pco X 300) Examples 0.07$ = 50% Sat. HbCO 4 Symptoms: Percent saturation of blood Headache 30 Unconsciousness 60 Early death 80 Toxicity i i ] HCN - n _J? a r t H23 j s / m i 1 1 i o n GO j. Arsine Slight Symptoms after ; several hours 20-40 100-150 300-400"] 30 Maximum allowable for 1 hour 30-60 200-300 400-500*f“ Dangerous 30-60 min. 120-130 500-700 i 50 i 1 Fatal in few minutes to half hour 3000 1000-3000 T~ 250 1 Loss of smell i_ . 100 | 1 Lethal dose for man absorbed j 50 mg L— - - f ” 1 i-0998-?99-NOBU-GOa-WP GENERAL TOXICOLOGY OF WAR GASES By'Robert A, Kehoe, M, D, Kettering Laboratory of Applied Physiology, College of Medicine, University of Cincinnati, Cincinnati, Ohio I, Certain .general considerations Classification based at present on main effects, as for example, pulmonary irritation or cutaneous vesicant action. Tendency to think of these in terms of physical properties, with gases as pulmonary irritants, and liquids as vesicants. This tendency to be avoided as a generalization, since it may well be found to bo erroneous in case of new war gases. Bettor to think in terns of the general methods of inducing exposure and the effects that are sought for in the use of war gases,. The former is concerned with the mode of attack on the human organism i,e, avenues of entry. The latter has co do with the means by which noxious substances interfere with physiological mechanisms. Present discussion aims to give practical information on the chemical agents now known to be available, as a means of providing protection against these specific substances, but it also uses, them to illustrate certain general principles that may serve as guides in avoiding the worst consequences of new agents, II• Physioloileal considerations A, Mode of absorption or injurious contact - in order of decreasing practical Importance 1, Inhalation a. Effect may be irritation (local injury) and/or general toxic effect, b. Matter of volatility or fine state of subdivision in air breathed through nasal, pharyngeal and bronchial passages, c. Degree of volatility in physical sense not so important as relative toxicity of vapor, e.g., mustard gas with vapor pressure of only 0.065 mm, Hg at 20° and volatility of only 0.625 mg/L is highly dangerous, since a concentration of 0.15/L may produce death if inhaled for 10 minutes or longer. Likewise, Lewisite has a vapor pressure of only 0,s95 ram Hg at 20°, and a volatility of 4-. 50 mg/L, while the lethal concentration for 10 minutes of inhalation is only 0.12 mg/L, The saturated vapor of those materials at ordinary temperatures must be diluted 4 times axid 37 times respectively, if fatal effects are to be avoided from oven brief exposure. A-O998-PIOI-BU-COS-WP Notes Neither those nor many other toxic vapors can be detected by their odor to such an extent as to provide safety. They do not give adequate warning of their presence, and many others give no warning at all. An odor or a sensation of stinging or burning of eyes, skin, or nasal mucosa must bo taken as a sharp warning, 2, Skin contact a. Effect may bo local injury, and/or general toxic effect. Local injury due to corrosive or burning action - immediate or delayed. Local injury duo to absorption into skin with subsequent "breakdown of compound, releasing poisonous radicals. General intoxication from absorption of compound, b. Non-persistent gases absorbed thru skin only in high con- centration - skin absorption implies a liquid material, with relatively low volatility of a fat soluble type, c. Except in case of immediately irritating substances that give their own warning, skin injury or absorption is rela- tively slow and'materials can be removed without injury if done quickly and thoroughly, i.e, within 5 to 30 minutes dependent upon the compound and the size of the dose re- quired to produce injury. Notes There may be no warning of any kind, other than that of noting the presence of some foreign material on the skin or clothing, or on objects in the environment. Dependence cannot be put upon the existence of an odor or an irritating effect upon the eyes or nose. The latter, if present, will be helpful, 3, Ingestion (Swallowing) a. Poisonous materials taken into the gastroenteric- tract may be decomposed by water, food, or the digestive juices into harmless materials, or into others equally or loss toxic compounds, There may be no chemical change, in which case, the poisonous materials may produce local effects like those on the skin or lungs, or they may be absorbed with such general or specific effects as are characteristic of the compound, or they may be evacuated from the alimentary tract without injury or illness, b. In general the lethal dose of a material taken by mouth is considerably greater than if it is inhaled or injected intravenously. It is usually less than if it had been applied on the skin, in the case of oil-soluble components the lethal dose by mouth may be four to ten times the lethal dose by inhalation, and if the material is irritating, it may be evacuated promptly, thereby preventing more than slight absorption. I1.-0998-P102-BU-00S-WP Note; Warning is usually given against inadvertent ingestion of food con- taminated with chemicals of the type employed as war gases, by reason of a foreign taste. Food or water that has had an opportunity for contamination should not be,eaten if it has any foreign taste, unless export examination indicates that it is safe for use. B, Types of injurious effects - in decreasing order of toxicologic importance, 1. Systemic poisons - alkaloids, heavy metals and metaloids, narcotics, catalytic poisons and asphyxiants a. None available for practical use at present with possible exception of arsenic compounds, b. Entrance into body may be by any route. 2. Production of injury to lungs, a. Immediate effects (acute irritation), b. Delayed injury - (without warning), j. c. Permanent injury - (complications, scarring), 3. Production of injury to skin a. immediately painful injury - (acute irritation), b. Delayed insidious injury with disability, c. Permanent injury - (infection, scarring), A, Production of acute irritation of eyes or nasal mucosa, res- piratory tract, or gastroenteric tract, with temporary acute disability, as nuisance in itself, or as means of breaking down protective measures (compelling removal of gas masks, etc,), 5. Combination of two or more of above effects in same compound or in mixtures of compounds. Ill, Specific effects of certain presently available agents A, Pulmonary injurants - in decreasing order of toxicity 1, Phosgene and diphosgene a. Characteristic odor but little irritant effect and, there- fore, little warning, except in high concentration. b. Relatively little effect upon upper respiratory tract and eyes, therefore, little in way of upper respiratory symp- toms, except from quite high concentrations. 4-0998-P101-BU-C0S-WP c. Injury to lung tissue mainly, with pulmonary edema after short or long latent period. Chest constriction, cough, blood-streaked sputum, becoming later pink and frothy, with increasing amounts of fluid. d. Little difficulty from contaminated food. Bad taste. Warning. Insidious* All casualties to lie down as soon as possible, to bo carried on a stretcher and put to bed at com- plete rest at earliest possible moment after exposure, 2, Chloropicrin a. Characteristic odor and irritant effect upon eyes and nose, therefore, sharp warning, b. Symptoms are those of upper respiratory irritation and dis- comfort, lung irritant with cough constricting pain, blood- stroak sputum, and general lung damage of a severity depend- ing upon concentration to which one is exposed. c. Gastro-enteric symptoms, nausea, vomiting, abdominal pain and diarrhoea from swallowing material in foods or in socrotions from upper respiratory tract, d. Burning, stinging of eyes and weeping. Warning. Used to produce intolerable burning of oyos and vomiting so as to cause removal of gas mask and induce exposure to more toxic gases (phosgene, etc.) with which it is mixed. Masks must be kept on, 3. Chlorine a, Immediate Irritant effect upon eyes and upper respiratory tenet,, therefore adequate warning, (Hot so irritant to oyos as chloropicrin), b. Extensive acute upper respiratory irritation and injury, hoarseness and loss of voice, sore throat, with cough, chost pain, and constriction, and often delayed pulmonary edema, c. Most important effect is injury to lung, with general edema of lung and danger of asphyxia, d, Li hole or no trouble from contaminated food. May bo strong caste. Warning, All but the lightest cases of exposure are in danger of developing pulmonary edema, and all casualties should lie down and be transported, and kept in bed for not less than twenty-four hours of observation. L-0998-PI04-BU-COS-WP B, Vesicants 1, Mustard a. Primary injurious effect on skin, latent period of some hours, after which redness, followed by blistering, develops, b. Serious injury to eyps from droplets, with latent period before damage shows up, c. Acute injury to nose, throat, larynx and lungs from in- halation of vapor, some time after breathing, with sore throat, cough, loss of voice, pain on talking, chest pain, bloody sputum, and hemorrhage from nose, throat, or lungs, d. Salivation, upper abdominal pain, nausea, vomiting, watery, bloody or tarry diarrhoea, weakness, emaciation, beginning from 1 to 12 hears after swallowing .contaminated food or other material. Warning. There is little or no immediate irritation of the skin, eyes, nose and throat or chest, and, therefore, no recog- nition of danger, immediate decontamination is necessary to prevent disabling injury if material comes in contact with skin or clothing. Prompt use of mask and continuous use until liquid and vapor is disposed of is absolutely necessary. There is likely to be little recognizable taste or other objectionable quality to food. Great care necessary, therefore. Suspected food must be discarded or subjected to rigid chemical examination before use. 2, Lewisite a. Primary injurious of fact on skin, with short latent period and perhaps early stinging and redness of skin, followed by blistering and ulceration, b. Serious injury to eyes fror: droplets, with short latent period, c. Acute injury to nose, throat, larynx, and lungs from in- hale, tion, beginning shortly after exposure and developing in severity, v/ith sore throat, cough, loss of voice, pain in ohost, prostration, d. Abdominal pain, nausea, vomiting, with v/atory, bloody, or tarry diarrhoea, with also weakness and emaciation, the first symptoms occurring within an hour or less after, inges- tion of contaminated food or other material. Symptoms of acute or sub-acute arsenic pensioning may result if ono survives tho initial acute toxic effect of the whole molecule, i.c, gastro-enteric ulcoration, jaundice, bronchitis, paralyses of legs and/or arms, scaling skin lesions, loss of hair and nails, etc. 4-0998-P105-BU-COS-WP Warning, There may bo little warning of the presence of Lewisite in the atmosphere. The compound used may be entirely odorless. The presence of droplets of material on objects may be noted. Prompt use of the mask, and immediate decontam- ination of skin is necessary to afraid disabling injury. Food in the involved area must bo regarded as unfit for use, unless completely protected. Questionably contaminated food must be discarded, unless shown to bo safe after chemical examination, IV, Toxicity data for certain agents Toxicity of Vapors Inhaled In Milligrams per Liter of Air Phoseeno Chloropicrin Chlorine Mustard I i Lewisite Ethyldi- chlorarsine Sat. Vapor i Gone, 20° C Gas 165 Ga,s 0.57 4.50 47.0 j Fatal 30 min. 0.36 0.8 2.5 0.07 1 I 0.05 0.80 i Fatal 10 rain. 0.50 2.0 5.6 0.15 ( 0.12 0.50 ' Toxicity of Vapors in Contact with Skin In Milligrams per Liter of Air Mustard Lewisite Sat. Vapor Gone. 20° G 0.625 k. 50 Vesicant concentration 0.005 0.33 Toxicity of Liquid in Contact with Skin Mustard Lewisite Speed of absorption Latent Period of First Effect Lethal Dose for man 20-30 min* 120 min, ? 3 min, 30 min, 2,6 gram L-0998-P106-BU-C0S-1VP Roughly Estimated* Lethal dose when Swallowed Agent Lethal Do: sc for Man* Phosgene Chlorine - Chloropicrin 1200 to 24-00 mg Mustard 60 to 120 mg Lewisite 70 to 150 mg Ethyldichlo rars ine 300 to 600 mg * Not to bo taken as correct. Calculated indirectly from the lethal con- centration for inhalation. Experimental data not available. k-0998-P107 -NOBU-COS-WP SUBJECT: OUTLINE OF THE PREVENTION AND FIRST AID TREATMENT OF CHEMICAL CASUALTIES . Leon Goldman, M,D, GENERAL REMARKS: A knowledge of the chemical warfare agents will not only do much to dispell the fear and panic inspired by them, but also this knowledge will serve to show how relatively simple the outlines on both prevention and the very important first aid measures are, I. Prevention - by planning to avoid contact with the chemical warfare a.gonts A - Personnel not required to bo on streets X, Inside - doors and windows closed 2, Ascending to higher floors 3. Gas protection shelters as available U, Try to evacuate in advance, old people, invalids, and children B - Personnel authorized to be on streets 1. Gas mask 2. Protective clothing - type depending upon duties 3. If situation warrants - a station much above street level II, Prevention - during and immediately after a chemical warfare attack A •• Personnel not required to be on streets 1, Direction of movement - up wind; right angle to the gas cloud 2, Go Inside house; close doors and windows tightly - turn off air conditioning - ascend to higher levels - avoid remaining in low, poorly ventilated areas, basements, etc. 3, Improvised gas masks - wet handerchief or cheese-cloth with wo.ter or baking soda solution A, Improvised protective clothing - rain coat, collar up, sleeves down; heavy clothing; cover head to prevent contamination of scalp and hair 3, For vesicant contamination of clothes - discard as rapidly as possible or go in doors and put clothes in metal container - (ash can or garbage can) if-0998-P109-BU-C0S-WP Porsoas with contaminated clothing should not be permitted in any public shelter. Bathing and use of any active chlorine com- pound .(or hydrogen peroxide for lewisite) or baking soda paste if these other materials are not available, 6, For vesicant contamination of the skin do as much of the approved skin cleansing technic as possible after discarding the contam- inated clothes. To remove the agents, use soap and water. After mechanical removal, use prophylactic agents if available. Con- tamination by liquid vesicants is a definite medical emergency! A shower with hot water and soap after initial decontamination finished is always necessary, 7, Vesicant contamination of eye is a definite medical emergency! Irrigate with ?/ater or baking soda solution or put face in pan of water. Medical attention should be obtained as soon as possible, 8, Vesicant contamination of hair. Wash with soap and water and any active chlorine compound available. If lewisite, use hydrogen peroxide| cut hair off quickly if Contaminated by liquid. B, Civilians authorized and required to be on streets 1. Put on gas mask in the approved fashion. 2. Use protective clothing or protective covering as indicated. 3. If contaminated - proceed according to instructions previously given. III. Treatment A. Irritants of the respiratory tract 1. Sternutator or sneeze gas type - there may be delay in onset of ' symptoms a. Remove to fresh air b. Smell chlorine from bottle containing bleaching powder. c. Sodium bicarbonate gargle and mouth wash and if necessary nasal irrigation, then spray with neosynephrin and pontocaine if available, 2, Pulmonary irritation - phosgene group - every individual not wear- ing a mask exposed to nheavy” concentrations of phosgene must be considered as potential casualty or may be actual casualty, Rem- ember the onset of symptoms may bo very insidiousi At times, dislike of cigarette smoking or smoke may be indicative of pul- monary irritation. The exposed persons may pass successfully A-0998-P110-BU-C0S-WP through the stages a, b, and c below. The final stage reached will depend upon the severity of the exposure, a. The mild case - good color, no difficulty in breathing, vote, (1) Rost, heat, drinks (coffee or tea) (2) Stretcher evacuation (3) Observation in hospital for appropriate period b. Tho moderate case - chest pain, slight cough, etc, (1) Rest, heat, drinks (coffee or tea) (2) Should have priority in evacuation over "a" (3) Treatment in hospital necessary - oxygen if available, c. The severe case - cyanosis blue or gray (shock) type, pul- monary edema. (1) Same emergency treatment as above (2) Immediate evacuation to hospital (3) Hospital and not casualty station treatment (4) Oxygon, sedation, plasma, venesection if increased venous pressure, ($) Long period of observation and later observation of res- ponse to effort. B, Treatment of trio lesions from vesicants - all personnel treating casualties contaminated with vesicants must be protected themselves with gas masks and some form of protective clothing* There is a great difference in lesions from vapor and from, liquid contact,, 1. Eye lesions - profuse irrigation with plain water or 2% soda bicarbonate, in the approved fashion avoiding all pressure on eye. Do not use any of the strong agents recommended for decon- tamination of the skin* After irrigation may instill ophthalmic ointment of various types; a. Bland b. "Sulfa” ointment c. 2% Sodium bicarbonate k-0998~Plll-BU"C03~WP d, Kb cocaine, if local anaesthetic needed in the oye, uso butyn or pontocaino, Do not bandage the eyosl If lesion develops it is much bettor to socuro immediate consultation from an ophthalmologist, For any burns of the skin around the eye, treatment of bland therapy should be done but do not allow bandage to come over the eye. Remember- eye bums may develop insidiously also, 2, Treatment of the skin area contaminated with vesicant before appearance of lesion - ideal period for lewisite five minutes and for mustard maximum one-half hour. Questionable whether protective treatment of any value with pure vapor contamination ( a. Removal of contaminated clothing but continued wearing of gas mask until main sources of contamination are removed, b. Determining the approximate area of cutaneous contamination, the approved method of cleansing technic (see above) fol- lowed by prophylactic materials such as protective c’rcam of the Chemical Warfare Service, bleaching paste mixtures, Chlorox, sodium hypochlorite, dichloramino, a30chieramide. For lewisite, hydrogen peroxide preferred to those chlorine compounds. Baking soda pastes may be used if none of the above are available. If none of those materials are avail- able rinse with water, since no time should be lost. If possible take a shower using plenty of hot water and laundry soap, 3, Treatment of the actual skin lesions from vesicants - Do not use any medications recommended for prophylactic use vixen this phase develops. The treatment of the blister stage should bo done by medical personnel. Do not break the blisters. Do not cover the blisters with greasy ointments. Avoid getting the skin dirty. The skin may be covered with clean, dry bandages. G - Treatment of Lesions from Cyanides 1. Artificial respiration as soon as possible - Use portable pulmotor apparatus if available 2, Inhalation of amyl nitrite D - Treatment of burns from Incendiaries and the like 1, Phosphorus Burns - specific emergency treatment important, cover immediately with 2% copper' sulphate solution, if none available cover with oil or warn water or 5$ soda bicarbonate solution until phosphorous particles can be removed. Instead of baking soda the following alkaline paste may be used Mo.gnesium oxide (heavy) 10$ Borax % Soda bicarbonate (Godding and Notion) 1.-0998-P112-BU-G0S-WP Instea.d of the 2% copper sulphate solution the following copper paste may be used; Copper sulphate 22,5% Glycerine 67,5^ Starch 5,0% Water 5,0% 2. Heat Burns A, Extensive - use no greases, tannic acid jollies or the like| cover burns with clean bandages; do not get dirty; keep patient warm; arrange for immediate transportation to medical installation, B, Mild - use only simple ointments here. Cover with clean bandages and protect from dirt -E03IJ-C0S-WP THE CHEMISTRY AND METHODS OF DECONTAMINATION By Eugene h. Scott Kettering Laboratory of Applied Physiology, College of ’Medicine, University of Cincinnati, Cincinnati, Ohio Introduction The number of chemical agents which have boon used in war is relatively small considering the vast field of organic compounds that have toxic offsets on nan. The important factors to selection of practical chemical warfare agents are tho physical and chemical properties of the agent and its availability in large quantities. At present, there are twenty to tliirtg chemical c- aapounds which could be used in offensive and defensive warfare. In war on civilians, however, only a few of these compounds would bo of value, either for their demoralizing effect or for impairment of manufacturing facilities. Non-persistent gases such as phosgene and clilor 'pierin could not bo maintained in sufficient concen- tration in largo enough areas to bo practical. Tear gases and stemulators are not sufficiently toxic and incapacitating. Certainly, from a practical standpoint, the vesicants, such as mustard, lewisite, and the nitrogen mustards, should bo the chemical agents of choice for attack on a civilian populace. Their persistence and toxicity in low concentrations are arguments in their favor. Of the several possible methods of dissemination of the chemical' • agent, only two will be mentioned. The material can bo dropped from the air by bomb or spreyed from a low-flying airplane. In attempting to obtain an effective concentration of gas or liquid over a moderately largo area, it would seem that spraying or sprinkling would bo the most effective method, while for a maximum effect in a relatively small arod, bombing could probably be employed. According to the method used, gassed areas may consist of small or medium-sized areas of heavy contamination caused by a bomb, or fairly large areas of moderate to light contamination duo to springing or spraying of the gas, A further distinction, that between vapor contamination and liquid contamination, must also be noted. In the case of vapor, in most instances, decontamination is accomplished simply by aeration. However, contamination by liquid requires more strenuous measures, since' aeration alone causes only a slow destruction of vesicant agents, particularly mustard gas. Of the vesicant gases recognized as practical chemical warfare agents, mustard gas and lewisite are the best known, most effective, and most easily available. Both of these materials are classed as persistent gases and are very active vesicants. Their vapors are extremely irritating to tho lungs in low concentrations, Ethyldiclilorarsino is another vesicant which might bo employed although it is generally regarded as a non- persistent gas. The recent disclosure that the nitrogen mustards are effective vesicants brings a new problem to tho doc ntaainatic-n personnel. However, the present methods of decontamination are general rather than specific and arc applicable thu&e materials in most instances. H-O998-PII5-BU-COS-NP Chemi s tagvo f D ec o n t agination In order to understand the reactions involved in decontamination, some knowledge of the physical and chemical properties of the gases likely to be employed, is necessary. If the use of non-persistent gases, tear gases, and irritant smokes is ruled out on the basis of impracticability, then a discussion of the properties and reactions of mustard gas and lewisite is sufficient for the present purpose. All the chemical agents which closely resemble either of those two materials in chemical structure will show the same chemical reactions oven tin ugh they may differ appreciably in their physical and toxic properties. Very little can bo said about the nitrogen mustards since their formulas are secret. Mustard gas, 2,21-dichloroothyl sulfide, is a liquid boiling at 217,5°. It is slightly soluble in water and readily soluble in most organic solvents. It is stable to air and only slowly hydrolyzed by water or water vapor at ordinary temperatures. At hi.,her temperatures, i.e,, 100°, it is rapidly hydrolyzed according to the following equation. (C1CH2CH2)2S -?• 2H20 ">(H0CH2CH2)2S 2HC1 The compound, hydroxys tiny 1 sulfide, is nun-toxic. Mustard reacts readily with oxidizing agents such as H202, and with the formation of a sulfoxide or sulfone, depending upon the conditions employed. (gich2gii2)2s -h fpj >(cich2ch2)2s = 0 {ClCa20H2)2S -*• [0!■ --r^(ClCH2CH2)2S Dichloroothyl sulfone has boon reported to have vesicant action on the skin and therefore oxidation is not a completcly satisfactory nothud of decontamination, Mustard as a liquid reacts violently with dry chloride of lino with the formation of numerous products, but v/hen a slurry of bleaching powder is used, dichloroothyl sulfoxide is formed. (C1GH2GH2)2S CaOCl2--~—>(C1CH2GH2)2S = 0-r- GaCl2 Dichloroothyl sulfide reacts v;ith chloranino-T forming a non-toxic sulfilinino compc und, (CLCH2CH2)2S 4- CH3C6H^S02 3G6H,S02N = S(CH2CII2C1)2NaCl Another reaction of dichloroothyl sulfide which nay bo used as the basis of a decontamination procoduro is that with sodium sulfide. C1(CH2CH2)2S-J- Na23 -^S(CH2GHQ)23 -+ 2NaCl The product domed, dicthyleno disulfide or dithianc, is non-toxic. U-0998-P116-BU-C0S-WP The reactions of lewisite with the reactants mentioned above are not as well worked out end in certain instances the final products are not known. Furthermore, although the term nlewisiten is applied to A-chlorovinyldichloroarsine, di(p-chlorvinyl) chloroarsine and tri (b- chlorovinyl) arsino arc eiso present in the material which is used cts a chemical warfare agent. The last mentioned compound has no vesicant or irritant properties, fi-chlorovinyldichloroarsine is readily hydrolyzed by water and is broken down rapidly in a damp atmosphere. C1CH - CHAsG12 * H20 C1GH = GHAs = 0 -*• 2HC1 The product^-chlorovinylarsenious oxide is toxic because of its arsenic {group end on contact acts as a vesicant. Alkalies completely destroyyS-chlorovinyldichloroarsine with the formation of acetylene and. sodium arsenite. C1GH = CHAsClo “<• oNaOH >G H -f»Na As0o 3NaCl 3Ho0 2 2 3 3 2 Oxidising agents such as nitric acid and hydrogen peroxide react readily with fjf-chlorovinyldichloroarsine, forming £-chlorovinylarsonic acid. /OH C1GH = CKAsClp ■* /0 1 2HoO > G1CH » CHAs-OH -t- 2HC1 yg-chlorovinyl arsenic acid formed, on treatment with warm concentrated sodium hydroxide gives sodium arsenate and acetylene. ✓ 0H C1GH = CHAs-OH + 4NaOH 3AsO/ + C2H2 ■* NaCl -»• 3H20 d p-chlorovlnyIdle hloroarsine reacts readily with chloride of line, but the reaction has not been studied and the products formed have not been reported. It is reasonable to assume that oxidation and hydrolysis arc the first steps. C1GH = CHAsC12 «• CaOCl2 H20 =>C1CH * CHAs03H2 * CaCl2 Genoral Decontamination Procedures The reactions given above fora the basis of most of the decontam- ination procedures in use at present. The general effectiveness of chloride of line and its cheapness make it the agent of choice for chemical destruction of the vesicant gases on sites and articles when the effect of the decontamination agent is not a detoront. In many instances, how- ever, other decontaminating agents or procedures must be used in order to avoid harm to the material being decontaminated. An outline of the possible methods of decontamination is given below. A-0998-PH7-BU-COS-WP D ocontemination Removal Destruction Sealing Weathering; Hosing Burning Earth end Sand Sun Solvent Boiling Wind Mopping Chemical Agents Sodium Silicate Rain ..Under weathering is found tho effect of the sun, wind, and rain, • The heat of tho sun will cause vaporization of the liquid'material from contaminated surfaces and dilution with air dissipates the toxic vapor with the aid of wind. Rain and moisture will rapidly decompose lewisite, but mustard is only slowly affected, • However, a contaminated area can be marked off as dangerous and decontamination will proceed naturally until after several weeks all of the gas in tho area will have been vaporized or decomposed by moisture. Sealing is another general method of decontamination. This is generally used as a temporary measure when it is desirable to keep a con- taminated area in use. Earth and sand can be used for ground areas, paths, and dirt roads. Brick work, concrete, arid plaster contaminated with liquid vesicants can bo treated with sodium silicate solution which will seal in the liquid and prevent its vaporization. This is a method of expediency and should not be used except in cases requiring a quick occupancy of the contaminated building. The third method of decontamination which can be employed is removal with an organic solvent or with water. Streets and concrete surfaces can bo vigorously hosed to wash off liquid vesicants. In the case of lewisite this will also decompose the chemical agent and wash off the product of hydrolysis. Any dichloroethyl sulfide removed in this manner, however, will collect in the bottom of the drains and in the bottom of pools near the building or area treated and evaporation of the water will permit this material to vaporize, causing a fresh contamination. Mopping can bo used for floors not equipped with drains but it is not particularly recommended. Metal objects which would be corroded by the use of bleaching powder can be wiped with rags wetted with kerosene or gasoline to dissolve the contaminant, The thin film of vesicant and solvent remaining can be removed by repeating the process several times. Solvent removal of the contaminant is satisfactory when care is used in the handling of tho rags containing tho dissolved vesicant. Frequently this method is used to remove the gross contamination, then a bleaching powder slurry is employed, and this is followed'by oil to prevent rusting. The most important of tho general decontamination procedures is destruction of tho contaminant by chemical means. This is the preferred method and is used unless the character of the contaminated item prevents its use. It has boon previously mentioned that chloride of lime is generally effective in destroying chemical agents. This is used in a 4-0998-P118-BU-C0S-WP mixture with water to form a slurry or is mixed with earth and sand. Several other substances containing active chlorine can bo used when the contaminated articles would be destroyed or harmed by bleaching powder* These a,rc chlo r an in e -T, Clorox, and HTH, which in dilute solutions do not have the corrosive action of bleaching powder. Sodium sulfide can bo used for machinery and vehicles. Although there is no report on its effectiveness in destroying lewisite, it should react with this agent, The reaction of sodium sulfide with dichloroethyl disulfide has been above. Alkalies such as lye and washing soda in solution can also be used effectively to destroy lewisite. Burning is another chemical process for decontamination, Wooden parts badly soaked with mustard end lewisite can bo removed and burnca, and clothing and furniture if grossly contaminated should also be aes- troyed by burning. Care must be exercised in burning such materials, how- ever, as there is danger of producing a toxic concentration oi the vapors in tho surrounding atmosphere,. Boiling or steaming is effective in destroying both mustard^and lewisite and can be applied to clothing and many small metal articles. When clothing is steamed to remove lewisite, the product formed is still a. vcsicant and must bo removed by treatment with an activo cnlorine compouu or dilute alkali. Nitrogen mustards arc also decomposed by water, slowly at room temperature, more rapidly at higher temperatures. It may, therefore, bo presumed that decontamination by boiling or steaming would be effective in the decontamination of articles contaminated with tnese vesicants. In the material presented here no attempt has been made to provine specific methods which could be used in decontamination of all items tnat might become contaminated during a gas attack. All that has been attempte was to explain the chemistry involved in the decontamination procedures in use at present, and to outline those procedures in a general way so that they can be adapted to specific problems as they a.riso. References Sartori, Mario, The War Gasos (translation of tno Second Eaition by L, WT, Marrison), D. Van No strand Company, Inc,, Nov/ Yorx, 1939 Willians, Douglas, Tho Decontamination of Buildings, J, Roy. Sanitary Institute, 6l, 167-70 (1911) Jacobs, Morris B., War Gasos, Their Identification and Decontam- ination, Interscience Publishers, Inc,, Nov/ York, New York, 1942 A-0998-P119-N0BU-C0S-WP DECONTAMINATION PROCEDURES By R. R, McNary Kettering Laboratory of Applied Physiology College of Medicine, University of Cincinnati, Cincinnati, Ohio The work of the decontamination squads is logically subdivided into the objects to be decontaminated such as streets, buildings, clothing, etc. First, however, let us consider briefly the personnel of the squads. Personnel Obviously individuals making up the decontamination squads must be trained and must be fully protected by special clothing, shoes, gloves, and gas mask. They should be inspected before commencing operations to insure that they are properly protected. Facilities should be provided for undressing and bathing after completion of their work, and the men should be taught to assist each other in removing protective clothing • without allowing it to touch the bare skin. Facilities for disposal or cleaning of contaminated do tiling should be provided. Decontamination Materials The materials most likely to be available for decontamination are; Earth vIncluding sand, ashes, soot, and sawdust) Water Chloride of lime Other suitable but less effective materials ares Sodium sulfide, 1% solution in water "Green solution," 1 lb, sodium bicarbonate dissolved in 1 gallon sodium hypochlorite solution Materials for use in special cases ares Kerosene (gasoline) Aqua ammonia Chloramine T Decontamination Eguipment The recommended supply of equipment for a decontamination squad or civilian decontamination center consists of; 4-0998-P121-BU-COS-WP 20 cans (50 lb. each) chloride of lime 1 gallon lubricating oil, medium 2 cans (5 gal, each) kerosene 4 brushes, white wash (long handled) 4 decontaminating apparatus, 3 gallon (pressure type) complete with paddle and funnel, M2 1 box (12 tubes) impregnite, shoe, Ml 10 yards cheesecloth, medium 2 feet wide 6 shovels (long handled) 4 rakes 4 brushes, scrubbing 4 picks or pick mattocks 4 scythes or sickles 4 brooms, stable 8 brooms, common 8 buckets, G,I., 14 quart 1 can, galvanized, 15 gallon 1 axe, single bit 20 lb, rags, clean 24 signs, "Danger — Gas" 2 hoses, garden, 50 foot lengths 25 lb, soap, issue 4 oilers, with spout, -g- pint 4 lanterns, kerosene 6 flashlights 1 screv/ driver, 6 inches 4 curtains, gas-proof 4-0998-P122-BU-C0S-WP In addition each squad should carry a first-aid kit consisting of? •g- lb. sodium bicarbonate 3 lb. soap, issue ■g- gallon kerosene 4- oz, hydrogen peroxide — 3$ solution tt pint high tost bloach powder (mix in glass jar ono part bleaching powder with ono or two parts water) 1 teaspoon 3 medicine droppers in sterile gauze (for use as applicators) 3 oz. 2$ sodium bicarbonate solution in w/ator Bleaching Powder The most useful neutralizing agent for both mustard and lewisite is bleaching powder, otherwise known as chloride of lime. This material is a white powder, not very stable, which readily gives up its chlorine when exposed to the air or moisture. Chlorine reacts with mustard to destroy it, but must bo brought into intimate contact with the gas. Bleaching powder should bo kept in air-tight containers until the moment of its use. Dry bleach should not bo placed directly upon liquid mustard gas because the chemical reaction which bakes place results in the evolution of heat and flame. This drives off- a high concentration of mus- tard vapor which may bo carried some distance by the wind, endangering people who would otherwise bo safe. In using bleach on mustard gas, the bleach is cither mixed with water as a paste or mixed with sand or earth. The use of bloach is affected by the percentage of available chlorine, which varies in the different types of bleach. Chloride of lime when freshly packed may have as much as 35$ available chlorine, Bloach with less than 15% available chlorine should not bo used except when none better is available. There are commercial compounds, under such name as H.T.H, and Perchloron, which contain as much as 70$ available chlorine. Also available arc commercial bleaching solutions such as Clorox and Zonito which contain from 5 to 15$ of available chlorine. In using a compound which varies from the standard of 30 to 35$ available chlorine, it is a safe rulo to combine with one part of bleach, one part of inert material for oach 10$ of available chlorine. Thus, with ono pound of 70$ H.T.H, or Perchloron, 7 pounds of earth may bo used; with ono pound of 30$ commercial chloride of lime, throo pounds of earthj and with one pound of 10$ chlorine, ono pound of earth. Slurry Slurry is a 50-50 mixture of. commercial 30$ chloride of lime and water. This proportion is obtained by mixing two gallons of water weighing i-0998-P123-BU-C0S-W? 16 pounds with three shovelfuls of bleach weighing about 16 pounds. With H.T.H, or Perchloron, one-half the amount (3 pounds) is mixed with two gallons of water. Thorough mixing to remove lumps is essential. First add about two quarts of water to the 16 pounds of bleach and work into a smooth paste; then add remaining water and stir thoroughly. Since one square yard of area requires one pound of chloride of lime for decontamination, the above amount, which fills a three gallon sprayer, will properly treat 16 to 20 square yards. The slurry is very corrosive to most metals and cotton fabrics. Therefore, it should never be used whore this corrosive action will cause excessive damage to material and equipment. Other less corrosive agents such as one per cent sodium sulfide, "Green Solution," chloramine T, or kerosene should bo substituted*, The mixing of slurry is not dangerous enough to necessitate wearing protective clothing, but this mixing is normally done at or near the con- taminated area. Consequently protective clothing is usually worn. Since chloride of lime is very corrosive, it must bo completely re- moved from the decontaminating equipment after use. To remove all traces, all spray apparatus, mixing buckets, brooms, and other pieces of equipment are washed in several changes of water. Hot soapy water will aid in the cleaning and a plentiful supply of strong laundry soap is an invaluable item in the supply list of a decontamination squad. Decontamination of Ground Areas The decontamination squad, even though fully protected with special clothing, should avoid all unnecessary contact with the liquid agent or vapor. The squad should approach a bomb crater from the upwind Side and commence spreading the neutralizing material at the edge of the contam- inated area. In the crater, the bleach mixture or whatever neutralizing substance is used should bo spaded into the soil to insure close contact with the gas. Pools of liquid mustard or lewisite or large visible splashes on ground or vegetation are rarely found. In most cases the mustard is only perceptible by its odor. The contamination is generally greatest in the bomb crater itself, while the area outside the crater is usually much more lightly contaminated. If this area contains high grass or brush which cannot be decontaminated as it stands, it should be cut down so that it can bo treated and disposed of. Neutralizing materials should bo most liberally applied to spots which are the most heavily contaminated. After the entire area is so treated it should be covered with a layer of fresh earth. All these facts should be borne in mind by the decontaminating detail. Decontaminating Streets and Roads Whether degassing work is practicable in the case of a contaminated stretch of road will depend upon the size of the affected area, the moans available, and the necessity for the work, whore drainage is assured, a contaminated hard-surfaced road may be rendered loss dangerous by wetting k-0998-P12^-BU-COS-WP it down with water| much of the contaminant, if it is mustard, will bo carried off in sowers and drainage ditches. Mustard gas will be decom- posed very slowly by this moans. The liquid mustard will sink to the bottom of pools and ditches end remain there in active form for a long time though the water seal will lessen the amount of mustard vapor given off. Consequently such a procedure is more applicable to roads and streets in eitics and towns whore ample drainage facilities exist. In any case, care should bo taken that such measures do not merely result in spreading the contamination. In the case of lewisite contamination of streets or roads, water will hydrolyze the gas but power flushing is needed to wash off solid hydrolyzatc, which is insoluble in water but is a contact vesicant. When time is limited, contaminated patches of paved road which cannot bo avoided may simply be covered with a layer of earth to render then comparatively safe for immediate passage over them. When time and facilities arc afforded, contaminated patches of paved road should bo covered with bleach paste and swabbed with it, A strong solution of bleach and water might bo used. The bleach should be allowed to stand for 24- hours if possible and then washed off with water. Dirt roads may be treated with bleach nixed with sane or earth. When available, a. tank truck with two spraying nozzles nay bo used on streets. Two men fully protected, as is the driver, ride on the front fenders and spray a 50-50 mixture of chloride of lime and water in advance of the truck. One tank load of slurry (1,600 lb, of chloride of lino and 200 gal, of water) can cover a gravel road B yards wide for a distance of 200 yards. Since mustard and lewisite will not penetrate concrete or other smooth surface roads as rapidly as it does gravel, dirt, and cinder road surfaces, a larger area of the former (8 yards wide and 400 yards long) can bo decontaminated. If lewisite has been sprayed on a road it may bo destroyed by hosing it down with water, A high pressure hose is preferable, though the modern street flushing truck may be used for this task. The resultant product may be an arsenic compound which is poisonous and must bo washed away. If lewisite and mustard are mixed, the normal slurry load in the power driven apparatus will destroy both vesicants. Decontamination of Buildings Buildings may become contaminated through direct hits by gas bombs, by the spraying or sprinkling of chemical agents from airplanes, by toxic vapors blown from nearby areas, or by the entrance of persons wearing contaminated clothing, A grossly contaminated structure should be disposed of by burning if this can be done with safety. If it is so isolated that it will not become a source of danger because of the vapor escaping from it, the building may simply bo opened and marked with a danger sign. If it is not so isolated, the building should bo closed up tight (windows boarded up, etc) A-0998-P125-BU-C0S-WP and abandoned after a warning sign has been posted. If essential, because of the importance of the building and/or its dangerous location as a sourco of contamination, or because of the impossibility of sealing the doors and windows, decontamination operations should bo conducted. Buildings contaminated by vapor only can be cleaned by opening all windows and doors and allowing fresh air to circulate freely through thorn. In warn bright weather, the sunlight and wind will soon eradicate the vapor, II' ventilation is poor or if the weather is cool and cloudy, the mustard vapor may persist for a week or more. Materials suitable for decontamination of buildings aro the some as those used in the field, A mixture of 50% chloride of lino and 50% water by weight is best* Concrete or wooden floors readily absorb mustard and lewisite and should be covered with a layer of freshly prepared slurry by moans of brooms and loft for at least 24 hours. The slurry is then removed by scrubbing the floor with water (hot soapy water is preferable,) Badly contaminated floors and woodwork should bo torn out and replaced with new structure if practicable. Walls and ceilings of a building, if not too heavily contaminated with mustard, may bo neutralised by spraying and swabbing with slurry, a mixture of 50% chloride of lime and 50% water by weight. The 3-gallon decontaminating apparatus (pressure typo) is particularly suited for spraying walls end ceilings which cannot bo reached with brooms or brushes. After 24 hours, the walls and ceilings should bo washed with hot soapy water and the room or building aired for several hours. If mustard gas odors arc still present, the decontamination process should bo repeated. If a building is contaminated with lewisite alone, it can be decon- taminated with water, preferably with a high pressure hoso. The resulting compound is an arsenic poison and must b.; washed away. Heavily contaminated parts should be torn out and destroyed with fire. Mustard and lewisite soak into wood, plaster, wall paper, and concrete and aro extremely difficult to eradicate. The vapor from the absorbed gas is given off for a long time after the surface layer is removed. It may help to coat the walls, ceiling and floor with a thin solution of water glass (sodium silicate) after surfc.cc decontamination. The water glass hardens and seals in the vapors, but this is not necessarily a permanent treatment, especially on floors whore it will wear off. Decontamination of Household Furnishings Household furnishings nado of fabric such as curtains, draperies, linens, and rugs which are easily removed may be destroyed by burning or burying or they nay be decontaminated by the same methods indicated for clothing. Mattresses may be treated with steam in apparatus ordinarily used for disinfecting mattresses. This is effective for mustard. Since there is no record in the literature on the effect of steam on lewisite beyond, simple hydrolysis, stoam may be insufficient treatment in this case. 4-0998-P126-BU-C0S-WP Upholstered furniture presents a difficult problem because the upholstery will soak up vapors of persistent gases as well as splashes of liquid agents. Decontamination is practically out of the question| hence, destruction by fire is normally carried out. Kitchen equipment made of metal may bo boiled in sodium sulfide or green solution or wiped off with kerosene followed by soap and water as described under machinery. Decontamination of Machinery Greasy or oily metal surfaces which have been contaminated with mustard or lewisite should first bo cleaned with kerosene or gasoline, (Careful, fire hazardJ) These solvents do not destroy the gases but dissolve thorn so that most of the poisonous material may bo removed. The very thin coating of contaminant remaining is then destroyed with steam, bleach paste, hot sodium sulfide, or Green Solution, The latter two arc loss corrosive than the bleach. After such treatment the surface should bo washed, dried, polished, and oiled. The rags,used should then be burned. Decontamination of Vehicles and Machinery Vehicles or other machinery may be decontaminated on the outside by slurry, followed by washing with hot soapy water. Bleach should not be used on the motors' of cars and other working parts because of its corrosive- ness, Such parts should bo treated in the same way as instruments, using alcohol or gasoline, hot water and soap, or -such other non-corrosive material as may be provided to remove the gas. Upholstery and other absorbent parts when contaminated should be torn out and burned. Decontamination of Clothing Clothing rnay be contaminated by vesicant agents such as mustard and lewisite end rendered dangerous to wear, either through direct contact with the liquid substance or through exposure to the toxic vapor. Liquid mustard and lewisite will penetrate ordinary clothing very quickly. Severe burns will result unless the contaminated clothing is imeuiaoely removed, or the contaminated portions cut away, and unless first-aid treatment is applied immediately thereafter to the affected parts of the body. In the case of exposure to mustard vapor, contamination is more gradual, the degree depending upon the concentration of the gas ana tne oime ox exposure, A very brief contact with mustard vapor might not cause contam- ination of clothing or produce a burn. On the other hand, clothing exposed to oven a low concentration ox mustard gas lor 1 hour '//ill oe so contaminated that burns would probably result from wearing it. In this connection, the highly insidious nature of mustard gas makes the protection problem a very difficult one. Vapor burns ao noo develop until several hours after contact and there is no pain or other immediate physicial indication of danger except the possible perception of the by its odorc The keenest sense of smell, however, gradually becomes fatigued by the odor of mustard gas so that after continued contact the odor may not, bo perceived at all. L-0998-P127-BU-C0S-WP It is evident that as a general rule of protection, whenever it is known that persons have been exposed to persistent gases they should bo removed as soon as possible from the contaminated area. They should bathe with hot water and soap raid put on fresh clothing if it is available. Other- wise their clothing should be decontaminated before it is worn again. Clothing contaminated only by the vapors of mustard nay bo decontam- inated by hanging up the garments so that they will be exposed to the sun and wind, in warm bright weather, two days’ airing will generally bo sufficient, Caro should be taken not to hang garments close together, especially not on top of one another. In cool weather this method should not bo relied on. Nor should this method bo used in the case of lewisite contamination since moisture of the atmosphere will hydrolyze the lewisite and leave an insoluble residue which is still vesicant on contact with the skin, A more positive method of destroying mustard gas in clothing is to subject it to steam. If contaminated with mustard vapor only, clothing nay be decontaminated by such treatment in 2 hours. If splashed with liquid mustard it. should be steamed for 4 to 6 hours. There is no accurate information available on the effect of steam on lewisite except that it causes simple hydrolysis* Consequently steam- ing of clothing cannot bo recommended until it has boon proved that no toxic residue remains. Various sorts of steam disinfectors can be improvised from materials, available on the spot. The simplest is merely a largo can provided with a false bottom. About 6 or o inches of water is placed in the can. The clothing is placed on the false bottom so that it does not touch the water. The can is covered but not so tightly as to prevent the escape of the steam. The capacity of such a disinfector can be increased by hanging additional clothing in an inverted canvas bag suspended over the com, the open end of the bag being tied about the sides of the can. Steaming, especially for wolion clothing, is much preferable to boiling. If a cylinder of chlorine and a suitable tube are available, the steam decontamination process can bo accelerated. The clothing is hung in a suspended inverted canvas bag, the open end of tho sack being tied or dram together. Chlorine from the cylinder is run in at the top by means of a rubber tube or a pipe. The sack from time to time is shaken to insure contact between the chlorine and all the clothing. Vapor-contaminated clothing should be treated with chlorine in this manner for 10 to 15 minutes and then steamed for half an hour. If splashed with liquid mustard the chlorine treatment should be given for 30 minutes followed by one hour’s steaming. If chlorine is used, it is essential that it be applied first and M the stoexi afterward. If this process is reversed, results will not be ■ satisfactory. fl 4-0998-P128-BU-COS-WP VJhon clothing which has boon splashed with liquid mustard gas is-, removed from the chlorine, a fduo whitish crystalline -substance will be seen on the cloth at the places whore it was splashed. This substance is the reaction product of liquid mustard and chlorine and should bo brushed off before the garments arc steamed. If such a substance is noted when ' treating clothing which was believed to have boon exposed to mustard vapor only, its presence is a certain indication that the clothing was actually splashed with the liquid agent. The clothing should then bo. treated accordingly, A considerable amount of clothing may be treated with chlorine at one time if hung in a tightly closed room, tent, or dugout, in which chlorine can bo released. This method should not bo attempted without expert operators end unless there is no danger of persons in the vicinity being gassed when the enclosure is opened. The method of sending men wearing gas masks into a chlorine chamber for chlorine treatment of the clothing they are wearing is not recommended, 3h no case should such a method bo undertaken without supervision of an export who is able to gauge and control the concentration of gas in the. chamber. In any case, this method is not highly effective. Another method of do contamination is to place the contaminated clothing in a receptacle containing a solution of sodium carbonate (soda ash, washing soda). The proportion should be % lb, of soda to each gallon of water. This should be hoatea t-_. about SO0 G, (loO°F) for about 2 hours. Do not allow to boil. Such treatment will cause some .deter- ioration of woolen cloth but will not harm cotton. This method is effective for lc• aisito as well as mustard, Little, if anything, can be done in the way of decontamination of shoes which are permeated with mustard. If the mustard has splashed only lightly and if it has not yet soaked into the leather, it may be neutralized by applying bleach or bleach paste. As a safety precaution it would be well for men subjected to mustard gas to shuffle their feet from time to time through a mixture of bleach and dry earth or sand. It is noteworthy that well-worn shoe leather absorbs mustard gas much more quickly than new. Chloramine T, when available, is useful for the decontamination of clothing containing mustard since the reaction is milder. However, details of its use arc not available. Hi .her cost is also a disadvantage. Ordinary dig7' cleaning will not suffice for treating contaminated clothes. Personnel engaged in decontamination of clothing should wear gas masks and protective suits. They should not touch contaminated garments with their bare hands. L-0998-P129-BU-C0S-WP Papers. Documents, etc, Papers, documents, etc, may be stored in an enclosed space for several days and treated with gaseous ammonia to remove mustard gas. If soaking with water will not destroy thorn, 1% sodium sulfide for mustard and sodium carbonate solution for lewisite is more effective. Only veiy important paper articles should be decontaminated| others should be burned- Jacobs, Morris B,, War Gases, Their Identification and Decontam- ination, Interscience Publishers, Inc,, New York, Nov/ York, 1942 Prentiss, Austin M,, Chemicals in War, McGrow Hill Book Coupany, Now York, New York, 1937 Sartori, Mario, Tn War Gases (translation of the Second Edition by L. W. Marrison), D. Van Nostrand Company, Inc., New York, Now York, 1939 Protection Against Gas, United States Office of Civilian Defense, Washington, D, C, * A Handbook for Decontamination Squads, United States Office of Civilian Defense, Washington, D. C. Reforoneos h-0998-P130-Finai-BU-C0S-WP OFFICE OF CIVILIAN DEFENSE WASHINGTON, D. C. Issued: January 11, 1943. Effective ; Immediately. 7 PAGES OPERATIONS LETTER NO. 104 (Supplement No. 3 to Operations Letter No. 42) Supersedes OCD Publication 220G, which was a tentative outline prepared for dis- cussion at Gas Specialist Course at War Department Civilian Protection Schools To: Regional Directors. From : James M. Landis, Director. Subject: Duties of U. S. Citizens Defense Corps in Gas Defense. Special Distribution Instructions : To all State and Local Defense Councils. Attention: State Gas Consultants and Senior Gas Officers. This operations letter details the duties of the State Gas Consultant, the Senior (local) Gas Officer and his staff, and describes the additional duties which units of the U. S. Citi- zens Defense Corps must assume in the gas protection program. The duties before, during, and after a gas attack of all such personnel are as follows : State Gas Consultant (Duties should be authorized under the authority of the State Defense Council) Duties before gas attack: 1. Provide technical advice to State De- fense Council in all matters relating to pro- tection of civilians within the State against, war gases. 2. Organize the State gas defense program and provide technical advice to Senior Gas Officers, through Commanders 'of the U. S. Citizens Defense Corps, in the organization of their local gas defense programs. 3. Make recommendations to the State De- fense Council in regard to funds necessary for the organization and operation of the gas de- fense program, including a contingent fund for use in an emergency. 4. Plan the gas defense educational pro- gram for civilian protection personnel in cooperation with the U. S. Office of Civilian Defense, State and local authorities, and assist in its execution. 5. Determine the availability and location of all decontaminating materials. 6. Recommend technical qualifications and urge the appointment of qualified Senior Gas Officers by Commanders of the local U. S. Citizens Defense Corps. 7. Assist Senior Gas Officers, through local Commanders of the U. S. Citizens Defense Corps, to determine the amount and nature of necessary equipment and to procure it. 8. Inform Senior Gas Officers of the loca- tion of the Chemical Warfare Service or other laboratories where samples of gas are to be sent. Duties during gas attack: 1, Be available for consultation with local Commanders and through them to Senior Gas Officers, by telephone or other method of communication. Duties after gas attack: 1. Consult, through local Commanders of the U. S. Citizens Defense Corps, with Senior Gas Officers of attacked areas, to ascer- 4-0882 PI of 7 bu-eos-tr-wp tain effectiveness of gas protection program and modifications necessary for protection against future attacks. Receive reports from local Commanders and transmit reports to Regional Office of OCD. Senior Gas Officer (Duties should be authorized under direction of the Commander of the U. S. Citizens Defense Corps) Duties before gas attack: 1. Develop and organize a gas defense pro- gram for the local community under the authority of the Commander of the U. S. Citi- zens Defense Corps. This will include ap- pointment of necessary assistants as described in Operations Letter No. 91 (Operations Let- ter No. 42, Supplement No. 2). 2. Study the meteorological and topo- graphical features of his area and their possi- ble relationships to gas attack. This may be based on reports of gas reconnaissance agents. 3. Plan and execute a training program for the technical instruction of protection per- sonnel actively concerned with gas defense in cooperation with the U. S. Office of Civilian Defense, State, and local authorities. 4. Make recommendations to the Com- mander in regard to funds necessary for the organization and operation of the Gas De- fense Program, including a contingent fund for use in an emergency. 5. Determine the amount and nature of necessary equipment and supplies and ar- range for their procurement and storage in appropriate locations and their issue to all services. 6. Arrange for issue of detector materials and instruct reconnaissance agents in placing indicators. _ 7. Develop lay educational programs to promote and maintain civilian morale, and educate the public in self-aid against gas with cooperation of the Chief of Emergency Medi- cal- Service (Operations Letter No. 46). 8. Arrange in cooperation with the Air Raid Warden Service for the development of an adequate gas alarm system and for the education of the public concerning recogni- tion of such alarms. 9. Organize laboratory services for the de- tection and identification of war gases. This should be provided in cooperation with the Local Health Department as described in the section on Health Department. 10. Cooperate with and supply technical as- sistance to the Chiefs of the various services of the U. S. Citizens Defense Corps in organ- izing their services and training their per- sonnel in gas defense. 11. Assign an Assistant Gas Officer to each divisional and district control center. 12. Assign Gas Reconnaissance Agents to each zone warden’s post. The air-raid war- den’s zone is the area of operation of the Gas Reconnaissance Agent. Where warden zones have not been established according to OCD recommendations, one Gas Reconnaissance Agent should serve an area containing a pop- ulation of approximately 25,000. 13. Supervise the Laundry Officer in the organization of facilities for the collection, transportation, decontamination or destruc- tion, and redistribution of clothing. Duties during gas attack: 1. Report at the main Control Center and serve as technical adviser in gas defense to the Commander and the individual services. 2. Recommend to the Commander the dis- patching of a Gas Reconnaissance Agent from a zone warden post to area from which gas is reported. 3. On the basis of reports of the Gas Recon- naissance Agents, make decisions and advise in regard tcv; A. Presence of gas. B. Nature of the gas used. C. Areas to be delineated, policed, and evacuated. D. Areas requiring immediate decontami- nation, and the order of their priority. 4. Provide information to the Commander regarding the presence and location of gas and the integration of the activities of the various services concerned with gas defense. Duties after gas attack: 1. Appraise and evaluate the extent and amount of contamination remaining, recom- mend to the Commander which areas should 4-0882 P2 bu bo decontaminated and the order of their priority and which should be left for weath- ering. Recommend when decontaminated areas may safely be opened for the public. This will be based on information supplied by the Gas Reconnaissance Agent. 2. Confer with Chiefs of all Services of the U. 3- Citizens Defense Corps in order to de- termine the effectiveness of the protection provided to and by those services in the previ- ous gas attack, and discuss plans for improve- ment of gas defense. 3. Make an inventory of the protective equipment available for use in future attacks and obtain additional equipment as neces- sary. Experience may require new items of equipment as well as replacements. 4. Obtain reports of laboratory analysis of gas samples and advise Health Department and other Services regarding action to be taken. Make certain that samples are for- warded to Chemical Warfare Service or other laboratory as necessary. 5. Integrate reports of gas reconnaissance agents and of other protection personnel in regard to gas incidents in a report for the Commander. Assistant Gas Officers Duties before gas attack: Assist Senior Gas Officer in his several duties. Duties during gas attack: 1, Report to divisional or district control center and serve in capacity similar to that of Senior Gas Officer at main control center. 2. Report periodically to Senior Gas Offi- cer and obtain instructions from him. Duties after gas attack: Same as before. Gas Reconnaissance Agent Duties before gas attack: 1. Study the meteorological and topo- graphical feature of his area and their possi- ble relationships to gas attack. 2. Prepare painted surfaces and issue them to each sector post when ordered to do so by the Senior Gas Officer, and maintain them following distribution. 3. Acquaint himself with the air-raid war- dens in the area and, upon their request, provide technical assistance to them in the instruction of residents in preparation against gas attack. Duties during gas attack: 1. Report for duty at designated post. 2. When directed from Control Center, proceed to suspicious area, verify or disprove the presence of gas and identify any chem- ical agents with the assistance of chemical detectors. 3. Check and correct, if necessary, actions taken by air-raid wardens in regard to gas attack. 4. Make report of incident to the Control Center. Report should include a statement as to the presence or absence of gas, nature of gas, boundaries of contaminated areas, and recommendations for decontamination and evacuation. 5. Collect sample of gas for transmission to laboratory for analysis. 6. Check the posting of gas warning signs at contaminated areas. 7. Provide technical assistance to wardens on request in advising citizens in evading gas and the use of masks. 8. Assist in the control of panic. 9. Provide technical supervision of the emergency decontamination of the strategic areas as ordered from the Control Center. Duties after gas attack: 1. Obtain information as to the extent and amount of contamination in his area and make written report to Senior Gas Officer. 2. Assist Senior Gas Officer in designating contaminated areas and in determining the areas to be decontaminated, the order of their priority, and the areas to be allowed to weather. 3. Under the authority of the Senior Gas Officer advise the air-raid warden as to the desirability of removing individuals from structures within the gassed area, and supply him with technical advice as to the means by which individuals may be removed. 4-0882 P3 bu 4. Inspect decontaminated areas, build- ings, machinery, and vehicles (including chemical tests) to see that decontamination is adequate and recommend to the Senior Gas Officer the removal of restrictions. Laundry Officer Duties before gas attack: 1. Prepare plans under the supervision of the Senior Gas Officer for the collection, transportation, decontamination or destruc- tion, and redistribution of clothing. This should include protective clothing. 2. Assist the Senior Gas Officer in educat- ing the public in procedures for the home de- contamination of clothing contaminated with vapor. 3. Supervise the training of personnel and the preparation of designated laundries to handle and decontaminate clothing, including protective clothing. Duties during gas attack: None. Duties after gas attack: 1. Provide for the collection, transporta- tion, decontamination or destruction, and re- distribution of contaminated clothing. This should include protective clothing. 2. Decontamination of laundry interiors, trucks, and any other necessary areas or objects, under the supervision of the Chief of Public Works. 3. Assist civilian population in cooperation with air-raid warden in decontaminating clothing contaminated with vapor. Commander Duties before gas attack: 1. Plan with the technical assistance of the Senior Gas Officer for the changes that a gas attack would necessitate in operation of the protection services of a community. Duties during gas attack: 1. Administer and coordinate defense against gas on the basis of the technical ad- vice of the Senior Gas Officer. Duties after gas attack: 1. Administer and coordinate defense against gas on the basis of the technical ad- vice of the Senior Gas Officer and provide that such defense will be effective against future attacks. Incident Officer Duties before gas attack: 1. Under direction of the Commander ac- quaint himself with the duties and responsi- bilities of the Senior Gas Officer and Gas Reconnaissance Agents, and the special duties of all units of the Citizens Defense Corps dur- ing a gas attack. Duties during gas attack: 1. With the advice of the Gas Reconnais- sance Agent, regulate the scope of operations of the services present within the gassed area. 2. Consult with the Gas Reconnaissance Agent at the site of the incident, and assist the latter to establish “gas limits” (similar to fire lines) beyond which the public shall not approaach. Duties after gas attack: 1. As a part of his report to the Com- mander, include a statement of the operations of the units present under conditions of gas exposure and recommend necessary changes to the Commander and Senior Gas Officer. Air-Raid Warden Duties before gas attack: 1. Store and care for his personal protec- tive equipment. 2. Provide for a supply of water in sector post for emergency cleansing. 3. Advise residents of sector in regard to gas protection and use of gas masks. 4. Be familiar with gas protection plans of each household in sector. 5. Maintain a list at sector post of homes in sector to which persons needing self-aid may be admitted. Duties during gas attack: 1. Place paint detector surface, distributed by Gas Reconnaissance Agent, outside the post at sound of air-raid warning. 4 4-0882 P4 bu 2. Suspect presence of chemical agent and report suspicion to the Control Center. 3. Don gas mask and sound gas alarm if presence of gas is strongly suspected and keep people indoors until danger has passed. 4. Rope off contaminated areas as deline- ated by Gas Reconnaissance Agent. 5. Inform Gas Reconnaissance Agent re- garding the presence of people in buildings and assist in the removal of persons from buildings unsafe for occupancy. 6. With the technical assistance of a Gas Reconnaissance Agent advise citizens con- cerning the methods of evading gas and the use of a mask in the attack. 7. Direct contaminated persons to places in sector where they may administer self-aid. 8. Provide gas casualties with all possible assistance and treatment, including eye irri- gation, without exposing himself to danger- ous contamination. 9. Notify Control Center of occurrence of gas casualties. 10. On advice of Gas Reconnaissance Agent notify householders that it is safe to leave their homes after a gas attack. 11. Cleanse himself at sector post or other suitable location when necessary. Duties after gas attack: 1. Check on materials available for protec- tion against further attacks and obtain neces- sary replacements. 2. Assist Laundry Officer in the collection of contaminated clothing and its distribution after decontamination, and in the education of civilians in the handling and decontamina- tion of clothing contaminated with vapor. 3. Assist persons returning to the sector after it has been decontaminated. Police Services Duties before gas attack: 1. Store and care for his personal protec- tive equipment. Duties during gas attack: 1. Police contaminated areas. 2. Assist in removing persons from areas designated by Commander on recommenda- tion of Senior Gas Officer. Duties after gas attack: 1. Police contaminated areas. 2. Assist in removing persons from areas designated by Commander on recommenda- tion of Senior Gas Officer. 3. Assist in the reoccupation of decontami- nated areas. Fire Services Duties before gas attack: 1. Store and care for his personal protec- tive equipment. Duties during gas attack: 1. Provide self-protection consistent with minimal interruption in fire defense. 2. Protect fire-fighting equipment against contamination. 3. Send contaminated vehicles and equip- ment vitally needed during the gas attack to vehicle decontamination facilities under supervision of public works. 4. Perform self-cleansing at cleansing sta- tions or elsewhere when necessary. Duties after gas attack: 1. Provide personnel and equipment for removing liquid contamination with water on request of Commander. 2. Check on materials and equipment avail- able for protection against further attacks and obtain' necessary replacements. Emergency Medical Service Duties before gas attack: 1. Plan with assistance of Senior Gas Offi- cer for the establishment of gas -cleansing stations for cleansing gassed patients with other injuries and for cleansing of civilian protection personnel. Each hospital of 150 beds or more should be provided with a cleansing station. Cleansing stations should be available in the ratio of one per 50,000 population and should be located at smaller hospitals or casualty stations where 150-bed hospitals are not available in this ratio. 2. Recruit, train, and assign personnel to gas cleansing stations for cleansing services. 3. Provide instruction, in cooperation with 5 4-0882 P5 bu the Senior Gas Officer, for general public and civilian protection personnel in self-protec- tion and self-cleansing (Operations Letter 46). 4. Provide for instruction of physicians in diagnosis and treatment of chemical casual- ties. 5. Assist hospitals in planning for han- dling of gas casualties. 6. Assure adequate distribution of protec- tive clothing and gas masks and other pro- tective equipment to members of mobile medical teams and train personnel in their use. 7. Make provision for training drivers of ambulances and sitting case cars in protection of their equipment against liquid-gas contam- ination; inform them of arrangements for vehicle decontamination by Emergency Pub- lic Works Service. 8. Arrange for the protection from con- tamination of the equipment used to trans- port contaminated casualties insofar as it is possible. Duties during gas attack: 1. Upon advice of the Senior Gas Officer and under the orders of the Commander, man the gas cleansing stations. 2. Advise other services of the U. S. Citi- zens Defense Corps in regard to first-aid cleansing of their personnel. 3. Assign a mobile medical team to gas cleansing stations for first aid. Duties after gas attack: 1. Evaluate the effectiveness of the cleans- ing procedures which have been used. 2. Provide follow-up treatment of patients. 3. Prepare inventory of protective equip- ment available for use in future attacks and obtain additional equipment as necessary. 4. Cleanse bodies of the dead to facilitate identification. Local Health Department Duties before gas attack: 1. Provide for analyses for war gases in samples of food and water. These tests may be performed in a local health department if laboratory facilities are adequate. In such case it is desirable to utilize the same labora- tory facilities for the analysis for war gases of air and other materials. Where labora- tory facilities other than those of the local health department are more suitable for use in the analysis of war gases, arrangements should be made by the local health department for the analysis of samples of water and food. 2. Advise the Senior Gas Officer regarding the nature of instructions to the public con- cerning precautions to be taken in the event of water-supply contamination. Such in- structions are to be promulgated by the health officer. 3. Cooperate with waterworks officials in planning for the protection and decontamina- tion of the water supply. Duties during gas attack: 1. Collect samples of food and water for laboratory analysis if contamination is sus- pected. 2. Inform the public regarding contamina- tion of food and water supplies, including recommendations in regard to self-protection. Duties after gas attack: 1. Decontaminate, destroy, or otherwise provide for the handling and disposal of con- taminated food supplies. 2. Assist the waterworks-in the treatment of contaminated water supplies. 3. Advise the Senior Gas Officer in regard to the safety of the public water and food supplies and inform the public regarding con- tamination of such supplies, and methods of dealing with it. 4. Obtain reports of analyses of samples of water or food and take appropriate action. Save specimens of contaminated water and food for transmission whenever necessary to a Chemical Warfare Service or other labora- tory, by the Senior Gas Officer. Public Works Duties before gas attack: 1. Organize decontamination squads. 2. Arrange for provision of decontaminat- ing equipment and materials and for their storage and issue. 4-0882 P6 bu 3. Designate suitable filling stations and garages for decontamination of vehicles. Personnel of designated facilities may be en- rolled in the decontamination service. 4. With advice of Senior Gas Officer train and instruct decontamination service per- sonnel. Duties during gas attack: 1. Perform emergency decontamination of critical facilities (e. g., hospitals), emergency vehicles (e. g., ambulances), areas where res- cue is required, and vital machinery, accord- ing to priority as assigned by the Commander upon recommendation of the Senior Gas Officer. Duties after gas attack: 1. Decontaminate streets, buildings, areas, machinery, and vehicles in the order of pri- ority assigned by the Commander, upon recommendation of the Senior Gas Officer. Public Utilities (Including Public Transportation Services) Duties before gas attack: 1. In consultation with Senior Gas Officer arrange for personal and collective protection of personnel required to operate vital facili- ties such as switchboards, power plants, pumping stations, and control centers. Duties during gas attack: 1. Perform emergency decontamination of areas and objects whenever necessary to maintain or restore service. Duties after gas attack: 1. Decontaminate public transport ve- hicles, equipment, and gassed areas in which utilities are to be repaired. Transportation Services (Including Drivers) Duties before gas attack: 1. Store and care for his personal protec- tive equipment. Duties during gas attack: 1. Protect interior of vehicles and drivers against contamination insofar as possible. 2. Be on alert for contamination of vehicles and deliver contaminated vehicles which are immediately necessary to designated vehicle- decontamination facilities operated under su- pervision of public works. Duties after gas attack: 1. Arrange return of vehicles after decon- tamination. Emergency Welfare Services Provide emergency food and housing for persons removed from contaminated areas. (This will not involve technical knowledge of chemical agents.) 4-0882 P7 nobu-flnal OFFICE OF CIVILIAN DEFENSE WASHINGTON. D. C. 2 PAGES Issued: January 20,194S. Effective: Immediately. OPERATIONS LETTER NO. 106 To: Regional Directors. FROM; James M. Landis, Director. Subject : Care and Distribution of Gas Masks. Special Distribution Instructions : State and local Defense Councils for the special atten- tion of States and communities to which gas masks have been allocated. Adult noncombatant masks are now being shipped from manufacturers and U. S. Office of Civilian Defense Supply Depots to com- munities which have received allocations of masks and have returned, properly executed, OCD Form No. 501. These will be in assorted sizes as follows: 9 percent large adult, 76 percent medium adult, and 15 percent child (small adult). Additional masks amounting to 5 percent of the total number allocated are being sent with each shipment for training use. The sizes of these will be assorted as follows: 25 percent large adult, 50 percent medium adult, and 25 percent child (small adult). Valuable and critical materials are used in the manufacture of gas masks. Hence, care must be exercised in their handling, distribu- tion, and storage in order that the usefulness of the present limited supply may be pre- served as long as possible. , It is recommended that 5 percent of the masks other than those designated for train- ing purposes be held in reserve by the Local Property Officer and that broken and defec- tive masks and those with exhausted canisters be replaced from this reserve. It is recom- mended that the remainder, other than those designated for training purposes, be distrib- uted to the protective services in communi- ties, in accordance with “Regulations No. 1, Governing Loans of Equipment and Supplies to Civil Authorities” (paragraph 7c) approx- imately as follows: * Per. cent Staff (Service Chiefs, Incident Officers, Senior Gas Officers, Gas Reconnaissance Agents, Chief Technical Intelligence Officer, Water- works Officer and assistants, Health Officer and assistants. Messengers, Drivers, non- medical) 12.5 Fire Service (Regular and Auxiliary Firemen) 10.5 Police Service (Regular and Auxiliary Police- men) 18.5 Air Raid Wardens Service (Wardens, Fire Guards) . 30.0 Rescue Service 1.5 Medical Service (Member of Emergency Med- ical Field Units, Stretcher Teams, Ambulance and Sitting Case Car Drivers, Cleansing Sta- tion Personnel) 12.5 Public Works (Decontamination Personnel and other regular and emergency personnel re- quired in gassed areas). 9.0 Public Utilities (all municipal and private util- ity personnel whose services are essential for emergency repairs in gassed areas or main- tenance of operation of utilities during gas attack) 5.5 * These percentages are set forth as a rough guide in distribution. Variations may be necessary to suit local conditions. It is recommended that approximately 20 percent of the number allocated to each serv- ice be stored by that service in places readily available to it, as for example, Police Sta- tions, Fire Stations, Sector Wardens’ Posts, Hospital and Casualty Stations serving as as- sembly points for medical teams, Rescue 4-1127 bu-wp sultant who may, in turn, request aid from the Regional Director of the U. S. Office of Civilian Defense. Repair of masks is not to be attempted locally except in case of extreme necessity. Broken and defective masks or those with exhausted canisters should be collected by the Local Property Officer and returned, prefer- ably in lots of 20 or more, to the nearest U. S. Office of Civilian Defense Supply Depot listed below for repair and replacement: Salt Lake City, Utah: 341 Pierpont Avenue. Chicago, Illinois: 1750 Wrightwood Avenue. Fitchburg, Massachusetts: Willow Street. Hanover, Pennsylvania. Birmingham, Alabama: 503 South 22nd Street (Long Furniture Manufactur- ing Co.). When a Local Property Officer has masks which he wishes to return he should so notify the nearest Depot Commander who will then send shipping instructions and a Government Bill of Lading which will authorize the trans- portation of the damaged masks without expense to the locality. After use, masks should not be worn by another individual ivithout proper steriliza- tion. Instructions for sterilization are given in Office Of Civilian Defense publication, “Protection Against Gas.” In addition to formaldehyde, as recommended, certain ger- micides such as dimethyl benzyl alkyl am- monium chloride (sold under various trade names such as Roccal, Zephiran, etc.) or closely related neutral substances can be used for sterilization. Every mask must be ster- ilized by the trainee upon conclusion of the drill class and before the mask is returned to the instructor in charge. Depots, Public Works, and Public Utilities Warehouse. Storage must be in a cool, dry place and masks should be kept from contact with sunlight, oils, or corrosive liquids and vapors. This increment of masks should be held as a reserve and should not be assigned to individuals. It is important that this re- serve be decentralized as a safeguard against fire or bombing and also to permit rapid distribution in case of an emergency. The remaining 80 percent allocated to the services may be issued to individuals in the services but should not be carried by them during their daily activities. These masks should be kept at the posts where the indi- viduals will assemble during drills or enemy action. Under no circumstances should masks be assigned to individuals before they have received training in their use and care, including proper storage. The Commander of the Local U. S. Citizens Defense Corps, through his Senior Gas Offi- cer, should immediately arrange a gas mask training program for those to whom masks are to be issued. If no Senior Gas Officer has been appointed, steps should be taken to ap- point one in accordance with Operations Letters 42 and 91. Training should follow the Outline for Gas Defense A in Office of Civilian Defense publication Training Courses for Civilian Protection. Protection Against Gas, also published by the Office ol Civilian Defense, contains valuable informa- tion on training and maintenance. In this training program, the Commander and Senior Gas Officer of the Local U. S. Citizens Defense Corps should utilize the services of individuals in the community who have attended the War Department Civilian Protection Schools. If there are no qualified individuals in the community, assistance should be sought from the State Gas Con- 4-1127 bu-final OFFICE OF CIVILIAN DEFENSE WASHINGTON. D. C. 1 PAGE Issued: April 8, 1943. Effective: Immediately. OPERATIONS LETTER No. 124 (Supplement No. 4 to Operations Letter No. 42) To: Regional Directors, From: James M. Landis, Director. Subject: Gas Cleansing Stations. Special Distribution Instructions: To State and Local Defense Councils and Hospital Administrators. 1. In order to avoid confusion in use of the term '’decontamination,” it is recommended that the term be reserved for areas and objects and that hereafter the removal of vesicant liquids from persons be termed "gas cleansing.” The facilities established for this purpose will be called "gas cleansing stations.” 2. The primary purpose of these facilities is the pro- tection of hospitals and casualty stations and their staffs and patients from contamination by injured per- sons who have been exposed to vesicant agents. Con- taminated persons, including Citizens Defense Corps members, who are not disabled, are expected to cleanse themselves in nearby private homes or other local facilities. 3. In large cities in the target areas, it is recom- mended that cleansing stations be provided at or adja- cent to hospitals in the ratio of one station for 50,000 inhabitants. A station should be provided at every hospital that has 150 beds or more, and if this does not bring the number up to the recommended ratio, additional stations should be established at smaller hospitals or casualty stations. At least one station should be established in every city of 25,000 or more in the target areas. 4. Under present conditions of scarcity of mate- rials and manpower, construction of new facilities is generally not justified. Cleansing stations should be established in connection with casualty receiving hospitals by conversion of sufficient existing facili- ties to cleanse persons who are both injured and contaminated. The necessity of using available establishments and materials and avoiding requests for priorities for con- struction of new facilities cannot be emphasized too greatly. Materials such as pipe, fittings, and shower heads must be obtained in the community from avail- able stocks and from suppliers of used and reclaimed equipment. 5. The chief of Emergency Medical Service and the senior gas officer should assist hospital superin- tendents in planning their cleansing facilities. In hospitals the facilities which should prove suitable for conversion to cleansing stations, roughly in the order of preference, are hydrotherapy rooms, nurses’ or internes’ locker and shower rooms, part of the out- patient department, garages, or other separate struc- tures. In the event these are not available, facilities must be arranged in nearby schools, gymnasiums, swimming pools, shower rooms, club houses, and com- munity centers. Plans should be fully made for immediate estab- lishment and equipment of necessary gas cleansing stations in event of need. It is desirable that each large community establish without delay at least one gas cleansing station for training purposes. 6. Cleansing stations should be equipped to take care of one-third to one-half of the hourly casualty receiving capacity of the hospital to be served. The professional staff will consist of mobile medical teams assigned when the station is activated, supplemented by an additional staff of attendants to assist in undress- ing the injured, moving stretchers, caring for clothing and valuables, maintaining supplies, and dressing wounds. A detailed description of the operation of a typical gas cleansing station will be provided shortly as a Medical Division circular. 7. The local chief of Emergency Medical Service is responsible for the development of these stations. The senior gas officer of the community should act as his consultant in helping to establish these facilities. Industrial plants working on war contracts that wish to provide cleansing facilities for employees should be given aid and advice by the chief of Emergency Med- ical Service and the senior gas officer. U. S. GOVERNMENT PRINTING OFFICE °.r.18574 OFFICE OF CIVILIAN DEFENSE WASHINGTON, D. C. I PAGE Issued: May 15, 1943. Effective : Immediately. OPERATIONS LETTER No. 128 (SUPERSEDES OPERATIONS LETTER No. 46) To: Regional Directors. From: James M. Landis, Director. Subject: How to Protect Yourself Against War Gas. Special Distribution Instructions: To State and local Defense Councils and all members of the Citi- zens Defense Corps, to supersede Operations Letter No. 46. 1. Stay indoors. A tightly closed room affords protection against war gas. All windows and doors should be tightly shut, and blankets (to be soaked with water) or cardboard should be kept in readi- ness to cover and seal shattered windows. Choose a room on an upper floor if possible; most war gases are heavier than air, although they may be carried up with air currents, 2. If caught outdoors in a gas attack, get out of the area at once. Look down and shield your eyes with your arm. Do not worry about any brief vapor exposure to which you may be subjected. The danger from this source is not great. 3. Prompt action will avoid serious effects. If you know or suspect that you have gotten any of the gas on your person or clothing, do not go hunting for a casualty station or gas cleansing station and expect someone else to help you. Knock on the first door you come to, and take whatever steps are necessary. Self-aid is the quickest and safest way. 4. This is what you should do. This routine should be memorized so it will be done automatically in an emergency: (a) Remove shoes and outer clothing and drop them outside the house, in a covered can if avail- able. Do not touch this clothing again except with sticks or gas-proof gloves. Do not cling to false modesty. To enter a house with contaminated clothing endangers everyone in it. (b) Get to a bathroom, kitchen, or laundry room as fast as possible. (c) If your eyes have been exposed to liquid gas or spray, flush them immediately. Plain water out of a faucet, shower-head, canteen, or douche bag will do, but a lukewarm dilute solution of bicarbo- nate of soda (heaping tablespoonful in a quart of water) is even better, if it is handy. Let anyone nearby help you. {d) If drops of liquid blister gas have splashed the skin, you can prevent serious burns by adequate cleansing. Promptly blot up the liquid with pieces of cleansing tissue, cloth, or a handkerchief, which should be disposed of carefully in order that it can- not contaminate anyone else. Then sponge the skin briskly with laundry bleach containing sodium hypochlorite, if it is at hs .id, and rinse off under the shower or in a tub. A thorough bath with a vigor- ous lathering is the final step, which should never he omitted. Dry the skin by patting. Do not rub. Dress in whatever clean clothing you can get. If blisters develop, you should seek medical advice. (e) If your nose and throat feel irritated, snuff and gargle with a dilute solution of bicarbonate of soda. If your chest feels heavy and oppressed, if you have any trouble breathing, or if smoking becomes distasteful, lie down immediately and stay perfectly still until you can be taken to a doctor. Do this even if you feel fine otherwise. 5. Remember: Cleanse yourself quickly and calmly. Follow the instructions of your air-raid warden. O. S. GOVERNMENT OFFICE 529791