AD/A-003 827

A REVI-EW OF THE TOXICOLOGY OF COLOREDCHEMICAL SMOKES AND COLORED SMOKE DYES

Edmund J. Owens, ec al

Edgewood ArsenalAberdeen Proving Gruund, Maryland

December 1974

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EB-TR-74064 I_^___/A_0a4. TITLE (and Subtitle) s: rYPE OF REPORT & PERIOD COVEREDA REVIEW OF TIIE TOXICOLOGY OF COLORED Technical Report

ICHEMICAL SMOKES AND COLORED SMOKE DYES 19666. PERFORMING ORG. REPORT NUMBER

7. AUTHOR(s) 8. CONTRACT OR GRANT NUMBER(s)

Edmund J. Owens and Dorothy M. Ward

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Commander, Edgewood Arsenal AREA & WORK UNIT NUMBERS

Attn: SAREA-BL-TE Project 1C522301A079Aberdeen Proving Ground, Maryland 21010

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Commander, Edgewood Arsenal December 1974Attn: SAREA-TS-R !3. NUMBER O , PAGES

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18. SUPPLEMENTARY NOTES

Toxicity Studies in Support of Research Tasks and Programs

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Colored-chemical smoke CarcinogenicityToxicity SensitizationLiter.,ure survey Inhalation

20. ABSTRACT (Continue on reverse aide If necessary and identify by block number)

This report is a review of the inhalation (total-body-exposure) studies performed by thislaboratory during 1966 with the MI 8 series of colored smokes. The acute toxicities of the smokes,the times to death, and the gross signs are compared. A literature survey and toxicologicalevaluation of the various dyes in the violet, green, and red smoke mixtures are included. Studiesnecessary for deliniion of the hazards incident to the use of the dye components in manufacturingand military operations as well as knowledge gaps are described.

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PREFACE

The work described in this report was authorized under Task IC522301A079, Non-Defense MedicalAspects of Chemical Agents, Toxicity Studies in Suppoit of Research Tasks and Programs. All phases of theinvestigations described herein and conducted in this laboratozy were conducted during 1966.

In conducting the research described in tlhs report, the investigators adhered to the "Guide for the Careand Use of Laboratory Animals," as promulgated by the Committee on Revision of the Guide for LaboratoryAnimals Facilities and Care of the Institute of Laboratory Aaimal Resources-National Research Council.

Reproduction of this document in whole or in part is prohibited except with permission of theCommander, Edgewood Arsenal, Attn: SAREA-TS-R, Aberdeen Proving Ground, Maryland. 21010; however,DDC aad the National Technical Information Service are authorized to reproduce the document for US Governmentpurposes.

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CONTENTSPage

1. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . 5

ii. CHEMICAL SMOKE INHALATION TOXICITY STU;IES.. ................ 5

A. Experimental ................... ......................... 5

B. Analytical ..................... ........................... 7

C. Results ..................... ............................ 8

ill. REVIEW OF TOXICITIES OF DYES USED 0• "'!iEMICAL SMOKES ..... ......... 11

A. l-Methylaminoanthraquinone . . . . . . . . . . . . . . . . . . . 1II

B. Dibenzo [b, def] chrysens-7, !4-dic) ........................... . .. 12

C. 7H-Benz [de] anthracene-7-one . .................. 16

D. 1,4-di-p-toluidinoanthraquinone . .................. 20

E. Dye Mix, Violet ....... ......... ........... . ........... 22

IV. DISCUSSION ............ .................................. 22

A. Acute Inhalation Toxicity of Chrwcal Smokes Disseminated from the M18 Grenade 22

B. Toxicity, Sensitization Prope:%.,s, and Carcinogenicity of Chemical Smoke Dyes. ..

V. C('NCLUSIONS .............. ........................... .... 24

LITERATURE CITED ................. ......................... 26

APPENDIX A - TABLES ................... ....................... 28

APPENDIX B - SPECIFICATIONS FOR DYE IN RED SMOKE .... ........... ... 34

APPENDIX C - SPECIFICATfON FOR DYE IN YELLOW SMOKE ........ ......... * 1

APPENDIX D -SPECIFICATIONS FOR DYE USED IN YELLOW AND GREEN SMOKES '49

APPENDIX E - SPECIFICATIONS FOR DYE USED IN GREEN SMOKE ... ....... 57

APPENDIX F - SPECIFICATIONS FOR DYE USED IN VIOLET SMOKE ........ 64

DISTRIBUTION LIST ................. ......................... 72

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A REVIEW 3F THE TOXICOLOGY OF COLORPD CHEMICALSMOKES AND COLORED SMOKE DYES

I. INTRODUCTION.

At the present time there are four standard colored signaling smokes. red. yellow, green, and violet.Operationally, they can be used to identify friendly units, to control the laying and lifting of artillery, mortar, andsmall arms fire, to identify targets, and to coordinate the fire and maneuver of combat arms engaged in local assaultoperatiens. Four characteristics of signaling smokes determine their value for military use. color, visibility, duration,and volume. In addition, the smokes must be nontoxic in ordinary field concentrations.1

Signaling smokes are produced by volatiliiing and condensing a mixture containing an organic dye. Of thedyes tested, the most satisfactory are azo, anthraquinone, azine, or diphenylinethane compounds. The filling for acolored-smoke munition is essentially a pyrotechnic mixture of fuel and a dye, with a cooling agent sometimesadded to prevent excessive decomposition of the dye. The heat priduced by the fuel volatilizes the dye which thenc-ondenses outside the munition to form the colored smoke. The fuel is made up of a mixture of an oxidizing agent,such as potassiuml chlorate, and a combustible material, such as sulfur or sugar. The burning time can be regulated byadjusting the proportions of oxidant and combustible material, and by the use of coolants such as sodiumbicarbonate.

1

Eri.h grenade contains a startei mixture and a colored-smoke mixture. Table I gives the ingredients, andthe percentare of each used in currently standard color mixtures and in the starter mixture for the M 18 grenade. Thestarter mixturt. is the same for eath color. Other colored smoke grenades have approximately the same compositionas the M 18.1

The operational use of signaling smu,.ý! can be expected to result in single and repeated inhalationexposures to low, moderate, and high concentrations of the disseminates. In addition, the materials maycontaminate soil, foliage, equipment, or vehicles, and may contact the skin, be rubbed into the eyes, or ingested iftransferred to rations. In most cases personnel will be exposed only occasionally, but in certain instances, i.e.,training exercises, drop-zone and helicopter-operations training, and field testing, personnel may be challengedrepeatedly by several routes. It is the purpose of this review to evaluate the hazard of the colored smokes tounprotected personnel exposed acutely or repeatedly.

II. CHEMICAL SMOKE INHALATION TOXICITY STUDIES.

A. Experimental.

In 1966 and 1967 the Toxicology Department, Medical Research Laboratory,* performed acuteinhalation studies for the Weapons Development and Engineering Laboratory of red, green, and violet smokesdisseminated from M18 munitions.** The work .ompares the toxicities of the standard smokes with M18 prototypegrenades .ontaining sodium picrate pyrutechnic fuels. Yellow smoke was not studied because in preliminary tests itproduced an unstable aerosol within the test .hambtr which resulted in rapid .oagulation of the smoke parthles andsubsequent fallout of the cloud.

The red, green, and violet smokes were tested in the monkey, dog, goat, swine, rabbit, rat, and guinea pig.The particles in these disseminates had an average mass median diameter (MMD) of 1.0 micron over concentrationranges of from 1450 tu 17,946 mg/cu m. Except for settling, the smoke clouds remained relatively stable (noparticle growth through coagulatirei) for exposure periods of 10 to 240 minutes.

Now Toxicology Dihision, Biomedical Laboratory.** Unpublished data. Toxicology Department, Medical Research Laboratory, Edgewood Arsenal, Maryland.

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All tests were conducted in a 20,000-4iter test chamber that was (merated statically during testing. Theexposure concentrations were maintained by firing grenades sequentially throughout each exposure period.Depending on the desired Ct.* from I to 12 grenades were used.

The rats and guinea pugs were housed in compaitmented cages during exposure; the monkeys were cagedseparately: and the rabbits were penned in groups of six. Dogs, swine, and goats were not caged or restrained.

All animals tested were observed for toxiz signs for 30 days postexposure.

B. Analytical.

1. Red Dye Mix.

The compound was analyzed in both the visible and ultraviolet regions. The solvent used in bothprocedures was absolute ethanol. The visible wavelength was 460 mp The ultraviolet wavelength was 312 nip.

A sample of the compound was collected after dissemination fromi an M%18 grenade and analyzed forspectral changes due to thermal decomposition. The spectra (before and after dissemination) showed no shift ofpeak locations Therefore. tile ultraviolet method of analysis was used for the entire program of study.

2. Violet Dye Mix.

The violet (lye mixture must be analyzed from the collected product of the grenade dissemination. Whenthe grenade mixture (before fir, ng) is analyzed in either the visible or ultraviolet regions, the following formationwas found: the visible region gave two peaks; one at a wavelength of 458 nip and the other at 486 mp. Theultraviolet spectra gave a peak at 248 nip.

Whc.' the mixiure was fired and disseminated from a grenade, it was found that the compound underwenta chemical change and gave a completely different set of spectra. The visible peaks now ai,peared at wavelengths of548 rip and 588 in,. The ultraviolet spectra showed peaks at 24,4 nip and 304 mnp. With further study of spectralshifts it was found that the major component (l,4-diamino-2,3.dihydroanthroquinone) underwent the largestspectral shift. "I he visible peaks were again found at 458 trip and 486 mnp. The ultiaviolet spectra gave onw intensepeak at a wavelength of 250 nip. With chemical oxidation, the spectral shift could be followed, but not completed.Since the thermal temperature of the grenade gave the oxidation wanted, tile collected and dissolved disseminationproduct was used to give standards for the analytical procedure. An ultraviolet wavelength of 304 mnp was used.Samples were dissolved in absolute ethanol.

3. Green Dye Mix.

The sample was dissolved in absolute ethanol and spectra obtained in both the visible and ultraviolett• regions. The visible peak appeared at 396 nip and the ultraviolet at a wavelength of 247 nip. Upon dissemination, the

green dye gave no spectral shirts. An ultraviolet wavelength o'" 47 Ing was used.

* Coneentration X time of exposure.

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C. Results.

1. Lethality.

A summary of the acute ithalation toxicities of the three 3mokes in the seven species tested is presented intable 2. The LCt 50 values shown represent a Bliss analysis of the combined mortality responses of the total numberof animals of all species exposed to the individual colors.

Table 2. Acute Inhalation Toxicities of Red, Green, and Violet Smokes Disseminated from M 18 (roenade

Smoke Ranges LCt5O

Concentration Exposure time (combined response of all species)

mg/cu m minutes mg min/cu m

Red 2753-17946 10-240 647, 470 (568, 611-737, 265)* 2.96

Green 3346-13085 18-112 319, 447 (296, 564-344,095) 5.50

Violet 1344. 7830 8.142 211, 205 (182, 107-244,952) 2.20

* Numbers in parentheses arc 95% confidence limits.

17he times to death of all species tested are shown in table 3.

The details of the inhalation testing in all species exposed to the three colored smokes are shown in tables

A-I, A-2, and A-3, appendix A.

2. Postexposure Observation.

During exposure, close observations of the animals were not possible due to the density of the smokeclouds. ','•,ting at the time animals were removed from the chamber, observations were recorded in fractions of anhour until the pattern of signs had stabilized, then daiiy over the next 30 days.

The frequency, onset, and duration of toxic signs seen in the animals exposed to red, green, and violet

smoke are described below and tabulated in table 4.

a. Red Smoke.

Immediately after exposur,,,, all animals showed signs of upper respiratory tract irritation, much like theeffects produced by dust exposures. All species salivated. Gagging was seen in the dog, swine, goat, and monkey asthe animals attempted to remove the dusts deposited in the upper respiratory trazt. Dogs, goats, monkey, and swineregurgitated a very thick, red mucus and their urine was dark red for 24 hours after exposure. Labored breathing,seen in all species, lasted 7 days. The swine and goat were the most resistant of the seven species tested. Most of thedeaths occurred in the first 24 hours (82%, all species cumulated); by 14 days, 97.4% of the deaths had occurred.

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b. Greer. Smoke.

All animnals exposed to the green smoke were initially affected by respiratory impairment followed bygeneralized weakness, dyspnea, and prostration. Prostration lasted as long as 96 hours in the dog; oth-r speciesgenerally recovered in 2 to 24 ,ours. Diaphragnmatic breathing lasted for as long as 21 days pos!exposure in the dogCnlred saliva or urine was not observed in any species. Of the seven species tested, the goat and swine were themnost resistant (had the highest LDS0's). Most deaths occurred in less than 24 hours, and by 7 days 98.3% (all speciesSumulated) of the deaths had occurred.

c. Violet Smoke.

In general, the signs caused by exposures to violet smoke mimicked those seen in tests with red and greensmokes. All animals showed most of the following signs: respiratory difficulty, gagging, vomiting, wheezing,gem..:alized weakness, ataxia, and prostiation. Prostration was noted in all species for I to 4 hours; after the animalswere able to stand, they remained weak and lethargic for at least 24 hours. Colored saliva or urine was not observedin any species. Most deaths occurred within the first week after exposure.

I11. REVIEW OF TOXICITIES OF DYES USED IN CHEMICAL SMOKES.

A. l-Methylaininoanthmquinone.

H _{CH 3I N

This dye crmprises 40% of the formulation of the red smoke grenade. In this grenade,1 -methylaminoanthraquinone is the only dye used. In the violet smoke grenade, 80 parts of1,4.diamino-2,3-dihydroanthraquincone are blended with 20 parts of Iniethylaminoanthraquinone to form the colormixture. This mixture comprises 42% of the violet grenade formulation. The military specification is furnished inappendix B.

1. Toxicology.

a. Local Effects.

This dye causes skin irritation and sensitization. that is, its acti,.n on the skin may be delayed b) 2 weeksor so and may cause the individual to become more sensitive to it on repeated exposures.*

9 b. Systemic Toxicity.

By 'he oral and inhalation routes, l.methylaminoanthraquinone is reported as having slight systemictoxicity when administered acutely, and slight local and systemic coxicity when given chronically.

Urpublished data. US Army Environmental Hygiene Agency, Edgewood Arsenal, Marylaaid. 9

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The US Naval Ordnance Laboratory, as cited by Parent,2 assigns a toxicity rating of "1." as defined bySax,3 to 1-niethylarninoanthraquinone when inhaled or swallowed. Rating I is defined as a slight toxicity, meaningthat any effects are temporary and disappear following termination of exposure wit) or without medical treatment.

c, Carcinogenicity.

On the basis of its structure, this dye may be a potential liver carcinogen. The carcinogenicity of theanthraquinone par, of the molectýle has been reported by Japanese investigators, but confirmatory reports have notbeen forthcoming. The carcinogen most closely related to this compound is i-aminoanthracene, which would not beformed from this compound in the body.*

In 1968 Griswold et al.4 evaluated the carcinogenicity of l-methylaminoanthraquinone using as a criterionthe exquisite sensitivity of the m, minary gland of female rats to certain carcinogens. Ten doses of 500 nag/rat, whichwas established as the maximally tolerated dose (hTD),5 were given 3 days apart to nineteen 40-day-old female ratsthrough an intragastric tube. A group of 40 positive controls was given a single dose of 18 nig of DMBA(7,12-dimtehylbenz[a] anthracene) as a check on the constancy of responsiveness of the animals. Another group of140 controls** was giver, only the sesame oil vehicle.

The animals were observed for 9 months to maximize the sensitivity of the test with respect to mainmarytumor formation and to discover lesions in other sites.

Eighte.en of the rats were ,. topsied. Grossly apparent lesions were recorded. The pituitary and adrenalglands, kidneys, spleen, and liver were weighed. Any diseased tissues as well as mammary tissue, intestinal tract,pituitary, liver ovaries, and adrenals were fixed in 10% formalin and processed for histologic examination.Representative portions of other viscera were fixed for later examination if indicated.

The results are shown in table 5. One rat died within 45 days, which wis shortly after termination of theadministration of the compound, andwhich reflects toxicityresultinS irmm the treatment. The survivors at the end ofthe experiment reveal the chronic effects, and 14 of the 19 rats survived the 9-month period.

From the data shown in table 5, Griswold ot al.4 concluded that 1-methylamninoanthraquinone had littletoxicity and no carcinogencity. However, a tubular adenocarcinoma of the kidney was seen in one rat given thiscompound and was not seen in a group of controls given only the sesame oil vehicle.

B. Dibenzo [b, def] chrypene-7,14-dione.

0

* Unpublished pri'ite communication. Alfred Tatyrek, Picatinny Arsenal, and Dr. Hans Falk, Chief, Carcinogenesis StudiesBranch, National CQ.'cer Insd'ute, National Institutes of Health, Bethesda, Maryland.

* Such large groups of cortrols were used because the authors were also testing 34 other compounds.

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Various sources refer to dibenzo [b, def] chrysene-7,14-dlone as the following:

a. Indantnrene Golden Yellow GK

b. Dibenzo [a, h] pyrene-7,14-dione

c. " ,4,8,9-Dibenzpyrene-5,1 0-quinone

This dye comprises 14% of the formulation oi the yellow smoke grenade, and benzanthrone(7-H-benz [del anthracene-7-one) comprises 24.5%. The dyes are not preb~ended before mixing with the othercomponents. The military specification is furnished in appendix C.

1. General Carcinogenetic Considerations.

No tumors were reported by Hartwell 6 in several animal experiments when dibenzo[b,-def] chrysene-7,14-dione was administered by subcutaneous injection and by the percutaneous rwtte. The details ofthese studies are shown in table 6.

Table 6. Evaluation of Carcinogenicity of Dibenzo [b, def] chrysene-7,14-dione

Animal Route Dose Effects Remarks(no. used)

Mouse (20) Subcutaneous 1.2 ml of 0.5% in oil No tumors 18 alive at 6 months.

Mouse (10) Subcutaneous 0.5 mg in sunflower No tumors 4 died. Experimentseed oil monthly lasted 170 days.

Mouse (10) Percutaneous 0.1% in sunflower No tumors All died. Experimentseed oil every lasted 3.5 months.five days.

Mouse (52) Percutaneous 0.4% in benzene No tumors 30 alive at 6 months.115 times. 10 alive at 12 months

Experiment lasted12 months.

Although this compound produced no tumors in the mouse, it is closely related to dibenzochrysene whichis a very potent carcinogen.6"8* If this latter compound should be present in quantities as small as 0.01% it wouldrepresent a considerable hazard.* Doses as small as 10 pg would be considered hazardous.*

Tatyrek 9 in 1965 stated that inasmuch as metabolic changes of quinone. to the parent hydrocarbons havenever been found, it is unlikely that metablic reduCion of dibenzo[b, def] chrysene-7,14-dione to dibenzpyrenewould result.

* Unpublished private communication. AilW e.tytrek, Piatinny Arsenal and Dr. Han. Falk, Chief, Carcinogenesis Studies Branch,National Canmr Institute, National Institutes ci Health, Bethesda, Maryiand. 9

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A literature silrvey from 1965 to the present writing did not reveal any additional information regarding ametabolic reduction of the dione compound to the carcinogenic dibenzocrrysene.

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Three manufacturers of the Indanthrene Golden Yellow have indicated that there is little possibility offormation of the carcinogenic hyarocarbon in their manufacturing process.* However, recent work (1965) by theCarcinogenesis Studies Branch, National Institutes of Health,* has revealed strong evidence of the presence of asignificant quantity (roughly estimated to be of the order of 0.1%) of dibenzochrysene contamination in twodifferent samples of specification grade Indanthrene Golden Yellow dye.

An equally important consideration with the yellow dye is the formation of dibenzpyrene upon burningof a smoke item rising compositions containing Indanthrene. Under the conditions of h-gh temperature and areducing atmosphere such as may be found in a burning smoke item it is possiblc that some of the quinone groupsof the dye may be reduced to the carcinogenic hydrocarbon. This possibility is being investigated and recent studieshave disclosed analytical evidence that such a pyrotechnic reduction does take place. Conclusive results cannot beobtained, however, until a pyrotechnic smoke item 's made from yellow dye which is entirely fiee of dibernzpyrene. 9

2. Local Carcinogenic Effects.

Salimon1 0 studied the influence rf five carcinogens and four noncarcinogens on the inflammatory processin ear tissue. The carcinogens were: 9,10-dimethyl-l,2-benzanthracene (DMBA), 1,2,5,6.dibenzanthracene,t3,4.benzpyrene,t" 3,4,8,9-dibenzpyrene (dibenzo[b, detlchrysene), and 20-methylcholanthrene.§ The fournoncarcinogens were: anthracene, phenanthrene, pyrene, and 3,4,8,9.dibenzpyrene-5,10-quinone (dibenzo[b,def] chrysene-7.14-dione).

A single application of a 1.5% solution of DMBA in oil upon the ear of rabbits did not cause inflammatorychanges visible to the naked eye, but caused marked changes in the capacity o.' that tF'-ue to react to phlogogenicagents. In the first 3 days the inflammatory reactivity increased and after the 4th and 5th days it decreased.

The hyporeactivity which developed was not accompanied by appreciable morphological changes andpersisted for a prolonged period (up to 8 months).

The decrease in the inflammatory reactivity of the ear of rabbits became apparent even after treatmentwith 0.02% and 0.12% DMRA solutions, i.e., after application of only 25 aiid 15 jug of that substonce, respectively.

The hyporeactivity arose in similar experiments 10 with the other four carcinogens in benzene (0.3%) oroil (M/1000).

* Unpublished private communications among Alfred Tatyrek, Picatinny Arsenal and personnel of Atlantic Chemical Corporatnon,General Aniline and Film Corporation, and National Aniline Division of Allied Chemical and Dye Corporation. 9

** Unpublished private communication. Alfred Tatyrek. Picatinny Arsenal, and Wr. Hans Falk, Chief, Carcinogenesis StudiesBranch, National Cancer Institute, National Institutes of Health, Bethesda, Maiyland. 9

t C. A. Subject Index name, dibenz(a, hIanthracene.

"t" Benzo(a)pyrene is C. A. Subject Index name.§ 3-Methylcholanthrcne is C. A. Subject Index name.

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Among noncarrinogenic hydrocarbons, solutions of pyrene In benzene (0.3%) were found to exert asimilar effect, whereas the following solutions had no effect: anthracene (0.3%, 0.5%), phenanthrene (0.3%) and asaturated solution of dibenzpyreneqoinone it oil.

A single :,ppl~catiott of a 50% solution of turpentine in oil under similar conditions did not produce apersistent decrease of the inflammatory reactivity.

A 1.5% solution of DMBA in oil applied 10 to 20 minutes or 3 to 5 iours after the application of the

inflammatory agent has no appreciable antipi-lorsuic acion.

Salinion 10 conclude5:

'The data discussed above show that carcinogenic hydrocarbons produce essential functional changes inthe state of tissu'es. The most important of these changes is, in our opinion, the prolonged decrease of theinflammatory reactivity. Such an effect ;ould be found under the influence of all five carcinogenih substancesinvestigated by us; other hydrocarbons (anthracene, phenanthrene and 5,10.quinone of 3,4.839.dibenzpyrene),which do not produce tumors, were inactive in the above asnect.

"The results of the experiment with pyrene warrant the conclusion that a substance which sometimescauses papillomas and decreases the inflammatory reactivity can be c!assif,,d as a 'subcarcinogen' agent, in otnerwords, represents a substance which occupies an intermediate position between absolute carcinogemc andnoncarcinogenic hydrocarbons.

"Fina!ly, we have to empi- .size oi.e more aspect regarding the above investigation: it cannot be excludedthat the decrease of the inflammatory reactivity tdking place unaer the influence of carcinogeric substances was, inactual fact, even more intensive than it appeared in our experiments. The method used by Ls enabled us to assessonly relative changes in the reactivity of the tissue in the area treated with the carcinogenic suostance, as comparedwith a symmetrical (control) area of the body. We gained, however, the impression that car,'.nogenic suibstancescause not only a marked !ocal but also, to a certain degree, a general decrease of the inflammatory reactivity all overthe body Ibis fact could be obser,''ed in experiments ia which the inflammation wes produced after a relat..vely longperiod had elapsed sincf' the carcinogenic substance had been apg-?'ed and hqd been manifest in the fact that theinflammatory process acquired the tendency to take a somewhat langticourse.

"If this prelininary conclusion is correct, the data presenteL',bove require a certain correction irs thesense that the decrease of the inflammatory reactivity under the influencu of carcinogenic hydrocarbons is o,; moreintensive and prolonged character than it appears from our experiments." 10

C. 7H-Berz [delanthiacene-7-one.

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Benzanthrone (7H-benz[de] anthracene-7-one) comprises 24.5% of the formulation of the yellow smokegrenade and dibenzotb. L." chrysene 7,14-dione comprises 14%. The military specification is furnished in append.xD.

1. Local Effects.

Benzanthrone was nonirritating when applied to both clipped intact and abraded skin of guinea pigs andallowed to remain 24 to 48 hours.1 *

Dermatitis has resulted in man from occasional contact with benzanthrone. It is said to exert aphotodynamic effect which results in the production of an actinic dermatitis and melanosis or leukoderma 12and Goldberg1 3 list benzanthrone as a cause of dermatitis in man, but only in hypersensitive individuals.

The incidence of hyperpigmentation (melanosis) in 25 employees of a dye factory is reported by Uebelinand Buess. Their study also described the skin irritanty ofrbenzanthrone postulating that the cutaneous irritation isprobably due to two substances which form at the time of the anthraquinone reduction in the d, e productionprocess. anthracene, which is undoubtedly still present in trace amount, and some nonsaturated fatty acids (likeacrylic acid) probably resulting from a transformation of glycerine. Of more interest to the authors, however, is theeffect described as thinning of the epidermis. flattening of papillary corpuscles, the edema caused by laxity of thepapillary layer and subpapillary layer, and the infiltration ut round cells into this stratum. In the superficial layer ofthe cells, just to the boundary between .he tipper third and middle third, there is a row of chromn.tophores arrangedin bands which encloses the melanin. These integumentary changes do not appear to affect t!'e general heall'i of thewurkers except that minor changes in liver function were noted. The degree of pigmentation was seen Wo varyconsiderabl) over the affected body areas with greatest intensities t oing noted around the eyes, at the neck and napeof the neck, the upper thorax, and sometimes also on the hands and forearms. The skin coloration takes on allshades from orange tu blue-black, paswing through brown. It is particularly intense in summer, in high temperatures.and after exposure to the sun. Various theories are presented to explain the creation of the pigment including thedegradation of adrenalin, hormonal inbalin,.es that are believed to be of hypophysic~l origin, and the existence ofnoxious factors absorbed by way of respiration. 14

Further evidence of skin discolorations in benzanthrone workers was reported by Trivedi and Niyogi.Medical examinations were performed on 48 workers employed in a benzanthrone plant where some individualswere reported as having a blackening of the skin. Thirty percent of those examined had blackening of the skin withor without other signs and symptoms, and 14 percent had only a burning sensation, nausea, cough, etc Noabnormalities were detected in blood or urine. The range of the incubation period for blackening of skin was I to 35months and the average was 8-1/2 months. Keratosis was noted in two workers. 1 5

2. Systenic Toxicity.

Benzanthrone intoxication in humans affects the funt.:onal state of the liver and is manifested bydisturbances of the autonomic nervous system. The functional state , r the liver may be used for diagnostic purposes,especially in cases of residual effects. 16 Apparently patients suffeiing froma benzan hrone intoxication will exhibitan increase of hippuric adid and its excretion, and an increase in the total content of' protein in blood and serumalbumins if given a therapeutic dose of carbocholine, H12NC(.O)OCH 2 -CH2N(CH 3)3 .CI, which explains thedisturbance of regulatory functions of the autonomic nervous system. 17

* Unpublished data. Jacobson, K. M. Monthly Technical Progress Report on Chemical Corps Research Development Projects.Project 4-61-14.002, US Air Force. Heakth Hazardg of Military Chemicals. 31 October 1959.

17

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The effect of benzanthrone on the blood, adrenal, and liver ascorbic acid levels in adult male guinea pigswhr investigated by Pandya, Singh, and Joshi. 1 8 Bnz:nthrone and ascorbic acid were administered intraperitoneallyand orally in doses of 25 mg and 50 nmg,'xg body weight respectively. Benzanthrone alone caused a sigr'ficantdecrease in ascorbic acid levels in the bood, ad;ena!s, and liver. Supplementrtion of ascorbic acid appreciablyrestored the blood ascorfic acid Ht,WcvL.. Jrena! and h•ci ,scorbic acid levels were restored only to some extent.Histochemical examinatior of ascorbL. a.ld in the adrenals revealed almost simetar changes. The mortality rate dueto benzanthrone toxicity (5100 mg,'ke) was towered by 40% in nonscorbutic as tompdred to s•.urbutic guinea pigs.

Benzanthrone was tested ty Epstein eta!. 19 to determine its mutagenic effects by the dominant lethalassay in the mouse. In this series, a tal ._, I "4 test agents, including pharmaceuticals, food additives, pesticides, andorganic extracts of air and water pollutants, %%ere tested. Less than 10% of all mateiialS tested were unequivocallymutageiiic as determined directly by increased early fetal deaths per pregnancy. Additionally, about 5% of allmaterials tested yielded data whikh fell beyund control limits but which, however, require further replicationbecause of internal inconsistenJes The cdrly ft.. deaths and preimplaritation losses produced b) benzanthrone werewithin control limits, categcr.zing this ,.ompound with the 85% that faiied to produce ether unequivocal mutageniceffects or other indications of reproduutive impairment. The authors point out, however, that while the induction ofdo.iinant lethal mutations is indiative of potential geietik hazards to man, inactive agents cannot be regarded asnonmutagenic until additionally t"sted by in vivo cytogenetics and in the host-mediated ass,,.

Slutskifl 7 reported that ben,.an- .one .ould be detected in the blood of only 6 o,'42 individuals poisonedwith the dye. This shows that bcnzarnthr.nc underjt s ..hanges in the blood (or before entkring the blood). Thechemical abstract of Slutskif's work did not state -,ujps of administration or subjective symptoms.

Thirty wvhite rats were given water satirated with benzanthrone (up to 400 mg/I) for .1 months.20 Thedose corresponded to a daily dose of 20 ng'kg of body weight for man. The weight of the animals did not changewhen compared with thý weight of a control group. There was no shift in the level of cholinesterase activity orchange in the cephalin-cholesterol flo•,ulation tests. Based on these studies, the permissible conc.entration ofbenzanthrone in reservoir water was formulated. These data ate shown in table 7.

Table 7. Permissible Concentration of Benzanthrone in Reservoir Water

Concentration Effects

mg/i

0.05 Imparts noticeable yellow color to wat. r.

, 5.0 or lower Daphnia activity not disturbed.

20-50 Taste becomes noticeable

50 Odor becomes noticeable.

50-100 Inhibits the biological oxygen demand butthe inhibition does not excee" 18% and hasno effect on the practical sanitary preservationof reservoir water. 'hfcre is no noticeable effecton the ammonification and ultrafiltration processes,nor on the growth and death of the saprophyticmicroflora of the water.

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3. Carcinogenicity.

At present there appear to be conflicting opinions as to whether this material is carcinogenic. 6 .

The tests for carcinogenic action, performed by Morozenskaya, 2 1 cited by Hartwell, 6 and ashown in table 8.reveal that benzanthrone is not carcinogenic in mice given dermal or subcutaneous doses. An evaluation of the samedata by Sawicki 2 2 classed 7H-benz[dej anthracene-7-one (benzanithrone) as having carcinogenik ictivity, but he alsostated that the carcinogenicity of this type of compound needs confirmation and more thorough investigation.

Table 8. Evaluation of Carcinogenicity of Benzanthrone

Route Dose Effects Remarks

Dermal 70-75 mg total dose; 13/50 mice alive at Morozenskaya believes tumors were0.5% benzene soln used, end of 6 months, not due to benzanthrone but arose140 applications, two of 50 animals spontaneously. Compound not

developed tumors blastomogenic.(one lung, one thyroid).

Subcutaneous 10 mg total dose; 16/32 alive at 6 months. Conch .:on same as above.0.5 soln in olive oil; Two of 32 animals5 injections of 0.4 ml, developed tumors (one10-15 days apart. lung, one jaw).

Studies by Epstein, et al.23 of 107 polycyclic compounds of "known carcinogenicity" (list includedbenzanthrone**) indicate that there is littkc rclationship between carcinogenicit, and charge-transfer complexformation as measured by certain .hemical tests. A positive relation did exist between carcinogenicity andphotodynamic action as measured with paramecia. Benzanthrone, however, is lsted as a + carcinogen within a rangefrom noncarcinogens to +++ carcinogens. Examples of each category are shown in table 9.

Table 9. Examples of Noncarcinogens and Potencies of Carcinogens

Type Examples

Noncarcinogens Anthracene, phenanthrene, carbazole

Carcinogens

Low potency (+) 2-Aminoanthracene, benzan lhrone, chrysene

Moderate potency (++) Dibenz [a, h] anthracene, benzo [c] fluoranthene, 1,2,3,4.dibenzpyrene

High potency (+..+) 7-Methylbenz [a] anthracene, benzo [a] pyrene, 3-mcthylcholanthrene

*Unpublished pr. fate communication. Alfred Tatyrek, Pikatinny Arsenal, ,rd Dr. Hans Falk, Chief, Carcinogencsis StudiesBranch, National Cancer Institute, National Instititue= of Health, Bethesda, Maryland. 9

** Article does not document the "known carcinogenicity" for benzanthrone.

19

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4. Hygienic Standard.

New sanitary standards for projected industrial plants were proposed by the KHARIKOV Institute ofLabor Hygiene and Occupational Diseases of Academy of Medical Sciences of the U.S.S.R. and the Department ofLabor Hygiene of the Central Institute of Post-Graduate Medicine in 1957.

Their proposed maximal allowable concentration for benzinthrone in the air of work rooms and workshops of industrial manufacturing and production plants is 0.002 mg/liter.24

S. Proposed Military Specification.

A proposed military specification, MIL-D-50074D, for Dye Benzanthrone (Project Number 6820.0049)v'as prepared on 16 November 1970. Paragraph 5.2 (Marking) states that: "Marking shall be in accordance withMIL-STD-129. In addition, each container shall be durably and legibly marked with contrasting letters andbackground to zhow the net weight of contents and the following information:

CAUTION

CAUSES SEVERE IRRIYATION TO SOME PEOPLE. AVOID CONTACT WITH SKIN OR CLOTHING. IN CASEOF CONTACT, FLUSH WITH WATER. WASH CONTAMINATED CLOTHING BEFORE RE-USE. INDIVIDUALSSENSITIVE TO THIS PRODUCT SHOULD NOT CONTINUE TO WORK WITH IT.2 5

The results of a review of the proposed specification by DA, USAEHA, Edgewood Arsenal, Maryland wasfurnished the Commanding Officer, Edgewood Arsenal, through the Surgeon General on 18 January 1971 It wasrecommended that a statemcnt restriating the use of benzanthrone to combat situations be included in the proposedspecification since the material is d potential carcinogen. Consequently, the proponent of subject specification isadvised to substitute for benzanthrone a dye that is potentially less hazardous.2ý

D. 1,4-di-p-toluidinoanxhrahuinone.

0 NH -o -H

0N

I 2 I

20

This dye comprises 28% of the formulation of the green smoke grenade. Two other dyes, Vat Yellow 4(4%) and benzanthrone (8%), are also present in the mix. The dyes are not preblended. The military specification isfurnished in appendix E.

1. Certification for Use (FDA)2 7

a. Drugs and Cosmetics.

D and C Green No. 6 may be certified for use in drugs and cosmetics. provided the following specificationsare met:

Volatile matter (at 135 0 C), not more than 2.0%.

Sulfated ash, not more than 1.0%.

Water-soluble matter, not more than 0.3%.

Mp.*ter, insoluble in carbon tetrachloride, not more than 1.5%.

Intermediate3. not more than 0.5%.

Pure dye (as determined by titration with titanium trichloride), not less than 96.0%.

Melting point, not less than 21 00C.

b. Polyethylene Terephthalate Surgical Sutures.

D and C Green No. 6 shall conform to the following specifications and shall be free from impurities otherthan those named to the extent that such other impurities may be avoided by good manufacturing practice*

Volatile matter (at 135 0C), not more than 2.0%.

Water-soluble matter, not more than 0.3%.

Matter insoluble in carbon tetraclhloride, not more than 1.5%.

Intermediates, not more than 0.5%.

Lead (as fb), not more than 10 parts per million.

Arsenic (as As), not more than I part per million.

Pure color, not I.ss than 96.0%.

D and C Green No. 6 may be :iafely used for coloring polyethylene terephthalate surgical suture°

2. Toxdeity, Sensitization Properties, and Carcinogenicity.

A survey of all pertmnent literatare failed to reveal an) information relating to the toxicity, sensitization,or carcinogenic properties of this dye. When mixed w.th Vat Yellow 4 and benzanthrone in the Green smokeformudatiunr, the effects or the miP.ture are unknown bt the sL•ne react.on would probably be evid•.nt that resultsfrom contact or Inaldation uf the yellow dyes alone.

21

E. Dye Mi-, Violet.

0 00 NH2 NHCH3

2I 3

0 20

/

The violet dye i.ix comprises 42% of the formulation of the violet smoke grenade. No other dyes arepiesent in this formulation. The militaty spefication is furnished in appendix F.

No biolcgical data were found for the mixture. No data subsequent to 1965 were found on the diaminecompound; Tatyrek 9 states that the compound has not been tested but is expected to be relatively safe because ofstructure. A review of the biological data pertinent to the violet dye mix is shown in table A-3 of appendix I.

IV. DISCUSSION.

A. Acute Inhalation Toxicity of Chemical Smokes Disseminated from the M18 Grenade.

The results of acute inhalation testing of the red, yellow, and violet smokes indicate that thesedisseminates from M18 grenades are of a low order of toxicity. The extremely high Ct's required to produce deathsand the toxic signs exhibited by the animals after exposure arc similar to the responses caused by exposures tonontoxic dusts. Deaths wtere probably due to suffocation caused by loading of the respiratory trea with smokeparticles and the inability of the animal to clear its lungs. A comparison of the toxicities of the smokes with that ofCS (0.chlorobenzylidene malononitrile), a commonly used riot control agent, is shown in table 10

Table 10. Acute Inhalation Toxicities of Chemical Smokes and CS

Material All species LCt50 value LD5 0 ratio

Smoke/CS

mg min/cu m

Red smoke 647,000 10.6

Green smoke 320,000 5.2

Violet smoke 211,000 3.5

CS2 8 61,000

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B. Toxicity, scensitization Properties, and C.rcinogenicity of Chemical Smoke Dyes.

1. 1 -Methylaminoanthraquinone.

This dye causes skin irritation and sensitization which may be delayed 2 weeks or more and may cause theindividual to become more sensitive to it on repeated exposures. It has only slight acute and chronic toxicity,however, when administered orally or inhaled.

On the basis of structure this dye may be a potential carcinogen. The carcinogenicity of the anthraquinonepart of the molecule has been reported by Japanese investigators but has not been confirmed.

In an evaluation conducted by Griswold 4 in 1968 the dye was shown to have little toxicity and nocarcinogenicity in the breast but single lesions were seen at other sites. This did not occur in controls.

It may be concluded from these studies that I-methylaminoanthraquinone could be considered to be askin initant and sensitizer with possible carcinogenic activity.

2. Dibenzo[b, def I ehrysene-7-14.dione.

This dye was judged to be nor,.arcinogenic by Salimonl 0 in comparative studies with carcinogenic andnoncarcinogenic hydrocarbons where the inflammatory process in rabbit ear tissues was used to deteimine thec! ,ssification of the test substances.

In suLiutaneous and percutaneous studies reported by Hartwell 6 the compound produced nu tumors inthe mouse But it was pointed out that the compound is closely related to dibenzochrysene, a potent carcinogen. Ifthis latter compound should be present in quantities as 5mall as 0.01%, it would represent a considerable hazard.Doses as small as 10 pg are considered hazardous. There is a distinct pussibility that this degree of contaminationmay be present as shown in recent studies of the National Institutes of w"ealth, where 0.1% of dibenzochrysenecontamination was found in two different samples of specification grade Indandhrene Yellow Dye 3.

An equally important consideration is the formation of dibenzpyrene from burning of a smoke item usingcompositions containing Indanthrene. It is distinctly possible that some of the quinone groups of the dye may bereduced to c,,icinogenic hydrocarbons. Recmnt studies have disclosed analytical e%,idence that sui..i a pyrotechnicreduction does take place.

This dye as commernially produced may be considered to be a potential carcinogen due to contaminantsnot defined by specifications and, of more importance, may break down during thermal dispersion to Lartinogenicmaterials.

3. 7 K-Benz [del anthracene-7-one.

Dcrmatitis has resulted in man from occasional contact with benzanthrone, exerting a photodynamiceffect which results in the production of actinic dermatitis, melanosis, or leukoderma.

Benzanthrone intoxication in humans affects the functional state of the liver and is manifested bydisturbances of the autonomic nervous system.

There are conflicting opinions as to whether benzanthrune is catcinogeniQ. Hartwell 6 and Morozx'nskaya 2 lreport negative results in mice tested dermaily and subcutaneously while Epstein 2 3 lists benzanthrone as a knowncarcinogen of (+) potency. This designation places the .ompound in the least .,arcinugenic categor., t ut wouldseriously restrict usage, and would strengthen the argtinent to replate benzanthrone with a dye potent..Ily lesshazardous.

25 .26

23

/

At th, very best, or until evidence is made available which would refute the rating assigned the compound

by Epstein, benzanthrone should be considered a weak carcinogen.

4. 1,4-di-p-toluidinoanthraquinone.

This dye has been certified for use in drugs and c3smetics, as well as for coloring polyýdhyleneterephthalate surgical sutures. There is no information available, however, on the toxicity, sensitization propfrties,and carcinogenicity of this dye nor on any other biological effects.

5. Dye Mix, Violet.

There are no biological data available relating to mixtures of 1,4-diamino-2,3-dihydroanthraquinone and1-methylaminoanthraquinone. Based on structure alone, however, the diamino compounc. may be considered to berelatively safe. The inhalatio-n toxicity of the violet dye mix is shown in table A-3. Since 20% of the violet dye mix is1-methylaminoanthraquinene, skin contact would most probably cause similar effects to those caused by the pu.ecompound (skin irritation and sensitization). V-- same carcinogenic hazard would be present in handling the mix asfor unmixed 1-methylaminoanthraquinone.

V. CONCLUSIONS.

Ffom a review of the available data relating to the disseminated smokes and the dyes used in chemicalsmoke formulations it is apparent that many knowledge gaps exist. To adequately characterize the dyes and todefine the hazards qncident to their use in manufacturing processes and in military operations, the following studiesshould be performed.

1. Subacute and chronic inhalation studies with red, green, violet, and yellow smokes (provided stableaerosol clouds can be maintained).

2. Acute and chronic skin and eye studies and dermal sensitization with the disseminated smokeproducts.

3. Cancer studies with either the smokes or with the disseminated smoke products.

4. Reproductive (mutagenic, teratogenic, etc.) studies with either inhalation of the smokes or parenteralinjection of the disseminated smoke products.

5. Definitive chemical studies to characterize the specification dyes as well as the disseminates from theM 18 grenade.

All studies should be performed with the following materials:

a. Dye, Disperse Red

b. Dye, Vat Yellow 4

U. Dye, Benzanthrone

d. 36/64% mixture of b and c

e. Dye, Solvent Green 3

f. 70/10/20% mixture of h, c, and e

24

_-_ 7/

g. 1,4-diamnino-2 ,3-dihydroanthraquinone

h. 80/20% mixture of a and g

In addition to the above work, concurrent research should be initiated to find substitutes for DisperseRed, Vat Yellow 4, and benzanthr. -.,e. Selected candidates could then be tested tc determine their relative potenc.esand possible hazards to unprotected individu'•,

25

1)

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LITERATURE CITED

1. Technical Manual 3-215, Air Force Manual 355-7, Military Chemistry and Chemical Agents,Departments of the Army and the Air Force.1 December 1963.

2. Parent, P. A. CRDL Special Publication 4-59. Biological Effects of Colored Smoke Ingredients.September 1964. UNCLASSIFIED Report.

3. Sax, Newton I. Dangerous Prope; Iies of Industrial Materials. 3rd Edition. Reinhold PublishingCorporation. New York, Nt.w York. 1968.

4. Griswold, D. P., Jr., Casey, A. E., Weisbu-ger, E. K., and Wei.,burger, J. H. The Carcinogenicity ofMultiple Intragastric Doses of Aromatic and Heterocyclic Nit. ,, ,r Am-::. irivatives in Young Female Spragite-Dawley Rats. Cancer Research 28, 924-933, May 196F.

5. Griswold, D. P., Jr., Casey, A. E., VWisburger, E. K., eisbargr, 1. H., anud Scliabel, •. M. Jr.On the Carcinogenicity of a Single Intragastric Dose of Hydrocarbons, N.ti osamines. Arormiatic Amines, Dyes,Coumarins, and Miscellaneous Chemicals in Female Spiague-Dawley Rats. Cancer Research 26, 621 (1966).

6. Hartwell J. L. Survey ef Compounds Which Have Been Tested for Carcinogenic Activity.Public Health Service Publication No. 149. 2d Edition. 1951, and Slbuik, P., and H7,;,welI, J. L. Supplement 1.1957. US Government Printing Office, Washington, DC.

-7 Clayson, David B. Chemical Carcinogenesis. Little, Brown and Company, Dobton, Massachusetts.1962.

8. Haddow, A., and Kon, G. A.R. Chemistry of Carcinogenic Compounds. British MedicalBulletin 4, 314 (1947).

9. Tatyrek, Alfred F. Picatinny Arsenal Technical Memorandum 1674. The Health Hazards ofCertain Smoke Dyes in Current Use. September 1965. UNCLASSIFIED Report.

10. Salimon, L. S. The Influence of Carcinogenic Aromatic Hydrocarbons Upon the Inflammatoryt'eactivity of Rabbit Ear Tissues. Voprosy Onkologii 5 (7), 11-18 (1961). (English translation).

11. Weeks, M. H., and Yevich, P. P. CWL Technical Memorandum 26-12. The Toxicity ofCombustion Products of Pyrotechnics. May 1960. UNCLASSIFIED Report.

12. Huepei, W. C. Occupational Tumors and Allied Diseases. C. C. Thomas, Springfield, Illinois.1942.

13. Lanza, A., and Goldberg, J. Industrial Hygiene. Oxford University Press, New York, NewYork. 1939.

14. Uebelin, F., and Buess, H. Melanodermatitis Due to Benzanthrone; Preliminary Note. Arch.Maladies Profess. 12 (16), 655.657 (1951).

15. Trivedi, D. H., and Niyogi, A. K. Benzanthrone Hazard in Dye Factory. Indian Journal ofIndustrial Medicine, 14 (1), 13-22 (1968).

16. Slutskif, L. I., Gigiena Truda i Professional. Zabolevaniya 1 (4), 40-46 (1957); Chem. Abstr. 52,2262f (1958).

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17. Slutskif, L. I. Uchenye Zapiski Ukr. Nauch. -lssledovatel. Inst. Gigieny Truda i Profzabolevanii27, 78.79 (1958); Chum. Abstr. 54, 13435b (1960).

18. Pandya, K. P., Singh, G. B., and Joshi, N. C. Effect of Bezanthrone on the Body Level ofAscorbic Acid in Guinea Pigs. Industrial Toxicology Research Centre, Lucknow, U.P., India. Acta pharmacol.et toxicol. 28,499-506 (1970).

19. Epstein, S. S., Arnold, E., Andrea, J., Bass, W., and Bishop, Y. Detection of Chemical Mutagens

by the Dominant Lethal Assay in the Mouse. Toxicol. Appl. Pharmacol. 23, 288-325 (1972).

20. Loshakov, Yu. T. Vop. Kommunal. Gig. 6, 33-36 (1966); Chem. Abstr. 68, 98504u (1968).

21. Morozenskaya, L. Arch. Sci. Biol. (U.S.S.R.) 60 (3), 100-101 (1940).

22. Sawicki, E., Airborne Carcinogens and Allied Compounds. Arch. Environ. Health, 14,45 (1967).

23. Epstein, S. S., Bulon, I., Kaplan, J., Small, M., and Mantel, N. Charge-Transfer ComplexFormation, Carcinogenicity and Photodynamic Activity in Polycyclic Compounds. Nature 204, 750.754 (1964).

24. a. U.S. SourceU.S.S.R. Literature on Air Pollution and Related Occupational Diseases 2, 37-47 (1960) (A

Survey by B. S. Levine, Ph.D. - Distributed by: United States Department of Commerce, Office of TechnicalServices, Washington 25, D.C.)

b. Ru3sian Literature Citation:Proposed New Sanitary Staudards for Projected Industrial Plants (To replace NO10-54), N. S. Isaev,

Z. B. Smelyanskii, L. K. Kotsyanov, and E. V. Khukhrin Gigiena Truda i Professional nyc Zabolevaniya, 1 (4),3-11, (1957).

25. (Proposed) Military Specification Dye Benzanthrone MIL.D-50074D. (Project Number 6820-0049), dated 16 November 1970. Superseding MIL-D-0050074C (MU), 9 May 1968, MILD-50074B, I July 1963.

26. USAEHA-MT (10 December 1970), 2nd Ind, Subject: Proposed Military SpecificationMIL.D-50074D, Dye Benzanthrone (Project Number 6820-0049), Thru: The Surgeon General, Attn: MERDD-SC,Department -'"the Army, Washington, D.C. 20315, To: Commending Officer, Edgewood Arsenal, Attn:SMUEA-QAES, Edgewood Arsenal, Maryland 21010.

27. Code of Federal Regulations. Title 21, Food and Drugs, Parts I to 119. Revised as of January 1,1971. Chapter 1. Food and Drug Administration. Part 8. Color Additives. Subpart F. Listing of ColorAdditive for Drug Use Subject to Certification. 8.4070 D&C Green No. 6.

28. Letter, Research Laboratories, Human Estimates Committee, to Dir.ctor, Research Laboratories.25 August 1966. Subject: RL Human Estimates; LCt50's on DM, CS and CS.DM Combinations andRelationship of CS-DM Concentrations with Percentage of Population Incapacitated and Time to Incapacitation.

27

/

APPENDIX A

TABLES

N- -- - q% ) o

M M n C4)' 0W('v 0% %0 SC,In'1% % W) cOWa, Snn-f cc

M' N 1-0C -t ,-0; cV0V 0 nc

~eU-)'. %4)%C0' 0 C

fn ON 0 M Sf;!-Olv C0I c!~ u't'.-C4 , 0 C

w' l c4 te en) Go 0 - CI Sn - C4) C)(4(IC

en VI . 4v0 % n %

.0.0

en0 0% e~n 'O0% 00 n WC)S ) tln C NO '-w 0%00'. %

.- 0 0 % ; n e

0

Ch W)W n 0e

00 O00 N (7% - %0 n00' %0' t, 000m 0% q m n w .SO 00 Wo , co 00 00' N m d* t- C,4 en -W *C') t- .C4 t n0t-

0 0

en tn 00. CP n 0 e nI

m m 00

-0 -co %. .o'00 - 00 C') 00 - 0

SC'4

o~~~~~~ Ct N e000 0 (0,inrC'0 0 ' 0 4- 0 ( S/ O 0 0. (C-4 C4

0

o )C 0 000 (D 0000000 o .4)00oco0 0-100%S W00In nO'0 00N - - - - - - - - - -- - - (4 --SnSC4 0SnC4'C4 u r 0.n" SC00 J5 ') )

00

rn %n N 0 4a ,0 mI omk 1 nW W 0m t )t 4c

d

:3 Sn0 000 0 00WOC000 .00000 ic.,00O 0000500kn O0 Wl0 vv %n %n %t CDt 0SfCt 00v 00 ( 0 o" t' 0% v a% 00*0 It a C4 nC% l0%40 00

C\ .5 00 %0co'.o- N1000 %D 00 comý C qv00. N -W .. 4.4 T 0054C00 In C%\00 - 00 en 0N -00 - 0 N ee ,e ,-- e %n en -. 0C"0 t cm n% 0. 0 cn

S0C 0r -% m t- we - -to e - 0r n0 ý1 r- t nl

00 0 c

28

le 00C8Cs W)t ~ 0 00-' en C-8 N 0 0% en 00 c- tn m c0 t n% o t n r-rr t 7 n D% V80 en~C~0 C,4 C 'r800!-.r

00m %- 0 t C4 W)It %~0 W) 00 r- t- v%0- w 0%

U m rt At nW -0 ) t-

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%D N-0%o a-0 en---~00 '00'00%D MN'00.0Z %0oor-6ý%A l o -o re. - Cý M N 0%O0C) w "0% %0 t-;%010

C. % 0n ellC~ 1vC3%0 0%I 00 D 0 i %De --tIlC Co0 . %D t t- 0 r

CD CD. 0%0 Ln C) (n W) Q !De n% 0% e1* 00%C-

%.0%CCD * C'C0%D0 1 0% - %D4%QO' 0%VCOD. 0 'C-r'0 0-en W'J 0(' a% M W) 00 0% e.0n )0O0 0% M W) 00ta

C- k-8 WC 00 en0 C~C-~ O 0

0

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0 000ON0 a, 0

to .o %n o 0

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eq N - - t, t

%0 0 Ii% -iI l I m

t-. CD W) 0 t-o C 0000%D .0 0 C4I

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Appendix A 29

0 N q

wiC0'0 0% 0 0 M -O n

Ch 0%9 W 4- 0A f nr D0co t n9 0 ,t N le n W%0

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Appendix A 30

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Appendix A 31

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Appendx A 3

APPENDIX B

SPECIFICATION FOR DYE .N RED SMOKE

MIL-D-3284C2. Juno 1971SUPERSEDINGMIL-D-003284B(MU)29 May 1968MIL-D-3284A15 July 1963

MILITARY SPECIFICATION

DYE, DISPERSE RED 9

This specification is mandatory for use by all De-partments and Agencies of the Department of Defense.

1. SCOPE

1.1 This specification covers Disperse Red 9 dye, chemically knownas 1-methylaminoanthraquinone.

2. APPLICABLE DOCUMENTS

2.1 Government documents. The following documents of the issue ineffect on date of invitation for bids or request for proposal form apart of this specification to the extent specified herein.

SPECIFICATIONS

FEDERAL

L-P-378 - Plastic Sheet and Film (Polyolefin).RR-S-366 - Sieve, Test.

MILITARY

MII-D-3464 - Desiccants, Activated, Bagged, Packaging Useand Static Dehumidification.

Fsc 6820

34

/

MIL-D-3284C

STANDARDS

MILITARY

MIL-STD-105 - Sampling Procedures and Tables for Inspection byAttributes.

MIL-STD-129 - Marking for Shipment and Storage.MIL-STD- 1 4T -- Palletized and Containerized Unit Loads, 4o" x 4811

Pallets, Skids, Runners, or Pallet-Type Base.

(Copies of specifications, standards, drawings, and publicationsrequired by suppliers in connection with specific procurement functionsshould be obtained from the procuring activity oro as directed by thecontracting officer.)

2.2 Other publications. The following documents form a part of thisspecification to the extent specified herein. Unless otherwise indi-cated, the issue in effect on date of invitation for bids or requestfor proposal shall apply.

UNIFORM FREIGHT CLASSIFICATION RULES

(Application for copies shoulc. be addressed to the Uniform Classifica-tion Committee, 202 Union Station, Chicago, Illinois 60606.)

NATIONAL MOTOR FREIGHT CLASSIFICATION RULES

(Application for copies should be addressed to the American TruckingAssociation, Inc., Attention: Tariff Order Section, 1616 P Street, N.W.,Washington, D. C. 20036.)

AMERICAN SOCIETY FOR TESTING AND MATERIALS (ASTM) STANDARDS

DJ1393-66 - Reagent Water.D1895-65T - Apparent Density, Bulk Factor, and Pourability of

Plastic Materials.

(Application for copies should be addressed to the American Society forTesting and Materials, 1916 Race Street, Philadelphia, Pennsylvania 19103.)

(Technical society and technical association specifications and standardsare generally available for reference from libraries. They are also dis-tributed among technical groups and using ?ederal agencies.)

3. REQUIREMENTS

3.1 Chemical and physical characteristics. Disperse Red 9 dye shallconform to the chemical and physical characteristics of table I whentested as specified therein.

Appendix B 35

1

MIL-D-3284C

Table I. Chemical and physical characteristics

: Ch&racteristic Requirement: Testparagraph

: Purity, percent by weight, minimum : 90 : 4.2.4.1: Volatile matter, percent by weight, maxi-:: mum : 2.5 : 4.2.4.2

Particle size, percent by weight passing:: . 4.2.4.3: 260 microns (No. 60), minimum : 97* 149 microns (No. 100), minimum : 90

74 microns (No. 200), minimum : 70: Apparent density, grams per milliliter: (dry basis) : 0.35 + 0.15: 4.2.4.4

4. QUALITY ASSURANCE PROVISIONS

4.1 Responsibility foi inspection. Unless otherwise specified in thecontract or purchase order, the supplier is responsible for the perform-ance of all inspection requirements as specified herein. Except asotherwise specified in the contract or order, the supplier may use hisown or any other facilities suitable for the performance of the inspec-tion requirements specified herein, unless disapproved by the Govern-ment. The Government reserves the right to perform any of the inspec-tions set forth in the specification where such inspections are deemednecessary to assure supplies and services conform to specified require-ments.

4.2 Quality conformance inspection.

4.2.1 Lotting. A lot shall consist of the Disperse Red 9 dye offeredfor acceptance at one time which has been produced by one manufacturer,at one plant, from the same materials, and under essentially the samemanufacturing conditions provided the operation is continuous. In theevent the process is a batch operation, each batch shall constitute a lot(see 6.3).

4.2.2 Sampling.

4.2.2.1 For examination of preparation for delivery. Sampling forexamination of preparation for delivery shall be conducted in accord-ance with MIL-STD-105.

Appendix B 36

//

MIL-D-3284C

4.2.2.2 For test. Three representative specimens of approximately 1/4pound each shill be randomly removed from the lot or batch of dye offeredfor acceltance and shall be plac.ed in separate clean, dry containers la-beled to identify the lot represented.

4.2,3 Inspection procedure.

4.2.3.1 For exe8zdnation of preparation for delivery. The sample unitshall be one filled and closed shipping container, ready for shipment.Sample containers and thn preparation for delivery thereof shall be exam-ined for the following defects ising an AQL of 2.5 percent defective:

(a) Contents per container not as specified(b) Container not as specified(c) Polyethylene liner or closure thereof not as specified

(level B only)(d) Container clo:,ure not as specified(e) Container damaged or leaking(f) Desiccant not as specified or missing (level B only)(g) Marking incorrect, missing, or illegible(h) Pallatization not as specified

4.2.3.2 For test. Each specimen taken in 4.2.2.2 shall be tested asspecified in 4.2.. Failure of any test by any specimen shall be causefor rejection of the lot represented.

4.2.4 Tests. Water in accordance with ISTM D1193 and reagent gradechemicals shall be used throughout the tests. Where applicable, blankdeterminations shall be run and corrections applied where significant.Tests shall be coL.ducted as follows:

4.2.4.1 Purity. Prepare and measure the absorbance of a standardDisperse Red 9 dye solution (see 6.4) and specimen solucion as follows:Weigh to the nearest milligram (mg) approximately 0.400 gram (g) of thedye and quantitatively transfer to a 500-milliliter (ml) volumetric flaskusing small amounts of isopropyl alcohol for washing. Dissolve the specimenin approximately 200 ml of isopropyl alcohol, stirring and breaking up alllumps to facilitate solution. Dilute to 500 ml with isopropyl alcohol.Shake thoroughly to insure uniform mixing. Remove a 20-ml aliquot, transferto a second 500-ml volumetric flask, dilute to 500 ml with isopropyl alcohol,and mix thoroughly. Using a suitable spectrQphotometer, read the absor-bance value of the more dilute solution at 500 + 2 millimicrons. Use theisopropyl alcohol used in preparing the solution as the reference liquidin the spectrophotometer. Cell spacer5 .-r variable path length cells maybe used in lieu of the prescribed dilution procedures. Calculate the per-cent purity as follows:

Appendix B 37

}

*

S. . .. . . . . ... . . ..

MIL-D-3284C

Percent purity = ABCDE

where: A = Percent purity of standard,B = Absorbance value of specimen,C = Weight of standard in grams,D = Absorbance value of standard, andE = Weight of specimen in grams.

4.2.4.2 Volatile matter. Weigh to the nearest milligram approxi-mately 5 g of the specimen in a tared, glaas-stoppered weighing bottle.Remove the stopper and dry to constant weight at 700 to 750 C. Cool toroom temperature in a desiccator and weigh. Calculate the percent vola-tile matter as follows:

Percent volatile matter = 100(A - B)W

where: A = Weight of specimen and stoppered bottle before heating ingrams,

B = Weight of specimen and stoppered bottle after heating ingrams, and

W = Weight of specimen in grams.

4.2.4.3 Particle size. Use sieves conforming to RR-S-366. Nest thesieves in order of decreasing mesh size (with the sieve of largest meshon top) on a receiving pan. Weigh to the nearest 0.01 g approximately10 g of the specimen and then use one of the following procedures:

(a) Dry method. Place the weighed specimen on the topsieve and brush the material with a camel's-hair brush until no morespecimcn passes through the sieve. Remove the sieve and weigh thematerial retained. Repeat this procedure with each of the other sieves.Calculate the percent material passing through each sieve.

(b) Wet method. Mix the weighed specimen with sufficientwater in a beaker by L-.irring with a glass rod to produce a smoothpaste. Carefully wash the thoroughly wetted specimen through thesieves. (The use of a wetting agent is permitted.) Dry the sieves inan oven at 700 to 750 C and weigh the material remaining on each sieve.Calculate the percent material passing through each sieve.

4.2.4.4 Apparent density. Determine apparent density in accordancewith ASTM D1895, method A except that the specimen shall be dried asspecified in 4.2.4.2 prior to testing.

Appendix B 38

MIL-D-3284C

5. PREPARATION FOR DELIVERY

5.1 Packing. Packing shall be level B or C as specified (see 6.2).

5.1.1 Level B. Uniform quantities of no less than 150 ind no more than300 pounds + IX percent of the marked net weight of dye shall be packedin a fiber drum conforming to rule 51, section 2 of the Uniform FreightClassification for a weight limit of over 225 but not over 300 pounds,with an aluminum barrier of 0.5 mil minimum thickness incorporated intoone of the inner plies of the sidewall. Each drum shall be providedwith a close fitting bag liner formed from polyethylene of 4 mils mini-mun thickness conformi.g to type I, grade and finish optional of L-P-378. Seams shall be completely heat sealed and shall meet the'heat-sealstrength requirements of L-P-378. The filled bag shall 'be closed byheat sealing, tying, or knotting. A minimum of eight units of desiccantconforming to MIL-D-3464 shall be placed on top of the closed liner.Drum closure shall be fully gasketed and shall form a tight seal betweenthe rim and the top of the drum.

5.1.2 Level C. Uniform quantities of no less than 150 and no morethan 300 pounds + 1/4 percent of the marked net weight of dye shall bepacked in containers which comply with the Uniform Freight ClassificationRules, the National Motor Freight Classification Rules, or other carrierrules as applicable to the mode of transportation. Containers shall becapable of being stacked aMq of supporting superimposed loads duringshipment and shall assure sL.. delivery to destination wit'hout damage tocontents. Containers shall be acceptable for shipment at the most favor-able rate of the applicable regulation provided that all requirementsspecified herein have becn met.

5.2 Marking. Marking shall be in accordance with MIL-STD-.129.In addition, each container shall be durably and legibly marked withcontrasting letters and background to show the net weight of contentsand the following information:

CAW•ION

Avoid contact with skin or clothing.In case of contact, flush with water.Avoid breathinE '.ust or fumes.Use with adequatt ventilation.

5.3 Palletization. Shipping containers shall be palletized in accord-ance with the applicable requirements of MIL-STD-147 except that thepallet shall be as specified in the contrsct or order (see 6.2).

Appendix B 39

/

MIL-D-3284C

6. NmE

6.1 Intended use. Disperse Red 9 dye is intended for use in themanufacture of colored signaling smoke mixtures.

6.2 Ordering data. Procurement documents should specify thefollowing:

(a) Title, number, and date of this specification.(b) Level of packing required (see 5.1).(c) Type of pallet required (see 5.3).

6.3 Batch. A batch is defined as that quantity of material whichhas been manufactured by some unit chemical process or subjected toso74 physical mixing operation intended to make the final productsubstantially uniform.

6.4 Standard dye. Standard dye for the purity determinatica may beobtained from Commanding Officer, Edgewood Arsenal, Quality AssuranceDirectorate, Edgewood Arsenal, Maryland 21010.

6.5 Significant places. For the purpose of determining conformancewith this specification, an observed or calculated value should berounded off "to the nearest unit" in the last right-hand place offigures used in expressing the limiting value, in accordance with therounding-off method of the Recommended Practices for Designating Signi-ficant Places in Specified Limiting Values (ASTM E29).

6.6 Nomenclature. Disperse Red 9 dye is commercially known undervarious names such as Celanthrene Red Y. It is listed in the ColourIndex under number C160505.

Custodians: Preparing activity:

Army~ - MU ArmV - MU(EA)S' ,~Navy,- AS Project No. 6820-0052

Review activities:

Army - MD, MU(FA)Navy - AS, OSDSA - GS

User activity:

A U.S. GOVERNMENT PRINTING OFFICE: 1971-714-156/278

Appendix B 40

/

APPENDIX C

SPECIFICATION FOR DYE IN YELLOW SMOKE (AND OTHERS)

MIL-D-O050029C( MJ)P6 April 1968

USED IN LIEU OFMIL-D-50029B15 July 1963SUPERSEDINGInterim Amendment 1 (NU)7 July 1965

MILITARY SPECIFICATION

DYE, VAT YELLOW 4

This limited coordination Military specification hasbeen prepared by Edgewood Arsenal based upon currentlyavailable technical information, but it has no$ beenapproved for promulgation as a coordinated revision ofMilitary Specification MiL-D-50029B. It is subjectto modification. However, pending its promulgation asa coordinated Military specification, it may be used inprocurement.

1. SCOPE

1.1 This specification covers Vat Yellow 4 dye, chemicallyknown as a dibenzpyrenequinone type dye.

2. APPLICABLE DOCUMENTS

2.1 Government documents. The following documents of the issuein effect on date of invitation for bids or request for proposal,form a part of this specification to the extent specified herein.

SPECIFICATIONS

FEDERAL

L-P-378 - Plastic Film (Polyethylene Thin Gage).RR-S-366 - Sieve, Test.

FSC 6820

41

/

l4L-D-0050029C( Mu)

MILITARY

MIL-D-3464 - Desiccants, Activated, Bagged, Packaging Use andSGatic Dehumidification.

MIL-P-15011 - Pallets, Material Handling, Wood, Post

Construction, 4-Way Entry.

STANDALRDS

MILITARY

MIL-STD-129 - Marking for Shipment and Storage.MIL-STD-147 - Palletized and Containerized Unit Loads, 401" x 48"

4 -way (Partial) Pallet Skids, Runners, orPallet-Type Base.

(Copies of specifications, standards, drawings, and publicationsrequired by suppliers in connection with specific procurement func-tions should be obtained from the procuring activity or as directedby the contracting officer.)

2.2 Other publicati.ons. The following documents form a jart of thisspecification to the extent specified herein. Unless otherwise indi-cated, the issue in effect on da. , of invitation for bids or requestfor proposal shall apply.

UNIFORM CLASSIFICATION COMMITTEE

Uniform Freight Classification

(Application for copies of these ratings, rules, and regulationsshould be addressed to Uniform Classification Committee, 202 UnionStation, 516 West Jackson Boulevard, Chicago, Illinois 60606.)

f

AMERICAN SOCIETY FOR TESTING AND MATERIALS

ASTM Standards

D1193-66 - Reagent Water.

(Application for copies should be addressed to the American Societyfor Testing and Materials, 1916 Race Street, Philadelphia, Pennsylvania19103.)

Appendix C 42

/

NIL-D-0OO5O29C(MU)

(Technical society and technical association specifications andstandards are generally available for reference from libraries. Theyare also distributed among technical groups and using Federal agencies.)

3. REQUIREMENTS

3.1 Chemimical and physical characteristics. Vat Yellow 4 dye shallconform to the chemical and phy.rical characteristics of table I whentested as specified therein.

Table 1. Chemical -nd physical characteristics

Characteristic Requirement Test1paragraph

Purity, percent by weight, minimum 80 i 4.2.4.1Volatile matter, percent by weight, maximum 1.0 I 4.2.4.2Particle size, percent by weight passing:

840 microns (No. 20), minimum 100 4.2.4.3297 microns (No. 50), minimum 97 4.2.4.3

44 microns (No. 325), maximum 40 4.2.4.3Percent "Mareol 52" (as anti-dusting agent) 2.0 + 0.5 4.2.4.4

4. QUALITY ASSURANCE PROVISIONS

4.1 Responsibility for inspection.

4.1.1 Supplier's responsibility. Unless othb,,Jise specified in thecontract or purchase order, the supplier is responsible for the perfor-mance of all inspection requirements as specified herein. Except asotherwise specified in the contract or order, the supplier may ase hisown or any other facilities suitable for the performance of the inspec-tion requirements specified herein, unless disapproved by the Govern-ment. The Government reserves the right to perform any of the inspec-tions cet forth in the specification where such inspections are deemednecessary to assure supplies and services conform to specified require-ments.

4.1.2 Objective evidence. The supplier shall provide objective evi-dence acceptable to the contracting officer that the requirements ofsection 5 for which specific inspection has not been provided in thisspecification have been satisfied.

Appendix C 43

/

I4CL-D-O50029C(MJ)

4.2 Quality conformance inspection.

4.2.1 Lotting. A lot shall consist of the Vat Yellow 4 dye offeredfor acceptance at one time which has been produced by one manufacturer,at one plant, from the sam,n- materials, and under essentially the samemanufacturing conditions provided the operation is continuous. In theevent the process is a batch operation, each batch shall constit.te alot (see 6.3)

4.2.2 Sampling for test. Sampling shall be conducted in accordanccwith table II. A representative specimen of no less than 1/4 poundshall be removed from each container in the sample and placed in aseparate clean, dry container labeled to identify the lot and containerfrom which it was taken.

Table II. Saepling for test

Number of containers in lot or batch Number of sample containers2-25 2

26-150 3151-1,200 5

1,201-7,000 87,001-20,000 10over 20,000 20

4.2.3 Inspection procedure. Each sample specimen shall be testedas specified in 4.2.4. Failure of any test by any specimen shall because for rejection.

4.2.4 Tests. Water in accordance with ASTM D1193 and reagent gradechemicals shall be used throughout the tests. Where applicable, blankdeterminations shall be run and corrections applied where significant.Tests shall be conducted as follows:

4.2.4.1 Purity. Prepare a standard dye solution (see 6.4) end spec-imen solution as follows: Weigh to the nearest milligram 0.100 gram (g)of the dye and transfer quantitatively to a 500-ml volumetric flask.Dissolve in concentrated sulfuric acid and dilute to 500 ml with concen-trated sulfuric acid. Mix thoroughly. Trensfer a 10-ml aliquot to a250-mi volumetric flask and dilute to 250 ml with concentrated sulfuricacid. Mix thoroughly. Transfer a portion of each solution to matched1-centimeter cells of a spectrophotometer and obtain the absorbance (abs)

Appendix C 44

/I

YZL-NM5OO29C4M

of each solution at 568 to 571 millimicrons using concentrated sul-furic acid in the reference cell. Calculate the per-.ent purity asfollows:

Percent purity = 100 (abs of specimen at 568 to 571 millimicrons)(abs of standard at 568 to 571 millimicrons)

14.2.4.2 Volatile matter. Weigh to the nearest milligram approxi-rmately 5 g of the specimen in a tared, glass-stoppered weighing bottle.Remove the stopper and dry to constant weight at 700 to 750 C. Cool toroom temperature in a desiccator and weigh. Calculate the percentvolatile matter as follows:

Percent volatile matter = 100(A-B)W

where: A = Weight of specimen and stoppered bottle before heating ingrams,

B = Weight of specimen and stoppered botttle after heating ingrams, and

W = Weight of specimen in grams.

4.2.4.3 Particle size. Use sieves conforming to RR-S-366. Nest thesieves in order of decreasing mesh size (with the largest mesh sieve ontop) on a receiving pan. Weigh to the nearest 0.1 g approximately 10 gof the specimen and then use one of the following procedures:

(a) Dry method. Place the weighed specimen on the top sieveand brush the material with a camel's-hair brush until no more specimenpasses through the sieve. Remove the sieve and weigh the materialretained. Repeat this procedure with each of the other sieves. Calcu-late the material passing through each sieve.

(b) Wet method. Mix the weighed specimen with sufficientwater in a beaker by stirring with a glass rod to produce a smoothpaste. Carefully wash the thoroughly wetted specimen through, tnesieves. (The use of a wetting agent is permitted.) Dry the sieves inan oven at 700 to 750 C and reigh the material remaining on each sieve.Calculate the percent material passing through each sieve.

14.2.4.4 Anti-dusting agent ("Marcol 52").

(a) Reference standard. Prepare a series of six standard"Mercol 52" solutions in carbon tetrachloride containing 0.20 to 0.60g of "Marcol 52" per 100 ml of carbon tetrachloride. (This is equiva-lent to 1.0 to 3.0 percent "Marcol 52" per 20 g of specimen.) Determine

Appendix C 45

I I//

f:- MIL-I•OO50029C(KJ)

the absorbance of the standard solutions at 2,310 or 3,1410 . 2 milli-microns using an infra-red spectrophotometer which has been balancedat zero or at a predetermined setting using a carbon tetrachlorideblank. Prepare a calibrstion chart of ?0sorbance versus percent"Marcol 52" in a 20-g specimen.

(b) Preparation of specimen. Weigh 20.000 g of the speci-men into a 250-ml beaker. Add 50 ml of carbon tetrachloride and agi-tate for at least 1/2 hour (the specimen will not dissolve). Filter

with suction. Wesh the funnel and precipitate with 20 to 30 ml ofcarbon tetrachloride. Quantitatively transfer the filtrate to a 100-mlvolumetric flask and dilute to 100 ml with carbon tetrachloride.

(c) Procedure. Determine the absorbance of the specimensolution prepared as specified in (b) at 2,310 or 3,410 + 2 milli-microns using the same instrument, balancing, and wave length as was usedin the standard solution measurements. Calculate the percent "Marcol 52"from the calibration chart prepared as specified in (a).

5. PREPAIRTION FOR DELIVERY

5.1 Packing. Packing snall be level B or C as specified (see 6.2).

5.1.1 Level B. Uniform quantities of no less than 150 and no morethan 300 pounds + 1/4 percent of the marked net weight of dye shall bepacked in a fiber drum conforming to rule 51, section 2 of the UniformFreight Classification with an aluminum barrier of 0.5 mil minimumthickness incorporated into one of the inner plies of the sidewall.Each drum shall be provided with a close fitting bag liner formed frompolyethylene of 4 mils minimum thickness conforming to type I, gradeand finish optional of L-P-378. Seams shall be completely heat sealedand shall meet the heat-seal requirements of L-P-378. The filled bagshall be closed by heat sealing, tying, or knotting. A minimum ofeight units of desiccant conforming to MIL-D-3464 shall be placed ontop of the closed liner. Drum cloaure shall be fully gasketed andshall form a tight seal between the rim and the top of the drum.

5.1.2 Level C. Quantities of Vat Yellow 4 dye as specified shall bepecked to provide adequate protection against contamination, deteriora-tion, and dtrnage and to insure carrier acceptance and safe delivery tothe first domestic destination. Containers shall be in compliance withUniform Freight Classification rules or the regulations of other commoncarriers applicable to the mode of transportation (see 6.2).

5.2 Marking. In addition to the marking specified in 5.2.1 and anyspecial marking required by the contract or order, containers shall bemarked in accordance with MIL-STD-129 (see 6.2).

Appendix C A6

1.I!

- -.- -.i- ~ -

5.2.1 Special markin_. Each container shall be durably and legiblymarked with contrasting letters and background as follows:

CAUTION

Avoid skin contact.Avoid breathing dust or fumes.Use with adequate ventilation.

5.3 Palletization. When specified in the contract or order, shippingcontainers shall be palletized in accordance with the applicable require-ments of MIL-STD-147 utilizing the hardwood, 4 -way, 4o- by 48-inch,double-wing pallet of MIL-P-15011 (see 6.2).

6. NOTES

6.1 Intended use. Vat Yellow 4 dye is intended for use in themanufacture of colored signalling smoke mixtures.

6.2 Ordering data. Procurement documents should specify thefollowing:

(a) Title, number, and date of this specification.(b) Level of packing required.(c) Quantity required for level C packing.(d) Special marking other than 5.2.1, if required.(e) Palletization, if required.

6.3 Batch. A batch is defined as that quantity of material which hasbeen manufactured by some unit chemical process and subjected to somephysical mixing operation intended to make the final product sub-stantially uniform.

6.4 Standard dye. Standard dye for the purity determination may beobtained form Commanding Officer, Edgewood Arsenal, Quality AssuranceDirectorate, Edgewood Arsenal, Maryland 21010.

6.5 Nomenclature. Indanthrene Golden Yellow GK is a typical com-mercial name for Vat Yellow h dye. It is listed in the Colour Indexunder number CI59100. Additional commercial names may be found onpage 2430, Volume 2 of the Colour Index.

6.6 Anti-dusting agent. "Marcol 52" is a highly refined petroleumoil obtainable from the Humble Oil Company.

Appendix C 47

/

MIL-D-0050029C(14)

6.7 Significant places. For the purpose of determining conformancevith this specification, an observed or calculated value shall berounded off "to the nearest unit" in the last right-hand place offigures used in expressing the limiting value, in accordance withthe rounding-off method of the Recommended Practices for DesignatingSignificant Places in Specified Limiting Values (ASTM E29).

Custodian: Preparing activity:

Ar• y - MU Arvy - M4(EA)

Project No. 6810-AO42

Appendix C 48

U. S. GOVERNMENT PRINTING OFFICE: 1968-301.519/5778

/

APPENDIX D

SPECIFICATIONS FOR DYE USED IN YELLOW AND GREEN SMOKES

MIL-D-00500714CV.iJ)9 May 1968

USED IN LIEU OFM•IL-D-5007hBi July 1963

MILITARY SPECIFICATION

DYE, BENZANTHRONE

This limited coordinated Military specification hasbeen prepared by Edgewood Arsenal based upon currentlyavailable technical information, but it has not beer.approved for pro:.nulgation as a coordinated revision ofMilitary Specification MIL-D-50074B. It is subject tomodification. Hcwever, banding its promulgation as acoordinated Military specification, it may be used inprocurement.

1. SCOPE

1.1 This specification covers benzanthrone dye, chemically known as

1,9-benz-10-amthrone.

2. APPLICABLE DOCUMENTS

2.1 Government documents. The following documents of the issue ineffect on date of invitation for bids or request for proposal, form apart of this specification to the extent specified herein.

SPECIFICATIONS

FEDERAL

L-P-378 - Plastic Film (Polyethylene Thin Gage).RR-S-366 - Sieve, Test.

MILITARY

MIL-D-3h64 - Desiccants, Activated, Bagged, Packaging Use andStatic Dehumidification.

MIL-P-15011 - Pallets, Material Handling, Wood, PostConstruction, 4-Way Entry.

Psc 6820

49

/

MIL-D-0O050OTC(MU)

STANDARDS

MILITARY

MIL-STD-129 - Marking for Shipment and Storage.MIL-STD-147 - Palletized and Containerized Unit Loads, 40" x 48"

4 -Way (Partial) Pallet Skids, Runners, orPallet-Type Base.

(Copies of specifications, standardi•, drawings, and publicationsrequired by suppliers in conncction with specific procurement func-tions should be obtained from the procuring activity or as directedby the contracting officer.)

2.2 Other publications. The following documents form a part of thisspecification to the extent specified herein. Unless otherwise indi-cated, the issue in effect on date of invitation for bids or requestfor proposal shall apply.

UNIFORM CLASSIFICATION COMMITTEE

Uniform Freight Classification

(Application for copies of these ratings, rules, and regulationsshould be addressed to Uniform Classification Committee, 202 UnionStation, 516 West Jackson Boulevard, Chicago, Illinois 60606.)

AERICAN SOCIETY FOR TESTING AND MATERIALS

ASTM Standards

Dl193-66 - Reagent Water.

(Application for copies should be addressed to the American Societyfor Testing and Materials, 1916 Race Street, Philadelphia, Pennsylvania19103.)

D

(Technical society and technical association specifications andstandards cre generally available for reference from libraries. Theyare also distribited among technical groups and using Federal aGencies.)

Appendix D 50

//

MIL-D-00500TOC( M)

3. QUIREMEM

3.1 Chemical and physical characteristics. Benzanthrone dye shallconform to the chemical and. phy-ical characteristics of table I whentested as specified therein.

Table T. Chemical and physica2 characteristics

Characteristic Requirement Test_aragraph

Purity, percent by weight, minimum 77 *.2.4.1Volatile matter, percent by weight, maximum 1.0 4.2.4.2Particle Gize, percent by weight passing:

840 microns (No. 20), minimum 100 4.2.4.3297 microns (No. 50), minimum 97 4.2.4.3

44 microns (No. 325), maximum 40 4.2.4.3Percent "Marcol 52" (an anti-dusting agent) 2.0 + 0.5 4.2.4.4

4. QUALITY ASSUriaCE PROVISIONS

4.1 Rea;ponsibility for inspection.

4.1.1 Supplier's responsibility. Unless otherwise specified in thecontract or purchase order, the supplier is responsible for the perfor-mance of all inspection requirements as specified herein. Except asotherwise specified in the contract or order, the supplier may use hisown or any other facilities suitable for the performance of the inspec-tion requirements specified herein, unless disapproved by the Govern-ment. The Government reserves the right to perform any of the innpec-tions set forth in the specification where such inspections are deemednecessary to assure supplies and services conform to specified require-ments.

4.1.2 Objective evidence. The supplier shall provide objectiveevidence acceptable to the contracting officer that the requirementsof section 5 for which specific inspection has not been provided inthis specification have been satisfied.

Appendhx D 51

//

MIL-D-0050074C(4J)

4.2 giality conformance inspection.

4.2.1 Lotting. A lot shall consist of the benzanthrone dye offeredfor acceptance at one time which has been produced by one manufacturer,at one plant, from the same materials, and under essentially the samemanuf&cturing conditions provided the operation is continuous. In theevent the process is a batch operation, each batch shall constitute alot (see 6.3).

4.2.2 Sampling for test. Sampling shall be conducted in accordancewith table II. A representative specimen of no less than 1/"- poundshall be removed from each container in the sample and placed in aseparate clean, dry container labeled to identify the lot and containerfrom which it was taken.

Table II. Sampling for test

Number of containers in lot or batch Number of sample containers2-25 2

26-150 3151-1,200 5

1,201-7,000 87,001-20,000 10over 20,000 20

4.2.3 I ion procedure. Each sample specimen shall be tested asspecified in 4.2.4. Failure of any test by any specimen shall be causefor rejection.

4.2.4 Tests. Water in accordance with ASTM D1193 and reagent gradechemicals shall be used throughout the tests. Where applicable, blankdeterminations shall be run and corrections applied where significant.Tests shall be conducted as follows:

4.2.4.1 Purity. Prepare a standard benzanthrone dye solution (see 6.4)and specimen so. 'ation as follows: Weigh to the nearest milligram (mg)approximately 0.350 gram (g) of the dye, which has been previously driedto constant weight at 700 to 750 C, and transfer quantitatively to a500-milliliter (ml) volumetric flask. Add approximately 250 ml of tolueneand thoroughly mix to dissolve the benzanthrone. Dilute with toluene to500 ml and again thoroughly mix. Transfer a 5-ml aliquot to a 200-Mlvolumetric flask, dilute to 200 ml with toluene., and thoroughly mix.Using a suitable spectrophotometer, measure the absorbance of +ne more

Appendix D 52

/

MIL-D-0050074c(MU)

dilute solution of standard dye and the more dilute solution of specimenat 388 + 2 millimicrons. Use the toluene used for preparing the solutionsas the reference liquid in the spectrophotometer. Calculate the percentpurity as follow :

Percent purity = 100 (absorbance value of specimen)(absorbance value of standard)

4.2.4.2 Volatile matter. Weigh to the nearest milligram approxi-mately 5 g of the specimen in a tared, glass-stoppered weighing bottle.Remove the stopper and dry to constant weight at 700 to 750 C. Cool toroom temperature in P. desiccator and weigh. Calculate the percentvolatile matter as follows:

Percent volutile matter = I00(A-BýW

where: A = Weight of specimen and stoppered bottle before heatingin grams,

B = Weight of specimen and stoppered bottle after heatingin grams, and

W = Weight of specimen in grams.

4.2.4.3 Particle size. Use sieves conforming to RR-S-366. Nest thesieves in order of decreasing mesh size (with the sieve of largest meshon top) on a receiving pan. Weigh to the nearest 0.1 g approximately10 g of the specimen and then use one of the following procedures:

(a) Dry method. Place the weighed specimen on the topsieve and brush the material with a camel's-hair brush ,ntil no morespecimen passes through the sieve. Remove the sieve and weigh thematerial retained. Repeat this procedure with each of the othersieves. Calculate the percent material passing through each sieve.

(b) Wet method . Mix the weighed specimen with sufficientwater in a beaker by stirring with a glass rod to produce a smoothpaste. Carefully wash the thoroughly wetted specimen through thesieves. (The use of a wetting agent is permitted.) Dry the sieves inan oven at 700 to 750 C and weigh the material remaining on each sieve.Calculate the percent material passing thr3ugh each sieve.

4.2.4.4 Anti-dusting agent ("Marcol 52").

(a) Reference standard. Prepare a series of six standard"Marcol 52" solutions in carbon tetrachloride containing 0.20 to 0.60 g

Appendix D 53

1

MIL-D-0050074C(Ki)

of "Marcol 52" per 100 ml of carbon tetrachloride. (This is equivalentto 1.0 to 3.0 percent "Marcol 52" per 20 g of specimen.) Determine the-b--rr.bac. of thA standArd solutions at 2,310 or 3,1*0 + 2 millimicronsusing an infra-red suectrophotocreter wehich has been balanced at zero orat a preletermined setting using a carbon tetrachloride blank. Preparea calibration chart of absorbance versus percent "Marcol 52" in a 20-gspecimen.

(b) Preparation of specimen. Weigh 20.000 g of the specimeninto a 150-ml beaker. Add 50 ml of carbon tetrachloride and agitatefor at least 1/2 hour (the specimen will not dissolve). Filter withsuction. Wash the funnel and precipitate with 25 to 30 ml of carbontetrachloride. Quantitatively transfer the filtrate to a 100-mlvrolumetric flask and dilute to 100 ml with carbon tetrachloride.

(c) Procedure. Determine the absorbance of the specimensolution prepaied as specified in (b) at 2,310 or 3,410 + 2 milli-microns using the same instrument and balancing as was used in thestandard solution tests. Calculate the percent "Marcol 52" from thecalibration chart prepared as specified in (a).

5. PREPARATION FOR DELIVERY

5.1 Packing. Packing shall be level B or C as specified (see 6.2).

5.1.1 Level B. Uniform quantities of no less than 150 and no more than300 pounds + I/T percent of the marked net weight of benzanthrone dye shallbe packed in a fiber drum conforming to rule 51, section 2 of the UniformFreight Classification with an aluminum 1, rier of 0.5 mil minimumthickness incorporated into one of the irnmer plies of the sidewall.Each drum shall be provided with a close fitting bag liner formed frompolyethylene of 4 mils minimum thickness conforming to type I. gradeand finish optional of L-P-378. Seams shall be completely he-,t sealedand shall meet the heat-seal requirements of L-P-378. The filled bagshall be closed by heat sealing, tying, or knotting. A minimum ofeight units of desiccant conforming to MIL-D-3464 shall be placed on

S/ top of the closed liner. Drum closure shall be fully gasketed andshall form a tight seal between the rim and the top of the drum.

5.1.2 Level C. Quantitie6 of benzanthrone dyc as specified shall bepacked to provide adequate protection against contamination,detetioration, and damage and to insure carrier acceptance andsafe delivery to the first domestic destination, Containers shallbe ±Ln compliance with Uniform Freight Classitication rules or theregulations of other common carriers applicable to the mode oftransportation (see 6.2).

Appendix D 54

/

MIL-D-0050074C(MU)

5.2 Marking. In addition to the marking specified in 5.2.1 andany special marking required by the contract or order, containersshall be marked in accordance with MIL-STD-129 (see 6.2).

5.2.1 Special marking, Each container shall be durably andlegibly marked with contrasting letters and background as follows:

CAUTION

Causes severe irritation to some people.Avoid contact with skin or clothing.In case of contact, flush with water.Wash contaminated clothing before re-use.Individuals sensitive to this product should not

continue to work w. it.

5.3 Palletization. When specified in the contract or order,shipping containers shall be palletized in accordance with theapplicable requirements of MIL-STD-147 utilizing the hardwood,4 -way, 40-by 48-inch, double-wing pallet of MIL-P-15011 except thatthe strapping shall have a minimum width of 1.25 inch and a minimumthickness of 0.035 inch (see 6.2).

6. NOTES

6.1 Intended use. Benzaithrone dye is intended for use in themanufacture of colored signaling smoke mixtures.

6.2 Ordering data. Procurement documents should specify thefollowing:

(a) Title, number, and date of this specification.(b) Level of packing required.(c) Quantity required for level C packing.(d) Special marking other than 5.2.1, if required.(e) Palletization, if required.

6.3 Batch. A batch is defined as that quantity of material whichhas been manufactured by some unit chemical process and subjected tosome physical mixing operation intended to make the final productsubstantially uniform.

6.4 Standard dye. Standard dye for the purity determination may beobtained from Commanding Officer, Edgewood Arsenal, Quality AssuranceDirectorate, Edgewood Arsenal, Maryland 21010.

Appendix D 55

, z/

MIL-D-0050OT4C( m)

6.5 Anti-dusting agent. "Marcol 52" is a highly refined petroleumoil obtainable from the Humble Oil and Refining Company.

6.6 Significant places. For the purpose of determining conformancewith this specification, an observed or calculated value shall berounded off "to the nearest unit" in the last right-hand place offigures used in expressing the limiting value, in accordance with therounding-off method of the Recommended Practices Zor DesignatingSignificant Places in Specified Limiting Values (A'TM E29).

Custodian: Preparing activity:

Army - KI Army - MU(EA)

Project No. 6820-A043

Appendix D 56

U. S. GOVERNMENT PRINTING OFFICE: 196i,301.519/5994

/

APPENDIX E

SPECIFICATIONS FOR DYE USED IN GREEN SMOKE

MIL-v-003277B( Iu)26 March 1968USED III LIEU OFMIL-D-3277A25 May 1962SUPERSEDINGInterim Amendment 1(0)9 may 1966

MILITARY SPECIFICATION

DYE, SOLVENT GREEN 3

(FOR GRM-N SMOKE MIXTURES)

This limited coordination Military specification hasbeen prepared by Edgewood Arsenal based upon currentlyavailable technical information, but it has not beenapproved for promulgation as a coordinated revision ofMilitary Specification MIL-D-3277A. It is subject tomodification. However, pending its promulgation as acoordinated. Military specification, it may be used inprocurement.

1. SCOPE

1.1 This specification covers Solvent Green 3 dye, chemically known

as 1,4-di .o-toluidinoanthraquinone.

2. APPLICABLE DOCUMENTS

2.1 Government documents. The following documents of the issue ineffect on date of invitation for bids or request for proposal, form apart of this specification to the extent specified herein.

SPECIFICATIONS

FEDERAL

L-P-378 - Plastic Film (Polyeihylene Thin Gage).RR-S-366 - Sieve, Test.

MILJITARY

MIL-D-3464 - Desiccants, Activated, Bagged, Packaging Useand Static Dehumidification.

MIL-P-15011 - Pallets, Material I',ndling, Wood, PostConstruction, 4-Way Entry.

57 FSC 6820

A

1

MIL-D-003277B(Kt)

STANDARDS

MILITARY

MIL-STD-129 - Marking for Shipment and Storage.MIL-STD-147 - Palletized and Containerized Unit Loads, 40" x 48"

h-Way (Partial) Pallet Skids, lb:nners, orPallet-Type Base.

(Copies of specifications, standards, drawings, and publicationsrequired by suppliers in connection with specific procurement functionsshould be obtadined from the procuring activity or as directed by thecontracting officer.)

2.2 Other publications. The following documents form a part of thisspecification to the extent specified herein. Unless otherwise indi-cated, the issue in effect on date of invitation for bids or requestfor proposal shall apply.

UNIDORM CLASSIFICATION CO1VITTEE

Uniform Frieght Classification

(Application for copies of these ratings, rules and regulationsshould be addressed to Uniform Classification Committee, 202 UnionStation, 516 West Jackson Boulevard, Chicago, Illinois 60606.)

.AMERICAN SOCIETY FOR TESTING AND MATERIALS

ASTM Standards

DU93-66 - Reagent WaterD1895-65TP - Apparent Density, Bulk Factor, and Pourability of

Plastic Materials.

(Application for copies should be addressed to the American Societyfor Testing and Materials, 1916 Race Street, Philadelphia, Pennsylvania19103.)

tTiechnical society and technical association specifications and standardsare generally available for reference from libraries. They are also dis-tributed among technical groups and using Federal agencies.)

Appendix E 58

1'

MIL-D-003277B(NMU)

3. REQUIREMFINTS

3.1 Cheical and physcal characteristics. Solvent Green 3 dye shallconform to the chemical an," physical characteristics of table I whentested as specified therein.

Table I. Chemical and physical characteristics

TestCharacteristic Requirement pagraph

Purity, dry basis, percent by wt, 90 h.,..,T.l 2 1minimum

Volatile matter, percent by wt, maximum 2.5 4.2.11.2Particle size, percent by wt passing:840 microns (No. 20), minimum 100 4.2.-,.3297 microns (No. 50), minimum 97 4.2.4.3

414 microns (No. 325), maximum 1O 14.2.4.3Apparent density, grams per 0.38 4.2.4.24• milliliter, minimum (dry basis)

4. QUALITY ASSURANCE PROVISIONS

4.1 Responsibility for inspection.

4.1.1 Supnlier's responsibility. Unless otherwise specified in thecontract or purchase order, the supplier is responsible for the perfor-mance of all inspection requirements as specified herein. Except asotherwise specified in the contract or order, the supplier may utilizehis own or any other facilities suitable for the performance of theinspection requirements specified herein, unless disapproved by theGovernment. The Government reserves the right to perform any of theinspections set forth in the specification where such inspections aredeemed necessary to assure supplies and services conform to specifiedrequirements.

14.1.2 Objective evidence. The supplier shall provide objective evidenceacceptable to the contracting officer that the requirements of section 5for which specific inspection has not been provided in this specilicationhave been satisfied.

4.2 Quality conformance inspection.

4.2.1 Lotting. A lot shall consist of the Solvent Green 3 dye offeredfor acceptance at one time whici has been produced by one manufacturer,at one plant, from the same materials, and under essentially the samemanufacturing conditions provided the operation is continuous. in theevent the process is a batch operation, each batch shall constitute a lot(see 6.3).

Appendix E 59

/

MIL-D-0032TTB(MU)

4.2,2 Sampling for test. Sampling shall be conducted in aetoyd~ance withtable II. A representative specimen of no less than 1/4 pound shallbe removed from each container in the sample and placed in a s*parate clean,dry container labeled to identify the lot and container from which it wastaken.

Table II. Sampling for test

Number of containers in lot or batch Number of sample containers

2-25 226-150 3

151-1,200 51,201-7,000 87,001-20,000 10over 20,000 20

4.2.3 Inspection procedure. Each sample specimen shall be tested asspecified in 4.2.4. Failure of any test by any specimen shall be causefor rejection.

4.2.4 Tests. Water in accordance with ASTM D1193 and reagentgrale chemicals shall be used throughout the tests. Where applicable,blank determinations shall be run and corrections applied wheresignificant. Tests shall be conducted as follows:

4.2.4.1 PariEy. Prepare and measure the absorbance of a standard SolventGreen 3 dye jolution (see 6.4) and a specimen solution as follows: Transfer0.361 gram (g) of the dye, which has been dried to constant weight at 700to 750 C as specified in 4.2.4.2, to a 500-milliliter volumiitric flask,using small quantities of benzene to rinse the weighing container or paper.Dissolve in about 200 ml of benzene, stirring and breaking up all lumps tofacilitate solution. Dilute to 500 ml with bienzene. Shake the flaskthoroughly to insure uniform mixing. Transfei a 20-ml aliquot to a second500-ml volumetric flask, dilate to 500 ml with benzene, and mix thoroughly.Measure the absorbance of the solution at 642 millimicrons, using a suitablespectrophotometer, 1-centimeter light path cells, and benzene as the referencesolution. Calculate the percent purity as follows:

Percent purity = 100 (Absorbance value of specinen)Absorbance value of standard

Appendix E 60

MIL,-D-O03277B( 14J)

4.2.4. Volatile matter. In a tared, glass-stoppered weighingbottle, weigh to the nearest milligram approximately 5 g of the specimen.Remove the stopper and dry to constant weight in an oven at 700 to750 C. Cool in a desiccator and weigh. Calculate percent volatilematter as follows:

Percent volatile matter = 100 (A-B)A

where: B = Weight of residue in grams andA = Weight of specimen in grams.

4.2.4.3 Particle size. Use sieves conforming to RR-S-366. Nest thesieves in order of decreasing mesh size (with the largest mesh sieve ontop) on a receiving pan. Weigh to the nearest 0.1 g approximately 10 gof the specimen anj then use one of the following procedures:

(a) Dry method. Place the weighed specimen on the top sieveand brush the material with a camel's-hair brush until no more specimenpasses through the sieve. Remove the sieve and weigh the materialretained. Repeat this procedure with each of the other sieves. Calcu-late the material passing through each sieve.

(b) Wet method. Mix the weighed specimen with sufficientwater in a beaker by stirring with a glass rod to produce a smoothpaste. Carefully wash the thoroughly wetted specimen through thesieves. (The use of a wetting agent is permitted.) Dry the sieves inan oven at 700 to 750 C and weigh the material remaining on each sieve.Calculate the percent material passing through each sieve.

4.2.4.4 Apparent density. Determine apparent density in accordancewith ASTM D1895, method A except that the specimen shall be dried asspecified in 4.2.4.2 prior to testing.

5. PREPARATION FOR DELIVERY

5.1 Packing. Packing shall be level B or C as specified (see 6.2).

5.1.1 Level B. Uniform quantities of no less than 150 and no morethan 300 pounds + 1/4 percent of the marked net weight of dye shall bepacked in a fiber drum conforming to rule 51, section 2 of the UniformFreight Classification with an aluminum barrier of 0.5 mil minimumthickness incorporated into one of the inner plies of the sidewall.Each drum shall be provided with a close fitting bag liner formed frompolyethylene of 4 mils minimum thickness conforming to type I, gradeand finish optional of L-P-378. Seams shall be completely heat sealed

Appendix E 61

/

MIL-D-003277B(M&)

and shall meet the heat-seal strength requirements of L-P-378. The filledbag shall be closed by heat sealing, typing, or knotting. A minimnm ofeight units of desiccant conforming to MIL-D-3646 shall be placed on top ofthe closed liner. Drum closure shall be fully gasketed and shall form atight seal between the rim end top of the drum.

5.1.2 Level C. Quantities of Solvent Green 3 dye as specified shallbe packed to provide adequate protection against contamination, deteri-oration; and damage and to insure carrier acceptance and safe deliveryto the first domestic destination. Containers shall be in compliancewith Uniform Freight Classification rules or the regulations of othercommon carriers applicable to the mode of transportation (see 6.2).

5.2 Marking. In addition to the marking specified in 5.2.1 and anyspecial marking required by tha contract or order, containers shallbe marked in accordance with MIL-.STD-129 (see 6.2).

5.2.1 Special marking. Each container shall be durably and legibly

marked with contrasting letters and background as follows:

CAUTION

Avoid skin contact.Use with adequate ventilation.

5.3 Palletization. When specified in the contract or order, shippingcontainers shall be pa.letized in accordance with the applicablerequirements of MIL-STD-147 utilizing the hardwood, 4-way, 40- by 48-inch,double-wing pallet of 141L-P-15011 (see 6.2).

6. NOTES

6.1 Intended use. Solvent Green 3 dye is intended for use in green smokemixtures.

6.2 Ordering data. Procurement documents should specify the following:

(a) Title, number, and date of this specification.(b) Level of packing required.(c) Quantity required for level C packing.(d) Specia2 marking other than 5.2.1, if required.(e) Palletization, if required.

6.3 Batch. A batch is defined as that quantity of material which hasbeen manufactured by scme unit chemical process and subjected to somephysical mixing operation intended to make the final product sub-stantially uniform.

Appendix E 62

._7

I

MIL-D-00327TB(MU)

6.4 Standard dye. Standard dye for the purity test may be obtainedfrom Commanding Officer, Edgevood Arsenal, Quality Assurance Directorate,Edgewood Arsenal, Maryland 21010.

6.5 Significant places. For the purpose of determining conformancewith this specification, an observed or claculated value shall be roundedoff "to the nearest unit" in the last right-hand place of figures used inexpressing the 'Limiting value, in accordance with the rounding-off methodof the Recommended Practices for Designating Significant Places inSpecified Limiting Values (ASSAM E29).

Custodian: Preparing activity

Army - NJ Army - MU(EA)

Project No. 6820-AO41

Appendix E 63 r U. S. GOVERNMENT PRINTING OFFICES 1M.301.513/3O54

/

APPENDIX F

,PECIFICATION; FOR DYE USED IN VIOLET SMOKE

MI4L-D-3691B20 'uLj1970SUPERSEDIINGMIL-D-3691A15 July 1963

MILITARY SPECIFICATION

DYE MIX, VIOLET

This specification is mandatory for use by all De-partments and Agencies of the Department of Defense.

1. SCOPE

1.1 This specification covers a mixture of two anthraquinone dyes.

2. APPLICABLE DOCUME4TS

2.1 Government documents. The following locuments of the issue ineffect on date of invitation for bids or request for proposal, form apart of this specification to the extent specified herein.

SPECIFICATIONS

FEDERAL

L-P-378 - Plastic Sheet ,tnd Film (Polyolefin).RR-S-366 - Sieve, Test.

MILITARY

MIL-D-328h - Dye, Disperse Red 9.MIL-D-3464 - Desiccants, Activated, Bagged, Packaging Use and

Static Dehumidific a':ion.MIL-D-3668 - Dye, 1,4-Diamino-2,3-Lihydroanthraquinone.

STANDARDS

MILITARY

MIL-STD-105 - Sampling Procedures and Tables for Inspection byAttributes.

MIL-STD-129 - Marking for Shipment and Storage.

FSC 6820

/64

miL-D-3691B

(Copies of specifications, standards, drawings, and publications re-hired by suppliers in conWectt@n with specific prop~ement functions

4yoi4d be obtained from the pruring activity or as directed by theqontrocting officer.)

2.2 Other publications. The following documents form a part of thisspecificatiQL to the extent specified herein. Unless otherwise indicated,the issue in effect on date of invitation for bids or request for proposalshall apply.

UNIFORM FREIGHT CLASSIFICATION RULZES

(Application for copies should be addressed to the Uniform FreightClassification Committee, 202 Union Station, 516 West Jackson Boulevard,Chicago, Illinois 60606.)

NATIONAL MOTOR FREIGHT CLASSIFICATION RULES

(Application for copies should be addressed to the National Classifica-tion Board, 1616 P Stre:t, N.W., Washington, D.C. 20036.)

AMERICAN SOCIETY FOR TESTING AND MATERIALS (ASTM) STANDARDS

Dl193-66 - Reagent Water.D1895-67 - Apparent Density, Bulk Factor, and Pourability of Plastic

Materials.

(Application for copies should be addressed to the American Society forTesting and Materials, 1916 Race Street, Philadelphia, Pennsylvania 19103.)

(Technical society and technical association specifications and standardsare generally availa=',_e for reference from libraries. They are also dis-tributed amorng technical groups and using Federal agencies.)

3. REQUIREMENTS

3.1 Composition. Dye Mix, Violet shall be a uniformly blended mixtureof dyes and shall conform to the composition of table I when tested asspecified in 4 .2. 4 .1.

3.2 Chemical and physical characteristics. Dye Mix, Violet shall con-form to the chemical and physcial characteristics of table II when testedas specified therein.

Appendix F 65

'!/

MIL-D-3691B

Table I. Composition

Peront byDye ,. ht

Dye, Disperse Red 9 conforming to MIL-D-3284 20 + 2Dye, 1 ,4-Diamino-2,3-dibydroanthraquinone conforming

to MIL-D-3668 80 + 2

Table II. Chemical and physical characteristics

: . TestCharacteristic :Requirement: paragraph

:Volatile matter, r.-rc.nt by weight, maximum : 2.5 : 4.2.4.2:Particle size, minimum percent by weight

passing: . : 4.2.4.3250-micron (No. 60) sieve : 97149-micron (No. 100) sieve g 907 4-micron (No. 200) sieve . 70

:Apparent density, grams per milliliter :0.35 + 0.15: 4.2.4.4

4. QUALITY ASSURANCE PROVISIONS

4.1 Responsibility for inspection. Unless otherwise specified in thecontract or purchase order, the supplier is responsible for the perform-ance of all inspection requirements as specified herein, Except asotherwise specified in the contract or order, the supplier may usehis own or any other facilities suitable for the performance of theinspection requirements specified herein, unless disapproved by theGovernment. The Government reserves the right to perform any of theinspections set forth in the specification where such inspections aredeemed necessary to assure supplies and services conform to specifiedrequirements.

4.2 quality conformance inspection.

4.2.1 Lotting. A lot shall consist of the Dye Mix, Violet offeredfor acceptance at one time which has been produced by one manufacturer,at one plant, from the same materials, and under essentially the samemanufacturing conditions provided the operation is continuous. In theevent the process is a batch operation, each batch shall constitute alot (see 6.3).

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4.2.2 Sampling.

4.2.2.1 For examination of preparation fwr deliveIZ. Sampling forexamination of preparation for delivery shall be conducted in accordancewith MaL-STD-105.

4.2.2.2 For test. Sampling for test shall be conducted in accordancewith table III. A representative specimen of approximately 1/4 pound shal.be removed frora each sample shipplug container and placed in a suitable clean,dry container labeled to identify the lot and container from which it was taken,

Table III. Sampling for test

" Lot size, nounds Number of sample shipping containers:

3,000 or less 23,001 to 5,000 3

Over 5,000 5

4.2.3 Inspection procedure.

4.2.3.1 For examination of preparation for delivery. The sample unitshall be one filled and closed shipping container, ready for shipment.Sample containers and the preparation for de:ivery thereof shall beexamined for the fo.llowing defects using an AQL of 2.5 percent defective:

(a) Contents per container not as specified(b) Container not as specified(c) Polyethylene liner or closure thereof not as specified

(level B only)(d) Container closure not as specified(e) Container damaged or leaking(f) Desiccant not as specified or missing (level B only)(g) Mar'Uing incorrect, missing, or illegible

14.2.3.2 For test. Each sample specimen taken in 4.2.2.2 shall betested as specified in 4.2.4. Failure of any test by any specimen shallbe cause for rejection of the lot represented.

4.2.4 Tests. Water in accordance with ASTM Dll93 and reagent gradechemicals shall be used throughout the tests. Where applicable, blankdeterminations shall be run and corrections applied where significant.Tests shall be conducted as follows:

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MIL-D-3691B

4.2.4.1 Composition.

(a) Preparation of standard curves. Prepare a stz.-dardcurve of absorbance versus concentration for dye of known purity(see 6.4) conforming to MIL-D-3284 and dye of kncown purity (see 6.4)conforming to MIL-D-3668. Both dyes will dissolve in ethanol ý,. theconcentrations required; however, a slight warming on a steam bathmay be necessary. Prepare solutions of the dye conforming to MIL.D-3668 in ethanol with concentrations ranging from 5 t9 20 microgramsper milliliter (ml). Transfer a portion of the solution for eachconcentration tc a spectrophotometer cell and measure the absorbanceof each solution at 458 millimicrons (visible region) and at 314millimicrons (ultraviolet region) using ethanol in the reference beam.Plot the absorbance values versus concentration for each of the wave-lengths. A straight line should result. In the same manner, preparesolutions of the dye conform.ng to MIL-D-3284 in ethanol with con-centrations ranging from 5 to 20 micrograms per milliliter and usingethanol in the reference beam, plot the absorbance values versusconcentration for each of the solutions at 314 and 458 millimicrons.A straight line should result.

(b) Procedure. Prepare a solution of the specimen inethanol having a concentration uf 21 to 22 micrograms per milliliter,Place the specimen solution in a cuvet and place in the spectrophotometer.Use ethanol in the reference beam. Obtain spectral curves in boththe visible and ultraviolet regions. Calculate the concentrationof each dye as follows:

Ca = AlKb2 - A2Kbl

B(Kal_ 2 - K

Cb = AiKa2- A2 Kal

B(KblKa - Kb2Kal)

where: C = Concentration in grams per liter,a = Dye conforming to pure dye component of MIL-D-3668,

b = Dye conforming to pure dye component of MIL-D-3284,1 = Wavelength (314 millimicrons),2 = Wavelength (458 millimicrons),A = Absorbance read from spectral curve,B = Cell length in centimeters (unity for a 1-centimeter cell),

andK = Absorbance value divided by solution concentration.

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MIL-D-3691B

Calculate the dye content of the specimen as fol1'vs:

Percent dye conforming ýc CiL-D-3668 - lOOCa

Pa C

Percent dye conoiorming to aIL-D-3284 = .OOCb

PbC

where: Ca = Concentration calculated above,Cb = Concentration ca-lculated above,C = Concentration of specimen in grams per liter,Pa, = Origina± percent purity of dye conforming to MIL-D-3668

prior to blending, t,dPb = Original percent purity of dye conforming to MIL-D-3284

prior to blending.

4.2.4.2 Volatile matter. Weigh to the nearest milligram approxi-mately 5 g of the specimen in a tared, glass-stoppered weighing bottle.Remove the stopper and dry to constant weight at 700 to 750 C. Coolto room temperature in a desiccator and weigh. Calculate the percentvolatile matter as follows:

Percent volatile matter = 100(A - B)W

iwhere: A = Weight of specimen and stoppered bottle before heating ingrams,

B = Weight of specimen anO stoppered bottle after heating ingrams, and

W = Weight of specimen in grams.

4.2.4.3 Particle size. Use sieves conforming to RR-S-366. Nestthe sieves in order of decreasing mesh size (with the sieve of largestmesh on top) on a receiving pan. Weigh to the nearest 0.1 g approxi-mately 10 g of the specimen and then use one of the following procedures:

(a) Dry mtthod. Place the weighed specimen on the topsieve and brush the ma' •ial with a camel's-hair brush until no morespecimen passes through the sieve. Renove the sieve and weigh thematerial retained. Repeat this procedure with each of the other sieves.Calculate the percent material passing through each sieve.

(b) Wet method. Mix the weighed specimen with silfficientwater in a beaker by stirring witl a glass rod to produce a smoothpaste. Careftly wash the thorougaly wetted specimen through the

Appendix r' 69

MIL-D-3691B

sieves. (The use of a wetting agent is permitted.) Dry the ioves inan ON at 700 to 750 C and weigh the material remaining on each *Love.Calculate the percent material passing through each sieve.

4.2.4.4 Apparent density. Determine apparent density in accordance

with ASTY D1895, method A.

5. PREPARATION FOR DELIVERY

5.1 Packing. Packing shall be level B or C as specified (see 6.2).

5.1.1 Level B. Uniform quantities of no less than 150 and no morethan 300 pounds + 1/4 percent of the marked net weight of dye shall bepacked in a fiber drum conforming to rule 51, section 2 of the UniformFrsight Classification for a weight limit of over 225 but not over 300pounds, with an aluminum barrier of 0.5 mil minimum thickness incorpo-rated into one of the inner plies oi the sidewall. Each drum shall t-,provided with a close fitting bag liner formed from polyethylene of 4mils minimum thickness conforming to type I, grade and finish optionalof L-P-378. Seams shall be completely heat sealed and shall meet theheat-seal strength requirements of L-P-378. The filled bag shalh beclosed by heat sealing, tying, or knotting. A minimum of eight unitsof desiccant conforming to MIL-D-3464 shall be placed on top of theclosed liner. Drum closure shall 1- fully gasketed and shall form atight seal between the rim and the top of the drum.

5.1.2 Level C. Uniform quantities of no less than 15v and no morethan 300 pounds + i/4, percent of the marked net weight of dye shall bepacked in containers which comply with the Uniform Freight ClassificationRules, the Nat oual Motor Freight Classification Rules, or other carrierrules as applicable to the mode of transportation. Containers shall becapable of being stacked and of supporting superimposed loads duringshipment and shal-l assure zafe delivery to destination without damage tocontents. Containers shall be acceptable for shipment at the most favorablerate of the applicable regulation provided that all requirements specifiedherein have been met.

5.2 Marking. Marking shall be in sccord.ance with MIL-STD-129. Inaddition, each container shall be durably and legibly marked with con-trasting letters and background to show the net weight of contents andthe folloving information*

CAUTION

Avoil skin contact.Avoid breathing dust or fumaes.Use with adequate ventilation.

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MIL-D-3691B

6. NOTES

6.1 Intended use. Dye Mix, Violet in \tnemde4 for use in the manu-facture of vlole6 sig.aling smoke mixtures.

6.2 Ordering data, Procurement documents should specify the following:

(a) Title, number, and date of this specification.(b) Level of packing required (see 5.1).

6.3 Batch. A bach is defined as that quantity of material whichhas been manufactured by some unit chemical process or subjected tosome physical mixing operation intended to make the final productsubstantiasly uniform.

6.4 Dyes of kDown purity•. Dyes of known purity ccnforming to MIL-D-3668 and MIL-D-328L, respectively, may be obtained from CommandingOfficer, Edgewood Arsenaj., Quality Assurance Directorate, FdgewoodArsenal, Maryland 21010.

6.5 Significant places. For the purpose of determining conformancewith this specification, an observed or calculated value should berounded off "to the nearest unit" in the last right-hand place offigures used in expressing the limiting value, in accordance with the

rounding-off method of the Recommended Practices for DesignatingSignificant Places in Specified Limiting Values (ASTM E29).

Custodians: Preparing activity:

Army - MU Army - MU(EA)Navy - OS Project No. 6820-0048

Review activities:

Army - HD, MU(FA)Navy - AS, OSDSA - GS

User activity:

Army - SM

" U. S. GOVERNMENT PRINTING OFFICEI WO .433.689/1066

Appendix F 71

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