I.Final - DTIC

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AD _ _

A HEALTH AND ENVIRONMENTAL EFFECTS DATA BASE ASSESSMENT

OF U.S. ARMY WASTE MATERIAL

I.Final Report

PHASE I1 REPORT

by

C" J. C. Uhrmacher, Principal InvestigaLorP.F. Werschulz0.0. Schultz

D.O. Weber

March 4, 1984

Supported by

C UvS. Army Medical Research and Development CommandFort Detrick, rrederick, Maryland 21701-5012

Contract No. DAD7-84-C-4133

Carltech Asnioc~iates, 7nc,

Colubia, Maryland 21045 DEC

Coati ng Of icer's Technical Representative:

Mitchell SmallHealth Effect3 Research Division,

US. Army Medical Btonaineering Researchand Developaent Laboratory

Fort Derrick, Frederick, Ktryland 217OL-5010

Approved for pulalic rulease; distribution unlamited.

The findings in this report are not to be construedas an official Departuent of the Army pL.'sition unless

t ( so designated by other authorized doeumeuts.

86 12 15 042

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SECURITY CLASSIFICATION OF TH~IS PAGE M%007 DateEnte)_ _________________

REPORT DOCUMENTATION PAGE BEFORE COMPLETING FORM

T. 'REPORT NUMBER J GOVTr ACCESSION 040. 3. RECIPIENT'$ CATALOG NUMBER

4. TITLE (amdSubtiIll) 448

A Health and Envirornmental Ef'fects Final Report 348

Data Base Assessment of U.S. Army 6. PIFRFORM1ING ORO. REPORT NUMBER

WasteMateial.CARLTECH No. 8447

7. AUTHOR(&) S. CONTIACT 0R (54ANT NUMBERWa)

J. Carl. Uhrrnacher, Principal. Investigator DA1DI7-84-C-4+133

S. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT. PROJECT, TASKCARJTEC1 ASSCIATS IAREA 4 WORK UNIT NUMBERS___________________________________________

______________Inc._______________________

Overlook Ctr., 5457 Twin Knolls Road A.1Columbia, 1VD 21045___ _________

11- CONTROI..LING OFFICE NAME AND ADDRESS 12. REPORT~ DATE

U.S. Army Medical Res. & Dev. Command March 4, 1986Fort_____Detrick____________NUMBER_____or___________

Frederick:- MD 21701-5012 --_____451._____

14. MoAt-YORIlie G JSIOICY NAE # APODRESS( 01ttio",I hus. Z.tInte m~g oWl) Is. X&C50R~y CLASS. (4,1 ship n~art

U.S.. A~rmy Medical Bioen~gineering Research Unlssfeand Developmentý !Aboravory

___0_

FrederiLck, = 21701-510 -0

ts- DiSTRI SUTtON WtAygEVENT (at Wea RE'ee)

Approved for public rel.ease; distributionunlimited.

Ill. O&STOAGUTIO0 3TATWEWET (011 OWN. OW000 Med L1 840" 20, il WIleIfali 6JO X4Pe$

It. 5M,0.RMNTANY "OTC&3

Toxic, 'Waste, Hazardous, Explosive, Obscur'ant, Environmental,Hlealth

methods. Humans and the environment may be exposed to them in- varying amounts. Proper research planning requires knowledge

ofgp nhat n niometldt ntoecmons

OA.RLTECH was contracted to develop a data base on health and

Un 103 usow orIov' NOV 04Wo.Lte

scczw" M$,"CAT V-N*Ui 04-2c (ft" DOI "1

stcuvRv~ 1 cSI FwICAY10"or THIS PAGI(ftbm Do& snfed)

environmental eff~ects of waste materials generated bythe U.S. Army.

The project was divided into two phases:

Phase I which consisted of identification of Army-uniquematerials for inclusion in the data base.Phase 11 which consisted of researc'ning,.aggregating andreporting data on physical, chemical, health andenvironmental properties of the substances. This reportczovers Phase II efforts.

J.ix~ty-one substances were studied during Phase 11 of thisproject. Data on chemical and physical properties, Armyand other uses, analytical methods, health effects,environmental- effects, standards and regulations, anddisposal methods were obtained on each substance researched.

Results of this project with respect to data gaps are -4presented below. Physical and chemical data; analyticalmethods; and health effects areas had the better datacoverage. Twenty substances had insufficient direct healtheffects data and were characterized using structuralanalogues. Additional research is required for these20 substances.

AREA ESSENTIALLY SOME SEVERECOMPLETE GAPS GAPS

Physical andChemical Data 40 1.5 5

AnalyticalMethods 43 8 9

Health Effects 35 24 1

Environmental 1

Standards andRegulations 1.5 33 12

Disposal Methods 35 23 2

SCCUOWYV CLASS4FSC*IOII Of TIMIS PAGOIWft~ VWO tftftf*O

EXECUTIVE SUMMARY

The U.S. Army uses a variety of substances on a regular basis inaccomplishing the missions of training, defense, and weapons development.These materials include pyrotechnics, fuels, explosives, obscurants,propellants, solvents, lubricants, preservatives, and chemical intermediates.The diversity of the substances brings about a wide range of uses, storageand disposal methods. Humans and the environment are exposed to thesesubstances in varying amounts.

The U.S. Army Medical Bioengineering Research and Development Laboratory(USAMBRDL) was charged with identifying hazards of materials currently beingused by the Army. Proper research planning required identification of thecompound and,especially, informational gaps in health and environmental data.What is required, therefore, is development of a data base on health andenvironmental effects of waste materials generated by the U.S. Army.

This project was divided into two phases:

"o Phase I consisted of identification of Army-unique materials forinclusion in the data base.

"o Phase II consisted of researching, aggregating, and reporting dataon physical, chemical, health, and environmental properties of thesubstances identified in Phase I and identifying data gaps.

"This report covers Phase !I efforts. Phase I efforts are reported indetail in a separate document prepared under this contract, "Phase I Report,May 1, 1985."

The following types of data were obtained on each substance during thisstudy:

o Chemical and physical datao Army and other useso Analytical methodso Health effectso Environmental effectso Scandards and regulationso Disposal methods.

Both manual and computerized methods of literature search were used. Twenty-four computerized databases were consulted.

The methodology included searching twenty-four computerized databases forphysical and chemical properties. Handbooks, such as the Chemical RubberCompany Handbook of Chemistry and Physics, and Army references were used toconfirm, and supplement database'information. Material Safety Data Sheetsand Hazardous Component Safety Data Sheets were used as alternate sources for

Ssupplementing database information.

DAMDI7-84-C-4133 I

Preceding Page 5 Blank

Army Hazardous Component Safety Data Sheets and Army TechnicalPublications provided Army use data. Interviews with Army personnel alsoprovided information. Civilian use information was obtained from handbooksand from databases* Army technical literature, and vendors were consulted ifother sources were inadequate.

Analytical methods were obtained from databases and were evaluated usingthe following criterion: Trace or forensic analytical methods or those usingseparation were preferred. If more than one method satisfied the abovecriteria, both were reported. Environmental, health effects, and healthrelated standards and regulation data were obtained from the literature, fromspecialized computerized databases, and by estimation. Bioconcentration

* factors were estimated using the Veith equation whenever possible. Wheneverliterature reported experimentally-determined values of bioconcentrationfactor, both estimated and experimental values were reported together.

( Data from Section 8(e) of the Toxic Substances Control Act supplemented* handbook data. Characterization of toxic effects for substances with little

or no toxicity data was completed using information based on structure/activity relationships (SAP.).

Environmentally related standards and regulai~ions were obtained from theFederal Register, and from specialized databases.

Three types of disposals were considered during Phase II.-

0 Current Recommended Army Disposal Practiceso Alternate Disposal Practices under Consideration by the Army0 Other Disposal Practices Employed.

Disposal practices were obtained from Army reports, privatecommunications, manuals, and chem~ical supply catalogs.

Sixty-one substances were studied during. Phase II (Exhibit 11-1) of thisproject. Acetic anthydride was eliminated from further consideration in phae.11 because rapid hydrolysis poses a minimal threat on release to theenvironment.

Potassium dinitroben.zofuroxan was particularly difficult to characterizebecause data on empirical sod structural forinulaa were significantlydifferent from data reported in Army ref orence.1. A recent article confirmingthe structure through infrared and nuclear magnatic resonance spectroacon'ywas avaluot-ad and incorporated. Lead Otypimate bad four different formulas.structuret, Registry N~umbers, molecular weights and index riemes.

1< Tweay substances had little or no toxicity data (Exhibit III-)), Ina theabsence of data,.tuxicity infortiation about structurally rvlated substances

or sustance classes was reported. tew, if any,* substances had ccupleteouvironaent*l covertge. Physical &ad hernicel data, oanaytical sbdadbeath ares. Wa the bettor data coverage. Regulations bapo cerage

but nowteaula i~ ort Viloon b issued coveng ~ u ofi~b subst4anca

Dat ga intboproject ar itdbelow adisoedetail i xii

DAIWI7-44C-4133 2

ESSENTIALLY SOME SEVEREAREA CON2LETE GAPS GAPS

Physical and Chemical Data 40 15 5Analytical Methods 43 8 9Health Effects 35 25 1Environmental Effects 18 26 16Standards and Regulations 15 33 12Disposal Methods 35 23 2

Based on results presented in Section III, the largest number of datagaps were found in the following areas:

o Environmental Effectso Health Effects.

In no case did Environmental Effects have total data coverage, even for well-documented compounds. This lack of coverage is believed to be caused by lackof research in some specialized areas. Additional research would be requiredfor total coverage if desired. Twenty substances had insufficient directhealth effects data and were characterized by using structural analogues(Exhibit 1II-1). Additional research is required to conclusively identify

* health effects of those 20 substances.

In general, waste preservatives, inorganic obscurants and new orexperimental ordnances appeared to have less data available than othersubstances. Ulmost no data were available for magnesium thorium alloy, whichhas fairly widespread use and possesses many apparent environmental andoccupational hazards. It is recommended that research be conducted onhazards of this waste substance. While data were available on analyticalmethod descriptions, data coverage of lower limits of detection was poor.Further research is needed to clarify this area.

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CONTENTS

EXECUTIVE SUMMARY ............. ............. .. 1 ........ 1

I. INTRODUCTION ................. .. ............ ....... ... 7

A. BACKGROUND ......... ................... ... ....... 7Be PURPOSE ............................ . .. ...... . 7C* ORGANIZATION . . . . .9......... . .... .... 6 7

II. METHODOLOGY ................... 8

A. DATABASE AGGREGATION AND ORGANIZATION .......... . 8B. CHEMICAL AND PHYSICAL DATA......................... 8

1. Structural and Chemical Formulasand Molecular Weight 8..... ................... 8

2. Alternate Names and Registry Numbers .......... 83. Chemical and Physical Properties ,............ 8

C. USES 9. ..... .,.,....... ..... , 9D. ANALYTICAL METHODS ,...9........ .... .........BE. HEALTH EFFECTS .......... ,..,, ... ..... ,,,.,,, 10

1. Literature Retr1eva,.......................... 102. Structure Activity/Related Data................, 113. Data 1ega1tow....................,..........., 1

F. ENVIRONMENTAL EFFECTS. * ......... 114 G. STANDARDS AND REGULATION .......... . ...... ..12

H 121. REVIEWS 06600660066000000.06..13

SIII. RESULTS ...... ..................... .. ..... .......... 21

A. ChMICAL AND PHYSICAL DATA.. .... .....-..... ...-.. 21 •:

1. Structure and Chemical Formulasand Molecular Weight... ..... . 6.0.0..... 21

2. Al.ternate Nazue and Registry Ntumbers.......... 21

B. HLEALTH EFFECTS.......... , ....... ...... ,...... 2C. ENVIRO, S.. ..AL..,00600,.. 22

E. DIATA GAPSAL .,,o .. ... ,..... .....o. 6 ........ 6 0 . 23

IV. 606IONS AND 0 6ATIONS .. ... 32

... V. - .EM-CESC. ..... ,,,,..,-,......,.. 33

0AiD17-84--C-4133 4

APPENDIX A: ANALYTICAL SEARCH METi{ODOLOG'................... A-i

APPENDIX B: DATABASE...... . .... 9 . ....... ... ......... 11

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DND17-8A-C-413 5

LIST OF EXHIBITS

EXHIBIT II-I. WASTE SUBSTANCES STUDIED DURING PHASE II,SUBSTANCE NAME VS. CHEMICAL ABSTRACTSSERVICE (CAS) REGISTRY NUMBER................ 14

EXHIBIT 11-2. CHEMICAL SUBSTANCE REPORT FORMAT,,,.......... 17

EXHIBIT 11-3. ABBREVIATIONS USED IN ENVIRONMENTAL ANDHEALTH EFFECTS TABLES...... ......... ,.... ..... 20

EXHIBIT II-1 . CHEMICALS REQUIRING ANALOGUES TO PROVIDEAPPROXIMATE HEALTH EFFECTS ................... 24

EXHIBIT 111-2 DATA GAPS IDENTIFIED....................... 25

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I.INTRODUCTION

( A. BACKGROUND

The U.S. Army uses many substances on a regular basis in accomplishingthe missions of training, defense, and weapons development. These materialsinclude a wide range of pyrotechnics, fuels, explosives, obscurants,pro pellanits, solvents, lubricants, pres ervati~ves, chemical intermediates, andchemical-bacteriological warfare agents*

These Army materials have a broad range of uses, storage, and disposalpractices. At any time, humans may be exposed to these materials in varyingamounts. The U.S. Army fe~lt that a complete assessment of the effects ofthese subs tances on the environment and on human beings was necessary sothat consistent and valid handling and disposal standards could bedeveloped.

The U.S. Army Medical Bioengineering Research and Development Laboratory(USAKIBRDL) was charged with the responsibility for dev~eloping a data base onenvironmental effects of waste materials generated by the U.S. Army. Thisdata base was to include state-of-the-art knowledge about both health, andenvironmental effects of release of these substances, chemical and physicalproperties, current uses (both military and civilian), methods of analysis,and current, proposed, or alternate disposal methods. This data base willbe used by the Army to develop internal environmenLal Standards for safe andeffective handling of these substances.

This project was divided into two phases accordin6 to the contract.Phase I consisted of identification of Army-unique materials so thatUSAMMRD could select materials to be included in the data base. Phase 11consisted of researching, aggregating, and reporting dars on physical,chemical, health, and environmental properties of the aubstances identifiedIn Phase I 4nd locating data gaps to be completed by additional research.This report covers Phase 11. Phase I efforts are reported in detail in aseparate document prepared under this coutract, 'Pbaae I Report, May 1,

B98. PR

~.In accordance. with the goals discussed above, the UtS. Army has

contracted with CARL.TECH ASSOCIATES, INC. to prepare a list of Army-uniquecompo~rnds and to assemble a data b&.se on these substances. This reportpresents both the data base and the results of efforts identified 61

L cbezica1s in Phase I and analyzed them in Pha"* 11.

Co O!RGAIUZAION4

Section 11 of this report covers w.ethodologi..a used to oabtain thephysic~, cemlwical. envirormental, and health data required for Phase IlaSectioa III praegauts rssult# of thit research. Seetion IV covert.conclusions and recommaudat ions, Appendiz A contains oplanatory materialk ~and Apptadix I co*tatna 0bA data base of 60 tubatanu~ea Each vast-substoanc ise described inc aself-contained chsaical report which presentsdata and also iacmudes references and otber luformation usead.

D M 17-84-C-4133 '7

II. METHODOLOGY

A. DATA BASE AGGREGATION AND ORGANIZATION

Sixty-one waste substances were identified in Phase I (Exhibit I-i).Twenty-one waste substances were discussed in an earlier series of chemicalreports prepared by the Atlantic Research Corporation (ARC) (1). Only datamore recent than ARC were reported. A data form was developed to recordaggregated data on each individual waste substance (Exhibit 11-2).

B. CHEIICAL AND PHYSICAL DATA

1. Structure and Chemical Formulas and Molecular Weight

Structures and chemical formulas were obtained from several sources andwere cross-checked whenever possible. Both the Chemical Abstract RegistryFile (CAS Online) and the Structure and Nomenclature Search System (SANSS),available through Information Consultants, Incorporated-Chemical InformationSystem (ICIS) were used to supply structure and chemical formula data forall compounds. Use of these online databases is discussed in more detail inthe following section. Handbooks and other references were consulted toconfirm or supplement database informazion.

Molecular weight could not be found for a few compounds, so molecularweight was calculated, using the CAS or SANSS empirical formulas and thecurrent International Union of Pure and Applied Chezistry (IUPAW) atomicweights for the constituent eltents.

S2,, Alternate Names and Re.gi,,try Numbers

This segment of the project identified the comwon or trivial name of acompound, the correct CheaIcal Abstracts Collective Index name(s), syuonyms,W Registry Number, and RTECS Registry Nuabers, where possible.Determination of the correct CAS reg.ary uamber was the first step inpreparation of a dato base substance file. Obtaining subsequent data such asphysical and chemical properties and bealth effects depended on successfulcompletion of twis step.

Information on sources included the follouinp:

o ICiS dat abae system was searched for physical and cheamicalproperties using CAS Regis try 1Nuabrs and synonym*.

;6- o 011 wd Aaardous K(aterial Technical AseistUce Data System,(O aADS) was searched for reactivity, corrocivity, syneSisetic,ater1ls-, anzagoedstlc Rateriaso, fieldoand itborstory detectiona

L fitaabilityv, flash point, autoigc4iiioa point, oxptoisvausass,salting aMW bolitg points, Solubiltty, specific gravity, vapor! ssuro and vapor denIty.

DO17-84-C-4133 8

ENVIROFATE, an ICIS databa.se, supplied solubility and vapor pressuredarta and a few octanol/water partition coefficient3.

o Information Consultants, Inc.-Chemical Information Systet.,A.•. Information for Hazardous Organics in Water (ICIS ISHOW), supplied

octanol/water/partition coefficients. Some partition coefficientswere estimated by Drs. Leo and Hantsch (7).

0 Handbooks included Chemical Rubber Company Handbook of Chemistry andPhysics (2), the Merck Index (3), the Encyclopedia of Explosivesand Related Items (4), the Army Engineering Design HandbookProperties of Explosives of Military Interest and the Urbanski fourvolume monograph on chemistry of explosives (5) (6).

o Alternate sources were Material Safety Data Sheets and HazardousComponent Safety Data Sheets.

C. USES

Army use data were obtained from interviews with Army personnel, ArmyHazardous Component Safety Data Sheets, Army Technical Publications, and 1literature published or sponsored by the Army in the Civilian sector.

Civilian use information was obtained from the same sources listed in thechemical and physical properties section. If the compound was listed in the1985 Chemical Buyers' Directory, the manufacturer or vendor was coutacted ifno other source of information was available*

D. ANALYTICAL HETBODS

Analytical methods were obtained fro -citations retrieved by an onlinedatabase search of STN International's Chemical Abstracts File, which is thecomputerized searchabte form of the printed Chemical Abstracts. Usingadvanced search strteegy, a query "hedge* was formulated to retrieve relevantcitations from Chemical Abstracts.

Highly posted compounds such "s ethylene glycol were searched by limitingthe range to a particular time period which would provide the most roce tinformotion. The search ou these oarticular coapounds was Imted toJanuary, 1984 to present.

Substances not considered analytical reagents or solvents were searchedusing the Soolean "AND." Substance reports which were ARC updates werelimited by range to January, 1964 to prueat since only updating wasrequired.

Bard copies of citations were retrieved from libraries. Because mamyarticles vere inatcesible through usual retriev&l setbods, an extendedabstract, including all bibliographic and indexing iuforuato.on, was retrievedfrom the CA file and used in this project. Search methods are discussed inmore detail in Appendix A.

DAMD17-8.-C-4133 9

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Analytical methods for each compound were evaluated using the followingcriteria: I

0 Methods for trace or forensic analysis, when available, were chosenover quality control methods. Trace methods were more applicablefor the evaluation of health or environmental effects. If no tracemethods were published, then quality control methods were includedto indicate a direction for analytical chemists to follow.

o Preferred methods included separation or the compound-specificmethod. These methods are more applicable for the evaluation ofhealth or environmental effects because the compound is usuallyfound in complex analytical matrices such as soil, water, urine, orblood.

o If more than one method satisfied the above criteria, both werereported because the best available method for a laboratory is onecapable of using available equipment to reach the requiredsensitivity. However, the most sensitive method published on agiven technique was chosen for discussion.

o For inorganic salts, if no methods were available for the compoundas a whole species, methods were discussed for each component part.For each method chosen, the application, the technique, theequipment required, sample type, and limit of detection werereported.

E. HEALTH EFFECTS

Collection of health effects data involved retrieval and extraction of* ~-~i [ information dealing with the toxicity of the chemicals examined.

I# Literature Retrieval

L- Data were obtained from computerized databases and literature listedbelow,

o Chemical Hazard Information Profiles (CHIP's), Office ofPesticideci and Toxic Substances, U.S. Environmental ProtectionAgen..y

"L' o IARC Monographs on the Evaluation of the Carcinogenic Risk of"Chemicals to Humans (Volumes 1-29 on Chemicals, IndustrialProcesses, and Industries Associated with Cancer in humans)

o Natioral Cancer Institute, National Toxicology Program Technical

Reports on the Toxicology and Carcinogenesis Studies of Various• L Chemicals

0 NIOSH Criteria Doculentsa

- o0 Several health-effects handbooks were also searched on a routinebasis fo health data (2,3,8,9,10,11,12,13,14,15,16,17,18,19,20,

"21,22,23)

DA)W17-84-C-4133 I.

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0 Material safety data sheets

o Section 8(e) of the Toxic Substances Control Ac:, EiivironmentalProtection Agency

0 MEDLARS, National Library of Medicine (used for data retrieval).

The NIOSH Registry of Toxic Effects of Chemical Sabstances (RTECS) (22)data record was examined to determine the existence of positive data onspecific chemicals. If RTECS and other handbooks contained necessarytoxicity data, no further searches were conducted. TOXLINE and its twobackfiles were searched for back-up data. Chemicals in the 1978 AMC updatesand in the TOXBACK 1965 file (1965 to 1974) were not searched. The workscopeof this project limitee the number of articles or reports to six. Thus,

* original research reports were selected for chemicals with limited data baseand manual citations. Recent review articles, when available, were selectedfor chemicals with more than 30 citations in the bibliographic databases.

Foreign language -rticles generally were not used, but English abstractsof foreign language articies were used for soma chemicals with limited data.Articles and reports wera obtained fro•. Washington D.C. area libraries;Defense Technical information Center (DTIC), Alexandria, Va; and NationalTechnical Infor . ton Service (NTIS), Springfield, Va.

2. Structure Activity/Relationshi2 Data

Considerable project effort was devoted to toxic effects characterizationof substances with little or no toxicity data. Information based on

* structure/activity rela:ionships (SAR) was obtained for these chemicals.Preliminary research was necessary to determine a feasible application of SARdata for incorporation in this report. Several SAR methods were researched(See Section ItI-B).

3. Data Aggregation

Data from reference books and the RTECS data base were not evaluated.

1Data from primary sources, i.e., original research reports, were evaluatedfor test results and uethodology, author's conclusions, proper laboratorypractices, statistical analyses, cmpletaness of data, and applicability tot•he toxic effects characterization, Study inadequacies ouch as the lack of atest group or failure to specify the physical State of the test chesical were

reported. Data were extracted and organized Into a tabular format andIncluded in the substance reports.

Abbreviations ustd in both environmental and health effects tables aref ound in Exhibit 11-3.

V. ENVIRD•OtEKTALT EFFECTS

Eavitonsental data were obtained from the literature and by Utiaation.Potential literature citations were located using enviroMentally orieatedI computerized database& which Lncluded the following.,

WIDl 7-84-C-4133 A1t L

ENVIROLINEAQUALINEENVIROFATERTECSOHMTADSCHEMICAL REGULATIONS AND GUIDELINESCHER SEARCHNIOSHNTISENVIRONMENTAL BIBLIOGRAPHYGPOPOLLUTION ABSTRACTSTSCA INITIAL INVENTORYIDTIC.

Citation titles from the databases were examined; for titles appearingpromising, journ•ls were ordered. For titles considered doubtful, abstractswere requested and reviewed. Handbooks were also used (24). Occasionally,databases such as RTECS, £NVIROFATE and OHMTADS contained directly relateddata. If the data appeared consistent with that found on the liter6ture,then the information was included in the report.

Bioconcentration factors were estimated usi•g the Veith equation wheneverpartition coefficient data were available:

Log BCF a 0.76 Log P + 0.23 (25)., where P is the Octanol-Water Partition coefficient.

Wherever literature had experimentally-determined values of bioconcentrationfactor; both estimated and experimental values were reported together.

G. STANDARDS ANDi REGULATIONS

hUealth-related standards and regulation were obtaiued principally from

the Fire Protection arnual (26) and the OUKTADS, RTECS, and OccupatioalWoSatcy and Health Databases.

. Envirotmental related standards and regulations were obtained from the

Federal -Reister. and from the ENVIKOFATE, OU•ADS, aWd TSCA INITIAL11 INVENTO&Y computerized databases.

V H. DISPOSAL

Three zypea of disposal were cousidered during Fhase II:

o Current Recoomanded Army Disposal Practiceuo Alteruto Diapogl Practicts under Consideration by the Armyo Other U1iip"&L POraittces Esployed.

L Current Army disposal practices are those now used by U.S. Army±zia•a.&taacons to rmove wate %ttrte contetnrng uae c matre of the 6 0isubstances idetified itn Phase I of this ptoject. These were identified from"ArWy reports (21) and ftow private coamuoications uwth U.S. Army person"el

"" D7-8' --C--4133 12

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(28). Data on alternative disposal practices, i.e., those underconsideration by the military, were obtained from USATIIAMA personnel, fromthi U.S. Navy CHIL Manual (ii), and from Army reports. Data an civilian andother disposal practices were obtained from the same sources discussed aboveand B.so •rom em~ica suo~y canalog 12tc)hechemi

u.sposanytApormation s eva uatei in the chemicalreport for a substance whenever one of two conditions was achieved:

o The substance was identified specifically by name in the referencecited; or

0 The waste substance belonged to a class of materials discussed inthe reference cited. Examples of such classes included explosives,pyrotechnics and obscurants.

I. REVIEWS

Each chemical report received three sets of reviews prior to issuance ofthis report. The aggregated reports were reviewed by colleagues. Afterincorporating comments, an "outside review," was performed by scientists andengineers who had not contributed to the earlier phases of the project.After incorporating cownents, the 60 chemical reports were given final reviewby -the tezhnJ :'el _Jitor and the project manager.

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EXHIBIT 11-1

WASTE SUBSTANCES STUDIED DURING PHASE II

SUBSTANCE NAME VS. CHEMICAL ABSTRACTS SERVICE (CAS) REGISTRY NUMBER

CAS COMPOUND PROJECT

NUMBER NAME FILE NUMBER

7446-70-0 aluminum chloride 02

2582-30-1 aminoguanidine 03bi carbonate

1.253-51-3 iso-amyl alcohol 04

110-46-3 iso-amyl nitrite 05

1345-04-6 antimony trisulfide 06

1304-29-6 barium peroxide 07

59744-77-3 battery lithium 08

4 94-'36-0 benzoyl peroxide 09

9007-13-0 calcium resinate 10

1592-23-0 calcium stearate 11

16774-21-3 ceric ammonium 12

2-,- nitrate

127-65-1 chloramine-T 13

10380-28-6 copper 8-quinolinolate 14

L 1338-02-9 copper naphthenate 15

108-94-1 cyclohexanoue 16

106-19-4 dipropyl adipate 17

; 4682-03-5 diazodiaitrophenol 18•_ ~87-31.-0 -

116-52-5 dichlorodimethyl- 19hydantoin (DAN)

* 97-23-4 dichloropheno 20

DMW17-84-.C-4133 .14

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• .• . •.•',•'., :',':L•' •'" -•• : , . ," -:.', " "' .... • -;•', *f•,• ; k';•i'•,'"*

693-21-0 diethylene glycol 21dinitrate

111-40-0 diethylene triamine 22

4096-88-2 dinitrophenyl azide 23

(2,4-)

122-39-4 diphenylamine 24

85-98-3 ethyl centralite 25

107-21-1 ethylene glycol 26

628-96-6 ethylene glycol 27dinitrate

L 10-80-5 ethylene glycol 28monoethyl ether

i 75-21-8 ethylene oxide 29

80-13-7 halazone 30

302-01-2 hydrazine 31

13465-08-2 hydroxylammonium 32nitrate

13424-46-9 lead azide 33

51331-05-6 lead styphnate 3415245-44-012403-82-6.63918-97-8

592-87-0 lead thiocyanate 35L12438-53-8 magnesium thoriun 36i ~alloy."

2385-85-5 mi rex 37

86-30-6 N-nitrosodiphanyl- 38

3156-73-8 nitro,2-propamol 39

119-75-5 b-ui trodiphanylamine 40

2899-02-7 octsachlor carluiJ.lde 41

100-02-7 p-nitrophenol 42

DAMDI7-84-C-4133 15

.•-,15

78-11-5 pentaerythritol 43

tearanitrate ¾

7719-12-2 phosphorus trichloride 44

29267-75-2 potasoium dinitro- 45benzfuroxan

7778-74-7 potassium perchlorate 46

6423-43-4 propylene glycol 471,2-dinitrate

3457-90-7 propylene glycol 481,3-dinitrate

7723-14-0 phosphorus, red 49

26628-22-8 sodium azide 50

7601-89-0 sodium perchlorate 51anhydrous

814-95-9 strontium oxalate 52

28453-24-9 tetranitrocarbazole 53

479-45-8 terryl 54

7550-45-0 titanium tetrachloride 55

S67539-61-1 triaminotriui ro- 563058-38-6 benzene

L

L 27096-29-3 triethanolazouium 57nitrate

rL 111-22-8 triethylene glycol 58

dinitrate

128-66-5 vat yellow 4 59

12185-10-3 white phosphorus 60

LAND AND7723-14-0 phosphorus (includes

all forms)

L 12001-85-3 zinc naphtheu4te 61

+I

I;DAHD17-84-C-4133 16

L, 7iiii

EXHIBIT II-2

SC•EMICAL SUBSTANCE EEPORT FORMAT(i

I. CHEMICAL AND PHYSICAL DATAr

itSA. Structural and Chemical Formulas and Molecular WeightS. i ii .•mmmm•imm•.mw •mmIM. |ll

Chemical Formula:

Molecular We±gh•:SStructural formula:

B, Alternate Names and ReEistrv NumbersS.i / " i i I

CAS Registry Number:

,- Deleted Cas R•gtstry Number:

L CA Name (9CI) :

CA N•ne (8C1) :

i /"

• RTECS Number:

Physlcal State:

i: L Colo•:

I t, Odor: i

!' Melti• Point:,

F L Freezing Point:: / I

Bo£11ng Point" .;o.S•': t'

L. Solubilities:-.:•,•

f Water: •;•,S•o•tquoouB Solvents: !i•i

L Octanol Water Part£t£on Coefficient: :!:il)

i:: , "yS'•cop£cit¥; i:••.

Specific Gravity (Liquid):

Vapor Pressure: -

Flash Point:

Specif ic Heat:

Heat of Combustion:

Reactivity:

Refractive Index:

Vapor Density:

Autoignition Temp:

Stability:

Flaumabil~ity:

II* USES

A* Army Unique Use

B, Other Uses

III. ANALYTICAL 14ETHODS)

A. Best Acceptable Method

B. Limit of Detection

IV. HEALTH EFFECTS

V. ENVIRONMENTAL EFFECTS

A. Environmental Fate

LAl. Transport

Ala* Adsorpcion:

Alb. Vol~atilization:

Ales Infiltration:

Aid. Bioaccuasilationl:

A2. Trawf ormat ionA~a. Biodegradation:

DAMWI7-84-C-4133 18

, •: A2b. Hydrolysis :

A2c. Phocolysis:

A2d. Other chemical reaction:

t4e. Half-lif e:B. Effects on animals

B1. Avian species:

B2. Mammalian wildlife species:

B3. Terrestrial invertebrates:

B4. Reptiles:

B15. Amphibians:

B6. MicroorganiSms, aquatic and soil:

117. Aquatic species (fish and invertebrates):

Fish:

Invertebrate:

SC. Effects on •iants

,.tC1. Phytotoxicity:

L C~. UptALe

C3. Metabolism:

VI. STANDARDS AND REGULATIONSI.

A &. He!ath

TLV:- TWA:•" L STEr.:

B. Envlronmental

VII. DISPOSAL

Lit. Crct Recoma~nded~ AMY Ding Practtic-ea

B* Alturatik Die o ac)tices Uader Consideration by the Ar

"C. Other 01! Practit•c

VIII. KUEZNCE.S

"OjI-44.C-4133 19

EXHIBIT 11-3

ABBREVIATIONS USED IN ENVIRONMENTAL AND HEALTH EFFECTS SECTIONS

Route Effects

inh - inhalation LD ' lowest dose expected to cause deathsc - subcutaneous of 50Z of an animal test populationip - incraperitoneal LCLC - same as LD 50 for inhalation studiesiv - intravenous Lo - lowest reported lethal doseim - intramuscular LC - same as LD_ for inhalation studiesoccup occpatioal T50 boccup. -occupational TD lowest reported toxic doseexp. - exposure TC Lo same as TDLO for inhalation studies

NS - nor specified

)d

tt

DAKD-81.-C-43.33 20

tk

111. RESULTS

Sixty-one chemicals were studied during Phase II of this project. kcetic( anhydride was not included in Phase II because it undergoes rapid hydrolysisin water to form acetic acid, a common chemical readily metabolized by mostplant and animal life. Data obtained on acetic anhydride indicated that itshalf-life at neutral pH and normal ambient temperature (assumed to be 25 C)was less than one hour, thus not posing a significant environmental threat (31).

* ~A. CJOAEICAL AND PHiYSICAL DATA

1. Structure and Chemical Formulas and Molecular Weight

Several compounds, such as calcium resinate, copper naphthenate and zinc* naphthenate, do not have defined structures, formulas or molecular weights

because they are salts formed from acid mixtures aud are, therefore, notprecively defined.

2. Alenate Nme :ndRegistryNumbers

The Chemical Abstracts Registry File, a computerized database, lists sixmillion compounds. each thteoretically with a unique Registry Number.Hiowever, because of inherent vagueness in indexing chemical literature,compounds occasionally have more than one number. CAS makes every attempt todelete duplicate numbers, but to make a complete and comprehei~sive searchrequires identificacion of deleted Registry Numbtrs.

Two compounds, triaminotrinitrobenzene (TATB) and tetranlitrocarbazole* ~(TNC). are examples of two active registry numbers for the slue compound.

TNC is indexed under 9H-Carbazole, 1,3,6,8-tetranitro- &and 9&I-C~arb~az~ole,tetranitro-; UTJB is indexed under 1,3.3-Bentaentriamine, 2,4,6-trinitro andBenzenetriamine, ar,ar,ar-trinitro-. Wheo authors do not explicitly statethe locants for the functional groups, WCASaigns citations to the generalrather than the specific chezical name.

Diazodinitrophanol is listed in GAS under two completely different names.The struictures appear differenit, but are resonance structures for the 9azecompound. This cross-over was retrieved through the ICIS SAINSS database.Tho Chesi~.l Abstracts system was notified and Registry File experts agreedthat this vas the sawe compound.

White and rMx phosphorus posed & special problem because of identicalchemical oeaposition, but different physical properties. In addition, thereWere tVo Ragistry Numbersi, one for phosphorus in geuora~l and orm fortetrohedral phosphorus. White phoophorus Is gonerally considered to betvtrahodri._ , but a search must -also include the Registry N~umber forphosphor". Retrieved. literature must be checkeAd to "asure data ar-e asaignedto the proper allotropet

t iniottial evauation of &outeof the namat sppliedindicat~ed insuffkicient

dinitrophenyl aside existed as several geometric ivdmers. BatteryLithium"

anihydrous &Md bydraced fOES.o Furthesr cJarificatio& vas obtawi~d ft=m Army .

~)L.DANDI7-44-C-4133 21

Additionally, dinitrophenyl azide had r olhe- ,roblem. Searching underthe compound name, dinitrophenyl a.ide, in ICISý aANSS, two entries wereretrieved: Benzene, I-azido-:,4-n i itro-, RN 4096-88-2; and Hydroxylamine, 90-(2-4-dinirophenyl) RN 17508-17-I. These compounds are not the same,although they are related. Both listed the same RTECS number and synonyms,but the structures were different. In checking the CAS entries there was nocross-over of names or synonyms. The problem was eventually traced to amechanical failure in the tape sold to ICIS by CAS and CAS was forced torecall the tape. The extent of this problem is unknown, but future searcheswill require both numbers to be used in databases other than CAS.

Potassium dinitrobenzofuroxan was a particularly difficult compound.The empirical and structural formulas found in CAS were significantlydifferent from the Army references, including the Encyclopedia of Explosivesand the Army Engineering Design Handbook. CARLTECH discussed with ChemicalAbstracts experts the source of their information in order to explain thedifferences. CAS's source was an article published in France in 1969. Arecent article (30), pubt.ished jointly by the Naval Weapons Center at ChinaLake, CA and the Materis Research Laboratories of Australia, confirmed theCAS structure throug" infrared and nuclear magnetic resonance spectral data.The article states t•,•t thi, correct structure is not widely recognized in theexplosives communityo However, GAS also was not completely correct and theEighth Collecti-,L Index Name was wrong and was corrected at the behest ofCARLTECH.

Lead s*-jhnate posed a different type of problem. Lead styphnate hadfour different formulas, structures, Registry Nvmbers, molecular weights, andindex names. The ratio of lead to styphnate moiety varies and is sometimesundefined. Hydroxyl groups also varied. All four compounds and theirRegistry Numbers were included for completeness.

B. HEALTH EFFECTS

When all means of data acquis'.tion had been exhausted, there remained 20chemicals with little or no toxicity data (Exhibit I11-1). Searches of the

National Library of Medicine and citations contained in the TOXLINE data baseidentified work primarily in the area of drug analogues and pharmacologicreceptor sites. Information obtained from an American Chemical SocietyConference on SAR analysis and other sources indicated that work in the pastfocused on mathematical and computer modeling techniques. EnvironmentalK Protection Agency, Premanufacture Notification (PhN) submissions and otherdocuments were examined for insight regarding the current practicalapplication of SAR ar•zlysia. As a result of this research, the decision -asthat in the absence of toxicity data on the chemical of interest, toxicityedta of structurally related chemicals and chemical classes would beretrieved and presented. The manual resources and automated data baseslJsted above were used to ubtain this information.

C. ENVINHNOTAL EFFECTS

:ew substances had totally complete environmental effects descriptions.Even well-documented substances such as ethylene oxide had eavironmental datagaps. CVearly, the literature did not explore all enviroamental issues.This is discissed in more detail in section IIt-E.

DAMD17-84-C-4133 22.1i''"

": " I• : "•'l / li • • llla'li Il il l !l , • '•' ',- , - ' , s:• • •,- - .,.,- ".." .. .. ..

D. DISPOSAL

A single chemical needed to be chosen for Battery Lithium, since sourceslisted little or no data under this heading. Lithium Dithionite is achemical present in spent Latteries. This chemical was chosen because it ismost likely to be present in disposal of batteries and is most likely to betoxic in some form.

E. DATA GAPS

Lata gaps identified during this project are presented in Exhibit ITI-2.Briefly, Exhibit 111-2 shows that 40 waste substances had essentiallycomplete information for Physic:al and Chemical Data. Fifteen substances hadgaps in Physical and ChemicUl Dsta, and five compounds had severe gaps.

Analytical Methods showed 43 compounds had essentially complete data,eight compouads had a few g~aps, and nine compounds had severe gaps."Health Effects data coverage was good, 35 compounds had essentially completedata, 24 compounds had some gaps, and one compound had severe gaps.

I - Environmental Effects found 18 compounds with essentially completeinformation and 26 waste substances with some gaps. Sixteen compounds hadsevere gaps in Environmental Data, Simultaneously, Standaras and Regulations

* had 15 waste substances w'ith essentially complete information. There were 33substances with some gaps in information and 12 substances with severe gaps.

Disposal Methods showed 35 waste substances had essentit,.ly completeinformAtion. There were 23 ccmpounds with some gaps in the information and

L� ~two substances had severe gaps in Disposal Method data.

L

L.

S- IL2i

V

-.--- '-.,f-*----

EXHIBIT III-1

CHE.MICALS REQUIR(ING ANALOGUES TO PROVIDE APPROXIMATE HEALTH EFFECTS)

Aminoguanidine bicarbonate

Calcium resinate

Ceric ammonium nitrate

Chioramine T

Copper 8-qu~inolinolate

Di azodini trophenol

S, 3-Dichloro-5 ,5-dimethylhydantoin

Dinitrophenyl azide,

lialazone

Hydroxyl ammonium nitrate

Lead azide

Lead styphnate

Lithium dithionite

Magnesium thorium alloy

LI-Ni tro-2-propanol

Octactilor carbattilide

P~otassiuma dini trobeazfuroxan

Strontium oxalate

Tetranitrocarbazole

j ~Triethanol amznaium vitrate4

ZAN,

DAND17-84-C-4133 24

EXHIBIT 111-2DATA GAPS IDENTIFIED

PHYSICAL. CHEMICAL DATA

ESSENTIALLY COMPLETE SOME GAPS SEVERE GAPS

Aluminum Chloride Calcium Stearate DinitrophenylAminoguanidine Ceric Ammonium Nitrate AzideBicarbonate Chloramine t Magnesium Thorium

Iso-hmyl Alcohol di-n-Propyl Adipate AlloyIso-Amyl Nitrite Dichlorophefle i-Nitro-2-Antimony Trisulfide Halazone PropanolBarium Peroxide Hydrazine Octachlo'rBattery Lithium Hydroxyl Ammonium CarbanilideBenzoyl Peroxide Nitrate TriethanolCalcium Resinate n-Nitrosodiphenylam±Zle Ammonium NitrateCopper 8-Quinolinolate Nit rodiphenylamineCopper Naphthenate 1,2 Propylene GlycolCyclohexanone Dini trateDiazodinitrophenol 1,3 Propylene, GlycolDischlorodimethyl- Dinitratehydantoin Tetrani trocarbazole

Diethylene Glycol Vat YellowDinitrate Zinc NaphthenateDiethylene Triamiae-Diphenylamine

V Ethyl CentraliteEthylene Glycol

( Ethylene GlycolDinitrate

L Ethylene Glycol?tonoethyl Ether

Ethylene Oxide

Lead ThiocyanateMirexp -NitrophenolPentaerythri to!.Tetranitrate

Phosphorus TrichloridePotassiumDinitrobentfuroxanI L Potas sium Perchlorate

Sodium Azide Yj L Sodium Pe rchlorateL Tetryl

DinitrateW~ hite Pbasphorus X

DAMDW7-84-C-40332

ESXHIBIT 111-2 CONTrINUEDDATA GAP IDENTIFIED

ANALYTICAL METHODS

ESSENTIALLY COMPLETE SOME GAPS SEEEGAPS

Aluminum Chloride Barium Peroxide Battery Lithium

Aminoguaflidifle Calcium Resinate Ceric Ammonium Nitrate

Bicarbonate Diethylene Triamine Dichiorodimethyl-

Iso-Amyl Alcohol Lead Styphnate hydantoin

I~so-Anyl Nitrite 1,3 Propylene Glycol Dinitrophenyl Azide

Antimony Trisulfide Dinitrate M'agnesium Thorium Alloy

Benzoyl Peroxide Strontium Oxalate 1-Nitro-2-Propanol

Calcium Stearate TriaminotrinitrO- Octachlor Carbanilide

Chioremifle t benzene Potassium

Copper 8-Quinolinolate Zinc Naphthe~nate Dini trobenzf uroxan

* Copper Naphtheuate Tetrani trocarbazole

* ~Cyclohexanofledi-n-Propyl AdipateDiazodinitropho1nolDichlorophefleDiethylene GlycolDinitrate

DiphenylamifleEthyl CentraliteEthylene Glycol

U -- Ethylene GlycolDinitrate

Ethylene GlycolA ?4onoethyl Ether

~! i Ethylene OxidelialazoneHydrazinleHydroxyl AmmiociumNitrate

Lead AzideLead ThiocyanateMirex14-NitrooodiphenylymifletNitrodiphanylamifle

- -~ .p-Nit rophenolPentaerythritol

Tetranitrato (PETN)Phosphoruso TricbloridePotassgium Porhlorot

1 2-propyioen& Gl~ycolDinitrate

Red Phosphor"sSodi.um AtidsSodi.um ft.-Ceborate

Titodua* ITerraehloride

TriothyowWcC2l DinJitrate

DUuJ17-84-C-412 332

Vat Yellow 4

WhitePhosporusEXHIBIT 111-2 CONTINUED

DATA GAPS IDENTIFIEDHEATH EFFECTS

ESSENTIAL.LY COMPLETE SOME GAPS SEVERE GAPS

Aluminum Chloride Aminoguanidine Bicarbonate Magnesium ThoriumIso-Amiyl Alcohol Battery Lithium AlloyIso-Amyl Nitrite Calcium ResinateAntimony Trisulfide Ceric Ammonium NitrateBarium Peroxide Chioramine-tBenzoyl Peroxide Copper 8-quinolinolateCalcium Stearate DiazondinitrophenolCopper Naphtheuate 1, 3-Dichloro-5 95-dimethylhydantoinCyclohexanone Di-n-propyl AdipateDichlorophene, Dinitrophenyl AzideDiethylene Glycol lialazoneDiniteate Hydroxyl ammonium nitrate

Diethylene Triamine Lead azideDiphenylamine Lead styphnate

vEthylene Glycol Lead thiocyanateEthylene Glycol Lithium dithioniteDinitrate 1-nitro-2-propanol

Ethylene Glycol Octachior carbanilide(Monoethyl Ether Potassium dinitrobenzfuroxan

Ethylene Oxide 1,3-Propylene glycol dinitrateHydrazine Strontium oxalateMirex TetranitrocarbazoleN-Nitrosodiphenylami~ne Triaminotrinitrobenzenep-Nitrophenol. Triethanol ammonium nitrate

L PentaerythritolTetranitrate (PETN)

Phosphorus Trichioride

L

bA)M17-84-C-4133 27

EXHIBIT III-2 CONTINUEDDATA GAPS IDENTIFIED

HEALTH EFFECTS CONTINUED


Potassium Perchlorate1,2-Propylene GlycolDinitrate

Red PhosphorusSodium AzideSodium PerchlorateTetrylTitanium TetrachlorideTriethylene Glycol DinitrateVat Yellow 4White Phosphorus

;)

L

i

AA--

SDAMD7-84-C-4133 28, iDIao

EXHIBIT III-2 CONTINUEDDATA GAPS IDENTIFIEDENVIRONMENTAL EFFECTS

Cc ESSENTIALLY COMPLETE SOME GAPS SEEEGP

ls-mlAluminum Chloride AminoguaflidifleCiSoramifl Ntrt Iso-Amyl Alcohol Bicarbonate

Cyclohenanofle Barium Peroxide Antimony

DihoohfeBattery Lithium Trisulfide

Dipenyamile alium Resinate Beazoyl Peroxide

Ethylenle Glycol Copper ClimSert

Ethylene Glycol 8-Quinolinolate Ceric Ammoniium

MonothylCopper Naphtheflate NitrateEthoer h di-fi-Propyl Adipate Diazodinitrophenoll

Ethlen OxdeDiethylene Triamifle DischlorodimetbYlEthlezne Oxd.Ethyl Centralite hydantoiti

Hlydrazinle Ethylene Glycol Diethylefle GlycolMiexDinitrate Dinitrate

p-Nitrohefl~lHydroxyl Amnmonium Dinitropheflyl zdpeNiterythrtol Nitrate I-Nitro-2-Propanoll

Tetranitrate Lead MAide Otc3o abnld

potassiumlY Lead Styphnate Potassium Dinitro- l

Perchlorate Lead Thiocyaflate benzfuroxafl

Sodium Mzide magnesium Thorium 1,2 Propylene

Sodium Alloy Glycol Dinitrate

Perchlorate U-Nitroaodiphenyl- Triamiflotrili tro-

Tetylamine benzene

White phosphorus Nitrodipheflyl TNiethatoe mmnamine tae

Phosphorus Zinc Naphthenate

TrichloridejL. 1,3 Propylene G3lycolDinitrate

F Red phosphorusStrontium oxalateTetranitrocarbazoleTitanium TetrachlorideTriet'k.;ene GlycolDini trate

Vat Yellow 4

DMM1784-C-133 29 '

7 77,w 8 4 C 44,

EXHIBIT 111-2 CONTINUEDDATA GAPS IDENTIFIED

STANDARDS AND REGULATIONS

ESSENTIALLY COMPLETE SOME GAPS SEVERE GAPSAluminum Chloride Aminoguanidine Iso-Amyl AlcoholAntimony Trisulfide Bicarbonate Ceric Ammonium NitrateBarium Peroxide Iso-Amyl Nitrite Dinitrophenyl AzideCalcium Stearate Battery Lithium Magnesium Thorium AlloyCyclohexanone Benzoyl Peroxide I-Nitro-2-PropanolDichiorodimethyl- Calcium Resinate NitrodiphenylamineDiheylantin (AN Chioramine t Potassium

DpeyaieCopper DinitrobenzfuroxanEthylene Glycol 8-Quinolinolate 1,3 Propylene GlycolDinitrate Copper Naphthenate Dinitrate

Ethylene Glycol Di-n-Propyl Tetranitrocarbazo2leMonoethyl Ether Adipate Titanium

Hydrazine Diazodini tro- TetrachlorideLead Azide phenol Triaminotri~nitro-Lead Styphnate Dichiorophene benzeneLead Thiocyanate Diethylene Glycol Triethanol AmmoniumRed Phosphorus DinitrateWhite Phosphorus Diethylene Triamine

Ethyl CentraliteEthylene GlycolEthylene OxideHalaz oneHlydroxyl AmmoniumNitrate

Mirexn-Nit ros odi-phenylamiae

OctachiorCarbanilide

p-NitrophenolPentaerythri tolTetranitrate

PhosphorusTrichloridePotassiumPerchlorate1,2 PropyleneGlycol Dinitrate

Sodium AzideSodium PerchlorateStrontium OxalateTetryl

Glycol DinitrateVat Yellow 4Zinc Naphthenate

~ ~ i D00I-84-C-4133 30

EXHIBIT 111-2 CONTINUED__ DATA GAPS IDENTIFIED

- DISPOSAL


Aluminum Chloride Iso-Amyl Alcohol Antimony TrisulfideAminoguanidine Iso-Amyl Nitrite Magnesium Thorium Alloy

Bicarbonate Ceric AmmoniumBarium Peroxide NitrateBattery Lithium Chloramine tBenzoyl Peroxide di-n-Propyl AdipateCalcium Resinate DiazodinitrophenolCalcium Stearate Diethylene TriamineCopper Dinitrophenyl Azide

S8-Quinolinolate Ethyl CentraliteCopper Naphthenate Ethylene GlycolCyclohexanone Monoethyl EtherDichlorodimethyl- Lead Thiocyanatehydantoin (DANC) n-Nitrosodiphenyl-

Dichlorophene amineDiethylene Glycol 1-Nitro-2-PropanolDinitrate Octachlor Carbanilide

Diphenylamirne PotassiumEthylene Glycol DinitrobenzfuroxanEthylene Glycol 1,2-Propylene Glycol

S... Dinitrate Dini trateEthylene Oxide 1,3-Propylene Glycol

, Halazone DinitrateHydrazine Strontium OxalateHydroxyl Ammonium Triaminotrinitro-Nitrate benzene

Lead Azide Triethanol Ammonium

Lead Styphnate NitrateMirex Triethylene GlycolNitrodiphenylamine Dinitratep-Nitrophenol Vat Yellow 4Pentaerythritol Zinc NaphthenateTetranitrate (PETN)

PhosphorusTrichloride

Potassium PerchlorateRed PhosphorusSodium AzideSodium PerchlorateTetranitrocarbazole (TNC)Tetryl

L. Titanium Tetrachloride- White Phosphorus

U,3

IV. CONCLUSIONS AND RECOMMENDATIONS

Based on results presented in Section I11, the largest number of datagaps were found in the following areas:

o Environmental Effectso Disposal Technology.o In no case did Environmental Effects have total data coverage even

for well-documented compounds such as ethylene oxide. The lack ofcoverage is believed co be caused by a lack of research inspecialized areas. Additional research would be required shouldtotal coverage be desired.

o Twenty substances had insufficient direct health effects data andwere characterized using structural analogues (Exhibit Ill-1).Additional research is required for these 20 substances to identifyhealth effects.

In general, waste preservatives, inorganic obscurants, and new orexperimental ordnance appeared to have less data available than othersubstances.

Magnesium thorium alloy, while in fairly widespread use and possessingmany apparent environmental and occupational hazards, had almost no dataavailable. It is recommended that research be performed on hazards of thiswaste substance.

I - While data were available on analytical method descriptions, datacoverage of lower limits of detection was poor. Further research is neededto clarify this area.IL

L 4

I 'L

L

I DAKDI7-84-C-4133 32L

7.A

i77

V. REFERENCES CITED

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DAND17-84-C-4133 .33

• ,, . . .. ." .. T.:

jib -A

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* 25. Lyman, 4.J., Reehl, W4. and D. Rosenblatt. 1982. HandbooLk of ChemicalU Propertjy EsrL stiou Hethodet-Enviro.putnal Behavior of OrgAine

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-tion, Quiatyl, MA.27. Forsten, I. 198C. Disposal Of UHaardous Toxic Munition Waote,

Proceeding of the 1980 National Conference of EBvirosenftl Englneer-

Ru iv.Yrk, Jul 8-1 19-80. aZceE EsiroaitlEguarviiinh • .• ,," - o r k .4. ...

•2S, Rnard, David* Personal CcsaUnica*oc. U.S. Atry Toxic and HazardouwsL"Me-ials 4ency p",soane. 19C5

29, Aldtrih Chesales Co. 1984-85. Alfrich t tIOtndbook of Pine KChemicals. Aldrich Cbemical CoP VatYIW -

DAM17-,8-C-4133 34

L,,% : .': ,• ,,,

•:. , ii•• :>:,: " A

30. Spear, R.J., and W.P. Norris. 1983. Structure and Properties of thePotassium Hydroxide-Dinitrobenzfuroxan Adduct (KDNBF) and RelatedExplosive Salts. Propellants, Explosives, Pyrotechnics. 8:85-88.

(31. Gold, V. Hydrolysis of Acetic Anhydride. 1948. Transactions of theFaraday Society. Vol 44. pp 506-518.

r

jL

7

p.

LpL

APPENDIX A

ANALYTICAL SEARCH METHODOLOGY

Analytical methods were obtained from citations retrieved by an onlinesearch of STN International's Chemical Abstracts File, which is the com-puterized searchable form of the printed Chemical Abstracts.

Using advanced search strategy, a query "hedge" (i.e., a reusable setof search terms which builds a search profile for specific topics) wasformulated to retrieve relevant citations from Chemical Abstracts. Thequery used to bearch for analytical methods is as follows:

"QUE (ANAL OR ANALY? OR DETERMIN? OR DET# OR ASSAY OR MONITOR?OR DETECT? OR QUANT? OR MICROANAL? OR XICRODET? OR CHROMATOG?OR IDENTIF?)."

The "OR" is a Boolean "OR" instructs the computer to retrievereferences indexed with either term. The "?" is the indefinite truncationsymbol instructing the computer to retrieve references beginning with thestem. The "?" represents uero, one, or more letters. For example, "NALY?"instructs the computer to retrieve analysis, analyze, analyti..al, etc,Indefinite truncation symbols ar-e used only at the end of a term. The "V"is the definite Internal truncation symbol instructing the computer toretrieve any references with that stem, except for one letter. For example,"SULF#TE" would result in the retrievals of salfates and sulfites. In theabove example, the internaC. truncation symbol was used at the end to requireonly one character be present, not zero or more. "DET#" was used toretrieve the various abbreviations used for determination such as detn.,

L deta., or detr.

Thits query was linked with the CAS Registry Number(s) of a compound byeither a Boolean "AND" or, in special cases, the "Lo proximity operator. TheBoolean "AND" instructs the computer to retrieve all citations where bothsearch terms appear iu the same record. This operator can be used to searchthe entire file or a previously retrieved answer set to include anadditional term. The terms do not have to appear in the same indexing term

like the title, but anywhere in the same citation record.

SL. The "L" proximity operator was used in cases such as ethylene glycol orcyclohexanone. "L" instructs the computer tV retrieve only those referenceswhere the Registry Number and a query term appeared in the sake indexingterm. It cannot be used iL searching an answer s.et, but must be used in the

L CA file. For example, the "LV operator would retrieve an article on thedetection of ethylene glycol in-workplace air, but would not retrieve an

* article on ethylene glycol used as a oolvent in the analysis oa anothercompound, which would have been retrieved usiug "AND".

There are, however, two disadvantages to .using this method: (1) STNlimits the number of postings in an sru.wer set; and (2) the search is veryslow. This creates problems because both the analytical terms and the

• particular compounds are highly posted; the search-exceeds .the limit before. completion and aborts. There are two wAys to solve this problea: (1) use

"AND" instead of "L." Search only the answer set created by the analytical

DAMDi7-84-C-4133 A-4

que-y "hedge" (which gives too many false hits); or (2) limit the range to apaiticular time period. The time limited query was preferred since thisproject required updating the data base with only the most recent informa-Stion. The search on these particular compounds was limited to January, 1984to present, which retrieved and abstracted articles published since 1983.

The Boolean "AND" gave quicker results with compounds which were notanalytical reagents or solvents. Also, ARC update compounds were limited byrange to January, 1984 to present because the basic information onlyrequired updating.

Citations identified from the above searches were retrieved fromlibraries. Many articles were inaccessible through usual retrieval methods.In that case, the extended abstract, including all bibliographic andindexing information, was retrieved from the CA file.

DAMDI7-84-C-4133 r

2. .

APPENDIX B. Database

TAUBLE OF CONTENTS

Acetic Anhydride ...................................... 0 -1

Aluminum Chloride ..... ,............. o ... 2-1

Aminoguanidine Carbonate ............. 9999• 9 ..... •• 3-1

Iso-Amyl Alcohol ....................................... 4-1

Iso-Amyl Nitrite ... 5-1

Antimony Trisulfide .................... . 6-i

Barium Peroxide ...................... 7-1

Battery Lithium .......................... 9....... 8-1

Ben.-oyl Peroxide 9............. , ....9, • • • .. 9-"

Calcium Resinate .... ...... ,,..,.,.999... 10-1

Calcium Stearate ......... 11-1

Ceric Ammonium Nitrate ............... , .... ,,,,9.... 12-1 )Chloramine-T 13-1

Copper-8-Quinolinolate 14-1

Copper Naphthenate ,,..,.,.,,,...9 ........ ,,..., 15-1

Cyclohexanone .......... 9....9.9... ...... 9.......9... 16-1

Di-n-Propyl Adipate ,,0.... ,... ...... , ... ,,.,.,.. 17-1

Diazodiiitroplenol ..... 9 18-1

Dichlorodisethylbydantoin 19-1

Dichloropdane .,......,, ....... 2................... 20-1

Diethylene Glycol Dinitrate (DEGN) .... ,..........,.. 21-1

Diethylene Trieaine ,,.,,.,,...,..........,,.....,..,. 22-1

DinitropheanyL Atde .. ,.......,,, .9.. .-..-. ,.. 23-1

Dipbenylmi-ne • •••"•• ••• ••.•• •• • •• •• 24-1

Ethyl Centralte 25-1

Ethylene Glycol .,-.......

U Ethhylene Glycol Dinitrate 27-1S(

Ethylene Glycol Monoerhyl Ether ..... 28-1

i Ethylene Oxide *.... * ................. 9-1

Halazone ooos....oooooose.oso*....30-1

Hydrazine ........ os@ossss*eosos31-1

Hydroxyl Aoamoiu Nitrate ............... 32-1

Lead Azide 3.3-.................................... 33

Lead Sryphnate .......................... ............. 34-1

Lead Thiocyanare 3- 1..................................o,, 31

Magnesium Thorium Alloy ........ OO .................. 36-1

Mirex op.... s ..... s.................. ....o ..s 37-1

N-Nitrosodiphenylamine ............................... 38-1

I-Nitro-2-Propanol .o..oo...o................... . 39-1

S( 2-Nitrodiphenylamine .......... s . *. . .0......040-1

Octachlor Carbanilide ......................... •...... 41-1

ft p-Nitrophenol o........ ......................... 42-1

Pentaerythritui Tetranitrate . 43-1

Phosphorus Trichloride • ...... •• • • •.•• •...•44-1

i Potassium Dinitrobenzfuroxan esosssoosoossos... . os 45-1

L Potessium Perchlorate 46-

Propylene Glycol 1,2-Dinicrare . ..................... 47-1

f Propylene Glycol 1,3-Dinitrate ....................... 48-1

Rad Phosphorus ...... 0.0........................ 49-1

Sodium Azide *0000046000050*0040t*51

SSodium Perchiorate ... 51-23 L_-o°. o 4o o o o o io o @ o@t ,.\

Strontium Oxalate *sesoseosseeo~sss .52-1l

Tecranitrocarbazole ................. ............. 53-1

Tetryl .b 54-1

t• . "' ,, ,.'"a . - .

Titanium Tetrachloride *..~. .... .............. 55-1

Triaminotrin-itrobenzene ... ,............ 56-1

Triethanol A~onium Nitrate .............. 57-1

Triethylene Glycol Dinitrate 58-1

Vat Yellow 4 .................... 59-1

White Phosphorus *.......... ... *....*.. 60-3

Ip

.4

477

ACETIC ANHYDRIDE

Chemical No. ], Acetic Anhydride, was eliminated from further considerationafter being found a minimal environmental threat. Acetic anhydride was notincluded in Phase II because it undergoes rapid hydrolysis in water to formacetic acid, a common chemical readily metabolized by most plant and animallife. Data obtained on acetic anhydride indicated that its half-life atneutral pH and normal ambient temperature (assumed to be 25 C) was less thanone hour, thus not posing a significant environmental threat (31).

(is

3 L

.AD7,4C43 1-

S.77

A-}!

ALUMINUM CHLORID)E)

I. CHIEMICAL AND PHYSICAL DATA

A* Structural and Chemical Formulas and Molecular Weight

Chemical Formula: AiC3

Molecular Weight: 133.34 (1)

Structural Formula: See exhibit 2-1

B. Alternate Names and RgitE Numbers

CAS Registry Number: 7446-70-0

Deleted CAS Registry Number: 41630-01-7

CA Name (9C1): Aluminum chloride (AlC1i.)

CA Name (SCI): Aluminum chloride

RTECS Number: BD0525000

Other significant synonyms: Alum.knum trichloride

C. Chemical and Physical Prpeties .

Physical State: Hexagonal crystals (2)

Color: White (pure); gray or yellow to greenish (1)

Odor: Odor of hydrc-3en chloride 'ý1)

Melting Point: 190 0Cat 2,5 atmos'pheres (2)

Boiling Point: 177.8 Csublime~s (2).

Water: Coniiuine with waterwith explosive violencS an ieaino

much hear -%'); 69.9 g per 100 aL cold water at 15 C (2)

4 I-. as benzophenone, benzene, a.dtrobenzene, carbon tetrachloride, andchlorofterm (1); 12Q g/100mL in absolute alcohol at 12.5 0C; 0.072 inchloroform at 25 C; soluble in ether, chloroform; slightly solublein benzene (2).

LOctanol Water Partition Coefficient: Not applicable

Hygroscopicity: Deliquesent (2)

DAMD17-84-C-4133 1

ALUMINUM CHILORIDE (cc nt*)

EXHIBIT 2-1

Cl-Al -Cl

loCl

HP H20

H:\

-i

DA11D17-84-C-4133 2-2

t Ot,

ALU14MINW CHLORIDE (cont.)

Density (Crystal): 2.44 glcc at 25 'C (2)

*Specific Gravity"(Liquid): 1.31 at 200 'C (2)1)

Volatility: Fumes in air. Volatilizes without melting when heated insmall quantities (.1).

Vapor Pressure: Data not available

Specific Heat: Data not available

Heat of Combustion: Data not available

Reactivity: Reacts violently with water (1,21)

Stability: Data not available

Flammability: Data not available

II. USES

A. Arm Unique Use

Smokes and obscurants

B. OthrUses

Acid catalyst, especially in Friedel-Crafts type reactions; in cracking* of petroleum; and in the manufacture of rubbers and lubricants (1).

III* AN~ALYTICAL METHODS

A. Best Accepable Method

A thin-layer chromatography method has been reported for alum~inumchloride and other components of water gel explosives. This method can.separate and determine the various components in these mixtures. Thiswould be the method of choice for analysis of this compound when it is

41found in an explosive mixture (3). *


Data not available

L

DAND17-84-C-41332-

. 4

ALUMiINUM CH1LORIDE (cont.)

1V. HEAILTH EFFECTS

TABLE IV-1 * TOXICITY OF ALUMINUM CHLORIDE

Spe~cies Route Dose/Duration Effects Reference

Human oral 0.5-5 g/kg Estimated lethal dose (4)

Human contact NS* Irritating to eyes, (5)dust nose and throat

Human contact NS Will produce skin, eye, (5)with and mouth burnssolid

NS NS NS May cause allergic (4)reactions

Rat oral 3.7 glkg LD 50 (6)

Rat NS Acute Incr~eased blood glucose;decreased liver gly- (7)cogen

Mouse oral 770 LD 50(8)

( mg/kg

Mouse oral 425 mg/kg; Effects on newborn(8multigenera-tion study

Mos p100 mmol/L Chromosomal aberrations (8)

NoiseifeL

LiDAM.D17~8-"-413324

ALUTMINUM CHLORIDE (cont.)

V. ENVIRONMENTAL EFFECTS)


Al. Transport -- Data not available

Ala. Adsorption -Data not available

Alb, Volatilization -- Data not available

*Aic. Infiltration -- Data not available

*Aid. Bioaccumulation - In Carp (.2 pdnus, carpio L.) expýDsed to 8 ppmaluminum chloride for 43 hours, c-oucentratieon of alumintz in thegills exceeded 60,00) ug!&.. In viscear .1.i o,:.he, parctý' of the fish,the aluminum concentratioxn w" less ia~n 6,000 ug/g (9).

A2. Transformation -- Data not availabl.e

A2a. Biodegradation.- Data not available

A2b. Hydrolysis - Data not available

A22c. Photolysis - Data not available

A2d. Other chemical reaction - Data not available)

A2e. Half-life -Data not available

B, Effects on animals

B1. Avian species*- Data not available

I.B3. Terrestrital invertebrates -Data not availjabl~e

B34. Reptiles -Data not available

B5. Amphibians - Data not available

B6. blicroorganisms, aquatic and &oil -~ Data not available4

All37. Aquatic species, fish and invertebrates - In Carp (Cypjinus qarpio L.)exposed to 8 ppo aluminum chloride for 48 hours, coucentration ofaluminum. in the gills exceeded 60,000 ug/g. In viscera and otherparts of ttm fitsh, the alumiuum concntration was Ie*" than 8,1000

DA1-84-C-41332-

ALUMINUM CHLORIDE (cont.)

C. Effects on plants

C1. Phytotoxicity -- Data not available

( C2. Uptake - Data not available

C3. Metabolism - Data not available

V1. STANDARDS AND REGULATIONS

A. Health3

TLV: TWA 2 mg(Al)/m (8).

B. Environmental

R eported in LPA TSCA Inventory 1980 (8).

VII. DISPOSAL

A. Current Recoimended r Disposal Practices

A recent programmatic life cycle environmental assessment indicates thatincineration is the preferred method for disposal of smoke/obscurantmunitions (3). Munitions containing aluminum chloride should beincinerated in a unit eqiipped with afterburner and a scrubber;scrubber overflow should be aeutralized prior to discharge.

( B. Alternate Dpal Pvact4ces Under Coasidorptionz. zhe

Data not available

C. Other Disposal Practices ýUloyed

Data not available

VIII. REFERENCES

1. Windholz, Ho, Budavari, S., Blumetti, R.F., Otterbein, E.S., ede.* ~198a. Iho Merck Index, 10th e4.. p. 50. Mterck &Md Co., Rahvay.

'"NMw Jersey.•

2. Weast, RC. 1968. CRC Handbook of Chezistrv and Phypics, 48ti ed.,p. B-149. The ChezicaEl s Ru-brCosmpiny, Cleveland, Ohio.

3o You, RL., Dr, Randal1 S, Wentsel, and Johnu H.ane . 1983.L f Progra.atit Life Cycle Environmental Asassoeet for SmOeI0bscirranet,

Volume 2-W- , White, and Plasticited White Phosphorus. T.ch ucalIUeport No. 83004, AD A135910. Chaxical Raest h and Develop=antCenterl, Aberdeen Proving Ground, 100.

U " 1DMl17-84-C-4133 2-6

- v

ALUMINUM CHLORIDE (cont-)

4. Gosselin, Rober E., Dr., Dr, Roger P. Smith, Dr, Harold C. Hodge, andJeannette E. Braddock. 1984. Clinical Toxicology of CommericalProduzts, 5th ed. Williams and Wilkins, Baltimore.-

5. U.S. Coast Guard. 1978. Chemical Hazardous Resyonse InformatiorSystem (CHRIS) Hazardous Chemical Data-Aluminum Chloride. U.S.Department of Transportation, Washangton, DoC.

6. Sax, N.I. 1979. D_.angetros Properties of Industrial Materials, 5th ed.Van Nostrand-Reinhold Co., New York, NY.

7. Clayton, George D. and Florence E. Clayton. 1961. Patt's IndustrialHygiene and Toxicology, 3rd ed. (revised), Vol. ZA. John Wiley andSons, New York, NY.

8. Chemical Information Sysem (CIS), Registry of Toxic Effects ofChemicil Substances (RTECS). Accession No. BDO525000. 1985.

9. Muramoto, S. 1981. Influence of Comple-vans (NTA, EDTA) on theToxicity of Aluminum Chloride and Sulfate to Fish at RighConcentrations. Bull. Znviron. Contaz,. Toxicol. 27: 221-225.

AAR:

, )

; I

W17~8~C~413:2,

( AZINOGUANIDINE CARBONATE

I. CHEMICAL AND PHYSICAL DATA

A* Structural and Chemical Formulas anc Molecular Weiht

Chemical Formula: CHR N 4 CHU 03

Molecular wt-igbr: 136.1

Structural Formula;

142N -C -NH --NH 2

N-H

-0-

B. Al tate Names andI 'Regi try Numbers

PASRgistry Number: 2582-30--I

CA Nome (9CI)- Carbonic acid. com-pound with tqydrafluacarboximidasadui,hvdrcziaecarboxnmdm±azmde, carbonate

CA Naze (OCX): 4uauidine, amiwo-, carbonate, carbonic acid coiapovndwith aminogu"Widin

RThC$ Number: Not ava~ilabl~e in RThCS

catSynonyms: .inaaronnntaa

C. calc uw b sip~ ft1 ~er Iti es

Physical $ttaei; Solid,, powder (I.)

Color: White or Ughc-. Vellow 1

Odor: '04or.s

-. txK

£ Se~;ig Vo-nt 170- 4'20Cw~t~ denpott~o AI

AIMINOGUANIDINE CARBONATE (cont.)

Solubilities:Water: 0.3% at 30°C; 0.2% at 200 .Nonaqueous Solvents: Data not available

Density (Crystal): 1.47 g/cc (1)

Volatility: Not applicable

Vapor Pressure: Not applicaDle



Reactivity: No incompatability (1)

Stability: Stable (1)

Flammability: No unusual fire or explosion hazards (1)

II. USES

A. A Unique Use

Used in the manufacture of the explosive tetracene (2)

B. Other Uses

Chemical Intermediate

Ill. ANALYTICAL METHODS


Tana:,e et al. (3) proposed a colorimetric method for guanindine andmonos'ibstituted guanidines. The compounds were reacted with 0.04%9,10-phenanthroquinone in dioxane:ethanol(1:4) and 2% 3,5-dihydroxybenzoic acid in ethanol and 2N potassium hydroxide; theabsorbance was measured at 615 nim. This method did not include anyseparation from other compounds.


Tanabe et al. (3) claimed 0.3 to 2 micrograms.

D -3

!DAMD1 7-84-C-4133 3-2

AMINOGUANIDINE CARBONATE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF AHINOGUANIDINE CARBONATE

Dose/Chemical Species Route Duration Effects Reference

Aminoguani- Rat oral 15 mg/g Death in 3-4 days (4)

dine bi- (feed)carbonate

Rat oral 20 mg/kg Specific diamine (5)oxidase inhibitor;increased urinaryexcretion levels ofhistamine and tele-methylhistamine af terL.stamine ingestion

Aminoguani- Rat subcu- 1,258 LDb 0 (6)dine taneous mg/kg

Rat intra- 7.8 mm 50% inhibition of (7)venous his tidine decarbox-

ylase activity bymuscular stomach

'I' homogenate or par-S~tially purified

enzyme preparationfrom stomach muscle

Mouse subcu- 963 mg/kg LD50 (6)taneous

Guinea intra- 1.7 mti 50% inhibition of (7)pig venous activity of histamine

methyltransfe-aseisolated from brain

LCat intra- 7.4-74 Augmented cholinergic- (7)

venous mg/qg induced salivary ex-

cretion

Aminoguani- Human subcu- I mg/kg Abolished heparin-in- (8)

dine taneous duced inhibitiou of

oulf ate gastric secretion;90-95% of plasma di-$mine oxidase Activitywas inhibited

Rat oral 500 mg/kg LD0 (7)

DAKDI7-8M-C-4133 3-3

]MAN

AMINOGUANIDINE CARBONATE (cont.)


No information was found regarding the environmental fate or effects ofaminoguanidine bicarbonate.

VI. STANDARDS AND REGULATIONS

SA, Health

Data not available

B. Environmental

Listed in EPA TSCA Inventory.

VII. DISPOSAL METHODS

A. Current Recommended Army Disposal Practices

Review of past Installation Assessmont Reports indicates that currentmethods of disposal of waste explos:%ves and propellants involve open "burning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beenconfirmed by private communications t•rom the U.S. Army Toxic andHazardous Materials Agency (USATIHAMA> which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (9).

B. Alternate D sal Practices under Cono.deration by the

Future plans for disposal of waste expi,);ives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARDCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and H"thorne NavalA~munition Depot (10).

C. Other Disposal Practices I

"* Data not available

1. H•te• -ll4:y Data Sheet-A naoganfdine Bicarbonate. Fairsount

L chý *ý C jut*,. Nqvark, NJ~

2. Di , T4,. -1 93; Thu., C , -strk Of - -wder -nW Explostves,p. 446-450. V

""D,7-84-*"l'.•- 1-4

"!i:; I " • '"+:•: "•"" " :•..... :""•• .. . " -"" : ""'••=W O N :::'•

AMINOGUANIDINE CAR3ONATE (cont.)

3. Tanabe, S., T. Oya. and T. Sakaguchi. 1975. Reaction of Guanidineswith Alpha.-Diketones. I. New Colorimatric Method for theSDetermination of Guanidine and Monosubstituted Guandines with 9,10-Phenanthroaquinine and 3,5-Dihydroxybenzoic Acid. Chemistry andPharmacy Bulletin. 23(8):1657-1663.

4. Bergner, H., R. Goerach, and P. Pritze. 1969. Toxicity of New NonproteinNitrogen Compounds in Rats. Arch. Tierernaehr. 19(6):421-432.

5. Benedette, M.S., J.F. Ancher, and N. Sontag. 1980. Monoamine OxidaseInhibitors and Histamine Metabolism. Experiential. 36(7):818-820.

6. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substances, Vol. 1. National Institutefor Occupational Safety and Health, Cincinnati, OH.

7. Sewers, W.B., J.W. Gordon, M.A. Beane, and S. Jacobsen. 1970.Aminoguanidine Pharmacology. 3(4):201-208.

8. Hansson, R. and G. Sundstrom. 1970. Diamine Oxidase (histamines) andHeparin Inhibition of Gastric-Secretion in Man. Scand. J. Clin. Lab.Invest. 26(3):263-269.

9. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (?ersonal communication). 1985.

10. Forsten, I. 1980. Dilposal of Hazardous Toxic Munition Waste.Proceedings of the 195, National Conference on EnvironmentalEngineering. New ,ork, July 8-10, 1980. ASCE Environmental EngineersDivision, New York, KY.

i 1

AfMD172-84-C-4133 3-5

ISO-AKYL ALCOHOL


A. Structural and Chemical Formulas and Molecular Weight

Chemical Formula: C5 H 120


Structural Formula: (CH3 )p 2CCH2C 2 O

B. Alternate Names and Registry Numbers

CAS Registry Number: 123-51-3a

CA Name (9CI): 1-butanol,3-methyl

CA Name (8CI): Isopentyl alcohol

RTECS Number: LV5600000, EL54250OU

Other Significant Synonyms: Isobutyl carbinol (1); amyl alcohol

c. Chemical d Physical Ppies

4, Physical State: Liquid (1)

Color: Clear, oily (2)

Odor: Disagreeable, pungent, repulsive, poisonous vapors (1)

Melting Point: -17*.2°C (1)I 0

"Boiling Pointl: :28.5 C (2)

¶ ISolubilities:L Water: 2g/100 &L at 14°C

Nonaqueous Solventa: Hiscible vith alcohol, ether, benzene,t chloroform, petroleum ether, glacial acetic acid, oils (1); very i

Schsoluble o n acetone (2); soluble in most organ•c tolvente (2). j

Partition Coefficient: Log P . 0. 46

Hlygroscopicity: Data not available

Specific gravity: 0.813 at °15C

S.Volatility: Volatile

NA; " Vapor Presure: 28 ms Hg at 2 0 C (2)

DA-D17-84-C-4133 4"..

ISO-ANYL ALCOHOL (cont.)



Reactivity: Can react vigorously with reducing materials (2).

Stability: Explodes when exposed to flame (2).

Flammability: Flash point, closed cup 45°C; open cup 550C (1)

II. USES

A. A Unique Use

Preparation of isoamyl nitrite explosive

B. Other Uses

Solvent for fats, resins, alkaloids, etc.; manufacture of isoamylcompounds, isovaleric acid, mercury fulminate, pyroxylin, artificalsilk, lacquers, and smokeless powders; in microscopy; for dehydratingcelloidin solutions; and for determining fat in milk (1).

III* ANALYTICAL METHODS

A. _est Acceptable Method

Gas chromatography is the method of choice. Krull et al. (3) reportedan extremely sensitive method using a photoionization detector todetect the pentafluorophenyldimethylsilyl chloride (flophemsyl)derivative. Isoamyl alcohol was chromatographed on a Permabond PEGcolumn with temperature programming. An electron capture detector(ECD) was also used.

L

Masuda et al. (4) reported a gas chromatographic method forunderivatized iso-amyl alcohol on a 5% phenylmethyl silicone capillarycolumn with a flame ionization detector (FID).


Krull et al. (3) reported 38.7 picograms for PID and 20 picograms forECD for the flophmesyl derivatives and 0.852.nanograws for PID and 3.37

l n snograw for ECD for the underivatized alcohol.

-asuda at al. (4), 0.UmV/L or 500 ppb.

DAMD17-84-C~-4133 4.-27 l..

ISO-AMYL ALCOHOL (cont.)

IV. HEALTH EFFECTS )TABLE IV-1. TOXICITY OF ISO-AMYL ALCOHOL

, ,1Species Route Dose/Duration Effects Reference

Human local NS Irritant; vapors rapidly (5)produce intense irrita-tion of nose, eyes, andthroat

Human NS High conc. May cause central ner- (5)vous system depression,narcosis, headache, andnausea

Rat oral 1,300 mg/kg LDs 0 (6)_

Rat oral 27 g/kg Carcinogenic, producing (6)(total dose), liver and blood tumors**intermittentlyfor 75 wk

Rat intraperi- 813 mg/kg LDLo (6)toneal

Rat intraperi- 2.3 mmol/kg Ataxia (7)toneal

SRat subcu- 3,800 mg/kg Carcinogenic, producing (6)taneous (total dose) liver and blood tumors**

intermittently for 85 wk

Mouse intraperi- 233 mg/kg LDLo (6)toneal

House intra- 234 mg/kg LD (6)

venous 5

Mouse subcu- 7,480 mg/kg LDLo (6)taneous.

House iuhala- 41,514 ppm 50% decrease in zespir- (8)tion atory rate

Rabbit oral 4,250 mg/kg LDL. (6)

{Rabbit intra- 1,570 mg/kg IL;behavioral symptoms (6) -

venous

Rabbit *kin 3,212 mg/kg D(6)SIDAMDl17-84-C-4133 4-3

... ...... ..-.... .......... . ......... .................................................. ..-...... . '..,, .. -4 _

tic SO-AKYL AL.COHOL (conte)

* TABLE IV-1. TOXICITY OF ISO-AMYL ALCOHOL (Cont.)

Species Route Dose/Duration Effects Reference

Rabbit eye 20 mg/24 hr Severe irritation (6)

Cat intra- 210 mg/kg LD~ (6)venous

**Conclusion taken from RTECS; studies were not evaluated

TABLE IV-2. MUTAGENIClTY AND REATED EFFECTS OF IS0-AM1YL ALCOHOL

Test System Dose Effects Reference

Saccharomyces 10 mmol/tube Induction of chromosomal (6)cerevisiae aberrartions

Escherichia coli "drop" Negative results f or (9)( K12 infected with stimulation of Tri9 trans-phage: lambda Tn9 position

V. EN~VIRONMENTAL EFFECTS



Ala. Adsorption -Data not available

Alb. Volatilization -- Data not available

Alc. Leachability -- Data not available

Ald. Bioaccumulation -- Data not available

A2, Transformation -- Data not available

A.2a. Biodegradation -Activated sludge BOD, 30 days acclimation, 20 C, 1-5pdays observed, feed: 333 uag/L$ 79% SOD removed (10).

A2b* Hiydrolysis -Data not available

A2c* Pbotolysix Data not available

DAMD17-84-C-4133 4-4k

1V.


A"d. Other chemical reaction -- BOD 0.150, normal sewage as seed material, )standard dilution techniques, 0.162, normal sewage as seed material,standard dilution techniques; COD: 77% of ThOD; ThOD: 2.740 (10).

A2e. Half-life - Data not available

B. Effects on animals

B1. Avian species -- Data not available

* B2. Mammalian wildlife species -- Data not available

B3. Terrestrial invertebrates -- Data not available

B4. Reptiles -- Data not availabla

B5. Amphibians -- Data not available

B6. Microorganisms, aquatic and soil -- Data not available

B7. Aquatic species (fish and. invertebrates) - Data not available


Ci. Phytotoxicity -- Data not available

C2. Uptake -- Data not available

C0. Metabolism -- Data not available

KVI. STANDARDS AND REGULATIONS

A. Healthi-

SL.. Data not available

B. Environmental

Data not available

VII. DISPOSAL

A. Current Recommended A Disposal Practices

Indication In lolaton Installation Asnesoment chat open burning isthe only Army approved method for disposal of explosive wastes,

SLSolvents containing up to 80-90% water are burnmd ln clay lined pitsat liolaton (11),

I,.......

fANDI7-84-C4133 4-.5 "._ _,

..7.7 .

S:'.'• ,AID


B. Alternate Disposal Practices under Consideration by the Army

( .Data not available

R C. Other Disposal Practices Employed

AEHA: NSN 6810-00-142-8764, 106-8925, 2811999

Dispose of through a commercial contractor (12).

VIII. REFERENCES

1. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed,, p. 747. Merck and Co. Incs.,Rahway, NJ.

2. Chemical Information System (CIS), Oil and Hazardous MaterialsTechnical Assistance Data System (OHMTADS). Accession No. 7216593.1985.

3. Krull, I.S., M. Swartz, and J.N. Driscoll. 1984. Derivatizations forImproved Detection of Alcohol by Gas Chromatography and PhotoionizationDetection (GC-PID). Analytical Letters. 17:2369-84.

4. Masuda, Me, M. Yamamoto, and Y. Asakura. 1985. Direct GasChromatographic Analysis of Fusel Alcohols., Fatty Acids and Esters of

( Distilled Alcoholic Beverages. Journal of Food Science 17:264-5.

5. Reynolds, James E.F. and Anne B. Prasad, eds. 1982. Hartindale-TheExtra Phracooeia, 28th ed. The Phazmaceutical Press, London,England.

6. National Library of Medicine (NLUI), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. EL5425000. 1985.

7. Shoemaker, W.J. 1981. Proceedings of the Conference on theNertoxici~z of Oraic Sovents and Acry-lamd Raleigh, NC,

I June 26-27* 1981o 431-36.

8. Alarie, Y. 1981. Dose-Response Analyis in AnImal Studies: Predicrlonof Human Responses. Environmental Health PeýrpecrL ve. 42: 9-13.

9. Datta, A.R., B.W. Randolph, and J.L Rosner. 1983. Detection oiL Chemicals that Stimulate TN9 Transposition in E•chericia Coll K12.

Mol. Gen. Genet. 189: 245-250.

10. Verschueren, Karel. 1983. Handbook 6f Enviromtntal Data on Organicchamias, Znd ad. Van Nostrad-R hold Co., N#V 15rk,.M"

"""11. U*S* Amy Toxic and Hazardous aterials Agency. 1980. tallation

AssessOenc of Holston Arty Ai"nituion Plant. Report No. 148.U.S. Army Toxic *ad iia~dous, Materials &geuty, Aberdeen Proving

•DGround, M D.

-- B ND1 7-84-C-4133 4-6. .- . "

. : _ _ •] r . ... .. . -. . . . • : . .. . . . ... ... . . 4.. . . ..-

ISU-AKYL ALCOHOL (cont.)

12. U.S. Army Environmental Hygiene Agency (AEHA), 1983. Waste Disposal 9K. Waste Disposal Instructions* TG-126, HSHB-ES-H.'/WP. U.S. Army

ENvirommental Hygiene Agency, Aberdeen Proving Ground, MID.

A ~ \

VA1784C43 44

(ISO) AKYL NITRITE

1 . CiILUICAL AND PHYSICAL DATA

A. Structural and Chemical Formulas and Molecular Wegh

Chemical Formula: C 5 1 NO2


Structural Formula: (CH3) CHC1 CH ONO

B. Alternate Names and Resgistry Numbers


CA Name (9C1): Nitrous acid, 3-methylbutyl ester

CA Name (8C1): Isopenty2. alcohol, nitrite

* RTECS Number: NT0187500

Other Significant Synonyms: Isoamyl nitrite, isopentyl nitrite, 3-methylbutanol nitrite, 3-methylbutyl nitrite.

C. Chemical and Phsial Properties

( Physical State; Liquid (Z); decomposes on exposure to air,light or water.

Color: Clear yellowiiah (2)

Odor: Fragrant odor and pungent aromatic caste (3)

Haeltiog Point: Data not available

- Boiling Point 96-99 C (2)

Solubilities:Water: Very slightly solul (~~1) loo o~r~ehrNonaqueoveSolet:Hsil ihachlclrfrehrand light petroleum (4).

D ~ensity: 0-.8526 glen at 40C (2)

Octanol Vater Tartii ion Coeffiemeint:- Data otAvailable

ft'groscopicity: Data-niot available

Dnmsicy-(Vapozr). 4.0 (2)

.4D78-C43 -

u' - -.

(ISO) AnYL NITRITh (con:.)

Volatility: Volatilizes readily (1)

Vapor Pressure (p): 60 Torr (30 0 C)

Flash Point: 100 C


Heat of Combustion: 6,930 cal/g

Autolgnirion Temperature: In air 2090C; in oxygen 202°C (5)

Reactivity: Oxidizing material, can react with oxidizing or reducingmaterials (2). Dangerous fire risk (4), Floats on water. Producespoisonous gas on contact with water. Combustion products includetoxic oxides of nitrogen. Decomposes on exposure to air, light, orwater; evolving toxic oxides of nitrogen (6). Incompatible withalcohol, alkaline, carbonates, caustic alkalis, bromides, iodides,ferrous salts, and phenazone (3). Forms an explosive mixture withair or oxygen (I).

Stability: Unstable, decomposes on exposure to air and light (1)

Flammability: Very flammable (1); moderate fire hazard whenexposed to heat or flame or by spontaneous chemical reaction.Vapor explodes when heated (2).

Ii. USES

A. Army Unqu Use

Explosive &ad chemical agent .antidote.

B. Other Use

Perfuses, diazouium compounds (4), vasodilator (10), treateant ofcyanide poisoning and H potsouit (3).

i.III* A LYTI MCL TDS

B.uet Accetotdbe Methd'- Carignan ad UIcktaa published a quantitative intnred spectropho'o-

i. " metric method for the detetizInation of isoZyl 'titctre (7) Des eot a!.reported a cheaicol ionizatiOn. nass Spectromecry, In -ooiuncciou with

1. , s-as chrootatogr~tphy, that cam be used for quantitati.vo-e &ai.ot o:

trace sant. (s).

t of Dttection

V ~Dac* not aviIia"

flA!07-84-C-'41335-

*i • '-. +.+. , +, .+-L ,+'•+ +.++:.... ."+

(ISO) AKYL NITRITE (cont.)3

IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF AMYL NITRITE

Dose/species kciute Duration EfetRfrnc

Human oral or NS* Methemoglobinemia, (6)inhalation rachacardia, headache,

veakness, confusion,restlessness, faintness andloss of consciousness

Hu-n skin (Liquid) Severe skin irritation (6)and eye damage; secondand third degree burnson short contact

Human inhalation Therapeutic Headache, dizziness, (9)Level weakness, postu~raldoses(O..18 hypotension, skin rarh,or 0.3 mL) and mcthezoglobinemia

iatoral 505 mgIkg LD so (10)

Ra, inhalation 1,274 ppm/ihr LC 50 G~O)

( * ?Not specified

TAB'~ IV-2. KUTAGENICIn. Of AMY NITRITE

Test. System Dose Effects tei erence

4i abstract.)

No~t sipe~ltlia-

Vs

.1I-4C-13 -

--- .. ..

(ISO) AMYL NITRITE (cont.)

V. ENVIRONMENTAAL EFFECTS


A!. Transport -- Data not available

Ala. Adsorption -- Data not available



Aid. Bioaccumulation -- No potential for concentration in the food chain (6).

A2. Transformation -- Data not available

A2a. Biodegradation -- Data not available

A22b. Hydrolysis -- Decomposes on exposure to water, evolving toxic oxidesof nitrogen (6).

A2c. Photolysis - Decomposes on exposure to light, evolving toxic oxidesof nitrogen (6).

A2d. Other chemical reaction -- Decomposes on exposure to air, evolving

toxic oxides of nitrogen (6).

A2e. Half-life -- Data not available

B. Effects on animals -- Data not available

C. Effects on plants -- Data not available


A. Health

Data not available

L B. Environmental

Reported in EPA TSCA Iuventory 1983.

L VlI. DISPOSAL METHODS


Review of past Installation Assessment Reports indicate that currentmethods of disposal of waste explosives and propellants involve openbu:ning, open detonation, or hauling by a licensed r•ontractor andlandfilling. Cutrent us, of methods discussed above has also be been

t . DAMD17-84-C-4133 5-4

I N


IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF AMYL NITRITE

Dose/Species Route Duration Effects Reference

Human oral or NS* Methemoglobinemia, (6)inhalation rachacardia, headache,

weakness, confusion,restlessness, faintness andloss of consciousness

Human skin (Liquid) Severe skin irritation (6)and eye damage; secondand third degree burnson short contact

Human inhalation Therapeutic Headache, dizziness, (9)level weakness, posturaldoses(O.18 hypotension, skin rash,or 0.3 mL) and methemoglobinemia

Rat oral 505 mg/kg LD5 0 (10)

Rat inhalation 1,274 ppm/lhr LC5 0 (10)

* Not specified

TABLE IV-2. MUTAGENICITY OF AMYL NITRITE


S. typhimurium NS* Mutagenic with or with- (11)Satrain not statd out metabolic activationin abstract)

Not specified

l•A•D17-84-C-4133 5-3

I


V. ENVIROIOIENTAL EFFECTS

A. Environmental Fate)




Alc. Leachability- Data not available

Ald. Bioaccumulation - No potential for concentration in the food chain (6).



A2b, Hydrolysis -- Decomposes on exposure to water, evolving toxic oxidesof nitrogen (6).

A2c. Photolysis -- Decomposes on exposure to light, evolving toxic oxidesof nitrogen (6).

A27d. Other chemical reaction - Decomposes on exposure to air, evolving

toxic oxides of nitrogen (6).


B. Effects on animals - Data not available

C. Effects on plants - Data not available

VI. STANDrDS AND REGULATIONS

A. Health

|L. Data not available

B. EnvironmentalReported in EPA TSCA Inventory 1983.

SVII. DISPOSAL METHODS

A. Current Reco=ended Am D al Practices

Review of past Installation Assessment Reports indicate that current* asethods of disposal of vaote explosives and propellants involve open

burning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be been ()

I DAMD.17-84-C-4133 5-4


confirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAMA), which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (12).

B. Alternate Disposal Practices under Consideration b the

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration:, This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and H&wthorne NavalAmmunition Depot. (13)

C. Other Disposal Practices Employed

Data not available

VIII. REFERENCES

1. Wiiidholz, M., S. Budavari,JR.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 738. Merck and Co., Inc. kahway,NJ.

2. Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5thed., p. 377. Van Nostrand-Reinhold Co., New York, NY.

3. Reynolds, JAmes E.F., and Anne B. Prasad, ads. 1982. Martindale-TheExtra Pharmacopoeia, 28th ed. The Pharmaceutical Press, London.

4. Hawley, Gessuer G. 1981. The Condensed Chemical Dictionary, 10thed., p. 69. Van Nostrand-Reinhold Co., New York, NY.

5. Fedoroff, Basil T. 1960. E co•edis of Ep ives and RelatedItems, Vol. 1, p. A397. U.S. Army Armament and Research Command,Dover, NJ.

6. U.S. Coast Guard. 1978. Chemical Hazardsous Response InformationSystem (CHRIS) Hazardous Chemical Data-Training Edition-Iso-amylAlcohol. Abridged, CG-446-2. U.S. Department of Transportation,Washiugton, D.C.

7. Carignan, Y.P., and C.L. Hickman. 1972. Quantitative Infrared* Spectrophotometry of Organic Nitrate Esters. AD A753938. U.S. Army

Armament Research and Development Command, Dover, J. A

* , 8. Das, R.C., O. Koga, and S. Suzuki. 1979. Chemical Ionization MassSpectrometry of Alkyl Nitrates and Nitrites. Bu!letn of theChemistry Soct of Jgan. p. 65-8.

9. Goodman, Louis S., Dr., and Dr. Alfred Gilman. 1975. ThePhamaco~gial asis of Therapeutics, 5th ed., p. 733-34. Macmillan

Publishing Co., Inc., New York, NY.

DAi4D17-84-C-.433 5-5I.

. .{

(ISC) AMYL NITRITE (cont.)

10. National Library of Medicine (NLM), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. NT0187500. 1985.

11. Quinto, I. 1980. Mutagenicity of Alkylnitrites in the Salmonella.Soc. Ital. Biol. Sper. 56(8):816-20.

12. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communication). 1985.

13. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference on EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575.

itv

4. .

i I : ..AND'7-84-C 4133 5-6

--- M~lk

Q ANTIMONY TRISULFIDE

Update of Atlantic Research Corporation Study

SUMMARY OF PREVIOUS STUDY

The toxicological and environmental hazards of antimony trisulfide have beenreported in the Atlantic Research Corporation's (ARC) report, A PreliminaryProblem Definition S of the Toxicological and Environmental Hazards of 48Munitions Related Chemicals. The report concluded that the compound is nothighly toxic to mammals, aquatic organisms, microorganisms or plants. Asummary of chronic inhalation toxicity of antimony trisulfide to mammals waspresented and the effects of antimony exposure on workers was summarized.Antimony trisulfide occurs in nature as stibuite ore. The acute toxicity ofseveral antimony compounds to aquatic organisms was reported in the study.Phytotoxicity information is very limited.



Chemical Formula: Sb 2 S3

Molecular Weight: 339.69I

Structural Formula:

S SSb Sb Qb'I I

S *--. Sb S". Sb-...

S S

B. Alternate Names and Registry Numberi

Deleted CAS Registry NuWber: 12138-10-2; 28767-59-1

CS R�giotry Number: 1345-04-6

CA Name (9C1)t Antisoty sulfide (Sb 2 S3 )

-DAD17-84-C-4133 6-1

Am F,

ANTIMONY TRISULFIDE (cont.)

CA Name (8CI): Antimony sulfide

RTECS Number: CC9450000

Other Significant Synonyms: Antimony sesquisulfide, antimonoussulfide, antimony glance, antimony orange, antimony trisulfidecolloid, crimson antimony sulphide, needle antimony (8).

C. Chemical and Physical Properties

Physical State: Crystals or powder (1)

Color: Gray, gray-black, orange-red to black (1)

Odor: Data not available

Melting Point: 546 0C (2)

Boiling Point: 1150°C (3)

Solubilities:Water: Insoluble (3), 0.0-0.00175 g/cc (18°C)Nonaqueous Solvencs: Soluble in alcohol, hydrochloric acid, ammoniumsulfide, potassium sulfide; insoluble in acetic acid (4); soluble insulfide salts (5); soluble in fixed alkali hydroxides (W).

Octanol Water Partition Coefficient: Data not available

Hygroscopicity: Data not available

Density (Crystal): 4.64 g/cc for gray crystals and 4.12 g/cc foryellow-red solid (6).

Volatility: Data not available

Vapor Prgesure: 0.033 = lg at 4000 C; 1.17 mm HS at 5000 C; 244.00 Ugat 850 C (2).



Reactivity: Can react vigorously with oxidizing materials and producetoxic fumea of. oxides, sulfur. and antizony.

Stability: Stable in air at room taperacure (2)

Flammability; Moderate fLire and combu tion baard (2)

"" DA. D17-8,4-C-4133 6-2

A -.

N *~~4~*~'~'4

" '" ...... in /i illlll~ lll Ill lI• I• 1•1 1r I ii ' *


) II. USES

A. Army Unique Use

Used in pyrotechnic and primer formulations, as well as camouflage

paints (2).

B. Other Uses

Used in the manufacture of vermillion or yellow pigment, antimorL;salts, matches, percussion caps, fireworks, and ruby glass. Also usedin flame-proofing formulations (2).



No analytical methods have been found by surveying the chemicalliterature from 1983 until present that significantly replace or updatethe findings in the Atlantic Research Corporation study.


Data not available

A O DAW17I84-Cm4133 6-3

.1.A-

A


IV. HEALTH EFFECTS

TABLE IV-1. HEALTH EFFECTS OF ANTIMONY TRISULFIDE* (7)

Compound Species Route Dose/Duration Effects

Antimony Human inhalation 0.58-5.5 ECG changes, cardiactrisulfide (occup. mg/m , deaths, ulcers

exp.) 8-24 mo,urinarylevel:0.8-9.6 mg/L

Antimony Human inhalation urinary Female reproductivetrisulfide, (occup. level: problems, infant weightmetal, and exp.) 5-182 mg/L gain lower than normaltrioxide

Antimony Rat intra- Single sub- Chronic heart changestrisulfide peri- lethal dote

toneal

* Antimony Rat intra- Single 20 mg Weight reduction,trisulfide or tracheal dose macrophage reactiontrioxide

Information not included inthe ARC report

V. ENVIROKMENTAL EFFECTS

No information was found regarding the environmental fate or effects ofantimony trisulfide which would update the Atlantic ResearchCorporation study*

AI

IT-4 6-4

'S- riAl

ANTIMONY. TRISULFIDE (cont/.)


S(9 A. Health

TLV: TWA 0.5 mg (Sb)/m 3 (8).

B. Environmental

Reported in the EPA TSCA Inventory 1983.

EPA TSCA 8(a) Preliminary Assessment Information, final rule (9).

VII. DISPOSAL


Data not available

B. Alternate Disposal Practices Under Consideration by the Am

Data not available


Data Not available

VIII. REFERENCES

1. Windholz, H., S. Budavari, R.F. Blumetri, and E.S. Otterbein, ads.1983. The Merck Index, 10ch ed., p. 104. Merck and Co., Inc., Rahway,NJ*

2. Kitchens, J.F., W.E. Uarward II, D.H, Lauter, and R.S. Weatsel.1978. Preliminary Problem Definition Study of 48 Munitions-RelatedChemicals, Vol. IV, Primer and Tracer Related Chemicals-AncimonyTrioulfide. Final Summary Repot, AD A066310. Atlantic ResearchCorporation, Alezandria, VA.

3. Clayton, George D. and Florence B. Clayton, eds. 1981. Part5'sS Industrial Hygiene and Toxicology. Vol. 2A, 3rd revised edtion,

j Weat, R.C. 1984-85. CRC Handbook of Chemistry a Ph sics, 48th ed.,p. B74. he C-zmcal Rbber Ceany, Cleveland, OH.0

5. Hawley, teiner G. 1981. The Conden:ed Chomical Dictionary, 1Oth ed.,S~p. 81. Van Nost~and-Reinhold Cov,,New York, W,•,:

A

DAW1.D7-84-C-4133 6-5 -.I.

• ?, :, I . " :'• .:" .'... . "'"


6. Kaye, Seymour M. 1980. Encylopedia of Explosives and Related It ms,Vol. 9, p. 5235. U.S. Army Armament Command, Dover.O, ire-

7. National Institute for Occupational Safety and Health (NIOSH). 1978.Criteria for a Recommended Standard: Occupational Exposure toAntimony. Publication Number 81-226060. U.S. Department of Health,Education, and W~elfare, Cincinatti, OH.

8. Chemical Information Search (CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. CC9450000. 1985.

9. Federal Regitr Vol. 47, No. 82, p. 26992.

DAD1 6-6

1~A~rn7~77 777"3

BARIUM PEROXIDE

Much of the available data on barium peroxide has been reported in a previousstudy by the Atlantic Research Corporation (ARC) entitled, A PreliminaryProblem Definition Study of 48 Munitions-Related Chemicals. Data reportedherein reflects information more recent than that reported by ARC in 1978.

1. CHEMICAL AND PHYSICAL DATA


Chemical Formula: BaO2

Molecular Weight: 169.36

Structural Formula: +2. . . -.O-1"2

B. Alternate NMmes and RegistrZ Numbers


Alternate CAS Registry Number: 16678-58-3

Deleted GAS Registry Numbers: 55346-27-5; 61233-09-8

CA Name (9C1): Barium peroxide (Ba&O)

( •CA Name (8CI): Barium peroxide

RTECS Number: CRO175000.

Other Significant Syaonyms: Barium dioxide; barium superoxide;barium oxide.

Ca Chemical and Phvsical Properzies

Physical State: White Powder

Color: White or Grayish

Odor: 0dorless (1)

0HeltiNg Point: 450°C '

Boiling Point: 800 . decompose& (2):Solubi It tioa.:,,

Water*: Slightly, decaspos ou contact vith vater (3)

-- S-olvents: Stightly soluble in acid = soluble inacetoae (4).

,AHD17-84-C-4 133 7-1

Si -; .- v

BARMUM PEROXIDE (cont.)

Octanol Water Partition Coefficient: Not applicable

Hygroscopicity: Data aot-available

Density (Crystal): 4.96 g/cat 200C (Solid) (1)




Flash Point: Not flammable ()


Reactivity: Can ignite spontaneously'if mixed with finely dividedmetals. Oxidizer, will react with organics or reducingagents. Mixtures with oxidizable material are explosiveand ignite easily by friction (5).

Stability: Slowly turns into BaO2 k 8H20 on contact withwater (6).* Decomposes slowly in air (3). Reacts vithdilute or strong HCI to generate hydrogen peroxide (5).

Flammability: Not flammable (5), but conta:ýur may emplode it fireand may cause fire on contact with combustables or increaseintensity of fire (I).

A. Uniqu Use

As an oxidizer in igniter, tracer *-nd pyopetiaL toruulao, Impartsa green color to pyrotechnics (5).

•leachig animal sb .- , vegttable fibers and straw; glassS, decolorizer; gsnzufctjse IL10• aud oxyaen; dyeing and printing

"textiles; vith poWerad lua-n•u in welding; in cathodes; in.iguite6-r compofitr4fan$ &ridi4i~g 4agnt in organiC syntlassie.

I t-

it.

I•, . . " , .".- .' . -: . ..' ' ". .. .,. .: , : , :..: ,:

BARIUM PEROXIDE (cont.)

III- ANALY11CIAZ METUODS

A. Best A Method

( A survey of the chemical literature from 1967 on did not result inany significant change from the Atlantic Research Corporation report.


Data not available

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF BARIUM PEROXIDE


*,Human ingestion NS Excessive salivation, vomiting, (1)

colic, diarrhea, convulsivetremors, slow, hard pulse, andelevated blood pressure;hemorrhages may occur in thestomach, intestines, and kidneys;muscular paralysis may follow

Human inhalation NS Irritation of mucous membranes, ()

throat and nose

Human topical NS Severe burns of eyes and skin ()

Mouse subcuta- 50 mg/kg Lso (7)neous

e Information not included iG the ARC report

N* kot specified

V. •ENVILO TAL FFFE`rS

As Environmental Fate

All Tranaport - Data not available

-" Ala. Adsorption -- Data not available

Alb, Volatiliatiou -'Data not available

-1- 133 7-3

o I

)l • "


Aic. Leachability -- Leaching of barium war studied under controlledconditions similar to conditions in which bafium-containing wastesare co-disposed with domestic waste in a landfill. Eighteen to 39% 1of the barium leached out of the material, probably mainly in theform of organic barium complexes. Leaching of barium is higherwhen the barium-con'ainng salt is located below the groundwaterlevel. Barium chloride was the salt used in the study (8).

Ald. Bioaccumulation - Data not available


A2a. Biodegradation -- Data no, available

A2b. Hydrolysis -- Data not available

A2c. Photolysis Data not available

A2d. Other chemical reaction -- Data not available

A2e. Half-life -- Data not availab]e

B. Effects on Animals

BI. Avian spccies - Data not avai±able

B2. Mammalian wildlife species -- Data not available


B4. Reptiles -- Data not available



B7. Aquatic species, fish and invertebrates -- Data not available





* VI. STANDARDS AND REGULATIONS

TLV-TWA 0.5 mg (Ba)/m 3 (7); OSHA standard--air 0.5 mg(Ba)/m 3;

DOT: oxidize:

* 7 -( •" DAMDI 7- t 34-C-4 133 7-4 ;


V 11. DISPOSAL METHODS


Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involves openburning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAMA) which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (9).

B. Alternate Disposal Practices under Consideration y the Army

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and Hawthorne NavalAmmunition Depot (10).

Disposal Methods Suggested for Related Materials: Barium flouride(careful precipitation with soda ash or slaked lime). The resultingsludge should be sent to a chemical waste landfill. Barium nitrate,barium sulfide (chemical reaction with water, caustic soda, andslaked lime). The precipited metal sludge should be landfilled.Barite barium sulfate may be recovered for reuse in drilling muds(A-57) as an alternative to disposal (1i).


Disposal of Laboratory or other small amounts: Cover with at leastdouble amount of sand to soda ash 9:1 mixture. Mix completely anduniformly. While stirring, add slowly to a large beaker of sodiumsulfite solution with plastic spoon. Carefully neutralize with dilutedsulfuric acid. After settling, decant the sulfate solution into a sewerwith sufficient water and .transport the sand to a landfill site (6).

VIII. REFEUENCES

.. U.S. Coast Guard. 1978. Chemical Hazards Response Information System(CHRIS) Hazardous Chemical Data, Training Edition-Barium Peroxide.Abridged, C6-446-2. U.S. Department of Transportation, Washington,DEC.


3. Windholz, M., S. Budavari, R.F., Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 141. Merck and Co., Inc., Rahway,NJ.

DAMD17-64-C-4133 7-5


4. Weast, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed.,p. B-7. The Chemical Rubber Co., Cleveland, OH.

5. Kitchens, J.F., W.E. Harward III., D.M. Lauter, R.S. Wentsel, andR.S. Valentine. 1978. Preliminary Problem Definition Study of 48Munitions-Related Chemicals, Vol. IV, Primer and Trace RelatedChemicals-Barium Peroxide. Final Report, AD A066310. AtlanticResearch Corporation, Alexandria, VA. DAMDI7-77-C-7507.

6. International Technical Information Institute (ITI). 1982. Toxic andHazardous Industrial Chemicals Safety Manaual, p. 61. InternationalTechnical Information Institute, Tokyo, Japan.

7. Chemical Information System (CIS), Registry of Toxic Effects (RTECS).Accession No. CR0175000. 1985.

8. Lagas, P., C.M. Boon, M.J. Hart, H.A.M. De Kruiff, and J.P.G. Loch.1981. Model Experiments on the Behavior of Cyanide and Barium in aLandfill and in the Soil. Stud. Environ. Sci. 17:539-43.


10. Forsten, I. 1980, Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental Engineers,Durbin, NY. 440-575.

11. Sittig, Marshall. 1981. Handbook of Toxic and Hazardous Chemicals,Noyes Publication, Park Ridge, NJ.

- DAM.D17-84-C-4133 7-6

i':

(. BATTERY LITHIUM

LITHIUM DITHIONITE

I. CHEk'ICAL AND PHYSICAL DATA


Chemical Formula: LiS2 04 (1)


Stuctural Formula:

O'Li÷ O'i/



CA Name (9CI): Dithionous acid, dilithium salt

CA Name (8CI): Data not available

RTECS Number: Not in RTECS

Other Significant Synonyms: Data not available


Physical State: Crystalline solid (1)

Color: White to grayish white (1)


Melting Point: Data not available

DAMD17-84-C-4133 8-1

BATTERY LITHIUM (cont.)

Solubilities: )Water: Soluble in cold water, decomposes in hot water (1)Nonaqeous Solvents: Data not available



Density (Crystal): Data not available




Heat of Combustion; Data not available

Reactivity: Is readily oxidized to bisulfite and bisulfate; whenheated to decomposition in water, emits toxic vapors (1).



Unique Use

Lithium/sulfur dioxide battery; by-product formed within the

lithium battery (I),

B. Other Uses

No commercial use found

III. ANALYTICAL METHODS

S A3 Best Acceptable Method

* No method for lithium dithionite was found. Lithium could easily bedetected by atomic absorption spectrocopy, but the determinationwould not specifically quanitify the amount present as the dithionitesalts


SData not available

DAMD1I7-84-C-4133 8-2


IV. HEALTH EFFECTS

C TABLE IV-1. TOXICITY OF LITHIUM DITHIONITE

Chemical Species Route Effects Reference

Lithium No toxicity data located on* dithionite the specific compound;

related data follow below

Lithium Human oral Nausea, vomiting, diarrhea, (2)anorexia, dehydration, poly-urea, apathy, lethargy, mus-cular weakness, ataxia, handtremor, myoclonic twitchings,acne and exacerbation or pre-cipitation of psoriasis, leuco-cytosis, headache, cogwheelrigidity; severe intoxicationis associated with seriouslyimpaired consciousness, hyper-flexia, convulsions, epilepticseizures, coma, and kidney,brain, and heart damage

Rat NS* Polyurea leading to oliguria (3)and azotemia; behavioralchanges begin at plasma levelsof approx. 3 nmtol/L; deathsabove 8 mmol/L

NS NS Implicated in the development (4)

of aplastic anemia

Sodium NS NS Skin irritant; presumably (5)dithionite shares the toxic potentials

of bisulfite and sulfite towhich it is rapidly oxidized

Human in Incubation of normal erythro- (6)vitro cytes with sodium dithionite

resulted in the formation ofHeinz bodies; Heinz body for-mation was increased by super-oxide dismutase and decreasedby catalase

DAMDI7-84-C-4133 8-3 N

L


TABLE IV-i. TOXICITY OF LITHIUM DITHIONITE (Cont.)


Sodium NS NS Concentrated solutions are (5)bisulfite irritating to the skin and

mucous membranes; in fatalpoisonings, death in 30-45 minfollowing irritability, rest-lessness, clonic convulsions,apnea, cyanosia, and terminalrespiratory and cardiovascularcollapse

Micro- in Mutagenic in several test sys- (7)organisms vitro tems

Sulfites Human inges- May cause irritation of the (4)tion stomach by liberating sulfurous

acid

Animals NS Large doses have been shown to (4)cause retarded growth, nerveirritation, atrophy of bone mar-row, depression, and paralysis

* Not specified

I, V. ENVIRONMENTAL EFFECTS


Al. Transport



Alc, Leachability - Data not available

Aid. Bioaccumulation - Data not available

A2., Transformation -- Data not available

A2at Biodegradation -- Data not available


DAMHD7-84-C-4133 8-4

½• • I I p l !I! I


A2c. Photolysis Data not available

A2d. Other chemical reaction -- Lithium dithionite is easily oxidized to thebisulfite and the bisulfate salts in open air (8).



BI. Avian species - Data not available

B2. Mammalian wildlife species - Data not available

B3. Terrestrial invertebrates - Data not available

B4. Reptiles - Data not available



B7. Aquatic species, fish and invertebrates -- Lithium dithionite isexpected to have toxicity similar to that of other lithium salts.Lithium chloride is the best documented in Table V-I (below)

TABLE V-1. LETHAL FISH EXPOSURES (8)

COMPOUND ANIMAL CONCENTRATION EXPOSUREmg/L

Chloride Goldfish 3750 22 to 27 BoursChloride Mature Small 2600 24 Hours

Freshwater FishChloride Freshwater Fish 1950-3770 24 Hours

V8

'.'

{. • DAMDI7-84-C- 133 85i

FI> 'i2....'

iS• .~m ., •mlmmm m


TABLE V-2.

LETHAL EXPOSURES OF FRESHWATER INVERTEBRATE, PROTOZOA AND BACTERIA (8)

COMPOUND ANIMAL PARAMETER CONCENTRATION EXPOSUREmg/L

Chloride Daphnia magna Immobilization <7.2

Chloride Daphnia magna Poison threshold 16 48 HoursChloride Scenedesmus No toxic effect 1000

(bact.)Chloride E6 Coli No toxic effect 1000Chloride Microregna Food intake 66

InhibitionChloride Water beetle Excitation 19500Chloride Fly larvae Toxic effect 848


CI. Phytotoxicity - Concentrations of lithium ion above 30 ppm have beenfound to be toxic to plant species including soybeans, mustards,flax, vetch, corn, citrus, avocado and wheat (8).




A. Health

Data not available

B. Environmental

The EPA has proposed the following limits for lithium ion in

irrigation waters max 2.5 mg/L, avg 0.075 mg/L (8)

"VII. DISPOSAL METHODS 21

A report (1) recommends securad landfills or lined disposal ponds as"racommended means of lithium battery disposal.

DAN)17-84-C-4133 8-6

~ '


VIII. REFERENCES

1. Crumrine, D., E. Juergens, M. Selinak, J. Fried, C. Colburn and• L. McCandless. 1978. Investigation of the Environmental

Consequences of Disposal of the Lithium Organic Electrolyte/SO2Battery. Final Report, AD A059512. U.S. Army Electronics ResEarchand Development Command, Fort Monmouth, NJ.

2. Reynolds, James E. F. and Anne B. Prasad, eds. 1982. Martindale-TheExtra Pharmacopoeia, 28th ed. The Pharmaceutical Press, London,England.

3. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial Hygiene and toxicology, Vol. 2B, 3rd Revised ed. JohnWiley and Sons, New York, NY.

4. Sax, N.I. 1979. Danaerous Properties of Industrial Materials, 5thed. Van Nostrand-Reinhold Co., New York, NY.

5. Gosselin, Robert E., Dr., Dr. Roger P. SMith, Dr. Harold C. Hodge,and Jeannette E, Braddock. 1984. Clinical Toxicology ofCommerical Products, 5th ed. Williams and Wilkins, Baltimore, MD.

6. Iminashi, ii., K. Hosokawa, and H.A. Itano. 1981, Induction of HeinzBody Formation by Sodium Dithionize. Hemoglobin. 5 (5):453-61.

7. National Institute of Occupational Safety and Health (NIOSH). 1981-82. Registry of Toxic Effects of Chemical Substances, Vol. 3.U.S. Department of Health and Human Servics, CIncinnat±, OH.

8. Slimak, M., J. Freid, D. Denuedy, E. Juergens, and Le McCandless.1977. Investigation of the Environmental Consequences of Disposal ofthe Lithium- Organic Electrolyte/SO2 Battery* Phase I Report, ADA059512. U.S. Army Elecuronics Cownad, Fort Monmouth, NJ. DAAB07-76-C-1752.

L

L

:ta:A!i

.. ,17-8'-.4133 8-7W .:.I."

"j~ " -!'"

+ )

BENZOYL PEROXIDE



Chemical Formula: C14 H100 4


Structural Formula:

- 0-0



Deleted CAB Registry Number: 37370-29-9

-CA Name (9C1): Peroxide, dibenzoyl

CA Name (OCI): Benzoyl peroxide

RTECS Number: DM8575000

Ocher Significant Syuonywn: Benzoyl superoxide

C. Chemical and Physica1 Properties

Physical State: Crystalline solid (I)

Color: White (2)

Odor: Bitter aldond (2)

Melting Point: 103-106°C (1), decomposes (3)1.i

' $~~olubiliLties: ,,

Water: Sparingly (1)W Noniqueous Solvents: Soluble in benzene, chloroform, ether I g/40 mL; \

carbon disulfide: g/50 mL olive oil (1).

S DA0.7-84-C-4I33 9-1

BENZOYL PEROXIDE (cont.)

Octanol Water Partition Coefficient: Log P - 1.87 (estimated)







Reactivity: Spontaneously explodes when heated; highly reactive;sensitive to shock, heat and friction (3)

Stability: May explode when heated (1), autoignition point 680C (3)

Flammability: Very flammable (3)

It. USES

A. Use

Igniter formulations for explosives, pyrotechuics, and obscurants.

B. Other Uses

Oxidizer in bleaching oils, catalyst in the plastics industry,initiator in polymerization, keratolytic (I).

l11, ANALYTICAL HETHODS

'BestA. Acceptable Method

Purnell et al. (4) reported a high-performance liquid chromatographymethod to determine trace levels of benzuyl peroxide and otherorganic contaminents in workplace atmospheres. High performanceliquid chromatography is used widely for quality assurance ofproducts containing bcnzoyl peroxide in the pharmaceutical industryand may methods have been reported.


0.01 ppm 2)

flA1D17-44-C-4133 2


IV. HE.ALTH EFFECTS

TABLE IV-I. TOXICITY OF BENZOYL PEROXIDE

Dose/

Species Route Duration Effects Reference

Human oral 0.5-5 g/kg Estimated lethal dose (5)

Human local N$* Eye and skin irrita- (5)tion, skin sensitiza-tion

Human inhalation 1.34317.0 Nose and throat irrita- (6)mgim tion

Human inhalation 2.58582,.5 Eye, nose, and throat (6)mg/m irritation

Rat oral 7,710 mg/kg LD 50 (7)Rat oral 950 mg/kg No Mortality (5)

Rat oral 2.8-2,800 Testicular atrophy (6)pp• in diet (not clearly cheical-for 120 wk related)

Rat subcutaneous 120 ag/rat No effects (6)

Rat subcutaneous 50 mg for No tumors attributed (6)implant 24 Mo to ben:oyl peroxide

Rat inhalation 24.3 zg/L Efe squint, increased (6)for 4 hr and decreased reapira-

tory rates, salivation,lacrimation, erythema;no effects after 48 hrexcept lingering eyeirritation

House intra- 250 mg/kg Mortality (5)pert-toneal

Mouse intra- 4.8 mg/mouse LD 50 (6)(hybrid periconealhairless CB)Dalbino; R and CB) -

S~DAH•I 7-84-C-4133 9-3 !,

SBENZOYL PEROXIDE (cont.)

TABLE IV-1. TOXICITY OF BENZOYL PEROXIDE (Conte)


Mouse intra- 54-62 mg/kg No effects (6)pertineal

Mouse subcutaneous 50 mg/mouse No effects (6)

Guinea pig dermal Dry powder Slight irritation (5)

Gulinea pig dermal 10% solution Slight to moderate (5)in propylene erythema and edemaglycol without systemic

toxicity

Rabbi: eye 500 mg/24 hr Severe irritation (7)

* Not specified

TABLE IV-2. ?UTAGENICITY AND REULTED EFFECTS OF BENZOYL PEROXIDE

lest System Dose Effects Reference

Salmonella NS* 78Z ben-oyl peroxide was (6)"Pvphimurium nonmutagenic; zested withTAA535, TA-537, tissue homogenate fromTA1536; mice, rats, and monkeys,eaccharomyces for metabolic activation;terevisiae D4 ben-oyl peroxide was noL

soluble in the vehicle DMSO

Mouse cells I umol!,' Hutagenic (*)(type notspŽcif ltd)

Mouse (ICR/Ha 54 and 62 Negative (b)Swiss) dominant ag/kg; iplethal assay

"N tot specified

* fMlDI7-84-C-4033 9-4



No information was found regarding the environmental fate or effects ofbenzoyl peroxide.


A. Health

3TLV: TWA 5 mg/m3 (7)

SB. Environmental

Data not arailaable



Review o& past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andH•azardous Materials Agency (USATHAKA) which has the responsibility co"review current disposal practices and to develop plans for futuredisposal practices (8).

B. A.Iternate Disposal Practices under Consideration Z Lh~e A

Future plans for disposal of waste explosives and propellants are1.projected to emphasize fluid-bed incineration, This method has beentested successfully by ARRADCOt4 and is planned for use at installationssuch as Savanna Army Depot, Tootle Army Depot, and Hawthorne NavalhAtmunition Depot (9).

C. Other Disoal Practices Fmhploved

Submerge in alkali solution 102 NaOH at 4 times weight of peroxide.Waste pastes can be charged with 50% nonflammable material (i.e.,"Vermiculite), dried and burne6 under controlled conditions. Emptycontainers should never be up.ed for other purposes, but should beburned (3).

".o9-

"•'•., LMD1 7-84-C-4133 9-5

BENZOYL PEROXIDE (coat.)

VIII. REFERENCES

1. Windholz, M., S. Budavari, R.F. Blumetti, E.S. Otterbein, eds. 1983.The Merck Index, 10th ed., p. 159. Rahway, NJ.

2. New York State Department of Health. 1984. Chemical Fact Sheet. NewYork State Department of Health, Albany, NY.


4. Purnell, C.J., D.A. Bagon and C.J. Warwick. 1982. The Determinationof Organic Contaminant Concentrations in Workplace Atmospheres byHigh Performance Liquid Chromatography. Analytical Techniques inEnvironmental Chemistry. pp. 203-19.

Gosselin, Robert Z., Di, Dr. Roger P. SmithE, Dr. Harold C. Hodge, andJeannette E. Braddock. 1984. Clinical ToxicoloAy of CommercialProducts, 5th ed. Williams and Wilkins, Baltimore, MD.

6. National Thstitute for Occupational Safety and Health (NIOSH). 1977.Ctiteria for a Recommended Standard Occupational Exnosure to BenzoylSPeroxide, pp. 70-72. Department of Health, Education, and Welfare.

L 7 National Library of Medicine (NLM), Registry of Tcxic Effects ofChemical Substances (RTECS). Accession No. UM857000. 1985.

8. David Renard, U.S. Army Toxic and Hazardous Hater.'als Agency, toJ. Carl Uhrmacher (personal commun ication), 1985.

9. Fovaten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings 1980 National Conference on Environmental En_ neerin. NewYork, July 8-10, 1980. ASCE Environmental Engineers Division, NewYork. 440-J75,

L

IC,

CALCIUM RESINATE*

*Name does not refer to a specific compound but a group of compounds, whichmay include the calcium salts of abietic acid, dihydroabietic acid anddehydroabietic acid (1).

*Resin acids include abietic-type acids, the pimaric-type acids and otherresin acids such as elliotinoic acid (5).

I. CUFMICAL AND PHYSICAL DATA

A. Ztructura2 and Chemical Formulas and Molecular Weight

*Chemical Formula: Not applicable

*Molecular Weight: Not applicable

*Structural Formula: See Exhibit 10-1.




CA Name (9CI): Resin acids and rosin acids, calcium salts

CA Name (SCI): Same

RTSCS Number: EW3970000, EW3971000

Other Significant Synonyms: Limed rosin

C, 'Chemical and Physical Prprte

Physical State: Amorphous powder or lumps (2)

Color: Yellowish white (2)a -*

odor:, Rosin odor (2)

* Melting Pointz Does not apply to mixtures

'a Solubilities:Water: Insoluble (2)Nonaqueous Solvents: Soluble in acid, amyl acetate, butyl acetate,ether,, amyl alcohol (2)


H.ygroscopicity: Data not available Q iDensity (Crystal): Data not available

",in..

CALCIUM RESINATE (cont.)

EXHIBIT 10-1

H63C<H

Abietic acid Hj

H3C COON

CH-CH 2

H~C CH3

Pimaric acid

H3 COON

H3C

Elliotinoic acid

H)C COC

DAI1D17-84-C-4133 1-






Reactivity: Can react with oxidizing materials (3)


Flammability: Flammable, dangerous fire risk, spontaneous heating (3)

II. USES

A. Army Unique Use

Fuel, binding and water-proofing agent in primers and tracers (5).

B. Other Uses

Waterproofing, manufacture of paint driers, porcelains, perfumes,cosmetics, enamels; coatings for fabrics, wood and paper; and tanningleather (4).


A. Best eabe Method

D ata not available


t Data not available

t VV'I!'

""01 1 A• 4:-C... -:


IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF CALCIUM RESINATE*


Calcium resinate NS** inges- Irritation of nose and (6)tion throat

NS top- Contact with eyes causes (6)ical irritation

NS NS When rosin is heated, (Ii)fumes are irritants

Resin acids:

NS oral Moderate acute toxicity (4)

Mouse intra- LD5 0 : 180 mg/kg (7)venous

Dehydroabietic Rat oral LD 0:1,710 mg/kg (7)acid

* Information not included in the ARC report** Not specified

V. WFNIROMW TAL EFFECTS

No information was found regarding the environmental fate or effects ofcalcium resinate which would update the Atlantit Research Corporationdocument.

VI. STAMDARDS AND REGULATIONS

A. Health

Data not available

SB. Environmental

Reported in EPA TSCA Inventory 1983.

l, DI 7-84-C-4133 10-4

CALCIUM RESINATE (cont,)


A. Current Recommended Arm Disposal Practices

Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAMA) which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (8).

B. Alternate Disposal Practices under Consideration .the Arm


C. Other Disnosal Practices Employed

Data not available

VII1I. REFERENCES

1. Windholz, Ki., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 1191. Merck and Co., Inc.,Rahway, INJ.

2 Kitchens, J.F., W.E. Harwards I11, D.M. Lauter, R.S. Wtntsel, R.S.Valentine. 1978. Preliminary Problem Defeinition Study of 48Munitions Related Chemicals, Vol, IV, Primer and Tracer RelatedChemicals - Calcium Resinate. Atlantic Research Corporation,Alexandria, VA. D&ADI7-77-C-7057.

3. National Library of Medicine, Chemical Information On-line (CHEMLItNE).Accession No. 0961. 1984.

4. Sax, N.I. 1979. Danrous Properties of Industrial Materials. 5thed., p. 464. Van .ostrand-Reinhold Co., New York, h.Y

5. Howley, Gessner G. 1977. The Condensed Chemical Dijtonary, 48thed., p. 155. Van Nostrand-Reinhold Co., New York, NY.

6. U.S. Coast Guard. 1978. Chemical Hazards Reponse Information System.(CHRIS) Hazardous Chemical Data-Traintng Edition, Abridged, CG-446-2.U.S. Departnt of Transportation, Washington, D.C.

7. Chemical Information Systet (CIS), Registry of Toxic Effects ofK Chamical Stbstances (RTECS). Accession No. EW3970000. 198$.

8. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uh-brmacher (personal co= -cation). 1985.

1v6,--

CALCIUM ,RESINATE (cont.)

9. Forsten, I. 1980. Dispoal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental Engiaeers"Division, New York. 440-575.

I\.

i

.-•-.

- -C413 0-

CALCIUM STEARATE

i. CHEMICAL AND PHYSICAL DATA


Chemical Formula: C H70CaO3670 4


Structural Formula: Ca+2 (CH3 (CH 2) 16 C00- 2


CAS Registry Number: 1592-23-0.

CA Name (9CI): Octadecanoic acid, calcium salt, stearic acid, calciumsalt

RTECS Number: None

Other Significant Synonyms: Calcium distearate

C. Chemical and Phvsical Properties

Physical State: Granular fatty powder (1)r

Color: White

Odor: Slightly fatty odor

?Melting Point: 179-180 C

Solubilities:Water: Practically insoluble (I)Nonaqueous Solvents: Insoluble in ether, chloroform, acetone, coldalcohol. Slightly soluble in hot alcohol and hot vegetable oil.Quite soluble in hot pyridive (1), hot ethanol, and hot mineraloil (2).

Octanol Water Partition Coef.tclent: Data not available

Hygroscopicity; Data not available

"Density (Crystal): 20 lb/ft 3 (I)


Vapor Pressure (p): Data not available

specific Beat: Data not available

"Alrn7-84-C-4133 I1-1

.I1

CALCIUM STEARTE (cont.)


Reactivity: Decomposed by many acids and alkalies (3)

Stability: Data aot available


II. USES

A. r Unique Use

Binder and waterproofing agent for explosive mixtures

B. Other Uses

Water repellent, paint flattening agent, lubricant in makingtablets, emulsions, cements, stabilizer for vinyl resins, foodadditive, cosmetic ingredient (3).

Also used for waterproofing fabrics, cement, stucco; as a releasingagent for plastic molding powders; as a stabilizer for polyvinylchloride resins; as a lubricant in pencils and wax crayons. Food gradecalcium stearate, derived from edible tallow, is used as a conditioningagent in certain food and pharmaceutical products (I).

III. ANALYTICAL IMTHODS


Hayashi et al. (4) describeJ a high-performance liquid chromatographymethod using fluorescence pre-labeling with 4-(bromomethyl)-7-methoxycoumarin. The fluorescent derivatives of fatty acids wereseparated by reverse phase liquid c romatography followed byfluorometric detection.

B, mit of Detection

Hayashi et al. (4) reported approximately 7 picomoles as the limit ofdetection in river water*

DA1017-84-C-4133 11-2

!4

CALCIUM STEARATE (cont.)

IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF CALCIUM STEARATE

Species Route Dosee/Duration Effects Reference

Rat, oral Repeated dose, Not toxic (5)mouse (conc. and

duration NS*)

Rat, dermal, NS Not: toxic (5)mouse eye ap-

plication

Guinea dermal Emulsion (rone. Significant decrease (6)pig NS) in egg yolk in body weight by

and water, day 6 relative todaily for 14 d controls

Rat intra- 50 mg in 0.5 mL Severe lesions of (6)tracheal saline and 0.01 blood vessels in pul-

mL egg yolk; monary tissue at 2 mo;2 or 6 mo peribronchial sclerosis,

foci of alveolaremphysema, singlesmall areas of hemor-rhage, and pigment ag-gregations at 6 to;results in controlsnot reported

&at intra- 10 ng in 0.5 %L Varying degrees of (6)tracheal saline and 0.01 lung pathology in-

mL egg yolk; 4 cludinwg peribronchialor 8 mo sclerosis, alveolar

telectasiov and dif-fuse brochlectasis;recults in controlsnot reported

SNot specified

V * ENV 1O4NTAL EFFECTSV. MEV IROM'@.TLL FE

INo information was found on the envlronaental fate or effects ofcalcium atearace.

0 .,

CALCIUM STEARATE 'cont.)

Vi. STANDARDS AND REGULATIONS

A. Health

The Food and Drug Administration has affirmed that calcium stearateis generally recognized as safe as a direct human food ingredient (7).

B. Environmental

Listed in TSCA inventory.


A. Current Recommended AMy Disposal Practices

Review of past Installation Assessment Reports indicate thet currentmethods of disposal of waste explosives and propellants involve opeaburning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beei,confirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATRA.MA), which has the responsibility toreview current disposal practices and to develop plans ior futuredisposal practices (8).

Pure or concentrated calcium stearate may not require conservativedisposal met hods.

B. Alternate Dis•osal Practices under Consideration by the Army

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and Hawthorne NavilAmmunition Depot (9).

C. Other Dlspos-,a r'a.tices Enployed

Landfill in accordance with applicable local, st&te, and federalregulations (10).

VIII. REFERENCES

1. Windholz, Y.., S. buda-ari, R.F. bluzetti, and E.S. utterbein, eds.1983. The Merck Lnde•:, 10th ed., p. 234. The Merck Co., Inc., Eahway,NJ.

2. Kaye, Seymour. 1980. Encyclopedia of Explosives and Related Items.Vol. 9, PATR 2700, p. 21'. U.S. Army Armament Research and Developmen:Comand, Dover, IJ.

MWD 17-84-C-4133 11-4

CALCIUM STAF.RATE (cont.)

S3. Hawley, Gessner G. 1981. The Condensed Chemical Dictionary, 10thed., p. 186. Van Nostrand-Reinhold Co., New York, NY.

4. Hayashi, K., J. Kawase, K. Yoshimura, K. Ara, and K. Tsuji. 1984.Determination of Trace Levels of Fatty Acid and Metal Salts by High-Performance Liquid Chromatography with Fluorescence Prelabeling.Analytical Biochemistry. 136 (2):314-20.

5. Komorova, E.N. 1976. Toxic Properties of Some Additives forPlastics. Plast. Massy. 1(2):30-1.

6. Cosmetic, Toiletry, and Fcagrance Association (CTFA). 1982. FinalReport of the Safety Assessment of Lithium Stearate, AluminumDistearate, Aluminum Stearate, Aluminum Tristearate, AmmoniumStearate, Calcium Stearate, Magnesium Stearate, Potassium Stearate,Sodium Stearate, and Zinc Stearate. J. Am. Coll. Toxicol.1(2);143-77.

7. Federal RegLster, Vol. 48, No. 224, p. 52444.


9. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of 1980 National Conference on Environmental Engineering.New York, July 8-10, 1980. ASCE Environmental Engineers Division, NewYork. 440-575.

10. Material Safety Data Sheet-Calcium Stearate. 1976. Diamond Shamrock ICorporation, Morristown, NJ.

i7 - 11

! DAMg)l7-84-C-4133 I 1-5 :

CERIC AKMONIUM NITRATE


A. Structural and Chemical Formulas and MolecularWsight

Chemical Formula: CeH8N8018 (N)


Structural Formula: (NH,,), (Ce[NO 3 ] 6 )

B. Alternate Names &nd Re&istry Numbers

CAS Registry Number: ]6774-21-3

Deleted CAS Registry Numbers: 25567-1--3; 15306-26-0

CA Name (9CI): Cerate(2-), hexakis(:Aitrato-0)-, diammonium(OC-6-11)-

"CA Name (8CI): Cerate(2-), hexanitrato-, diammonium

RTECS Number: Data not available

Other significant synonyms: Ammonium cerium nitrate; Diammoniumhexanitratocerate; Ammonium hexanitratocerate; Diammonium ceriumhexanitrate; Ammonium cerium hexanitrate; Ceric(IV) ammoniumnitrate


Physical State; Crystalline solid; monoclinic (1)

Color: Orange-red (0)


Melting Point. Datr not available

SolubilitiesWater: 141 g/100 mL at 250C; 227 &/100 mL at 80 CNonaqueous Solvents: Soluble in alcohol, as well aa nitric acid (2).


(;.'deHygroscopicity: Data not available

Density (Crystal): Dlata not avai'labl.

WDAH17-84-C-413.3 12-1

[A*

CERIC AMMONIUM NITRATE (cont.)





Reactivity: Data not available

St•oili:y: Data not available

Flannability: Data not avdilable

II. USES

A. Arm Unique Use

Explosive

B. Other Uses

Catalyst for polymerization of olefin; standard in oxidimetry (1).

SDAD 7-$4-C•-4,133 12-2

!

CERIC AMIMONIUM NITRATE (cont.)

III. ANAILYTICALL METHODS


iio methods of analysis for this compound have been reported in the)ast five years in Chemical Abstracts.

B. limit of Detection

Data not available

I34

AA

DAMW17-84-C-4133 12~-3


IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF CERIC AMMONIUM NITRATE


Ceric No toxicity dataammonium locatednitrate

Nitrates Human oral Large Dizziness, abdominal (3)amounts cramps, vomiting,

bloody diarrhea, weak-ness, convulsions, andcollapse

Small May lead to weakness,repeated general depression,doses headache, and mental

impairment

. Cerium Rat oral 3,630 LD(4) (nitrate mg/kg

, • ~Ce(N03)C Rat intrates- 26,092 TD o; effects on (4)

ticular mg/kg speomatogenesis andsex organs

Cerium Rat oral 4,200 LD (4)•. :1,50nitrate mg/kghexahyd-rate Rat intraper- 290 mg/kg LDso (4)Ce(N i itoneal

2

Rat ±ntra- 4 mg/kg LD~ (4)venous.

.Mouse intraper- 470 mg1/& LD (4)V itoneal, Cerium salts NS* us NS Increase in blood (3)

coagulation rate

Cerium Human intra- 3-12.5 Anticoagulant effect (5) ___

venous m-/kg, for 8 hr; chills,single fever, headache,and muscle pains, abdowi-

M.D. .- 84-C-4133 12-4

4, 7i-


repeated nal cramps, hemoglo-daily binemia, hemoglobin-doses uria

* Not specified

TABLE IV-1 TOXICITY OF CERIC AMMONIUM NITRATE (Cont.)


Cerium Rat intra- NS Fatty infiltration (5)(cont.) venous of the liver charac-

terized by an in-crease in neutral fatesters; total choles-terol and phospholipidof liver were un-changed; effects morepronounced in females

Lanthanide Rat oral (feed) 0.01, No influence on (5)compound 0.1, and growth or hematolo-(not 1% in gic variables; tis-specified diet for sues of 8 internalwhether 12 wk organs showed no his-Ce was tological changes attested) 0.01 and 0.1%; ani-

mals given Gd, Tb,TIm and Yb showed non-specific liver damage(perinuclear vacuoli-zation and granularcytoplasm) at 1it;

*Not Specified

V. ElVIRMENTAL EFFECTS

No information was found regarding the envi.con ntal fate or effectsof carit aonium nitrate.

U&2W17-64-C-4133 12-5 "



A. Health

Data not available

B. Environmental

Data not available



Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or occasionally, hauling by a licensedcontractor and landfilling. Current use of methods discussed above hasalso be been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices and to developplans for future disposal practices (6).

B. Alternate Disposal Practices under Consideration a the Army


C. Other Disposal Practices Emploved

Data not available

VIII. REFERENCES

I . Windholz, H. S. Budavari, RF. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 76. Rahway, NJ.

72. Weast, R.C. 1968. CRC Handbook of Chemistrv and Physics, 48th ed.,! B-151. The Chemical Rubber Company, Cleveland, OH.

3. ,v, N.I. 1979. Dangerous Properties of Industrial Materials, 5thed., p. 476. Van Nostrand-Reinhold Co., New York, NY.

4v Tatken, lRogr L., and Richard J. Lewis, Sr., eds. Registry, of Toxic;Effecs of Chemical Substances, Vol. 1, p. 878. Nationl Institute

or Oc--upationalSafey i Galth, Cincinnati, 0H.,

DAMDI7-84-C-4133 12-6

CERIC A.MM1QNIUM NITRATE (cont.)

5. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial Hygiene and Toxicology, Vol. 1, 3rd revised edition. JohnWiley and Sons, New York, NY.

6. David Renard, U.S. Army Toxic and Hazardous M~aterials Agency, toJ. Carl Uhrmacher (personal communication). 1985.

7. Forsten, 1. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575.

&

DAMD17-84-C-4133 12-7

CHLORAMINE-T



Chemical Formula: (C71 7 So 2N(Cl))Na


Structural Formula:

S02NCI

Na +

H__C

)B. Alternate Names and Ristr Numbers

GAS Registry Number: 127-65-1

Deleted CAS Registry Numbers: 75532-46-6; 72793-59-0; 1576-40-5;8045-11-2

CA Name (9CI): Benzenesulfonamide, N-chloro-4-rmethyl-, sodium salt

CA Name (8CI): p-Toluenesulfonamide, N-chloro- sodium salt

RTECS Number: 217815

Other Significant Synonyms: Sodium tosylchloramide N-Chloro-4-methylbenzyl sulfonamide, sodium salt, halamtd, chlorazone


Physical State; Trihydrated crystal; prisms (1)

Color. White or faintly yellow (11)


DVIDI7-84-C-4133 13-1

..................................-.... --- ,----.--..--:

CHLORAMINE-T (cont.)

Melting Point: 167-170 0 C (11)

Solubilities:Water: Fairly soluble in water (1)Nonaqueous Solvents: Practically insoluble in benzene, chloroform,ether; decomposes in alcohol (W).








Reactivity: Reacts with water to release HOCI

Stability: Decomposes slowly upon exposure to air and under theinfluence of light (1). May decompose violently if heated above

0130 C (15).


II. USES

A. A U Use

Field water purification chemical

B. Other Uses

Antibacterial, veterinary antiseptic, laboratory detection of halogensa.nd bromate (1).

14

ii4 4 1

CHLORAYiNE-T (cont.)

III. ANALYTICAL MtTHODS

A. Best Acceptable Method )

A titrimetric method for the determination of Chloramine-T andaldoses is based on Leipert determination of iodide by reduction withexcess iodide and extraction and subsequent reduction of the iodineliberated (2).


0.01 mg/L (2)

J,3

• " " DAID17-84-C-4133 13-3 •

ILIA•.


IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF CHLORAMINE-T

3,1 Chemical Species Route Effects Reference

Chloramine-T Human ingestion Vomiting, cyanosis, circu- (3)latory collapse, frothingat the mouth, and respira-tory failure can occurwithin a few minutes,fatalities have occurred

Human intravenous In tap water it has cause (3)bemolysis in patientsundergoing dialysis

Human inhalation Can cause vasomotor (4)rhinitis and asthma

Human occupational Nasal irritation and/or (5)excposure wheezing; fever; cough;

asthmatic reactions

Human occupational Immiediate asthmatic bron-- (5,6){.exposure chial obstruction and/or

a laate-type asthmatic re-action accompanied by leu-kocytosis after inhalationtests of Chior imine-T; animmediate type of whealand flare reaction follo'u-ed by a late-type inf 11-trative reaction afterprick tests; specific IGEantibodies occur in thesera of exposed patients

Human ingestion An occasional reaction is (7)rapid and violent, suggest-ing hypersensitivity; poi-soning characterized by pain,vomitikng, muddep lots ofconsciouisness, circulatory andres~piratory collapse, and

death; it has been auggested

DAMD17-84-C-~4133 1-

CHLORAMNNE-T (con:.)

TABLE IV-i TOXICITY OF CHLORAIMINE-T (Cont.)


Hypochlorous Human local Highly irritating to (4)acid skin, eyes, and mucous(available membraneschlorine)

Human ingestion Irritation and corrosion (3)of mucous membranes withpain and vomiting; a fallin blood pressure, delir-ium, and coma may occur

Human inhalation Coughing, choking; may (3)cause severe respiratorytract irritation andpulmonary edema

TABLE IV-2, MUTAGENICITY AND RELATED EFFECTS OF CHLORAMINE T

Test system Dose Effects Reference

Salmonella 4-2,500 NVnmutagenic with Aroclor (8)typhimurium ug/plate 254-induced rat liver S9

•. (TA98, TA100,

TA11535, TA1538)

S. typhimurium several Nonnutagenic with or with- (9)(TA98, TAI00, dose levels out Aroclor 1.54-inducedTA1535, TA1537 rat liver S9TA1538)

Drosophila 25 m.-; oral No incre"e in frequency (9)_oelanogaster (approx. of sex-linked recessiveBase test LDs 0 ) lethal mutations

Micronucleus 35 and 70 No increase in frequency (9)test on mouse t8g/i; !p of zicronucleibone marrow

Human lymph- 100 ppo/2 4 Induction of chromosomal (10). ocytes in br (Cheor- aberrations

vitro aine-T trF-hydrate) )

DAfD1J)7-84-C-4133 13-5

CHLOR."iINE-T (cont .)

V. ENVIRONe4ENTAL EFFECTS



Ala. Adsorption - Data not available





Aa. Biodegradation -- Data not available

.2b. Hydrolysis - Releases hypochlorous acid (HOCI) in water (1I)

A2c. Phctolysis - Data not available

A2d. Other chemical reaction - Data not available


B. Effects on animalsY


B2. Hamalman wildlife species -- Data not available


B4. Reptiles -D Data not available

BS. Amphibians - Data not available

B6. Microorganisms, aquatic and soil - Data not available

B7. Aquatic specie, fish and invertebrates t- tr a 60-zinuteexposure at 250C to 1.0 mg/L applied Chloramine-T significantly lowe.-increases in dry w.aight and significant r•.uctions in standardrespiration rate were measured aong exposed larval lobsters (Nomaruss ericanus), compared to control organisms. Greater differences weredetected aaoqg Chloramine-T-exposed organisms than were measured fororganisms e"osed to 1.0 mg/L appiied free chlorine (12).

,'DU 17-84-C-4133 13-6

: ,,|4

CH. . .....E-.. (cont.)

Chlorazine-T was more toxic to rotifers (Brachionus plicatilis) thanwas the free chlorine forn. with IX s values for 30-minute exposuresat 20 of 0.35 rmg/L applied C l-oramine-T ano 1.20 mg/l applied freechlorine, 0.02 mg/L and 0.1' mg/L residual evel respectively.Increased temperat'lrc had a syner,,-Atic effect on the toxicity ofboth Chloramine-T and free ciilor" .e. Rotifers surviving exposure toeither halogen toxicant had significantly lower filtration rates andegg production rates than control animals. The reduced reproductiverates were not sustained by the second generation (13).

Shrimp (Penaeus setiferus): In a 24-hour toxicity test at aconcentration of 40,000 ug/L Chloramine-T, at 21 to 220C, 6 of 140shrimp died (14).

Lethal concentrations: Ptychocheilus oregonensis, 0-3 hour exposure,11.7 0: 10 ppm; Coho and Chinook salmon, 1-2.5 hour exposure,11.7 C: I ppm; Rainbow trout, I hour exposure, 12.8 C: 5 ppm;Bluegill, 5 hour exposure, 12.80 C: 5 ppm,; Pitromyzon marinus, 14hour exposure, 12.8 C: 5 ppm (13).


C11 Phytotoxicity - Dat" ..or available

C2. Uptake - Data nr.t available

C.), Metabolism -- Daca not available )


A. ealth

Data not available

B. Environmental

Reported in EPA TSCA Inventory.

V11. DISPOSAL

A. Current ,ecoendled A Disposal Practices

Data not available

B. Alternate Dsol Practices Under Consideration b theA Amy

Data ntevailable

DAMD)17-84-C-4133 13-7

OW N7"

CH.'ORAMINE-T (cont.)

C. Other Disposal Practices Ewployeýd

The U.S. EPA recamnends dilution in a flammable solvent followed byburning in an incinerator ecuipped with an afterburner and aneffl~uent scrubber for Chlorwnine-T disposal. Scrubber overflow is

tob-eurlzdpior to dischargt. Incinerator ash should be

buriedi in a hazardoxas or sanitary landfill (11).

*VIII. REFERENCES

*1. Windholz, M4., S. Budavari, R.F. Bliuietti, E.S. Otrerbein, eds. 1983.The Merck Index, 10th ed., p. 29_ý Merck and Co., Inc., Rahway, NJ.

2. Amnin, D., K.Y. Sa2.eem, and W.A. Bashir. 1982. TitrimetricDetermination of Chloramine-T and Some Aldoses by AmplificationReactions, Taianta. 29(8):694-6.

3. Reynolds, Jaw±es E.F. and Anne B. Prasad, eds. 1982. Martindale-TheExtra Pharzacopoeia, 28th ed. The Pharmaceutical Press, London,England.

4. Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5thed., p. 48.1, Van Nostrand-Reinhold Co., New York, NY.

5. Dijkman, Joop H., Piet H. Vooren, and Johannes A. Kramps. 1981.Occupati~onal Asthma Due to InhAlation of Chlor;'mine-T-ClinicalObservations and Inhalation-Provocation Studies. Int. Arcbs. Allergyhppl. lImmun. 64:422-27.

6. Kramps, Johanues A., Albert W. van Toorenenbergen, Piet H. Vooren,and Joop H. Dijkman. 1981. Occupational Asthma jflue to Inhalationof Chloramine-T-flemonstratior of Specific IgE Antibodies. Int.Archs. Al pA.Inn 64:428-38.

7. Gosselin, Rober E., Dr., Dr. Roger P. Smith, Dr. Harola C. Hodge, andJeanette E. Braddock. 1984. Clinical Toxcology of CommercialProducts 5th ed. ilim nd~WTnVi6e D

8. Anderson, D. and J.A. Styles. 197B. An Evaluation of 6 Short-TermTest for De~tecting Organic Chemical Carcinogens. Appendix 2.

The Bacteri~t Mutation Test. '"to J. Cancer, 37:*924-930.

9. Gocke, E.., M-T. King, R. Eckhardt, and D. Wild. 1981. Mutagenicityof0 Cosmetics Ingredients Liscensed by the Euiropeau Communitites.Mutate Res# 90;91-1099

10. Tatt~.n. Rodger L. and Richard Jo Lowite, Sr., eds. 1981-82. Registr~of Toxic Effects of Chemical Stfbtwigg; Vo.34.7e National

et~ituU*'for Occpa~tional Safety and Realth (MiOM), Cincinatti$ Oh.

flAMD17-84-C-4133 13-8


II. Chemical Information System (CIS), Oil and Hazards. MaterialsTechnical Assist. Data System (OHMTADS). Accession No. 7217324.1985.

12. Capuzzo, Judith M. 1977. The Effects of Free Chorine and Chloramineon Growth and Respiration Rates of Larval Lobsters. Water Reseal-ch.11:1021-1024.

13. Capuzzo, Judith M. 1979. The Effects of Halogen Toxicants onSurvivsl, Feeding and Egg Production of the Rotifer BrachionusPlicatilis. Estuarine and Coastal Marine Science. 8:307-316.

14. Dialog Search, Aquatic lnformation On-line (AQUIRE). Accession No.235654. 1985.

15. Aldrich Chemical Co., 1984-85,, Aldrich Catalog/handbook of FineChemicals, p. F15-617. Aldrich Chemical Co., Milwaukee, WS.

)

I 3'

COPPER-8-QUINOLINOLATE



Chemical Formula: Cu(C 9 H6 ON) 2


Structural Formula:

N

SB. Alternate Names and Registry Numbers


Deleted CAS Registry Numbers: 29713-19-7; 132-71-8; 37220-44-3; 37233-

52-6

CA Name (9CI): Copper, bis(8-qu±nolinclato-N1,08)

CA Name (SCI): Copper, bis(8-quinolinolazo)-

RTECS Number: VC5250000

"Other Significant Synonyms: Copper-8-quinolinclate, copper quinolate,Copper oxinate, Copper 8-hydroxyquinoline, Quinolate (1)

C. Chemical and ha8l Properties

Physical State: Powder (1)

Color: Yellow-Green

Odor; Odorless

Melting Poi.nt: Decomposes at 2iO C (2)

.. V

ii,:DA D 7- 4-'4 3 14 ,,,........,_..:'0,•. ..

COPPER-S-QUINOLINOLATE (coat.)

Solubilities-Water: Insoluble (1)Nonaquecus Solvents: Somewhat soluble in weak acids, solublein strong acids; insoluble in most organic solvents (1).

Octanol Water Partition Coefficient: Log P u2.70 (3)

Hygroscopicity; Nonhygroscopic (1)









Ii. USES

A. m Unique Use

Mtilitary anti-mildew agent

B. Other Uses

Fungicide and mildew-proofing of fabrics; reagent for the analysis of

copper (1); wood preservative.

111. ANALYTICAL M4ETHIODS


No work has been done on the determination of trace amounts of thiscompound. 8-Quinolinoline is a strong chel~ating agent and mayinterfere with some methods of analysis of copper* Work has been doneon the size exclusion (4) and thin-layer chromatographic behavior (5)of this compound* Application to trace analysis of this tompound isdifficult to predict* Potentiomettic titratiou with N-bro~ophthalinise

.ýY in aqueous acetic acid has been reported by Wohanadao and Indrasenan

(6).* but no method ~of. Beparation wat reported* ~

B. Lmt of Detection

Data not available

DAMD17-84-C- 4 133 14-2

COPPER-8-QUINO'LINULATE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1 TOXICITY OF COPPER -1.-QUINOLINOLLTE


Copper 8-quin- Human, NS* Low toxicity; does (7)olinolate Animal not irritate the skin

Copper 8-quin- House minra- LD50: 67 mg/kg(8olinolate peritoneal s

8-Hydroxyquin- Animal NS CNS stimulant (2)oline

8-Hydroxyquin- Rat oral t.D5 -: 1200 mg/kg (2)oline

8-Hydroxyquin- H1ouse minra- LD)0 48 mg/kg (2)oline peritoneal

( Copper salts Human eyes May cause conjurictiv- (9)Itis, ulceration andturbidity of the cornea

Copper salts Human inhalation M~ay cause congestion of (9)the nasal mucous mea-branes and pharynx, andulceration with perf or-ation~ of the nas-alseptum

Copper salt3 Human ingestion Salivation, nausea, (9)vominting, gastric pain$hemorrhagic gastritis,[ ~and diarrhea

N ?ot ;ezlcf M

DW78-4133 14-3

COPPER-8-QUINOLINOLATE (cont.)

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF COPPER 8-QUT:.OLINOLATE

Test System Dose Effects Re±terence

S. typhimurium 5 ug/plate Nonmutagenic with or (10)(TA98, TA100, without Aroclor 1254-TA1535, TA1537) induced rat liver S9

S. typhimurium 0.5-50 ug/ Weakly mutagenic: 1.30 (11)(TAIO0) plate revertants/nmole in the

presence of S9

E. coli up to 5,000 Nonmutagenic with or (11)(WP2 hcr) ug/plate or without $9

toxic dose



Data not available )




"B3. Terrestrial invertebrates - Data not available



B6. Microorganisms, aquatic and soil -- 8-Hydr-oxyquinoline causes 75%inhibition of nitrification process in non-acclimated activatedsludge at 73 mg/L (12).

"7. Aquatic species, fish and invertebrates, - Snails: CYpangoPaludinaf malleata: 48-hour LC.: 20,000 ug/L; Semisulcospina libertina: 48-StrL 7700 ugILj 0 ndoglanorbis_ exuatus: 48-hour LC ,000

ug/L; P : 4-hour LC5o: 13,000 ugiL (13).


Cl. Phytotoxicity -- Treatment of seeds with copper 8-quinolinolate (wet •Q)dressing with 2 cc of 15% copper 8-quinolinolate per kg of wheatseed) Us effective against fungi and has a low phytotoxicity (14).

-4 , ,1


,C2. Uptake -- Data not available



A. Health

Data not available

:B. Environmental

Reported in EPA TSCA Inventory, 1983.

VII. DISPOSAL


Disposal practices recommended by the U.S. Navy in their ConsolidatedHazardous Item List for Copper Naphthenate, a related compound used fora related purpose, are to turn the bulk chemical into a pesticidecollection center, to the original supplier or to a commercial wastedisposal service (15). Data were not available on disposal of itemstreated with Copper Naphthenate.

i B. Alternate Disposal Practices Under Consideration by the Arm

Data not available

C. Other al Practices Employed

Data not available

4

VIII. REFERENCES

1. Hawley, Gessner G. 1981. The Condensed Chemical Dictionary, 10th ad.,p. 278. Van Nostrand-Reinhold Cot, New York, NY.

2. Sax, N.I. 1979. Dangerous erties of Industrial Materials, 5th

,ed., pp. 517-518.

3. Chemical Information System (CIS), Information System for HazardousOrganics in Water (ISHOW), Accession No. 315616. 1985.

4. Shibukawa, M., H. Saito, and R. Kuroda. 1984. Size-ExclusionChromatographic Behavior of Metal Chelates of 8-liydroxyquinoline.Fresenius Zeit fur a Chemie, 319:410-414.

5. Schnesweis, Go and K.H. Koenig. 1983. Chromatography of MetalChalates. VII. Thin-Layer Chromatography of Metal Chelates of 8-

Vz___________________ 14,-5-

A ~


Mercaptoquinoline Analytic Chemie. Fresenius Zeitung fur Analytic)Chemie. 316:16-22.*

6. Mohanadas, C. and P. Indrs_ýnan. 1984. Potentiometric Titratians; withN-Bromophthalimide in Aqueous Acetic Acid Medium. Inia Journal ofChemistry. 23A:869-871.

7. Ashland Chemicals. 1972. 8-Quinolinol and Its Derivatives-ALiterature Review. Ashland Chemical Co., Columbus, OH.

8. Tatken, Rodger t. and Richyard J. Lewis, Sr., eds. 1981-82. Registry,of Toxic Effects of Chemical Substances, Vol. 3, pp. 532-533. NationalInstitute f or Occupational Safety and Health (NIOSH), Cincinatti, Ohio.

9. Sittig, Marshall. 1981. Handbook of Toxic and Hazardous Chemicals andCarcinogens, 2nd edition, p. 257. Noyes Publications, Park Ridge, NJ.

10. Rasanen, L, M.L. liattula, and A.U. Arstila. 1977. Mutagenicity ofMCPA and Its Soil Metabolites, Chlorinated Phenols, Catechols andSome Widely Used Slimicides in Finland. Bull. Environ. Contain.Toxicol. 18:565-18.

11. Moriya, M., T. Ohta, K. Watanabe, T. Miyazawa, K. Kato, Y. Shirasu.1983. Further Mutagenicity Studies on Pesticides In Bacterial RevisionAssay Systems. Mutat. Res. 116:185-216.)

12. Verschuerea, Karel. 1983. Handbook of Environmental Data on OrganicChemicals, 2nd ed., p. 757. Van Nostrand-Reinholc Co., New York.

13. Dialog Search, Aquatic Information On-line (AQUAINE). Accession No.239973. 1985.

14. National Library of Medicine (NLM), Toxicology On-line (TOXLINE).Accession No. 051565W. 1985.

15. Consolidated Hazardous Item List (CHIL). 1981. NAVSUP PUB 4500. NavyFleet Material Support Office, Mechanicsburg, PA.

till

4,

COPPER NAPHTHENATE

*NAPHTHENE is a term used in petroleum chemistry to denote certain saturatedhydrocarbons, specifically five- and six-carbon cycloparaffins and theiralkyl derivatives, found in crude petroleum. It is sometimes used toinclude polycyclic members found in higher-boiling fractions (I). This isnot a unique chemical substance (CAS) but represents the Copper (+2) saltsof naphthene carboxylic acids.

I. Chemical and Physical Data


Chemical Formula: Undefined

Molecular Weight: Undefined

Structural Formula: Undefined



* -CA Name: Napthenic acid, copper salt

RTECS Number: QK9100000

Other Significant Synonyms: Data not available


Physical State: Solid (2)

Color: Green-blue (2)

Odor: Gasoline-like (3)

Boiling Point: 154-2020 C (3)

Solubilities:Water: Insoluble"Nonaqueous Solvents: Soluble in gasoline, benzene and mineral oildistillates (4)


Hygroscpicity: Data not available


DAMD17-84-C•4133 15-1

COPPER NAPHTHENATE (cont.)

Volatility: Data not available )

Flash Point: 41 0C

Heat of Combustion: 9,8000 cal/g (3)

Autoignition Temperature: 282 0C (mineral spirit) (3)



Flammability: Flammable, moderate fire risk (2), combustible (3)

II. USES

A. Army Unique Use

Military anti-mildew agent

B. Other Uses

Wood, canvas, and rope preservative; insecticide; fungicide;antifouling paints (2)

LII. ANALYTICAL METHODS


No methods were found for either copper naphthenate or naphthenicacid in searching the Chemical Abstracts System back to 1967. Coppercan be analyzed by either atomic absorption spectroscopy or atomic,emission spectrometry. Recently, a method was reported by Heeet al. which enhances the detection of copper by simultaneousinductively coupled plasma atomic emission spectrometry (4).


The lower determination range for copper is 0.001-0.005 ug/L. Theapparent linear range is 2-500 ug/L (4).

DAMD17-a4-C-4133 .13-2

A1

7 ... .

COPPER NAPHTHENATE (cont*)

IV. HEALTH EFFECTS

"TABLE IV-i. TOXICITY OF COPPER NAPHTHENATE


Human skin Liquid If spilled on clothes (3)

and allowed to remainmay cause smarting andredness of skin

Human in- Liquid Irritation to stomach (3)gestion

"Human inhal- Liquid Mild irritation of the (3)ation respiratory tract; aspir-

ation causes severe lungirritation and rapidlydeveloping pulmonary edema;central nervous systemexcitement followed bydepression

Human eye Liquid Kild irritation (3)

Rat oral 4,000-6,000 LD (3)mg/kg

Sprague- intra- 10,000 mg/kg No signs of fetal toxicity (5)Dawley per * or teratogenicityrat, toneal1-15 d

- preg

Rat, in- * Flaccidity and narcotic (6)mouse gestion effects

mouse oral 110 M/ 1Lo (L7)

SNot speciti W;hther the chemical was liquid or solid

DANDI7-84-C-4133 15-3

-Nl

'•' 'k. ,,

i•,' •÷ i~i i • • -o- • •- 7 :• ,.•['•'-"-------------,

COPPER NAPUTHENATE (cont.)

V. ENViRONMIENTAL EFFECTS


Al. Transport - Data not available

Ala. Adsorption Data not available


Aic. Leachability -- Data not available


A2. Transformation


A/b. Hydrolysis - Under certain conditions can hydrolyze to copperhydroxide and naphthenic acid (8).

A2c, Photolysis - Data not available


SA2e. Half-life -- Data not availablef



B2. Mammalian vildlife species D- Data not available


84. Reptiles -- Data not available

j B5. Amphibians - Data not available

B6. .Microorganisms, aquatic and soil - Daza not available

B7. AquaL. S species, fish and invertebrates - Freshwater blue-green

"algae: 72-hour LC O: 2.0 ppo (3).

C. Effects on -lants

CI. Phytotoxicity - Burlap treated with up to 4.0 copper nk-htheitatewas not phytocoxic to Cotoneaster divarecata when balle4 roots werewrappod iu the burlap for 40 ~~8()

"" C2. Upzake - Data uot available

C3. Metabolism - Data aot available

DAKH1I7-84-C-4133 15-4



A. Health

Data not available

B. Environmental


VII. DISPOSAL


Disposal practices recomended by the U.S. Navy in their ConsolidatedHazardous Item List for copper naphthenate are to turn in to apesticide collection center, to the original supplier or to acommercial waste disposal service (10).

B. Alternate Disposal Practices Under Consideration bthe Army

Data not available


Adsorb on filter aid or inert powder and incinerate in approvedfacility, not in closed container (8).

V-111. ERErURNCES

1. Windhol:, M., S. Budavari, R.F. Blumetti, and ES. Otterbein, eds.1983. Th.e Heyck Index, 10th ed., p. 915. tarck and Co., Inc*, PKahvay.NJ.

Ii 2. Hawley, Geszner G. 1981. The Condensed Chemical Dictionary, 10thed., p. 277. Vnn Nostrand-Reinhold Co., Ne1 York, N%.

3. US. Coast Guard. 1978. Chemic•al Hazards Response Informatio! Systen(CURS) iHazardous Chemical Data-Trainin& Edition-Co per Naphthenate,

4U.S. Li~iGepa t'eto -wtrausportat ion, Washington, D.C.

4. Hee, S.S.G., TJ. Kacdosald, and J.R. Boyle, 1985. Effects of AcidType and Concentration on the Determination of 34 Elements bySiuultaneous Inductively Coupled Plasma Atomic Emission Spectrometry.An_•lytical C!epstry. 57(7):1242-1252.

5. lardin, Bryan D., Gaty P. Bond, Dr. K.R. Sikov, Dr. F.D. Andrew, Dr."Robert P. Beliles, and Dr. Richard W. Niemeier. 1981. T'esting ofSelected Workp-iee Choucalt for Teratogenic Potential. Scand.J. Work. Environ. Health. 7(4):66-75.

DAD17-84-C-4133 15-5


6. Gizhlaryan, M.S. 1983. Toximetric Parameters of Copper Naphthenate.Gig. Tr. Prof. ZABOL. 0(2):53.

7. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981082. Registryof Toxic Effects of Chemical Substances, Vol. 2, p. 810. NationalInstitute for Occupational Safety and Health, Cincinatti, OH.

8. Chemical Information System (CIS), Oil and Hazardous MaterialsTechnical Assistance Data Systems (0HKTADS). Accession No.1 7215095.1985.

9. National Library of Medicine (NLM), Toxicology On-line (TOXLINE).Accession No. 07028. 1985.

10. Consolidated Hazardous Item List (CHIL). 1981. NAVSUP PUB 4500.Navy Fleet Material Support Office, Mechanicsburg, PA.

1AD-4C43 15.

Ii

I.

I

1Kl AD -4C4131-

CYCLOHEXAONE


SUMIMARY OF PREVIOUS STUDY

It hais been reported that the Army has a need for research on thetoxicological and environmental haz.ards of cyclohexanons (4). The reportstates that the compound is moderately toxic in acute doses by all routet ofadministration. Sublethal doses cause profound narcosis accompanied bycentral nervous system depression. Teratogenic effects had been reported inchick embryos'. There was no information on carcinogenic or mutagenicpotential of cyclohexanone. The few aquatic toxicity studies availableindicated a low toxicity of cyclohexanone to aquatic life.


A. Structural and Chezical Formulas and Molecular Wih

Chemical Formula: C 6 H 10 0

( Molecular Weight: 98.14

Structural Formula:

(jJ H

M*Aternate Names and Registry Numbers

CAS Registry bluabert: 108-94-1

Del.eted Ces Registry INumbaert 48090-9r5-5

CA ftze (9Cl): cycloheauone

DAMD17-84-C-4."33 16-1

......-......... A )

CYCLOHEXANONE (cont.)

CA Name (8C:): Cyclohexanone

RTECS Number: GW1050000

Other Signficant Synonyms: Ketohexamethylene, pimelic ketone, pimelinketone, sextone (1).

C. Chemical and Physical Prprt

Physical State: Oily liquid (6)

Color: Colorless or pale yellow (6)

Odor: Peppermint and acetone (6)

Melting Point: -16.4 C

Freezing Point: -32.1 0

Boiling Point: 155.6 C at 760 mmHg (2)

Solubilities:Water: 50g/L at 30 0C (2)Nonaqueous Solvents: Soluble in alcohol, ether and other commonorganic solvents (2); acetone, benzene, chloroform (3), nitrobenzene,n-hexanone, naptha, xylene, ethylene glycol, isoamyl acetate,dimethylamine (4).

Octanol Water Partition Coefficient: Log P -0.61 (5)

HygrosCopicityi Data not available

Specific Gravity (Liquid): 0.95 (18)

Vapor Pressure: 3.95 mm Ng at 200C (4); 4.0 mm Hg at 200C 25); 4.5 mmHg at 20 C (5); 10 =m Ug at 38.7 C (6); 60 Hg at 77.5 C (6).

Flash Point: 54 C, open~ cup (4); 630C (2).

Specific Heat: 0.433 cal-/g at 15-18 C (4)

K utaaea of C.ombusti~on: -8570 cal/g (4)

Reactivity: Strong oxidizers will convert cyclohemanone to adipicarcid. Susceptable to au~cloophilic attack (4).

* Refractive Index: (N 20/0) 1.4507 (7)

0Autcoigni~tiori Temip: 420 CU

Stability: Stable under normal conditions (4) V.

DAMD17-84"C-4133 16-2 i

.14

:n Ik

CYCLOHEXAINONE (cont.)

Flammability: Limits (Z), 1.-.,moderate, flash point, 63%,'combustion with moderate heating, slight explosive hazard in vaporform when exposed to flame (6).

I. USES

A. Army Unique Use

Recrystallization solvent for RDX (4)

BO Other Uses

Organic synthesis of adipic acid and caprolactam (8). Solvent forcellulose acetate, nitrocellulose, natural resins, vinyl resins, cruderubber, waxes, fats, shellac, DDT. Also used in the production ofcyclohexanone resins (2).

Ill. AN~ALYTICAL METHODS


Recent methods developed for monitoring cyclohexartone and itsmethylatlon products in aqueous solution involve introducin.5 the sampleis introduced into a tandem mass spectrometer through semipermeablecapillary tubing with a membrane interface (9). Additional methods ofanalysts are reported in the Atlantic Research Corporation Report. Gaschromatography is still used in the monitoring of air and watersamples.


Detection limits are reported to bim 0.0004 -0.0005 pppe (6).

DAND1W7-84-C-4133 16-3


IV. HEALTH EFFECTS

ItTABLE IV-1. TOXICITY OF CYCLOHEXANONE*

Species Route Dose/Duration Effect Reference

Rat oral 1,535 mg/kg LD5 0 (1)

Rat intra- 50 and 100 No adverse effects on opthal- (10)(Wistar venous mg/kg, Ix/d mologic, histopathologic,or Gunn) for 28 d hematologic, or clinical

chemistry parameters

Rat subcu- 2,170 mg/kg LDs 0 (5)4 taneous

Rat inhala- 105 mg/m3 /4 hr, TCLO, effects on fertility (1)tion days 1-20 of

gestation

Mouse oral 800 mg/kg days No fetotoxic effects (11)(CD-I) 8-12 of gestation

Mouse subcu- 1,300 mg/kg Lflo (1)taneous

Mouse inhala- 308 ppm/4 h' 50% decrease in imobilicy (12)* (Swiss tion developed during a "behavioral

* OFI) despair" swimming test

Guinea dermal 0.5 ml, 3x/wk Cataracts (13)pig for 3 wk

subcu- 0.5 ml of 5% Cataracts (13)taneous solutiou in

saline, 3x/wkfor 3 wk

Dog intra- 284 mg/kg/d in Sigus of toxic•ity included: (14) i•ivenous sodium chloride vocalization, lacrimation,solution for scleral vasodilation, mydriasis,

18-21 d salivation, urination, defe-cation, restlessnuss, stupor"and ataxia, occasional convul-sive uovements, hypernea and/ordyspnsa, Inf3amation at injec-tion site, hesolysis, bone sar-

Srow hyperplasia, aud extrame- '.dullary heaxtopoiueis

DA.I17-84-C-4133 16-4

i ft l i I. ..

CYCLOlIEXANONE (cont.)

TABLE IV-2. K1UTAGENIC17Y AND RELATED EFFECTS OF CYCLOHEXANONE

Test System Dose Effect Reference

Human lymphocytes 5 ug/L Mutagenic (.1)

Human leukocytes 100 Mutagenic (1)uinol/L

Salmonella 3 umiol/ Not mutagenic with or without (15)typhimurium plate Aroclor 1254-induced rat liverTA98, TAIOO S9TA1535, TA1537

S. typhimurium 0.03-30 Not mutagenic with or without (15)TA98, TkXOO umol! Aroclor 1254-induced rat liver

plate S9

S. tyhmru NS* Mutagenic (16)YA98, TAIQO,'C TA1535, TA1537,TAl 538

Bacillus subtilis US Mutagenic (16)

V. ENVIR0O4ENTAL EFFECTS

A* Environmental Pate

Al. Transport

Ala. Adsorption -- Data not avail~ile

Alb. Volatilization -Data not available

Ale. Leachability -Data not available

Aid. Bioaccumulation -Log of bSioconcentration factor calculated fromoctanol/water partition coefifc±.nt: log BCP 0.56 (17)0

A2. mu mto

C AZ&.. Blodegradaitiou C"- yelobexanona is not biodegraded well (6).4

DA)W17'-84-C-4133 16-~5


Biodegradation by adapted activated sludge--cyclohexanone as solecarbon source: 96.0% COD removal at 30.0 mg COD/g dry in*ulum/hr(18).

A2b. hydrolysis -- Data not available

A2c. Photolysis -- Data not available

A2d. Other chemical reaction -- I BOD 1.232; 32% of ThOD; COD: 100% ofThOD; ThOD: 2.605 (18).








B6. Microorganisms, aquatic and soil -- Toxicity threshold by cellmultiplication inhibition test: bacteria (Pseudomonas putida), 180mg/L; algae (Kicrocystis ae osc), 52 mg/I, green algae(Scenedesmus quadricauda), 370 68g/L; protozoa (Entoshphon sulcatum),54Z5, mgL; protozoa (Uronemea ag zi Chatton-Lwoff), 280 mg/L (18).

B7. Aquatic species (fish and inv~ertebrates) -- 7ish.' Leuciscus idus LC(exposure not reported): 536000 uV/L (19)i Leuciscus idus LC(exposure not reported): 752000 uj,'L (20); Invertebrate: DaP~niamuns 24-hour LC5 0: 800,000 ug/L (21).

C. Effects on pat

CI. Phytotoxicity - Dat- not available

C21 Uptake - Data nor available

C3. hetabolism - Date not avalable

V1. STANDARDS AND REGUflTIONS

A. Health3"3

TV TWAt: 25 ppa or 100 g/M3; STEL: 100 ppi or 400 3(22).

DA1•07-84-C-4133 16-6

. :. .: .:.ii•< , • . • .. ...' :;• . ,,,,• ;.j ,.•'•.•, I'.'.


B. Environmental


Cyclohexanone has a statutory reportable quantity (RQ) of I lb underthe Comprehensive Environmental Response, Compensation and LiabilityAct. The National Response Center must be notified immediately whenthere is a release of this compound in an amount equal to or greaterthan the RQ (23).

VII. DISPOSAL


Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAMA), which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (24).

B. Alternate Disposal Practices under Consideration bythe Army

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineratiou. This method has beentested successfully by AR.ADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and Hawthorne Naval

r Ammunition Depot (26).

f." C. Other Disposal Practices Employed

Burn in a chemical incinerator equipped with an afterburner andscrubber (27).

Spray into incinerator or burn in paper packaging. Additionalflammable solvent may be added (6).

AEHA: NSN 6810-00-234-1992, 664-0055, 695-3801, 962-1873 1

Dispose of through a commercial contractor (27).

The Holston AAP Installation Assessment (28) indicates that openburning is the only Army approved method for disposal of explosiveSwstee. Solvents containing up to 80-90% water are burned in claylinedA pit$ at Holston. ,j

DAIMI7-84-C-4133 16-7

4 - .

j< mI 1


4 VIII. REFERENCES

1. National Library of Medicine (NLM) Search, Registry of Toxic Effects ofChemical Substances (RTECS) Database. Accession No. GWIO50000.

2. Windholz, M., S. Budavari, R.F. Blumetti, and B.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 2722. Merck and Co., Inc*,Rahway, NJ.

3. Weast, R.C. 1968. CRC Handbook of Chemistry and Phsis 48th ed.,p. C-251. The Chemical Rubber Co., Cleveland, OH.

4. Kitchens, J*F., W.E. Harwards III, D.M. Lauter, R.S. Wentsel, R.S.Valentine. 1978. Preliminary Problem Definition Study of 48Munitions-Related Chemicals, Vol. 1, Explosives Related Chemicals-Cyclohexanone. Final Report, AD A066307. Atlantic ResearchCorporation, Alexandria, VA. DAMID17-77-C-7057.

5. Chemical Information Systems (CIS) Search, Envirof ate (EnvironmentalFate). Accession No. 240358. 1985.

6. Chemical Information Systems (CIS) Search, Oil and Hazardous MaterialsTechnical Assistance Data System (OHMTADS). Accession 7216661. 1985.

7. Hawley, Gessner G. 1981. The Condensed Chemical Dicionary, 10th ed.,p. 297. Van Nostrand-Reinhold Cot, New York, NY.)

9. Brodbelt, J.S. and R.G. Cooks. 1985. An Exceedingly Simple MassSpectrometer Interface with Application to Reaction Monitoring andEnvironmental Analysis. Analytical Chemistry. 57(6):1153-1155.

10. Greener, Y., L. Martis, and N. Indocochea-Redmond. 1982. Assessmentof the Toxicity of Cyclohexanone Administered Intravenously to Wistarand Gunn Rats. J. Toxicol. Environ. Health, 10(3):385-396.

lit National Library of Medicine (NLM) Search, Toxicology Online (TOXLINE)Database. i.ccession No.1 21129211. 1985.

12. Chemical Information System (CIS), Toxicology On-line (TOXLINE).Accession No. 00623. 1985.

0. Cemial Iforatio Sytem CISt ToicoogyOn-line (TOXLINE). 195

13. Chemical Information System (CIS), Toio~y nln (TOXLINE). 195

15. Flrin I, L RtbugM. urall ad CR#Enzell.l 18. Screeningof obacoSmoe Cnsitunt fo MuaguictyUsing teAE'Test.

WA~D17.-84-C-4133 16-8


16. Chemical Information System (CIS), Toxicology On-line (TOXLINE).Accession No. 013912. 1985.

17. Chemical Information System (CIS), Oil and Hazardous MaterialsTechnical Assistance Data Systems (OHMTADS). Accession No. 240928.1985.

18. Verschueren, Karel. 1983. Handbook of Environmental Data on OrganicChemicals, 2nd ed., p. 423. Van Nostrand-Reinhold Company, New York,NY.

19. Chemical Information System (CIS), Aquatic Information Retrieval System

(AQUIRZ). 1985. Accession No. 202111.

20. AQUIRE, Accession No. 202112.

21. AQUIRE, Accession No. 224952.

422. American Conference of Governmental Hygienists (ACGIH). 1984.Documentation of Threshold Limit Values for Substances in Workroom Air,4th ed. American Conference of Governmental Hygienists, Cincinatti,OH.

23. Comprehensive Environmental Response, Compensation and Liability Act,secs. 102 and 103 (1980).

(i 24. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communication). 1985.

25. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980 ASCE Environmental EngineersDivision, New York. 440-575.

26. Aldrich Chemical Co. 1984-1985. Aldrich Catalog/Handbook of FineChemicals. Aldrich Chemical Co., Milwaukee, WS.

27. U.S. Army Environmental Hygiene Agency (AEHA). 1983. Waste DisposalInstructions. TG-126, HSHB-ES-H/WP. U.S. Army Environmental Hygiene

S, . Agency, Aberdeen Proving Ground, MD.

28. U.S. Army Toxic and Hazardous Materials Agency. 1980. InstallationAssessment of Holston Army Ammunition Plant. Report No. 148. U.S.4 Army Toxic and Hazardous Materials Agency, Aberdeen Proving Ground,MD&

DAMDI7-84-C-4133 . 16-9

DI-n-PROPYL ADIPATE



The Army's need for research on the toxicological and environmentalhazards of di-n-propyl adipate is reported in A Preliminary ProblemDefinition Study of 48 Munitions-Re.ated Chemicals. The repor t states thatthe compound has a low acute toxicity to mamials (g/kg), hut that it hasbeen shown to be teratogenic in rats receiving an acute doses Noinformation was found in the literature on the envirouetnaI fare of di-n-propyl adipate or on its toxicity to aquatic: life, to microorganisms or toplants.



Chemical Formula: C1 2H2 204 4

Molecular Weight: 230.34 (1)Structural Formula: CH3 CH2 CH2 OCO(CH2 )4 COOCH2 CH2 CH3

B. Alternate Names and Registry Nuonbers


CA Name (9CI): Hexanedioic acid, dipropyl eater

CA Name (SCI): Adipic acid, dipropyl ester

RTECS Number: AV1740000

Other significant synonyms: Dipropyl hexanedioate

,C. Chemical and Physical Properties

f Physical State: Liquid (1)

Color: Colorless (1)


Boiling Point: 143-50 at 10 mm Hg. (1)

il, DA11D17-84-C-4133 17-1

k•:•.•.•,

DI-n-PROPYL ADIPATE (cont.)

Freezing Point: -20.3 (1)

SolubilitiesWater: Insoluble (1)Noniaqueous Solvents: Soluble in athanol and ether (1)

Melting Point: Data riot available

Octanol Water Partition Coefficient: Log P -2.88 (estimated)

Hygrosaopicity: Data not available

Specific Gravity: 0.979 (1)


Vulat-ility: Data not nvailable



Heat of Combus Lion: Data not available


( Stability: Data not available

Flammability; Data not ava-:Zlabl~e

Ii. USES

A. Arm Unique Use

Plasticizer in rocket propellants (1)

Data not available

Ill. ANLYTICMaAL METHODSU


A gi~s chromatographic method of analysis has Ihen reported thet is inthe semi-micro range. The oven was temperature progranmed and a flazeiouization detector was used (2).

DAM(D17-84-C-4133 17-2

1~ _ _ _ _ _AD



Data not available

IV. HEALTH EFFECTS

No information updating that in the ARC report was located.


No information was found regarding the environmental fate or effectsof di-n-propyl adipate which would updatc the Atlantic ResearchCorporation document.


A. Health

Daza not available

B. Environmental

Reported in the EPA TSCA Inventory 1960.\I

Vil. DISPOSAL METUODS

A. Currtt Recommended A Disposa• Pýactices

Review if past Installation Assessment Reports indicate thaL currentwethods of disposal of waste explosives and propellants involve openburning, open detonation or hauling by a licensed co.rtractor and

landfilling. Current use of methods dlscussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAtA), which has the responsibility toreview current disposal practices and to develop plau for futuredisposal practices (3).

B. Alternate Disposal Practices undt-r Consideration b the Amy

V*uture plans ftr disposal of waste exploaives and propellants areprojected to f2uasi:e dui-bed incineration. Thi* aethod has beentested successfully by ARRADCOM and it planned for use at installationssuch ag Savanna Army Depot, Tooele Azy Depot, and Hawtheorn Naval

Am=unition Depot (4).C. Othet Disposal Practices Eaployed

Data uot available

DAM'I17-84-C-4133 17-3 Ii:.,• .. ?,,. :' .


. VIII. REFERENCES

1. Fedoroff, Basil T. and O.E. Sheffield. 1969. Encylopedia of

Explosives and Related Items. Vol. 5, p. D-1492. U.S. Army Armament

Research and Development Command, Dover, N.I

2. Alley, B.J. and H. W. H. Dykes. 1972. Gas-Liquid Chromatographic

Determinatnion of Nitrate Esters, Stabilizers, and Plasticizers in

Nitrocellulose-•-qe Propellants. Journal of Chromatography.71:23-37.

3. David Renard, U.S. Army Toxic and Hazardous Materials Agency, to

J. Carl Uhrmacher (personal communication). 1985.

4. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference on EnvironmentalEngineering. New York, July 8-10, 1980. ASCE EnvironmentalEngineers Division, New York. 440-575.

N.4

M nA1Dj7-84-C-4133 17-4

A.: - . .. . .. m.....

DIAZODINITROPHENOL


A. Structural and Chemical Formulas and Molecular Weiht

Chemical Formula: C6 F.2 N4 05

Molet-ular Weight: 210 (1)

Structural Formula: See Exhibit 18-1

B.1 Alternate Names and REgisr-'y Numbers (TSCA listing)


Deleted CAS Registry Numbers: 90030-95-8; 7008-81-3; 28655-69-8

CA Name (9CI): 2,4-Cyclohexadien-l-one, 6-diazo-2,4-; (7C1) dinitrc-

CA Name (8CI): Benzenediazonium, 2-hydroxy-3,5-dinitro-, hydroxide,inner salt


Other Significant Synonyms: DDNP

B.2 Alternate Names and Registry Numbers (RTECS listing)


CA Name (9C1): 1,2,3-Benzoxadiazole, 5,7-dinitro-

CA Name (t,'T): Same

RTECS Number- DM2600000

Other Significant Synonyms: DDNP

* C. Chemical and Physicel Properties

Physical State: Crystalline solid, needles (1)

Color: Yellow (1)


Melting Point: 157 C

DAMDI7-84-C-4133 18-1<7777..

DIAZODINITROPHENOL (cont.)

0 ~EXHIBIT 18-

N N=N +

0NN0 2 02N N02

CAS No. 87- 3 1-0 CAS No. 4682-03-5

CJ

tNý

DAD7-84-C-* 133

DIAZODIXITROPHENOL (cont.)

Solubilities:Water: 0.08% at 25%C (2)Nonaqueous Solvents: Soluble in nitroglycerin, nitrobenzene,aniline, pyridine, concentrated HCI and most organic solvents (1).Solubility at 500C in percentages (W:W) (1): Ethyl Acetate - 2.45%;Methanol - 1.25%; Ethanol - 2.43%; Ethylenedichloride - 0.79%; Carbontetrachloride - trace; Ch1orofor - 0.I1%' Benzene - 0.23%; Toluene -0.15%; Petroleum ether - insoluble (at 20 C); Ethyl ether - 0.08% (at30°C); Carbon disulfide - trace (at 300C).


Hygroscopicity: 0.04 at 90% relative humidity at 300C (1)


Volatility: Nonvolatile (1); unaffected; no weight loss at 500C 30months (2)



Heat of Combustion: 3243 cal/g (1); 2243 cal/g (2)

Reactivity; Destroyed by 0.5% sodium hydroxide (2). )Stability: Stable after wet storage for five months (2). Explodes when

shocked or heated to 180 C.

Flammability: Data not .available

II. USES

A. ArmyUniqgue Use

Percusson caps (1)

B. Other Uses

, ) Primary charge in blastiug caps.

""-

-, -,' q" • . ---

DIAZODINITROPHENOL (cont.)

II. ANALYTICAL METHODS

A- Best Acceptable MAethod

Bratin et al. (3) described 8 reductive/oxida;;ive electrochemicaldetection method with liquid chromatography that is sensitive and'$1 highly selective for explosive nitramine and nitrate compounds anddiphenylamines.


Picomole range (3)

VIV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF DIAZODINITROPHENOL


Diazodinitro- Unknown (4)phenol

2,4-Dinitro- Human oral. LDLO .36 mg/kg (4)j phenol L

Human dermal Yellow staining of skin; may (5)) cause primary irritation orallergic sensitivity

Human systemic Disruption of oxidative (5)phosphorylation causingincreased metabolism,oxygen consumption, andheat production; chronic

K.. exposure may result inkidney and liver damageand cataract formation

Rat oral LD5 0 30 mg/kg (4)

Rat intre- LI)5 1 20 mg/kg (4)peritoneal

Ra ubcu- LD50 25 mg/kg (4)taneous

Guinea dermal LD 700 g/kg (4)

Wild oral L 13 mg/kg (4)birds

DAMD17-'84-'C-4133 18-4

1!! _ _

DIJAZODINITROPHENOL (cont.)S~)

V. ENVIRONMNTAL EFFECTS

No information was found regarding the environmmental fate or effectsof diazodinitrophenol.


A. Health

Data not available

B. Environmental


VII. DISPOSAL

A. Current Recommended Army Disgsal Practices

Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or occasionally, hauling by a licensedcontractor and landfilling, Current use of methods discussed above hasalso be been confirmed by pri-vate communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices and to developplans for future disposal practices (6).

B, Alternate Rip2osal Practices under Consideraxtion the A

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRCOH and is plannud for use at installationssuch as Savanna Army Dtpot, Tooele Army Depot, aud H.avthorne Naval

J •Ammunition Depot (7).

C. Other D Practices Employed-

Data not available

D M 17-84-C-4133 18-5

DIAZQDINITROPHENOL (cont.)

VIII. REFERENCES

~ I. Army Materiel Command (AMC). 1971. Engineering Design Handbook:Properties of Explsives of Military Interest, p. 302-305. ArmyMateriel Command, Washington, P.C.

2. Fedoroff, Basil T., and G.E. Sheffield. 1964. Encyclopedia ofExplosives and Related Itms, Vol. 2, p. D-59. U.S. Army A-rmamentResearch and Development Command, Dover, NJ.

3. Bratin, K., P.T. Kissinger, R.C. Briner, and C.S. Bruntlett. 1981.Determination of Nitro Aromatic, Nitraine, and Nitrate Ester ExplosiveCompounds in Explosive Mixtures and Gunshot Re~sidue by LiquidChrcmatograptzy and Reductive Electrochemical Detection. AnalyticalChemistry. 130(2):295-311.

4. Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5thedl., p. 54.5. Van Nostrand-Reinhold Co., New York, NY.

5. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty' sIndustrial Hygiene and Toxicology, Vol. 2A, 3rd revised edition. JohnWiley and Sons, New York, NY.

6. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communication). 1985.U.S. Army Toxic andHazardous Materials Agency personnel, 1985.

7. Forsten, 1. 1980. Disposal of Uazardous Toxic Munition Wast~e.Proceedings of the 1980 National Conference of Environmental

& ~Engnearing. New York, July 8-10, 1980. ASCE Environmental Engineers

'7.1

AN NINON

DICHLORODIMETHYLHYDANTOI N



Chemical Formula: CH 6C12N20 2 (1)


Structural Formula:

C1b€I

k3e 1i

B. Alternate Names and i Numbers



CA Name (9CI): 2,4-Imidazolidinedione, 1,3-dichloro-5,5 dimethyl-)

CA Name (8CI): Hydantoin, 1,3-dichloro-5,5-dimethyl-

RTECS Number: MU0700000

Other Significant Synonyms: Dantoin, dichlorantin, N'N'-dichloro-5,5-dimethylhydantoin

C. Chemical and P~tyical Properties

Physical State: Crystalline, four-sided, pointed prisms (1)

Color: Data not available


L ~0..Melting Point: 132°C; sublimes at 100 C; turns browu and conilagrates

"at 212°C (I).

Solubilities:.Water: 0,21% at 25°C; 0.6% at 60°C (1)

J; Nonaqueous Solvents. Freely soluble in chlorinated and highly polarsolvents at 25 0 C: chloroform 14%, =ethylene chloride 30%, carbontetrachloride 12.52, ethylene dichloride 32%, sym-tetrachlorethane-.17%, benzene 9.2Z (1)#

Octmnol Water Partition Coefficient: Log P - 1.63 (estimated)

DAMD17-84-C-4133 19-1

DICHLORODIMETHYLHYDANTOIN (cont.)







Reactivity: On contact with water, especially hot water, hypochlorousacid is liberated; at pH 9, nitrogen chloride is formed (1).

Stability: Dry crystals can be stored without much loss of availablechlorine; after 14 weeks at 60°C, the chlorine loss was 1.5% (1).


•;II* USES

A. Army Unique Use


B. Other Uses

Chlorinating agent, disinfectant, industrial deodorant; in watertreatment; active ingredient of powder laundry bleaches; intermediatefor amino acids, drugs, insecticides; stabilizer for vinyl chloridepolymers and a polymerization catalyst (1).

r.

111. ANALYTICAL METHODS


No chemical means of detection was found in a search of Chemicalf-.i Abstracts dating back to 1967.


f 2Data not available

DANDI7-84-C-4133 19-2

DICHLORODIMETHYLHYDANTOIN (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF 1,3-DICHLORO-5,5-DIMETHYLHYDANTOIN


1,3-Dichloro- Animals local Caustic and corrosive to (2)5,5-dimethyl- the eyes, skin, and mucoushydantoin membranes; may produce

severe burns and irrevers-ible cellular damage inthe eye

Animals inhal- Irritating to lungs (2)ation

oral LD5 0 : 542 mg/kg (3)

Rabbit oral LD : 1,520 mg/kg; behav- (3)io al and pulmonary systemeffects

Guinea oral LD : 1,350 mg/kg; behav- (3)pig io al and pulmonary system

effects

Hypochlorous Human local Highly irritating to (4)acid skin, eyes, and mu-(available cous membraneschlorine) Human inges- Irritation and corrosion (5)

It tion of mucous membranes withpain and vomiting; a fallin blood pressure, delir-ium, and coma may occur

Human inhal- Coughing, choking, may (5)ation cause severe respiratory

tract irritation andpulmonary edema

DAMD17-84-C-4133 19-3

AM

DICHLORODIMETHYLHYDANTrOIN (cont.)

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF

I 3-DICHLORO'-5 ,5-DIMETfIYL-HYDANTOIN


Rat embryo cells 6,300 ng/plate Oncogenic transformation (3)


Log BCF - 1.01 Estimated

No other information was found regarding the environmental fate or

effects of dichiorodimethyihydantoin.


A. Health

3 3TLV: TWA 0.2 mg/rn STEL 0.4 mg/rn (3)

B. Environmental


VI. DISPOSAL


Disposal practices recomended on an interim basis by the U.So Navy intheir Consolidated Hazardous Item List for a "Mildew ResistantCompound," a related compound used for a related purpose, are to buryin a hazardous waste disposal site (6).

Be Alternate Disposal Practices Under Consideration the Arrnv

Data not available


The material is ignited in the presence of sodium carbonate and slakedlime (calcium hydroxide). The substance is mixed with vermiculiteand then with dry caustics, wrapped in paper and burned in a chemicalincinerator equipped with an afterburner and scrubber (7).

DAMD17-814-C-4133 19-4

DICHL0RODIMETHYLHYDANTOIN (cont.)

VIII. REFERENCES

2. Windholz, M., S. Budavari, R.F. Blumetti, E.S. Otterbein, eds. 1983.The Merck Index, 10th ed., p. 445. Merck and Co., Inc., Rahway, NJ.

2. Material Safety Data Sheet-Dichiorodimethyihydantoin. No. 40-572.Glyco Inc., Greenwich, CT.

3. Chemical Information Systems (CIS), Registry of Toxic Effects (RTECS).Accession No. MUO700000. 1985.

Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5thed., p. 560. Van Nostrand-Reinhold Co., New York, NY.

5. Reynolds, James E.F. and Anne B. Prasad, eds. 1982. Martindale-TheExtra Pharmacopoeia, 28th ad. The Pharmaceutical Press, London.


7. Aldrich Chemical Company. 1984-85. Aldrich Catalog/Handbook of FineChemicals, p. F16. Aldrich Chemical Company, Milwaukee, WS.

DAW?17-84-C-4133 -9-

DICHLOROPHENE

•, I. CHEMICAL AND PHYSICAL DATA


Chemical Formula: C H IOC1 0213 2


Structural Formula:

OH HO

/ CH2 /b/\c1 C1

B. Alternate Names and Registrv Numbers

(' CAS Registry Number: 97-23-4

CA Name (9CI): Phenol), 2,2'-meothylenebis [4-chloro-

CA Name (BCI): Same

RTECS Number: SMO?15000

.Other significant synonyms: I (Dihydroxydichloro)diphenyl]methane; 2,V'-dihydroxy-5,5t '-dichlorodiphenylmetzhane; 5,5'-dichloro-2,2'-dihydroxydiphenylmethane; bis[5-chloro-2-hydroxyphenyl ]methane; dij -chloro-2-hydroxyphenyllmethans


Physical State: Crystalline



Malting Point: 177-178°C (1)

DM.17-84-C4133 20-1

A•:": •!! - '

DICHLOROPHENE (cont.)

Solubilities:Water: Insoluble. Soluble in alkaline aqueous solutions withdecomposition (2).Nonaqueous Solvents: Soluble in methanol, isopropyl alcohol andpetroleum ether (2).











II. USES

A. Arm Unique Use

Malitary anti-mildew agent

B. Other Uses

Fungicide And i aatSericide; texture preaervative; Aome dermatologicaland cosmetic applications; veterinary zedicin-e; plant root growth

inhibt 2or0

•,AMDJI7-84-C:4133 20-2

DICHLOROPHENE (conE.)

~ III. ANALYTICAL M{ETHODS

jtA. Best Acceptable Method

High pressure liquid chromatography has been reported by Shah et al. (4)as a good method for quality control in veterinary products. A reverse-phase column was used with a variable wave-length detector set at 290nm. The mobile phase was methanol-water (75:25). This is not a methodfor trace analysis, but could be adapted for environmental samples.Thin-layer chromatography has also been reported for quality control inthe pharmaceutical industry.


Data noc available

[

Ut

N

SDAM. 7-84-C-4133 20-3


IV. HEALTH EFFECTS )

TABLE TV-I. TOXICITY OF DICHLOROPHENE


Human NS* NS Cramps, diarrhea (5)

Human de:mal 0.25% in a der- Caused allergic (6)matologic prep- dermatitis; con-aration (Unna t s firmed by patchBoot material) tests of dichloro-

phene in petrolatum

Human dermal 1% in yellow 22/4320 eczema pa- (3)petrolatum tients had weak(patch) positive sensitiza-

tion reactions; nopatients showedirritation reactions

Human dermal Induction: 20% 1/110 individuals (7)in petrolatum; showed signs of sen-challenge: 5% in sitization; 0/208 )petrolatum at 5% indvction con-(patch) centration

Rat oral 2,000 ppm in No toxicity (8)diet for 90 d

Rat oral 2,690 -.ng/kg LDs 0 (9)

Rat intra- 17 mg/kg LD (9)venous

house oral 1,000 mg/kg LD50 (9)

Guinea oral 1,250 mg/kg LD (9)pig

Guinea intradermal, Induction: 5% in Weak sensitizer (3)pig topical propylene glycol

intradermally +25% in yellowpetrolatum topic-ally; challenge:1% in yellowpetrolatum topic-ally (patch)

Not pecilied

DAMD17-84-C-4133 20-4


TABLE IV-1. TOXICITY OF DICHLOROPHENE (Cont.)


Guinea dermal 25% in yellow Not irritating (3)

pig petrolatum

Rabbit dermal 500 mg/24 hr Mild irritation (9)

Rabbit eye 50 ugi24 hr Severe irritation (9)

Dog oral 2,000 mg/kg LDSO (9)

Mammal NS* 1,000 mg/kg LDso (9)

*Not specified 50

TABLE IV-2. MUTAGENICITY OF DICHLOROPHENE


Salmonella 50 nmol/plate Mutagenic without Aroclor- (10)typhimurium induced rat liver S9(TA1535)

Drosphila 12.5 mM; oral No increase in frequency (I0)

Me.anogaster (approx. of sex-,liuked recessiveBasc test LDs 0 ) lethal mutations

Micronucleus 27, 54, or 81 No increase in frequency (10)test on mouse zg/kg x2; ip of micronucleibone marrow

DAMD7-8.4-C-4133 20-5


V. ENVIRONM1ENTAL EFFECTS


Al. Transport



AIc. Leachability -- Data not available

Ald. Bioaccumulation -- Log BCF: 3.36 (estimated)


A2a. Biodegradation -- After 3 weeks adaptation at 10 to 20 mg/L at 22°C:under aerobic conditions, 25% degradation when dichlorophene is solecarbon source, 50% degradation with synthetic sewage; under anaerobicconditions, no degradation, even with synthetic sewage (8).




4 A2e. Half-life - Data not available


B 81. Avian species - Dichlorophene added to the food of ducks daily for 5days at 0.5 g/kg body weight did not adversely affect the generalhealth or the serum protein levels (total and individual proteinfractions), even though the dose was the maximum therapautic doseused for treating helminthic infections in ducks (Ii).

B2. Mammalian wildlife species - Data uot available




86. Microorganisms, aquatic and soil -- The algicidal doses of"dichlorophene to four species of blue-green algae which are common inswimming pools, impoundments, wastewater effluents, and receivingwaters at pU 6.5 ranged from 4.0 to 9.0 ppm. The algicidal dosageincreased with increasing pH (12). )

DAD1i7-84-C-4133 20-6


B7. Aquatic species, fish and invertebrates -- Harlequin fish (Rasbora

heteromorpha) flow-through bioassay: 24-hour LC . 5.4 mg/L (sodiumsalt); 48-hour LCn: 4.8 mg/L (sodium salt); 962;.our LCs: 3.6 mg/L"(sodium salt) (8)?• 50


CI. Phytotoxicity - Dichlorcphene is used for inhibiting root grouwhtand preventing root twisting in containerized seedlings of pine andspruce (3).




A. Health

"Data not available

B. Environmental


VII. DISPOSAL

A. Current Recommended # Disposal Practices

Based on the disposal practices recommended by the U.S. Navy for asimilar compound, "mildew preventive," dichlorophene should be buriedin a hazardous waste disposal site (13).

B. Alternate Dpal Pract ices Under Consideration_ the Arm

Data not available


Dissolve or mix the material with a combustible solvent and burn in achemical incinerator equipped with an afterburner and scrubber (14).

VIII. REFERENCES

1. Chemical Information System (CIS), Information System on HazardousOrganics in Water (ISHOW). Accession No. 303266. 1985.

2. Windholt, H., S. BudavAri, R.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 3053. Merck and Co., Inc.

) Rahway, NJ.

DAM17-84-C,4133 20-7

A•'


3. Andersson, Barbro. 1982. Gas Chromatography-Mass SpectrometryAnalysis of Dichlorophene Used As A Growth Inhibitor in ContainerizedSeedlings of Pine and Spruce. Chemosphere. 11(4);357-361.

4. Shah, K.A., S.A. Samuels, M.K. Michaels, and J.W. Warren. 1984.Liquid Chromatographic Analysis of Dichlorophene and Its MajorImpurity. Journal of Pharmaceutical Sciences. 73(6):822-833.

5. Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5thed., p. 418. Van Nostrand-Reinhold Co., Cleveland, OH.

6. National Library of Medicine (NLM), Toxicology Information Online(TOXLINE). Accession No. 00944. 1985.

7. TOXLINE, Accession No. 0561810.


9. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substances, Vol. 1, p. 71. NationalInstitute for Occupational Safety and Health, Cincinatti, OH.

.10. Gocke, E. M.-T. King, K. Eckhardt and D. Wild. Mutagenicity ofCosmetics Ingredients Liscensed by the European Communities. MutationResearch. 90:91-109.

.11. TOXLINE, Accession No. 000790P.

12. TOXLINE, Accession No. 092242V.


14. Aldrich Chemical Company. Aldrich Catalog/Handbook of Fine Chemicals,p. 738. Aldrich Chemical Co., Milwaukee, WS.

,,lMD17-84-C-4133 20-8 ' -•.

1 '41 DIETHYLENE GLYCOL DINITRATE (DEGN)

Much of the available data on diethylene glycol dinitrate has been reported ina previous study by the Atlantic Research Corporation (ARC) entitled APreliminary Problem Definition S of 48 Munitions-Related Chemicals. Datareported herein reflects information more recent than that reported by ARC in1978.

I. CHE21ICAL AND PHYSICAL DATA


Chemical Formula: C4 H8 N2 07

Molecular Weight; 196.14

Structural Formula: 02NOCH CH OCH CH2ONO0N2 2 2 2 2



CA Name (9CI): Ethanol,2,2'-oxybis-dinitrate

CA Name (8CI): Diethylene glycol, dinitrate

RTECS Number: 1D6825000

Other Signficant Synonyms: DEGN, diglycol nitrate, dinitroglycol


Physical State; Liquid

Color: Yellow

Odor: Data not availableW•.

Melting Point: -11.3°C (1)

Boiling Point: 161°C, Decomposes (2)

Solubilities:Water: Slightly 0.40 g/lOOg (20°C) and 0.60 g/IOOg (60 0 C) (3).

Nonaqueous Solvents: Slightly soluble in alcohol and water solublein ether (3). Insoluble in ether alcohol, 2;1 ether:alcohol, acetone



"DADI 7-84-C-4133 21-1

A-.-

DIETHYLENE GLYCOL DINTITRATE (DEGN) (cont.)

Density (Crystal): 1.377 (4)


Vapor Pressure: 0.0036 mm Hg 20°C


Reactivity: Reacts vigorously with oxidizing or reducing material (5).

Heat of Combustion: 2792 cal/g (4)

Stability: Relatively stable at room temperature (6)

Flammability: Highly explosive when shocked or exposed to heat.Emits toxic fumes of NO when heated (5).

II. USES

A. Army Unique Use

Plasticizer in solid rocket propellants

B. Other Uses

Data not available



In addition to the methods previously reported in the AtlanticResearch Corporation Report, an HPLC/mass spectroscopy method forforensic and trace analysis is the most recent method for thiscompound. Yinon (I) described a custom-built mass spectrometerinterfaced with a high pressure liquid chromatograph that cansuccessfully analyze DEGN and other explosives.


Data not availablc

DDNI 7-84-C-4133 21-2

&I•'

DIETHYLENE GLYCOL DINITRATE (DEGN) (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF DIETHYLENE GLYCOL DINITRATE* (7)

Species Route Dose/Duration Effects

Human inhalation Above 5 mg/m3 Coronary occlusion in 4 workers who(workers in died suddenly (29-47 yr old, 5-7 yrDEGDN and exposure); 37 of 45 other workersnitrogly- reported precordial pain, headaches,cerin-pro- and rarely collapse conditions withducing plant loss of consciousness; signs of

coronary sclerosis in 3, symptoms ofintermediary coronary syndrome in 8,and I myocardial infarction; choles-terol blood level was at the upperborderline of normal (220 mg%) in mostand reached 300 mg% in some

Rat oral 777 mg/kg LD50

White rats oral 1,180 mg/kg LD 0; central nervous system damagein veget- and acute cyanosisable oil

( White rats oral 6x/wk for 6 mo: No effects(male) 0.05 mg/kg

0.5 mg/kg Minimum effective dose; changes inconditional reflex activity and immun-obiological response

5.0 mg/kg Decrease in blood pressure by 5th to6th month; change in the mitoticactivity of the bone marrow

50White mice oral 1,250 mg/kg LD ; central nervous system damage

in veget- and acute cyanosisable oil

50Guinea pig oral 1,250 mg/kg LD5; central nervous system damagein veget- and acute cyanosisable oil

*info;m-atiou not included in the ARC report

IDAMW17-84-C-4133 21-3

•'AMO


TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF DIETHYLENE GLYCOL DINITRATE


Escherichia coli 100 ug- Not active with or (8)W3110/polA', 10 mg without Aroclor 1254-p3478/polA induced rat liver S9DNA repair assay

Salmonella NS* Nonmutagenic with or (8)typhimurium without Aroclor 1254-TAIO0, TA1535, induced rat liver S9TA1537, TA1538

Saccaromyces NS Did not produce mitotic (8)cerevisiae recombination with or

without Aroclor 1254-induced rat liver S9

* Not specified


No information was found regarding the environmental fate or effects ofdiethylene glycol dinitrate which would update the Atlantic ResearchCorporation document.


A. Health

Data not available

1.B. Environmnental

"Reported in the EPA TSCA Inventory 1983.

VII. DISPOSAL


"Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburaing, open detonation, or hauling by a licensed contractor and

V.' AII.DI7-84-C-4133 21-4

*~? . ,,


landfilling. Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAMA) which has the responsibility to

'ILI. review current disposal practices and to develop plans for futuredisposal practices (9).

SB. Alternate Disposal Practices Under Consideration y the Army

Future plans of disposal of waste explosives and propellants areprojected to emphasize fluid bed incineration. This method has beentested successfully by ARRADCOM and is planned to be used atinstallations such as Savanna Army Depot, Tooele Army Depot, andHawthorne Naval Amunition Depot (10).


Data not available

VIII. REFERENCES

1. Yinon., J. 1983. Analysis of Explosives by LC/MS. Proceedings of theI, International Symposium on the Analysis and Detection ofExplosives. Washington, D.C. Federal Bureau of Investigation,Washington, D.C. 2277-234.

2. Army Materiel Command (AMC). 1971. Engineerin Design Handbook,pp. 103-106. AD A706177. Army Materiel Command, Washington, D.C.

3. Hawley, Gessner G. 1981. The Condensed Chemical Dictionary, 10th ed.,p. 346. Van Nostrand-Reinhold Co., New York, NY.

4. Kitchens, J.F., W.E. Harwards III, D,*. Lauter, R.S. Wentsel, R.S.Valentine. 1978. Preliminary Problem Definition Study of 48 MunitionsRelated Chemicdals, Vol. II, Propellant Related Chemicals-DiethyleneGlycol Dinitrate. Final Report, AD A066308. Atlantic ResearchCorporation, Alexandria, VA. DAMDI7-77-C-7057.

5. Fedoroff, Basil To and Oliver E. Sheffield. Encylopedia of Explosivesand Related Itmes, Vol. 5, PATR 2700. US. Army Armament Research andDevelopment Command, Dover, NJ.

6. Sax, N.I. 1979, Dangerous Properties of Industrial Materials, 5thed., p. 576. Van Nostrand-Reinhold Co., New York, NY.

7. Holleman, J.W* Problem Definition Study on the Health Effects ofDiethylene Glycol Dinitrate, Trietylene Glycol Dinitrate, andTrimethylolethane Trinitrate and Their Respective Combustion Products.ORNL/EIS-202, Order No. DE-83011068. Oak Ridge National Laboratories,Oak Ridge, TN.

- DAhD17-84-C-4133 21-5


8. McGregor, Douglas B., Colin G. Riach, Rowan M. Hastell, and Jack C.Dacre. 1980. Genotoxic Activity in Microorganisms of Tetryl, 1,3,-Dinitrobenzene and 1,3,5-Trinitrobenzen. Environmental Mutagenesis.2:531-541.


10. Forsten, 1. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575.

IDAMD7-84-C-4133 21..6

A--.

DIETHYLENE TRIAMINE



Chemical Formula: C4 H N3


Structural Formula: H2 NCH2 C 2NHCH 2CH2N2


CAS Registry Number: 111-40-0 (current)

Deleted CAS Registry Numbers: 59135-90-9, 54018-92-7, 26915-78-653303-76-7, 8076-55-9

CA Name (9CI): 1,2-Ethanediamine, N-(2-aminoethyl)-

f CA Name (8CI): Diethylenetriamine

RTECS Number: IE1225000

Other Significant Synonyms: 3-azapentane-1,5-diamine, bis[.beta*-amino-ethylJamine, 2,2'-diaminodiethylamine, bis(2-eminoethyl)amineN,N-bis(2-aminoethyl)amine, 1 ,4,7-triazaheptane, 1 ,5-diamino-3-azapentane

C. Chemical and Phvsical Properties

Physical State: Liquid (1)

Color: Yellow (1)

Odor: Ammoniacal (2)

"Melting Point: -39 C (I)

Boilinsg Point: 208 0 C (I)

Solubilities:.:. ~Water: Miscible (I).,

•Nonaqueous Solvents: Hiscible, with alcohol; insoluble in ether;soluble in ligroin (1).

Octanol Water Partition Coefficient: Log P = -1.27 (estizated)

DAMXI17-84-C-4133 22-1

i , "4V

A .

DIETHYLENE TRIAMNINE (cont.)

Hygroscopicity: Hygroscopic (1)


Volatility: Data not: available

Vapor Pressure: 0.2 Torr at 200C; 0.75 Torr at 200C (3)



Reactivity: Corrosive

Stability: Stable (4)

Flammability: Slight; combustion requires preheating (4); flash point-101 0C (2).

II. USES

A* Army Uaique Use

A component of DS2, a decontam-Iniant for cthemical agrnts (5).

B. Other Uses

Reactive hardener in epoxy formulatious (6). Solve•nt fr sulfur, acidgases, resins, dyes, fuel component.

III. ANALYTICAL •tTHODS

A. Beat Acceptable Method

Ng (6) recently reported a g•o ctromatographic/mass spectroscopic methodfor the detection of the ,er-butyldimethyls±1yl deriviative.

B. LImi• t of Detection

16a not availabl.e

In -AMDI47-8-C-4133 22-2

DIETHYLENE TRITALINE (cont.)

" IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF DIETHYLENETRIAMINE fDETA)


Human inhalation NS* Moderate, temporary ii-itation (7)

long May cause asthma (7)exposure

Human skin short Smarting and first- (7)exposure degree burns

long May cause secondary (7)exposure burns

Human skin NS* Can produce rash and (7,8)sensi tization

Human skin 10 and Allergic contact derma- (9)(2 workers) almost 20 yr titis from DETA in a

detergent

Human eye NS* Produces burns (7)

Human N SS* 'There are existing data (10)which indicate a theor-etical potential for theconversion of DETA tonitrosamines in the envi-ronment and chat personsmay be exposed to thesenitrosamines as a resultof release of DETA to

the environment. Nitros-iamine have been shown tob- corcinogenic."

oral 1,080 mg/kg LD; convulsious (II)

Rat intra- 74 mg/kg LD ; convulsions, peri- (11)peritoneal tou0tir

Rat inhalation Concentrated No efect (8)vapor and

300 pNp-

*Not specif ied

,D 17-84-C-1-3 3.-'

DIETHYLENE TRIA.MINE (cont.)

TABLE IV-1o TOXICITY OF DiETHYLENETRItlINE (Cont.)


Mouse intra- 71 mg/kg LD50; convulsions, peri- (1)peritoneal tonlitis

Guinea pig skin 162 mg/kg LDs 0 (l1)

Rabbit skin 10 mg/24 hr Severe irritation (11)

Rabbit skin 500 mg Moderate irritation (11)(open)

Rabbit skin 1,090 mg/kg LD (11)

Rabbit eye 750 ug Severe irritation (11)

* Not specified

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF DIETHYLENETRIAMINE

Test System Effects Reference

Salmonella typhimurium Nonmutagenic with ur without (12)Aroclor 1254-induced rat orSyrian hamster liver S9

Salmonella tvphimurium Slight mutagenic activity (13)TA100

Salmonella typhimurium Mutagenic without metabolic (14)TAI00, TA1535 activation; may be due to

impurity

DAtDI 7-84-C-4133 22-4

DIETHYLENE TRIAMINE (cont.)

V. E NVIRONMENTAL EFFECTS


Al. Transport


AMb. Volatilization -- Data not available


Aid. Bioaccumulation -- Data not available

A..a-. Biodegradation -- Bio-oxidation in fresh water in 15 days: 4% with non-acclimated microbial cultures, up to 70% at 20 days with acclimatedmicrobial cultures (15).


A2c. Photolysis -- Data not available

A2d. Other chemical reaction -- ThOD: 1.55 (15)



BI. A ian species -- Data not available






B7. Aquatic species, fish and invertebrates -- Brine shrimp TL 710 mg/Lat 24 hours (15)


Cl. Phytotoxicity -- Data not available


C3. MetaLalism -- Data not available

DAMDI7-84-C-4133 22-5



A. Health

TLV: TWA(skin): 4 mg/m3 or I ppm (16).

B. Environmental

Data not available

VII. DISPOSAL


Disposal practices recommended by the U.S. Navy in their ConsolidatedHazardous Item List for "Decontaminating Agent," a related mixture usedfor a related decontamination, are to bury in a sanitary landfill (17).

B. Alternate Disposal Practices Under Consideration bb the Army

Data not available


Emits highly toxic vapors when burned. Solution can be sprayed into anincinerator with afterburner and scrubber (16).

VIII. REFERENCES

1. Weast, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed.,p. C-289. The Chemical Rubber Company, Cleveland, OH.


3. Chemical Information System (CIS), Environmental Fate (Envirofate).Accession No. 248041. 1985.


5. Toro, A.L. 1984. Hazardous Component Safety Data Statement-Decontaminatng Agent, DS2--No. 20059. Aberdeen Proving Ground, Md.

6. Ng, L.K. 1984. Separation and Analysis of Ethylenediamines As TheirTert-Butyldimethylsilyl Derivatives by Gas-Liquid Chromatography and (Mass Spectrometry. Journal of Chromatography. 314:455-461.

DAMDI7-84-C-4133 22-6


7. U.S. Coast Guard. 1978. Chemical Hazardous Response Information System(CHRIS) Hazardous Chemical Data-Training Edition-Diethylene Triamine.Abridged, CG-446-2. U.S. Department of Transporation, Washington, D.C.

8. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial Hygiene and Toxicology, Vol. 2B, 3rd revised edition. JohnWiley and Sons, New York, NY.

9. Meding, B. 1982. Allergic Contact Dermatitis from Diethylenetriaminein a Goldsmith Workshop. Contact Dermatitis. 8(2):142.

10. Federal Register, Vol. 47, pp. 18386-18391.

11. Chemical Information System (CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. 1EIZ25000.

12. National Toxicology Program (NTP). 1982. Mutagenesis Testing Results.NTP Tech. Bull. 7:5-9.

13. Hulla, J.E., S.J. Rogers, and G.R. Warren. 1981. Mutagenicity of aSeries of Polyamines. Environmental Mutagenesis. 3:332-333.

14. Hedenstedt, A. 1978. Mutagenicity Screening of Industrial Chemicals:Seven Aliphatic Amines and One Amide Tested in the Salmonella/MicrsomalAssay. Mutat. Res. 53:198-199.

15. Price, Kenneth S., Gene T. Waggy, and Richard A. Conway. 1974. BrineShrimp Bioassay and Seawater BOD of Petrochemicals. Journal of WaterPollution Control Federation. 46(1):63-77.



DAMDI7-84-C-4133 22-7

)

DINITROPHENYL AZIDE



Chemical Formula: C6 H 3N04

Molecular Weight: Data not available

Structural Formula:

Nit

N

N

/N\



CA Name (9CI): Benzene, 1-azido-2,4-dinitro-

CA Name (8CI): Same

RTECS Number: CY6610000

*Under Benzene, I-azido-2,4-dinitro- on the ICIS System the followinginformation was obtained:


CA Name (9CI): Hydroxylamine, 0-(2,4-dinitrophenyl)-

DAMD17-84-C-4133 23-1

DINITROPHENYL AZIDE (cont.)

CA Name (8C1): Same as above.

RTECS Number: CY6610000 ¼

Other Significant Synonyms: Benzene, 1-azido-2,4-dinitro,

Dinitrophenylazide, DNPA

The structure displayed in the CIS System is not an azide; the

structure displayed in CAS under that Registry Number is not the same,but it is also not an azide. For sake of completeness, this RegistryNumber should be included in further search schemes with the caveatthat the search results will have to be screened for the correctcompound.


Physical State: Data not available




Solubilities:Water: Data not availableNonaqueous Solvents: Data not available

Octanol Water Partition Coefficient: Log P - 3.22 (1), 3.50 (2), 3.59

(3), 3.72 (2)









A' Flammability: Data not available

W.\

DAMDI7-84-C-4133 23-2

DINITROPRENYL AZIDE (cont.)

II. USES

A. .__my Unique Use

Initiator for explosives.

B. Other Uses

Data not available



No methods of analysis were found in Chemical Abstracts, searching backto 1967.


Data not available

I

DAMD1 7-84-C-4133 23-3

DINITROPHENYL AZIDE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF DINITROPHENYL AZIDE


Dinitrophenyl No toxicity data locatedazide other than mutagenicity

(see following table)

2,4-Dinitro- NS* NS Irritating to skin and (4)aniline mucous membranes; highly

toxic if absorbed

Rat oral LD5 0 : 418 mg/kg (5)

Rat intra- LDLo: 250 mg/kg (5)peri-toneal

Rabbi: eye Severe irritation (5)

Dinitrobenzene NS NS Anoxia due to methemoglo- (6)(all isomers) bin formation; respira-

tory tract irritation andanemia in prolonged exposure

* Not specified

DAMDI7-84-C-4133 23-4

7

DINITROPHEN'YL AZIDE (cont.)

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF DINITROPHENYL AZIDE*


Salmonella 5-20 ug/plate Mutagenic without liver (7)typhimuri um microsomes(TA98, TA100,TA1535, TA1537,TA1538)

Escherichia 1-400 ug/plate Nonmutagenic (7)coli (WP2s)

S* 2,4-Dinitrophenyl azide


No information was found regarding the environmental fate or effects ofdinitrophenyl azide.


A. Health

Data not available

B. Environmental

Data not available



Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USAThANA), which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (8).

DAMD17-84-C-4133 23-5

DIPHENYLAMINE

Much of the available data on diphenylamine has been reported in a previousstudy by the Atlantic Research Corporation (ARC) entitled, A PreliminaryProblem Definition Study of 48 Munitions-Related Chemicals. Data reportedherein reflects information more recent than that reported by ARC in 1978.



Chemical Formula: (C6Ht5 ) 2 NH


Structural formula:

H



CA Name (9CI): benzenamine, N-pheny!

CA Name (8CI): Diphenylamine

RTECS Number: JJ 7800000

Other Signficant Synonyms: Aniline, N-phenyl; N,N-diphenylamine; N-phenylaniline; N-phenylbenzenamine.


Physical State: crystals

Color: colorless

Odor: floral (1)

Melting Point: 52.85°C

DAMDI7-84-C-4133 24-1

-----------------------------------------

DIPHENYLAMINE (cont.)

Boiling Point: 302 0 C at 760 mmHg (2)

Solubilities:Water: Slightly soluble-0.03 g/100 g at 20C (3)Nonaqueous Solvents: Soluble in alcohol 44 g/100 g, very soluble inether. Methyl alcohol 57.5 g/100 g (3). Acetone-very soluble.Very soluble in carbon disulfide (4), glacial acetic acid.

Octanol Water Partition Coefficient: Log P w 3.5




Vapor Pressure: Imm Hg at 108.3%C (4)

Flash Point: 1530C (5)



Reactivity: inflammable



Vapor Density: 5.82 g/M3

Autoignitiou temp: 619.67 0C (4).

II. USES

A. ArmvUniue Use

Used as an explosive and a stabilizing comipound for propellants andexplosives.

B. Other Uses

Manual dyes; stabilizing nitrocellulose explosives and celluloid. Inanalytical chemistry for the d..tection of NO3 , CI'" and otheroxidizing substances with which, in the presence of H SO , it gives adeep-blue color. In veterinary medicine, it is used iopically inanti-screwworm mixtures and in tests for nitrate and nitrite poisoning.

DAM17-84-C-4133 24-2

DIPHENYLAKINL (cont.)



High pressure liquid chromatography has become the method of choice

for this stabilizer for quality control of propellants. Bender (6)

reported a qualitative and quantitative determination using UV

(ultraviolet) or TEA (thermal energy analyzer) detectors. Barth and

Zierath (7) reported HPLC, TLC, (thin-layer chromatography) and HP-TLC

methods for anaiysis in double-based powers. For determining

diphenylamine in waste water, Svechnikova (8) reported a chloroform

extraction followed by gas chromatography for the analysis of

effluents from antioxidant manufacturing. The applicability of this

method to propellant manufacturing effluent cannot be extrapolated.


Data not available

DAMD17-84-C-4 3 3 24-3

DIPHENYLAL4INE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF DIPHENYLAMINEa


Human oral, NS* Headache; fatigue; (9)dermal, cyan-osis; fastinh pulse; hypertension;

bladder injury;chemical asphyxiafrom methemoglobin-emia

Human inh or NS Eye and mucous (9)contact. membrane irritationwith dust

Human dermal. 1% in petrolatum No sensitization or (10)(patch) irritation reactions

Rat oral 1.2-3.2 g/kg LD5 o (10)

Rat oral 1.6 g/kg Decreased hemoglobin (10)and oxyhemoglobin

levels; increasedmethemoglobin andHeinz-body formation

Rat oral 2.5.% in feed for Renal cystic disease (10)3-6 wk to 0.1% infeed for 2 yr

Rat oral 7,500 mg/kg given TD for (10)during gestation deelopmentaldays 17- abnormalities

Rat oral 3,000 mg/kg LDLo (11)

Guinea oral 300 mg/kg LD0 (11)pig

Rabbit dermal full strength Not irritating (10)(intact or for 24 hr

abraded (patch)

skin)

DAW17-8a4-C-4133 24-4

DIPHEN-LAMINE (cont.)

TABLE IV-I TOXICITY OF DIPHENYLAMINE (Cont.)


Dog oral 1% in feed for Severe growth inhi- (10)2 yr (99.9% pure) bition, low hemoglo-

bin levels and redcell counts, crenatedred cells, increasein red cell fragil-

ity, fatty livers,ihemosiderosis of thespleen, kidney, andbone marrow

Cat oral I mmol/kg in Methemoglobin (ION

aqueous suspen- formationtion

a. Not included in ARC Report* Not specified

DAM)I7-84-C-4133 24-5

I,

"DIPHENYLAMINE (cont.)

TABLE IV-2 MUTAGENICITY AND RELATED EFFECTS OF DIPHENYLA INE


Escherichia coli 100 ug-Not active with or (12)W3110/polA, 10 mg without Aroclor 1254-p3478/polA , induced rat liver S9DNA repair assay

Salmone.lla NS* Nonmutagenic with or (12)yhizurium without Aroclor 1254-

TAI00, TA1535 irduced rat liver S9TA1537, TA1538

S. typhimurium 10,000- Nonmutagenic with or (12)"•T1 strains), fold conc. without Aroclor 1254-E. coli rauge induced rat liver S9•2 strains)

Saccharozyces NS Did not produce mitotic (12)cerevisiae recombination with orD5 without Aroclor 1254-

induced rat liver S9

"Priziary rat up to Did not induce un- (13)hepatocyte I zmol/mL scheduled DNA synthesisculturea

Rat kidney 2.5-20 Dij not signifieantly (14)cells infected ug/mL increase the frequencywith rutine of viral transformationsarcoma virus with or without Aroclor-

induced rat liver S9

: I V, ENVIROENTIAL EFFECTS

A* Environmental Pate


A!a. Adsorption - Data no: available

MAb. Volatilization - DatL 4ot available

DAkWI7-&4-C-4133 24-6


AIc. Leachability -- Diphenylamine's relatively low solubility in water (18mg/L at 10 C) and moderately high octanol/water partition coefficientindicate a relatively high tendency to associate with sediments inthe hydrosphere and to migrate slowly in soils containing organicmatter (15).

Ald. Bioaccumulation -- Bioconcentration factor (BCF) - 30, determined with

the fathead minnow (Pimephales promelas) in 32-day exposure (16).A2. Transformation - Data not av•ilable

A2a. Biodegradation -- Diphenylamine undergoes progressive oxidativemetabolism by sewage sludge organisms. Some of the metabolites (4-.bydroxy-diphenylamine, ýndole and aniline) are more acutely toxicthan the parent compound, buc these metaboliteu are not persistent inthe sludge mixed liquor after they are formed. After f houraincubation (common digestion period in sewage treatment plants) themicrobial degcadalion of diphenylamine vas incomplete, with more than35% undegraded (17).


A1c. Photolysis -- Photochemical reactions may be possible sincek ,diphenylamine does absorb light around 285 nm (15).

A;d. Other chemical reaction - COD: 90% of ThJD (0.05 U r0 7 )ThOD: 2.39 (18). When used as r propeannc stabilIzer, diphenylamineundergoes oxidation with autrous a-.lo to form diphenyl-N-nitrosamine.Subsequent reactions with rd.trogen oxides in the propellants can takeplace (if mineral acids are present) with the eventual formation of2,4,4'-trinitrodiphenylamine (15).

A2 e. Half-life -- Data not availableBo Effects on Animals

BI. Avian species - Data nor available

B2. Maamalien wildlife species -- Data not available




SDA•JDI/-8•-C-4133 24-7

DIPHENrYLAMINE (coat. )

B6. Microorganisms, aquatic and soil -- Impact on biodegradation processes:At 100 mg/L, no inhibition of NH3 oxidation by Nitrosomonas sp. (18).In 7-day test at 25oC, 5 mg/L resulted in death of algae(unspecified) cultures (15). The median growth-inhibiting dose(IDn) of diphenylamine to the ciliate Tetrahymena pyriformis was 25ug/t (10). Diphenylamine was found to be inactive in bacterial DNArepair and reversion tests and yeast mitotic recombination assaysmade to assess the qualitatve nature of the compound's genotoxicpotential (12). Numerous studies have been conducted on the effectof diphenylamine on various biochemical reactions in microorganisms.Particular attention has been paid to the stimulation or inhibitionof carotenoid (pigment) synthesis and the resulting alteredphotosensitivity of the organisms. Inhibition of growth_ as beennoted for some organisms with concentrations of about 10 M. Severalinvestigators have observed that diphenylamine is taken up in theplasma membrane and that certain adverse effects on the membrane

result (15). Diphenylamine is applied to the surface of apples andpears to be kept in long cold storage to control the microoganismsassociated with scald and rot (15).

B7. Aquatic species, fish ang invertebrates - Bluegill sunfish: 96-hourLC - '.18 mgfL at 21 C. (Cyclocypris 2p.): 48-hour LC50 2.53mg?2 at 21 C (15). -

C. Effects on Plants

C1. Phytotoxicity -- Diphenylamine has been shown to affect the foliarmorphogenesis, germination, rhizogenesis, heteroblastic developmentand senescence in the tomato (Lcopersicon esculentam Kill) (15).

C2. Uptake - Data not available

C3. Metabolism -- Diphenylamine has been shown to be an effective inhibitorof overall carotene synthesis in a soluble tomato plastid enzymesystem; and in pumpkin cotyledons, the compound also reduced caroteneaccumulation (15).

VI. STANDARDS AND REGUIATIONS

A. Health

tTIN: TWA 10 i/STEL 20 mg/to (11)

The Food and Drug Administration (21 CFR 175 and 176) has placedrestrictions on the use of diphenylazine in food packaging materials (15).

DAMDI7-84-C-4133 24-8


B. Environmental

Reported in EPA TSCA Inventory, 1980.

The EPA has established (40CFR 180.190) tolerances for the residues ofthe fungicide diphenylamine as follows:

10 ppm in or on apples from preharvest or postharvest use,including use of impregnated wraps, for scald control;

Zero (0) in milk and meat (apple processing residues - cores,skins, etc* - are sometimes used as a feed supplement for cows) (15).

qA

t 2 -.

iV

:U'' IAMDI~7-844-C-.413 3 24-9 ••

i . .. ... ,

DIPEh•.YLAMINE (cont.)



Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or hauling by a licensed contractor andlandfilling, Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAMA) which has the responsibilityto review current disposal practices and to develop plans for futuredisposal practices (18).

B. Alternate Disposal Practices under Consideration by the A

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Aamy Depot, and Hawthorne NavalAmmunition Depot (19).

C. Other Disposal Methods Employed

Disposal Method Suggested: Burn in admixture with flammable solventin furnace equipped with afterburner and scrubber (20).

t SAFETY AND CONTROL MEASURES. Disposal personnel handling theseitems shall wear safety glasses, impervious gloves, and a protectivelaboratory coat. A NIOSH respirator approved for this item should be

available.

VIII. REFERENCES

1. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 3333. Merck and Co., Inc.,Rahway, NJ.

2. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial gyien! and T, Vol. 2A, 3rd revised editionp. 3333. John Wiley and Sons, New York, NY.

3. Sax, N.I. 1979. Aagrous Properties of Industrial Materials, 5th.-- ed., p. 622. Van Nostrand-Reinhold Co., New York, KY.

r 4. International Agency for Research on Cancer (IARC). 1974. IAR,Honographs on the Evaluatin of Carcinogenic Risk of Cheuicals to H.n, (<'7)4t Some Aroiattic Awines, Hudratine 4nd Related Substanes,4 N-titroso

¼ Compounds and Miacell.neous ,glatinAgeUts, p. 127. Lyon, France.

DAMDI7-84-C-4133 24-10

. .' . . .-. ., . '!.-.e . •

DIPHENYLAXINE (coat.)

5. Bender, E.C. 1983. Analysis of Smokeless Using UV/TEA Detection.Proceedings of the International Symposium on the Analysis andDetection of Explosives. Washington, D.C., 1983. Federal Bureau ofInvestigation, Washington, D.C.

6. Barth, P., J.Zierath. 1980. Possible Application of High-PressureLiquid Chormatography (HPLC) in Qualitative and Quantitative Analysisof Explosives. Int.-Jahrstag-Fraunhofer-Inst. Treib-Explosivst. p.665-686.

7. Svechnikova, E.N. 1982. Quantitative Analysis of Diphenylamine, 4-Aminodiphenylamine and Diaphene FP in Wastewater from the Production ofAntioxicants. Document SPSTL 921 khp-D82.

8. U.S. Coast Guard. 1978. Chemical Hazardous Response InformationSystem (CHRIS) Hazardous Chemical Dat-Trainng ition-Diphenylamine.Abridged, CG-446-2. U.S. Department of Transportaion, Washington, D.C.

9. Opdyke, D.L. 1978. Monographs on Fragrance Raw Materials. FoodCosmet, Toxicol. 16(0):723-727.

10. Chemical Information System (CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. JJ7800000.

11. McGregor, Douglas B., Colin G. Riach, Rowan M. Hastwell, and JackC.Dacre. 1980. Genotoxic Activity in Microorganisms of Tetryl, 1,3-

SDinitrobenzine and 1,3,5-Trinitrobeuzene. Environmental Mu nesis.2:531-541.

12. Probst, G.S., R.E. McMahon, L.E. Hill, C.Z. Thompson, J.K. Epp, andSB. Neal. 1981. Chemically Induced Unscheduled DNA Synthesis inPrimary Rat Repatocyte Cultures: Comparison with Bacterial MutagenicityUsing 218 Compounds. Environmental Mutsgenesis. 3:11-32.

S13. Wilson, W.W., and N. Khoobyarian. 19512. Potential Identification ofChemical Carcinogens in a Viral Tran..-?-. ,icv Syatem. Cm-,-BiolInteract. 38(2): 253-259.

14. Berkowitz, Joan B., Dr,, Muriel H. Goyea, Dr. Judith C. Harris, Dr.Warren J. Lyvman, and Leslis H. Welken. Literature Review-ProblemDefinition Studies on Selected Chemicals. Voiume III-Chemistry,Toxicology, and Potential Environmental Effects of Selected OrganicPollutants. Final Report, AD B059480. Arthur C. Little, Inc.,Cambridge, MS.

15. Gardner, Albert H., George H. Alvarez, and Yuok Ku. 1982. MicrobialDegradation of C-Diphenylazinein a Laboratory Model SewageSludge Sy•tem. Bull# Environ. Contam. Toxicol. 28:91-96.

D•MD17-84-C-4133 24-11


16. Veith, Gilman D., David L. DeFoe, and Barbara V. Bergstedt. 1979.Measuring and Estimating the Bioconcentration Factor of Chemicals inFish. J. Fish. Res. Board. Can. 36:1040-1048.



19. Forsten, I. 1980. Disposal of Hazardous Toxic Munition WastesProceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575.

20. Sittig, Marshall. 1981. Handbook of Toxic and Hazardous Chemicals,p. 282. Noyes Publication, Park Ridge, NJ.

DAMD17-84-C-4133 24-12 ,

ETHYL CENTEALITE

Much of the available data on ethyl centralite has been reported in a previousstudy by the Atlantic Research Corporation (ARC) entitled, A PreliminaryProblem Definition Study of 48 Munitions-Related Chemicals. Data reportedherein reflects information more recent than that reported by ARC in 1978.



Chemical Formula: C1 7 H9 ON2 0


Structural Formula:

--C2" • C2HsH.C2

B. Alterncte Names and Registry Numbers


CA Name (9CI): Urea, NN'-diethyl-NN'-diphen.yl

CA Name (SCl): Carbanilide, N,N'-diethyl

RTECS Number: Fr0350000

Other Slgnficant Synonyms: Bis(N-ethyl-N1-pheny1)urea; carbamite;

centralite; centralite-1; sym-diethyldiphenylurea; centralite;urea, 1,3-diethyl-!,3-diphenyl.


Physical State: Crystalline solid (1)

Color: White (1)

Odor: Peppery (1)

melting Point: 79°C (1)

SDA 7-84'-C"• 133 25-1

........

ETHYL CENTR.ALITE (cont.)

Boiling Point: 325-3300 C (1)

Solubilities:Water: InsolubleNonaqueous Solvents: Soluble in organic solvents.

Octanol Water Partition Coefficient: Log P - 5.02 (2)


Density (Crystal): 1.12 g/cc at 200 C (3)



Flash Point: 150 0C


Heat of Combustion: 8409.3 cal/g (4)


:hability: S,.vare expiosion hazard when shocked or heated (1)


II. USES

:iA, Arr±v Unicue Use

SStabilize- for nitrocellulose-based smokeless powder in roket•e

propellanis (3).

B. Other Uses

Proposed retarder Aor preventing aging of vulcanized rubber (5).

MII. ANALYTICAL ,ETHODS


Little work has been done on the quantitative analysis of ethylcentralite at trace levels, Most methods have ueen developed for[ •quality control and stability analysis of propellants. In addition tothe methods described in the Atlantic Research Corporation report,

21here is a ga-liquid chromatography method by Alley and Dykes (6)reported in 1972 that successfully separated and identified the

""component of double-based propellants including ethyl cen-ralite.

DA)I 7-8&-C-4133 25-2 ,

ETHYL CENTRALITE (cont.)

Alley and Dykes used a flame ionization detector and a silicone-basedstationary phase.

Additionally, a high-pressure liquid chromatographic method wasdeveloped to study the stability of double-base powders. Ethyl

centralite, along with 29 other components and derivatives, wasdetected under isocratic conditions within 35 minutes, or 50 minutesrunning a gradient (7). This method could possibly be adapted fortrace analysis of environmental and other samples.


Data not available

IV. HEALTH EFFECTS

TABLE IV-1. MUTAGENICITY AND RELATED EFFLCTS OF ETHYL CENTRALITE*


E. Coli 100 ug- Not-active with or (8)W31-/polA, 10 mg without Aroclor 1254-

( p3478/po!A induced rat live-. S9

S, jyp2hiurium NS** Noumutagenic with or (8)-- I.535T without Aroclor 1254-TA1537, TA1538 induced rat liver $9

S. cerevisiae KS Did not prodaee mitotic (8)D5 recombination with or

without Aroclor 1254-induced rat liver S9

I nforwation not included in the ARC report"N** ot specified

V. ENVIRIE LNMAL EFFECTS

No inforuation was found on the enviroameuta. fate or effects of hthylcentralite vhich would update the Atlantic Researcb Corporation

dotumontp

DAJMDI7-84-C-4133 25-3

-'1



A. Health

Toxic (1)

B. Environmental


V:I. DISPOSAL tTHODS

A. Current Recommended Armv Disposal Practices

Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or occasionally, hauling by a licensedcontractor and landfilling. Current use of methods discussed above hasalso be been confirmed by private communications from the "US. A=myToxic and Hatardous Materials Agency (USAThAMA), which has theresponsibility to review current disposal practices and to developplans for future disposal practices (9).

B. Alternate Dssal 1Practices under Cons iderat; of the

Future plans for disposal of waste explosives and propel lints ar•e )projected to emphasize fluid-bed incinerat~on. This method has beentested successfully by ARRADCOM and is planned for vie at installationssuch as Savanna Arzy Depot, Tooele Army Depot, .a&d Haw,.horne NavalA~munition Depot (10).

C*..Other P.r-osal Practicer. Empiged

Data not available

1. Hawley, Gesoner G. 1961, Tbe Condensed Chemical Dtionary,- lothed.-, p. 3,i5. Van Kostrand-Zeinho.d Co.. go , ;Y.

2. Chemical Infortation Systems (CIS), Information Systim 1or Ua-ardousOrg•oica in Water (lSi0O). Accession No. 302096. 1985.

3. Uitchena, J.., W.E. Harv~rds 1II, -.H. Lauter, R.S. Ventsel, R.S.Val-tatine. 1978. Preliminary Problez 'Definition Study of 48 Munitions'.Related Chemicals, Volume Ii, Propellant Related Chemicals. EthylCentralite. FirAl .Report, AD A066308. Atlatigtc Research Corp>oratio.,Ala.ria, VA. .,

:D'-8 ... 5-4

Z.


4. Fedoroff, Basil T. and Oliver E. Sheffield. !962. Encyclopedia ofExplosives and Related itmes, Vol. 2, p. C127. U.S. Army ArmamentResearch and Development Command, Dover, NJ.

Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed. Merck and Co., Inc., Rahway, NJ.

6. Alley, B.J. and H.W.R. Dykes. 1972. Gps Liquid ChromatographicDetermination of Nitrate Ester, Stabilizer, and Plasticizers inNitrocellulose-Based Propellants. Journal of Chromatography.71:23-37.

7. Lindblom, T. 1979. Determination of Stabilizer and ItsNi:roderivatives in Double Base Powders by RPLC. Proceedings'..the Snposium on the Chemical Problems Connected with theStablilityZ of Explosives. 5(0):107-125.

8. McGregor, Douglas B., Colin G. Riach, Ronan M. Hastwell, and Jack C.Dacre, 1980. Genotoxic Activity in Microorganisms of Tetryl, 1,3-Dinitrobenzene and 1,3,5-Trinitrobenzene. Environmental Mutagenesis.2:531-541.


10.- Forsten, I. !9F0. Disposal of Hazardous Toxic Munition Waste,Proceedings of the 1980 National Conference of EnvironmentalEn~neeripl, New York, Juy F-10,T 10.ASE &nviroumentalEngineers Division, New York. 440-575.

"00~.17-84-C-4133 25-5

" ! N

ETHYLENE GLYCOL



Chemicai Formula: C1H1 0 (1)262


Structural Formula: HOCH 2CH2OH



Deleted CAS Registry Number: 71767-64-1, 37221-95-7

CA Name (9CI): 1,2-Ethanediol

CA Name (8CI): Ethylene glycol

RTECS Number: KW2975000 .

Other Significant Synonyms: Glycol, monoethylene glycol, 1,2-dihydroxyethane, 2-hydroxyethanol


Physical State: Liquid (slightly viscous) (1)

Color: Clear

Odor: Sweet (2)

Melting Point: -13 0 C (1)

B5oiling Point: 198°0 (1)

Solubilities::W.ter: Miscible with water (1)SNoraqueous Solvents: Miscible with lower aliphatic, alcohols,glycerol, acetic acid, acetone and similar ketones, aldehydes,pyridine and similar coal tar bases; slightly soluble in ether(1i200); practically insoluble in benzene and its homologs,chlorinated hydrocarbons, petroleum ether and oils (1).

* Octanol Water Partition Coefficient: -1.93 to -1.36 (3,4) ( 'i

DAMD1"-84-C-4132 26-1

-,- -

ETHYLENE GLYCOL (cont.)

Hygroscopicity: Very hygroscopic, adsorbs twic-2 i•ts weight of water at100% relative humidity (I).



Vapor Pressure: 0.05 Torr at 200 C (6), 0.12 Torr at 20 0 C (7),0.2 Torr at 30 C (6)

Specific Heat: 0.561 cal/g/ C (1)

Heat of Combustion! Data not available

Reactivity: Reacts violently with chlorosulfonic acid and oleum (2)

Stability: May be explosive w'ien heated (2)

Flammability: Slight, combuition requires preheating (8), flash point,open cup: III°C (8)

* Il. USES

A. A Unique Use

Intermediate In the production of explosive ethylene glycol dinitrate.

B. Other Uses

Antifreeze; hydraulic brake fluids; industrial humectant; ingredient inelectrolytic condensers, where it serves as solvent for boric acid andborates; solvent in the paint and plastics industry; formulation ofprinters' inks, stamp pad inks, inks for ball point pens; softeningagent for cellophanes; stabilizer for soybean foam used to extinquishoil and gasoline fires; synthesis of safety explosives, glyoxal,unsaturated ester-type alkyd resins, plasticizers, elastomers

j I .and synthetic Libers (Terylene and Dacron) anW synthetic waxes (I).

III* ANALYTICAL~ MiNODS O


Gas chromatography would be the method of choice and many have beenreported. Two of the most recent methods apply to environmental andhealth effecte studies respectively. Nevinnaya and Kofawov (9) formedthe acetyl •Jerivative, and used an XE-6O0 column wtrih flame ionitationdetection to determinine ethylene glycol ia wastewater. A capillary

DA1017-84-C-.4133 26-


gas chromatographic method has been developed by Smith (10) todetermine ethylene glycol. in human blood serum. Smith formed thebutylboronate derivative before injection onto a methylsilicone bondedfused silica column.


Nevinnaya and Kofanov reported 10 ppb as the lower limit of detection (9).

)

•.I.

D hMI 7-84-C-4133 26-3

i I


"I';. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF ETHYLENE GLYCOL


Human ingestion 1.4 mL/kg Approx. lethal dose (1)(100 ML)

Human ingestion NS* Transient stimulation (1, 11)of the central nervoussystem followed by de-pression; vomiting,drowsiness, coma, res-piratory failure, con-vulsions; exudativepathological changesin the brain; renaldamage which may pro-ceed to anuria, uremia,cdeath

Human ingestion "Sip" to Neuromuscular distur- (I)approx. 120 uL bance with myositis(anciftieze after deposition of.olution) calcium oxalate crys-

tals; circulatory de-pression with rapidbreaching, cyanosis,and edema of the lungs;renal failure; deathafter consumption o!90-120 ml

Human in.estiou 710 mg/lkg LDLo (13)

Human ingestion 7,400 mg/kg TDo (13)(child)

Human local Liquid Irritating to skin and eyes (14)

Human contact NS M'ot irritating to the (14)with vapor eyes and throat

Not specifie.

D-'iD17-84-C-4133 26-4 ¾

i• .:: .. .[>.2•: "


TABLE IV-i. TOXICITY OF ETHYLENE GLYCOL (Cont.)


Human inhalation 10,000 mg/m3 TCLO (13)

Human inhalation Vapors above Nystagmus and recurrent (11)100 0 C chronic attacks of unconsciousness

Rat oral 4,700 mg/kg LD5 0 (13)

Rat oral 0.0-1.0 No maternal toxicity, (15)g/kg/day, embryotoxicity, or increaseddays 6-15 incidence of malformations inof gestation fetuses of dosed dams

Rat intra- 5,220 mg/kg LD50 (13)peritoneal

Rat intra- 2,800 mg/kg LDLo (13)venous

Rat subcu- 5,300 mg/kg LD50 (13)Staneous

Rat intra- 3,300 mg/kg LDLo (13)4 muscular

I3LRat inhalation 12 Mg/M Corneal damage and apparent (11)r blindness without signs ofsystemic intoxication

Mouse oral 7,500 mg/kg LDs 0 (13)

mouse intra- 5,614 mg/kg 14)50; chronic pulmonary (13)peritoneal edema or congestion, effects

on the spleen, kidney tubulesand gloneruli

Mouse intra- 3,000 mg/kg LD 0 (13)venous

H Mouse subcu- 2,700 g/kg LDo (13)taftous

- Guinea pig oral 6,610 zg/,'kg (13)

Guinea pig vubcu- 5,000 a/kg o(13)

DAH1D17-44-C-4133 26-5


) TABLE IV-1. TOXICITY OF ETHYLENE GLYCOL (Cont.)


Rabbit intra- 1,000 mg/kg LDLo (13)peri tonal

Rabbit intra- 5,000 mg/kg LDLo (13)venous

Rabbit intra- 5,500 mg/kg LDLo (13)muscular

Rabbit skin 19,530 mg/kg LD5 0 (13)

-- Rabbit skin 555 mg (open) Moderate irritation (13)

Rabbit eye 100 mg/1 hr Mild irritation (13)

Rabbit eye 1,440 mg/6 hr Moderate irritation (13)

( Cat oral 2,000 mg/kg LD5 0 (13)

Cat subcu- 2,000 mg/kg (13)

taneous

*Not specified

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF ETHYLENE GLYCOL

Test System Dose Eftects Reference

Human lymphocytes 320 mmol/L DNA synthesis inhibition (13)

House )ymphocytes 100 amol/L Hutagentic (13)

DA.'D•17-84-C-4133 26-6

-Ax


'. ENVIRONMENTAL EFFECTS





Alc. Leachability -- The adsorption of ethylene glycol onto different soiltypes was studied at 6 0C. No adsorption was observed onto samples ofsubhorizons of sandy till, clayey till, and melt water sand.Leaching experiments with undisturbed soil cores of sandy till showedthat CI, labelled ethylene glycol closely followed the movement ofwater wien chloride ion was used as a water tracer (16).



A2a. Biodegradation -- Adapted activated sludge, with ethylene glycol assole carbon source: 96.8% removal at 41.7 mg COD/g dry inoculum/hr(6). Biooxidation of ethylene glycol was 96Z in 20 days in alightly seeded dilution-bottle test without prior ecclimation ofmicroorganisms (17). Anaerobic metabolism of ethylene glycol by)culture from sludge of municipal anaerobic digester is dominated bytwo morphological types of bacteria, tentatively identified as a,ethanobacterium op. and a Desulfovibrio sp. Decomposition productsare acetate and ethanol. Formation of methane as a product ofiethanol oridation apparently occurs only after ethylene glycoldegradation is complete (18).

&2b, Hydrolysis - Data not available


A2d. Other chemical reactions - BOD5 " 38% of ThOD, COD: 94% of ThOD,ThOD: 1.26


B.- Effects on animals


B20. Mammalian wildlife species -- Chimpanzees exposed to an ethyleneglycol-satursted atmosphere for 28 days displayed no seriously harmfuleffects, Serious behavioral disturbances, such as have beer observedin both man and the chimpanzee following ingestion or injection ofethyleae glycol, did nor occur during the periods of glycol inhalation (19).'

DAMD17-84-C-4h.33 26-7

.7-





B6. Microorganisms, aquatic and soil -- Toxicity threshold (cellmultiplication inhibition test): bacteria >10,000 mg/L; algae - 2,000mg/L; green algae >10,000 mg/L; protozoa >10,000 mg/L; bacteria (toxic)at 250 mg/L (6).

B7. Aquatic species (fish and invertebrates) -- guppy: 7 day LC50 , 49,300

ppm (6); shrimp: 48 hour LC5 0 , greater than 100 ppm (8).


Cl. Phytotoxicity - Data not available




A. Health

Data not available

B. Environmental

Listed in EPA TSCA Inventory 1980.


AEHAA: NSN 6850-00-181-7929, 7940

A. Current Recommended A Disposal Practices (20)

1. Sanitary Sewer -- Ethylene glycol/water mixtures of the following-* strengths shall be disposed in the sanitary sewer system assuming an

allowable daily increase of 25 ppm biological oxygen demand (BOD)loading for a flow of 1,000,000 gallons pir day. The allowable dailyincrease is only applicable where the installaton is meeting itsNational Pollution Discharge Elimination System Permit with acomfortable margin approaching 2 mg/L of BOD. The discharge shall becoordinated with treatment plant operations to ensure properperformance during discharge.

DN17-84-C'4133 26-8

77


TABLE VIIA-I. DISCHARGE/TREATMENT PLANT OPERATION

% Mixture Gallons/I mgd for 25mg/L(Ethylene Glycol/Water) BOD Increase*

10 24020 12030 8040 6050 40

* Smaller allowable BOD increases will result in proportionally

less waste loading.

The above material shall be metered uniformly over a 12-hourperiod with enough water to assure adequate flushing. An easy way todetermine the percent ethylene glycol in the solution would be with anantifreeze tester and the chart given below. Thoroughly mix theantifreeze/water solution and test with the antifreeze tester;determine the percent ethylene glycol from the chart.

TABLE VIIA-2. ETHYLELE GLYCOL/TEMPERATURE (20)

% Ethylene Glycol Temperature ProtectedDegrees Fahrenheit

10 +2320 +1230 -0140 -2450 -54

2. Safety and Control Measures - Particular attention should be given topreventing skin contact. Disposal personnel should wear at leastmid-arm impervious gloves and a full-length impervious apron. Afaceshield and/or full face respirator approved for this item shouldbe available if any odor is noticed during mixing or loading (20).

S3. Incineration-- Do not incinerate (20).

4. Sanitary Landill Do not bury (20).

DAMD17-84-C-4133 26-9L

S i


A:*

B. Alternative Disposal Practices Under Consideration y the Army

Data not available


Data not available

VIII. REFERENCES

1. Wiudholz, Mc, S. Budavari, R.F. Blumetti, and E.S. Otterbien, eds.1983. The Merck Index, 10th ed., p. 550. Merck and Co., Inc., Rahway,NJ.

2. Chemical Fact Sheet-Ethylene Glycol. 1985. Bureau of Toxic SubstanceAssessment, New York State Department of Health, Albany, NY.

3. Chemical Inforamtion System (CIS), Information System for HazardousOrganics in Water (ISHOW). Accession No. 304702. 1985.

4. Chemical Information System (CIS), Information System for HazardousOrganics in Water (ISHOW). Accession No. 304699. 1985.

5. Weast, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed., p.p. C-309. The Chemical Rubber Co., Cleveland, OH.

6. Verschueren, Karel. 1983. Handbook of Chemistry and Physics, 48thed., p. C-309. The Chemical Rubber Company, Cleveland, OH.

7. Fay, R.H. 1978. Kirk-Othmer Encvlovedia of Chemical Technology,Vol. 3, 3rd edition, p. 79-91. John Wiley and Sons, New York, KY.

8. Chemical Information System (CIS), Oil and Hazardous MaterialsTechnical Assistance Data System (OUHTADS). Accession No. 7216718.1985.

9. Nevinnya, LV* and N.I. Kofano. 1904. Gas-Chromatographic

Determination of Glycols in Wastewater. Khimica Tekhnologii 1dy.6(4) :326-329.

10. Smith, N.B. Determination of Serum Ethylene Glycol by Capillary GasChromatography. Clinica Chimica Act. 144(Q,3):269-272.

V 11. Gosselin, Robert E., Dr., Dr. Roger P. Smith, Dr. Harold C. Hodge, andJeanette E. Braddock. 1984. Clinical Toxicology of Commerical Products,5th ed. Williams and Wilkins, Baltimore, MD.

12. Reynolds, James E.F. and Anne B. Prasad, eds. 1982. Martindale-TheExtra Pharmacopoeia, 28th ed. The Pharmaceutica. Press, London,,

S DA•D17-84-C.-4133 26-10

I '---• - . . •.: . .• .. . -.... '•• ..- • . .. • .. .. ,


13. Chemical Information System (CIS), Registry of Toxic Effects ofChemical Susbstances (RTECS). Accession No. KW2975000. 1985.

14. U.S. Coast Guard. 1978. Chemical Hazardous Response Information System(CHRIS) Hazardous Chemical Data-Training Edition-Ethylene Glycol.Abridged, CG-446-2. U.S. Department of Transportation, Washington,D.C.

15. Maronpot, R.R., J.P. Zelenak, E.V. Weaver, and N.J. Smith. 1983.Tertogenicity Study of Ethylene Glycol in Rats. Drug and ChemicalToxicology, 6(6):579-594.

16. Dialog, Pollution Abstracts. Accession No. 84-06866. 1985.

17. Conway, Richard A., Gene T. Waggy, Milton H. Spiegel, and Ronald L.Berglund. 1983. Environmental Fate and Effects of Ethylene Oxide.Environmental Science Technology. 17:107-112. -

18. Dwyer, Daryl F. and James M. Tiedje. 1983. Degradation of EthyleneGlycol and Polyethylene Glycols by Methanogenic Consortia. Apl aed nEnvironmental Microbiology. 46();: 185-190,

19. Dialog, Air Pollution Technical Information Center (APTIC).Accession No. 027588. 1985. )

20. U.S. Army Environmental Hygiene Agency (AEHA), 1983. Waste DisposalInstructions. TG-126, HSHB-ES-H/WP. AEHA, Aberdeen Proving Ground,KD.i

I

.. I.

DL).17-84-C-4133 26-11

..

ETHYLENE GLYCOL DINITRATE

Much of the available data on ethylene glycol dinitrate has been reported in a previousstudy by the Atlantic Research Corporation (ARC) entitled, A PreliminaryProblem Definition Study of 48 Munitions-Related Chemicals. Data reportedherein reflects information more recent than that reported by ARC in 1978.



Chemical Formula: C2H4N206


Structural Formula: 03 NCH2 CH2 NO3

B. Alternate Names and R Numbers


CA Name (9CI): 1,2-Ethanediol, dinitrate

- CA Name (BCI): Ethylene glycol, dinit-rate

RTECS Number: K.W5600000

Other Signficant Syionyws: DiniLtUglycol, EGDN, ethanediol dlnitrate,ethylene dinitrate

SC. 6hamicl aid PhvZical ?ronert.es

Physical State:. Oily liquid (1)I" .Color': -•ieow .

O Dta not - wailable

)., -8lCi n oi7-1

S•DAMDI 7-84-C-4133 27-1 ',

ETHYLENE GLYCOL DINITRAIE (cont.)

Solubilit•ies :

Water: 6.2 giL at 150C (2)Nonaqueous Solvents: Soluble in ether, acetone, chloroform,benzene, ni:robenzene, and toluene. Slightly soluble in carbon

5 tetrachloride and benzine (2).

Octanol Water Partition Coefficient: Log P - 0.55

Hygroscopicity: Not hygroscopic (2)


Specific Gravity: 1.488 at 20 0 C (2)

Volatility: Volatile. 0.14% loss at 200C after 24 hours; 0.37% lossafter 48 hours. 100% loss after 40 days at 350C (2).

Vapor Pressure: 0.00025 mm Hg at 200 C (1)

Specific Heat: 0.4 cal/g (2)

Heat of Combustion: 1764 kcalik& (3)

Stability: Stable at 750 C (2)

Flammability: Ignites when contacted with flame, may explode (1).Autoignition Tvsperature: 114-116 0 C (4). Lxpl-sive Tem~perature:257C.-6

II. USES

A. U

Liquid high explosive - Class A explosive (4)

B. Oh,,er Uses

Used with nitroglycerin to wake dynamite and other explosives.Occupational exposure involves mixing ethylene glycol dinitrate sndnitroglycerin aod considering th. two chemicals together (1).

II* ANALYTICAL MTHODS

A* Best Acceptble Method

Many analyticeal methods have been reported recently for this compoundand choice of method depends on the purpose of the analysis. CoPon etal. (6) reported an Ion Nobility Spectometer (IMS) which can detet parts p'.trillion of explosive in air.

~JlJ~A~C-4l3327-2

ETHYLENE GLYCOL DINIT"ATE (cont.)

Lloyd reported a high performance liquid chromatography methoo that usesa pendant mercury drop electrode at the detector. This method comparesfavorably with electron capture detection in gas chromatography and wasdeveloped for forensic analysis, but could be applied for other types oftrace analysis (7).

Yu et al. (8) reported a method to determine thia compound withnitro/nitroso spetific detector with either a gas or liquidchromatograph. This method can be used in the analysis of wastewater orbiological fluids. The detector is a Thermal Energy Analyzer (TEA) andcan also be applied to wecabolites of nitrate esters.Cumming and Park reported a gas chromatography/single ion monitoring

mass spectroscopy method (9).

B. Limit of ".tection

Lloyd reported a detection limit of 2-20 picogram/10 microliters ofinjected sample (7).

7

D&XDI7-84.-C-4 33 2- """" "-.". " .T.

ETHYLENE GLYCOL DINITRATE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXi.. iTY OF ETHYLENE GLYCOL DINITRATE*


Human inhal- NS** May cause severe, throbbing (1)ation, headache with small exposures,dermal and nausea, vomiting,

cyanosis, coma, and deathwith heavier exposures

Rat sub- 0.5 mL/kg bw, Increased liver, kidney, (10)cutaneous 10% EGDN in and spleen weight to body

olive oil, weight ratios; increaseddaily for 9 wk serum glutamic oxaloacetic

transaminase and acetyl-cholinesterase activities;methemoglobin not detected

Rat, uhlal- 500-j,500 Sleepiness, Heinz body (11)Mouse, ation mg/mr for 3 wk formation, anemia, in-Guinea pig to 3 mo creased reticulocyte count

douse inhal- 8Vo mg/m , Lethargy, cyanosis, Heinz (11)ation 8 hr/d, 6d/wk, body formation, increased

for 10 wk reticulocyte count, hemolyticanemia, skin erosion, thincoats, spasms; 23/30 animalsdead after 24 wk

Rabbit sub- 1.5 mL/kg bw, Increased plasma activities (12)cutaneous 10% EGDN in of lactic dehydrogenase,

olive oil, alkaline phosphatase, andonce aldolase; inhibition

of plasma monoamineoxidase activity

Rabbit sub- 3.0 mL/kg bw, Methemoglobin formation, (14)cutaneous 10% EGDN in highest levels at 2-4 hr

olive oil, after administrationonce

*-Information no't included in the ARC report** Not specified

flAMD17-84-C-4,33 27-4

i loom"

ETXhYLENE GLYCOL DINITRATE (cont.)

V. ENVIRONMENTAL EFrECTS

No information was found regarding the environmental fate or effects ofethylene glycol din'Irrate which would update the Atlantic ResearchCorporation docum'enc.


A. Heaith

TLV: TWA: 0.05 ppm or 0.3 mg/rn ; STEL: O0.1 ppm or 0.6 mg/rn3 (15).

B. Environmental

Kepozted in TSCA Inventory 1983.



Review of past Inst 'allation Assessment Reports indiates that currentmethods of disposal okf waste explosives and p:opellants involve openburning, open detonation, or hauling by a licensed couazractor andlendfilling. Current use of methods discussed above has also be beenconfirmed by private communicat'lons fr-im the U.S. Army Toxic andHIazardous Materials Agency (USa1iAMA), which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (16).

B. Alternate Dsoal Practices under ConsIderation ~the

Future plans for dispostl of waste explosives and propellants areprojected to emphasize fluid-bed incineration* This zethod has beentested accesufully by ARRADCOkI and is planned for use at installationssuch as Savanna Army Depot,, Tooele Army Depot, and Hlawthorne NavalAmmunition Depot (17).

C" O','er Disposal Practices Employed

Spills and leakage: Overspread stufficient sodium hydroxide and sprinklewater. Drain into the sewer with abundant water.

a)Disposal and Waste Treatment: Dissolve in a combabstible solventsuch as alcohol, oet. Burn in an open furnace b'y igniting from~ asafe distance ulth the utmost care or sprinkle into the fire chamberof a furnace with afterburner and scrubber.

AV(b) Laboratory Scale Quantities: Pour into sodium bioujf ate in a larget evaporating dish* Sprinkle water and neutralize. Drain into the sewerwith sufiiciont water.

DAND17-84-~C-4133 27-5


(c) Disposal Method Suggested: Controlled incineration in the scrubberequipped Deactivation Furnace incinerator (The Chemical Agent MunitionDisposal System) (A-31). Also, ethylene glycol dinirrate can berecovered from wastewaters (A-58) (18).

VIII. REFERENCES

1. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial Hygiene and Toxicology, Vol, 2A, 3rd revised edition,p. 2464. John Wiley and Sons, New York, NY.

2. Fedoroff, Basil T. and O.E. Sheffield. 1974. Encyclopedia ofExvlosives and Related Items, Vol. 6, p. E-259. U.S. Army ArmamentResearch and Development Command, Dover, NJ.

3. Fedoroff et al., Vol. 4, p. D-380.

4. Snook, R.W. 1978. Major Component Safety Data Statement-EthyleneGlycol Dinitrate (EGDN), U.S. Army Azmament Research and DevelopmentCommand, Dover, NJ.


6. Cohen, M.T., R.F. Wernlund and R.M. Stimac. 1984. The Ion MobilitySpectrometer for High Explosive Vapor Detection. Nuclear MaterialsManagement. 13:42.20-225.

S7, Lloyd, J.B.F. 1983. Screening for Organic Explosives Components byHigh Performance Liquid Chromatography with Detection at a PendentMercury Drop Electrode. Proceedings of the International SY onthe Analysis and Detection of Explosives. Washington D.C., 1983.Federal Bureau of Investigtion, Washington, D.C. 31-39.

8. Yu, W.C., E.V. Goff, and D.H. Fine. 1983. Determination of NitrateEsters, Nitramidsnes, Nitroaromatics and Their Metabolites inBiological Fluids and Wastewater by Gas and Liquid Chromatography witha Nitro/Nitroso Specific Detector. PE2cedi o.f the InternationaliSy-m-osi on the Analysis and Detection of Explosives. Washington,D.C., 1983. Federal Bureau of Investigation, Washington, D.C. 329-340.*

9. Cumming, A.S. and K.P. Park. 1983. The Analysis of Trace Levels ofExplosive by Gas Chromatography/Mass Spectrometry. Proceedings of thePirtmrntional Sypsimon the Anl~is and Detection of Explosves.&2 augton, D.Co, 1983. Federal Bureau , f IxvEgation, Washington,DC. 259-265.

10. Furana, J. and N. Sugabara. 1976. Experimental Studies on Subacute

Poiaoning by Nitroglycol. lianzaigaku Zasehi. 42(2)*:37-43.

DAMDI7-84-C-4133 27-6 --I.. ______7_


1. National Institute for Occupational Safety and Health (NIOSH). At. Recommended Standard for Occupational Exposure to Nitroglycerine andEtyl~ene Glycol Dinitrate. U.S. Department of Health, Education, andWelfare, Cincinnati, OH.

12. Furano, J. and N. Sugawara. 1977. On The Alterations of LacticDehydrogenase, A~lkaline Phosphatase, and Aldolase Activities in RabbitsPlasma by Nitroglycol. HANZAIGAXU ZASSHI. 43(5-6):186-198.

13. Furano, J. and N. Sugawara. 1978. Alternation of Monoamine OxidaseActivity in Rabbit Plasma After the Administration of Nitroglycol andNitroglycerin. Hanzaigaku Zasshi. 44(l):20-23.

14. Furano, J. and N. Sugawara. 1977. A Comparitive Study on the Capacityfor Forming Methemeglobin Among Three Nitric Esters. HanzaigakuZasshi. 43(2):49-53.

15. American Conference of Governmental Industrial Hygienists (ACGIH).1984. Documentation of Threshold Limit Values for Substances inWorkroom Air. American Conference of Goverrnmental Hygienists,Ci.ncinnati, OH.


17. Forsten, It 1980. Disposal of Hazxardous Toxic Munition Waste.Poceedings of the 1980 National Conference of Environmental

Engineeripg. New York, July 8-10, 1980. ASCE EnvironmentalEngineers Division, New York. 440-575.

18. Sittig, Marshall. 1981. Handbook of Toxic and Hazardous Chemicals,p. 4286 Noyes Publications, Park Ridge, NJ.

DAHD17-84-C-4133 27-7

ETHYLENE GLYCOL MONOETHYL ETHER



Chemical Formula: C4H1 0 02


Structural Formula:

H H H H

HO -C--Co-O-C--C - H

H H



CA Name (9C1): Ethanol, 2-ethoxy-

CA Name (8CI): Same

RTECS Number: KK8050000

Other Significant Synonyms: ethyl cellosolve, cellosolve, ethyl 2-hydroxyethylether, Ethylethylene glycol, glycol ethyl ether, hydrox)'ether, 2-ethoxyethyl alcohol, monomethyl ether of ethylene glycol

C. Chemical and scal Propeies



Odor: Odorless (1)

Melting Point: -70 C (1)

Boiling Point; 135 C (1)

DAMDI7-84-C-4133 28-1

• .I.•%• • .r ""•. .. • • .. " ..... .. . --. ... ... .- !• • i Ž.. .% • •

ETHYLENE GLYCOL MONOETHYL ETHER (cont.)

Solubilities:Water: Completely miscible (1)Nonaqueous Solvents: Miscible with alcohol, ether, acetone andliquid esters (1).

Octanol Water Partition Coefficient: Log P - -0.17(2); -0.54(3).


Specific Gravity: 0.931 at 200 C (1)

Volatility: Vapor density of 3 g/L (4)






0Flammability: Flammable; flash point: 44 C, open cup,490 C, closed cup(1). Autoignition temperature, 273 C (4).

C

I1. USES

A. Ar% Unique Use

Solvent for nitrocellulose

B. Other Uses

Solvents for lacquers and dopes; in various remnvers, cleansingsolutions and dye baths; finishing leather with water pigments and dyesolutions; and increasing the stability of emulsions (1).

777

ETHYLENE GLYCOL MONOETH-YL ETHER (cont.'"



Gas chromatography is the method of choice. Sidhu (6) reported a gaschromatography method for 2-ethoxyethanol in air. Samples were firstobtained by adsorption onto activated carbon followed by desorptionwith carbon disulfide/isopropyl alcohol. Detection was by flameionization detector. An FFAP column was used isothermally at 130°C.Sakai et al. (5) also used FFAP mixed with BX-10 to determine andseparate paint thinner components in air, including 2-ethoxyethanol.Smallwood et al. (6) reported a gas chromatographic method ofmonitoring 2-ethoxyethanol in blood and its urinary metabolites bydetermining the pentafluorbenzyl derivatives.


Sidhu (6) reported 0.1 ppm as the limit of detection in air samples.

.)

DAMD17-84-C.,4133 26-3

"''•• ? :':< i :": 44- : • ••'•••','


IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF ETHYLENE GLYCOL MONOETHYL ETHER


Human inges- 0.5-5 g/kg Estimated lethal dose (7)tion

Human inges- NS* Central nervous system (7)tion depression; kidney

injury; hematuria

*Human inhal- NS* - May cause moderate ir- (8)ation ritation of the respir-

atory tract

Human contact 0.6% vapor Irritation of the eyes (9)withvapor

( Human eye NS* Fain, mild irritation, (8)and transient corneal.injury

Human skin Prolonged or Mild irritation (8)repeatedexposures

Test inhal- 0.6% vapor Congestion and edema of()animals ation for 18-24 hr the lungs and conges-

tion of the kidneys

Rat oral 3,000 mg/kg LI)5 (10)

Rat oral 1,890 mg/kg Mortality (10)for 90 daysin drinking

* water

Rat intra- 1,200 mg/kg LDLO (10)peritofleal

4

DAMi7-84-C-4133 28-4 -


TABLE IV-2. TOXICITY OF ETHYLENE GLYCOL MONOETHYL ETHER (Cont.)


Rat intra- 2,400 mg/kg LD5 0 (10)venous

Rat inhal-ation 4,000 ppm/4 hr LCo (10)

Rat, mouse various Teratogenic (10)rabbit

Mouse oral 4,300 mg/kg LD5 0 (10).50

Mouse intra- 1,707 mg/kg LD5 0 ; chronic pulmonary (10)peritoneal edema or congestion,

effects on kidney tu-bules and the spleen

Mouse intra- 3,900 mg/kg LD 50 (10)venous

Mouse sub- 5,000 mg/kg LDLo (10)cutaneous

i Mouse inhal- 1,820 ppm/7 hr LC, 0 ; analgesia, dysp- (10)ation nea, hematuria

* Guinea pig oral 1,400 mg/kg LD5 0 (10)

Guinea pig eye 10 ug Mild irritation (10)

Guinea pig inhal- 3,000 ppm/24 hr LCLO (10)ation

Rabbit oral 3,100 mg/kg LD50 ; anesthesia, (10)hemolysis

Rabbit skin 3,500 mg/kg LD5 0 (10)

Rabbit skin 500 mg (open) Mild irritation (10)

Rabbit eye 50 mg Moderate irritation (10)

4 Dog inhal- 840 ppm, Slight decrease in red (10)ation 7 hr/day for cells and hemoglobin

12 Wk and an increase in im- ..mature white cells

DArMD7.-84-C-4133 28-5


V . ENVIRO*IENTAL EFFECTS


Al. Transport



ic. Leachability -- Data not available

Ald. Bioaccumujlation -- Data not available


A~a. Biodegradation -- Bio-oxidat ion in 20 days with non-acclimatedmicrobial cultures: 100% in fresh water; 62% in synthetic salt water

A2b. Hydrolysis -Data not available

Af A2c. Photolysis -- Data not available

A2d. Other chemical reaction - BOD :1.58 at 5-10 ppm, normal sewage asseed material, standard dilution technique; COD: 1.92 (12);Freshwater BOD 5: 36% of theoretical, with sewage seed; SaltwaterBOD 5:5% of theoretical, with sewage seed (4); ThOD: 1.80 (11).

A~e. Half-life -- Data not available

B, Effects on animals

Bi. Avian species -Data not available

32. Mammalian wildlife species -Data not available

33. Terrestrial invertebrates -- Data not available


B5. Amphibians -Data not available

B6. Microorganisms, aquatic and soil -Data not available

37. Aquatic species, fish and invertebrates - Vish: Levotis macrochirus96-hour LC. >10,000 ppm; Menidia beryllina 96-hour LC i>10,0000ppm; guppys Poecilia reticulata, 7-day LC 1: 16,400 ppa'?4);goldfishl Caras ius aulritus, 24-ou ?C5 >5,000,000 ug/L (13).

DKI-84-C-4133 286 ,i



CI. Phytotoxicity - Data not available




A. Health

TLV: TWA 5ppm (skin) (10)

B. Environmental

Reported in TSCA Inventory 1980.


A. Current Recommended ArmX Disposal Practices

Review of past Installation Assessment Reports indicates that current )methods of disposal of waste explosives and propellants involve openburning, open detonation, or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also be beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHA•A), which has the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (14).

B. Alternate Disposal Practices under Consideration & the .. m

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by APRADCOM and is planned for use at installations

such as Savanna Army Depot, Tooele Army Depot, and Hawthorue NavalAmmunition Depot (15).

C. Other D osal Practices Employed

I. Spray into incinerator or burn in paper packaging. Flammable solventmay be added (4).

DAMDi17-84-C-4033 28-7


S VIII. REFERENCES

1. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., p. 545. Merck and Co., Inc., Rahway,NJ.

2. Chemical Information Systems (CIS). Information System for HazardousOrganics in Water (ISHOW). Accession No. 305433. 1985.

3. ISHOW, Accession No. 305434.

4. Chemical Information Systems (CIS), Oil and Hazardous MaterialsTechnical Assistance Data Systems (OhMADS). Accession No. 7216720.1985.

5. Hawley, Gessner G. 1981. The Condensed Chemical Dictionary, 10th ed.,p. Van Nostrand-Reinhold Co., New York, NWY.

6. Sidhu, K.S. 1984. The Determination of Environmental 2-Ethoxyethanolby Gas Chromatography. Archives Toxicology. 55(4):272-275.

7. Gosselin, Robert E., Dr., Dr. Roger P. Smith, Dr. Harold C. Hodge, andJeanette E. Braddock. 1984. Clinical Toxicolo' of CommercialProducts, 5th ed. Williams & Wilkins, Baltimore, MD.

8. Material Safety Data Sheet-Ethylene Glycol Ethyl Ether. No. 0047. DowChemical Company, Midland, MI.

9. Sax, N.I. 1979. Dangerous Propcrries of inustrial Materials, 5thed., p. 475, Van Nostrand-Reiuhold Co., New York, NY.

10. Chemical Information Systems (CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. KX2450000. 1985.

11. Price, Kenneth, Gene T, Waggy, and Richard A. Conway. 1974. BrineShrimp Bioassay and Seawater BOD of Petrochemicals. Journal WPCF,46(0);63-71-

12. Verschueren, Karel. 1983. Handbook of Environmental Data on OrganicChemicals, 2nd ed., p. 649. Van Nostrand-Reihold Company* New York,

r NY .

13. Dialog, Aquatic Information Retrieval System (AQUIRE). Accession No.203161. 1985.

14. US. Army Toxic Hazardous Materials Agency personnel. 1985.

15. Forsten, I. 1980. Disposal of laardous Toxic Munition Waste.Aftoeee~ins of the 1980 National Conlerence of ENvlrotwntal

.ero July 8-10, 1980. ASGE aviroanta-l-tgineersDivision, NOW York. 440-575.

DANDI 7-84-C-4133 28-8

-N,:

ETHYLENE OXIDE



Chemical Formula: CIH4 0 (1)


Structural Formula:

H H

C O0/




CA Name (9CI): Oxirane

CA Name (8CI): Ethylene oxide

RTECS Number: IM2450000

Other signi-icant synonyus: Dihydrooxirene, dimethylene oxide, 1,?-epoxyethane, oxycyclopropane, oxirene, dihydro-

C. Chemical and Pbysictl Properties

Physical State: Gas at room temperature and pressure; liquid below12,C.


Odor: Sweat, ether-like. Hinim= detectable by odor is 700 ppm (2)

Boiling Point: 1007 0C (1)

R DA•J17-84-C-4133 29-I

---------

ETHYLENE OXIDE (cont.)

Solubilities:Water: Soluble in water (1)Nonaqueous Solvents: Soluble in alcohol and ether (1), soluble inbenzene (3).

Octanol Water Partition Coefficient: Log = -0.3 (4)


Vapor Density (Gas): 1.52 (5)

Specific Gravity (Liquid): 0.882 at 100C (3)

Volatility: Gas at room temperature.

Vapor Pressure: 779.1 Torr at 110 C, 1,305 Torr at 25 0 C (6)



Reactivity: May rearrange chemically and/or polymerize violently withevolution of heat on contact with catalytic surfaces (5).

Stability: Explosive (1). Do not expose to sunlight (2).

Flammability: Very flammable, flash point -18 0 C (I).

I1. USES

A. Ary Unique Use

Chemitcal intermediate In production of explosives.

B. Other Uses

Fumigant; sterilization of surgical instruments; agriculturalfungicide+ organic synthesis, especially it the production of ethyleneglycol and the starting material for the manufacture of acrylouitzileaid nonionic surf actants (I).

i1:. ANALYTICAL METHODS

A. Best Acceptable Hethod

Gas, chromatography is the method of choice. The official National.Intitutt of Occupational Safety and Health (NIOSH) aethod useactivated charcoal and carbon disufide to collect and r-'zorb ethylene

( . oxide (ETO) onto a gas chromatography with a flame ionxzatiou detector.Esposito et e1. (6) reported a U.S. Army Enviroumental Hygiene Agency(USAMHA) gas chroaatography vethod usiag a cheac*.Uy ispregnated

DAHD17-84-C-4133 29-2

• • I ...


sampling tube to collect the ETO before chromatography. Ambersorb 347was treated with HBr and placed in air sampling tubes. Air was drawnthrough the tube;s where ETO was converted to 2--bromoethanol. The tubesare desorbed with a mixture of acetonitrile and toluene andchromatographed on diethylene glycol succinate on Chromosorb WHP columnwith an electron capture detector (ECD).


Esposito et al. reported 0.5 ppm (6).

IV. HELALTE EFFECTS

TABLE IV-1. TOXICITY OF ETHYLENE OXIDE

Spe'ies Route Dose/Duration Effects Reference

Human oral 50-500 mg/kg Estimated lethal dose (7)

Human, skin, Acute Primary irritation or (8)animals inhal- burns of skin, eyes,

ation lungs, and respiratotyinges- tract; skin sensitiza-tion tion; vomiting; diarrhea

Human, eye Liquid or Severely irritating (8)animals vapor

Human, skin, Min dose: Potential adverse (8)animals inhal- 1 ppm avg. effects on lungs, liver,

ation exposure for kidneys, adrenal glands,15 yr testes, blood, and the

central nervous system

Human, inhal- Min. dose: Evidence o4 rever'sible (8)rat, rabbit, ation 204 ppm periphera! neuropathymonkey repeated exp.

.or 176 days

Human occu- 4-10 yr Increased rate of (9)pational leukemiaexposure

Human inhal- 12t5O0 ppm, TCo; ef.ecta on Souse (10)S • Euan •al- 00 pm, T ; effects on sn (10) '

ation 10 sec organs

Human inhal- 50U ppm,, T% ; convulsions, (10)ation 2 min na Sea, respiratory

DAMD17-84-C-4133 29-3


changes

Rat oral 30 or 7.5 Squamous-cell carcinomas (1)mg/kg 2x/wk of the forestomach;for up to hyperkeratosis, byper-150 wk plasia, papillomas of

the stomach squamous epi-thelium

Rat oral 72-330 mg/kg LD5 0 (10,8)

TABLE IV-1. TOXICITY OF ETHYLENE OXIDE (Cont.)


Rat inhal- 1,462 ppm, LC ; lacrimation, (10)a.ion 4 hr sal~vation, diarrhea

Rat, mouse various Terarogenic (10)

Rat inhal- 0, 50, or Increased incidences of (10)ation 100 ppm for mononuclear cell leuke-

104 wk mia, peritoneal mesothe-S11 wa, and mixed cellbrain glioma

Rat, mouse inhal- Min. dose: Testicular atrophy; (8)guinea pig ation 1.98 ppm dominant lethal effects

for 66 days

Mouse intra- 100 mg/k LD L (10)peritoneal

Mouse intra- 290 mg/kg LDo (10)venous

Mousa sub- 292-2,576 Lymphomas and injection- (10)cutaneous mg/kg, total site tumors

dose, inter-mitt:ently for95 wk

House inhal- 836 ppm, 4 hr LCo (10)at-ion

Guinea pig oral 270 ag/lkg LO (10)

G*. uinea pig inhal- 7,000 ppii,, (10)!•• •- ation 150 min oI.N.,"

DANDI7-84-C-4133 29-4 M

S... ... ... - " '.. ::' ••.:,• ••a; :•. ',.y.v


Rabbit eye 18 mg, 6 hr Moderate irritation (10)

Rabbit intra- 175 mg/kg LDLo (10)venous

Dog intra- 125 mg/kg LD5 0 (10)venous

Dog inhal- 960 ppm, 4 hr LCs^; lacrimation, (10)ation nausea, diarrhea

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF ETHYLENE OXIDE

Test System Effects Reference

Bacteria, Drosophila Produces mutagenicity and (10)melanogaster, related effects in manymammalian cells in test systemsvitro, mammals invivo

Human Chromosomal aberrations in (8)workers accidentally exposedto ethylene ox.de at approx. -1,500 ppm for 2 hr

V. ENVIRONMENTAL EFFECTSA. Environmental Fate

Al. Transport


Alb. Volatilization -- The desorption rate of ethylene oxide from naturalwaters is about 0.36 times that of oxygen under the same conditions(12).

W Ale. Leachability - Data not available

Ald, Bioaccumulation - Data not available

A2. Transformation - Data not available%V

t A2a. Biodegradation - Possible metabolites include ethylene glycol,ethylene chlorohydrin and glyoxal, Biooxidation of ethylene oxideproceeds at rates indicating noupersistencet In a lightly seeded BODtest, 521 of ethylene okide was oxidized in 20 days without prior

DANDI7-84-C-4133 29-5

.A :.

SETHYLENE OXIDE (cont.)

acclimation. In a biological waste treatment system with a highconcentration of adapted microorganisms, biooxidation would be muchfaster, perhaps a matter of hours (12).

A2b. Hydrolysis - In fresh water ethylene oxide hydrolyzes to ethyleneglycol. In salt water systems, ethylene chlorohydrin is also formed;the ratio of chlorohydrin to glycol formed is directly proportionalto the salt concentration (about 0.2 at 3% NaCI) (12).

A2c. Photolysis - Degrades in atmosphere by free radical processes;intermediate radicals include CH . and HCO or H + CO2 (13).

32

A2d. Other Chemical Reaction - Data not available

A!2e. Half-life - The hydrolysis half-life of ethylene oxide is about 14days in fresh water at 250C. Temperature effects are greater than pHeffects at pH levels usually encountered. Thehydrolysis/hydrochlorination half-life of ethylene oxide in saltwater is about 9 days at 250C (12).


BI. Avian species -- Data not available

TB2. Mammalian wildlife species -- Data not available

( B3. Terrestrial invertebrates -- Data not available



B6. Microorganisms, aquatic and soil -- The adverse effect level ofethylene oxide on activated sludge microorganisms or the LC5(concentration that inhibited growth 50%) was determined tobge in therange of 10 to 100 mg/L (12).

B7. Aquatic species, fish and invertebrates - 96-hour LC.^ for fathendminnow: 84 mg/L, 48-hour LCK for n magna: 212 mg/L48-hour LCSO for brine shrim :745 =mTL (12).


Cl. Phytotoxicity - One percent aqueous abstracts of manure, activatedsludge and digested sludge, stored for 2, 26, 27 or 65 days,inhibited seed germinatiion and root growth in Brassic.i arachinensis. Inhibition appeared to be associated with high levelsof ammonia, and to a lesser extent, ethylene oxide (14),

C2, Uptake - Data not available

I., " C3. Metabolism - Data not available

DAMD17-84-C-4133 29-6 1

"ETHYLENE OXIDE (cont.)


A. Health

Data not available

B. Environmental

Reported in TSCA Inventory 1983.

EPA TSCA 8(a) Preliminary Assessment Information, final rule (15).

Ethylene oxide has a statutory reportable quantity (RQ) of I lb underthe Comprehensive Environmental Response, Compensation and LiabilityAct. The National Response Center must be notified immediately whenthere is a release of this compound in an amount equal to or greaterthan the RQ (16).

VII. DISPOSAL


Data not available

B. Alternate Disposal Practices Under Consideration the

Data not available


Dissolve in higher alcohol, beuzene, or petroleum ether. Incinerate.

Ether of long standing may contain peroxides. Transport to isolatedarea in padded containers. Uncover and arrange excelsior train. Fromdistance, puncture with rifle fire and ignite excelsior (5).

AELU: NSN 6505-O0-C99-3878, 3962, 3405, 5298

3i Dispose of through a commercial contractor (17),

VI11. REFERENCES

I. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.

1983. Th Nerck Index, 10th ed., p. 550. Merck and Co., Inc., 8ahway,NJ*

2. Chemical Fact Sheet-Ethylene Oxide. 1984. Bureau of Toxic Substance) h.sesfetnt, New York State Department of Health, Albany. NY.

S DAN-7-84-C-4133 29-7


3. Weast, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed.,p. C-307. The Chemical Rubber Co., Cleveland, OH.

4. Chemical Information Systems (CIS), Environmental Fate Database(ENVIROFATE). Accession No. 240258. 1985.

5. Chemical Information Systems (CIS), Oil and Hazardous MaterialsTechnical Assistance Data System (OHMTADS). Accession No. 7216724.1985.

6. Esposito, G.G., K. Williams, and R. Bongiovanni. 1984. Determinationof Ethylene Oxide in Air by Gas Chromatography. Analytical Chemistry.56:1950-1953.

7. Go-selin, Robert E., Dr., Dr. Roger P. Smith, Dr. Harold C. Hodge, andJeanette E. Braddock. 1984. Clinical Toxicology of CommercialProducts, 5th ed. Williams and Wilkins, Baltimore, MD.

8. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial Hygiene and Toxicology, Vol. 2A, 3rd revised edition. JohnWiley and Sons, New York, NY.

9. Hogstedt, C., N. Malmquist, and B. Wadman. 1979. Leukemia in WorkersExposed t6 Ethylene Oxide. J. Am. Med. Assoc. 241(16):1132-1133.

10. Chemical Information Systems (CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. KX2450000. 1985.

11. Dunkleberg, H. Carcinogenicity of Ethylene Oxide and 1,2-PropyleneOxide Upon Intragastric Administration to Rats. Br. J. Cancer. 46:924.

12. Conway, Richard A., Gene T. Waggy, and Milton H. Spiegel, and Ronald L.SBerglund. 1983. Environmental Science Technology. 17:107-112.

13. Chemical Information Systems (CIS), Environmental Fate Database(Envirofate). Accession No. 245256. 1985.

14. Dialog, Aquatic Information On-line (AQUALINE). Accession No. 183750.1985.

15. Federal Regitser. Vol. 47, No. 82, p. 26992.

16. Comprhensive Environmental Response, Compensations and Liability Act,sacs. 102 and 103 (1980). 7

j

17. U.S. Army Environental Hygi*ue Agency (AEHA), 1983. Waste DisposalInstructions. TG-1.Z6, HStH8-ES-H-/iFPI U.SM Army EnvironmentalHygiene Agency, Aberdeen Proving Ground, MfD.

DAIM17-84-C-4133 29-8

BALAZONE


A. Structural and Chemical Formulas and Molecular EWeh

Chemical Formula: C7H5C12 NO4 S


Structural Formula:

0U

C-OH

iK

SO2 NC1 2

B. Alternate Names and Reistry Numbers


CA Name (9CI)" Be-azoic acid, 4-[(.dichloroamino)sulfonyl]

CA Name 8C1): Benzoic acid, p-tdichlorosulfamoyl)

RTECS Number: DG8050000

Other Signl--ant Synonyms: Carboxybenzenesulfonedichloroamide; p-N,N-dichlorov.,lfamyl bennoic acid; p-sulfonedichloramidobenzoic acid.

C. Chemical .,nd Pyial Properties

Physical State: Crystalline powder (1) SI

Color: White (1)

Odor: Strong chorine odor

M alting Poin84 195C (decomposition) (1)

•,.,; . • .. DAND)17-84-C.-4133 30-1

HALAZONE (cont.)

Solubilities:Water: slightly (1)Nonaqueous Solvents: soluble in glacial acetic acid, benzene;slightly soluble in chloroform; insoluble in petroleum ether (1).










( ,Flammability: Data not available

II. USES

A. A Unique Use

Field water treatment

B. Other Uses

Water disinfectant (1)

"III. ANALYTICAL METHODS


No appropriate methods were found for trace analysis of this compound.

AB Limit of Detection

Data not available

DAMD17-84-C-4133 30-2-,.3 • "..'' . . .. . .. .... . . . ..

,ALAZONE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF HALAZONE


Rat oral 3,500 mg/kg LDso (2)

Rat intra 300 mg/kg LDLo (2)venous

V. ENVIRONMNTAL EFFECTS

This material releases free chlorine on reaction with water. Whilelittle information on specific environmental fate of halazone isavailable, the compound is believed to have effects similar to thatof high levels of free chlorine.


Al. Transport - Data not available )A2. Transformation -- Data not available


Bi. Avian species -- Data not available





B6. Microorganisms, aquatic and soil -- Halazone was found to have aconsiderable disinfecting action in river water. Doses ranging from1.0 to 50.0 mg/L of halazone reduced bacterial counts, on average, by73.31% to 99.41% after 48 hours' incubation. At doses of less thanA 1.0 zg/L the bacterial count generally increased (3).

B7. Aquatic species, fish and invertebrates - Data not availableIIC. Effects on plants -- Data not available

DAMD17-84-C-4133 30-3• ' • • • •F~l • l• • .. .. .. .. . .. . ... . . .. ..

.. . . .m

HALAZONE (cont.)


A. Health

Data not available

B. Environmental


VIl. DISPOSAL


Disposal practices recommended by the U.S. Navy in their ConsolidatedHazardous Item List for Water Purification Kit (the principal use ofhalazone) is burial in a sanitary landfill (4).

B. Alternate Disposal Practices Under Consideration the Army

Data not available

S - C. Other Disposal Practices Employed

Data not available

VIII. REFERENCES

1. Hawley, Gassner G. 1981. The Condensed Chemical Dictionary, 10th ed.,p. 515. Van Nostrand-Reinhold Co., New York, NY.

2. National Library of Medicine (NIM), Registry of Toxic Effects (RTECS).Accession No. DH6820000. 1985.

3. Dialog, Aquatic Information On-line (Aqualine). Accession No. 102804.1985.

4. Consolidated Hazardous Item List (CHIL). 1981. NAVSUP PUB 4500. NavyFleet Material Support/Office, Mechanicsburg, PA.

• DAMDI7-84-C-4133 30-4

HYDRAZINiL

1. CHEMICAL AND PHYSICAL~ DATA


Chemical Formula: N 2 F


Structural Formula:

NHHI t

H-N-N-H



CANm 9() yrzn

CA Name (9C1): Hydrazine

UTECS Number: HU7175000

Other Signficant Synonyms: t)±aiine


Physical State: Fuming, colorless* hygroscopic$ liquid (1) or whitecrystals (2)

Color; Colorless

Odor: Penetrating$ resembling that of ammonia (3)

Odor Index: 5,300 at 20 C (4)

Threshold Odor Concenltrat ion: 3-4 ppm (4)

melting Point: 2.0 C (3)

Boln Poinrt: 113.;5 C (3)

DAMDI7-84-C-4133 31-1NAM

A-AD

HYDRAZINE (cont.)

Solubilities:

Water: Miscible with water (3).Nonaqueous Solvents: Miscible with methyl, ethyl, propyl,and isobutyl alcohols (3). Slightly miscible with hydrocarbons andhalogenated hydroc~arbons (5). Insoluble 4fn chloroform and ether (1).

Octanoll Water Partition Coefficient: Log P --1.1.1 (6),

HYgroscopicity: Hygroscopic: readily forms hydrate, N ZL'4-R2O 7

Specific Gravity: 1.0083 at 4 0C (5)

Vclatility: bJata Dot available

Vapor Pressure: 10.4 mm Hg at 20 C (8)

Flas~h Point: 38-52 0 C (Open cup) (8)

Saturation Concentration: 18,900 ppm at 25 0C (8)

Refractive Index: n (35 C) 1.4644.(5)

Autoignition Temperature; 24 0 C, iron-rtist surface; 270 0C gl-sssurface (8).

Heat of GombustioL: 148.6 cal/mol (1)

Reactivity: Explosion hazard when exposed to beat or flame or bychemical reaction with alkali metals, NUl CL *chrozates,~CuO, Cu++ salts, F , H 0.,* iron rust, me &1119 oz-1des, NJ.(C1O )., NO, N4 0, 0.~ 7 Na CrO 0 tetryl, ciuc, disaide, andZn (t G;i. z1oaes ~ur tng didiklialon it traces of air atepr set ls affected by UV. Strong redu~cing agent, diacicdii' haS."(pkB*5.52) (3).

Stability: Thermodynamically unstable and may d-itcompose toammonia and uitrogen,4 the reaction rate is reportedly sl2,twý zý:t r>oo

*temperature but is rapid at elevated tespratureso partizýJl&Ay in thepresence of aetals such as copper (8)* tf sit is "ecluded, hydrazinecan be stored, preferably in tha form of the hydrate, withoutdecosposition for a long time ±in pataffin bottles (5). Can be storedsealed in Slass and kept in a cool, dark place (3), U'sually storedunder nitrogen (9).

Flammability: Fire hazard dangerous, vhon exposed to beat, flame oroxidisins uagets (2). Coabustion highly oxothermic (1)

Flammable limitst 4-7-100Z by volume in air, combustion producestoxic vapor (10).

nAMrn7-s4-C-~4133 31-2

HYDRAZINE (cont.)

II. USES

A. Army Uniqu Use

Propellant

B. Other Uses

dydrazine is used as a polymerization catalyst, blowin6 agent, reducingagent, oxygen scavenger, and short-stopping agent. Other uses includeSpAndex fibers, explosives, antioxidants (petroleum, detergents),plating metals on glass and plastics, fuel cells, solder fluxes,scavenger for gases, photographic developers, corrosion inhibitors,oil-well drilling in soils containing kaolinite, buoyancy agent forundersea salvage, diving equipment, boiler feedwater, and reactorcooling water. Rydrazine is used in the synthesis of agriculturalchemical (maleic hydrazide) and the manufacture of pharmaceuticals(antibacterial and antihypercensive agents) (1).


Uydrazlne can be determined by titration, colorimetry,poten'ioscry, or gats chromatography. Small qusntities (less thanI ppm) can be determpLed photometrically after reaction with p-dimechylaminobenzsldehyde to yield an intease red color with aminimum traaesmittance at 445 nm or 455 um (6).

A. Dest Acceptable Method

For the analysis of hydrazine, aethylhydrcaine., 1,1-diaethylhydrazine,and ph'nylhydraflne in workroom air, the National Institute ofOccupational Safety and Health (NIOSH) (8) recommends the Wood-Andersongas chromatographic zethod because of its high sensitivity andspecifiCit'y. With thIs method, air samples are collected in a sulfuricacid-coated silica gel sorbant and the hydrafatzum hydrogen sulfates.•re deorbed from the gel with water. The resulting sution is

neutralized with sodium acetate and reacted with 2-furaldehyde. Thederivatives for=ed are ex-rocted into ethyl acetate and determined bySga eXozgogrepoby with ftain iotitation ditectio•.,

Recently, two rapid methos easily adapted for field monitoring, havebeen repo @ed. Uoltzclaw et *1. (11) reported a simplified trappingsystem us-in, a chilled acetone collection mediun, where a stablederivative of hydrazine is formed. The acetone solution can then be

-- directlýy- injected into & gas hromatogreph equipted with triarconic anda TEA nitrc; aed analyzer (11). Andsracn et al. report*d a highpressure liquid chronatographic method using chetoaorption tube iicontaining benzaldehyde-coaced XAD-2 resin (12).

* ADAŽCDIZ-84--C-4133 31-3

*.• . ,'

HYDRAZINE (cont.)

B. Limit of detection

4 ppb (11)

1 35 ug/m (12)

IV. HEALTH EFFECS

TABLE IV-I. ACUTE TOXICITY OF HYDRAZINE* (13)

Species Route TD50 or LC50

Rat oral 60 mg/kgRat ip 59 mg/kgRat iv 55 mg/kgRat inh 570 ppm/4hrMouse oral 59 mg/kgHouse ip 62 mg/kgMouse iv 57 mg/kgMouse inh 252 ppm/4hrM Mouse unknown 200 mg/kg

. Guinea pig skin 190 mg/kg**Rabbit iv 20 mg/kgRabbit skin 91 mg/kg

lDog iv 25 mg/kg

*8Data from RTEC5 (19M4) except **from NiOSH (8)

.1,.

NO[ ~ DMD'W7-84-C-4133 3-A 4

HYDRAZI14E (cont.)

TABLE IV-2. TOXIC EFFECTS OF HYDRAZINE


Human inhal- NS Eye and upper respir- (9)ation atory sensitization-type

dermatitis, eye and skinburns, lethargy, tremors,vomiting, diarrhea

Rat inhal- 20-225 ppm, Death of 83% in (8)ation 6 hr/d, 5 d/wk, 1-6 wk

x6 wk

Rat inhal- 5-14 ppm, 6 hr/d, Some deaths (8)ation 5 d/wk, x6 mo

Dog int=a- 25-100 mg/kg Hypoglycemia, (8)venous single dose convulsions

Dog intra- 16-20 mg/kg Impaired kidney (8)venous single dose function

Dog subcu- 16-25 mg/kg Elevated plasma (14)tanecus single dose ammonia levels without

significant elevationof blood urea nitrogen

Dog inhal- 150-168 ppm-hr/wk Weight loss, fatty (8)ation x6 mo liver, anemia

Dog inhal- 14 ppm, 6 hr/d, Fatty liver, anemia, (8)ation 5 d/wk, x6 mo death in 2 of 4

Dog inhal- 5 ppm, 6 hr/d, Weight loss, vomiting, (8)ation 5 d/wk, %6 mo irregular breathing

Rhesus intra- 5-20 mg/kg, Weight lo.;s, slight (8)monkey peri- 25-33 doses anemia, fatty liver,

toneal kidney, and heart

Rhesus intra- 32 mg/kg, Inhibition of insulin (8)monkey peri- 2 doses release

toneal

. 3!. MDuT-84-c-41 3j-5

HYDRA.ZINE (cont.)

TABLE IV-3. TERATOGENIC/REPRODUCTIVE EFFECTS OF H{YDR.AZINE* (13)

Species Route Duration TD Loor TC Lo Effects

Rat intra- Gestation days 100 mg/kg Effects on fertilityperi- 6-15toneal

Rat intra- Gestation days 50 mg/kg Embryotoxicityperi- 6-15toneal

Rat intra- Gestation days ',0 mg/kg Developmental abnormal-peri- 7-9 ities, effects on fertility,toneal. embryotox.icity

Rat sub- Gestation days 80 mg/kg Embryotoxicity, newborncutaneous 1-20 effects

Rat skin Gestation 50 mg/kg Effects on fertilityday 9

3Rat inhal- Gestation days 1 Mg/in /24 hr Embryotoxicityation 1-11

PMouse intra- Gestation days 48 mg/kg Developmental abnormal-peni- 6-9 ities, einbryotoxicitytone~al

house intra- Gestation days 80 mg/kg Developmental abnormal-per- 6-9 'tiestonea3.

I.N

DAHDI7-84-oC4133 3-

HYDRAZINE (cont.)

TABLE IV-4. CARCINOGENICITY OF HYDRAZINE* (13)

Species Route Duration TD or TCo EffectsLo Ado

Rat inhal- 6 hr, I yr I ppm Equivical evidence foration intermittently natal tumors

Mouse oral 2 yr, contin- 1951 mg/kg Neoplastic effects:uously pulmonary system, blood

Mouse intra- 5 wk, intermit- 400 mg/kg Carcinogenic effects:peri- tently bloodtoneal

Mouse inhal- 6 hr, I yr I ppm Equivical evidence foration intermittently nasal tumors

Hamster inhal- 6 hr, I yr, 5 ppm Equivical evidence foration intermittently nasal tumors

N

TABLE IV-5. MUTAQENICITY AND RELATED EFFECTS OF HY.DRAZINE* (13)

Test System Dose Effects

E. coll 10 umol/L DNA damageS. thmurium .12 gm/L ftcrosomal-mediated mutationB. subtilis 10 mmol/L Nt't specifiedx. inilun•zae 2 mol/L Mttation'5 G.lboasner 20 mmol/L(oral) Specific locus mutationD. w g er 10 nol/L(oral) NondisjunctionS. cerevisiae 200 mol/L MutationHuman liver cells 80 ug/L Oncogenic trarwtormationRat liver cells 3 uol/L DNA damageRat lung cells 250 ug/L Unscheduled DNA synthesisMouse lymphocytes I mol/L MutatlonMouse host-mediated 3100 ug.14; Mutation

assay with Socyphlmurum.

Hamster t•0t,. oelj,1. 80 v4g/L Oucogenic transformationa sHast wrO y oO. 10 .2$.'ug/iL Unscheduled DNA synthesislHamst~e•3,r cail- 2150 ug/L Unscheduled DNA synthesisHM.stwcone'rv. Q"*-140 L -tol/t Sister chromatid exchange

-Hmww-'ug'c1U.. I, W&lfL Sister chromatid exchn..

I • ". A

__ .HYDRAZINE (cont.)



Al. Transport


Alb. Volatilization -- MacNaughton et al. reports that hyd~azine evaporationrates from liquid pools ranged from 16 to 100 mg/cm'/hr. These rateswere considered sufficient to generate hazardous atmosphericconcentrations (greater than 3 ppm) up to 2 km downwind under worst-case meterological conditions, following release of hydrazine intothe environment. Hydrazine evaporation decreases as a function oftime due to absorption of H2 0 and CO2 (15).

Alc. Leachability -- D,.ta not available

Ald. Bioaccumulat.on -- None of the hydrazines on which metabolic studieshave be-n conducted seem to preferentially concentrate the chemicalsor metabolites in specific organs (16). Hydrazine does notconcentzate in the food chain (11).


A2a. Biodegradation -- About 50% of hydrazine administered to laboratorymammals has been observed to be excreted unchanged in the urine (16).Hydrazine ici co-metabxlized to nitrogen gas by Nitrosomonas with the

:major jroduct.being nitrogen (17).

k. Ab. Uydroiysis .. Decomposition slow in water at room temperature (9).(See A2e). Degradation in fresh or saline water is rather slor;therefore, degradation will not be a significant sink for hydrazinein aq-eous environments, and downstream concentration of hydrazine-will be a function of dilution and dispersion (15).

*A2c. Photolycis - Hydrazine does not photolyze in the solar actinic region-(lambda > 290 nm) (18).

A2d. Other chemical reaction Based on simulated atmosphere studies,consumption by ozone and hydroxyl radicals is expected todominate the fate of hydrazine in the atmosphere. The half-

X., life for the reaction of hydrazine with ozone is expected torange from less than 10 minutes in ozone pollution to less .than2 hours in the natural atmosphere; the major reaction productis hydrogen peroxide. For reactions with OH , the tropospherichalf-life for hydrazine should range from less than one hour inpolluted urban atmospheres to 3 to 6 hours in unpolluted"atmospheres. Due to the apparent efficient conversion ofhydrazine nitrogen to N2 , hydrazine release should have

D M 1l7-84-C-4133 31-8ri: t_

"'

HYDRAZINE (cont.)

relatively little impact on the levels of NO , nitrates, orother forms of active nitrogen in the atmosplere (18).Hydrazire degradation was faster in hard water than in softwater samples and also in relatively polluted samples whichwere rich in organic matter (19).

A2e. Half-life

In air, at 25 C: approximately 6 hours; in oxygenated aqueous solutions(pond and sea water): 5 days (15).


Bl. Avian species - Data not available

B2. Mammalian wildlife species -- Adequate studies in differentspecies of laboratory mice have demonstrated that hydrazinegiven mainly as the hydrazine sulphate (HS) produces a highincidence of multiple pulmonary adenomas and adenocarcinomas(6).


B4. Reptiles -- Data not available )5B. Amphibians -- The teratogenic effect of hydrazine on embryos of

toad (20) and frog (17) was 10 mg/L and 40 mg/L, respectively.

B6. Microorganisms, aquatic and soil -- EC values (concentrationsnecessary to reduce substrate metabolism by 50%): Nitrobacter14.6 Qg/L; Nitrosomonas 94.8 mg/L denitrfying bacteria 65mg/L anaerobic bacteria 145 mg/i. (17). At a concentration of48 mg/L, hydrazine produced a 7.% inhibition of thenitrificati~n process of non-acclimated activated sludge (5).

BT, Aquatic species, fish and invertebrates - For Daphnia, LC -1.2 mg/L. For several species of fish, the 24-hour LD 5nasabout or less than 4mg/L (17). Perturbation of trout 3Ldetected at 0.7 mg/L after 24-hour exposure, and a

A• concentration of 146 mg/L was fatal to rainbow trout after 22minutes exposure (5). Fertilized eggs of fathead minnowPimhales promelas were exposed to hydrazine for 48 hours atvarious concentrations; 5 mg/L was lethal and 1.0 mg/L causedsuch deformation that the larvae which did hatch had littlechance of .survival. For bluegill, Lepomis macrochirus, 96 hour LC.0-1080 mg/L (21) ..

C. Effects on Plants•'••i -' .. .. * = "

Cl. Phytotoxicity -- fydrazine is mutagenic in higher plants (22).

4

WDA17-84-C-4133 31-9

HYDRAZINE (cont.)




A. Health

TWA 0.04 mg/m 3 (0.03 mg/L, free base) (9).

R. Environmental

TLV I ppm (1.3 mg/m 3 ), 1974 (5).

VII. DISPOSAL


Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also beenconfimed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USAXHAMA), who have the responsibility toreview current disposal practices and to develop plans for futuredisposal practices (23).

B. Alternate Disposal Practices Under Consideration by the Lrm

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by AIRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot and Hawthorne NavalAmmunition Depot (24).

C. Other D al Practices E

S(a) Dilute with water to produce a 40% solution. Neutralize

with sulfuric &aid. Drain into the sewer with abundant water (25).

(b) Dissolve in a combustible solvent (alcoholabenzene, ett.). Burnin an open pit with utwost care. Ignite from a safe distance (25).

Lunn and Sansone report a one-step approach to conversion of hydrazinesto innocuous products in laboratory waste& or in the environment, usingoue of two nickal-based catalytic reduction procedures (26).

DANlD7-84-C-4133 31-10

IrI!+1

HYDRAZINE (cont.)

VIII. REFERENCES

I. Hawley, Gessner, G. 1981. The Condensed Chemical Dictionary, 10thed., p. 539. Van Nostrand-e hold Co., New York, NY.

2. Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5th ed.,p. 726. Van Nostrand-Reinhold Co., New York, NY.

3. Windholz, Mi, Budavari, S., Blumetti, R.F., and E.S. Otterbein. 1983.The Merck Index, 10th ed., p. 690-691. Merck and Co., Rahway, NewJersey.

4. Verschueren, Karel. 1983. Handbook of Environmental Data on OrganicChemicals, p. 740. Van Nostrand-Reinhold Co., New York.

5. International Agency for Research on Cancer (lARC). 1974. IARCMonographs on the Evaluation of Carcinogenic Risk of Chemicals to Man,4, Some Aromatic Amines, Hydrazine and Related Substances, N-NitrosoCompounds and Miscellaneous Alkylating Agents, p. 127. Lyon, France.

6. Chemical Information System (CIS), Environmental Fate (ENVIROFATE).Accession No. 248093. 1985.

7. International Technical Institute. 1982.1 Toxic and HazardousIndustrial Chemicals Safety Manual, p.1 269-270. internationalTechnical Information Institute, Tokyo, Japan.

8. National Institute for Occupational Safety and Health (NIOSH). 1978.A Criteria for a Recommended Standard-Occupational Exposure toHydrazine. 285 pp. Publication Number 78-172. US Department ofHealth, Education, and Welfare, Cincinatti, OH.

9. Clayton, George D. and Florence E. Clayton. 1981. Patty's IndustrialHygieie and Toxicology, Vol. 2A, 3rd ed., p. 2798. John Wiley andSons, New York, NY".

10. U.S. Coast Guard. 1978. Chemical Hazardous Response Informations (CHRIS) Hazardous Chemical Data-Training Edition-Hydrazine.

Abridged, CG-446-2. U.S. Department of Transporation, Washington, D.C.

11. Holtzclaw, J.F., S.L. Rose, J.R. Wyatt, D.P. Rounbehler, and D.H. Fine.1984. Simultaneous Determination of Hydrazine, Methylhydrazine and1 ,1-Dimethylhydrzine in Air by Derivatization/Gas Chromatography.SAnalytical C 56: 2952-56.

12. Andersson, K., C. Halgren, J.O, Levin, and C.A. Nilsson, 1984..Liquid Chromatographic Determination of Hydrazine at Sub-parts-per-

Million Levels in Workroom Air as Benzaldehyde-Coated Amberlite XAD-2.Analytical Chemistry, 56: 1730-31.

t DA)UU7-.84-C-4133 31-11

'-5' HYDRA-ZINE (cont.)

13. National Library of Medicine (NLM), Registry of Toxic Effects ofChemical Substances (RTECS). 1985.

14. Floyd, W.N. Jr. 1980. The Importance of Alimonia in the MetobolicEffects of Hydrazine. Aviation, Space, and Environmental Medicine.51:899-901.

15. Farmwald, JeAo and M.G. MacNaughton. 1981. Effects of Hlydrazine onthe Activated Sludge Process. Journal WPCF. 53(5):565-575.

16. Clayton, George D. and Florence E. Clayton. 1981. Patty's IndustrialHygiene and Toxicology, 3rd ed., Vol. 2A, p. 2796. John Wiley andSons, New York.

17. Kane, Donald A. and Kenneth 3. Williamson. 1983. Bacterial Toxicityand Metabolism of Hydrazine Fuels. Arch. Environ. Conatm. Toxicol.121:447-453.

18. Tuazon, Ernesto C., William P.L. Carter, Arthur M. Winer, and James N.Pitts, Jr. 1981. Reactions of IHydrazines with Ozone Under SimulatedAtmospheric Conditions. Environ. Sci. Technol. 15: 823-827.

19. Slonim, A.R. and J. Brennan Gisciard. 1976.. Hydrazine Degradation inAquatic Systems. Bull. Environ. Contain. Toxicol. 16 (3): 301-309.

20. Greenhouse, Gerald, Dr. 1976. Effects of Pollutants on Embryos andLarvae of Amphibian Species. Technical Report 7659, AD A033560.

* . Aerospace Medical Research Laboratory, Wright-Patterson AFB, Ohio.

A21. Fisher, J.W., D.S. Meyers, and M.L. Meyers. 1980. The Effects ofSelected Ilydrazines Upon Fish and Invertabrates. Technical Report7993, AD ,Air Force Aerspace Medical Research Laboratory, Wright-Patteson APB, Ohio.

22. Clayton et al., p. 2791.

23. David Renard, U.S. Toxic and Hazardous Materials Agency, to J. CarlUhrmacher (personal communication). 1985.

2. Forsten, 1* 1980. Dispodal of Hazardous Toxic Munition Waste.2. Proceedings.of the 1980 National Conference of Environmental

Engineerin&* New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575. !

25. Consolidated Hazardous Item List (CHIL). NAVSUP Publication 4500. 1

Navy Fleet Material Support Office, Mechanitcsburg, PA.

26. Lunno George and Eric B. Sansone. 1983. Reductive Destruction ofHydrazines as an Approach to Hazard Control. Envron, Sci Teho17 (4): 240-43.

DAD17-4-Cn4133 1-1Ut

HYDROXYL AMMONIUM NITRATE



Chemical Formula: NH 404


Structural Formula: HONH3+1 NO3-1

I B. Alternate Names and Registry Numbers


CA Name (9CI): Hydroxylamine, nitrate (salt)

CA Name (8CI): Same

RTECS Number: Data not available )Other Significant Synonyms: Hydroxylamine mono nitrate

C. Chemical and phY~ical Properties

Physical State: Crystal (1)

Color: White (1)


Melting Point: 48 0 C (i)

Solubilities:Water: Very soluble (cold); decomposes (hot) (1).Nonaqueous Solvents: Very soluble in alcohol (i)




41 Volatility: Data not available

Vapor Pressure: Data rot available - ,.

Specific Heat: Data not availableWVD.AMD17-84-C-4133 32-1

~J-5~~S~¾ - - --- W

HYDROX`YL AMMONIUM NITRATE (cont.)

Heat of Combustion: Data nor available

Reactivity: Reacts with inorganic and organic soil components.(2

Stability: Decomposes at 100 C (1). Unstable in water (2).


Ii. USES

A. ArmyZ Unique Use

Propellant

B. Other Uses

Data not available


( A. Best Acceptable Method

Kaplan et al. (2) determined hydroxylammonium nitrate byspectrophotometer at 705 urn. The aqueous solutions were 50 ppm and

below. No separation was performed.


Data not available

DAUD17-84-C-4133 32-2

k... 77.

HYDROXYL AMMONIUM NITRATE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF HYDROXYLAMMONIUM NITRATE


Hydroxyl- Rat oral 882 mg/kg LD5 0 (3)ammoniumnitrate Rat, NS* NS Cyanosis, respiratory (3)(grade not rabbit distress, and convul-specified) sions

Rabbit oral 100 mg/kg Approximate lethal dose (3)

Rabbit dermal 70 mg!kg LDo50 (3)(unoc-cluded)

Hydroxyl- Rabbit dermal 5 d/wk Chronic and ulcerative (3)amonium (nonoc- for 3 wk: dermatitisnitrate clusive 0.7-11.7(technical patch) mg/kggrade; SO:aqueous 1.5-11.7 Red blood cell de-solution) mg/kg struction and Heinz

body formation

2.9-11.7 Splenic hematopoiesis;mg/kg increased spleen-to-

body weight ratio

5.9-11.7 Hepatic he.matopoiesis

mg/ks

11,7 mg/kg Increased heart-to-body weight ratio

Nitrates Human oral Large Dizziness, abdominal (4)amounts cramps, votitinug,

bloody diarrhea, weak-nets, tonvulsious, andcollapse

Small Hay lead to weakness,repeated general depression,doses haaduche, and mental

-impairment

Dh1ID17-84.-C-4133 32-3

Si[.i•AH 1 32.". .,,,,':,•' ,'

A,. m =, mm m . •• • • ,w , As


TABLE IV-1. TOXICITY OF HYDROXYLAMMONIUM NITRATE (Cont.)


Hydroxyl- Rat intra- 59 mg/kg LD5 0 (5)amine venous

Rat subcu- 29 mg/kg LD5 0 (5)taneous

Mouse intra- 60 mg/kg LDo (5)perito-neal

Mouse unknown 175 mg/kg LDs50 (5)

NS local NS A moderate irritant (4)to skin, eyes, andmucous membranes

NS sys- NS Can cause methemoglo- (4)temic binemia

SNot specified

U01 7-84-C-4133 32-4

V

& 'i


TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF HYDROXYLA!4INE(5)


Salmonella typhimurium 5 pph Mutation; effects onDNA repair

Escherichia coli 5 pph MutationE. coli 50 mmol!L DNA damageBacillus subtilis I mol/L MutationB. subtilis 100 mmol/L DNA damageHaemophilus influenzae .140 mmol/L Mutation

5 minMicroorganisms 10-1,000 Mutation

mmol/LMicroorganisms I mo!!L Unscheduled D14A synthesisDrosophila melanogaster 30 mmol/L Sex chromosome loss and

nondisj unctionNeurospora crassa I mol/L MutationSchizosaccharomyces I mol/L MutationpombeHuman lymphocytes 360 umol/L DNA synthesis inhibitionHuma-. fibroblasts 300 umol/L Chromosomal aberrations

Human leucocytes L5 mg/L Chromosomal aberrationsMouue embryo cells 50 umol/L Chromosomal aberrationsH amser lung cells 5 mmol/L Sister chromosome exchangeHamster ovary tells 150 g/i Mutation

16 hrMonkey kLidney cells 25 w/ L Chromosomal aberrationsMonkey kidney cells 50 mg!L Induction of micronuclei

V. ENVIROtwNTAL EFFECTS

A. Envirormental fate




Alc. Leachability -- Data not. available

Aid. Bioac~umulation - Data not av2&hle

AZ. Transfoozation -- Data not t•. ,abi• .

D&MD7-64-C-4133 A^-I


A2a. Biodegradation - Data not available

A2b. Hydrolysis - Hydroxlammonium nitrate was stable at pH 4.9 and below.The compound was found to be chemically unstable above a pH of about5.9 (2).

A2c. Photolysis --- Data not available

A2d. Other chemical reaction - Reports in the literature indicate thathydroxylamine rapidly disappears from soils through a number ofchemical reactions with inorganic and organic soil components (2).

.5 A2e. Ualf-life - Data not available


B1. Avian species - Data not available

B2. Mammalian wildlife species -- Data not availabla


B4. Reptiles -- Data not available-



1B7. Aquatic species, fish" and invertebrates - Data aot available

C4 Effects on plants


CZ. Uptake - Data uot available


V1. STANDARDS AND RGULATI0•SA. Health - Data nat available

B. tavironmental


DA--17-84-C--4133 32-6

- . :: " ..

HYDROXYL AHMONIUM NITRATE (cont.)

VII. DISPOSAL

A. Current Recommended Army Dispoal Practices

Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation or occasionally, hauling by a licensedcontractor and landfilling. Current use of methods discussed abovehas also been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (6).

B. Alternate Disposal Practices under Consideration theeA

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use atinstallations such as Savanaa Army Depot, Tooele Army Depot, andHawthorne Naval Ammunition Depot (7).


Data not available

VIII. REFERENCLS

1. Weast, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed.,p. B-181. The Chemical Rubber Co., Cleveland, 011.

2. Kaplan, David L., Patricia A. Riley, David J. Emerson, and Arthur M.Kaplan. 1984. Degradation of Ammonium Nitrate Propellants in Aqueousand Soil Systems. Environ. Sci. Technol. 18:694-699.

S3. Asaki, A. 1982. Health Hazard Evaluation of Liquid Monopropellants.Phase 2. Effects of Dermal Administration of Hydroxylammonium Nitrate.USAEHA 75-51-0132-82, AD A118415. U.S. Army Environmental HygieneAgency, Aberdeen Proving Ground, MD.


5. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substances, Vol. No. 2, p. 473.National Institute for Occupational Safety and Health, Cincinnati, 0E.


DAMDI7-84-C-4133 32-7


S 7. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575.

8. Consolidated Kazardous Item List (CHIL). 1981. NAVSUP PUB 4500. NavyFleet Material Support Office, Mechanicsburg, PA.

A

A.

DAýM)I7-64-C-4133 32-8w

LEAD AZIDE


The Army's need for research on the toxicological and environmental hazardsof lead azide was reported in A Preliminary Problem Definition Study of 48Munitions-Related Chemicals by the Atlantic Research Corporation (ARC).Specific data on the toxicity or environmental effects of lead azide werenot reported. It was concluded, however, that lead azide is toxic to man,based on the toxicities of both lead and the azide ions, hydrazoic acid.Toxicity to aquatic organisms was expected to be low due to the insolubilityof lead azide in water. The report concluded that the compound willaccumulate in sediments. Some information was provided on the phytotoxicityand effects on microrganisms of other insoluble lead compounds, which may berelated to the environmental effects of lead azide. The report documentedthat before the Army disposes of lead azide, it is treated with eithersodium hydroxide or sodium nitrite and acetic acid to eliminate theexplosion hazard. Thus, little if any lead azide enters the environment (1).



Chemical Formula: PbN6


Structural Formula: Pb+2 (N-N-N) 2 -I

B. Alternate Names and R Numbers


CA Name (9CI): Lead Axide, Pb(N 3 )2

CA Name (8CI): Lead Azide, Pb(N3)2

RTECS Number: OF8670000

Other Signficant Synonyms: Initiating explosive, lead azide


Physical state: Crystalline solid; alpha form is orthorombic, betaform is monoclinic. Beta form slowly converts to alpha form at160.C (2).

Color: Colorless

Odor: Data not available (.

DAk4PI7-84-C-4133 33-1

LEAD AZIDE (cont.)

Melting Point: 245-2500C - decomposes when heated slowly

Solubility: Insoluble in aqueous ammonia; 0.125 g in 100 mL ofconcentrated sodium nitrate at 180 C; 0.487 g/100mL at 80'C 1.542 gper 100 mL of concentrated sodium acetate; 2.020 g per 100 mL at 80°C (2).


Hygroscopicity: 90% Rh and 300C

Density: 4.71 g/cc alpha form; 4.93 g/cc beta form (2).



Specific heat: 0.110 cal/g at -50 to 50 0.100 cal/g at 1O0°C (I).

Heat of Combustion: 630 kcal/kg (3)

Reactivity: Violent reaction with brass, explosion hazard severewhen shocked or exposed to heat or flame. Detonates at 3500C (4).

Stability: Decomposes slowly by ultraviolet light (1). Should alwaysbe handled under water. Explosions have occurred where azidecompounds have reacted with Pb in plumbing after being washed down asink (4).


II. USES

A* Unique Use

Initiating explosive in detonators, priming compositions, andcommercial blasting caps.

B. Other Uses

Primary detonator for high explosives. Inforzation storage on stvrene-butadiene resins, preparation of electrophotographic layers.

! • 111. ANALYTICAL METHODS -

•:AO Best Acceptable Method

•{! ""Forensic scientists are currently uv~ng X-ray photoelectron

•:•. ~spectroscopic (XPS) detection for th.i~s compound in explosive residues"•::'•m: ( 5 ). Differential pulse polarogrsphy is used for analysis for.•;

,specifications (6)j but not for trace analysis. Aspluud (7) reported a

voltammetric method of determination that can be used for both quality A

DAMDI7-84-C-4133 33-2

A.11

LEAD AZIDE (cont.)

control and trace environmental samples. Trace analysis was reportedfor azide as the sodium azide. Boehm (8) reported a TLC (thin-layerchromatography) method.


Sharma reports ng/cc for XPS (5).

Asplund (7) reports 0.05 mg per cubic meter of air as the sodium azide.

IV. HEALTH EFFECTS

No information updating that in the ARC report was located.

V. ENVIROMINTAL EFFECTS

No information was found regarding the environmental fate or effects oflead azide which would update the Atlantic Research Corporationdocument.


A. Health )TLV: TWA 0.15 mg (Pb)/m ; STEL 0.45 mg(Pb)/m3 (9).

The Occupational Safety aid Health Administration standard - airborne,

8-hour TWA is 50 ug(Pb)/m

B. Environmental


VII. DISPOSAL

A. Current Recommended r Disposal Practices

B. Data not available

Bo Alternate Disposal Practices Under Consideration b the Army

A method for disposal of large quantities of lead atide by electrolyticdecomposition has recently been developed and has been isplmented atSavannah Army Depot. In this technique, lead azide is dissolved in theelectrolyte NaOHl; lead is plated out on the cathode and nitrogen isreleased at the anode (1O), (

Aý

DA.MD7-84-C-4133 33.-3"F-A*

LEAD AZIDE (cont.)

S C. Other Disposal Practices Employad

Data not available

VIII. REFERENCES

1. Kitchens, J.F., W.E. liarwards III, D.M* Lauter, R.S. Wentsel, R*S.Valentine. 1978. Preliminary Problem Definition Study or 48 MunitionsRelated Chemicals, Vol. IV, Primer and Tracer Related Chemicals-LeadAzide. Final Report. AD A066310. Atlantic Research Corporation,Alexandria, VA. DAMDI7-77-C-7057.

2. Federoff, Basil T. and G.E. Sheffield. 1964. Encyclopedia ofExplosives and Related Items, Vol. 4, p. D-380. U.S. Army ArmamentResearch and Development Command, Dover, NJ.

3. Urbanski, T.. 1967. Chemstry and Technology of Explosives, Vol. 3,p. 169. Pergamon Press, Elmsford, New York, NY.

4. Hawley, Gessner G. 1981. The Condensed Chemical Dictionary, 10th ed.,p. 605. Van Nos trand-Rein~o-ld Co*, New- York, NY.

5. Sharma, J. 1983. X-Ray Photoelectron Spectroscopic (XI'S) Detectionand Identification of Explosives Residues. Proceedings of theInternational Symposium on the Analysis and Detection of Explosives.

Washinton, E.C.'1983. Fe-dera-lBureau of Investigation, Washington,

6. 9emlTH0 A Rapid Chemical Analysis of the Ingredients of NOL-130 Primer Mix. Int. Jahrestag-Fraunhofer Institute Treib.

7. Asplund, J, 1984. Voltametric Determination of Azide and Lead in LeadAzide. Proceedings of the-9th International Pyrtehnical Seminar.

8. Boehm, 0. 1968. Thin-Layer Chromatography of Lead Azide, MercuricFulminate and Lead Trinitroresorcinate. Syv jim oCemicalProblems Connected with Stability of Exoivs Stockholm-,Sweden,

9. American Conference of Governmental Industrial Hygienists (ACCIHO.1984-85. Thres hold Limit Values for Chemical Substances and Pyia

r Aents in the Work Environment and ~cal Exosr Indices withIntende'd hngs 2nd edition, p. 22. American Conference of -

Governmental Hygienist, Cincinnati, OH.

10. Forsten, 1. 1980. Disposal of Hazardous Toxic Munition Waste.Procedins of the 198 Conference of Environmental E-ýerS NewYork, Ju~ly 87O 190 SEE ronmental Engineers Division, NewYork. 440-575.

DAMD17-84-C-4133 33-4

LEAD STYPHNATE



Chemical Formula: C6 H3N308 Pb (1)

Molecular Weight: Anhydrous 450.30; monohydrate 468.3 (1)

Structural formula: See Exhibits 34-1, 34-2 and 34-3.



Deleted CAS Registry Numbers: 59286-40-7; 4219-19-6

CA Name (9CI): 1,3-Benzenediol, 2,4,6-trinitro-, lead(2+) salt (1:1)

CA Name (8CI): Resorcinol, 2,4,6-trinitro-, lead (2+) salt (1:1)

RTECS Number: 0G6425000

Other significant synonyms: Initiating explosive lead styphnate, leadtricinate; lead trinitroresorcinate (2).


Physical State: Monoclinic crystals

Color: Orange-yellow

Odor; Data not available

t Melting Point: Data not available

Boiling Point: Data not available

Solubilities: Data not availableWater: Very slightly soluble in water (0.041 at room temperature)(1)lNouaqueous Solvents: Insoluble in ether, chloroform, CC14 , HCL.

Slightly soluble in 10 aqueous ammonia acetate. Decomposed byconcentrated nitric or sulfuric acid (1).


Hygroscopicity: Data not availableAl

U _ _ _ _".•?,, .

LEAD) STYPUNATE (cont.)

EXHIBIT 34-1

0-

02N N02Pb +2

0-~N02

Lead styphnate compound 1: lead trinitroresorcinate

OPbOH

02N N02

%%IOPbOH) N02

Lead styphnate compound 11: Dibasic lead styphnate

OPbOH

02N NO2

OH

Lead styphnate compound Ill: Monobasic lead styphnate

LEAD STYPHNATE (cont.)




Heat of Combustion: 1251 kcal/kg (1)


Stability: Very sensitive explosive. Shock-sensitive, has detonated whendry (1).

Flammability: Easily ignited by flame or electric spark (1).

II. USES

A. A Unique Use

Primer initiating explosive (1)

B. Other Uses

A weak primary explosive, used in non-corrosive ignition cups such asSinoxyd. It is added to lead azide detonators to facilitate ignitionand is used as a covering layer to protect lead azide against carbondioxide (3).

SUsed in primer blends for non-military ammunition (4).

11I. ANALYTICAL METHODS

A. Best Aeable Method

Voltametry is now the method of choice for process control, andproduct control (5). Differential Pulse Polarography, a voltametricmethod, is described by Semel (4). No methods for trace analysis werereported.


Data not available

L. .. • . . . ..... .. . .. . .


IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF LEAD STYPHNATE


Lead styph- No toxicity data located; data (6)

ate on chemical classes and structuralanalogues follow below

Lead Human inges- General:tion Pallor, weakness, loss of weight,inhal- malnutritionation

Gastrointestinal:Metallic taste, increased saliva-tion, pyorrhea, anorexia, nausea,vomiting, constipation, abdominalcolic and tenderness, Burton'slead line on gums

"Genitourinary:Nocturia, albuminuria and hematuria,increased bilirubinuria, secondaryhyperurice•ia, azotemia

Neuromuscular:Numbness and tingling of extrem-ities and associated sensory dis-

*: turbance; extensor weakness ofwrists and ankles, brachial palsyhas also been described; loss ofmuscle tone, tremor, increaseddeep-tendon reflexes, muscular

cramps and aching, arthralgia, mus-cular atrophy

Central nervous system:Visual disturbances, headache, diz-ziness, nervousness or depression,insomnia, sental confusion and del-irium, convulsions, coma; encephae-opathy may be acute or chronic -"acute usually associated with blood

:-f levels above 120 ug Pb; retinalhemorrhages and optic neuritis; graystippling of lead pigment about theoptic disc has also been reported

I -"

LEAD STYPFiATE (cont.)

TABLE IV-1. TOXICITY OF LEAD STYPFNATE (Cont.)


Lead Human inges- Hematopoietic: (7)(cont.) tion, Erythrocyte stippling, hypochromic

inhal- normocytic anemia, increased per-ation ipheral reticulocytes

Styphnic Unknown (see following table (8)acid for mutagenicity data)(2,4,6-Trinitro-resorc-inol)

Nitrates Human oral Large amounts produce dizziness, (8)(As analogue for abdominal cramps, vomiting,Styphnic acid) bloody diarrhea, weakness, con-

vulsions, and collapse; smallrepeated doses may lead to 6ieak-ness, general depression, head-ache, and mental impairment

Picric Human topical Local or generalized allergic (9)acid reactions(-2,4,6-Trinitro- Human inges- Nausea, vomiting, diarrhea, ab- (9)phenol) tLion or dominal pain, oliguria, anuria,(As analogue for percut- yellow staining of skin (notS:yphaic acid) aneous icterus), pruritis, skin erup-

absorp- tions, stupor, convulsions,tion death

Various oral, High acute toxicity (10)animal skin, (6)

* species sc

AD'


TABLE IV-2. KUTAGENICITY AND RELATED EFFECTS OF STYPHNIC ACIDa


Salmonella NS * Nonmutagenic with or (11)typhimurium without Aroclor 1254-TA98, TAI00, induced rat liverTA1535, TA1537 fraction or treatmentTA1538 with ozone or chlorine

Salmonella up to 25 No-mutagenic with or (12)typhimurium mmol/plate without Aroclor 1254-TA9S, TA00, induced rat liver S9TA1535, TA1537TA1538

Saccharomvces NS Did not produce mitotic (11)cerevisiae inhibition with or with-D3 out Aroclor 1254-induced

rat liver fraction ortreatment with ozone orchlorine

No mutagenicity data located on lead styphnate* Not specified

V. ENIVIRONMENTAL EFFECTS


A10 Tronsport -- Data not available


Alb. Volatilization - Data not available



A2. Transformation - Data not available

A~a. iodegradation - Data not available

A2b.b Hydrolysis - Data not available

( A c. Photolysis - Data not available



LEAD STPHNATE (cont.)


BI. Avian species -- Data not available





B6. Microorganisms, aquatic and soil -- Concentratrion of 2,4,6-trinitroresorcinol (styphnic acid) at which inhibition of cell.multiplication starts: Bacteria (Pseudomonas putida); 100 mg/LAlgae (Microcystis aeruginosa): 0.32 mg/L (12).

B7. Aquatic species, fish and invertebrates - A survey of literaturefrom July, 1974 to the present revealed no data concerning thetoxicity of lead styphnace or styphnic acid (trinitroroeozcinol) toaquatic organii*ms (14). The effects of 2,4,6-trinitroresorcinol onfish are LC5 0,) 96 hours; 2.58 mg/L EC, 96 hours; 0.46 mg/L.,behavioral response (12)a


C1. Phytotoxicity - Data not availala

CZ. Uptake - Data not availlaile

C3. Metabolism - Data not availa!le

1 VI. STANDARDS AND REGUIATIONS

-A- Health

Recomaendad alr1 ndird: TWA 0,10 mg(Pb)/m 3 .

B. Environmental


.•..


VII. DISPOSAL


Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants i 1volve open burning, opendetonation or hauling by a licensed contractor and landfilling. Thishas also been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (15).

B. Alternate Disposal Practices Under consideration b_ Lthte.r

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use atinstallations such as Savanna Army Depot, Tooele Army Depot, andHawthorne Naval Ammunition Depot (16).


Destruction of lead styphnate by chemical decomposition: dissolve in atleast 40 times its weight of 20t NaOH solution (or in 100 times itsweight of 0% ammonium acetate solution) and add sodium dichromateequal to half the weight of lead styphnste, dissolved iu 10 parts oftap watber (1).

Vill. R~EUNCES

Fedoroff, Basil T. and G.E. She.field. 1964. Elo4ia ofExlosives and Related Items, Vol. 4, p. D-380. Army Armament Researchand Dewelopment Command, Dover, NJ,

il 2. IewleF, Gessner G. 1981. The Condensed Chemical Dictionary, lOthed.,p. 609. Van Nostrand-Relnhold, Nev Yor, N.. '

3. Urbanski, To 196. hi r and Technology of Explosives, Vol. 3, p.213. Permagon Press, Elmsford, KY.

4. Saferstien, R. 1977. Critinalistics: An Introduction to ForensicScience, p. 316. Prentice-Hall Incs., Englewood Cliffs, W,.

5. Asplund, J. 1983. S"evi Examples of Modersn Volmtetric Analysis-Methods f tr the Tnapt-;z. of Propellants and High Explosivea. I t.Jahrii..-Fraunhofqi 3'n;•itute tre!,btExplolsivit. 313-335.

f Seamel, So 1980. A Rapid Chemical Analysis of the Ingredients of NOL-BO Primer Kix. Int. Jahrestag-Fraunhofer Ins titue Treib-Explosfivit.339-410.


7. Plunkett, F.R. 1976. Handbook o.F industrial ToxicoloyZ. ChemicalPublishing Co., Inc., New York, NY.

8. Sax, N.I. !979. Dangerous Properties of Industrial Materials, 5thed., p. 771. Van Nostrand-Reinhold Co., New York, NY.

9. Windhoiz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbien, e:Is.1983. The Merck IndeT;, 10th ed. Merck and Co., Inc., Rahwcy, NJ.

10. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substances, Vol. 3, p. 2. NationalInstitute for Occupatioal Safety and Health, Cincinnati, OH.

11. Simmon, V.F., S.L. Eckford, A.F. Griffin, R. Spanggord, and G.W.Newell. Abstracts: Sixteenth Annual Meeting. Tox. and Appl.Pharmoacol. 41:1977.

12. Whong, Wen-Zong and GorL 3. Edwards. 1984. Genotoxic Acitivity ofNitroaromLic Explosives and Related Compounds in SalmonellaTyphimurium Mutation Research. 136:209-215,

13. Verschueren, Karel. 1983. Handbook of Environmental Data on OrganicChemicals, 2nd ed., p. 622-623. Van Nostrand-Reinhold Company, NewYork, NY.

14. Burrows, Dickenson, Dr., and Dr. Jack C. Dacre. 1974. Toxicity toAquatic organisms and Chemistry of Nine-Selected Waterborne PollutantsFrom Munitions Manufacture-A Literature Evaluation. Technical Report7503, AL: A010660. U.S. Army Medical Research and Development Command,Washington, D.C.


16. Forsten, I. 1980. Disposal of Hazardous Toxic Munitions Waste.Proceedings of 1980 National Conference on Enhvironmental Engineering.ASCE Environmental Engineering Division Specialty Conference. 440-575.

LEAD THIOCYANATE

.ý Much of the available data on lead thiocyanate has been reported in a previousstudy by the Atlantic Research Corporation (ARC) entitled A PreliminaryProblem Definition Study of 48 Munitions-Related Chemicals. Data reportedhe~re flects information more recent than that reported by ARC in 1978.



Chemical Formula: PbC2 N2 S2 (1)


Structural Formula: S C,.N

B. Alternate Names and egistry Numbers



CA Name (9Cg): Thiocyanic acid, lead (2+) salt

CA Name (SCI): Same

. RTECS Number: Not available on RTECS

Other Significant Synonyms: Lead sulfocyanate (1)


* Physical State: Powder (1)

Color: White (1)

Odor: Odorless (1)

Melting Point: 190°C decomposes (2)

Solubilities:Water: In about 200 parts cold; in about 50 parts boiling withdecomposition; soluble in alkali hydroxide, nitric acid, andthiocyanate solutions (1).Nonaqueous Solvents: Data not available

Octanol Water Partition Coefficient: N/A



' DAMDI7-84-C-4133 35-1

LEAD THIOCYANATE (cont.)


Vapor Fressure: Data not available



Reactivity: Interaction with calcium and magnesium (2). May reactwith aqueous chlorine to form the highly toxic compound cyanogenchloride (3).


Flammability: Slight, flammable when exposed to heat or flame (2).

Ii. USES

A. Army Unique Use

Fuel used in detonators, primers and igniters (3).

B. Other Uses

"Reverse dyeing with aniline black; manufacture of safety matches andcartridges (1).



This compound must be analyzed by determination of the component parts.Lead can be determined by atomic absorption, polarography orcolorimetrically as stated in the ARC report (3). For thiocyanate,colorimetric, atomic absorption, and high performance liquidchromatography have been reported, All three methods rely on theformation of a dithiocyanatodipyridyl copper (II) complex, which isdetected by each method (4).


Ingersoll et al. (4) reported 100 ppb.

IV. HEALTH EFFECTS

No data updating the ARC report was found.

DAMD17-84-C-4133 35-2U



No information was found regarding the environmental fate or effects oflead thiocyanate which would update the Atlantic Research Corporationdocument. The environmental effects of the compound are chieflyrelated to the effects of lead, which is highly toxic andbioconcentrative. Toxic combustion products of thiocyanate includecyanide and sulfur oxides.


A. Health

3 3TLV: TWA 0.15 mg/m3 as lead; STEL 0.45 mg/mi as lead (5).

B. Environmental


Lead thiocyanate hab a statutory reportable quantity (RQ) of 5000lbs under the Comprehensive Environmental Response, Compensation, andLiability Act. The National Response Center must be notifiedimmediately when there is a release of this compound in an amount equalto or greater than the RQ (6).




B. Alternate Disposal Practices under Consideration by L

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has been

tested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and Hawthorne NavalAmmunition Depot (8).

C. Other Disposal Practices Emploed

Convert to nitrates with a minimum of nitric acid (concentrated),Evaporate in a fume hood to a thin paste. Add about 500 mL water andsaturate with hydrogen sulfide filter wash and dry the precipitate. sPackage and ship to the supplier (9).

DAMD17-84-C-4133 35-3


VIII. REFERENCES



3. Kitchens, J.F., W.E. Harwards III, D.M. Lauter, R.S. Wentsel, R.S.Valentine. 1978. Preliminary Problem Definition Study of 48 MunitionsRelated Chemicals, Vol. IV, Primer and Tracer Related Chemicals-LeadThiocyanate. Final Report, AD A066310. Atlantic Research Corporation,Alexandria, VA. DAMD17-77-C-7057.

4. Ingersoll, D., W.R. Harris, D.C. Bombergen, and D.M. Coulson. 1983.Development and Evaluation of Procedures for the Analysis of SimpleCyanides, Total Cyanide and Thiocyanate in Water and Wastewater. EPA-600/54-83-054. Environmental Monitoring and Support Laboratory.Cincinnati, OH.

5. Federal Register/Vol. 48, No. 102-Proposed Rules.



8. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste,Proceedings of the 1980 National Conference on Environmental"Engineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York, NY.

9. Chemical Systems Search (CIS), Oil and Hazardous Materials TechnicalAssistance Data System (OHMTADS). Accession No. 7217410. 1985.

DAMD17-84-C-4133 35-4

MAGNESIUM THORIUM ALLOY

19 CHEMICAL AND PHYSICAL DATA


Chemical Formula: Mg 2 Th

Molecular Weight: Data not available

Structural Formula: Mg ---- Th--Mg



CA Name (9CI): Magnesium, compound with thorium (2:1); thorium,compound with magnesium (1-2)

CA Name (8CI): Same

RTECS Number: Not available in RTECS

Other Significant Synonyms: None



Color; Data not available



Solubilities:Water; Data not availableNonaqueous Solvents: Data not available


Hvgroscopicity: Data not available




DAMD17-84-C-4133 36-1

MAGNESIUM THORIUM ALLOY (cont.)






Ii. USES

A. Army Unique Use

Casings for electronic weapons systems

B, Other Uses

Data not available


SA. Best Acceptable Method

No analytical methods were found for this compound in a search of thechemical literature from 1967 to the present.

4 B. Limit of Detection

Data not available

7fY3

4-,DAMNI 7-84-C-4 133 36-2


IV. HEALTH EFFECTS

Data on Magnesium thorium alloy was not found. Toxicity of separate parts of

the alloy, used as analogues, appears below.

TABLE IV-1. TOXICITY OF MAGNESIUM THORIUM ALLOY


Magnesium Human Skin Partic- May produce a severe (I)(metal or perfo- ulate local lesion charac-alloy) ration form terized by the evolution

of gas and acute inflam-matory reaction, frequentlywith necrosis; may causelymphangitis that is veryslow to heal

Magnesium Human Intra- Plasma Symptoms of hypermag- (2)salts venous Mg conc. nesemia which may

above occur include flushing2 mmol/L of the skin, thirst,

hypotension due tovasodilation, drowsi-ness, loss of tendonreflexes due to neuro-muscular blockade,weakness, respiratorydepression, cardiacarrhythmias, coma, andcardiac arrest

Thorium Human NS* Acute Has caused dermatitis (3)

Thorium and Human occup. 30 yrs; No reported toxic (4)thorium expos- conc. in effects

compounds ure excess ofcurrentstandards

Colloidal Human, Injec- NS* Tumors at various (4)thorium animal tion siLes attributed to (3)dioxide radioactivity(Thoro-trast)

Thorium Animal Various Acute Low toxicity (4) ( "K compounds routes

DAMDI7-84-C-4133 3b-3


* Not specified

TABLE IV-1. TOXICITY OF MAGNESIUM THORIUM ALLOY (Cont.)


Thorium Dog Inhal- 26-7• O nly toxic effect: (4)compounds ation mg/m for abnormal leucocytes(cont.) 2-10 wk;

mean par-

ticle dia-meter I um

* Not specified


No information was fol~nd regarding the environmental fate or effects ofthe alloy of magnesium and thorium.


A. Health

Data not available

B. Environmental

Data not available

VII. DISPOSAL


Data not available

B. Alternate Disposal Practices Under Consideration by the Armv

Data not available

-Co Other Disporal Practices Employed

Data not available

g DAM• 7-84-C-4133 36-4

t 6,


VIII. REFERENCES

1. Sax, N.I. 1979. Dangerous Properties of Industrial Ma-.rials, 5thed., p. 781-782. Van Nostrand-Reinhold Co., New York, NY.

2. Reynolds, James E.F. and Anne B. Prasad, eds. 1982. Martindale-The

Extra Pharmacopoeia, 28th ed. The Pharmaceutical Press, London.

3. Sax, p. 1031.

4. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial Hygiene and Toxicology, Vol.2A, 3rd revised edition. JohnWiley and Sons, New York, NY.

( 3

"1.$ DAMDI 7-&4,-C4133 36-5

MIREX

Much of the available data on Mirex has been reported in a previous studyLy the Atlantic Research Corporation (ARC) entitled, A Preliminary ProblemDefinition Study of 48 Munitions-Related Chemicals. Data reported hereinreflects information more recent than that reported by ARC in 1978.



Chemical Formula: CO Cl12


Structural Formula:Cl

CiCICI ci C

Cl Cl

C1Cl,

0

B. Alternate Names and Rgsry Numbers


Alternate CAS Registry Number; 6842-16-6

Deleted CAS Registry Numbers: 20594-49-4; 56449-78-6; 12557-88-9;12707-43-6; 12766-04-0

SCA Name (9C) : 1,3,a-Metheno-IH-cyclobutaicd]pentaleue,1, la,2,2,3,3a,4,5,5,5a,5b,6-dodecachlorooctahydro-

CA Name (SC)0: Same

RTECS Number: PC8225000

Other Significant Synonyms: Dechlorane (1),' perchloropentacyclodecane,perc.hlorodihomocubane, hexachlorocyclopentadiene dimer


Physical State: Crystal (1)

Color: Snow-white (1)

DANDI7-84-C-4133 37-1[ "

MIREX (cont.)

Odor: Odorless (1)

Melting Point: Decomposes at 485 0 C (1)

Solubilities:Water: Practically insolubleNonaqueous Solvents: Dioxane 15.3% (room temp.), xylene 14.3% (roomtemp.), benzene 12.2% (room temp.), carbon tetrachloride 7.2% (roomtemp.), methyl ethyl ketone 5.6% (room temp.) (0).

Octanol Water Partition Coefficient: LOG P - 6.89 (2)



Volatility: See Section IV, Alb.

Vapor Pressure: 6 X 10 mm Hg at 25 C (3)



Reactivity: Reacts, with strong oxidizers such as dichromates andchlorine (3).

Stability: Breaks down above 485°C and in sunlight (3).

Flammability: Non-flammable; used as a fire retar-ant (1).

II. USES

A. Army Un~ique Use

Fire retardant in tracer ammunitions.

B. Other Uses

Insecticide, fire retardant for plastics, rubber, paint, paper,electrical goods (1).

DAMDI7-84-C-4133 37-2

MIREX (cont.)


A. Acceptable Methods

Gas chromatography (GC) is a well-established technique for analysis of

Mirex. Electrolytic conductivity detector is especially well-suitedfor this poly-chlorinated compound (4). Recent work has resultedin development of a new electrochemical detector for GC that uses apyrolysis furnace to decompose halogenated compounds with analysis via apotentiometric chloride electrode (5). Driscoll et al. claimed a 1-2

orders of magnitude increase in sensitivity to polychlorinated

compounds such as Mirex.

Bush et al. (6) have developed a high performance liquid chromatographymethod using Ultra Violet (UV) photolysis with electric conductance to

measure common pollutants including Mirex at sensitivity of less than10 nanograms.

Methane chemical ionization (CI) selected ion monitoring (SIM) massspectrometry is the most sensitive method reported. Hergesheimerreported ppt (parts per trillion) sensitivity for polychlorinatedcompounds in complex matricies including Mirex (7).


World Health Organization WHO (4) reported 0.2 pg general and 0.001micrograms/liter for gas chromatography with electolytic conductivitydetector. Driscoll et al. reported a 1-2 order of magnitude increaseover the ECD detector (5).

Bush et al. reported <10 ng for UPLC (6).

Hergesheimer reported parts per trillion for CI-SI?1 massspectroscopy (7).

10

I"

I t

MIREX (cont.)

IV. HEALTH EFFECTS

TABLE !V-1. TOXICITY OF MIREX*


Human oral 50-500 mg/kg Estimated lethal dose (8)

NS** dermal NS Moderate skin irritant (9)

Rat oral 235-3,000 LD50 (10)mg/kg

Rat oral 50 mg/kg Liver hypertrophy (11)single dose;observed for28 days

Rat oral 1.0 mg/kg Liver hypertrophy; (11)(male) (corn oil) for 14 days induction of mixed-

function oxidaseenzymes

Rat oral 5 or 30 ppm No affzcts on liver (11)in diet for up weight; proliferationto 36 mo of smooth endoplasmic

reticulum after 12 mo

Rat oral 50 or 100 ppm Increased incidence of (11)in diet for 18 neoplastic nodules inmo; observed high-dose male rats;until 24 mo of 17 rats from all

groups, 6 animals in-cluding 4 high-dosemales had lver-cell

carcinom; no metau-^ases were observed

Rat NS Acute Mluscle tremors, diar- (U)rhea, and depretionfollowed by death

"Rat Intre- 365 mg/kg (L)(female) perltoneal

Rat dermal 2,000 mg/kg 0-

1. L•rmaclon not LIcluded in the ARC report

No t 7 8 -c -7 4d

Ul"t17-8i4-C-4133 37-4

MIREX (cont.)

TABLE IV-I. TOXICITY OF MIREX (cont.)


Mouse oral 1-90 ppm in Increased liver weights (12)diet for up at 5 ppm and higher; in-to 70 wk creased mixed-function

oxidase activity, totalliver DNA and protein,and mitochondrial res-piration at i ppm after70 wk

Mouse oral 1-30 ppm in Increased liver weights (12)diet for up at 1 ppm in females, atto 18 mo.- 5 ppm and higher in

males; histologicalchanges at 5 ppm andhigher; proliferation cfsmooth endoplaswic re-ticulum observed ultra-structurally at I ppmand above

kabbi de-mal 3.33 or 6.7 g No compound-related (13)mirex bait/kg, gross or histoatho-6-7 hr/d, logical cnangee5 d/wk for 9 wk

Dog oral .1,000 mg!k& LD50 (13)(male) (corn oil)

Dog oral 100 ppm in Liver enlargement (13)diet for 13 wk

Monkey oral 0.25 or 1.0 No effect on liver (14)Smg/kg, 6d!wk weights, liver histo-

for up to 26 logy, or liver ultra-mo structure

Hamster oral 125-250 mg/kg LDS (13)

Duck oral 2,400 mg/kg LDS 0 (10)

" Bird inhalation 1,400 ppm LC 50 (10)

*.Information not included in the ARC report** Not specified

D=7- 84-C-4i33 37-5

MIREX (cont.)

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF MIREX


Rat (Wistar) 1.5-6 Negative (15)dozinant lethial mg/kg/dayassay by gavage

for 10 days

'Stand.rd Ames NS* Negative; test included (14)becterial -,s..y" liver microsomal activation

-Not specified


This substance has been listed as a carcinogen in the Second AnnualReport on Carcinogens (16).

Mirex is covered in the "Preliminary Problem Definition Study onMunitions-Related Chemicals" (1). The ARC report statesthat Mirex has been used as a pesticide and flame retardant forplastics. The Army's principal current use is in tracer mixes. The )material is persistant and mobile in the environment, Its highbioconcentration and biomagnification is noted in the literature.Mirex has been shown to be teratogenic and may also be carcinogenic.Based on the extensive environmental and toxicological studies, use ofMirex has been restricted by the US EPA and the chemical is no longermanufactured in the USA. The small amount used by the military as atracer is imported.

Mirex is one of the most environmentally stable of the organochlorineinsecticies. It degrades slowly and its breakdown products are astoxic and stable as Mirex itself. Hirez bioaccumulates at all trophiclevels and biomagnifies in the food chains. Biomagnification in thefood chain is enhanced by the delayed mortality typical of Mirexpoisoning. Chronic toxicity is a better indicator of the true toxicityof Mirex and is uniformly high (17).

This report is an update; only information since 1978 is discussed

below.A. Enviromental Pate


Ala.o Adsorpt:ion Data not available

,.DAMD17-84-C-4133 37-6

... ............................................ ...... , ' •,-•-

MIREX (cont.)

_ Alb. Volatilization -- Mirex has a very low vapor pressure under normalconditions. The World Health Organization reports that they assumethat release of dust is the principal cause of observed airborneMirex transport (18).

AIc. Leachability -- Mirex has a very low water solubility. Ifconcentrations exceed I ug/l, Mirex would be found in suspendedparticulate matter. Mirex applied to land has been found to betransported to adjacent water bodies (18).

Ald. Bioaccumulation -- BCF: algae = 12,200; snails - 4,900; daphnids,14,650; fish = 2,580; crayfish - 16,860-71,400 (20).as determined with fathead minnow (Pimephales promelas) in 32-dayexposures: 18,100 (2).


A2a. Biodegradation -- Mirex is highly resistant to microbial degradationand thus can persist in soil for long periods. However, it has beenreported that in sewage sludge under anaerobic conditions in thedark, about 80% of mirex was degraded into unknown metabolites (19).

A2b. Hydrolysis -- Aquatic reactions: Exposure to sunlight and UV light baveindicated slow degradation; resulting compounds included chlordeconehydrate, undecachloropentacyclodecane, and nonachloropentacyclodecan-5-one hydrate (20).

A21c. Photolysis -- Mirex undergoes photolytic dechlorination to photomirex(8-monohydroxymirex) and lesser amounts of 5,8-dihydromirex whenexposed to sunlight in organic solvent and in duck eggs, Studiesexamining aged Mirex residues recovered from soil showed fairly largeconcentrations of photomirex (21).

A d. Other chemical reaction -- Data not available

A2e. Half-life - The environmental half-life of Hirex can be many yearsS~(22).


B1. Avian species - Available data indicate low Mirex toxicity to birds(23).



B4. Reptila - &La w-t available

B5. £mplhibiens - Data not available

-. B f6. Hicroor.ganis, aquatic and soil - Data not available

NDMI7-84-C-4133 37-71~. -.

MIR.EX (cont.)

B7. Aquatic species fish and invertebrates -- Mirex degradation productswere found to be highly toxic for fresh and saltwater bacterialcultures and may be more soluble in water than Mirex itself.Exposure of phytoplankton and algae to Mirex result in reducedproductivity and growth rate. Mirex is highly toxic for crustacea.Effects of Mirex on fish are variable (24).


Cl. Phytotoxicity - What little work has been done on Mirex effects onterrestrial plants has shown reduction in germination and emergenceof grass seeds.

C2. Uptake -- Available data indicate uptake accumulation and translocationof Hirex in plants (23).

C3. Metabolism -- Available data indicate no metabolic transformation (23).


A. Health

Mirex meets criteria for proposed OSHA Medical Records Rule (25) and isincluded in the Michigan Critical Materials Register,

B. Environmental

Data updating ARC report not available

VII. DISPOSAL

A. Current Recomended A Disposal Practices

Disposal practices recomended by the U.S. Navy in their ConsolidatedUazardous Item List for DDT, a pesticide of related structure, is todilute or dissolve in a flamable subsiance, followed by burning in anincinerator equipped with an afterburner and a, effluent scrubbgr.Incineration should be conducted at temperatures exceeding 1000 C witha minimut of 2 seconds svell time in the combustion :one. Scrubberoverflow is to be neutralized prior to discharge. Incinerator ashshould be buried in a hazardous or sanitary landfill (26).

While Mirex isoknown to be resistant to pyrolysis even at temperaturesas high as 950 C, it ti believed that incineration using the proceduretbove would destroy most Hirex feed.

8. Alternate Disposal Practies ee dr Consideratlon b the

Data updating ARC report not avaialable

DAMD17-84-C-4133 37-8

MIREX (cont.)


Data updating ARC report not available

VIII. REFERENCES

1. Kitchens, J.F., W.E. Harwards III, D.M. Lauter, R.S. Wentsel, and R.S.Valentine. 1978. Preliminary Problem Definition Study of 48 MunitionRelated Chemicals, Vol. IV, Primer and Tracer Related Chemicals-Dechlorane (Mirex). Final Report, AD A066310. Atlantic ResearchCorporation, Alexandria, VA. DAMD17-77-C-7057.

2. Veith, G.D., David L. Defore, and Barbara V. Bergstedt. 1979.Medsuring and Estimating the Bioconcentration Factor of Chemicals inFish. J. fish Res. board Can. 36-1040-1048.

3. Chemical Fact Sheet-Mirex. 1982. Bureau of Toxic SubstanceAssessment, New York State Department of Health, Albany, NY.

4. World Realth Organization (WHO). 1984. Environmental Health Criteria44-Mirex, p. 12-13. ISBN 92 4 154184 9. World Health OrgaaizatiOn,Geneva, Switzerland.

5. Driscoll, J.N., D.W. Conron, and P. Ferioli. 1984. Comparison of a

New Elctrochemical Detector for Gas Chromatographic Analysis with theElctorlytic conductivity Detector. Journal of Chromstograhy.

302:269-276.

4 •6. Bush, B., R.M. Smith, S.A. Narang, and C.S. Hong. 1984."Photionization Conductivity Detection Limits for EnvirounentalPollutants witha du without Chromphores. Analytical Letters.17(A6) :467-474.

H7. Hargesheimer, E.F. 1984. Rapid Determination of OrganchlorinePesticieds and Polychlorinatid Biphenyls. Use'. Selected Ion Monitoring

Mass Spectrometry. Journal of the Assogiat.', C . ýIclcal AnalyticalChemists. 67(6): 1067'7. - -

8. Goisselin, Robert E., Dr., Dr. Roger P. Smith, 'jr. Harold C. Hodge, andJeanette E. Braddock. 1984, Clinical T of Commercial KProducts, 5th ed. Williams and Wilkins# Baltimore, MD.

9. Hawley, Geesner G. 1981. The Condensed Chemical Dictionary, 10th ed.,p. 697. Vain Moatraad-Rainhold Co., Now York, NY.

1O. Chemical Information Search (CIS), Registry of Toxic Effects (RTECS).* .Accession No. PC8225000. 1985.

* 11. World Health Organiztion (WHO), PP. 26-27.

DAmDI7-84-C-4133 37-9

MIREX (cont.)

12. World Health Organization (WHO), pp. 29.

13. World Health Organizaiton (WHO), pp. 26.

14. World Health Organization (WHO), pp. 30.

i5. International Agency for Reserch on Cancer (IARC). Mongraphs on theEvlauation of the Carcinogenic Risk of Chemicals To Humans, Vol. 20,Soime Halogenate Hydrocarbons. International Agency for Research onCancer, Lyon, France.

16. Second Annual Report on Carcinogens. NT? 91-43, pp. 157-158.

17. World Health Organization (WHO), p. 49.


19. Lal, Rup and D.M. Saxena. 1982. Accumulation, Metabolism, and Effectsof Organochlorine Insecticieds on Microorganisms. MlcrobiologiclReviews. 46(1):95-127.

20. Verscueren, Karel. 1983. Handbook of Environmental Data on OrganicChemicals, 2nd ad., p. 879. Van Nostrand-Reinhold Company, New York,NY.



23. World Health Organization (WHO), po 41.

24, World Health Organiztiou (WHO), p. 34.

25. Federal Register, Vol. 47, No. 82, p. 30420.

26. Consolidated Hazardous Item List (CHIL). NAVSUP PUB 4500. Navy FleetMaterial Support Office, Mechanicsburg, PA.

DAMDI17-84-C-4133 37-10 j

N-EITR0S0DIPHENYLAMIN'E

Much of the available data on N-Nitrosodiphenylamine has been reported in aprevious study by the Atlantic Research Corporation (ARC) entitled, APreliminary Problem Definition Stud_ of 48 Munitions-Related Chemicals. Datareported herein reflects information more recent than that reported by ARC in1978.



Chemical Formula: C Ii N 012 10 2

Molecular Weight: 198.22 (estimated)

Structural Formula:

.NN=O

B. Alternate Nimes and egistry Numbers

CAS 4gistry Jumber: 86-30-6

CA Nc.e (9CI): Benzenamine, N-nitroso-N-phenyl

CA Name (OCI): Diphenylamine, N-nitroso

-RTWS Number, J3J9800000

Other Significant Synonyms: Retarder J, N-Nitroso-N-phenylaniline,Diphenylnitrossaine, NN-Diphenylnitrosamine, N,N-Diphanyl-N-uitrosoamifle

C. ChemicaL and Physical Properties

Physical State: Solid (1)

Color; Yellow to brown or or~age pouder or flakes (1)

Odor: tMldly ar4ie (1)

Melting Point: 64-66°C (!)

V DAiMD17-84-C-4.133 38-1:: •F..•

N-NITROSODIPHENYLA"INE (cont.)

Solubilities:Water: Practically insoluble (1)Nonaqueous Solvents: Soluble in acetone, benzene, alcohol, andethylene dichloride. Somewhat soluble in gasoline (1).

Octanol Water Partition Coefficient: Log P 3.96 (2)


Density (Crystall): 1.23 g/cc (1)





Reactivity: Comparable to benzene (1)


Flammability: Data not available/I

t1. USES

A* Army Unique Use

A degradation product of diphenylazine, a propellant (1).

B. Other Uses

Vulcanization retardant in the treatment of rubber. Currently beingphased out of industry (1).

III. ANALYTICAL HETHODS

A. Best Acceptable Hethod

The Envirosuental Protection Agency published an official method.nurmber 607, for detection of nitrosamines in water. The method callsfor an initial entraction, separation on an alumina column andinjection into a gas chrmatograph equipped with a nitrogen-phosphorus detector.

D-i) •-

S• m [ ..

N-NITROSODIPHLENYLAMINE (cont.)

Difficulty has been reported in separating diphenylamine from N-nitrosodiphenylamine in Method 607 (3). One of the most recentreported methods is a tandem mass spectrometry method by Bunt et al.that eliminated all preparatory steps including chromatography (4).


EPA Method 607 has been reported to 8.22 ug/l (3). Hunt et al,reported a limit of 10 ppb for their mass spectrometry method (4).

DAHDI7.-84-C-4133 38-3

44 2

N-NITROSODIPHENYLAMINE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF N-NITROSODIPHENhYLAMINE*


Rat oral 0, 1,000, or Significantly lower (5)(Fischer 4,000 ppm in survival in high-dose344) feed for 100 females; significantly

wk increased incidences oftransitional-cell car-cinomas of the urinarybladder in high-dosegroups; males: con-trols 0/19, low-dose0/46, high-dose 16/45;females: controls 0/18,low-dose 0/48, high-dose 40/49

Rat oral 1,650 mg/lg LD50 (6)

Mouse oral Males: 0, Chronic inflammatory (5)(B6 C3 F3) 10,000 or lesions of the urinary

20,000 ppm bladder; no significantin feed for incre&ses in tumor in-101 wk; cidences compared withFemales: 0, controls2,315, or5,741 ppm

(time-weighted

average) infeed for98 wk

Hiouse oral 3,850 mg/kg L.DO (6)

Rabbit eye 500 mg/24 hr Severe irritation (6)

"Inforation uded in W QCRo

DAiID17-84-C-4133 38-4

N-NITROSODIPHENIYLAMINE (cont.)

TABLE IV-2. MUTAGENICITY OF N-NITROSODIPRENYLARINE


Salmonella typhimurium 50 ug/plate Mutagenic with microsomes (6)

Rat embryo cells 1,500 ug/L Oncogenic transformation (6)

-' Rat liver 300 umol/L DNA Damage (6)

Rat liver 500 nmol/L Unscheduled DNA synthesis (6)

Hamster embryo cells 5,300 ug/L Oncogenic transformation (6)

Hamster kidney cells 97 mg/L Oncogenic transformation (6)

Hamster fibroblasts 100 umol/L Sister chromatid exchange (6)

Various assays in pro- Negative results (7)karyotes and eukaryotesfor muragenicity andother chromosomaleffects

* V. ENVIROMENTAL EFF•CTS





Alc. Leachability - Data not available

Aid. Bioaccumulation - Log BCF - 2.34, bioconcentration in bluegill sunfish(Lepeomis macrochlrus), 14-day exposure (8).

AZ. Transformation - Data not available

A2&. Biodegradation N--•Nitrosod6phenylasine was shown to biodegradeeasily. Mcliuitization to 5 mg/L in culture sedia was rapid;aceliaitization to P0 *S/L, gradual. Biodegradation In tests tingedftom 87% to 100% at 5 ug/L and fros 47Z to 98% at 10 xg/L dosage (9).

A2'b. Htydrolysis - Data not available

DANDI 7-84-C-4 133 38-5

,38-



A2d. Other chemical reaction -- Data not available




B. Mammalian wildlife species -- Data not available




B6. Microorganisms, aquatic and soil -- N-nitrosodiphenylamine was found to

be inactive in bacterial DNA repair and reversion tests and yeastmitotic recombination assays made to assess the qualitative nature ofthe compound's genotoxic potential (10).

B7. Aquatic species (fish and invertebrates) -- Data not available



N C2. Uptake -- Data not available

C3. Metabolism -- Data not available'

VI: STANDARDS AND REGULATIONS

A. health

Data not available

B. Environmental


N-Nitrosodiphenylamine has a statutory reportable quantity (RQ) of Ilb. under the Comprehensive Environmental Response, Compensation and

Liability Act. The National Rtsponse Center must be notifiedimmediately when there is a release of thi compound in an amount equal (to or greater than the RQ (11).

. 3

,-DAMD 17-84-C-41 3 3 38-6

N-NITROSODIPHENYLWAINE (cont.)

VII. DISPOSAL


Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve open burning, opendetonation or, occasinnally, hauling by a licensed contractor andlandfilling. This has also been confirmed by private communicationsfrom the U.S. Army loxic and Hazardous Mnterials Agency (USATHAMA)which has the responsibility to review current disposal practices andto develop plans for futur• disposal practices (12).

B. Alternate Dispogal Practices uiider Conaideration l the Ary

Future plans for disposal of waste explosives and propell-ents areprojected to emphasize fiuid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savann Army Depot, Tooee Army Depot, and Hawthorne NavalAmmunitiou Del , k.)


Data not available

4-VIII. REFERENCES

10I Kitchens, J.F., W.E. Har-oards III, D.H. Lauter, R.S. Valentine.1978. Preliminary Problem Definition Study of 48 Munitions Related

Chemicals, Volume II, Propellant Related Chemicals-N-Nicrosodiphenylamine. final Report. AD A066308. Atlantic ResearchCorporation, Alexandria, VA. DAMD17-77-C-7057.

2. Chemical Information System (CIS), Information System for HazardousOrganics in Water (ISHOW). Accession No* 302105. 1985.

3. Millar, J.D., R.E, Thomas, and H.J. Schat~enberg, 1984, EPA MethodStudy 17, Rethod 607-Nitrosamines. EPA 600/54-84-051. EnvironmentalMonitoring and Support Laboratcry$ CincinuatL,, OH.

4. Hunt, D.F., J. Shabonowitz, J.M. Harvey, and M. Coates. 1985, Schemefor the Direct Analysis of Organics in the Environment by Tandem MassSpictrometry, Analytical Chemistry. 57(2):525-537.

5. National Cacmtr Institute (NCI). Sioaasay of N-Nitrosodiphanylamine forPossible Carcinogenicity. NIH Publication No. 79-1720. National

- Institute for Occupational Safety and Health, Cincinnati, OR.

DAMD17-84-C-4133 38-7


6. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substances, Vol. 2. National Institute forOccupational Safety and Health, Cincinnati, OH.

7. World Health Organization (WHO). 1982. IARC Monographs on theEvaluation of the Carcinogenic Risk of Chemicals to Humans-Some AromaticAmines, Anthraquinones, and Nitroso Compounds, and Inorganic FluoridesUsed in Drinking Water and Dental Preparations. Vol. 27. InternationalAgency for Research on Cancer, Lyon, France.

8. Dialog, Environmental Fate (Envirofate). Accession No. 240714. 1985.

9. Tabak, Henry H., Stephen A. Quane, Chazles I. ftashni, and 'dwin F.Barth. 1981. Biodegradability Studies w/Organic Priority PollutantCompounds. Jo-jrnal WPCE. 53(10):1503-1518.

10. Mc~regor, Douglas B., Colin G. Riach, Ronan M. Hastwell, and Jack C.Dacre. 1980. Genotoxic Activity in Microorganisms of Tetryl, 1,3-Dinitrobenzene and 1,3,5-Trinitrobenzene. Environmental Hutagenesis.2:531-541. - . . . .. .

11. Comprehensive Environmental Response, Compensation and Liability Act,sec. 102 and 103 (1980).

12. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communication)* 1985.

13. Forsten, 1. 1980. Disposal of Hazardous Toxic Munition Waste._Proceedi48s of the 1980 National Conference of EnvironmentalEngineerig. New York, July 8-10, 1980. ASCE Environmental EngineersDivisiou, New York.. 440-575.

DAHD17-84-C>4133 3-8

1-NITRO-2-PROPANOL

CHEMICAL AND PHYSICAL DATA


Chemical Formula: C3t, 7N03

Molecular Weight: 105.09 (Estimated)

Structural Formula:

B. Alternate Names and Re-istry Numbers

CAS Regisvry Number: 3156-73-8

CA Name (9CI): 2-Propanol, 1-nitro

CA Name (BCI): Same

RfECS Number: Data not available

Other Significant Synonyms: NPL (1)

C. Chemical and Physical Propcrties

Pbysical State; Data not availabl.


Odor: Deta uot available


Solubilities;,Water: Data not available

IF .-; Vonaqueous Solvents: Date: not available

Octanol Water Partitioa Coeiiicieut: Data t.t available

Hygroacopicity: Data not available


( NW1T-84C--4133 39-1

jz-77.

I-NITRO-2-PROPANOL (cont.)







Flammability: Flash point - 930C; autoignition temperature - 420 0 C (1).

II. USES

A. Army Unique Use

Explosive

B. Other Uses

Data not available

III. ANALYTICAL METUODS


No analytical methods were found in a computerized search of ChemicalAbstracts dating back to 1967. Gas chromatography is the most promisingtechnique for development of new methods.


Data not available

DAMD17-84-C-4133 39-2

1-NITRO-2-PROPANOL (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF I-NITRO-2-PROPANOL


1-Nitro-2-propanol No toxicity datalocated; data onanalogues appear below.

Nitrates human oral Large amounts produce (2)dizziness, abdominalcramps, vomiting,bloody diarrhea, weak-ness, convulsions, andcollapse; small re-peated doses may leadto weakness, headache,and mental depression

2-Nitroethanol Mouse intra- LD 50 2,000 mg/kg (3)peri-toneal

( 2-Nitro-61,3-propanediol Mouse intra- LD50: 765 mg/kg (3)peri-"toneal

2,2-Dinitro-l-propanol Mouse intra- LD50:280 mg/kg (3)peri-• toneal

3(3Isopropyl nitrate Mouse inhala- LCLo 65 g/ 2hr (3)

tion

n-Propyl nitrate Rabbit intra- LD5 0200 mg/kg (3)F venous

Dog intra- LLo 200 mg/kg (4)venous

Cat intra- 100 mg/kg (4)Ven ou s:•

I.7-,

_. DAMD17?-84-C-"4133 39-3 ••

V.• -

I-NITRO-2-PROPANOL (cont.)


No information was found regarding the environmental fate or effects ofi-nit ro-2-propanol.

VIl STANDARDS AND REGULATIONS

A. Health

Data not available

B. Environmental

Data not available

VII. DISPOSAL


Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve open burning, opendetonation or, occasionally, hauling by a licensed contractor andlandfilling. This has also been confirmed by private communicationsfrom the U.S. Army Toxic and Hazardous Materials Agency (USATHAMA),which has the responsibility to review current disposal practices, andto develop plans for future disposal practices (5).

B. Alternate Disposal Practices Under Consideration by the Army



j Data not available

V1II. REFERENCES

I. Snook, R.W. 1978. Major Component Safety Data Statement-1-Nitro-2-Propanol. No, 701. U.S. Army Armament Research and DevelopmentCommand, Dover, NJ.

-2. Sax, N.I. 1979. Dansero's Properties of Industrial Materials, 5thed., p. 853. Van Nostrand-Reinhold Co., New York, NY. (NY)

S- DAMDI7-84-C-4133 39-4

.. . ,

1-NITRO-2-PROPANOL (cont.)

3. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registry:of Toxic Effects of Chemical Substances, Vol. No. 2. National

Institute for Occupational Safety and Health, Cincinatti, OH..

4. Tatken and Lewis, Vol. 3.


6. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference on EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575.

..

X 4

Ali

DANDI7-84-C-4133 39-5

VX

2-NITRODIPHENYLAMINE

Much of the available data on nitrodiphenylamine has been reported in aprevious study by the Atlantic Research Corporation (ARC) entitled APreliminary Problem Definition Study of 48 Munitions-Related Chemicallso Datareported herein reflects information more recent than that reported by ARC in1978.


A. Structural and Chemical Formulas and Molecular WeightChemical Formula: C12 H1N202


Structural Formula:

'l N

H NO2

B. Alternate Names and ry Number


CA Name (9CI): Benzenamine, 2-nitro-N-phenyl

CA Name (8CI): Diphenylamine, 2-nitro

RECS Number: Not available on RTECS

Other Significant Synonyms: o-Nitro-N-phenylaniline, o-Nitrodiphenylamine, 2-Nitro-N-phenyl beazenumlne

C# hemcaland ______ Properitis"•!C. Chemical, __ Physical _____

Physical State. Crystalline powier (1)

Color: Rad-broun (1)

DAKID*17-84-C-4133 40-19z1

2-NITRODIPHENYLAMINE (cont.)


Boiling Point: 224° C (2)

Melting Point: 75-760C (0)

Solubilities:Water: Data not availableNonaqueous Solvents: Data not available


Hygroscopicity; Data not available





Reactivity: Combustible




Flammability: Slight (2)

II. USES

A. _.Z~ Unique Use

Data not available

B. Other Uses

Stabilizer for nitroglycerin, chemical intermediares

DAMHI17-84-C-4133 40-2




Bender reported qualitative and quantitative determinations of 2-nitrodiphenylamine and other components of smokeless powders by highperformance liquid chromatography with ultraviolet or thermal energyanalyzer detectors.

Thin-layer chromatography and high performance thin-layer chromatographywith liquid chromatography, have been reported by Ammann et al. toanalyze the stabilizers iu double-base propellants including 2-ni trodiphenylamine.


Reductive and oxidative electrochemical detection with liquidchromatography is applied to the determination of explosives-e.g.nitroglycerin, 2,4-dinitrotoluene and diphenylam;Lne in militaryexplosives and single- and double-base smokeless gunpowders (3).

l4

3.

DAMD17-84-C-4133 40-3


IV. HEALTH EFFECTS

TABLE IV-1. MUTAGENICITY AND RELATED EFFECTS OF 2-NITRODIPHE.NYLAMINE*


E. coli 100 ug- Not active with or without Aroclor (4)W3110/polA+ 10 Mg 1254-induced rat liver S9p3478/polA

S. typhimurium NS** Nonmutagenic with or without (4)TAIO0, TA1535, Aroclor 1254-induced rat liver S9TAM537, TA1538

S. cerevisiae D5 NS Did not produce mitotic recombination (4)with or without Aroclor 1254-inducedrat liver S9

*Information not included in the ARC report** Not specified






Ac.l Leachability - Datea not availablet Aid. Bioaccumulation-- Data not available

A2). Transform*tion a- ata not available

A2a. Biodegradation - Data not available

.AZb. Hydrolysis -- Data not available

AUC. Phoatolysis - Data not available

A2d. Other chemical reacticm Data tot sv•alabl

A2e. Half-life o, Data siot Available

B. Uffects on attisall

DARD17-84-C-4133 40-4







B6. Microorganisms, aquatic and soil -- 2-Nitrodiphenylamine was found tobe inactive in bacterial DNA repair and reversion tests and yeastmitotic recombination assays made to assess the qualitative nature ofthe compound's genotoxic potential (4).

B7. Aquatic species fish and invertebrates - Data not available



Ca. Uptake -- Data not available

C0. Metabolism - Data not av<4ilable


A. iHealth

Data not available

B. tnvtronmental

•Data not available

VII. DISPOSAL

Current Apcommanded • Dispoal Practices

Review of past Installation Asesevment Reports ind.cates that currentmethods of disposal of vas'e explosivea and propellants involve openburaing, open detonation or hauling by a licensed contractor andleadfilling. Current use of methode discussed above has also beenconfirmed by private communications from tbA U.S. Amy Toxic andUizardous Materials Agency (USIAThM). Uhich has the rosponsibility torevlew current disposal practices, and to develop plans for futuredisposal practice (5).

DAMtD7-8-C-4133 4-


B. Alternate Disposal Practices under Consideration IX the Army

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and Hawthorae NavalAmmunition Depot (6).


For 4-nitrodiphenylamine, the following disposal method is given:Dissolve or mix the material with a combustible solvent and burn in anincinerator equipped with an afterburner and scrubber (7) Also,Eastman Kodak Company recommends disposal in an approved incineratorequipped with an afterburner and a scrubber (8).

VIII. REFERENCES

1. Hawley, Gessner G. 1981. The Condensed Chemical Dictionar, 10th ed.,,p. 732. Van Nostrand-Reinhold Co., New York, NI.

2. Batson, R. 1983. Hazardous Component Safety Data Sheet-2-NitrodiphenylamAne. No. 405. U.S. Army Armament Research andDevelopment Command, Dover, NJ.

3. Bratin, K., P.T, Kissinger, R.C. Briner, and C.S. Bruntlett. 1984.Detervination of Nitro Aromatic Nitramlne, and Nitrate Ester ExplosiveCompounds in Explosive Hixtures and Sunshot Residue by ".quidChromatography and Reductive Electrocbehica.l Detection. Anal. Chem.Act&. 130(2):295-311.

4o McGregor, Dsuglas Bo, Colin G. Riach, Ronan R. Hastmell, avtd Jack C.Dacre. 1980. Genotoxic Activity in Microorganisms of Tetryl, 1,3-Dinitrobetmene and 1,3,5-Trinitrobeusene. 1980. EnvironmentalMutmgeneas. 2:531-541.

5. David Renard, U.S. Army Toxic and Hazardous 1•aterials Agency, toJ. Carl Uhruacher (persona: communication), 1985.

6. Foroten, .. 1980. Disposal of Hazardous Toxic Munition Waste.Proteeadttmjt of the 1980 National Conference of EnvironmentalEngineer n. New Vork,' July 8-10. 1980. SCE Enuvironaautal EngineersDivision, New York. 440-575.

.-7. A~ldrich Chemical Co. 1984-1985. Aldrich Catao!andok ie

Chamhicagl, p. F15-F16. Aldrich Cheical Co., Milwaukee, WS.

___.__ KOAK______ aos195 Chemical N.3906,p.372 EWAs Xodim Company, Rochrter, W.

DAHPIf 7-84-C ,133 40.6

V,'+.

CCTAC0%LOR -4iRBANILIDE

it CHEMICAL AND PHYSICAL DATA


Chemical Formula: C1 3 H4 Cl8N20

Molecular Weight: 487.8 (estimated)

Structural Formula:

Cl Cl

NNC"00

L Cl

B. Al•ernate Names and Registry Numbers


Ca Name (9CI): Urea, N,W'-dichloro-NN t -bis (2,4,6-trichlorophenyl)-

CA Name (8CI): Carbanilide, (NN',7,2t.,4,4',6,6'-) octachlor

RTECS Number: Not in RTECS

Other Significant Synonyms: C02, Sym-dichlorzbis (2,4,6-tri-chlorophenyl) urea


* Physical State: Solid (I)

Color: kWhito, turns pink to red with decomposition (1)

Odor: Uhlorine (1)

MeltinC Point: Decomposes on heating above 150°C (1)

"DAID17-64-C-41•3 41-1

OCTACHLOR CARBANILDE (cort.)

Solubilities:Water: Insoluble (1)

It Nonaqueous Solvents: liot ethanol; glacial acetic acid (I)

Octanol Water Partition Ooa':ficiunt" Data not available

lHygroscopicity: Not hygroscopic

Den=ity (Crystal): Data not available


Vapor Pressure: 2mm Hg (1)

Specific heat: 43 kcal/mole (1)

HeaL of Combustion: Data not available

Reactivity: Fxplosive with compounds that react with chlorine (1).Octachlor carbanilide reacts explosively with dimethylsulfoxide(DMSO) (2).

Stability: Unstable; decomposes photocbemically and in •he presence ofoxygen. Must be kept in dark and under vacuum (1).


II. USES

A. A Unique Use

Chlorinating Agent (1); ingredient in anti-chemical agent impregnationmixture, often used to impregnate clothing.

B. Other Uses

Potential use as fire retardant, bactericide, and anti-vesicant (3).

III. ANALYTIrZ;. MTODS

A, Beat Ac tabla Rthod

Nn methods of analysis were found in a search of Chemical Abstractsfrom 1967 through the present.


Data not available

flMD17--8-C-4133 41-2

KV.

OCTACELOR CARBANILIDE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF OCTACHLOR CARBANILIDE


Octachlor carbanilide No toxicity data located;(N,N' ,2,2' ,4,4' ,6,6'- data on structural analo-Octachlorocarbanilide) gues and chemical classes

follow below

2.2',4,4',6,6'-Hexachloro- Rat oral Mortality: (4)carbanilide 1/10 at 50 mg/kg,

0/10 at 100 mg/kg

2,3',4'-Trichlorocarbanilide Mouse intra- LD50o: 63 mg/kg (4)venous

3,4,4'-Trichlorocarbanilide Mouse intra- LD5 0 : 2,100 mg/kg (4)peri-toneal

1,2,3-Trichlorobenzene, NS* NS Moderate irritant (5)1,3,5-TrLchlorobenzene to skin, eyes, and

( •mucous membranes;causes hair loss;liver injury has

been reported with1,2,3-trichloro-benzene

Hypochlorous acid Human local Highly irritating (6)(available chlorine) to skin, eyes, and

mucous membranes

Human inges- Irritation and (7)

tion corrosion of mu-cous membraneswith pain ad vo-miting; a fall inblood ptessure,delirium, andcoca may occur

Human inhal- Coughing, choking; (7)ation may cause-severe

respiratory rractirritation and pul-

D 4M17-84-C-4133 41-3

"iii,

OCTACHLOR CARBANILIDE (cont.)


Little information was found regarding the environmental fate oreffects of octachior carbanilide.

Octachior carbanilide decomposes at high temperature with the formationof Sym-2,4,6-trichlorophenyl urea (8).


A. Health

Data not available

B. Environmental


VII. DISPOSAL

A. Current Recommendad &ryDsoa Practices

The disposal practice recommended by the U.S. Navy in theirConsolidated Hazardous Item List for Impregnite, a related compoundused for a similar purpose, is burning in an incinerator equipped withan effluent scrubber. Scrubber overflow is to be neutralized prior todischarge. Incinerator ash should be buried in a hazardous or sanitarylandfill (9).

B. Alternate Disposal Practices Under Consideration ýj theAr

Data not available

C. Other Disposal Practices Emloe

D ata not available

VIII. REFERENCES

1. Clifford Owens. Rutgers University,, to P. P. Werachulz (personalcommunication). 1985.

2. Chemical Abstracts On-Line, Chemical Abstracts System (CAS). AccessionNo. CA89(7):59390to

3. Chemical. Abstracts On-Line, Chemical Abstracts System (CAS). AccessionNo., CA92(12):95127b.

flAND17-84wIC-4133 41-4

........

OCTACHLOR CARBANILIDE (cont.)

4. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substances, Vol. No. 2, p. 852.National Institute for Occupational Safety and Health, Cincinnati, OH.

5 Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5th

ed., p. 1043. Van Nostrand-Reinhold Co., New York, NY.

6. Sax, p. 739.

7. Reynolds, James E.F. and Anne B. Prasad, eds. 1982. Martindale-TheExtra Pharmacopoeia, 28th ed. The Pharmaceutical Press, London.

8. Chemical Abstracts On-Line (CAS ON-LINE), Chemical Abstracts System(CAS). Accession No. CA97(1):5654d.


Si )

K

AA

1'1

_ANDI 7-84-C-4133 41-5

p-NITROPHENOL

I.- CHEMICAL AND PHYSICAL DATA

A. Structural and Chemical Formulas and Molecular Wih

Chemical Formula: C H. NO3 (1)


Structural Formula:

OH

N02

Be Alternate Names and Registry Numbers


CA Name (9C1): Phenol, 4-nitro

CA Name (8C1):. Phenol, p-nitro

RTECS Number: S&1275000

Othe Sinfcn1yoys4-yrxyirbnee -yrxntobenz ene

C, Chemical and Physical Pro erties

Physical State: Crystals (1)

Color: Colorless to slightly yellow (1)

__ Odor: Odorless (1)

Maelting Point: 113-!1140C; sublimes (1) .

XDAiD17-84-C-4133 42-1

p-NITROPKENOL (cont.)

Boiling Point: 279 C; decomposes (2)

Solubilities:Water: Slightly soluble in cold water; soluble in solutions of fixedalkali hydroxide and carbonates (1): 1.6% at 25°C; 2.7% at 900 C (3).Nonaqueous Solvents: Soluble in alcohol, chloroform, ether (1).


Dissociation Constant: 7.0 x 10-8 (5)


Density (Crystal): 1.270 g/cc

Volatility: Sublimes (1)

Vapor Pressure: Less than 1 mm Hg at 38 C



S* Reactivity: Data not available )Stability: Data not available

Flammability: Slightly ,flammable; combustable solid, may thermally

decompose in absence of air (3).

II. USESA. Army Unique Use

Explosive

B. Other U-.es

Acid-base indicator (0.1% alcohol solution, pH: 5.6, colorless; pH:7.6, yellow) (1). Intermediate in organic synthesis; production ofparathiou; fungicide for leather (3).

DAMD17-84-C-4133 42-2" * -' - ? 4"

p-NITROPHENOL (cont.)

TII. ANALYTICAL METHODS


Two high pressure'liquid chromatographic methods for determining p-nitrophenol in complex was tewater matrices have been reported. Nielenet al. (6) reported that using precolumn separation and diode-arraydetection, 29 chemicals found in wastewater, including p-nitrophenol,can be separated and quantitized in a fully automated system.Kruempelman and Danielson (7) reported the use of Picolyl Kel-f toseparate nitrophenols.

Eichelberger et al. (8) reported success using both packed column andfused silica capillary column GC/MS. Chudyk et al. (8) reporteddetecting p-nitrophenol in contaminated groundwater in situ at a depthof 25 m by laser-induced fluorescence at below parts-per-billion level.


Eichelberger et al. (8) reported 16.3 micrograms/liter for the packed

column method and 20 micrograms/liter for the capillary column.

(AD78--134-

77

p-1NITR0PHEN0L (cont.)

IV. HEALTH EFFECTS

TABLE IV-1 * TOXICITY OF P-NITROPHENOL

Species Route Effects Reference

Human inhalation, Headache, drowsiness, nausea, (0ingestion, loss of consciousness; blueskin color in lips, ears, and

fingernails (cyanosis)

Human local Dust is irritating to eyes, (10)nose, and throat; solid isirritating to skin and eyes

Human oral Estimated lethal dose: (10)50-500 mg/kg

Test animals N*Central and peripheral vagus (12,13)stimulation, central nervoussystem depression, methemoglo-binemia, dyspnea, and hyper-

thermia

Rat oral LD50 : 350 mg/kg (14)

Rat subcutaneous LD o: 200 mg/kg (14)

house oral L.D5 : 380 mg/kg (14)

House intra- L5075 mg/kg (14)peritoneal

Guinea pig subcutaneous LD, 200 mg/kg (14)"Mo

Dog intravensous LDLO: 10 mg/kg (14)

CatNS LD: 150 mg/kg (14)

Pigeon intra- LD : 65 mg/kg (14)muscular L

Frog subcutaneous LDL: 60 mg/kg (14)

*Not spec$.fied

DU7-84-C-4133 4-DAMD- 42-4


TABLE IV-2 * MUTAGENICITY AND RELATED EFFECTS OF 2-NITROPHENOL


Escherichia coli 50 umol./L Induction of DNA damage (14)

Microorganism 10 mg/plate Effects on DNA repair (14)(unspecified)

Hamster fibroblasts 1 mmolIL Inhibition of DNA syn- (14)thesis


A* Environmental Fate

Al. Transport

Ala. Adsorption -Tests performed on four soil types reported that p-nitrophenol appears to follow a Freundlich Isotherm for soiladsorption. Freundlich parameters k and n appear to correlate withliammet (G) and hydrophobic (pi) parameters (5)o


Ale. Leachability -Data not available

Ald. Bioaccumulat ion - The strongly hydrophobic nature of p-ni trophenolaugges ts that it could accumulate in cell lipids, particularlymembrane lipid bilayers. The kinetics of killing of culturedmammalian calls revealed that the cells became more sensitized to thepollutant with time of exposure, and this may also reflect a time-dependent accumulation of the compound into the hydrophobic regions

4 of the membranes (15).

A2. Transformation -Data not available

A2a# Biodegradation - Adapted culture: 22 removal after 48-hourincubation, feed; 200 mg/Lo Decomposltion by a soil microf lore in 16~

carbon source: 95.02 COD removal at 17.5 ag CO)D/& dry inoculum/hI.Lag period for degradation of 16 mgIL bg wastewater st pU 7.3, 0 WC:

* 3-5 days; soil suspension at pH '7.3, 30 C: 7-14 tlayu. P-klitrophenolwas found to biode-zade rapidly under both aero'bic and anaerobicconditions In the presence of ezogenout orgsxAi nutrients,, but itspersistence increased considerably in the absence of such nutrients

DMM7-8-C(17).2-












B6. Microorganisms, aquatic and soil - The o-. m- and p-nitrophenolsreduce the rate of algal photosynthetic oxygen production by asmuch as 70% at the relatively high exposure of 50-100 mg/L (18).

Toxicity threshold (cell multiplication inhibition test): bacteria(Pseudomonas putida), 4 mg/L; algae (Microcystis aeruginosa), 56.0mg/L; green algae (Sceneedesmus quadricauda), 7.4 mg/L; protozoa( ihon sulcatu0.83 g/L; protozoa (Uronema parduczi Chatton-Lwoff), 0.89 mg/L (16).

B7. Aquatic species, fish and invertebrates - Fish: Vairo-n (F): TLm 6 hr:distilled water: .4-6 mg/L; hard water. 30-33 mg/L (16).

Daphnia magna: 24-hour LC5 o: 24000 ug/I1(19).

Lepomilmacrochirus: 24-hour LC50 ; 12000 ug/L; 96-hour LCSO: 8300 ug/L (21).

•;• ~ ~Shrimp (_C.agnon F~e.mstinosa=): 96-hour Letha,1 threshold: 26.4 rag/L;

Clam (M& arenaria)i 96-hou ethal threshold: 29.4 tg/L; (22)


1C. Phytotoxicity -. Data not available

C2. Uptake - Data not avail4ble

;..:";, •C3. -etabolstm - Data. not available . .

DAND17-84-C-4133 42-6

AV. - -_____



A. Health

Data not available

B. Environmental

The compound p-nitrophenol has a statutory reportable quantity (RQ) ofI lb. under the Comprehensive Environmental Response, Compensation andLiability Act. The National Response Center must be notifiedimmediately when there is a release of this compound in an amount equalto or greater thrn the RQ (23).

VII. DISPOSAL


Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve open burning, opendetonation or hauling by a licensed contractor and landfilling. Thishas also been confirmed by private communications from the US. ArmyToxic and Hazardous Materials Agency (USATHAKA), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (24).

B. Alternate Disposal Practices Under Consideration • the A

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by APAADCOM and is planned for use atinstallations such as Savanna Army Depot, Tooele Army Depot, andHawthorne Naval A~munLtion Depot (25).


Wastewater treatment: ion exchange; adsorption on Amberlite XAD-2; 100retention effective; influent 04ppe, effluent nil (19).

VIT.I I. •iUENCES

S Windholz, H, So Sudavori, R.F. Blumetti, and E.S. Otterbein, ads.SThe Merck , 10th ed. vp. 950. Karck and Co., Inc.. Rahway,

0 • Weast, R.C. 1968. CRC Handbook of Cmlet Physics, 48th ad.,S..... ~~p. C-.470. ZGGle•c ....- ;r- CO..The Chemical bClveland OH.

42-T7


3. Chemical. Information System (CIS), Oil and Hazardous M1aterialsTechn~ical Assistance Data System (OHH1TADS). Accession No. 7800022.1985.

4. Chemical Information System (CIS), Information System for HazardousOrganics in Water (ISHOW). Accession No. 303717. 1985.

5. Artiola-Fartuny, Juan and Wallace H. Fuller. 1982". Absorption ofSome Monohydroxybenzene Derivatives by Soils. Soil Science. 133(l):18-25.

6. Wie2.en, M.W.F., 0.A. Th. Brinkman and R.W. Frei. 1985. IndustrialWastewater Analysis by Liquid Chromatography with PrecolumnTechnology and Diode-Array Detection. Anal. Chem. 57.-806-810.

7. Kruempelman, Haribeth and Neil D. Danielson. 1985. LiquidChromnatographic Characterization of Picolyl Kel-F as a Reverse-Phase,Weak Anion Exchange Column Packing. Anal. Chem. 570340-346.

8. Eichelberger, James W., Edward H1. Kerns, Paul Olynyk, and William L.Budde. 1983. Precision and Accuracy in the Determination of Organicsin Vater by Fused Silica Capillary Column Gas Chromatography/MIassSpectrometry. Anal. Chem. 55:1471-1479.

9. Chudyk, Wayne A., flichael H. Carrabba, and Joniathan E, Kenny. 1985.Remote Detection of Groundwater Contaminauts Using Far-UltravioletLaser-Induced Fluoreecente, Anal. Chem* 57:.1237-1242.

10. U.S. Coast Guard. 1978. Chemical Ua-zardous Response InformationSystez (CHRlS) Hazardous Chemical Data-p-Nitropbenol. U.S.Department of Transportation, Washington, D.C.

11. Gosselin, Robert E., Dr., Dr. Roger P. Smith, Dr. Harold C. Hodge,and Jeanette E~. Braddock. 1984. Clinical Toicolo&Xo C~rcaProducts, 5th ad. Williams & Wilikins, Balti~mor, tED.

12. Clav-ton, George D). and Florence B. Cl~aytou, eds. 1981. Patty'sIndustrial HXgiene ad T~o lo08, Vol. 2U, 3rd revised .di't1on

13. Sax, N.l. 1979. Da erous roertie; of industrial Materials, 5thet., .84. aN ost~m&-R~einbold Coo, New# York. IJY.

14. Chemical lutoreation. System (CIS), Registry of Toxic Effects ofChemical Substonces (RTECS). Accessiott No. S=275000. 1985.

4

LIM17-84-C-4133 42-8


15. Packham, E.D., C.L. Duxbury, C.T. Mayfield, W.E. Inniss, J. Kruen,and J.E. Thompson. 1982. Quantitative Analysis of Pollutant-InducedLethal and Sublethal Damage in Cultured Mammalian Cells. Bull.Environ. Contam. Toxical. 29:739-746.

16. Verschueren, Karel. 1983. Handbook of Environmental Data on Organic

Chemicals, 2nd ed., p. 919. Van Nostrand-Reinhold Company, NY.

17. Dialog, Pollution Abstracts. Accession No. 82-05874. 1985.

IS. Huang, J.C., and E.F. Gloyna. 1968. Effect of Organic Compounds on

Photosynthetic Oxygenation I. Chlorophyll Destruction and Suppressionof Photosynthetic Oxygen Production. Water Res. 2:347-366.

19. Verschueren, Karel. 1983. Handbook of Environmental Data on OrganicChemicals, 2nd ed., p. 920. Van Nostrand-Reinhold Company, New York,NY .

20. Chemical Information System (CIS). Aquatic Information RetrievalSystem (AQUIRE). Accession No. 221304. 1985.

21. Dialog, Auatic Information On-line (AQUIRE). Accession No. 223960.1985.

22. McLeese, D.W., V. Zitko, and R.R. Peterson. 1979. Structure-Lethality Relationships for Phenals, Anilines and Other AromaticCompounds In Shrimp and Clams. .2eosphere. (2):53-57.

23. Comprehensive Environmental Response, Compensation and Liability Act,sec. 102 and iO (1980).

24. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communication)- 1985.

25. Forsten, I. 1960. Disposal of Hazardous Toxic Munition Waste.

Proceedings of the 1980 Notional Conference of Env~romental

r . New York, July 8-10, 1980o ASCE EnvironmentalEngineers Division, Neu York. 440-575.

SI•EDAMD7-84--C-4,133 42-9

V429

PENTAERYTHRITOL TETWANITRATE



Chemical Formula: CsH8 N4 01 2


Structural Formula:

H2C-O- NO 2

02 N O-CH2 --C -CHM 2-- O- NO2HI H 0 - N022C---- 2



CA Name (9CI): 1,3-propanediol, 2,2-bis (nitrooxy) methyl-dinitrate(ester)

CA Name (8CI): Pentaerythritol, terranitrate

RTECS Numoer: RZ2623000

"Other Signficant Synonyms: 2,2-Bis(dihydroxymethyl)-i,3-propanediol,

tetranitrate; Nitropentnerythritol; PETN


Physical State: Tetragonal crystals (1)

Color: White (2)

Odor: Odorleso

Melting Point: 141 C (2) (

DAMDI7-84-C-4133 43-1

PENTAEMRYTRITOL TETRANITRATE (cont.)

Solubilities:Water: Practically insoluble (3); 0.01g/100 g at 50°rNonaqueous Solvents (200C): Acetone, 24.95% (very soluble); methylacetate, 13%; beta-ethoxy ethyl acetate, 1.5% (2)


Hygroscopicity: 0 at 30 0 C, 90% relative humidity (2)


Volatility: Nonvolatile (2)

Vapor Pressure (p): Below measurable limits.

Specific Heat: 0.26 cal/g/°C (2)

Heat of Combustion: 1,960 cal/g (2)

Reactivity: The explosion hazard is severe when shocked or exposed toheat. One of the most powerful high explosives, it is particularlysensitive to shock. Explodes at 205-215 C. On decomposition, emitshighly toxic fumes of NO x; can react vigorously with oxidizing.materials (5).

Stability: Due to its symmetrical structure, PETN Ss highly resistantto nany reagents. PETN differs from the majority of nitrate estersbecause it is not readily decompoeed by sodium sulfide at 50 C. It isdecomposed quickly, however, by boiling in a ferrous chloridesolution. Boiling with a 2.5% solution of sodium hydroxide causesvery slow decomposition.

PETN ig hydrolyzed by treatment with water at approximately 100°C.At 125 C under pressure, hydrolysis proceeds quickly and isconsiderably enhanced by the presence of 0.1% HNO * A dilute sodiumhydroxide solution causes PETN to hydrolyze more ?apidly thanacidified water. Hydrolysis produces mainly pentaerythritoldinitrate (6).

Flammability: Will not continue to burn (2)

II. USES

A. &Xy Valque Use

PEIT• is used in Class A-detonating fuse and boosters and Class B-priming., compositions , as a bases charge in anti-aircraft shells and mixed with

TNT (70-30) in mines, explosive bombs and torpedoes. It is a ve'yeffective demolition explosive. It is also used in blastiog cap&combined with lead azide and diazodinitrophanol. PETN was knownto an explosive in 1894; it was not used on a practical basis untilafter World War I (5,2).

SDAM17-84-C-4133 43-2

PENTAERYTURITOL TETRANITRATE (cont.)

B. Other uses

PETN is used therapeutically in the treatment of angina pectoris (7).



Several chromatographic methods were reported in recent literature.Lloyd reported an high performance liquid chromatography method thatuses a pendant mercury drop electrode at the detector. This methodcompared favorably with electron capture detection. in gaschromatography (8).

A Thermal Energy Analyzer (TEA) interfaced with a gas or liquidchromatograph was reported by Fine et al. (9) to detect explosives indebris without prior clean-up.

Yu et al. (10) reported a method to determine this compound withnitro/nitroso specific detector with either a gas or liquidchromatograph. This method can be used in the analysis of wastewateror biological fluids. The detector is a TEA and can also 1e applied tometabolites of nitrate esters.

Cantu et al. (11) reported success using a Fourier transform infraredspectrometer coupled with HPLC.

Yinon (12) described a custom built mass spectrometer interfaced withan HIPLC that can successfully analyze PETN and other explosives.Curaming and Park (13) reported a gae chromatography/single ion monitoring%ass spectroscopy method.

Malotky and Dowmes (14) reported a field kit for the 3nalysis of 28different explosives, including PETN, using thin-layer chromatoraphy.


Lloyd (8) reported a detection limit of 2-20 picogram/10 microliters of* injected sample.

Fine et al. (9) reported a detection limit of <10 picograms.

r

i~4

*, :D.AD17-84-C-4133 43-3

www5T

PENTAERYTHRITOL TETRANITRATE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1 * TOXICITY OF PETAERYTURITOL TETRANITRATE


Human oral Therapeutic Cutaneous vasodilation; (7, 15)dose levels rash; headache; in-

creased intraocularpressure; dizziness,weakness, other signsof cerebral ischemiaassociated with posturalhypotension

Human oral 10 mg, 4x/d, Erythroderma (16)(63-yr-old x8 yr; withman) glyceryl tri-

nitrate, 1 or2x/Mo

Human oral $0 mg/d Rosacia with strong (17)(74-yr-old flushingman)

TABLE IV-2. MUT.AGENICITY AND RELATED EFFECTS OF PENTAERYTHRITOL TETL4ITRATE


Salmonella NS* Nonmutagenic with or without (16)typhimurium TA98, Aroclor 1254-induced ratTA100t TA1535, liver fraction or treatment

TA1537, TA1536 with ozone or chlorine

Salmonella 0.625, 1.25 mg Nonmutagenic with or (19)Zyhiaurium (spot test); up without Aroclor 1254-

* TAS8 AIO to 2.5 mg/plate induced rat liver S9721.1TA1535, TAI537 (plate incorpo-

TA1538 ration a"say)

Saceharoevees NSDid not. produce mitotic (8cerevisiae inhibition with or with-.D3 out Aroclor 1254-induced

rat liver fraction or treatmentwith ozone or chlorine

* ot$-pc*Rfiled

DAMDI7-84-C-4133 43-14

PENTAERYTHRITOL TETR.ANITRATE (cont.)



Al. Transport


Alb. Volatilization -- Non-volatile (2) .7

Aic. Leachability -- Insoluble in water-(6)


A2. Transformation -- Data not availabl.

A2a. Biodegradation -- Studies in rats have shown that PETN is degraded tothe mono-, di-, and trn-nitrates by the bacterial flora of theintestine. Studies both in vivo and in vitro have indicated thatnitrite rather than nitrate is the product of biodegradation of PETN(20).

A2b. Hydrolysis - The water solubility of PETN is so low (about 2 mg/L at20 C), that almost all hydrolysis studies have been carried out inmixed solvents at reflux temperatures, and reactions were promoted bystrong acid or base. Therefore, the experimental data are notdirectly applicable to the assessment of hydrolysis of PETN innatural waters and wastewaters (20).

A2c. Photolysis -- Burrows and Dacre report that there have been studies ofthe decomposition of solid PETN exposed to ultraviolet light, butthey state that it is not known whether this relates in any way todegradation of dissolved PETN or its. metabolites in the environment(20).



B. Effects on animalsS------ -- ----

j BI. Avian specieas - Dtta not available

S2, Mtammalian wildlife species - Data not available

B3. Terre.trial invertebrate -s Data not available

,3B4. Roptiles - Data not available

B5, Amphibians Data not available (Y-2)0..

B6. Microorganims,, aquatic and soil - Data not available

DAMD17-84mC-4133 43-5 -

S', . . . .• . , ° • . . .• . . . . , , , . , :. . .. ,


B7. Aquatic species, fish and invertebrates -- Water flea (Daphnia magna):48-hour LC. : 292 mg/L; Bluegill (Lepomis macrochirus): 96-hour LC50 :>2230(3430 mg/L; Fathead minnow (Pimephales promelas): 96-hour LCso926 mg/L (21).


C1. Phytotoxicity - Data not available



VI. STANDARDS AND REGUIATIONS

A. Health

Data not available

B. Environmental




Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation, or occasionally, hauling by a licensedcontractor and landfilling. Current use of methods discussed above hasalso be been bonfirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices and to developplans for future disposal practices (22).

B. Alternate Disposal Practice, under Consideration b the A

Future plans for disposal of waste explosives and propellants areSprojected to emphasize fluid-bed incineratidn. This method has been

tested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and .awthorne NavalAmmunition Depot (23).

"c. Other Disposal Practices Y

[.Data not available ý 01DMI 7~-84-C•4133 43-6

DAD74

PENTLAERYTHRITOL TETRANITRATE (cont.)

VIII. REFER.ENCES

.1. Kirk, R.E. and D.F. Othmer, eds, 1980. Encyclopedia of ChemicalTechnologY, 3rd ed., Vol. 9, p. 567. John Wiley and SýAs, New York,NY.

2. Army Material Command (AMC). 1971. Engineering Design Handbook,pp. 1-390'. AMCP 706-177, AD) A764340.- Army Mater'ial Com-mr~ad,Washington, D.C.

3. Windholz, M., S. Budavari, R.F. Blumetti, and B.S. Otter'beina, eds.1983. The Merck Index, 10th ed., p. 6975, Merck and Co., Inc.,Rahway, NJ.

4. Chem~ical Information Systems (CIS), Information System For HazardousOrganics in Water (ISHOW). Accession No. 305125. 1985.

-5. Sax, N.I. 1979. Dangerous Properties of Industrial. Materials, 5thed., p. 889. Van Nostrand-Rinhold Co., New York, NY.

6. Kaye, Seymour M. 1978. Encyclopedia of Explosives and Related Items,PATR 2700,'Vol. 8, pp. 86-94. U.S. Army- Armament Research and

V Development Command, Dover, NJ.7. Gilman, Alfred Goodman, Dr., Dr, Louis S. Goodman, and Dr. Alfred

Gilman, eds. 1980. Goodman and Gilman's The Pharmacological Basis ofTheraeuics, 6th ed., p. 824. MacMillan Publishing Co., Inc., NewYork, KY.

8. Lloyd, J.B.F. 1983. Screening 'for Organic Explosives Components byHigh Performance Liquid Chromatography with Detection at a PendentMercury Drop Electrode. Proceedings of the International Symposium onthe Analysis and Detectit.n 'of ' 'xplosives. Washington D.C,193Federal Bureau of Investigation, Washington 1).C. 31-39.

9. Fine, D. H. , W. C. Yu, and ;.. off. 1.983. Applications of theNitro/Nitroso Speci,.'ic Detector to Explosivie Residue Analysis.Proceedinis of the International Symposium on the Analysis andDetection of Exp1 .cs~ves Washington D.r, 1983. Fe'deral Bureau ofInvestigation, W~ahington, D.C. M26-340,

10. Yu., W.C. E.U* (1off, and D#R. Fine. 1983. -Determination ofNirtEsters, Witramines, Nitroaromatiica, and their Metabolites in BiologicalFluids and Was;ewater by Gas and Liquid Chromatography with A

fNitro/Nitroso Specific.Ditector. Proceedings of the International4 Sm~osium on the Analzasl~ and Detection of Ex~lohives. Washington,

D.C.,0 1983. Federal Bu-.-e& f~ Inestlgation, WVashington, D*C,329-340.

Ei

DAMD17-84-C-4133 43-7

--- - ..-.... ~Ab4A


11. Cantee, A.A., W.D. Washington, R.A. Strobel, and R.E. Tonarski. 1983.Evaluation of FTIR As A Detector for the H.PLC Analysis of Explosives.Proceedings of the Analysis and Detection of Exgosves. WashingtonD.C., 1983. .Federal Bureau of Investigation, Washington, D.C. 349-363.

12. Yenox, J. 1983. Analysis of Explosives by LC/MS. Proceedings of theInternational Symposium on the Analysis and Detection of Exloies.Washington, D.C., 1983. Federal Bureau of Investigation, Washington,D.C. 227-234.

13. Cumming, A.S. and K.?. Park. 1983. The Analysis of Trace Levels ofExplosive by Gas Chromatography/Mass Spectrometry. Prceig of theInternational Symposium on the Analysis and Detection of Explosives.Washington, D.C., 1983. Federal Bureau-of Investigation, Washington,D.C. 259-265.

14. Malotky, L. and S. Downes. 1983. Explosives Analysis Kit.Proeedngsof the International Sypsu on the Analysis and

Detection of Explosives. Washington, D.C., 1983. Federal Bureau ofInvestigation, Washington, D.C. 63-65.

15. Physicians' Desk Reference, 1983, 37th ed., p. 595.. Medical EconomicsCompany, Inc., Oradele, NJ.

16. Ryan, F.P. 1972. Erythroderma Due To Peritrate And GlycerylTrinitrate. Br. J. Derm. 87:498.

)17. Wilkin, Jonathan K., 1980. Vasodilator Rosacea. 116-598.

18. Siumon, V.F., S.L. Eckford, A.F. Griffin, R. Spauggord, and G.W.Nemell. 1977. Munitions Wastewater Treatments: Does Chlorinationor Ozonat ion of Individual Components Produce Microbial Mutagens.

Toxicol. Apl Pharmacol. 41:197.

19. Whong, Wen-Zong, Norman D. Speciner, and Gordon S. Edwards. 1980.Mutagenic Activity of Tetryl, A Nitroaromatic Explosive, in ThreeMicrobial Test Systems. Toxicology Letters. 5:11-17.

20. Burrews, Dickenson, Dr. and Dr. Jack C. Dacre. 1975. Toxicity toAquatic Organisms and Chemistry of Nine Selected Waterborne PollutantsFrom Munitions Manufacture-A Literature Evaluation. Technical Report7503. AD A010660, U.S* Army Medical Bioengineering Research andDevelopment Laboratory, Ft. Detrick, MD*

*21. Bentley, R*E*, B.We Sleight III, and K*J. Maceo. 1975. PreliminaryEvaluation of the Acute Toxicity of Desensitized Primer Compounds andPrimer Waste Effluents to Representative Aquatic Organismus. Final0Report, AD. EG&G, Bionomics, Wareham, XhA DAMD17-75-C-5050.

22. David Renard,, U.S. Army Toxic and Hazardous Materials Agency,, to JNJo Carl Ubruacher (personal communication). 1985, 1

DAM'D17-84-C-4133 43-8

-. ,.

V, 1.

PENTAERYTHRITOL TETRANITRATE(on.

23. Forsten, 1. 1980. Disposal of Hazardous Toxic Munition Waste.Procedings of 1980 National Conferenice on Environmental Eninering.New York, July 8-6 1980. ASC Environmental Engineers Div-ision, New

Af)

DAD78-I134-

77 7'.77 -

PHOSPHORJUS TRICHLORID)E

I. CXHE•ICAL AND PHYSICAL DATA


Chemical Formula: PCl 3


Structural Formula:

0I- P 0




CA Name (9C1): Phosphorus trichloride

SCA Name (8C1): Phosphorus chloride

RTECS Number: TH3675000

Other Significant Synonyms: Phosphine, trichloro-, phosphoruschloride

C. Chemical and Ph~sical Properties

Physical State: A fuming liquid (1)


S"Odor. Data not available

Melting Point: -112C (1)

Boiling Point: 76°C (1)

Solubilities: A

Water Decomposes (1)Nonaqueous Solvents: Decomposes in alcohol (1); soluble in benzene,ether, chloroform, carbon disulfide (1); soluble in carbontetrachloride (2)

' ' " "" ' "" " " . '... " " ' ': .. .. ' N,';" m '• • '

PHOSPHORUS TRI.HLORIDE (cont.)


Hygroscopicity" Decomposes on contact with water (1)


Volatility: Fuming (1)

Vapor Pressure: 100 mm at 21 0 C (1); 400 mm at 56.9 0 C (3); vapordensity 4.75 g/L (3)





Flammability: Nonflammable (3)

II. USES

A. A_• Unique Use

Obscurants and chemical intermediates. )B. Other Uses

Same uses as phosphorus oxychloride (chlorinating agent); in themanufacture of phosphorus pentachloride and phosphorus oxychloride,producing iridescent metallic deposits (1).

I11. ANALYTICAL MEITHODS

As Best Acceptable Method

Phosphorus can be detected in trace amounts by atomic emissionspectrometry, fee et al. recently reported a simultaneous inductivelycoupled plasms atomic emission spectrometric method for phosphorus and33 other elements (4).

Be Limit of Detection

lHee et &I. reported a lowest quantifiable limit (LQL) of less than 0.1

micrograra per milliliter (4)..

4.

DAMDf7-84-C-4133

PHOSPHORUS TRICHLORIDE (coat.)

IV. HEALTH EFFECTS

4 TABLE IV-1. TOXICITY OF PHOSPHORUS TRICHLORIDE

Species Route Dose/Duration EffectsReference

Human contact NS* Highly irritating to (5)with skin, eyes, throat, andvapor respiratory tract

Human contp-z-t NS Severe burns of the eyes (5)with liquid and skiu

Human inhal- Mino~r Acute pulmuonary edema; (6)ation expo~sures may be delayed 2-6 hr

Moderate Acute pulmouary edema; (6)to severe may be delayed 12-24 hrexposures

Human inhal- Exposure Effects included burning (7)(27 ation folloving a eyes~, shortness of breath,patients) railroad yard throat irritation, eye

accident lacrivation, headache,nausea, burning skin, sputumproduction, generalized chestpain, pleurigit chestpaiu, rash with or vthout iteb, wheezing, blur-red vision, vomiting,abdominal prain, pulmonrychanges, hyeoxeda

Human inhal- Intermittent Increased incidenceo of(chemical ation exposure to respiratory distress

*workers) PCI and POM consisting of w~heeting,con(entrapione breathlessness, and chastof PCI3 tightness in 37 exposedfeiceeded 3 mg/ vs. 22 unexposed workersm standard in original study and inin 2 of 13 air 26g exposd vs. 11 unex-d

! samples in posed workers 2 yearsoriginal study later in a follow-up study(respiratorsworn in thesecases); no air

saspinginfollow-up study

ULM l7-84-C4133 44-o3

-AD

PHOSPHORUS TRICHLORIDE (cont.)

TABLE IV-1. TOXICITY OF PHOSPHORUS TRICHLORIDN (Cont.)


Rat oral 550 mg/kg LDs5 0, (9)

Rat inhalation 104 ppm/4 hr LC50 (9)

Guinea pig inhalation 50 ppm/4 hr LC5 0 (9)

* Not specified

TAB"E IV-2. N'3TAGE1ICITY OF PHOSPHORUS TRICHLORIDE


Salmonella 0.1-1,000 Nonmutagenic with or (10)Oyphimurium ug/ml; without Aroclor 1254-(8 s.r&ias); gradient induced rat liver S9""scherichil plat•tcoli (2 methodstrains)

V. ElýV •IOR •NTAL EFFECTS

A. Environmental fate


"Ala. Adsorption - Data pot available


Alc. Leachability - Data not available

A,. AAd, BiobZ- •",lti.on - Dark not available

A2. Tranzfow.tion m ,-- Data not available

Aa.. Biodegradation D- ata not available

&2b. Hydrolysis - Decomposes in vater to hydrodhloric arid :ad H3 PO (3).

AZc. Pbotolyal* -- Data not available

DhMD1i7-84-C-4133 44-4

-w .*-











B7. Aquatic species, fish and invertebrates - Data not available




* C3. Metabolism - Data not available


A. Health

Data not available

3B. Environmental

Phosphorus trichloride has a statutory reportable quantity (RQ) of 5000lb under the Comprehensive Response, Coupensation and Liability Act.The National Response Center must be notified when there is a release

lOf this compound in an amount equal to or greater than the RQ (11).

t VII. DISPOSAL

A. urrent Reconen!Led ArMy ig-a Practices

'A recent programatic life cycle environaautal assesuent indicates thati•ncineration is the preferre.d method for disposal of smoke/obscurantmunition#. Hunitions containing phosphorus would be incinerated in aunit equipped with afterburner and a scrubber (12).

IN

¶:: D, 1T-84-C-133 44-5

A t•,,, • .•.•: ....... ... .. ..... ... .. .... ...... . ., • ..,. a



Data not available


Phosphorus trichloride can be syphoned into a running stream andneutralized. However, the danger of forming explosive or toxic fumesdictates the work be done in an isolated ar-a with all personneladequately protected (3). (Editor's note; The recommendation that thematerial be neutralized is very important when using this disposalmethod; the pre-disposal pH of the stream should be maintained. Thismethod may contribute to algal growth downstream due to excessivephosphorus application.)

VII. REFERENCES

1. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.

1983. The Merck Index, 10th ed., p. 1061. Merck and Co., Inc.,Rahway, NJ.


3. Chemical Information Systems (CIS), Oil and Hazardous MaterialsTechnical Assistance Data Systems (OHMTADS). Accession No. 7216858.1985.

4. Hee, S.S.Q, T.J. Macdonald, and JR. Boyle. 1985. Effects of Acid Typeand Concentration on the Determination of 34 Elements by SimulataneousInductively Coupled Plasma Atomic Emission Spectrometry. AnalyticalChemistry. 57(7):1242-1252.

5.. U.S. Cost Guard. 1978. Chemical Hazards Responne Information System(CHRIS) Hazardous Chemical Data-Training Edition-PhosphorusTrichloride. Abridged, CG-446-2. U.S. Department of Transportation,Washington, D.C.

6. Clayton, George D. and Florence E. Clayton, eds. 1981. PIndustrial Hýyiene and Toxicology, Vol. 2A, 3rd revised edition. JohnWiley and Sons, New York, NY.

7. Wason, S., I. Gomolin, P.Gross, and F.H. Lovejoy, Jr. i982.Phosphorus Tri-Chloride Exposure-A Follow-Up Study of 27 ExpasedPatients. Vet. Hum Toxicol. 24(4):275-276.

8. Moody, P.L. Health Hazard Evaluation Report. RETA-81-089-965, No.PB83-16i190. FMC Corporation, Nitro, WV.

9. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. R of -(oToxic Effects of Chemical Substances, Vol. 3. National Institute forOccupationel Safety and Health, Cincinnati, OH.

DAMD17-84-C-4133 44-6

• .t,•. .. . . . .... . . . ..


10. McMahon, R.E., J.C. Cline, and C.Z. Thompson. 1979. Assay of 855SL Test Chemicals in Ten Tester Strains Using a New Modification of the

Ames Test for Bacterial Mutagens. Cancer Research. 39:682-693.


12. Yon, R.L, Dr. Randall S. Wentsel, and Joh M. Bane. 1983.Programmatic Life Cycle Environmental Assessment for Smoke/Obscurants,Volume 2-Red, White, and Plasticized White Phosphorus. TechnicalReport No. 83004, AD A135910. Chemical Research and DevelpomentCenter, Aberdeen Proving Ground, MD.

4*I :

, KDkI•7-84-C-4J33 44-7

POTSSIUM DINITROBENZFUROXAN



Chemical Formula: C6H4N4 06K (1), C6H3 N4 07K (2)

Molecular Weight: 225 (1), 282 (Estimated)

Structural Formula:

NO2

K+ 0-÷ /02N*

ON H OH

0-

)

B. Alternate Names and Regitrv Numbers


CA Name (9CI): 4-Benzofurazanol, 1-4-dihylro-5,7-dinitro, 3-oxide,ion(-I) potassium

CA Name (8CI): Benzofura.zan, 46-dinitro-l-oxide, potassium salt*

RTECS Number: Not applicable

Other Significant $ynoozims: KDNBF

C. Chemical and .si~ca_ 2rorties

Physical State: Crystalivte solid (i.)

Color: . 'X&Ue ('i)

Odor: -Urta iot available

• !'N

,NDA17-64-C-4 3 3. 45-1

......................................... %.

ii oPOTASSIUM DINITROBENZFUROXAN (cont.)

Solubilities:Water: 0.245 g/100 g at 30°C (1)Nonaqueous Solvents: Data not available


Hygroscopicity: At 30°C - 75% Relative humidity - 0.11%

90% Relative humidity - 0.27% (1)




Specific Heat: 0.217 cal/g/°C (1)





II. USES

A. Army Unique Use

Primary explosive (1)

B. Other 'dses

Data not available

III. ANALYTICAL METHODSK1 •A. Bes.t Acceptable Methodr-

}None found under name or CAS registry number.

Be Limit of Detection

V4 None found under name or CAS registry number.

"'I•

f DA)1D17-64-C-4133 45-2

A~

______"_____ I

POTASSIUM DINITROBENZFUROXAN (cont.)

IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF POTASSIUM DINITROBENZFUROXAN

Chemical Effects References

Potassium dinitro- Moderately toxic by inhalation and (3)hydroxy hydro- ingestionbenzofuroxan

4,6-Dinltrobenzo- Inhibition of RNA synthesis in sheep (4)furoxan lymphocytes in vitro: 5% inhibition at

20 uM, 95% inhibition at 100 uM;reacts with nucleophiles

4-Nttrobenzofuroxan Mutagenic in Salmonella typhkmurium (5)strains TA98, TAi0O, TA1530R , TA1535R

Inhibition of DNA synthesis in mouse (6)leukocytes )

4-Nitrobenzofuroxan Inhibition of nucleic acid and protein (4)synthesis in animal cells

Nitrates Large amounts taken by mouth produce (7)dizziness, abdominal cramps, vomiting,bloody diarrhea, weakness, convulsions,and nollapse; small, repea:ed doses vay

lead to weakness, general depression,head&che, and mental impaiivent


No information was found regarding the environmental face or effects of. potassium dinitrobenzfuroxan.

"VI. STANDARDS AND REGULATIONS

A. Health,

Data not available

S. Environinental

Data not available

DA.HD17-84-C-4133 45-3

• .... .. .. A S • .. . .... . , .,. ,, ,, ... .. .. .. .. .. • . .... ....L • _i. k_

POTASSIUM DINITROBrNZFUROXAN (cont.)

VII. DISPOSAL~

*A. Current Recommended Army Disposal Practices

Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATHAMA), which has the responsibility toreview current disposal practices, and to develop plans for futuredisposal practices (8).




* 4Data not available

VIII. REFERENCES

1. Army Material Command (AMC). 1971. Engineering Design Hndbook, pp.302-305. AD 764340, AMCP 706-177. Army Material Command, Washington,

f D.C.

2. Spear, R.J., and W.P. Norris. 1983. Structure and Properties of thePotassium Hydroxide-Dinitrobenzfuroxan Adduct (KDNBF) and RelatedExplosive Salts. glanta Explosives, Pyrotechnics. 8:85-88.

3. Snook, R.W, 1979. Hazardous Component Safety Data Sheet-KDNBF(Potassium Dinitrobenzfuroxan). U.S. Army Armament Research andDevelopment Command, Dover, NJ.

4. Ghosh, P.B., and Kt.W. Whitehouse. 1968. fotential Antileukemic andImmunosuppressive Drugs. Preparation and In Vitro PharmacologicalActivity of Some Benzo-2,1,3-Oxadiazoles Benzfuroxans and Their N-Oxides Benzfuroxans J.. Med. Chem, 11(2):305-311.

"* 5. Thompson, So and L. Kellecut. 1977. Mutagenicity of Anti-CancerNitrobenzfuroxaus. Mutation Research. 48:145-154.

DAMD17-84-C"4133 45-4

A .b

POTASSIUM DINITROBENZFUROXAN (cont.)

6. Kessel, D. and J.G. Belton. 1975. Effects of 4-Nitrobenzfuroxans andtheir N-Oxides on Synthesis of Protein and Nucleic Acid by MurineLeukemia Cells. Cancer Res. 35:3735-3740.


8. David Renard, U.S. Army Toxic and Hazardous Materials Agency toJ. Carl Uhrmacher (personal communication). 1985.

9. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE Environmental EngineersDivision, New York. 440-575.

DAHD17-84-C-4133 45-5... -, .

•-<?l½"

ri!• POTASSIUM PERCHLORATE

J .i. CHEMICAL AND PHYSICAL DATA

A. Structural and Chemical Foimulas and Molecular WeightFill Chemical Formula: KClO4


*-1 Structural Formula:

O--CI--O10


CAS Registry Number: 7778-74-7S"CA Name (9CI): Perchloric acid, potassium salt

CA Name (8CI): Perchloric acid, potassium salt

"TECS Number: SC9700000

Other Signficant Synonyms: Potassium hyperchloride; Potassium hyperchlorate.


Physical State: Rhombic crystals or white crystalline powder (1)

Color: Colorless or white3 .

Odor: Odorless (2)~0

Melting Point: 610-620°C (3)

"Boiling Point: Data not available

Water: Soluble in 65 parts cold and in 15 parts boiling water (1)Nonaqueous Solvents: Very slightly soluble in alcohol and insolublein ether (4). Insoluble in alcohol (1).

K.,

DA•D17-84-C-4133 46-1y

..............-.

,--.

K • . • m m m•

m m• ••• •

.•

• m

..

•. •

•. m

POTASSIUN PERCHLORATE (cont•)

Density: 2.52 g/cc (5)





Specific Beat: Data not available


Reactivity: Decomposed by organic matter and agents subject tooxidation; strong oxidizing agent (5); violent reaction withaluminum and magnesium, fluorine, nickel and titanium (3).

Stability: Decomposed by0 concussion (1); decomposes at 400 °C

(4); decomposes at 530 -C (6); moderate explosion hazard (6).


K II. USES

A. A.my Unique Use

Pyrotechnics, oxidizer for rocket propellant

B. Other Uses

Fireworks, pharmaceuticals, oxidizing agent, analytical reagent.

III, ANALYTICAL METHODS

There is an ion chromatography method for determining potassiumperchlorate in Pyrodex, a commercial black powder substitute. Thismethod was developed for trace forensic analysis of black powders andtheir combustion products and residues,


"Data not available

SW,

44.

, DD17-84-C-4133 46-2fl'"

' ' " + . .. " " " + -. . . . - , +,++ , ,. : ++l •+. _-:: : • ::- : -: 2 -+ l "

POTASSIUM PERCHLORATE (cont.)

, IV. HEALTH EFFECTS

TABLE IV-i. TOXICITY OF POTASSIUM PERCHLORATE


Human oral Therapeutic Nausea, vomiting, and hyper- (2)sensitivity reactions such asmaculopapular rashes, fever,and lymphadenopathies mayoccur; fata aplastic anemiahas occured in a smallproportion of patients;agranulocytosis,thrombo cytopenia, andleucopenia have been reported.

72-yr-old lg/d for 1 monthfemale (treated then 200 mg/dfor thyrotox- for 22 yr No toxic effects (7)icosis)

Human inhal- NS* Irritation of skin, (3)ation contact eyes, and mucous mem-with branes; absorptiondust, can produce methemoglo-oral binemia and kidney injury

Rat oral 27,675 mg/kg TDL for developmental (8)gestation abuormali tiesdays 1-9

Eat intra- 10 mg Antithyroid activity (9)peri-toneal

Rabbit oral 2,100 mg/kg, TDL, for developmental (8)t:gestation days abkormalitie6

Guinea oral 35,700 mg/kg, TD for developmental (8)pig gestation abhor.alities

days 48-68

"DMD 17-84-C-4133 46-3

&




Al. Transport



AIc. Leachability - Data not available


AZ. Transformation -- Data not available

AZa. Biodegradation -- A few microorganisms are able to metaboliseperchlorate; most are not. It has been reported that perchlorate isreduced to chloride by several species of heterotrophic bacteria,including the very common E. coli and Pseudomonas aeruginosa, SomeStreptococcus and Flavobacterium sp were inactive (10).


A2c. Photolysis - Data not available )




B3. Avian species - Data not available




B5. Amphibians - Newts maintained at a level of'36 mg/L of perchlorateexhibit significant histological changes in the thyroid andpituitary. Continuous exposure to 360 mg/L results in arrestedmetamorphosis in tadpoles and a grossly enlarged thyroid inguppies (10).

B6. Microorganisms, aquatic and &oil - Toxicity thresholds, by cellSmultiplication inhibition test: bacteria (Pseudomonas 0 •d):

180m/;genalgae (Se~asQu4~&d) 360 (2)L

protozoa (Entosiphon sulcatu,): 23ugL (-1-f.

D 17-84-C-4133 46-4


, B7. Aquatic species (fish and invertebrates) -- LC5 0 for Daphnia magna in

24-hour exposure = 670000 ug/L (calc.) (12).0

Although few definitive studies have been conducted, it appears thatthe acute toxicity of perchlorate ion to aquatic animals andmicrooganisms is very low, with toxic levels probably exceeding 1000mg/L for periods of 24 hours and longer. Because perchlorate is animportant antithyroid agent, chronic effects may appear at much lowerlevels. Guppies (Lebistes reticulatus) exposed to 500 mg/L ofpotassium perchlorate for a year and longer suffered gross enlargementof the thyroid, followed by inactivation of the thyroid and arrestedsexual development (10).


Cl. Phytotoxicity -- Soybeans grown in water culture exhibit toxic symptomsat perchlorate levels as low as 2.5 mg/L four days after application.Soybeans grown in sand were noticeably less susceptible (10).

C2. Uptake - Uptake of iodide by the seaweed Fucus ceranoides iscompetitively inhibited by perchlorate at the 0.1 mg/L level inseawater (10).



A. Health

Data not available

i B. Environmental

Sj •Reported in EPA TSCA Inventory 1983.

%I. DISPOSAL

A A. Current Recommended Army Disposal Practices

Current methods of disposal of pyrotechnics involves open burning oropen detonation.

- 5. Alternate Disposal Practicos Under Consideration t he

Data not available

M DkD17-84-C-4133 46-5

K ,•

POTASSIUM PERCHLOR.ATE (cont.)

C. Other Disposal. Practices Employed

Use vast volume of concentrated solution of reducing agent (bisulfitesor ferrous salts with 3M-112SO4 or hypc). Neutralize with soda ash ordilute 1101. Drain into a sewer with abundant water (13).

For small quantities: Cautiously add to a large stirred excess ofwater. Adjust the pH1 to neutral, separate any insoluble solids orliquids and package them for hazardous waste disposal. Flush theaqueous solution down the drain with plenty of water. The hydrolysisand neutralization reactions may generate heat and fumes which can becontrolled by the rate of addition (14).

VIII, RZFERENCES

1. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index~, 10th ed., p. 7545. Merck and Co., Inc.,Rahway, NJ.

2. Reynolds, James E.F. and Anne B. Prasad, eds. 1981. Kartindale-TheExtra Phrracooeia, 28th ed., p. 358. The Pharmaceutical Press,London, England.

3. Sax. N-1. 1979. Dagru Properties of Industrial Materials, 5thed., p. 933. Van NostranA-Reinhold Co., New Vork, NY.

4. Weasit, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed.,p. D-81. The Chemical Rubber Co., Cleveland, OH.

5. Uawley', Gesener Go 1961. The Conde sed Chemical Dictionary, 10thad., p. 852. Van Nos tr~ad-Zitnh~old Co., NewYork, WY.

6. Material Safety Uita Sheet-Potassiuim Perchlorate* Not 108-94-1.

Aldrich Chemical Coo, Milwaukee* WS.

7. Connell, J.M.C. 1981. Long-Term Use of Potassium Perchlorate*Poutatraduate Medical Journal.* 57:516-517.

8. National Library of Hedicino ýNLH), Registry of Toxic, Effects ofChemical Subistances (RTECSI). Accession No. SC9700000. 198-3.

9. ontiya, ToshIma. Takashi Yamada, and Nicholas S. lialui. 1973.Thtrathyroidal Recycliug of Iodide in the Rat: 'Effects, ofGoitrogeas. Prpc.- Soc. ýý Biol. Ked. 129(2);551-556.

10. Burrcowa, Dickenson, Dr*, and Dr. Jack C. tvacxeý 10"ai to.ty toAquatic Organisms AMd Chemistry of Nii: ev-.v4i-ced aeowAPollutants Froz Muuitioos Hanufactur&a -r U'srat .tre f :1siuTechnical Report 7503, AD A010660. 0,,S. Army hib4iaal i.Zaaasrih 4-Development Command, Uasbington, UC.

DARD17-84-C-4133 46-6


11. Bringmann, G. and R. Kuhn. 1980. Comparison of the ToxicityThresholds of Water Pollutants to Bacteria, Algae, and Protozoa inthe All Multiplication Inhibition Test. Water Research. 14:231-241.


13. International Technical Information Institute (ITI). 1982. Toxicand Hazardous Industrial Chemicals Safet Manual, pp. 435-436.International Technical Information Institute, Tokyo, Japan.

14. Aldrich Chemical Co. 1984-85. Aldrich Catalog/Handbook of FineChemicals, p. F15-F16. Aldrich Chemical Co., Milwaukee, WS.

C

U"k17-84-C-4133 46-7

PRO?YLENE GLYCOL 1 ,2-DINITRATE

Much of the available data on propylene glycol 1,2-dinitrate has been reportedin a previous study by the Atlantic Research Corporation (ARC) entitled APrelimingry Problem Definition Study of 48 Munitions-Related Chemicals. Datareported herein reflects information more recent than that reported by ARC in1978.



Chemical Formula: C H N 06

Molecular Weight: 166 (1)

Structural Formula:

N02

O2NI-0CH2 C C3

B. Alternate Names and R~gsr Numbers


V CA Name (9C1): 1,2-Propanediol, dinitrate

CA Name (8CI): Same

RTECS Number: TY6300000

Orhet significant synonyms: Isopropylene nitrate

Co Chemical and Physical Properties



odor: Disagreeable (1)(

Boiling Point: 920C at 10=m Hg (1)

DAMD17-84-C-4133 47-11

PROPYLENE GLYCOL 1,2-DINITRATE (cont.)

Solubilities:Water: Soluble in water (1)Nonaqueous Solvents: Data not available



Density (specific gravity): 1.3774 (1)




Heat uf Combustion: Data not available

Reactivity: The glycol dinitrates hydrolyze rapidly in base,somewhat more slowly in acid and only at elevated temperatures inwater alone. The hydrolysis of alkyl nitrates can lead to a varietyof products including the parent alcohol, alkenes, aldehydes andcarboxylic acids. Thermal decomposition of alkyl nitrates initiallyyields alkoxy radicals which react further to give complex mixtureswhich include CO, CO2 , NOx. Photolysis also gives complex mixturesincluding NO (1).



II. USES

A. Amv Unqu Use

Principal constituent of Otto Fuel II for the Otto II torpedo (1).

B. Other Uses

1No civilian uses (I).

IlI. ANALYTICAL METHODS

As Best Acceptable Method

Fine and Miles have developed a portable voltammeter to monitor nitrate, "sters, particularly PGDN in waste water using a silver wire electrode

•:• :•(2).•

DMD17-84-C-4133 47-2


Erk et al. described a gas chromatography method using an electron

capture detector to determine PGDN in blood (3).


Miles and Fine reported in their patent application that 0.5 mg/L iseasily detectable (2).

Erk et al. claimed 10 ng/mL limit of detection by gas chromatograph (3).

Xi

DAHD17-84-C-4133 47-3


IV. HEALTH EFFECTS

TABLE IV-I. TOXICITY OF 1,2-PROPYLENE GLYCOL DINITRATE*


Human inhal- Mean exposure No significant differ- (5)(workers ation duration: 47.4 ences in mean scoresexposed to or 91.8 tio of oculomotor and ataxia1,2-PGDN) tests between exposed

workers and controls

Acute; peak Significant changes in (5)conc. equal to oculomotor test scoresor less than0.1 ppm

Guinea pig intra- 402 mg/kg LD5 0 (6)peritoneal

Rabbit eye 100 mg Mild irritation (6)

Cat subcu- 200 mg/kg LDLo (6)A taneous

Dog intra- 4-100 mg/kg Dose-related decreases (7)(Beagle) venous suspended in in systolic, diastolic,

polyethylene and pulse blood pres-glycol 400 sure; dose-related in-

crease in heart rate;whole red blood cellsin urine; vasodilation;methemoglobinemia athigh doses

Rhesus inhal- 0.3 ppm No significant changes (8)monkey ation increasing to in behavior or necropsy

4.23 ppm over and histopathologic125 days results

2-33 ppm for No unequivocal changes (8)6 hr in visual evoked

response

*Information not included In the ARC report

DAMDI7-84-C-4.133 47-4

LIL










Ala. Biodegradation - Data not available


Ac. Photolysis - Data not available

A2d. Other chemical reaction - Data not availablep


Bo Effects on animals

Bl. Avian species - Data not available

B2. Maimalian wildlife species - Data not available




B6. Microorganisms. aquatic and soil - Data not available



Ci. Phytotoyicicy - Data not available



DAHDI7-84-C-4133 47-5

r



A. Health

Data not available

B. Environmental

Reported in EPA TSCA Inventory 1983

VII. DISPOSAL


Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation or hauling by a licensed contractor andlandfilling. Current use of methods discussed above has also beenconfirmed by private communications from the U.S. Army Toxic andHazardous Materials Agency (USATWAI1A), which has the responsibility toreview current disposal practices, and to develop plans for futuredisposal practices (9).

B. Alternate Disposal Practices under Consideration b2.=the


C. Other Disposal Practices EmTloyed

Data not available

VIII. REFERENCES

1 . Kitchens, J.F., S.G. Brownlee, W.E. Harward, II, R.G. Hyde, W.E.Jones, III, D.A. Price, R.S. Wentsel, and R.S. Valentine. 1979.Preliminary Problem Definition Study on Munitions-Related Chemicals.Final Report, ADA099733. Atlantic Research Corporation, Alexandria,VA. DAND17-77-C-7057.

2. Fine, D.A. &nd H.H. Miles. 1984. Voltammetric Analysis of OrdnanceMaterials. Part I. Detection and Quantitation of Nitrate Esters andVarious Nitro Compounds in Water by Voltommetry. Technical Report,AD A142269. Naval Weapons Center, China Lake, CA.

DAMDI7-84-C-4133 47-6


3. Erk, S.D., C.H. Jarboe, P.E. Newton, and C. Pfledderer. 1982. GasChromatographic Determination of 1,2-Propandial Dinitrate in Blood.Journal of Chromatography. 240(l):117-123.

4. Miles, M.H. and D.A. Fine. 1984. Detection of Nitrate Esters Usinga Silver Electrode, US Patent 4436590.

5. Honath, E.P., R.A. Ilka, J. Boyd, and T. Markham. 1981. Evaluationof the Neurophysiologic Effects of 1,2-Propylene Glycol Dinitrate byQuantitative Ataxia and Oculomotor Function Tests. Am. J. IndustrialMed. 2(4):P365-378.

6. Chemical Information Systems(CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. TY6300000. 1985.

7. Erk, S.D., P.E. Newton, J.D. MacEwen, and E.H. Vernot. 1982.Evaluation of the Toxicokinetic Study of 1,2-Propandial Dinitrate(PGDN) in the Dog. Technical Report, AFAMRL-TR-82-27. Air ForceAerospace Medical Research Laboratory, CA.

8. Maltson, J.L., R.N. Young, C.R. Curran, C.G. Franz, M.S. Conan, andL.J. Jenkins. 1981. Acute and Chronic Propylene Glycol DinitrateExposure in the Monkey. Aeration, Space, and Environmental Medicine.52(6):340-345.

9, David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communication). 1985.

10. Forsten, 1. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEnineering. New York, July 8-10, 1980. ASCE EnvironmentalEngineers Division, New York. 440-575.

.I.

DAMDI7-84-C-4133 47-7

-7

" A- rm ... .

PROPYLENE GLYCOL 1,3-DINITRATE

Much of the available data on propylene glycol 1,3-dinitrate has beenreported in a previous study by the Atlantic Research Corporation (ARC)entitled A Preliminary Problem Definition Stud of 48 Munitions-RelatedChemicals. Data reported herein reflects information more recent than thatreported by ARC in 1978.



Chemical Formula: C3H6 N06

Molecular Weight: 166 (1)

Structural Formula: 0 3N(CH2 ) 3 NO3



CA Name (9CI): 1,3-Propanediol, dinitrate

CA Name (BCI): Same


Other Significant Synonyms: Trimetbylene dinitrate



Color: Colorless (I)


Boiling Point: 180°C at 1J Hm Mg (1)

Solubilities:Water: Data nor availableNonaqueous Solventst Data not available



Density (Specific Gravity): 1.3952 (1)

DAMDI7-84-C-4133 48-1

Avi

t h~i .. . .






Reactivity: The glycol dinitrates hydrolyze rapidly in base, somewhatmore slowly in acid and only at elevated temperatures in water alone.The hydrolysis of alkyl nitrates can lead to a variety of productsincluding the parent alcohol, alkenes, aldehydes and carboxylicacids. Thermal decomposition of alkyl nitrates initially yieldsalkoxy radicals which react further to give complex mixtures whichinclude CO, CO and NO. Photolysis also gives complex mixturesincluding NO p1).



II. USES

A, Unique Use

Explosive and plasticizer (1).

B. Other Uses

None found



No analytical methods were found in a computerized search of ChemicalAbstracts dating back to 19674 Several methods vere found for the 1,2-ester, including voltammetric and gas chromatographic analyses. Thesemethods could possibly be extended to this compound. See the report onpropylene glycol 1,2-dinitrate.


Data not available

DAMDW17-84-C-4133 48-2

................................................ .....iliiii--~-~~w'


IV. HEALTH EFFECTS

No information other than that in the ARC report was located. Seereport on 1,2-propylene glycol dinitrate.


No information was found regarding the environmental fate or effects of1,3-propylene glycol dinitrate which would update the Atlantic ResearchCorporation document.

VI . STANDARDS AND REGULATIONS

A. Health

Data not available

B. Environmental

Data not available

VII. DISPOSAL

" " A. Current Recommended Armv Disoal Practices

Review of past Installation Assessment Reports indicates that currentmethods of disposal of waste explosives and propellants involve openburning, open detonation or, occasionally, hauling by a licensedcontractor and landfilling, Current use of methods discussed above hasalso been confirmed by private communications from the U.S. Army Toxicand Hazardous Materials Agency (USTHAMA), which has the responsibilityto review current disposal practices, and to develop plans for futuredisposal practices (2).


Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARMADCOM and is planned for use atinstallations such as Savanna Army Depot, Tooele Army Depot, andHawthorne Naval Ammunition Depot (3).


Data not available

. DAD17-84-C-4 133 48-3


VIII. REFERENCES

1. KiLchens, J.F., S.C. Brownlee, W.E. Harward III, R.G. Hyde, W.E.Jones, I1l, D.A. Price, R.S. Wentsel, and R.S. Valentine. 1979.Preliminary Problem Definition Study On Munitions Related Chemicals.Final Report, AD A099733. Atlantic Research Corporation, Alexandria,VA. DAMDI7-77-C-7057.


3. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE EnvironmentalEngineers Division, New York. 440-575.

D4

1I

SD.AHD 7~-84..C-4 1 33 48-4 •.

RED PHOSPHORUS

The Army's need for research on the toxicological and environmentalhazardous of red phosphorus is defined in the Atlantic Research Corporation(ARC) report entitled, A Preliminary Problem Definition Study of 48Munitions Related Chemicals. The report states that red phosphorus isconsidered relatively non-toxic to mammals unless it contains some of thewhite form, and that there is no evidence that the compound is toxic toaquatic life.


A. Structural and Chemical Formulas and Nolecular Weight

Chemical Formula: P4

Molecular Weight: 123.92 (1) 124.08 (2)

Structura.l Formula:

B. Alternate Names and R rv Numbers

CAS Registry Number; 7723-14-0

CA Name (9C0): Phosphorus

CA Name (8CI): Phosphorus

RECS Number: T.3495000

Other Signlicant Synonys: Aorphous, red (2), phosphorus (3)


Physical State: Reddish-brown powder (2)

CoJor: Red to violet (4)


DAH317-.84 -C-4133 49-1...

RED PHOSPHORUS (cont.)

Melting Point: Sublimes at 41600 (5)

Boiling Point: 2800 (6)

Solubilities:Water: InsolubleNonaqueous Solvents: Insoluble in caustic alkali, carbon bisulfide,ether and ammonia solution (I). Insoluble in organic solvents,soluble in phosphorous tribromide (4).

Uctanol Water Partition Coefficient: Not applicable


Density (Crystal): 2.34 g/cc


Vapor Pressure: 0.181 torr at 25 C (6)

Vapor Density: 4.77 g/L


Heat of Combustion: Data no:o available

Reactivity: Reacts only at high temperature; lests roactive than whitephosphorus (4). Avoid contact with potassium chlorate, potassiumpermanganate, peroxides and other oidizing 4guts (4).

Flammability: Catches fire when heated in eir to about 2600

(autoignition temperature) and burns with form•atin of penroxide.Burns when heated in an atmosphere of cboriae (4).

Ignitiou Point: 2000C (1)

Autoignition Tewperaturat 260°C inu it (7)

11. usEs

A. Ar;Ly Unique Use

Obsturant, pyrotechnic (5)

B. Othor UNes

Manufacture of phosphoric acid (q.v.) and other phosphotrouscompounds, phosphor bronzes, metallic phosphideso additive toaem1iconductors, electroluminesecant coatiugs, incendiaries,safety matches, fertilizers (7).

DAMD17-84-C•4 133 49-2

AD".

RLED PHOSPHORUS (cont.)


A. Brst Acceptable Method

Phosphorus can be detected in trace amounts by atomic emissionspectrometry. iee et al. have recently reported a simultaneousinductively coupled plasma atomic emission spectrometric method forphosphorus and 33 other elements (8).

A photometric detector for gas chromatography, designed to monitor cold

chemiluminescence has been reported by Mielniczuk (9).


Hee et al. reported a lowest quantifiable limit (LQL) of less than 0.1mifcrogram per milliliter (8).

z"

DAMD17-84-C-4.13',9-

Z..


IV. HEALTH EFFECTS

TABLE IV-I. T3XICITY OF RED PHOSPHORUS


Human NS** 4,412 ug/kg LD, (10

Human NS NS Relatively nontoxic (4)unless it contains whitephosphorus as animpurity

Human NS NS Irritant to eyes (11)

Human Inhal- 40 mg/r 3 Acu, .'ypical pneumo- (12)ation nia of sudden onset

as observed in workersin plants producing redphosphorus by sublimationof white phosphorus

Human Inhal- 100-700 mg/rn Phosphorus smoke for- (12)ation for less mulations caused rever-

than 15 min sible pulmonary symptomsand mucous membrane ir-

ritation

F344 Oral >10,000 mg/kg LD5 0 (13)Rat

3Rat Inhal- 1,537 mg/m3/ Smoke caused mortality (12)ation 3. hr of 1/10

1,676 mg/m3/ Smoke caused mortality2 hr of 4/10

31,572 mg/m, Smoke caused morta]ity3 hr of 8/10

* Information not included in the ARC Report.

** Not specified.

DAMD1I7-84-C-4133 49-4

RED PHOSPHORUS (coat.)

TABLE IV-1. TOXICITY OF RED PHOSPHORUS (Cont.)


Porton Inhal 6,700-6,800 Smoke of two pyrotechnic (14)rat and ation ppm/30 min mixtures containing 95%New Zea- red phosphorus plusland 5% butyl rubber or 97%rabbit red phosphorus plus 3%

butadiene styrene caused

inflammation and epithelialnecrosis of the larynx andtrachea, alveolitis, andbroncho-pneumonia. Theeffects were attributed to

* pyrolytic production ofortho phosphoric acid

New Eyes 100 mg No irritation (13)Zealand dry material

New Intact 500 mg/L/in2 / No irritation (13)"Zealand and 24 hrabbit abraded

skin

Female Inhal- 352 ppm/iC min Smoke caused mortality (12)* Hartley ation of 4/10

Guineapig 800 ppm/lO min Smoke caused mortality

of 9/10

Female Intra- 0.1 mL of a Slight irritation (13)Hartley dermal 1 g/L solution but no sensitizationGuinea 3 x w for 10pig doses

Female Skin 0.5 mL of a No sensitization (13)Hartley 100 g/L sol,-Guinea ution 6 h/3xpig w for 10 doses

*-Information not included in the ARC report.

I DAMDI7-84-C-4133 49-5

RLED PHOSPHORUS (cont.)

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF RED PHOSPHORUS

Test System Dose Effects References

S.typhimurium NS* Not active with or without (15)TAiO0, TA1535, Aroclor 1254-induced rat liverTA1537, TA1538 S9

S. cerevisiae NS Not active with or without (15)Arcoclor 1254-induced ratliver S9

E. Coli 100 ug- Not active with or without (15)W311(0ipolAi, 10 mg Aroclor 1254-induced ratp3478/polA liver S9

** Not specified


No information was found regarding the environmental f.ate or effects ofred phosphorus which would update the Atlantic Research Corporationdocument.

VI. STANDARDS AND REGULATIONS P

A. Health

- Red phosphorus '. ecluded from designation as hazardous in that it isa nontoxic allotrope, although it is frequently contaminated with asmall amount of the yellow (16).

B. Environmental


t Phosphorus has a statutory reportable quantity (RQ) of I lb. under theComprehensive Environmental Response, Compensation and Liability Act.

4 - The National Response Center must be notified immediately when there isa release of this compound in an amount equal to or greater than the RQ(17).

1DA0 7-84-C-4133 49-6

1 4


VII. DISPOSAL


A recent programmatic life cycle environmental assesment indicates thatincineration is the preferred method for disposal of smoke/obscurantiunitions. Munitions containing phosphorous would be incinerated in a

unit equipped wIth afterburner and a scrubber (18).

B. Alternate Disposal Practices Under Consideration & theeLrm

Data not available


Controlled incineration followed by alkaline scrubbing and particulateremoval equipment (17).

Cautiously make a 5% solution of the product in water; vent because of

possible vigorous evolution of flammable hydrogen gas. Acidify thesolution to pH 1 by adding IM sulfuric acid dropwise. Acidificationwill cause vigorous evolution of hydrogen gas. Allow the solutiion tostand overnight. Evaporate to dryness and bury the residue in achemical landfill (19).

VIII. REFERENCES

1. International Technical Information Institute (ITI). 1982. Toxicand Hazardous Industrial Chemicals Safety Manual, p. 418.International Technical Information Institute, Tokyo, Japan.

2. Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5thed., p. 910. Van Nostrand-Reinhold Co., New York. NY.

3. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substances, Vol. 2, p. 101. NationalInstitute for Occupational Safety and Health, Cincinnati, OH.


5. Kitchens, J.F., W.E. Harwards III, D.M. Lauter, R.S. Wentsei, R.S.Valentine. 1978. Preliminary Problem Definition Study of 48Munitions Related Chemicals, Vol. I11, Pyrotechynic RelatedChemicals-Red Phosphorus. Final Report, AD A066310. AtlanticResearch Corporation, Alexandria, VA. DAMDI7-77-C-7057.

DAMiD7-84-C-4 133 49-7

RiD PHOSPHORUS (cont.)

6. Chemical Information Systems (CIS), Oil and Hazardous MaterialsTechnical Assistance Data Systems (OHMTADS). Accession No. 7216855.1985.

Hawley, Gessner G. 1981. The Condensed Chemical Dictionary, 10thed., p. 810. Van Nostrand-Reinhold Co., New York, NY.

8. Hee, S.S.Q., T.J. MacDonald, and J.R. Boyle, Jr. 1985. Effects ofAcid Type and Concentration on the Determination of 34 Elements bySimultaneous Inductively Coupled Plasma Atomic Emission Spectrometry.Analytical Chemistry. 57(7):1242-1252.

9. Mielniczuk, Z.M. and W.A. Ave. 1978. Construction andCharacteristics of A Cold Flame Photometric Detector. Journal ofChromatography. 166(1):1-7.

10. Chemical Information Systems (CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. TH3495000. 1985.

11. U.S. Coast Guard. 1978. Chemical Hazardous Response InformationSystem (CHRIS) Hazardous Chemical Data-Training Edition-Phosphorus,Red. Abridged, CG-446-2. U.S. Department of Transportation,Washington, DC.

12. Berkowitz, Joan B., G. Stuart Young, Rosalind C. Anderson, Anthony J.Colella, Warren J. Lyman, Alan L. Preston, William D. Steber, RichardG. Thomas, and Robert G. Vranka. 1981. Research and Development forHealth and Environmental Hazard Assessment-Task Order 5-Occupationaland Environmental Hazards Associated w/the Formulation and Use of WhitePhosphorus-Felt and Red Phosphorus-Butyl Rubber Screening Smokes.Final Report, AD A116956. Arthur D. Little, Inc., Cambridge, MA.DAMD17-79-C-9139.

13. Henry, Mary C., Jesse J. Barkley, Jr., and C. David Rowlett. 1981.Mammalian Toxicologic Evaluation of Hexachloroethane Smoke Mixture andRed Phosphorus. Final Report, AD A109593. Litton Bionetics, Inc.,Kensington, MD.

14. Marrs, T.C. 1984. Histological Changes Produced by Exposure ofRabbits and Rats To Smokes Produced from Red Phosphorus. ToxicologyLetters. 21:141-146.

15. McGregor, Douglas B., Colin G. Riach, Ronan M. Hastwell, and Jack C.Dacre. 1980. Genotoxic Activity in Microorganisms of Tetryl, 1,3-Dinitrobenzene and 1,3,5-Trinitrobenzene. Environmental Mutagenesis.2:531-541.

S16. Sittig, Marshall. 1981. Handbook of Toxic and Hazardous Chemicals, p.544. Noyes Publication, Park Ridge, NJ.

DAKD17-84-C-4133 49-8 (.2'


17. Comprehensive Environmental Response, Compensation and Liability Act,

secs. 102 and 103 (1980).

I 18. Yon, Roy L., Dr. Randall S. Wentsel, and John M. Bane. 1983.

Programmatic Life Cycle Environmental Assessment for Smoke/Obscurants,

Vol. 2-Red, White, and Plasticized White Phosphorus. Technical ReportNo. 83004, AD A135910. Chemical Research and Development Center,Aberdeen Proving Ground, MD.

19. Aldrich Chemical Co. 1984-85. Aldrich Catalog/Handbook of Fine

*Chemicals, p. 717. Aldrich Chemical Co., Milwaukee, WS.

Af DAMDI7-84-C-4133 49-9

I~i

SODIUM AZIDE



Chemical Formula: NaN3


Structural Formula: Na+1 (N=N-N)-I



Deleted CAS Registry Numbers: 20828-18-6; 12136-89-9

CA Name (9CI): Sodium azide NaN3

CA Name (8CI): Sodium azide

RTECS Number: VY8050000

Other Significant Synonyms: Smite


Physical State: Crystal (1) hexagonal (2)



Melting Point: Decomposes to nitrogen and sodium (I)

Solubilities:Water: 40.16% at 10iC (1); 41.7% at 17'C 1)Nonaqueous Solvents: 0.3% in alcohol at 25 C (1). Insoluble inether; soluble in liquid ammonia (1).



Density (Crystal): 1.846 g/cc (2) ..

DAMDI7-84-C-4133 50-1

SODIUM AZIDE (cont.)







Flammability: Moderate (3)

II. USES

A. Army Unique Use

Data not available

B. Other Uses

In the preparation of hydrazoic acid, lead azide, and pure sodium; as apropellant for inflating automotive safety bags; and in weed and fruit

A rot control (1).



Misovets (4) reported a thin-layer chromatography system for thedetection of sodium azide, using Silufol plates and 40:20:1acetone:water:formic acid mobile phase and 0.2% ninhydrin solution inbutyl alcohol as the visualizing agent, Asplund (5) reported avoltammetric determination of sodium azide in trace amounts from airusing a dropping mercury electrode.


M isovets (4) reported 0.01-0.1 mg; Asplund (5) reported 0.05 mg percubic meter.

- DAMD17-84-C-4133 50-2


IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF SODIUM AZIDE

Species Route Dose/Duration Effects References

Human NS Acute Hypotension (unresponsive (6)to pressor drugs), tachy-cardia, tachypnea, hypother-mia, acidosis, convulsions,severe headache

Human NS 0.2-4.0 Extremely potent directly (6)ug/kg acting vasodilator

Human oral "Several g" Collapse and death within (6)40 min; swelling of thebrain and lungs; mildfatty degeneration of theliver

Human oral 50-60 mg Collapse within 5 minutes (6)accompanied by hypotensionand tachycardia lastingalmost I hr

Human oral 150 mg (in Breathlessness and tachy- (6)aqueous cardia within 5 min; nau-solution) sea, vomiting, headache,

jifiesne~sfoid diarrheaw t e e aterpolydipsia, ECG changes,and leukocytosis occurred

Human oral 710 ug/kg Behavioral and urogenital (7)symptoms

Human oral 0.01-0.02 A drop in blood pressure (8)mg/kg for 10 to 15 min in hyper-

tensive patients

Human inhal- NS Vapor and fumes are irri- (6)ation tants of mucous membranes;

heavy exposure has causedbronchitis and pulmonaryedema

Not specifid

DAMDI7-84-C-4133 50-3

'(N


TABLE IV-1. TOXICITY OF SODIUM AZIDE (Cont.)


Rat oral 42 mg/kg LDLo (7)

Rat oral 2,730 or Equivocal evidence for (7)5,460 mg/kg, tumors of the endocrinetotal dose, system and skin78 wk

Rat oral 27 mg/kg LD5 0 (7)

Rat intra- 30 mg/kg LDLo (7)peri-toneal

Rat intra- 5-10 mg/kg, Severe intoxication; some (8)peri- 2-4x/hr for survivors show injury andtoneal 3-6 hr demyelination of myelinated

nerve fibers in the centralnervous system and testic-or kidney lesions

Rat sc 35 mg/kg LDLo (7)

House oral 27 mg/kg LD5 o (7)

Mouse intra- 18 mg/kg LD50 (7)peri-toneal

House intra- 19 mg/kg LDPO (7)venous

Rabbit oral 3-10 mg/kg 40-60:. reduction in blood 'd)pressure lasting over I hr

TABLE I'v-I. TOXICITY OF SODIUM AZIDE (Cont.)


Monkey NS* Repeated Central nervous system (8)doses effects: blindness and

attacks of rigiditywith abnormal motions

DAMD17-84-C-4133 50-4


TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF SODIUM AZIDE*


Salmonella 3 mmol/L/ Mutagenictyphimurium 2 hr

S. typhimurium I ug/ Mutagenic with metabolicplate activation

Escherichia 150 nmol/L Mutagenic

coli

E. coli 5 gm/L Effects on DNA repair

Insect 100 mg/L Dominant lethal mutationoral and heritable translocation

Human fibro- 50 mg/L DNA synthesis inhibitionblasts

Rat liver cells I mmol/L Mutagenic

Mouse lymphocytes 500 mg/L/ Mutagenic2 hr

Hamster lung 1 mmol/L Effects on DNA repaircells

*Data from RTECS (1985)

V, ENWIRONWENTAL EFFECTS








DAMDI7-84-C-4133 50-5



A.2b. Hydrolysis - In water, sodium azide will shift between the dissolvedsalt form and hydrazoic acid depending upon solution pH. Andesreact with many organics to form amines. They can also be oxidizedto nitrates or reduced to ammonia. The azide ion itself will notpersist in solution,C9).






B2. Mamalian wildlife species - Data not available



D5. Amphibians -f Data not available

B6. Microorganisms, aquatic and soil -- Sodium azide impairs the phototaxis(light-orienting capability) of the photosynthetic flagellate alga,Euglena gracilis (10).

B7. Aquatic species, fish and invertebrates - Threshold toxicities inriver water: Daphnia: 0.3 ppm; Hicroregma: 3.0 ppm; Scenedeamus: 4.0ppm,; Escherichia coli: 19.0 ppm (9).

Fish: 50% inhibition of carbonic anhydrase activity from the red bloodcells of Ictalurus punctatus at 5900 ug/L sodium azide (11).

Crustacean: Gasarus lacustris: 24-hour LC : 14000 ug/L; 48-hourLCo: 900o QL; 96-hour LC 0 : 5000 uo/L.50(12).


C-I Phytotoxicity - Data not available

C2. Upta•e - Data not available

( DAMDI 7-84-C-4133 50-6


C3. Metabolism - Sodium azide inhibits the two photosynthesis partialreactions of 3-phosphoglycerate photoreduction and oxaloacetatephotoreduction, as demonstrated by study in per-meabilizedcell preparations from wild type and mutants ofChlamydomonas reinhardtii (13).

VI. STANDARDS AND REGUL&TIONS

A. Health

Data not available

B. Environmental

Reported in EPA TSCA lIventory 1980.

Sodium azide has a statutory reportable quantity (RQ) of 1 lb. underthe Comprehensive Environmental Response, Compensation and LiabilityAct. The National Response Center must be notified immediately whenthere is a release of this compound in an amount equal to or greaterthan the RQ (14).


A. Current Recommended Army Dispos Practices

A7HA: NSN 6810-00-300-542'

a. Dispose of through a commercial contractor.

b. Dispose of using a special procedure.

Detonation o" this item shall be accomplished by ExplosiveOrdnance Disposal (EOD) experts only at a remote uninhabitedlocation. The U.S. Army Escort Unit, if requested, is availableto assist in the disposal of this item. AR 740-32 outlines theprocedure necessary to obtain their services. Liaison may beestablished with their Disposal Office, AUTOVON 584-4382. EODpersonnel shall determine the amount to be disposed of at a giventime in accordance with their Lange Safety and MovementRegulation. Movement of this material from a storage location toa range for disposal shall be in accordance with existingDepartment of Transportation regulations as well Stateand local regulations (15).

DAHD17-84-C-4133 50-7

kv SODIUM AZ:DE (cont.)

B. Alternate Disposal Practices Under Consideration by the Amy

Data not available


Data not available

VIII. REFERENCES


2. Weast, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed.,p. B-222. The Cheical Rubber Co., Cleveland, OR.

3. Chemica Information Systems (CIS). Oil and Hazardous MaterialsTechnical Assistance Data Systems (OHMTADS). Accession No. 7216887.1985.

4. Kisovets, V.G. 1983. Thin-Layer Chromatographic Determination ofSalts 6 Hydroxides of Alkali Metals. Zh. Anal. Khim. 38(11):2087-2090.

5. Asplund, J. 1984. Voltammetric Determination of Azide and Lead inLead Azide. Proceedings of the 9th International PyrotechnicslSeminar. Bofers, Sweden, 198'. A.B Bofers, Bofers, Sweden. 15-28.

6. Gesselin, Robert E., Dr., Dr. Roger P. Smith, Dr. Harold C. Hodge, an4Jeanetre E. Braddock. 1984. Clinical Toxicol2gX of CommercialProducts, 5th ed. Williams & Wilkins, Baltimore, MD.

7. National Library of Medicine (N11I), Registry of Toxic Effects ofChemical Substances (RTECS). Accessioa No. VY8050000. 1985.

8. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty.'sIndustrial Hygiene and Toxicoloty, Vol. 1, 3rd revised edition. Joh:nWiley and Sons, New York, NY.

9. Chemical Information Systems (CIS), Oil and Hazardous MaterialsTechnical Assistance Data Systems (OLDITADS). Accession No. 7216887.1985.

10. Colombetti, Guiliano, Donat-Peter Hader, Francisco Lenci, and MauritioQuaglia. 1982. Phototaxis in Euglepa Gracilis: Effects of SodiumAzide and Triphenylmethyl Phosphorium Ion on the PhotosensoryTransductiou Chain. Current Microbiology. 7:281-284.

Ar DANDi7-84-C-4133 50-S

SODIUM4 AZIDE (cont.)

11. Chemical Information System (CIS), Aquatic Information Retrieval(AQUIREE). Accession No. 235295. 1985.

12. Chemical Information System (CIS). Accession No. 207385.

13. Belknap, Williami R. and Robert K. Togasaki. 1982. The Effects ofCy~anide and Azide on the Photoreduction of 3-Phosphoglycerate andOxaloacetate by Wild Type and Two Reductive Pentose Phosphate CycleMutants of Chlamydomonas Reinhardriis Plant Physiology. 70:469-475.


15. U.S. Army Envircrimental Hygiene Agency (AEH.A), 1983. Waste DisposalInstructions. TG-126, HISHI-ES-H/WP. AEHA, Aberdeen Proving Ground,MD.

ji1-8--43

VO

SODIUM PERCHLORATE



Chemical Formula: NaClO4


Structural Formula:

+ ( I



CA Name (9CI): Perchlorate acid, soaium salt

CA Name (8C1): Perchlorate acid, sodium sal.

RTECS Number; SC 9800000

Other Stgnficant Synonyms: Irenat (1)

C. Chemical and Phycical Properties

Physical State: Deliquescent crystals (2)

Color: White

Odor: Odorless (3)

Melting Point: Decomposes at 4620 C (4).

Solubilities:Water: Very soluble (2)SNonaqueous Solveats: 51.4 g/lOOg methyl alcohol; 51.7 S/lOOg acetone;14.7 g/IOOg ethyl alcohol; 4.89 g/100g propyl alcohol-, 1.86 g/lOOgbutyl alcohol; 9.65 g/1OOg ethyl acetate; 0.786 g/l3tg iso-butylalcohol; insoluble in ether (5).

W0-D17-84-C-4133 51-I

SODIUM PERCHLORATE


Hygroscopicity: Deliquescent

Density (Crystal): Specific Gravity: 2.02 (2)



Specifi. Heat: Data not available

Heat ,f Combustion: Data not available

Reactivity: A powerful oxidizing agent, readily combustible if mixedpith organic material (6). Pure NaCIO, is insensitive to impact(5). Strong oxident when heated, particularly under acidicconditions. Forms an explosive with ammonium nitrate, calciumhydride, charcoal, magnesium, strontium hydride and with reducingagents (I).



II. USES

A. Ary Unique Use

Explosives, pyrotechnics'

B. Other Uses

Jet fuel, analytical reagent (2)

"III* ANALYTICAL METHODSSA* Best Acceptable Method

Sodium can be determined by atomic absorption or by atomic emissionspectrometry as described by Bee (7).

A perehlorate membrane selective electrode has been developed, but it:i/k may not be sensitive for trace analysis. Khokhlova et al. have used

this electrode to study activity coefficients of perchlorate ions (8).


Hee reports a lower determination range of 0.01-0.1 ug/ul for sodium (7). ."

DAMD17-84-C-4133 51-2

SODIUM PERCHLORATE

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF SODIUM PERCHLORATE


Human oral Therapeutic Nausea, vomiting, and (3)dose levels hypersensitivity re-

actions such as maculo-papular rashes, fever,and lymphadenopathiesmay occur; fatal aplas-tic anemia has occurredin a small proportionof patients; agranulo-cytosis, thrombocyto-penia, and leucopeniahave been reported;antithyroid activity

Human contact NS* Irritation of skin, (5)with throat, eyes, anddust nose

Rat oral 2,100 mg/kg LD 0 ; effects on (9)- be~av'ior, pulmonary

system, metabolism

Rat intra- 20 mg Antichyroid activity (10)peritoneal

Mouse intra- 551 mg/kg LD (9)peritoneal

Rabbit injection aqueous No long term toxic (5)solution; effects; "behaved asconc. and a mild muscularduration NS poison"; large doses

produced diarrhea andliver damageI *Not specified

II

N'

4 DAMD•7-84-C-4133 51-3 t

A-,(.-":' :•"'::? "" "• .••, 4 v .:,,. .

SODIUM PERCRLORATE

TABLE IV-2. MUTACENICITY AND RELATED EFFECTS OF SODIUM PERCHLORATE


E. coli 1500 pmol/ Active (9)DNA repair plateassay

* Not specified






Ale. Leachability - Data not available

MAd. Bioaccumulation - Data not available )A2. Transformation-- Data not available

A2a. Biodegradation - A few microorganisms are able to metaboliteperchlorate; most are not. It has been reported that perchlorate isreduced to chloride by several species of heterotrophic bacteria,including the very common E. coli and Paeudomonas a. SomeStreptococcus and Flavobscterihum. s were inactive (1i).


&2c. Photolysis - Data not available


{ A2e. Walf-life - Data not available


.•e. Avian species Data not available


3•: 3. Terrestrtal invertobrate - Data not available

34. Reptiles -D Data not available

iU.-

'U. DA•-17-84-C-4133 51-4L <.•

SODIUM PERCHLORATE

BS. Amphibians -- The acute toxic level of sodium perchlorate to tadpolesis reported to be 2000 mg/L. Chronic effects appear at much lowerlevels. Newts maintained at a level of 36 mg/L of perchlorateexhibit significant histological changes in the thyroid andpituitary. Continuous exposure to 360 mg/L results in arrestedmetamorphosis in tadpoles and a grossly enlarged thyroid in guppies(11).

B6. Microorganisms, aquatic and soil -- A 2% solution of sodium perchloratewill check the growth of E. coli; about 10% is required to check thegrowth of Staphylococcus aureus and Sterigmatocystic n (11).Sodium perchlorate added to incubated soil caused inhibition of therespiration activity and a decrease in the number of ammonifying,nitrifying and denitrifying bacteria. +In pure cultures of soilbacteria, the reduction of NO to NH4 , the reduction NO to N0-2and NO 3- utilization were inhibited. The C1O4- ions act in two ways:by liberating metabolites (CI-) toxic to the cells and by competingwith NO3 for the nitrate reductase A enzyme (12).

B7. Aquatic species, fish and invertebrates - Although few definitivestudies have been conducted, it appears that the acute toxicity ofperchlorate ion to aquatic animals and microoganisms is very low,with toxic levels probably exceeding 1000 mg/L for periods of 24hours and longer. Because perchlorate is an important antithyroidagent, chronic effects may appear at much lower levels (11).

, C. Effects on plants

C1. Phytotoxicity -- Soybeans grown in water culture exhibit toxic symptomsat perchlorate levcls as low as 2.5 mg/L four days after application.Soybeans grown in sand were noticably less susceptible (11).

Ql. Uptake - Uptake of iodide by the seaweed Fucus ceranoides is

* i:-i competitively inhibited by perchlorate at th"-e 0.1 gL level in

seawater (11).



SA. Health

Data not available

B. Envirpnx.ental

Reported in EPA TSCA Inventory- 1983.

WAMD17-84-C-4133 51-5

. .,".,

SODIUM PERCHLORATE

VII. DISPOSAL

A. Current Recommended A Dispual Practices

Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve open burning, opendetonation or hauling by a licensed contractor and landfilling. Thishas also been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (13).

B. Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by APRADCOM and is planned for use atinstallations such as Savanna Army Depot, Tooele Army Depot, andHawthorne Naval Ammunition Depot (14).

Co Other Disposal Practices Employed

Use vast volume of concentrated solution of reducing agent (bisulfitesor ferrous salts with 3M-H SO or hypo). Neutralize with soda ash ordilute with BC.. Drain inio i sewer with abundant water (6).

Bury in a landfill site approved for the disposal of chemical andhazardous waste (15). )

VIII. REFERECES

1. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds.1983. Tht Merck Index, 10th ed., p. 8501. Merck and Co., Inc.,Rahway, NJ.

2. Hawley, Gessner G. 1981. The Condensed Chemical Dictionary, 10thede, p. 948. Van Nostrand-Meinuold Co., New York, NY.

S3. •Reynolds, James E.F, and Anne B. Prasad, eds. 1982. Marti.ndale-TheExtra Ph.rmaopoeia, 28th ed., p. 358. The Pharmaceutical Press,

* ~~~London , ngad

4. Weast, R.C. 1968. CRC Handbook of Chemistry and Physics, 48th ed.,~.D-52. The Chezical u~bber Co., Cleveland, OH*~

"5. International Technical Information Institute (ITI), 1982, Toxicand, Hzardous Zndustrial Chamvcals Saf Hanual, p. 486.International Technical Infoftation Institute, Tokyo, Japan.

6. Kaye, Seymour. 1978., Eucyclopedia of xplosive and Related ltamr,"Vol. 8, p. 167. U..$ Army Armament Research and Developasnt Command,Dover, NJ.

D&aDO7-84-C-4133 51-6L

SODIUM PERCHLORATE

7. Hee, S.S.Q., T.J. Macdonald, and J.R. Boyle. 1985. Effects of AcidT-T Type and Concentration on the Determination of 34 Elements by

Simultaneous Inductively Coupled Plasma Atomic Emission Spectrometry.Analytical Chemistry. 57(7) :1242-1252.

8. Khokhlova, A.I., L.P. Shishin, and G.E. Chernikova. 1983. Study ofActivity Coefficients of Perchlorate lona and Hydration in AqueousSolutions. Zh. Fiz. Khim. 57(11):2736-2739.

9. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Registryof Toxic Effects of Chemical Substance, Vol. 3, p. 27. NationalInstitute for Occupatlonal Safety and Health, Cincinnati, OH.

10. Onaya, Toshimasa, Yamada Takashi, and Nicholas S. Halmi. 1973.Intrathyrodial Recycling of Iodide in the Rat: Effects ofGoitrogens. Proc. Soc. Exp. Biol. Med. 181-184.

11. Burrows, Dickenson, Dr., and Dr. Jack C. Dacre. 1974. Toxicity toAquatic Organisms and Chemistry of Nine Selected WaterbornePollutants From Munitions Manufacture-A Literature Evaluation.Technical Report 7503, AD A010660. US Army Medical Research andDevelopment Command, Washington, D.C.

12. National Library of Medicine (NIM), Toxicology On-line (ToYline).Accession No. 069954R. 1985.

. 13. David Renard, U.S. Army Toxic and Hazardous Material Agency, toJ. Carl Uhrmacher (personal communication). 1985.

14ý. Forsten, I. Disposal of Uazardous Toxic Munition Waste. Proceedingsof the 1980 National Conference of Environmental EngineerHi -NewSYo1, July 8-10, 198 ASCE Environmental Engineers Division, NetYork. 440-575.

L,

A.

Diifl-8-C413 1-

• •. .....i

STRONTIUM OXALATE

Much of the available data on strontium oxalate has been reported in aprevious study by the Atlantic Research Corporation (ARC), entitled APreliminary Problem Definition Study of 48 Munitions-Related Chemicals. Datareported herein reflects information more recent than that reported by ARC in1978.



Chemical Formula: SrC2 04 • H 20 (1)

Molecular weight: 193.64 (1)

Structural formula:

sr +--.

B. Aiternaae NaMes and Regisry Numbers


)Deleted CAS Registry Number 14529-93-2

CA Name (9CU): Ethanedioic acid, strontium salt (1:1)

CA Nam3 (eCI): Oxalic acid, strontium salt (1:1)


Other significant syuonyu : Data not available


Physical State: Crystalline powder (1)


Odor: Odorless (1)

"IMeltig Point: 150 °C with lose of 10 (1)

DAKDI 7-84-C-4133 52-1

STRONTIUM OXALATE (cont.)

Solubilities:Water: Slightly soluble (1), 1 in 20,000 parts water; I in 1900parts of 3.5% acetic acid; I in 1115 parts of 23% acetic acid, butless soluble in 35% acetic acid; readily soluble in dilute HCI orHNO3 (2).Nonaqueous Solvents: Data not available








Reactiv•,ty: Hydrolyzes to form oxalic acid and strontium hydroxide.Thermal decomposition proceeds with an initial loss of water,formation of strontium carbonate and finally formation ofstrontium oxide (1).



SII. USES

A. ArvRiu Use

Constituent of R-256 tracer mix used in the M-27, .50 calibertracer rounds (1).

B. Other Uses

Radiator cleaner (1)

DAMD17-84--C-4133 52-2

• •, .. , I:

I16




No methods have been developed to analyze strontium oxalate as acomplete entity since the publication of the ARC report. Newer methodshave been developed for the analysis of strontium such as simultaneousinductively coupled plasma atomic emission spectrometry as reported byHee et al. (3).


Hee et al. reported a lower determination limit range for strontium as<0.001 ugll,. (3).

I

" L4DI7-84-C-4133 52-3


iv. HEALTH EFFECTS

TOXICITY OF STRONTIUM OXALATE*

Chemical Route Effects Reference

Strontium No toxicity data located;oxalate data on chemical classes

follow below

Strontium oral, Moderately irritating; the (4)Salts inhal- strontium ion has a low order

ation of toxicity

Oxalates oral, High acute toxicity (4)inhal-ation

local Powerful irritant; corrosive (4)to tissue; when taken by mouth,oxalates produce a causticeffect on the mouth, esophagus,and stomach

" :Information not included in the .C-report

V. ENV1ROb{MNTAL QEFFECTS

No inforzation wat found regardit the envirotaental fate or efects ofstrontium oxalate which bioul updaaw the tlantic Research Corporationdocument.

-V. STADAUDS AND REGULATION'S

A. Health

Data not available

!•B. Envirorzental

Reported in EPA T'CA Inveatory.

""i1 £'..,.sa',.*"


VII. DISPOSAL


A recent programmatic life cycle environmental assessment indicatesthat incineration is the preferred method for disposal ofsmoke/obscurant munitions. Muuitions containing strontium oxalateshould be incinerated in a unit equipped with afterburner and ascrubber; scrubber overflow should bc neutralized prio: to discharge (5).


Data not available


Data not available

VIII. REFERENCES

1. Kitchens, J.F., S.G. Brownlee, W.E. Harward, III, E.G. Hyde, W.E.Jones, III, D.A. Price, R.S. Wentsel, and R.S. Valentine. 1979.Preliminary Problem Definition Study on Munitions-Related Chemicals.Final Report, AD A099733. Atlantic R(.search Corporation, Alexandria,VA. DAMDI7-77-C-7057.

2. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, ads.1983. The Merck Index, 10th ed., p. 1267. Merck and Co., Inc.,Rahway, NJ.

3. Hee, S.S.Q., T.J. Macdonald, and J.R. Boyle. 1985. Effects of AcidType and Concentration on the Determination of 34 Elements bySimultaneous Inductively Coupled Plasma Atomic Emission Spectrometry.Analytical Chemistr. 57(7):1242-1252.

4-. Sax, N.I. 1979. Danerous Properties of Industrial Materials, 5th

*I ed. Van Nostrand-Reinhold Co., New York,, NY.

5. YoU, R.L., Dr. Randall S. Wentsel, and John M. Bane. 1983.* - Programmatic Life Cycle Environmental Assessment for Smoke/Obscurants,

-iVolume 2-Red, White, and Plasticized White Phosphorus. TechnicalReport No, 33064, AD A135910. Chemical Research and DevelopmentCenter, A,'!rdeen Proving Ground, MD.

* .. 52-.K U•"A•7-84-C-413-3 52-5

........................................... '..

TETRANITRO CARBAZOLE

Much of the available data on tetranltorcarbazole has ben reported in aprevious study by the Atlantic Research Corporation (ARC) entitled APreliminary Problem Definition Study of 48 Munitions-Related Chemicals.Data reported herein reflects information more recent than that reported byARC in 1978.

SI. CHEMICAL AND PHYSICAL DATA

A. Structural a4d Chemical Formulas and Molecular Weight

Chemical Formula: Ci NsO


Structural Formula:

N

N0 2 H NO 2



CA Name (9CI): 9H-Carbazole, 1,3,6,8-tetran.tro

CA Name (8C1): Carbazole, 1,3,6,8-tetranitro

Alternate CAS Registry Number: 28453-24-9

* 'Alternate CA Name (9C!): 9H-Carbazole, tetranitro

Alternate CA Name (8CI): Carbazole, tetranitro

RTECS Number: Not listed in RTECS

SOther Significant Synonyms: TNC IF

CPhysical P tes

Physical State: Powder (1)WA

K DAX1D17-'84-C-4133 53-1 1A.*~

-~ *5,

TETRANITROCARBAZOLE (cont.)

Color: Yellow (1)


Melting Point: 285 0 C (1)

Solubilities:Water: Insoluble (1)Nonaqueous Solvents: Soluble in hot acetone (1). Soluble in benzene;insoluble in ether, alcohol and chloroform (2).


Hygroscopicity: Not hygroscopic (2)




Specific Beat: Data not available


Reactivity: Data not available,a

FStability: Data not available

* . lammability: Data not available

II. USES

LA AMY U Use

TNC is a constituent in a yellow first-fire mixture that is used toignite the primary explosive charge (1).

B. Other Uses

L Less than 25 pounds per year consumed for civilian purposes. Formerlyused in fireworks (1). Compound has been cited in a Japanese patent

" L and 1,3,6,7-TNC specifically for use in electrophotographicphotosensitive plates (3).


No analytical methods were reported in Chamical Abstracts in aV•[ computerized search of both registry numbers, dating back to 1967.

DAMPD17-84-C-4133 53-2

-. ,'•.-. .','-"---' lJ....

"T'ETRANITROCAR.BAZOLE (coat.)

IV. HEALTH EFFECTSJ . TABLE IV-1 * HEALTH EFFECTS RELATED TO TETRANITROCAE.BAZOLE*

Chemical Effects References

Tetranitrocarbazole Unknown, probably toxic (4)

Organic nitrates and Vasodilation, headache, (5)nitrites dizziness, weakness, and

other signs of cerebralischemia associated withpostural hypotension;large amounts may producecoma, convulsions, andcollapse

sJa~a On 'Analog -ý

2,4 ,7-Trinitro-9- Carcinogenic and mutagenic. (6)fluorenone**

27Dntoloee* Carcinogen 4.c and mutagenic (6)

L~jformation not includae in the ARC report**Struicturally related to tctrandtrocarbazole

V. ENVIRON&ENTAL EFFECTS

* No information was found regardin. the environmental fate or effects oftetranitrocarbazc'le that updates tb'i ARC report.

V1. STANDAP.DS AND REGUL&TIONS,

ko Health

Diata not available

Be Environmental

Data not available

iL.

L. 1-4--43 53-3

TETRANITROCARBAZOLE (cont-)




B. Alternate Disposal Practices under Consideration by the Amy

SFuture plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and Hawthorne NavalAmmunition Depot (8).


Small Spill: Absorb or sweep on paper. Burn in iron pan in fume hood.

Large Spill: Mix with sand. Package in paper carton. Transfer tosanitary landfill. Wash spill site with strong soap and water (4).

VIII. REFERENCES

t 1. Kitchens, J.F., S.G. Brownlee, W.E. Harward, I1I, R.G. Hyde, W.E.Jones, III, D.A. Price, R.S. Wentsel, and R.S. Valentine. 1979.Preliminary Problem Definition Study on Munitions-Related Chemicals.Final Report, AD A099733. Atlantic Research Corporation, Alexandria,VA. DAMDI7-77-C-7057.

2. Kaye, Seymour M. 1980. Encyclopedia of Explosives and RelatedItems, Vol. 9, p. T-82, PATR2700. U.S. Army Armament Research andDevelopment Command, Dover, NJ.

3. Copyer Co., Ltd. 1982. Electrophotographic Photoconductors,Japanese Patent 57/182749 A2 182/1882749].

4. Material Safety Data Sheet-Tetranitro Carbazole. 1977. SandozL Chemical Corporation, Charlotte, NC*

5. Gilman, Alfred Goodman, Dr., Dr. Louis S. Goodman, and Dr. AlfredGilman. 1980. Goodman and Gilman's The Pharmacological basie of

:q Th~erputies, p. 824. Macmillan"Publtfliing Co., Inc., NOw Yorot NY.

5 L DAMD1-94-C4133 3-4

$•. + •. -3

TETRANITROCARBAZOLE (cont.)

AN 6. Tatken, Rodger L., and Richard J. Lewis, Sr. 1981-82. Registry ofToxic Effects of Chemical Substances, Vol. 2, p. 321. NationalInstitute for Occupational Safety and Health, Cincinnati, OH.

7. David Renard, U.S. Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communication). 1985.

8. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1580. ASCE Environmental EngineersDivision, New York. 440-575.

A(II

A -4M

!R,

DIJ17-84-C'.4133 53-5

I ..

TETRYL



Chemical Formula: C7H5 N5 08


Structural formula:

H3C%,, N NO2

N02 -)



CA Name (9CI): Benzenamine, N-methyl-N,2,4,6-tetranitro-

CA Name (8CI): Aniline, N-Methyl-N,2,4,6-tetranitro-

RTECS Number: BY6300000

Other Signficant Synonyms: Nitramine; Tetralite; Tetril; 2,4,6-Tetryl;Trinitrophenylmethylni tramine; 2 , 4,6, Trini trophenyluathylnitramLne

C. Chql!cal and Physical P,,roperte

Physical State: Monoclinic crystals (X,•Ni

K Color: Yellow,q

D M 17-84-C-4133 54-1

TETRYL (cont.)


Melting Point: 1.30-132 00

Boiling Point: 180-190C

Solubilities:Water: Insoluble (1)Nonaqueous Solvents: Soluble in alcohol, ether, benzene, glacialacetic acid (1).






Specific Heat: 0.0523 + 6.62 X 10 T cal/g/ C

Heat of Combustion: 2,925 kcal/kg (2)

Reactivity: Severe explosive hazard when shocked or exposedto heat or flame. Sensitive to percussion (3). Dangerous firerisk (4). Highly resistant to attack by dilute u..aeral acids(5). Does not react with aluminum, tin, copper, nickel lead or Cu-plated steel, bronze and stainless steel (5).

ýiVapc~r Density: 9.92 g/cc

Stability; Fairly resistant to gamma radiation (6).

Rest of Combustion: 2,925 cal/g (6)

Flammability: Autoignition temp o1660 C; explosive temperature257 0 Co Explodes at 180 to 190 0C (7).

II. USES

As Amy Uniqu Use

9'High explosive

B6 Other Uses

Acid-base indicator;, pH 10.8 colorless; pH 13.0 reddish brown (1).

IL0 -6--43 54-2

TETRYL (cont.)

11. ANALYTICAL METHODS


Several chromatographic methods are reported in the recent literature.Lloyd reported a high performance liquid chromatography method thatused a pendant mercury drop electrode at the detector. This methodcompares favorably with electron capture detection in gaschromatography (8).

A thermal energy analyzer (TEA) interfaced with a gas or liquidchromatograph was reported by Fine (9) to detect explosive in debriswithout prior clean-up.

Cantu et al (10) reported success using a Fourier transform infraredspectrometer coupled with HPLC.

Yinon (11) described a custom built mass spectrometer interfaced withan HPLC that can successfully analyze tetryl and other explosisves.Malotky and Downes (12) reported a field kit for the analysis of 28

different explosives including tetryl using thin-layer chromatoraphy.


Lloyd (8) reported a detection limit of 2-20 picogram/10 microliters ofinjected sample.

Fine (9) reported a detection limit of <10 picograms.

L

. 5

' L DAMD1,-84-C-4133 54-3,i

TETRYL (cont.)

IV. REALTH EFFECTS

TABLE IV-1. TOXICITY OF TETRYL


lHuman inhal-ation NS* Potent sensitizer causing (13)skin and allergic dermatitis.eye Severe cases show massive

generalized edema withpartial obstruction ofthe trachea. Acutely irritating to themucous membranes of therespiratory tract and eyescausing coughing, sneezing,epistaxis, conjunctivitis,

t and palpebral edema.Systemic effects includeirritability, easyfatigability, malaise,headache, lassitude,insomnia, nausea, andvomiting. Anemia of boththe marrow depression ordeficiency type.

Human occupa- NS Powerful sensitizer (14)tional causing dermatitis. Localexposure irritation of the conjunc-

tiva, nose, throat andbronchial tubes, producingcommon cold-like symptoms,r nose bleed, cough, andoccasionally asthma-like symptoms. No reports

IV "of systemic or internalpoisoning.

Human inhal NS Gastrointestitkal symptoms (15)ation and anemia may develop.skin May cause tracheitis and

asthma.

t; Rat oral I g/kg Necrosis of the liver and(route daily up degeneration of the kidney (16)implied) to 3 so

SDAhMD17-84-C-4 133 54-4

'V

TETRYL (cont.)

TABLE IV-1. TOXICITY OF TETRYL (Cont.)


Dog sc 5,000 mg/kg LDLo (17)

* Not specified

TABLE IV-Z. CARCINOGENICITY OF TETRYL


Female oral 10 doses of 40 No effect, but study (18)Sprague- mg/rat at 3-d is inadequateDawley intervals;rat observed for 9 mo

:a• -

DAMWI7-84-C-41.13 54-5

>Vt%..

TETRYL (cont.)

TABLE IV-3. MUTAGENICITY AND RELATED EFFECTS OF TETRYL


Salmonella 33.3 or Mutagenic with and (19)typhimurium 100 ug/ without Aroclor 1254-TA98, TAi00 plate induced rat liver S9.TA1537, TA1538

Saccharomyces 62.5 and Increased frequency of (19)cerevisiae 125 ug/mi mitotic recombinationD5 in the absence of Aroclor

1254-induced rat liverS9. Not active with S9.

S. typhimurium 5 ug/plate Analytical-grade: muta-TA100, TA1535 genic in TA100 and TA1535% (20)

SMilitary-grade: mutagenicin TAI00 but less rothan analytical-grade

S. cervisiae 5 ug/p..ate Mutagenic causing mitotic (20).D4 gene cqnversiomý

at ado and trp

' NeurosRora 10 ug/ huta en.ic inducing (20)crassa plate ad-3 reversions.

Ve ENVIROMMNTAL EFFECTS

he 1Envirormental Fate

MA. Transport - Data not available

,Ala. Adsorption -- A six-month study showed very little detectable movement oftetryl or its trannformation products through soil columns in

Vii that time frme, This may be combined result of soil fixationand limited vater solubilities of the cwapounds (21).

Aib. Volatilization - Data not available

Ale. Infiltration - Data not available

Aid. tioaccuaulation Data not available

2A/. Transforwation- Data not available

ttA)W17-8-C-4133 54-6

TETRYL (cont.)

A2a. Biodegradation -- Biodegradation in 7 day tests: nil % degradation in

original culture, neither in Ist, 2nd or 3rd subculture (22).

A2b. Hydrolysis -- In natural waters tetryl is slowly degraded to picricacid. Authors recovered no information indicating that wastewatereffluents containing picric acid or its metabolite, picramic acid, inconcentrations anticipated from the degradation of tetryl, wouldpresent an environmental hazard, either directly or indirectly (23).The principal detectable product of the hydrolysis of tetryl in thedark, in borax buffer, is methylnitramine. Other identified productsinclude: picrate ion, nitrite ion, N-methylpicramide, and nitrateion. In a 110-day test, no degradation of the methylnitramine wasnoted (24).

A2c. Photolysis - Tetryl photolyzes under ambient lighting conditiong-at

least an order of magnitude faster than it hydrolyzes. The major

photoproduct is N- methylpicramide (trinitromethylaniline) (24).

A.d. Other chemical reaction - Tetryl reacts in concentrated sulfuric acid

to form N-methylpicramide (24).

A2e. Half-life - The hydrolysis half-life of tetryl was estimated for a"range of activation energies, for environmental conditions of 209C

and pU 6.8, to be approximately equal to 302 days (plus or minus 76

days). The author notes that some soils might have a strong

accelerating effect on tetryl's hydrolysis rate u-hich could

drastically alter its environmental hydrolysis half-life (24).


Bi. Avian species - Data not available

S2. amma.lian wildlife species - Data not available



85. Amphibians Data not available

B 6. ftcroorganisas, aquatic and soil Data not available

f B7. Aquatic specles, fish and invertebrates - Data not available

C. Efeacts on Plants


C2. Uptaka - Data not available

DAM4D17-84-C-.4133 5-

TETiYL (cont.)

C3. Mletabolism -- Date not available

Vi. STANDARDS AND REGULATIONS

A. Health

TLV: TWA 1.5 Ig/cu m (skin) (25)STEL 3.0 mg/mr (skin) (2p)PSHA-air: TWA 1500 ug/m (Skin) (26)DOT-class A explosive (27)Tentative STEL value: 3.0 mg/m3 (28)

B. Environmental - Data not available

VII. DISPOSAL

A. Current Recommended Arm ispoal Practices

Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve open burning, opendetonation or hauling by a licensed contractor and landfilling. Thishas also been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USAT1H1AI), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (31).

B. Alternate Disposal Practices under Zonsideration by the Armv

Future plans for disposal of waste explosives and propellints areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use atinstallations such as Savanna Army Depot, Tooele A"roy Depot, andHawthorne Naval Amunition Depot (32).


Pour into sodium bicarbonate or a mixture of gand-soda ash (9:1).J.-J After mixing, transfer into a paper carton filled vith packiag paper.

Burn ir an open furnace, or more efficiently, in a iuraace withaf terbu:ner and scrubber (4).

Tetryl can be decomposed by heating it with an aqueous sodium sulfidesolution. (kef ere-e provides specific procedure)* Supernatant liquidis discharged to a sump and any precipitate is burned in a burningground (29). Activated carbon with regeneration capacity wasrecoimended system for removal of tetryl aong other compounds frommunitions vastvater, In a study which compared carbon and polymericresin adsorbents for this purpooe (30).

"",DI 7-84-C-4133 54-8

T•TRL ( cont. )

VIII. REFERENCES

1. Windholz, M., Budavari, S., Blumetti, R.F., Otterbien, E.S., eds.1983. The Merck Index, 10th ed., pp, 942-943. Merck and Co., Inc.,Rahway, NJ.

2. Fedoroff, Basil T. and Oliver Eo Sheffield. 1964. Encyclopedia ofExplosives and Related irems, Vol. 4, p. 380. U.S. Army Armament Researchand Develpmenr Command, Dover, New Jersey.

3. Sax, N.I. 1979. Dangerous Properties of Industrial Materials, 5thed., p. 1023. Van Nostrand-Peinhold Co., New York, NY.

4. International Techni\.&l Information Institute (ITI). 1982. Toxic andHazardous Industrial aemic-.ls Safety Manual, pp. 514-515.InternatioDal Technical Information Institute, Tokyo, Japan.

5. Yaye, Seymour M. 1980. Encyclopedia of Explosives and Related Items,Vol. 9, p. 1. ,. U.S. A_-my Armament Research and Development Command,Dover, NJ.

6. Army Matcr'el Command (AMC). 1971. Engineering Design Handbook,pp. 335-340. AD 764-340. Army Materiel Command, Washington, D.C.

7. Batson, R. 1983. Hazardous Component Safety Data Sheet on Tetryl.No. 116. U.S. Army Armament Research and Development Command, Dover,NJ.

31. Lloyd, J.B.F. 1983, Screening for rrganic Explosives Components byHigh Performance Liquid Chromatography with Detection at a PendantMercury Drop Electrode. Proceedings of the International Symposium onthe Analysis and Detection of Explosives. Washington, D.C. FederalBureau of Investigation, Washington, D.C.

9. Fine, D.H., Yu, W.C., and goff, E.U. 1983. Applications of the Nitro/Nitroso Specifiec Detector to Explosives Residue Analysis. Proceedingsof the International Symposium on the Analysis arid Detection ofExplosives. Washington, D.C.

10. Cantu, A.A., Wahington, W.D., Strotel, R.A., Tonterski, .E. 1983.Evaluation of FITR as a Detector for the HPL3 Analysis of Explosives.Proceedings of the International Symposium on the Analysis andDetection of Expl e Washnon, D.C., _83. -Federal Bureau ofInv•'stigation, Washington, D.C. 349-363.

11. Yinor, J. 1983. Analysis of Explosives by LC/MS. Proceddings of theTexraational Symposittm on the Analysis and Detection of Lx logi*S-o

Waahington, .D.C., 1983. Federal Bureau of Investigaticn, Washington,DC. 207-234.

tAMDI7-84-C-4133 54-9

= m"l ,---

TETRYL (Con%.)

12. Maiotky, L., Downes, S. 1983. Explosives Analysis Kit. Proceedings'Aof the Internarional ESositm on the Analysis and Detection of

rxplosives. W-,whiuagton, D.C., T9 3. Fderal Bureau of Invesi~garion,Washington, D.C. 63-65.

13. Sittig, Marshall. 19R1. H~andbook of Toxic and Hazardous Chezicals,p.85-1. Noyes Publicatiocm, Fark Ridge, New Jersey.

14. MclConnell., William F., tolow..l, Lieutenant Colonel Robert G. FLinn, andL.ieutenant Colonel. Allen D. Brandt. 1946. Occupational lseases inGovernment Owned Ordnance Explosives Plants, Occupational Medicine1:551.

15. Sax, NI. 1979. Dangerous Properties of Industrial Materials, 5th ed,E p. 1.023. Van Nostrand-Reinhold Co., New York.

16. Fati, S. and E. Daniele. 1964. Istopathological Data cf ChronicalExperimental Intoxication of !,'r.ryl. Folia Medita. 47:269.

17. National Inszitute for Occupational Safety and Health 'NIOSH),Registry of Toxic Effects of Chemical Substances. 1991-1982oNational Institute for Occupational Safety-and Health.

4: 18. Griswold, Jr., D*P., A.E. Casey, E.K. Weisburger, and J.H. Weisburger.1968. The Carcinogenicity of Multiple Intragastric Doses of Aromaticand Ilerocyclic Nitro or Amino Derivotives in Young Female Sprague-Hawley Rats. Cancer Research 28:924-933.

19. McGregor, Douglas B3., Col~in G. Riach, Ronan M Hastvell, and Jack C.± ~. Dacre. 1980o Genotoxic Activity in Microorganisms of Tetryl, 1,3-

Dinitrobenzene and 1,3,5-Trin~itrobenzene. Environmental Mutagenesis2:531-541.

L 20. Whong, Wen-Zor;,, Norman D. Specimer, and Gordon S. Edwards. 1980.Mutagenic Activity of Tetryl, A Nitroaromatic Explosive, in ThreeMicrobial Test Systems. Toxicology Letters 5:11-17.

21. Hale, Vetrle G., Thomas B. Stanford, and Lee G. Taft. 1979. Evaluationof the Environmental Pate of Munition Compounds in Sodf.l. AD 082874.US Army Medical Research and Develpment Command, Fort Detrick,Frederick, MD.

22. Verschueren, Karel. 1983. Handbook of Environmental Data on OrganicChemicals. 2nd ed., p. 589. Van Nostrand-Reinhold Co., Now York, NY.

23. Burrows, Tlickensen, Dr. and Dr. Jack C. Dacre. 1975. Toxicity toAquatic Organisms and Chemistry of Nine Selected Waterborne PollutantsFrom Munitions Manuyfacture-A Literature Evaluation, Technical Report7503, AD A010660. US Army Medical Bioenginearing Research and

NIDevelopment L&boratory, Fort Detrick, Frederick, MD.p

DAMD17-84-C-4133541

*. ' If

TETRYL (cont.)

24. Kayser, Eleonore G., Nicholas E. Burlinson, and David Rosenblatt. 1984.Kionetics of Hydrolysis and Products of Hydrolysis and Photolysis ofTetryl. Technical Report 8648. Naval Surface Weapons Center, SilverSpring, MD.

25. American Conference of Governmental Industrial Hygienists (ACGIH).1984. TLV's Threshold Limit Values for Chemical Substances andPhysical Agents in the Work Environment and Biological Exposure Indiceswith Intended Changes. American Conference of Governmental IndustrialHygienists, Cincinatti, OH.

26. American Conference of Governmental Industrial Hygienists (AGIH).1984. Documeutation of THreshold Limit Values for Substances inWorkroom Air, 4th ed., p. 395. American Conference of GovernmentalHygienists, Cincinatti, OH.

27. Federal Register. Vol, 39, p. 23540.

28. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial h ie and Toxicology, 3rd ed., Vol. 2A, p. 2479. JohnWiley and Sons, New York, NY.

29. Fedoroff, Basil T. and Oliver E. Sheffield. 1966. Encyclopedia ofExplosives of Related Itmes, Vol. 3, p. 33. US Army Armament Researchand Development Command, Dover, NJ.

30. Szachta, James M. 1978. Analysis of Carbon Versus Resin. TechnicalReport 78013, AD A053863. Chemical Systems Laboratory, AberdeenProving Ground, MD.


32. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10,7180 SCE Environmental EngineersDivision, New York. 440-575.

DAMDI7-84-C-4133 54-11

• :• .''i . • .. .' ".... ...... .. -.. . - :•• -": ..A*.:i

TITANIUM TETRACHLORIDE

I. CHEMICAL AND PHYSICAL~ DATA

A. Structural and Chemical Formulas and Molecular Wih

Chemical Formula: TiC1 4 (1)


Structural Formula:

C1

0C.-1 Tit4-- Cl-

C 1

Bo. Alternate Names and Registry Numbers


Dele ted CAS Registry Numbers: 44246-22-2, 15612-71-2

CA Name (9C1): Titanium chloride (TiCl4)

CA Name (8C1): Titanium chloride (TiC14)

RTECS Number: XR1925000

I : Other Significant Synonyms: Tetrachiorotitanium


Physical-State: Liquid (1)

Color: Colorless (1); light yellow (2)

Odor: Panetrating acid odor (1)

Melting Pjorati -2. C (1)

IsDA0i7-~80-C-4133 55-1

TITANIUM TETRACHILORIDE (cont.)

Boiling Point: 136.4 0 C (I)

Solubilities:Water: Soluble in cold water, decomposed by hot water (1), solublein dilute HCl (2).Nonaqueous Stn.znts: Soluble in alcohol


Hygroscopicity: Hygroscopic (1)

Specific Gravity: 1.726

Volatility: Volatile, adsorbs moisture through the air and evolvesdense white fumes (1).

Vapor Pressure: 100 mm at 910C (3), 11.7 mm at 250C



Reactivity: Reactive only under extreme conditions (3). -


Flammability: Nonflammable (3)

1I. USES

A. A Unique UseI,

Smoke agent "FM" (4)

B. Other Uses

Formerly used with potassium bitartrate as a mordant in textileindustry, and with dyewoods in dyeing leather; also as smoke-producing

'4 screen with amonia and in the manufacture of iridescent glass andartifical pearls (1).

Laundering; chemical production; and in chemical laboratories (3).

4"4

DAMD17-84-C-4133 55-2- -4- 3i

}il -

I TITANIUM TETRACHLORIDE (cont.)

ii I!I. ANALYTICAL METHODS


Titanium can be determined through atomic absorption or atomic emissionspectrometry (AES). Kee reported a simultaneous inductively coupledplasma AES method for determining titanium and 33 other elements.

B. Limit of Detection1ee reported a lower determination limit range for titanium as <0.001microgram/milliliter.

At

j N

VV

DAMD17-84-C-4133 55-3

Af

TITANIUM TETRACHLORIDE (cont.)

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF TITANIUM TETRACHLORIDE


Human inges- NS* Nausea, vomiting, cramps, (6)tion diarrhea, and possible

tissue ulceration

Human contact NS Thermal and acid burns of (6)with eyes, skin, throat, andliquid stomach; lasting deep

brown pigment about theperiphery of the scarsand in areas of healedburns

Human contact NS Severe irritation and (7)with damage to eyes, coughing,vapor headache, dizziness, lung 7)

damage, and bronchialpneumonia

Human inhal- Approx. 2 Pulmonary burns followed (8)ation min after by diffuse endobronchial

industrial polyp formationaccident

Human NS NS Late development of upper (6)respiratory and nervoussystem disturbances

3Rat inhal- 460 mg/m LC5 0 (9)"tion 4 hr

3:!!!,:"Mouse inhal- 10 Mglm3 o. (9 )Mouse ation 2 hr

Guinea pig skin 2x/d for 3d Destruction of the outer (7)(albino) (liquid) layers of the skin comp-

arable to a second-degreethermal burn

DAMD17-84-C-4133 55-4•.•., • .", .

•i,

TITAN'IUM TETRACHLORIDE (coat.)

I ~TABLE IV- 1 * TOXICITY OF TITANIUM TETRACH{LORIDE (Coint.)

*Species Route Dose/Duration Effects Reference

Dog inhal- intermit- Respiratory distress with (7)ation tent expo- vomiting; decreased blood

sure; of pressure, increased pulse1-2 h-; and respiration rate;conc* not focal congestion and hem-measured orrhage of the lungs with

particulate deposits ofTi in the alveoli; mortal-ity due to intense bron-chitis and some edemainterpreted as liCL effects

FDog inhal- 6 hrld, 5 No weigh~t loss; increased (7)ation dhik, 9 wk; leukocyte count; lung

conc.: 8.4 foci consisting of mono-ppm Ti, 6.8 cytes with brown Ti gran-ppm, volatile ules grouped around the

-chloride bronchi and necrotic cells( ~associated with prolif era-tion of connective tissue

*Not specified

-:V. ENVIRONMENTAL EFFECTS

A. Environmental FateAlKrnpr at o vialAla. TAdsporptio - Data not available

Al1b. Volatilization -- Data not available

Ale. Leachability ~- Data not available

Id. Bioccmultio -Concentration fatr of' 200 t.o 10,000 f~or 6 speciesof browt algae are reported; invertebrates, 2000; fish, 1000 (3).

A2. Transformation - Data not available

-AA2a* Biodegradation -Data not available

& t A~b. Hydrolysis - Reacts vigorously with water to evolve 1101 gas andTI(0H) 4 ()

V7 DAnDl7-84-C-4133 55-5






Bi. Avian species -- Data not available






B7. Aquatic species, fish and invertebrates - Median threshold effect:Scenedesmus: 96-hour test, 2 ppm as titanium; Daphnia: 48-hour test,4.6 ppm as titanium; Microregma: 48-hour test, 4 ppm as titanium (3).


CI. Phytotoxicity -- Toxic to sugar beets at 12 ppm as titanium (3).




A. Health

Data not available

B. Environmental

Data not available

4

4 1

DAMDI7-84-C-4133 55-6

v'..' A'"'

F6


VII. DISPOSAL

A. Current Recommended Arm Disposal Practices

A recent programmatic life cycle environmnental assessment indicatesthat incineration is the preferred method for disposal ofsmoke/obscurant munitions (I0). Munitions containing titaniumtetrachloride should be incinerated in a unit equipped withafterburner and a scrubber; scrubber overflow should be neutralizedprior to discharge.

SB. Alternate Disposal Practices Under Consideration bthe r

Data not available


Sift or pour onto a dry layer of sodium bicarbonate in a largeevaporating dish. After mixing thoroughly, spray with 6M NH4 OH whilestirring. Cover with a layer of crushed ice and stir. When the smokeof NH 4Cl has partly subsided, add iced water and stir. Dump thisslurry into a large container. Repeat until all has been treated.Neutralize and slowly siphon the suspension into the drain with excessrunning water. Notify local sewage authority (3).

"* VIII. REFERENCES

1. Windholz, M., S. Budavari, R.F. Blumetti, and E.S. Otterbein, eds..* 1983. The Merck Index, 10th ed., p. 1357. Merck and Co., Inc.,

Rahway, NJ.


3. Chemical Information Systems (CIS), Oil and Hazardous MaterialsTechnical Assistance Data System (OHKTADS). Accession No. 7217310.1985.

4. Kaye, Seymour. 1980. Encclopedia of Eposives and Related Items,

Vol. 9, p. T-230. PATR2700. US Ary Armament Research andk Development Command, Dover, NJ.

5. Hee, S.S.Q., T.J. Macdonald, J.R. Boyle. 1985. Effects of Acid Typeand Concentration on the Determination of 34 Elements by SimultaneousInductively Coupled Plasma Atomic Emission Spectrometry. Analytical

I DAMD17-84-C-4133 55-7


6. U.S. Coast Guard. 1978. Chemical Hazards Response InformationSys te(CHRIS Hazardous Chemical Data-Training Edition-TitaniumTetrachloride. Abridged, CG-446-2. U.S. Department of Transportation,W ashington, DC.

7. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sI ndustrial H and Toxicology, Vol. 2A, 3rd revised edition.John Wiley and Sons, New York, NY.

8. Park, T., R. DiBenedelto, K. Morgan, R. Colmers, and E. Sherman.1984. Diffuse Endobronchial Polyposis Following a TitaniumTetrachloride Inhalation Injury. Am. Res. Respir. Dis. 130(2):315-317.

9. Chemical Information System (CIS), Registry of Toxic Effects ofChemical Substances (RTECS). Accession No. XR1925000. 1985.

10. Yon, R.L., Dr. Randall S. Wentsel, and John M. Bane. 1983.Programmatic Life Cycle Environmental Assessment forSmoke/Obscurants, Volume 2-Red, White and Plasticized WhitePhosphorus. Technical Report No. 83004, ADA135910, ChemicalResearch and Development Center, Aberdeen Proving Ground, MD.

'Ti

11)4. .

I

I)DAD7-4C-3335-

. *x

TRIAMINOTRINITROBENZENE

Much of the available data on triaminotrinitrobenzene has been reported in aprevious study by the Atlantic Research Corporation (ARC) entitled APreliminary Problem Definition Study of 48 Munitions-Related Chemicals. Datareported herein reflects information more recent than that reported by ARC in1978.



Chemical Formula: C H N 0

Molecular Weight: 258.15 (Estimated)

Structural Formula:

IM2

( O~~2N~% 0

NHj~

NO2

B. Alternate Names and Rgsr Numbers

i ""CAS Registry Number: 3058-38-6

CA Name (9CI): 1,3,5-BerzenetrAiane, 2,4,6,-trialtro-

CA Nate (8C1): Same

Alternate CAS Registry Number; 67539-61-1

Alternate CA Name (MC1): Ben.enetriamine, ar,arar-trinitro-

Other significant synonyms: 1,3.5-Tria.ino-2,4,6-Trrnitrobenzene.- TrImainotrinitrobentene, sym-Triazinotriultrobenzene, 2,416-

•DAWD17-4-C-4133 56-1

PA •

TRIAMINOTRINITROBENZENE (cont.)


Physical State: Triclinic crystals (1)

Color: Light yellow (1)


Melting Point: Decomposes at 450-451 0C (1); 350 0 C (2)

Solubilities:IWater: Soluble in acids, 20% wt/vol in concentrated sulfurinacid, fluorosulfoi-ic, chlorosulfonic and trifluorosethane sulfouicacids (1).

Nonaqueous Solvents: Soluble in approxim.-tely 1% wt/vol in aniline,dimethylformamide, ethylenediamine. Insoluble in benzene,chloroform, ethanol, ether, and glacial acetic acid (1).


Volatility: Not volatile (1)

Vapor Pressure: 10"5 torr at 171.3 C 10-7 torr at 131.4 C (1)

Heat of Combustion: 735.0 kcal/mol (1)

Stability: Relatively insensitive high explosive (3); excellent thermalstability up to 260-290 C (2).

Flammability: Low; autoiguition temperature 368°C (3)

11. USES

A. ~ Unique Use

Currently being processed at Holston AAP for DOE use (4)* It is coatedwith a binder and granulated, then shipped to the Amarillo, Texas DOEf aAlity.

Used in nuclear weaivons systems (1).

B. *)ther Uses

DOE unique (5).

DAID17-84-C-4• 33 56-2

"A , r • '=i l r

TRIAKINOTRINITROBENZENE (cont.)

I-II. ANALYTICAL METHODS


An assay method of analysis for TATB using high pressure liquidchromatography was developed by Schaffer. This is primarily designedfor production quality control, but could possibly be adapted for traceanalysis.


Data not available

IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF TRIAMINOTRINITROBENZENE*

EFFECTS REFERENCE

Although specific data are not available, the material (1)should be treated as highly toxic by ingestion, inhalation,and skin absorption

*-- formation not included in the ARC report.

V. ENVIRO•EN7AL EFFECTS

No information was found regarding the enviroumental fate or effects oftriamino trinitrobenzete.

Z. VI. STANDARDS AND REGULATIONS

A. Health

Data not available

B. Enviror•ental

Data not available

"D"AHD17-64-C-4133 56-3

\*

TRIArINORITNITROBENZENTE (cont.)

VII. DISPOSA.L

A. Current Recommended Arut Dispoal Practices

Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve open burning, opendetonation or hauling by a licensed contractor and landfillingo Thishas also been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (6).

B. Alternate Disposal Practices under Consideration by the ArmZ

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use atinstallations such as Savanna Army Depot, Tooele Army Depot, andHawthorne Naval Ammunijion Depot (7).

C. Other Disposal Practices EMpoyed

Data not availrble

VIII. REFERENCES1. Kaye, Seymour. 1980. Encyclopedia of Explosives and Related Items,

Vol. 9, pp. 34-54. PATR2700. US Army Armament Research andDevelopment Command, Do'.er, NJ.

2. Urbanoki, T. 1984. Chemistry and Technology of Explosives, Vol. 4,p. 204. Elmsford, NY.

S3. Snook, R.W. 1980. Hazardous Component Safety Data Sheet-DATB. No.

1029. US Army Armament Research and Development Command, Dover, NJ.

4. Holston Division Corporation personnel, 1985.

5. PENTAX-DOE personnel, 1985.

6. David Renard, U.S. Army Toxic and Hazardous Materials Agency, toJ. Carl Uhrmacher (personal communications).. 1985.

7. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proctedings of the 1980 National Conference of EnvironmentalEngineering. New York, July 8-10, 1980. ASCE EnvironmentalEngineers Division, New York. 440-575.

AbA

SDAMDIT-84-C-4133 56-4 ,

I .

I• ,TRIETHANOL AMMONIUM NITRATE



Chemical Formula: C6H15N03 O UNO3


Structural Formula: (HOCH 2 CH2 ) 3 NH NO3




CA Name (9CI): Ethanol, 2,2',2"-nitrilotris- , nitrate (salt)

CA Name (8CI): Ethanol, 2,2',2" -nitrilotri-, nitrate (salt)


C Other Significant Synonyms: Triethanolamine-nitric acid salt;Triethanolamine nitrate; Triethanolam-ine mononitrate; TEAN






"Solubilities:Water: Data not availableNonaqueous Solvents: Data not available

Octanol Vater Partition Coefficient: Data not available




DA0D07-84-C-4133 57-i

41r

TRIETHANOL AMMONIUM NITRATE (cont.)







II. USES

A. A Unique Use

Propellant

B. Other Uses

Data not available



Kaplan et al. (1) used gas chromatography to monitor soil degradation of "TEAN. The free amine was determined with a flame ionization detector(FID) eluted from a Tenax-GC packed column at 260°C. Kaplan et al.also performed GC analysis for the presence of TEAN in the headspacegas in the biodegradation studies. Carbosieve columns with a thermal4 iconductivity detector and temperature programming were used.


Kaplan et al. reported 175.8 ng as the limit of detection for ThAN asthe free amine using the FID.

DAMD17-84--C-4133 57-2 i

F5

Ah, TPJETHANOL AMMONIUM4 NITRATE (cont.)

I. HEALTH EFFECTS

TABLE IV-1 * TOXICITY OF TRIETHANOL AMM4ONIUM NITRATE


Triethanol No toxicity dataammonium located; data onnitrate structural analogues

and chemical classes

4 follow below

Nitrates Human oral Large Dizziness, abdominal (2)amounts cramps, vomiting,

bloody diarrhea, weak-ness, convulsions, andcollapse

Small May lead to weakniess,repeated general depression,doses headache, and mental

impairment

Triethanol Human skin 15 mg, Mild irritation (3)amine 3 days

Rat oral 8,680 LD5 (3)mg/kg

Rat oral 9,110 LD (4)

Rat oral 90 days: (4)(feed) 0.73 S/kg M~icroscopic lesions

and deaths

0.17 i/kg Changes in liver and

Mouse ~ o~ ~ kidney weights

Mue intra- 1,450 LD (3peri- mg/kg.toneal

Mous~e oral 0.03 or Significant increases (4)(feed) 0.3Z diet in iaeidenc" of,

females

DAHD17-84-~C-4133 57-3

TRIETHANOL AM40NIUM NITRATE (coat.)

TABLE IV-1. TOXICITY OF TRIETiA.NOL AM4MONIUM N~ITRATE (Cont.)

Dose!Chemical Species Route Duration Effects Reference

Triethanol Guinea oral 8,000 LDn (3)smine pig mg/kg 50cont.)

Rabbit skin 560 m~g, Mild irritation (3)24 hr

Rabbit eye 5,620 ug Severe irritation (3)

Rabbit skin 5 or 10% Not irritating (4)or rat solution

N-Nitroso Triethanolamine may (4)diethanol produce, or containamine as an impurity, di-(NDELA) ethanolamine, which

in the presence ofnitrite, nitrate, ornitrogen oxides maylead to the f ormationof the carcinogenNDEIA&

Rat drink- 600 - liepatocellular (3)ing 1,000 carc-inomaswater mg/kg

Hamster subcu- 565 mg/kg Nasal cavity adeno- (3)taneous 2x/wk. for carcinomas and

over 45 tracheal, tumorswk; killedat wk 78

*Not specified

V. ENVIROMTAL EFFECTS

No data available

VI, STANDARS AND EGULATIONS,

No data. available(1

: DM17-84-C-4133- 57-4

TRIETHANOL AMMONIUM NITRATE (coat.)


A. Current Recommended A Dispoal Practices

Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve open burning, opendetonation or hauling by a licensed contractor and landfilling. Thishas also been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (5).

B. Alternate Disposal Methods Under Consideration by the Army

Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use atinstallations such as Savanna Army Depot, Tooele Army Depot, and-Hawthorne Naval Ammunition Depot (6).

Disposal practices recommended by the U.S. Navy in their Consolidatedhazardous item list for hydroxylamine, the parent compound ofhydroxylammonium nitrate, is to return to the supplier (7).


Data not available

VIII. REFERENCES

1. Kaplan, David L., Patricia A. Riley, David J. Emerson and Arthur M.Kaplan. 1984. Degradation of Ammonium Nitrate Propellants inAqueous and Soil Systems. Environ. Sci. Technol. 18(9): 694-699.


3. Tatken, Rodger L. and Richard J. Lewis, Sr., eds. 1981-82. Rof Toxic Effects of Chemical Substances, Vol. 3, National Institutefor Occupational Safety & Health, Cincinnati, OH.

4 . Clayton, George D. and Florence E. Clayton, eds. 1981. Pty4Industrial H and Toxicology, Vol. 2B, 3rd revised edition.P. 3128. o-hn Wiley and Sons, New York, NY;

5. David Renard, U.S. Army Hazardous and Material Agency, toJ. Carl Uhrmacher (personal coamnication). 1985.

!•DAM'D17-84-,C"4133 57-5W

A.IiC43

i .. , .-.,-

li.:

TRIETHA1N0L AMMONIUM NITRATE (cont.)

6. Forsten, 1. 1980. Disposal of Hazardous Toxic Munition "'s t e.Proceedings of the 1980 National Conference of Environm~entalEngineering. New York, July 8-10, 1980. ASCE EnvironmentalEngineers Division, New-York. 440-575.

7. Consolidated Hazardous Item List (CHIL). 1981. NAVSUP PUB 4500.Navy Fleet Material Support Office, Mechanicsburg,.-PA.~

j)

:4i

DAID7-84-C-4133 57-6

7J .~~U

TRIETHYI2NE GLYCOL DINITRATE

Much of the available data on triethylene glycol dinitrate has beenreported in a previous study by the Atlantic Research Corporation (ARC)

entiledA Preliminary Problem Definition Study of 48 Munitions-RelatedChemicals. Data reported herein reflects information-more recent thanthat reported by ARC in 1978.


A. Structural and Chemical Formulas and Molecular Wegh

Chemical Formula: C H N2 08NIT ~~6 1


Structural Formula: 0 N0(CII2CH 0)3ONO2

5. Alternate Names and Registry Numbers


CA Name (9C1): Ethanol, 2,2 '-[1 ,2-ethanediylbis(oxy)Ibis-, dinitrate

( CA Name (8C1): Triethylene glycol, dinitrate

RTECS Number: YE5500000

Other Significant Synonyms: TEGDN


Physical State: Oily liquid (1)

*Color; Light yellow (1)


0

Melting Point: -19 C (1)V .Solubilities: AWater: Slightly soluble (1).kNonaqueous Solvents: Very soluble in acetone, ether, and 2:14"ether-ethanol; soluble in carbon disulfide (1).


Hiygroscopicity: Data not available

ItDAMD17-84-C-4133 58'-1

TRIETHYLENE GLYCOL DINITRATE (cont.)

Specific Gravity (Liquid): 1.335 (1)..

Volatility: 40 mg/cc/hr at 60 0C (1)

Vapor Pressure: 0.001 mm at 250C (1)


Heat of Combustion: 3428 callg or 819 kcaJlimole (1)

Reactivity: Data niot available

Stability: Do not expose to shock, heat, flame or electrostaticdischarge (2).

Flammability: M1oderate hazard (2); explosive temperature is 2230C.

11. USES

A. Army Unique Use

High explosive (2).

B. Other Uses)

Data not available

III* AN~ALYTICAIL MFT1R0DS


Malotky and Downes reported a field kit for the analysis of 28 differentexplosives including TEGDW using thin-layer chromatography.


Data not available

.4

DAMD17-44C-4133 58-2V

TRIETHYLENE GLYCOL DINT.TRTE (cont..)

IV- MUATH EFFECTS

TABLE IV-1. TOXICITY OF TRIETHYLENE GLYCOL DINITRATE


Human NS NS Organic nitrates produce (3)vasodilation, headache,dizziness, weakness, andother signs of cerebral.ischemia associated withpostural hypotension;may progress to loss ofconsciousness; drug rashis occasionally produced

Rat intra- 796 mg/kg Increased plasma activ- (4)(NMRI:O(SD) periconeal ities oi alkaline phos-Sprague-Daw- phatase, creatine kinase,ley-derived) aspartate aminotrans-

ferase, and lactic deh~y-drogenas e

4 Rat intra- acute, Convulsions, hyperactiv-(5(NNRI:O(SD) peritoneal lethal dose ity to auditory andSprague-Daw- tactile stimuli

½ ley-derived)

Rat sc 13.0 mmol/kg M1ethemoglobin formation, (4)(NMRI :O(SD) ataxia, lethargy, res-Sprague-Daw- piratory depression,ley-derived) violent tremors, hyper-

activity to auditory andtactile stimuli

Guinea intra- 100, z00, Decreased food intake (4)pig peritoneal and 400 and retarded weight(FTD:Hartley- mg/kg daily gainderived) for 15 d

Rabbit dermal 21 mmol/kg Death in 2-3'wk, 20% (4)(New daily for loss in body weight,Zealand) 3 wk emaciated appearance

Rhesus ina- 2.4 ppm No significant changes (6)monkey ation aerosol for in electroencephalograph

2 or 4 hr or visual evoked response;IPS! significant increase in

Sidmana avoidance response rate

DAHD17-84-C-4133 58-3.



No information was found regarding the fate or effects of triethyleneglycol dinitrate which would update the Atlantic Research Corporationdocument.


A. Health

Data not available

B. Environmental


VII. DISPOSAL

A. Current Recommended A Dispoal Practices

Past Installation Assessment Reports indicate that current methods ofdisposal of waste explosives and propellants involve oper burning, opendetonation or hauling by a licensed contractor and landfilling. Thishas also been confirmed by private communications from the U.S. ArmyToxic and Hazardous Materials Agency (USATHAMA), which has theresponsibility to review current disposal practices, and to developplans for future disposal practices (7).


Future plans for disposal of waste explosives and propellants areprojected to emphasize fluid-bed incineration. This method has beentested successfully by ARRADCOM and is planned for use at installationssuch as Savanna Army Depot, Tooele Army Depot, and Hawthorne NavalAmuuition Depot (8).


Data not available

A L VIII. REFERE.NCES

1. Kaye, Seymour. 1980. Encyclopedia of Explosives and Related Items,Vol. 9, p. T-57. U.S. Army •• ,at Re•sM ch and evelop-,nt Co=,ad,Dover, NJ.

N.,I

DAMDT-8C-4:-133 58-4 "•' .•lv ,

W. T,.•


4 2. Snook, R.W. 1980. Hazardous Component Safety Data Sheet-TriethyleneGlycol Dinitrate No. 1192. U.S. Army Armament Research and DevelopmentCommand, Dover, NJ.

3. Gilman, Alfred Goodman, Dr., Dr. Louis S. Goodman, and Dr. AlfredGilman. 1980. Goodman and Gilman's The Pharmacological Basis ofTherapeutics, pp. 804-825.

4. Andersen, Melvin E., Dr., and Dr. Raymond G. Mehl. 1973. AComparison of the Toxicology of Triethylene Glycol Dinitrate andPropylene Glycol Dinitrate. Am. Ind. Hygiene Assoc. J. 34:526-532.

5. Andersen, Melvin E., Randall E. Koppenhauer, and Lawrence J. Jenkins,Jr. 197b. Some Neurotoxic Properties of Tviethylene GlycolDiaitrate: A Comparison with Decamethonium. Toxicology and AppliedPharmacology. 36:384-394.

6. Hollenan, J.Vl,, R.W. Ross, and J.W. Carroll. 1983. ProblemDefinition Study on the Health Effects of Diethylene GlycolDinitrate, Triethylene Glycol Dinitrate, and TrimethylolethaneTrinitrate and their Respective Combustion Products. TechnicalReport, ORNL/EIS-202, No. DE83011068. Oak Ridge National Laboratory,Oak Ridge, TN-

7. David Renard, U.S. Army Toxic and H&azardous sat-rials Agency, toJ. Carl Uhrmacher (persontl comm.-ication). 19i3.

8. Forsten, I. 1980. Disposal of Hazardous Toxic Munition Waste.Proceeding of the 1980 National Conference oi EnvironmetalFinern.w orJl8-10, 1980. ASCE Environmental

Engineers Division, New York. 440-575.

i5

) -

U,,A tD 74-C•--4 133 58-5b

VAT YELLOW 4

Much of the data on Vat Yellow 4 has been reported in a previous study bythe Atlantic Research Corporation (ARC) entitled A Preliminary ProblemDefinition Study of 48 Munitions-Related Chemical7s (I, Dat reportedherein reflects information more recent than that reported by ARC in 1978.



Chemical Fo-mula: C24 1202


Structural Formula.

0

B. kiternate Names and lwistr Numbers

CAS Ugistry Numbtr; 128-66-5

Deleted CAS Registry Numbers: 39280-74-5, 12772-52-0

CA 'Name (9CT): Dibenaob,defilchrysene-7 , 14-dione

CA Name (8C1) : Same

VIECS Number: U07030000

Other Significa,•t Synonyu: Numerous (1), 3,8:8,9-Dibenzopyreae-5,10-diore

C. ChemicAl and Physica). Prop-rzies

Pbysical State: So.id (1)

Color: Yellow


Meltiug Point: Data not avail.able

DAM i 7-84-C-4133 S9-I

A AL . a

VAT YELLOW 4 (cont.)

Solubilities:Water: Data not availableNonaqueous Solvents: Soluble in nitrobenzene, xylene,tetrahydronaphthalene (1); slightly soluble in acetone, alcohol,benzene, chloroform, o-chlorophenol, Dyridine, toluene (W).


Hygroscopici'v: Data not available









Ii. USES

A* A U Use

Coloring agent to produce yellow smoke (U

B. other Uses

Dye

.. 111I. ANALYTICAL &THOD$k ",

A. Best Acctable Hethod

Vat Yellow 4 can be analyzed by column and thin-layer chromatographyand ultra violet, visible and fluorescence spectrophotometry. Thesemethods have been twed by Pierce and Katz (2) for air pollutionanalysis.

B. limit of De,_ction

Data not available

""- fl.IMD17-84-C-4133 59-2


IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF VAT YELLOW 4*


Rat oral 0, 3,500, or Decreased body weight (3)(Fischer 7,000 ppm in gain; no significant344) feed for 104 increases in tumor

wk incidences comparedwith controls

Mouse oral Males: 0, Increased incidence of (3)(B6C3F1) 25,000 or lymphoma in high-dose

50,000 1pm; males: controls 3/20Females: 0, (15%), low-dose 7/4712,500, or (15%), high-dose 22/5025,000 ppm (44%, P-0.019).in feed for Females showed no sig-106 wk nificant increases in

tumor incidences com-pared with controls

*Information not included in the ARC report

TABLE IV-2. MUTAGENICITY AND RELATED EFFECTS OF VAT YELLOW 4


Salmonella 0.1-1,000 Nonmutagenic with or (4)typhimurium ug/plate without Aroclor 1254-TA98, TAI00, induced ra. liver $9TA1535, TA1537TA1538

Salmonella NS* Now-utagenic with ur (5)typhimurium without Aroclor 1254-

i.nduced rat or Syrianhbmster liver S9

* Not specified


No information was found regarding the enviroumental fate or effects of. A

Vat Yellow 4 which would update the Atlantic Research Corporationdocumento

DAMD17-84-C-4133 59-3



A. Health

Data not available

B. Environmental


VII. DISPOSAL


Disposal practices recomended by tht U.S. Navy in their ConsolidatedHazardous Item List for Dye Solution, a related compound used for arelated purpose are to dilute with a flammable solvent and to burn inan incinerator equipped with an afterburner (6).

B. Alternate Disposal Practices Under Consideration b• the Am

Data not available


( Data not available

VIII. R.EFERENCES

1. Kitchens, J.F., W.E. Harwards III, D.M. Lauter, R.S. Wentsel, R.S.Valentine. 1978. Preliminary Problem Definition Study of 48Munitions Related Chemicals, Vol. III, Pyrotechynic RelatedChemicals-Vat Yellow. Pinal Report, AD A066310. Atlantic ResearchCorporation, Alexandria, VA. DAXýW.T-77-C.-7057.

• 2. Pierce, R.C.. and M, Katz. 1976. Chromatographic Isolation andSpectral Analysis of PolycyJlic Quinones. Application to Air PollutionAnalysis. Envirpnmental Science and T.holoyo Vol. 10(0):45-51.

3. National Cancer Institute (NCI). 1979. Bioassay of C.I. Vat Yellow4 For Possible Carcinogenicity. D ZW No.& NaioiInstitute of e-ulth, Bethosda, tD.

4. Salamone, M.P., J.A. Heddle, and M. Katz. 1979. The MutsenicActivity of Thirty Polycyclic Aromatic Hydrocarbons (PAK) and OW£desin Urban Airborne Particulates. Ln~irený. Int. 2;37-43.

"5. National Toxicology Program (NT•). 1982. Hutagenisis Tw•ha•a Results.N• Tch Bull. (7)M5-9.

DAMDI7-84-C-4133 59-4J

,..~-~ ...-'.,

VAT YELLOW 4 (cont.) 1 A

6. Consolidated Hazardous Item List (CRIL). 1981. NAVSUP PUB 4500.

Navy Fleet Material Support Office, Mechanicsburg, PA.

4

WH1ITE PHOSPHORUS

2. CHEM4ICAL AND PHYSICAL..DATAA. Structura~l and Chemical Formulas and Miolecular Weight

I. Chemical Formula: P4

Atomic Weight: 30.97

4 Molecular Weight: .123.89

4 Structural Formula:

p

Deleted CW Registry Number: 29879-37-6

CA Nme OI~iSame

RTECSNumb TH34950O0, Tki35O5000, T113500000

B* Alt~nateand !IE rX N4umbers

DeltedCAS$RegisttyNume:5218-

CANae IM.-Pbophor",k wo, 4 )

RTWS humbir ata -not available

DAMD17-84-C-4133 .60-1

WHITE PHOSPHORUS (cont.)

Other significant synonyms: Tetraphosphorus, Phosphorus tetraatomicmolecule, Tetrameric phosphorus, molecular phosphorus,Tetraphosphatricyclo-(1[1.o0.02,4]butane

*Chemical Abstracts Service assigns the same Registry Number,7723-14-0 for two forms of elemental phosphorus, white and red.


Physical State: Crystalline solid with two allotropic modifications:.alpha. form exists at room temperature as cubic crystals; -beta.form is formed at -79.6°C as hexagonal crystals (1).

Color: Colorless or white, transparent, waxy appearance; darkens onexposure to light (1).


Melting Point: 44.10C (1)

Boilirng Point: 280 0C (1) )Solubilities:

Water: One part in 300,000 (1).Nonaqueous Solvents: I g/400 mL absolute alcohol, 1 g/102 mLabsolute ether, I g/40 ml in chloroform, I g/35 ml, in benzene, 1 g/80mL in olive oil, I g/60 mL turpentine, I g/100 mL almond oil (1);Soluble in anhydrous ammonia and toluenc (2).

Octanol Water Partition Coefficient:' Data not available


Density (Crystal): 1.88 g/cc (1); 1.82 g/cc at 200 (2); 1.83 g/cc (3)

Volatility: Very volatile; gives off white fumes and a greenish lightwhen exposed to air in the dark (1)

Vapor Pressure: 0.181 mm Hg (1)



Reactivity: Very reactive, combines directly with halogens andustals, must be kept under water (1 . (.

Stability: Very unstable, will ignite at 30 0 C in moist aix (1).

DAL017-84-C-4133 60-2

WHITE PHOSPHORUJS (cont.)

Flammability: Very (1), autoignition point: 4500 (3).

I. USES

*A. Arm Unique Use

Obscurant

B. Other Uses

Rat poison (1)

Ill* ANALYTICAL METHODS


White phosphorus can be detected by some of the same methods as redphosphorus. For detection of white phosphorus, a photometric detectordesigned to monitor cold chemiluminescence has been reported byMielniczuk (4).


Data not available

D W 17-84-C-4133 60-3


IV. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF WHITE PHOSPHOROUS


Human oral 1,400 ug/kg LDLo (5)

Human oral Acute Gastrointestinal effects (6)including nausea, vomit-ing, belching may occurwithin 30 min; death fromcardiovancular collapsecan occur within 12 hr;a period of apparent re-covery lasting about 2days may occur followedby the return of gastro-intestinal distress withhepatic, renal, and car-diovascular effects in- -}cluding jaundice, pittingedema, oliguria, highpulse rate, and low bloodpressure; liver and kid-ney effects observed atdeath

Human inhalation Chronic Gastrointestinal dis- (6)tress; phosphorus odorof the breath; slightJaundice; necrosis ofbone, particularly the

• • jaw; laukcopenia, anemita

Human oral 0.2 mg/kg inimum toxic dose (6)

l uman oral 16 ag/kg Effect* on the gastro- (5)intestinal tract-; coma

-iman oral 2,600 ut/kg Effect, on the gastro- (5)ikntutinal tract and

:Human local NS*Severe burns of the (6)

skin; ocular damage

N ot ;pe~fie

1DA.0I17-84-C-4133 60-4

WHITE PHOSPHORUJS (cont.)

TABLE IV-1.* TOXICITY OF WHITE PHOSPHOROUS (Cont.)


3Human inhalation 100-700 mg/i Phosphorus smoke for- (7)for less than mulations caused rever-15 mnin sible pulmonary symptoms

and, mucous membrane ir-ri tat ion

IRat oral 11 ug/kg, Effects on fertility (5)days 1-22of gesta-tion

Rat oral 3,030 ug/kg LD 0 ; effects on behavior (5)ii~ athe pulmonary system

Mos rl4,820 ug/kg anD0 *hefet on behavior (5)Mous ora ang t'hepulmonary system

Rabbit sub- 10 mg/kg LDLo (5)

*Dog oral 50 mg/kg LDLO(5

Dlog sub- 2 mg/kg LDLO(5cutaneous

Pig oral 160 mg,/kg LDLO(5

Duck oral 3 mg/kg LL;cvusos(5)

N. ot specified

I 1' )MD17-84-C-4133 60-5


V. EN' IR0NIENTAL EFFECTS

Summary of Programmatic Life Cycle Assessment

White phosphorous is reported to be transformed into phosphate salts inthe environment by the action of water, air and sunlight. Unburnedwhite phosphorous was observed to burn exposed vegetation in theimmediate area of release. White phosphorous transformed intophosphates is rapidly complexed by soil constituents and absorbed bysoil particles or biota.

Aquatic toxicity of white phosphorous has been difficult to measurebecause of its reactivity, rapidly disproportionating to phosphorousand phosphoric acids. White phosphorous dissolved in water is toxic tofresh water aquatic invertebrates and fish. White phosphorous is alsotoxic to saltwater species, with the Atlantic salmon observed to be themost sensitive. One author cited recommended a water quality criterionof 0.6 ug/L for white phosphorous. Prolonged exposure to elevatedphosphorus levels in aquatic system can have adverse affects. Water pHmay be lowered in some water systems causing algae blooms and loweringof dissolved oxygen resulting in fish kills.

Toxicity was also reported in black ducks and mallards. Sublethal

effects of white phosphorous were reported for white phosphorous levels .in smokes obove 1000 milligrams per cubic meter and animals could

receive lethal doses of elemental phosphorus if they ingested unreactedmaterials containing white phosphorous (8).


Al., Transport


Alb. Volatilization Data not available

Aic, Leachibility - Data not available

Aid. Bioaccumulation -- Radioactive phosphorus has been concentrated bywaterfowl up to 75,000 times and by aquatic life by factors up to850,000. Cod and other marine fish concentrate up to 1,000 times (3). A

A2. Transformation - Data not available A

A2a, Biodegradation - Data not available

A2b. Hydrolysis - See A2e,.

A2ce Photolysis - Data not available

SAd, Other chemical reaction B- urns spontaneously in air (see Stability).

1DD17-84-C-4133 60-6ow ,-. 6..•i: " .. ~ ~ ~~ . .. ...... ....... ...................... ...... -.....

W•1ITE PHOSPHORUS (cont.)

Ale. Half-life -- Although there are no definitive published reports on thekinetics of oxidation of elemental phosphorus ii water, it appearsthat the rate is highly dependent on the degree of dispersion. Atconcentration (about 10 ug/L) well below the accepted solubilitylimit of 3 mg/L (dissolved oxygen concentration unspecified),elemental phosphorus disappears by a first order process, with ahalf-life of 2 hours at about 10 C, 0.85 hour at 300C. Atconcentrations (50 to 100 mg/L) well above the solubility limit, witha dissolved oxygen concentration of 6 to 7 mg/L, the same reactionhas a half-life of 80 hours at 30°C and 240 hours at 0 C. Therelatively small temperature effect combined with the large inverseconcentration effect is consistent with a diffusion-controlledprocess. The oxidation of colloidal phosphorus in sea water isreported to be measurably slower than in fresh water, suggesting thatthe high salt content brings about agglomeration of the phosphorusparticles (3).


*B1. Avian species - Data not available

B 32. Mammalian wildlife species -- Data not available

B 33. Terrestrial invertebrates Data not available






C1. Phytotoxicity - Data not available

C2. Uptake - Data not availableF C3. Metabolism - Data not available

V1. STANDARDS AND REGUIATIO&4S

A. HealthIa/3 STL0 3 u

ST W•: 0.1 STEL 0,3 .0 for 15 minute exposure. (3).

DAMDI7-84-C-4133 60-7


B. Environmental


Phosphorus has a statutory reportable quantity (RQ) of I lb. under theComprehensive Environmental Response, Compensation and Liability Act.The National Response Center must be notified immediately when there isa release of this compound in an amount equal to or greater than thereportable quantity (9).

VII. DISPOSAL

A. Current Recommended • Disposal Practices

A recent programmatic life cycle environmental assessment indicates thatincineration is the preferred method for disposal of smoke/obscurantmunitions. Munitions containing phosphorous would be incinerated in aunit equipped with afterburner and a scrubber (8).

B. Alternate Disposal Practices Under Consideration . . --the

AMCCOM anticipates future waste smoke munitions will be demilitarizedand white phosphorous recovered as phosphoric acid (8).


Data not available

VIII. REFERENCES

1. Windholz, M., S. Budaveri, R..F. Blumetti, and E.S. Otterbein, eds.1983. The Merck Index, 10th ed., pp. 1059-60. Merck and Co., Inc.Rahway, NJ.

2. Weast, R.C. 1966. CRC Handbook of Chemistry and Physics, 48th ed.,p. B-203. The Chemical Rubber Co., Cleveland, 0R.

3. Chemical Information System (CIS), Oil and Hazardous MaterialsTechnical Assistance Database (OWDTADS). Accbssion No. 7216854. 1965.

4. Hielneczak, Z.M. and W.A. Ware, 1978. Construction audCharacteristics of a Cold Flame Photometric Detector. Journal ofChroow.tgraphy. 166(l):1-7.

5. Chemical luforatioU SYst4=S (CIS)* R~lftry Uf TOIL. ElieCtl Of* Chemical SubsrAnces (RTECS). Accession No. TH3500000. 1985.

DAMI•7-84-C-4133 60-8

., .,;,;: • .:• .: :, 7 ... . . . . .... . .. ... . . ... . ..M


6. Clayton, George D. and Florence E. Clayton, eds. 1981. Patty'sIndustrial Hygiene and Toxicology, Vol. 2A, 3rd revised edition.John Wiley and Sons, New York, NY.

7. Berkowitz, Joan B., G. Stuart Young, Rosalind C. Anderson, Anthony J.Cobella, Warren J. Lymand, Alan L. Preston, William D. Steber,Richard G. Thomas, and Robert G. Uranka. 1981. Research andDevelopment for Health and Environmental Hazards Assessment-Task Order5. Occupational and Environmental Hazards Associated with theFormulation and Use of White Phosphorus-Felt and Red Phosphorus-ButylRubber Screening Smokes. Technical Report, AD A116956. U.S. ArmyMedical Bioengineering Research and Development Laboratory, FortDetrick, MD.

8. Yon, R.L., Dr. Randall S. Wentsel, and John M. Bane. 1983.Programmatic Life Cycle Environmental Assessment forSmoke/Obscurants, Volume 2-Red, White and Plasticized WhitePhosphorus. Technical Report No. 83004, AD A135910. ChemicalResearch and Development Center, Aberdeen Proving Ground, MD.


UM(1 7-84--C-4 133 60-9J

ZINC NAPUTHENATE



Chemical For-mula: Zn(C 6 H5CO00) 2


Structural Formula: Napthene is a term used in the petroleum industryto denote five- and six-carbon cycloparaffins and their alkylderivatives, found in crude petroleum. Sometimes used to includepolycyclic members found in higher boiling fractions (W). This is nota unique chemical substance (CAS), but represents the Zinc (+2) saltsof mixed napthene carboxylic acids.

B0 Alternate Names and Registry Numbers


CA Name (9CI): Napchenic acids, zinc salts

RTECS Number: QK9275000

Ocher Signficant Synonyms: Zinc uversol

C. Chemical and Phyical Provertles

Physical State: Mixture, Viscous, basic liquid (vith 8-10% Zu) orbasic solid (with 162 Zn) (1)

Color: Ambtr (1)


ftelklag Point: tNot defined for a mixture

Solubilities:Water: Data not availableNonaqueous Solvents: Very soluble in acetone. (1)

Octa•nl Water Partition Coefficient: Data not available

Hygroacopi.aty: Data not available

Density: Data not available


Vapor Pr-•sure: Datan•ot avalaU,.

DAHDO-84-C-4133 61-11_.

L. ',• ,? .. .. • ,~ • l l ;

ZINC NAPTHENATE (cont.)

I Specific Heat: Data not available


Reactivity: Combustible (1)



II. USES

A. A Unique Use


B. Other Uses

Drier and wetting agent in paints, varnishes and resins;insecticide, fungicide, and mildew preventive; wood preservative;waterproofing Lextiles; insulating materials (1).



No methods were found for either zinc napthenate or napthenic acid insearching the Chemical Abstracts System back to 1967. Zinc can beanalyzed by either atomic absorption spectroscopy or atomic emissiouspectrometry. Recently, a method was reported to enhance thedetection of zinc by simultaneous inductively coupled plasma atomicemission spectrometry by !iec e: al. (2).


The lower determination range for zinc reported by Hee et al. is 0.01-I.0 micrograz/milliliter. The apparent linear range is 2.0 to 250

P microgram/milliliter (2).

C. h Performance Liquid Chromatography

"Data not available

DAMDI7-84-C-4133 6,-Z(% ib

:+'X .. , , . . . . ... . . .. _. i .: .. : • 7


:V. HEALTH EFFECTS

TABLE IV-1. TOXICITY OF ZINC NAPFTHENATE


Human oral NS* Some soluble zinc salts (3)cause nausea and vomiting

Human eyes, NS Naphtnenic acids are (4)skin irritants

Rat oral 4,920 mg/kg LD50 (5)(in lard)

Rat oral 6,000 mg/kg Practically nontoxic (6)once

NS NS NS Low toxicity (1)

* Not specified

V. ENhVIROW-NTAL EFFECTS

No information was found regarding the environmental fate or effects ofzinc naphthenate.

* V1. STANDARDS AND REGULATIONS

A. Health

Data not available

B. Environmental

Reported in EPA TSCA Inventory 19M0.

V11. DISPOSLL


Disposal practices recommended by the U.S. Navy in. their ConsolidatedHazardous Item List for Copper 1Naphthenate, a related compound used fora relsted purpose, are to turn In to a pesticide collection center, tothe original supplier or to a commercial waste disposal service (7). (

DAMDI7-84-C-4133 61-3


., B. Alternate Disposal Practices Under Consideration by the

Data not available

C. Other Disposal Practices Emploved

Data not available

VIII. REFERENCES


2. Ree, S.S.Q., T.J. Macdonald, and James R. Boyle. 1985. Effects ofAcid Type and Concentration on the Determination of 34 Elements bySimultaneous Inductively Coupled Plasma Atomic Lmission Spectrometry.Anal. Chem. 57.,1242-1.252.

3. Sax, NoI. 1979. Dangerous Properties of Industrial Materials, 5th ed.,p. 1100. Van Nostrand-Reinhold Co., New York, NY.

4. Plunkett, E.R. 1976. Handbook of Industrial Toxicology, p. 283.Chemical Publishing Co., Inc., New York, NY.

5. Smyth, Henry F., jr., Ph.D., Charles P. Carpenter, Ph.D., Carrol S." Weil, Urbano C. Pozzani, Jean A. Striegll, and Judith S. Nycum. 1969.Range-Finding Toxicity Data: List VII. Am. Indust. H Ass. J.30(4) :470.

6. Rockhold, William To, Ph.D. 1955. Toxicity of Naphthenic Acids andTheir Metal Salts. AMA Arch. Indust. Health. 12:477-482.

7. Co nsolidated Hazardous Item List (CHIL). 1981. NAVSUP PUB 4500. NavySFleet Material Support Office, Mechanicsburg, PA.

.g4.

k.

AW'v

DA14D17-84-C-4133 61-4

ol*

DISTRIBUTION LIST

24 copies CommanderATTNz SGRD-UBGUS Army Medical Bioengineering Research and

Development LaboratoryFort Detrick, Frederick MD 21701-5010

2 copies CommanderUS Army Medical Research and Development ComandATTN: SGRD-RMSFort Detrick, Frederick# Maryland 21701-5012

12 copies Defense Technical Information Center (DTIC)ATTN: DTIC-DDACCameron StationAlexandria, VA 22304-6145

1 copy DeanSchool of MedicineUniformed Services University of the

Health Sciences4301 Jones Bridge RoadBethesda, MD 20814-4799

1 copy CommandantAcademy of Health Sciences, US ArmyATTNs AHS-CDMFort Sam Houston, TX 78234-6100

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Documents

I.Final - DTIC