¶F&Kl?AZE Ndmac

DISTRIBUTION LISP PDR ME&T 63-0970

D/596,6C1T D/5140, FB68 D/5143, FB66 Dr. R. Paton W .J. Costas M . Francis M. Mogg D/539, AC1O D/5614, n66 R. Schmued . Buckles J.A. Lieb W D/596, SSii R .P. Jevett M .C. Shoemaker F . 'Ii' J. Wooten D/031, SS32 D/539, A129 R. Johan W.T.- McFarlen C . Winzer W. Kappen R. McKovan D/539, HC92 3. Levis D/539, BA33 F . Schuler D/539, 33T R . Movers J. Rosengard D/539, BA71 3. Becker J J D/539, HC82 - K. Kirkhan ¶f&kl?AZE ~~}12 CI-~ oti NDMAc (14 ITZo5OD (ThYtAfl*Nt3 II0Imuimiiimmimiiiuumiiuiuu BNA00834964 HDMSE00609163 Internal Letter ® Rockwell International

Date. . November 28, 1983 No . MEAT 83-097 0

FROM : t Natne orQantraa °n . rnremal Andress . Pnonel TO rNaTe Orpan.: .'cn, lnleraar AU essl . Michael Francis Norma Fujikawa, Manager Environmental Task Team . SSFL Analytical Chemistry . 0/541, FB 12 . 0/539-169, SS 1 1 5448

) Subject : . Literature Search Findings on N-Nitrosodimethylamine (NDMA

At your request , the toxic levels, the general abundance of the compound, and the analytical methods for the determination of N-nitrosodimethylamine have been reviewed .

ABSTRACT

It is now generally agreed that N-nitroso compounds are among the most potent chemical carcinogens known . The U .S . Department of Health, Human .4 Services , and Public Health ~ervice has reported that a concentration of 1 10- grams /liter, or 0 .0000014 ppm) of parts per trillion (1 .4x e N-nitrosodimethylamine ( NDMA ) is estimated to limit cancer risk to on in a million . NDMA has been reported to be carcinogenic in all animal species tested and induces benign and malignant tumors following its administration by various routes , including ingestion and inhalation , in various organs in several species . It produces tumors mainly of the liver, kidney , and respiratory tract . It has been associated with the high incidence of esophageal cancer in Eastern China , in Iran, and with heavy cigarette smoking . The precursors of the N-nitroso compounds, such as nitrates , nitrites , and amines are in naturally occurring substances . N-nitroso compounds , including NDMA, may be found in soil, Consequently , . water, air , food, and the gastrointestinal tract of humans and animals The chemical analysis is conducted by gas chromatography /mass spectrometry for pert per billion levels . For part per trillion detection , a Thermal Energy Analyzer ( at a cost of $40,000) is required .

BACKGROUND AND CHEMICAL NATURE OF NDMA

N-nitrosodimethylamine ( NDMA ) is a yellow , volatile , non-hygroscopic liquid of low viscosity with a boiliij point of 150°C at 755 mm . It is _ considerably polar and has a molecular weight of 74 .1, with the chemical of : formula of C2H6N20 and the structural formula -N =0 CHI an intermediate Prior to April 1 , 1976 , NDMA was used in the United Sates as in the production of 1,1-dimethyl hydrazine ( UDMH ), a storable

IIOImuimiiimmimiiiuumumiu BNA0083496 5 HDMSE00609164 MEAT 83-0970 to Michael Francis From Norma Fujikawa November 28, 1983 p 2

liquid rocket propellant that contained 0 .1% NDMA as an impurity . (Past Rocketdyne programs which have utilized UDMH Include the Lance, Martin Transtage, and sane smaller research programs . Aerojet used larger amounts of UDMH because of the size of the Titan missile which loaded 50% NZH4 and 50% UDMN .) In addition to aerospace, NDMA was frequently used in the fiber, rubber and plastics industries as an antioxidant , a softener of copolymers , and additive for lubricants , syntheti c cutting fluids , and leather formulations . The pesticide 2,3,6-tri- chlorobenzoic acid with dimethylamine contains , as a contaminant , up to 640 micrograms/liter of NDMA . NDMA is found in foodstuffs such as frying bacon, cider distillates, beef, commercial sausage, and i n beer. It is present in cosmetics and in anti-histamines . More importantly, it is manufactured from amines and nitrates in the human GI tract . The presence of NDMA has been reported in deionized water and dialysate water ( as well as the blood of chronic dialysis patients) when a carbon bed or UV absorber in a particular sequence were not included in the purification process . The postulation has been that the quaternary ammonium ion of the strong anion resin may be the amine precursor for th e nitrosamine formation .

NDMA is regulated by the federal government under the Resource Conservation and Recovery Act (RCRA ), the Safe Drinking Water Act, the Clean Wate r Act, the Clean Air Act , and the National Pollutant Discharge Elimination System ( NPDES ) . The FDA established action levels of 5 parts per billion NDMA in malt beverages ( beer ) and 10 ppm in barley malt .

The tendency of animals to develop neoplasms upon exposure to carcinogens depends upon a number of factors, one of which is the ability to metabolize the compound . Nearly all chemicals believed to be carcinogens require enzymatic activation before they can transform normal cells to cancer cells . In the human body, the system which processes many foreign circulating substances prior to elimination is a network in the liver called the Cytochrome P-450 mediated mono-oxygenise system. The ultimate carcinogen ( active metabolite) is an electrophile which covalently bonds to cellular molecules---particularly DNA, protein molecules, etc . Cytochrome P-450 may be the transforming enzyme to convert an innocuous molecule to active cancer-causing substances by reacting to form carbonium ions . The carbonium ion free radical fragment acts as the alkylating intermediate which methylates the cellular components including the nucleic acids and proteins . Cytochrome P-450 is an essential part o f the body 's detoxification system ; it hydroxylates substances and makes them more water soluble . The potential formation of nitrosamines in the body is great . Many scientists believe that this endogenous pool of nitrosamines may prove to be a more important exposure than any single other contributor with the exception of a unique , high level industrial incident .

IIOImuimiiimmimiiiuumiuuiu BNA0083496 6 HDMSE00609165 ME&T 83-0970 to Michael Francis From Norma Fujikawa November 28, 1983 p 3

After ingestion, NDMA is metabolized within a few hours ; by twenty four hours not a trace of it can be found in body fluids . Chemical and Engineer - ingNe~ws has labelled it the ideal murder weapon except that in small doses, like other lethal agents, it takes years to produce liver damage . [As noted by Rocketdyne's Medical Director, Dr . Norton Stein, individuals can perform the same process on themselves with cigarettes, beer, and other modes of cell destruction by chemicals, chemical additives, and other products freely available to the general public in supermarkets, stores, and vending machines . Or . Stein stated that the "buzz" people get(from these voluntary purchases) is due to brain cell destruction . In an Omaha murder case, milk laced with NOMA was the cause of death (by massive brain hemorrhage) of a 25-year old man . Aside from extreme and pathological instances, the National Cancer Institute's Larry Keefer reported in 1980 that , excluding a high exposure level in certai n industrial settings, and with all the appropriate caveats, the nitrosamine exposure to the population at large would be scaled as follows, using arbitrary units : smoking at 1500, new car interiors at 400, beer at 90, cooked bacon at 50, and Scotch whiskey at 1 .

Nitrogen oxides are nitrosating agents , and elimination of this effec t or the amine is a step towards limiting the production of the nitrosamines . Depending upon the precursors and the presence of catalysts such a s ozone and metal ions , nitrosamines can be formed under acid , neutral, or alkaline conditions . Since nitrate-nitrite combinations are used in luncheon meats as bacteriostats ( up to 500 mg/ kg), this has become another foodstuffs source for the synthesis materials . The air we breathe in the L .A . basin has been found to contain 1-4 ppb nitrous acid in the night hours . Nitrous acid is a facile nitrosating agent and acts in this fashion in the body . Nitrosamine formation /synthesi s in soils and waters is considered a disturbing reality because experiments have been performed and the findings indicate that a pH of 5 is best for promoting the generation of the nitroso compounds .

Under the Clean Water Act, the EPA recommended ( tentatively ) a criteria of 5 parts per trillion in drinking water in 1980 , while , in contrast, the FDA's limit in beer was 5 parts per billion . The usual consideration is that drinking water is involuntary , and the public should be protected ; imbibing beer is a personal matter and voluntary . Some of the level s of NDMA in commonly ingested materials , or exposure (as with cigarette smoke ) are listed in the table below .

II0I I0I liD ID IID III III DD III 101 10 0 BNA0083496 7 HDMSE00609166 ME&T 83-0970 to Michael Francis From Norma Fujikawa November 26, 1983 p4

NDMA IN COMMONLY AVAILABLE/ INGESTED ITEM S per ~illion ) ( 1 microgram/kilogram = 1 x 10"g grams - I part

AMOUNT ITEM CHEMICAL INFORMATION

Contain the dimethyl amin o 0 .22-3 . 6 micrograms Antihistamines ; per kilogram Tricyclic - group which is easily nitrosated tranquillizers commonly found ingredients are methapyrilene hydrochloride and Cold/cough dophenhydramine hydrochloride . preparation s

One unfiltered Tobacco smoke contains both the up to 0 .043 micrograms per cigarette nitrogen oxides ( NOr) and the amines available for the formation cigarette for mainstream smoke of nitrosamines . These includ e NDMA, hydrazine , diethylnitrosamines, 0.680-0.823 micrograms etc . per cigarette for sidestream smok e

17 micrograms/kg Smoked salmon NDMA present 10-80 micrograms/kg Commercial sausage NDMA present 10-108 micrograms/kg Bacon NDMA present 34-242 micrograms/kg Fresh beef NDMA present 10 micrograms/k g Cider distillates NDMA present 5 micrograms/k g Beer NDMA present

IIOImuimiiimmimiimuunuuu BNA0083496 8 HDMSE00609167 ME&T 83-0970 to Michael Francis From Norma Fujikawa November 28, 1983 p 5

The chemical analysis of N-nitrosodimethylamine (NDMA) is performed using gas chromatography/mass spectrometry (GC/MS ) for the part per billion level of concentration of the compound . The Thermal Energy Analyzer (TEA), which Rocketdyne does not currently own, can detect nitrosamines down to the part per trillion range . The analysis of the Rocketdyne SSFL pond waters for the presence of NDMA will be conducted by the SSFL Analytical Chemistry tab utilizing the GC/MS during the next few months . A separate report will be issued providing the details and discussion of the analytical metho d upon completion of the assignment .

/vo N . S . Fujikawa Manager SSFL Analytical Chemistry Advanced Materials & Manufacturing Technology MATERIALS ENGINEERING AND TECHNOLOGY

Distribution list attached .

nsf

IIDImuimiiimmimiiiuumuu U BNA00834969 HDMSE00609168 Francis MEAT 83-0970 to Michael From Norma Fujikawa November 28, 1983 p6

REFERENCES Cance~o .a3d . , "Chemicals , . and Goff, Harold M . 59 , (1) Alexander , Lynett SJournal of Chemical Education , Vol Cytochrome p-450", March, 1982, PP 179 _ . 31, No . 3 , Smoker?", Better Nutrition , Vol (2) "Are You a passive 0981), pp 20-23 . ", Industrial Research . "Tannery Sources of Nitrosamine 3 Bailey, 0 . G , April, 1983 . () News ., "N-Nitroso Compound s ., and Davis , W ( IARC), ., Walker, E .A for Research on Cancer (4) Bogovski , P International A enc in the Environment", Lyon, France (1975) . . or H69ardous Way, California Dep't• f 5 California Assessment Manual { } June,ervices, 981, r of Health S Relative Risk", : Assessing the 20at (6) Ember, Lois R .,"Nitrosamines March, 1980, P P i mical and Engineering News Che , and Watts,. , J .O ., . W . , White, R . H n ., DeterminationDamico, J . N ., Howard, and Mass J Spectrometric Confirmatio (7} Fazio, 7 5 --3ourn l--o- "Gas Chromatographic 250_2J5 . of Nitrosodimethylamine in SmVol . 19CeNoe2 ,~197 , pps2 Agricultural Food Chemistr , ++N-Nitroso Compounds . M. , hler , D . P ., and Belcher, N arch on Cancer , (8) Finn, 0 . H . . Rounbe for Rese i n Air and Wa ter" , 40l -406 . No . 14, (1976 PP Wood, B .J ., A Comparison .S ., Pringuer, M .A . . uMethod for the (9) Gough, T . A ., Webb, K of Various Mass Spectrometrisaa""ChJournalnofcAnrics Estimation of Volatile Nitro97m 1ne PP 663-667 . Chemistr Vol . 25, No . 3 , "Carcinogens", Introduetion to Environmental (10) TGuthri 338-339 . e oxicoloand 198t~,~PP .G ., gsueh , S .S ., Van Dongen, C .H ., Soto, E• , (ll) Homburger, L ., Handler,. "Adenocarcinoma A of the Glandular Stomach .B . r or andFollowing Russfield, 3-Methylch0lanthre1e1 A DiethYlnitrosamineti,b o Inbred Feeding in Carcinogen-SusceP 1976, Syrian Hamssters",lamine Journal of National Cancer Institute, July, Syrian Hamsters" , pp 141-143 . "Role., and Fiddler, W of. , . . Carre, J (12) Kimono, Dooley , C .J n on Exchange nge Re14nsN, 869i876Formation in Water", Strong Io . •(1980 pp Water Researc h Vol

IIOI IOI liD ID IID III III DD III ID iium U BNA0083497 0 HDMSE00609169 ME&T 83-0970 to Michael Francis From Norma Fujikawa November 28, 1983 p7

REFERENCES, continue d (13) Kirkwood , R . G., Dunn, S ., Thomasson , L ., and Simenhoff, M .L ., "Generation of the Precarcinogen Nitrosodimethylamfne in Dialysate Water", Trans American Society of Arti ficial Internal Organs pp 168-171 . , (1981), (14) Mills, A . L ., and Alexander , M., "Factors Affecting Nitrosodimethylamfne Formation in Samples of Soil and Mater ", Journal of Environmenta l ualit Vol . 5, No . 4 , ( 1976), pp 437-440. (15) Peyton , Thomas 0 ., "N-Nitrosodimethylamine : A Literature Search and Evaluation for the EPA ", Stanford Research Institute, Menlo Park , CA, (1975) . (16) Rademacher , P ., Gilde , H ., " Chemical Carcinogens ", Chemical Education , Journal of Vol . 53, No . 12, December , 1976, pp 757-761 . (17) Rhoades , J. W . and Johnson, D .E of N-Hitrosamines ., " Gas Chromatography and Detection ", Journal of Chromatographic Science , Vol October , 1970, pp 616-617 . . 8,

(18) Ross, R .R ., Morrison , J ., Rounbehler , D.P ., Fan , S ., and Fine, D .H ., N- NI troso Compounds as Impurities in Herbicide Formulations", Journal of Agricultural Food Chemistry , Vol T416-1418 . . 25 , No . 6, (1977), pp

(19) Shank, R . C., " Recent Advances in the Toxicology of N-Nitroso and Hydrazine Compounds ", Aerospace Medical Research Lab ., Wright Patterson Air Force Base , Ohio , (1974) .

(20) "Subduing the Terror of Lin Xian ", Fighting Cancer (1981 ) , TIME/LIFE Books,

(21) Taylor , P ., and Braddock, P ., "Analysis of N-Nitrosodimethylamine in Antihistamines and Cough/Cold Preparations A enc for Cancer Research ", Sixth International Symposium on Nitroso Compounds, Budapest, Hungary, Oct . 16-20, 1979, pp 575-587 .

(22) Technical Data on the Thermal Energy Analyzer Corporation , Thermo Electron , Massachusetts , (1980) .

(23) U . S. Department of Health , Education , & Welfare , NIOSH, "Hazard Review of Nitrosodimethylamine ", Maryland, July, 1973 , (24) U . S . Department of Health , Human Services , b Public Health Services, "Nitrosodfinethylamine", second Annual Reopr Carcipg _ December , 1981, pp 175-177 . ' U . S . Federal Register , Vol (25) . 45, No . 98 , Monday, May 19, 1980, p 33125 . (26) Wolf , H .W., and McKee , J.E ., "Amfnes and Organic Compounds ", Water Duality teria California State Water Quality Control Board , CA, 6 p 132. Sacramento , IO II BNA00834971 HDMSE00609170 'rAN POi D . R. S E ACM

III LITERATURE SURVEY j j A. Chemical and Physical Propertie s 1. General .

To understand the behavior of dimethjinitrosamine (DMNA) in the environment , a brief summary of chemical and physical properties is

helpful . DMX has a molecular weight of 74 .1, (C2HSZO), and has the structural representation (1) : _

CH O=N-N` 3 (1) CH I 3 J The compound is found in the published literature under the following synonyms : dimethylamine , N-nitroso- ; dimethylnitrosamine ; N, N-

dimethylnitrosamine ; methylamine , N-methyl-, N-nitroso-; DMN; and DMA . il / The chemical abstract services registry number is 62759 .

I Fridman and co-workers ( 1971)* have published an excellent review article concerning the chemistry of aliphatic N-nitrosamines . The I following paragraphs summarize their review .

DMNA is a yellow, volatile , non-hygroscopic liquid of low

viscosity . It is considerably polar and consequently is miscible in

water as well as common organic solvents and lipids . The replacement

of each methyl group by a phenyl group tends to decrease the dipole

moment . DMNA has a melting point of 150°C (755 mm) and a density of 1 .004840 .

* See references for alphabetical list of cited sources .

BNA0083497 2 HDMSE00609171 NAVWEPS Report 8798

ABSTRACT . The autoxidation of 1,l-dimethyrlhydra- zine I gives formaldehyde dimethylhydrazone II, nitrogen , and water as its major products . Minor ones are ammonia, dimethylamine , dimethylnitrosamine, diazomethane , nitrous oxide , methane, carbon dioxide, and formaldehyde . This reaction is of first order in I and of zero order in oxygen . It is catalyzed by metals and metal salts , inhibited by added 1,3- butadiene , and accelerated by ultraviolet light . A free-radical chain mechanism is postulated as the rate-determining reaction sequence . The 1,1-di- methylhydrazyl- 2-hydroperoxide so formed is presume d

(Contd . on Card 2 )

U.S. Naval Ordnance Test Station Autoxidation of . . . (Card 2 ) to give the products II, hydrazine , and hydrogen peroxide via a rapid sequence of wall reactions (established in the study of liquid-phase autoxidations of 1,1-diallylhydrazines) . Nitrogen and most minor products probably result from further wall reactions of hydrogen peroxide with I, II, and hydrazine . Autoxidations of hydrazines resemble those of hydrocarbons .

NAVWE~S Report 8798

BNA0083497 3 HDMSE00609172 L

~s (2 0 (9 ~ _- 24_I ----

1-(- ;;311- 311-~ 5T. ~R.AGt-~an t -e± CJ . a!~.°-- ii ~--- - ~ El?a_s~- ? ° ---° I '? _FJ --G 51 LC --

S_ M/c )C -2 5 L~FIN S X -- 5 % (~5 -757o G~soL/ 'Jt - M A 1 ii BLS- -- w ~r ► ~! !? - - z-?o° C (moo °lo-_tt a o_eIE -

5 2 FLT c1 - _\------$ moo! -D - a O c 6L~ rNS ___ , . 7-- 2 5~5J'------5c------ph' of synthetic r dye for wool. Orgem u)- series the I o es of chrome organO)bospb*tesperfume bases . : OrotY osphone esters tar (Or- of 1, glyco and other po Orot i Special ingr to r use with Oreo by 'c aleohollss, . zer tea Oroti c. on Dacron . ents• dis- l ate-stand.): co l Z (Organic): sul- Organoso m oson-St solver film r dichromate; oxi- pew Orox fitment agent for mating comnpound Orox es orient yellow: cadmium de; pig- SC( pro- went. an I (Organic) : ): series& com- it electrostatic re- Oriental (Polak's es for toilet orper : from nylon pound e perfumep b (ol a V Orph ~ deodorant for r I W (Organic) : liq- Oriental 443 (D & 0 for wool, aerosol bombs . Orrin whitener O). deodorant tra . Oriental 9516 (D --r -ti c fibers nd p-dichloroben- Orrin ~ A (Organic) : liquid, for naphth alss. m. erring agent for ~e crYst . ►.r oriental blue : Vi blue, dye color od goods .W .): eom- . C (Organic) : optical oriental Dream jN.B Orris . so: t for cotton and pounded a base: oil for per- Origan A (Ben French) Orr'S : complex poly- fume extra orsei anic) Origanol (P•, = s): series of com- fro - ••rith vegetable oil rfvme bases for toilet Orso oil-o$, and dye- B oon eta an : vermilion; pigment. re des of direct Orinoco (S- j . Orisia (Frij rsche): synthetic perfume Orta ,acron en (Organic): allyl base, . Oriziba (S V): vermilion dry color airing polyglycol ant); acrylic syntheti c orfit :d dispersing Orion (du Ortb for naphthol and fiber . ] :en. Chem.): insecticide to Omatox Orth ;anic): emulsifiable fun * e. & g): synthetic in. .g agent or carrier Orogl Ortb for Dacron, mate: sif ): stabilized azotice bronite : various . : ~' Orth or printing cotton ormulation3 sit rganic) : prophet . prsulfo prunite)with h short alkyl side Ortb r in textile finish- tt zE fatt acid pr m a roximately C,, ; y chulsichains w PPfor cutting oils , Ord ecron and wool anionic emulsifier so ikO ents. breakers, rust preventive, emulsion combined a oil) : solvent fo fat aplittuif, 1 y S= de is Oft' ony tannates. orate and sodium naph- o sodium of zW ubricant inert t thenate. Orti ,..e Solvents)- series 'p~p]'J{ synthetic i gh Grinding)t alumi- petroleum plasticizers fo Ord brasive . . mixturer rubber of fo pigment dye for all Oropon (Rohm & Haas) : Ord proteoylic enzymes with added am- : heavy oriental- ; for audan ) monium chloride or sulfate to ie base leer bateing Ord : orange-typa>. odor . solubilized, rnich) Orotan (Rob= & Bans) ; ~sinetics.

BNA0083497 5 HDMSE00609174 UNCLASSIFIE D

50/50 UDMH /N 204 (AEROZINE 50 )

Composition : 51% N H 49% (H3)2NNH2

C) Physical Propertie s : Boiling Point : 70.1°C Freezing Point : 17 .3°C 2 Density : 0.899 g/cc @ 25° C AEA Heat of Formation :* 12.251 Kcal/mole @ 25°C (calc) Vapor Pressure : 142 1 mm Hg @ 25° C Critical Temperature : 334aC (calc ) Critical Pressure : 115 .4 atm (calc ) Heat of Vaporization : 236.7 cal/gm (calc ) Viscosity : 0.91 centistokes @ 25°C Specific Heat 0.694 cal/gm°C

Preparation : 50/50 is a mixture of commercial concentrate d and commercial 1UDMH in approximately equal portions by Typical composition : N2H4 51.07., UDMH 48 .27., H2O 0 .57, impurities 0 .3%. (10)

Toxicity : UDMH constitutes 90% of the vapor . It may be a through the intact skin, by inhalation of fumes and by 50/50 can cause irritation of the mucous membranes of t respiratory passages , lungs and gastrointestinal tract, symptoms of inhalation are chest pain, coughing, wheez i and vomiting . If large amounts have been inhaled, pu] may occur . Allowable concentration, 0 .5 ppm . (11)

Sensitivity : Both constituents react with air so that 5 0 be kept under a nitrogen blanket . (See UDMH and Hydra

Compatibility : Compatible with : stainless steel , alumina and nickel alloys , Diamine Nylons , Teflon, certain bu t compounds, graphite and some silicone -base greases . 4 copper may be used only in specific applications upon metallurgist . Alloys of magnesium and zinc are not r

Availability : Readily available at $ .66/lb .

Remarks : For further information see references (10)

*Based on the composite formula C0 .678H5 .356N2 . 0

Military Specification, Mil-P-27402, Propellant, Hydr a uns-Dimethylhydrazine (50% N2H4 - 50% UD

BNA0083497 6 HDMSE00609175 Formula : CH1 .9532 Physical Properties : Boiling Point : 177 to 274°C (9) Freezing Point : -40°C (maximum) (9) Density : 0.801 to 0 .815 g/cc @ 20C (Mil Spec ) Heat of Formation : -5.76 Kcal/mole (3) Vapor Pressure : 0.36 psis @ 66°C (1) Critical Temperature : Critical Pressure : Heat of Vaporization : Viscosity : Specific Heat :

Preparation : RP-1 is a straight-run kerosene fraction, which is sub- jected to further treatment, i .e. acid washing, sulfur dioxide extraction. Unsaturated substances which polymerize in storage are removed, as are sulfur-containing hydrocarbons . The kerosene must be obtained from crudes with a high naphthene content . (9) Toxicity absorbed : RP-1 produces moderate skin irritation and after more tha n ingestion . momentary contac t can cause scaling and fissuring of the skin . The the eyes, main danger ca ' from accidental swallowing ; while not especiall y Immediate toxic by t -asping while swallowing or aspiration from lug, nausea improper lc~ introducethe liquid and monary edema r°Pfe J tormwano etps Oroaite -(Oroj . Sulfonate sodium b wool sh enzum 0rt~ sins total ort alkyl sides Si , sruonic ezxnjj Y '"mate, C„ Oxtb emulsion breal c"tthi8 or75, re~ fat splitta °i g 12 gdrae~ de prveativ Ori sntf an o sodium so dpesodium na s 04 vans Solvents) Pefioleinm pJastjj : of of T for synthej0 04 Or m wth added am Ieatbea bateia~ or $UIf h; for on? ~~ ~O~' ~c ~s)s solnbilizea, 0r#

uM d'AssiFIEn IIMuu BNA0083497 7 HDMSE00609176 METHOD 827 0 t GC/MS METHOD FOR SEMIVOLATILE ORGANICS : CAPILLARY COLUMN TECHNIQU E

1 .0 Scope and Applicatio n

1 .1 Method 8270 is used to determine the concegtration of semivolatile organic compounds in a variety of solid waste matrices . 1 .2 This method is applicable to nearly all types of samples, regard- less of water content, including aqueous sludges liquors, waste solvents, oily wastes, , caustic liquors, acid mousses , tars, fibrous wastes, poly- I meric emulsions , filter cakes, spent carbons, spent catalysts, soils, and sediments .

1 .3 Method 8270 can be used to quantify most neutral , acidic, and basic organic compunds that are soluble in methylene chloride and capable of being eluted without derivatization as sharp peaks from a gas chromatographic fused silica capillary column coated with a slightly polar silicone . Such compounds include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons an d pesticides , phthalate esters, organophosphate esters, nitrosamines, haloethers, aldehydes , ethers, ketones , anilines , compounds pyridines , quinolines , aromatic nitro , and phenols , including nitrophenols . 1 .4 The detection limit of Method 8270 for determining an individual compound is approximately 1 µg/g ( wet weight ) . For samples that contain more than 1 mg/g of total solvent extractable material, the detection limit is proportionately higher . 1 .5 Method 8270 is based upon a solvent extraction , gas chromatographic/ mass spectrometric (GC/MS ) procedure .

1 .6 This method is restricted to use by or under the supervision of analysts experienced in the use of gas chromatograph/mass spectrometers and skilled in the interpretation of mass spectra . Each analyst must demonstrate the ability to generate acceptable results with this method .

2 .0 Summary of Metho d

2.1 Prior to ..using this method, the waste samples should be prepared for chromatography (if necessary ) using the appropriate sample preparation method - i .e ., separatooy funnel liquid - sonication liquid•extraction (Method 3510), (Method 3550), or soxhlet extraction ( Method 3540 are a problem , ) . If emulsions continudus extraction techniques should be used . This method describes chromatographic conditions which allow for the separation of the compounds in the extract .

U BNA0083497 8 HDMSE00609177 A( LVLQQA

(c p, "j- n} ~k v t roZw cuC. 1-( I-- '1. z , --- z b 4s

O( O, . - ,4tii a,c,e a A4t O l r i X.

1 7c Gc/s fry ~vj-' ( . o r C cor i l ~uscK„~ -t-~ h N t qrd>

1o k txX. {~Qj2 tkit ~' it r- r- c i C,al11z. No f a- M a.~L4L ( ems- l 5 cootM4Ze M c)

, which is sub- Preparation : RP- 1 is a straight-run kerosene fraction sulfur dioxide jected to further treatment , i.e. acid washing , extraction. Unsaturated substances which polymerize in storage are removed, as are sulfur-containing hydrocarbons . The kerosene must be obtained from crudes with a high naphthene content. (9)

Droa to (Oronite)s sodium benzene salfonate with short alkyl side gains totaling aP ately C,,; anionic emus er for cutting on. emulsico breakers, nut preventive, fat splitting, 12 grade is combined ,~e~atesodium ~nna0e and sodium naph. I U BNA0083497 9 HDMSE00609178 _2 35 7_ -- ---•------

1 o overcome the disadvantages of JP- 3, the Reid vapor pres- suYE-was reduced to 2 to 3 pounds , and JP-4 was developed in 1951 . This fuel is a blend of 25 to 35°°4 kerosine and 65 to 75 o gasoline components and has proved satisfactory for mili- z~ 3~r tary requirements . An important Navy turbine fuel, developed J(ca 1Ns f" iUrt.. JO5+Yau d f for carrier operation during the Korean War, was a mixture ~a of a special kerosine and aviation gasoline. The latter was stored 65~fi~z il; _N c y c to PE'D_ i ~►-- p- - - in tanks in the central zones of carriers to minimize the possibil- ity of hazardous fuel leaks in event of battle damage. But, space GgSDUwte - was limited for such storage. Thus, JP-5 fuel was developed £ a .t4 Ca aces t, I r: e for aircraft carriers. This was a special 140°F (60°C) flash point kerosine . Because of its low volatility , it could be stored safely in outer tanks of carriers. When mixed with aviation gasoline ,

GP TRO L'Eu t Althou8h the boilrng ranges of mponents ( or fractions) vary between refrneries , a typical rude ' tillation until will resolve the crude into the following r ions : ► Petroleum ether Ce-a .t f 20-60 By distillation at atmospheri c pressure, Solvent naphtha 60-120 1 . A light straight- run fraction , consisting primarily of CS Gasoline 40-200 and C6 hydrocarbons. These also will contain any C4 and lighter gaseous hydrocarbons that are dissolved in Kerosene r 175-325 the crude. Gas oil P ti. Ott- 300-500 2 . A naphtha fraction having a nominal boiling range f Vacuum distillatet X401 1 200°-400°F (93°-204°C) C NA P'Tft Residual petroleum coke or asphal t 3. A light distillate with boiling range of 400 °-540°F (204°-343°C) . By vacuum flashing, 1 . Heavy gas oil having a boiling range of 650°-1,050°F (343°-566°C) . A nondistillable residual pitch . Nof(~rl P 759 ALICYCL C COMPOUND~ MS ~, Alicyclic compounds are cyclic compounds having aliphatic properties . In a strict sense the term should apply to both carbocyclic and heterocyclic compounds, but in practice it usually is limited to carbocyclic compounds . The saturated alicyclic hydrocarbons frequently are called cycloparafna or cyclanes although petroleum technologists usually call them naphlhenes because cyclopentane (pentamethylene) and cyclohexane (bexamethylene) and their homologs have been isolnted from the naphtha fraction of petroleum . Those compounds obtainable by the hydrogenation of aromatic rings fre- Th!a following analyti quently are called hydroarornalic compounds . for the detection and quantification of petroleu * hydrocarh'+tt" and fuel consituente . These techniques are to be followed when analysis is required for evaluation of either a ruspected or confirmed tank leek as presented in the ' guidellnss . ThcGe analytical techniques cover the full range of petroleum fu'1 hydrocarbons from gasoline (C4-C1 2) to let fuel (C1t)-Cl ), t!i diosel ( C9-C,2) in either a liquid or solid matrix . Detec ion o f complex hydrocarbon mixtures -"are best achieved using a Gee Chrometograph with a Flame Ionization Detector tGC/FID) .

II BNA0083498 0 HDMSE00609179 RP- 1

CH1 Formula - .9532 ph•yssical Properties : Boiling Point : 177 to 274°C (9 ) (1 L Freezing Point : -40°C (maximum ) ° (9) Density : 0.801 to 0 .815 g/cc @ 20_ C (Mil Spec) - Heat of Formation : -5.76 Kcal/mole (3) Vapor Pressure : 0.36 psia @ 66°C (1) ` -- Critical Temperature : Critical Pressure : Heat of Vaporization : Viscosity : 6.5 centistokes @ -34.4°C Mil Spec) Specific Heat:

Preparation : RP-1 is a straight-run kerosene fraction , which is sub- -o 5 _ jected to further treatment, i .e. acid washing, sulfur dioxide extraction. Unsaturated substances which polymerize in storage CI are removed , as are sulfur-containing hydrocarbons . The kerosene 0 must be obtained from crudes with a high naphthene content. (9)

r~ ICI D LL.E 2 CM 5TST2/ / n F

C `"' cco. ~ m 't3 Chapter 39 r `i59 `'ti,ovo ~ o .c~ i v ALICYCLIC COMPOUNDS. TERPENES AND STEROIDS U E l~~c

ALICYCLIC COMPOUND S Alicyclic compounds are cyclic compounds having aliphatic properties . In a strict sense the term should apply to both carbocyclic and heterocyclic compounds, but in practice it usually is limited to carhocyclic compounds . The saturated alicyclic hydrocarbons frequently are called cycloparaftuns or cyclones although petroleum technologists usually call then : naphihenes because cyclopentane (pentamethylene) and cyclohexane (hexamethylene) and their homologs have been isolated from the naphtha fraction of petroleum . Those compounds obtainable by the hydrogenation of aromatic rings frequently are called hydroaromalie compounds .

TABLE 30.7 Typical Petroleum Fractionation

Petroleum ether 20-60 Solvent naphtha 60-120 Gasoline 40-20 0 Kerosene 175-325 Gas oil . PIEtt i. O% .. 300-500 Vacuum distillate t X400 Residual petroleum coke or asphal t b ~AMM ®/.1117

Iis811ahor tbmpereture is lower N redusd pressure. '`O AA'Z P 713

BNA0083498 1 HDMSE00609180 gasoline. CAS: 8006.61-9 . A mixture of volatile hydrocarbons suitable for use in a spark-ig- nited internal combustion engine and having an kerosene. (kerosine). CAS: 8008-20-6. octane number of at least 60. The major compo- Properties: Water-white, oily li quid; strong odor. nents are branched-chain paraffuvs, cycloparaf- D 0.81, boiling range 180-3000, flash p 100- _ fins, and aromatics. There are several methods 150F (37.7-65 .5C), autoign temperature 444F of production : distillation or fractionation which (228C). Combustion properties can be greatly yields straight-run product of relatively low oc- -- improved by a proprietary hydrotreating process tame number, used primarily for blending ; involving a selective catalyst. thermal and catalytic cracking; reforming; poly- De rivation : Distilled from pet roleum . merization; isomerization; and dehydrocyclo- Hazard : Moderate fire risk, explosive limits in air dimerization. All but the fast are various 0.7-5.0%. Toxic by inhalation. means of converting hydrocarbon gases into Use: Rocket and jet engine fuel , domestic heating, motor fuels by modifications of chemical struc- solvent, insecticidal sprays, diesel and tractor fu- ture, usually involving catalysis. The present els. source of gasoline is petroleum , but it may also be produced from shale oil and Athabasca tar cycloparaffin. An alicyclic hydrocarbon in which sands as well as by hydrogenation or gasification three or more of the carbon atoms in each mole- of coal. cule are united in a ring structure and each of antinock gasoline A gasoline to which a low these ring carbon atoms is joined to two hydro- percentage of metbvl tert-butyl ether (MBTE) gen atoms or alkyl groups. The simplest members has been added to eliminate knocking and in- arc cyclopropane (C,Hs), cyclobutane (C4Ha), crease octane number . This compound has al- cyclopentane (C5H10), cyclohexane (C6H12), and most completely replaced tetraethyllead. Gaso• derivatives of these such as methylcyclohexane lines of octane number 100 or more are used (CBH11CH,) . Hazard: All members of the cycloparaffm series chiefly as aviation fuel; those having a research are narcotic and may cause death through•respi- octane number of approximately 90 are in gen- ratory paralysis eral automotive use. . For most of the members there ' See also antiknock agent, octane number . appears to be a narrow range between the concen- casinghead gasoline, see natural gasoline (be- tration causing deep narcosis and those causing death . low). crocked gasoline Gasolines produced by the alicyclic . A group of organic compounds charac- catalytic decomposition of high-boiling compo- terized by arrangement of the carbon atoms in nents of petroleum. In general, such gasolines closed ring structures sometimes resembling have much higher octane ratings (80-100) than boats, chairs, or even bird cages. These com- that produced by fractional distillation . The dilr pounds have properties resembling those of ali- ference is due to the prevalence of unsaturated , phatics and should not be confused with aromatic aromatic and branched -chain hydrocarbons in C . The actual p pe ies vary compounds having the hexagonal benzene ring. the cracked gasoline ro rt rial Alicyclics are comprised of three subgroups: widely with the nature of the starting mate (t) cycloparaffins (saturated), (2) cycloolefins and the temperature , time, pressure, and catalyst (unsaturated with two or more double bonds), used in cracking . and (3) cycloacetylenes (cyclynes) with a triple high-octane gasoline A gasoline with an octane bond. The best-known cycloparafl'ms (sometimes number of 90-100. called naphthenes) are cyclopropane, cyclohex- See antiknock gasoline , octane number. -- ane, and cyclopentane; typical of the cycloolefins lead free gasoline An automotive fuel contain- 1 are cyclopentadiene and cyclooctatetraene . Most ing no more than 0. 05 S of lead per allo de- wit catalytic alicyclics are derived from petroleum or coal tar . signed for use in engines equipped Many can be synthesized by various methods. converters. See also subgroups referred to above. natural gasoline A gasoline obtained by recov- ering the butane, pentane, and hexane hydrocar- L bons present in small proportion in certain natu- Chapter 39 rai gases. Used in blending to produce a finished gasoline with adjusted volatility but low octane number. Do not confuse with natural gas . ALICTCLIC COMPOUNDS. TERPENES AND STEROIDS polymer gasoline A gasoline produced by polymerisation of low molecular weight hydr o- O LL€12) "CN >M tST(t/ ~Of orrG,4Ntc carbons such as ethylene, propene, and butenes. _ . M n Used in small amounts for blending with other C~~-i~'OU1.9DS gasolines to improve their octane number. ALICYCLIC COMPOUNDS X pyrolysis gasoline Gasoline produced by ther- _ Alicyclic compounds are cyclic compounds having aliphatic properties. mel cracking as a byproduct of ethylene manu- facture. It is used as a source of benzene by the In a strict sense the term should apply to both carbocyclic and heterocyclic on process. ;- - compounds. hydrodealkyla ti compounds, but• in practice it usually is limited to earboeyclie reformed gasoline A high octane gasoline ob- The saturated alicyclie hydrocarbons frequently are called cycloparq,QSns tained from low octane gasoline by heating the r- or cyclanes although petroleum technologists usually call them naphlhenes be- vapors to a high temperature or by passing the cause cyclopentane (pentamethylene) and cyclohexane (hexamethylene) and vapors through a suitable catalyst . - ' their homologs have been isolated from the naphtha fraction of petroleum. straight-run gasoline Gasoline produced from petroleum by distill ation without use of cracking - Those compounds obtainable by the hydrogenation of aromatic rings fre- or other chemical conversion processes. Its cc- quently are called hydroaromatic compounds . tame number is low .

aNnaoaaasas HDMSE00609181 Formula •1 .9532 Physical Properties : Boiling Point : 177 to 274°C (9) Freezing Point : -40°C (maximum) (9) Density : 0.801 to 0 .815 g /cc 0 20_°C (Mu Spec ) Heat of Formation : -5.76 Kcal /mole (3) Vapor Pressure : 0.36 psis 0 66°C (1) Critical Temperature : Critical Pressure : Heat of Vaporization : Viscosity : Specific Heat:

Toxicity: RP-1 produces moderate skin irritation and after more than ~e absorbed momentary contact can cause scaling and fissuring of-the skin . The by ingestion . main danger comes from accidental swallowing ; while not especially if the eyes, toxic by this route , gasping while swallowing or aspiration from . Immediate act improperly induced vomiting can introduce the liquid into the lungs, nausea eezing , and pulmonary edema may ensue . pulmonary edem a Sensitivity : RP-1 is chemically stable and insensitive to shock . It shows good thermal stability over a wide range of ambient storage . 50/50 should temperatures , but exposure to high temperatures accelerates the _ rdrazine) (10 ) formation of gtmi and_ s ediment .

:minuet, titaniu m butyl-rubber JQ LLER , M,( 9Tt .Y o f Alloys o f C coM POU N~ S ° ,on advice of a c2-C, AN t recommended . Chapter 39

ALICYCLIC COMPOUNDS . TERPENES AND STEROIDS and (11) .

ALICYt UC COMPOUNDS Alicyclic compounds are cyclic compounds having aliphatic properties. X In a strict Irazine - . sense the term should apply to both carbocyclic and heterocyclic compounds, but in practice it usually is limited to carbocyclic compounds . )MH) The saturated alicyclic hydrocarbons frequently are called eycloparafns or ryclonrs although petroleum technologists usually call them naphlhrnes because cyclopentane (pentamethylene) and cydohexane (hexamethylene) and their homologs have been isolated from the naphtha fraction of petroleum . Those compounds obtainable by the hydrogenation of aromatic rings frequently are called hydroaronu lk compounds .

IIOImuimiiimmimiiiumuumiu BNA0083498 3 HDMSE00609182 RP- 1

Formula : CH1 .9532 physical Properties : Boiling Point : 177 to 274°C (9) - - Freezing Point : -40°C (maximum) (9) Density : 0.801 to 0. 815 g/cc @ 20°C (Mil Spec ) Heat of Formation : -5.76 Kcal/mole (3) Vapor Pressure : 0.36 psis @ 66°C (1) - Critical Temperature : Critical Pressure : M Heat of Vaporization : Viscosity : 6.5 centistokes @ -34 .4°C Mil Spec ) Specific Heat :

tJ O LLE R. 1 C4-f ~ti-tL 5T O F o C, AtI t C COff l'OV J D S Chapter 39 .r~59 a

-- ALICYCLIC COMPOUNDS . TERPENES AND STEROID S ~ U FIwI G

ALICYCLIC COMPOUND S Alicydic compounds are cyclic compounds having aliphatic properties . In a strict sense the term should apply to both carbocyclic and heterocyclic compounds, but in practice it usually is limited to carbocyclic compounds . The saturated alicyclic hydrocarbons frequently are called cycloparafns or cyclanes although petroleum technologists usually call them naphihenes because cyclopent.ane (pentamethyleue) and cyclohexane (hexamethylene) and their homoloos have been isolated from the naphtha fraction of petroleum. Those compounds obtainable by the hydrogenation of aromatic rings frequently are called hydroaromatIc compounds.

L TABLE 30.1 Typical Petroleum Fractionation [~~oaol3 -by~ n ~g N ~ C ... v7 C O ~ N ~ f? G t7 ri

V ~ O ~ P ~ •~ ~ ~ M M ~' Petroleum ether 2()-60 -- • V 7 4. ~ v u ~ ~ ~ p •~ ~ ~iD Solvent naphtha Gasoline 40-200 Kerosene 175-325 E Gas oil - PIESte- On g 300-500 o a a °; g y'~ ~ •~ - Vacuum distillatet X400 Residual pet roleum coke or asphal t H tv l oNt - CR A . l4tolatia' $ jnper.ture n lower it reduced pessure I,ORUA~J~c CtF~

BNA00834984 HDMSE00609183