Document myMb21Ja6QBZ5j4nYJeEM7w4

Appendix III "N-Nitrosodiethanol in Synthetic Cutting Fluids: A Part-Per-Hundred Impurity" / -> /-/ l tmmmkrt. 114. I2S4 <197**. f ft. ft. NrMa, It ft. Ir+mtm. ft. W. Inn, ftd. fw. )4,2544 (tear.) (197ft. 11. C ft. AaaaUi.Ibid. 31. 24ft <br.>(l977>; N. Aokt mi *. T. VomITm*. Pme. Sot. Exp. Hoi. Htd m. 101(1949). 12. J. O. MmU. I. Goo&afofcy. L H. Lepow. Im* mottochemittn If, )4I (1975). 13 0 Ux mi H. I. M41ar<-Ebcrter4, 7. . Med 134 (Stiff!.). 90i 0971); J.O^MitMdl H. Upo*. ta prppmtkam. 14. M. A. Sellnmr, ti ai.. Cttm. tmmmwmol. ImmmtopotW. 9. 251 (1974). 234(1974). 15 J. I kkidiif. /nr. Arch. Allergy Appt. Immmmoi. 7. 105 (1955). 16 L hlkowr. L. Bhim. I. H. Lepow. L. Win. E. W Toii.J. txp Med 193. I (1956). 17 A P Oaltwuo and H. J MOItr-Eteriurt. J. Immumot. 97.640(1946). 14 S Ruddy. L. G Hunuckvr. K. F. AuMen Ibid. 164. 657 (1977). 19 T A E PUuvMUUwid K. IMakA.tbid. 113. 344(1974). 39. C. A. AW. ft. J. F.4.1 j. MidTm. m amt 21. LH. WtMW.i ADW.EH. MrflWi. I. ft. ft intern. Wr 144. 542 (797JV 22. S. 14. Onvdy m4 J. P. Krdm.Ajm. Trip. Mod. ftfuM. 24. 194 (1974V 23. N Noam mi Z. Cote. J. 9. M. Ml. 1492 (1974). 24. ft. jack W P. A. Wi, mpiiH lnl eW* tiOM. 25. ft. H. Sibtemc. ft. Mite. M. Rink. H. W. Cot. Am. Tnp. Med. hemtbot. 4). 327(1949). 24. ft. Ltefe. M. Atewo. H. S/mi. / /<W. 55. 633 (1949). 27. Supported ia pari by cr*M Al 09451 ftua the NMonel Imucmic* of H*M. Sonne frooi the patacoc with PLO was kindy lufiphed by ft. McLean. The proneidia comet of RP was it- termined by J. Cmptth Pbriiai factor B end the aouscnia to ihei factor wore prepared in I. H. Lepow's laboratory. 23 Aufust 1974; revised 15 November 1974 A'-Nitrosodiethanolamin* in Synthetic Cutting Fluids: A Part-Per-Hundred Impurity Abstract. bl-nitrosodielhanolamine has beenfound to he present at a concentration of 0.02 to J percent in several brands of synthetic cutting fluids. Its identity was confirmed by three independent techniques: (i) by measuring the retention times on two different high-performance liquid-chromatography columns, (ill by dehydration 10 bi-nitrosomorpholine. and (Hi) by preparation of the O-melhyl ether derivative. Cutting fluids are widely used to reduce the temperature of the mctal-tool interface during metal cutting and grinding. The majority of cutting fluids used in the United States are synthetic: they contain up to 45 percent triethanolamine and 18 percent sodium nitrite and have pH values in the range 9.0 to 11.0. Lyinsky el al. (V) demonstrated that tri ethanolamine could readily be nitrosated to form /V-nitrosodiethanoiaminc (NDEIA). Using a model system. Zingmark and Rappe (2) recently showed that triethanolamine would be expected to undergo in vivo nitrosalion under simulated gastric conditions. Af-Nitrosodiethanolaminc is of interest because it has been shown to produce liver turnon in rats u). We report here on its presence in relatively larger amounts as an impurity in commercial cutting fluids. Cutting fluids were obtained com mercially in the Boston area. Authentic NDEIA was prepared as described by Druckrcy et al. (J). The identity of the compound was confirmed by chemical ionization mass spectrometry and elec tron impact high-resolution mass spec trometry. A high-pressure liquid chro matograph-thermal energy analyzer (HPLC-TEA) was constructed from a high-pressure pump (Waten model 6000A). an injector (Waten model U6K). a column (Waters), and a TEA detector (Thermo Electron model 502) (4. 5). Cutting fluid was chromatographed as purchased without any treatment on a p Forasil column (Waters), using as a solvent system 50 percent hexane and 50 percent acetone at a flow rate of2 ml/min. A peak eluting al the retention time of NDEIA was determined. Since no clean up was used, the possibility of artifact formation was discounted. Because crude fluid rapidly degraded the column, routine analyses were carried out after first extracting with ethyl acetate in the presence of magnesium sulfate. The ex tract was Altered through sodium sulfate and then injected onto the HPLC-TEA (A). The results are presented in Table 1. In order to confirm the identity of the peak eluting at the retention time of NDEIA. the compound was isolated (7) and studied by three independent tech niques. I) High-pressure liquid chromatogra phy. The isolated sample was iqjected on to an HPLC-ultraviolet spectrometer or HPLC-TEA by using either a p Bond- Tabic I. Concentration of N-nitrosodiethanolamine in several brands of synthet ic cutting fluids. Brand NDEIA (%> A 2.99 B 1.04 C 0.42 D 0.25 E 0.11 F 0.06 G 0.06 H 0.02 ^ NH, or a jt Feral cekeaaa <). Wi* bothpifi wvalweyicriaervedai--- rial ctatisw al the same retention tfcne aa authentic NDEIA. 2) Dehydration. The isolate* temple, when dehydrated srith concentrated suL furic acid (96 percent) at I55*C tot 25 hours, yielded Af-nitrosoaorphotine as the dehydration product. Af-Nfcroaomorpholine was detected by combined gas chromatography and high-resolution mass spectroscopy (9). The isolated sample did not give an At-nitrosomorpholine peak before dehydration. 3) Derivative formation. The O-meth yl ether derivative of the isolated sample was prepared by methylation with methyl iodide, with sodium hydride as a catalyst (/0). The methylated sample was distilled and the distillate extracted with meth ylene chloride. The concentrated extract was then introduced into a gas chromato graph fitted with a Coulson electrolytic conductivity detector in the nitrogen mode (//). The presence of the NDEIA derivative in the isolated sample was con firmed when the retention time was com pared with that of the O-methyl ether de rivative of authentic NDEIA. The cutting fluids that we tested repre sent only a small fraction ofthe total num ber of commercial brands that are avail able. On the basis of results reported here, we expect that most cutting fluids that contain triethanolamine or dietha nolamine and nitrite as additives will be contaminated with NDEIA. To assess the magnitude of the problem, we recom mend screening all brands of synthetic cutting fluids. The N-nitrosamine content of cutting fluids is about 40 times higher thaa the nitrosamine contamination in some herbi cides (12) and 10* timet higher than that found in foodstuffs preserved with ni trites (13). Persons who use cutting fluids could well be exposed to nitrosamine. Even though the fluids are diluted 10 to 100 times before use. the amount of the nitrosamine present is such that it may pose a carcinogenic hazard to ail users. In the past 30 years, cutting oils have been frequently cited as related to cancer of the scrotum among machine operators (14. 13). Several cutting oils were found to be carcinogenic to laboratory animals (13.16). and compounds such as polycy clic aromatic hydrocarbons and hetero cyclic compounds were believed to be the carcinogens (17). Over the pest 20 to 30 years, synthetic formulaliooi have re placed the original mineral odt. Almost all of the "cutting oils" used today art of the synthetic variety. Tim synthetic cat ting fluids described htre hove been in arnwci. vou t*s BFG10680 21129052 widespread um for about 20 yean and, because of the 20-ycar latency period ex pected for human cancer (18), we would not expect cancer incidence among ma chinist! to be related to NDEIA. How ever, machinists may have been exposed to relatively large amounts of NDEIA by skin absorption and inhalation. We sug gest that epidemiological studies be ini tiated to screen workers who have been subjected to NDEIA for prolonged peri ods. Until now. A'-nitrosamines have not been directly associated with human can cer because no population groups had been identified that were inadvertently exposed. Cutting fluid users have the dubious honor of being the first such pop ulation group to be identified. Note addtd in proof'. Zingmark and Rappc initially reported NDEIA to be ab sent from grinding fluid Q). Since submis sion of this manuscript, we were in formed by Rappe of a second manuscript (IV) reporting the presence in grinding fluid stored for 4 to 6 months of a compound which was claimed to be NDEIA. Tsai Y. Fan, John Mokkison David P. Rounbehler Ronald Ross, David H. Fine Thermo Electron Cancer Research Center, Waltham, Massachusetts 02154 Walter Miles, N. P. Sen Health Protection Branch, Food Research Division, Ottawa, Ontario, Canada RWwaWMl 1. W. tJigunky. L. Keefer. E. Conrad. R. Von de Boon. J. */. CfUKfT /air. 49. 12)9 < 1772). 2. F. A. ZtagaMfk tad C. Rapp*. Ambio ?. M (1976). 3. II. Dntcfcray, R. Pmmmnn. S. Ivenkovic. D. Scfraufcl. Z. Krtbifortck. 49. 103 (1997). 4. D H. Fine. F Rufefc.D. Ueb, Nofurr iLamdom) 247. )4<I774>. 5. O. H. Ftm. D. F. Rraabehler, A. Silvcnfa**. R. Rote, in S+co*4 Symposium om Nitrite ** Kief Products (Ceocral lasthutt for Notridon and Food Reward* TWO. Zeaat. Netliertaade. in prtw). 6. Tfce recovery of NDEU after iJdi procedure war 100 r--rn 7. A 0.1 -ml portion of cutting fluid (brand O war c itncted with 30 mi ofdicwrl etherorctbyt aon> Uie in the pretence of 10 g or miff him wlfete. The extraa wne AkerW thrauch 20 g c4 lod--t ntfaie. The Akrate vu concentrated with a itrmn of momu to epprcu--fly 300 pi and kwded onto a ufcca nai conoan (I by 5 cm), which wae waalied with 30 ed of diethyl ether and then chafed with &ml ofethrt ecetme. The eiuefe wne concentrated to eoproiimnteiy JOO pi as the flnal ieointed enmpie. An eQunoue eohnion containing ethenoinadne wm tranced by the tama boMon procedure need far tbe cattiatt fluid. Ho artdhct formation rfNDfitA wnefoanddaring the preendura. I. The echunt lyma wne 3 percent methenoi ami 97 pervem eaathyiene chiortde far the p Brmd aped HHg cotamm, and 30 percent eclcne end 70 nerornt hexane for the Foraafl cchmm. The how nee far both coirnmne war l eilak 9. The cohamm (4 fact by M inch) wae packed vtth 3 percent Carbnwax M Id on 109* to 200 m--h caroemaem w rupi ^meneenco eno eeeu ikmdr las-C TW In nM of WWW cmikfptvult attain. TW am pnliluxWwRi I AMUL I9T7 ML N. P. too. MX P. MW. S. r* Iwwacr.l. C1Weaaeaaer..iaaraai. II. The cofnaan wae parked aid 13 percent Carbo- wax 29 M centaniag 2 percent NaOH on Ob' to Mfameah Chrnmaeorb P. The mnanomme cfthe rnhiaan waaweintnined iaothemral)i at !47Cfar 3 ndaieie and rhee pmnia--ad lo )gPC at e race of IQ^C per edouro. TV lo* rale of the hchem carrierjaa war 23 adtada. 12. O. H. FUe. IL Rosa. D. P. RimMu^r, 9. Fan. paper pen anted el the American Chemical So il. P. Boapvki and E. A. Walkar.N-NiooaoCW pounds la the Cmviremmeni (letereebooel Anew cy for Reacmch on Cancer. Lyon. France. 1974). 14. 0. N. D. Cnockxhaak md J. R. Sotnrv. Be. J. tnd. Mad 7,1 11930): R. Toumc. Frette Mad. 72. 2009 (1994); j. E. H. Milne, hied. J. Ami. 2. 13 (1970). 13. H Deaoilie. M. Pfalben, G. Ripauh. A. CavisBeaui, H. RoaiienoM. ArrA. Mai, Prof. Med. Tnv. Seeme. 5or. 134. 699(1973). * E-Mnmcminn Jr./MAfa*a.>*<mA. 17. ImcrnmionM Agency far Raaenrrh m Cancer. ofCmHmet Mr H* efdee Chmmrat a Mm Cirun 4mwdr Ihd* feriou end Herawryuflt Cenpamd (Cyaa, France. 1971). **t. ). p. 30. II R. 1. Waawcder. S. Str^er. I. K. Wmr. |. Joar*. H. Falk. C. Car**, in Omuadrad Cm fimmtmeats. U SaOod and J. K. Wmeir, Eda. (New York Academy of Soeacea, New York. 1779). p. 40; I D Guham. I. M. Demmm. t A. Umea. 1 K. Wagoner. V. E. ArcVr. H. P. Bte- ftr. in ibid.. p. iJk 19. C. Rappe. Amhie. in pram. 20. We thank R. Carripan and G Gordon of tV Nn- tional Science Foundebon far vMunbie Arv cuuionft. and F. Benoit of the HaaJth Pnnectma Brancli. Ottawa, for canyon the r4a*-'-l kmoatioo mass pectrcanctry. The wort U Thermo Electron m Mipported by NSF pw ENV75-200Q2 4 October 1979; revised 12 November 1974 Perception ofImpossible Limb Positions Induced by Tendon Vibration Abstract. When the wristflexor muscle is vibrated and the wrist is passively extend ed to a position close lo its anatomical limit, the hand is felt to be bent to a position about 29* beyond its maximum operating range. The mechanism of position sense must in this ease be operating on the basis of extrapolation. Ambiguity of sensed position can occur in this situation. Some subjects, when opposing the vibrationinduced contraction of biceps, report experiencing multiple forearms. Until recently, position sense in limbs was thought to be due solely to the re ceptors associated with the joint capsule and pericapsular tissue (I). However, evidence now strongly suggests a role for muscle receptors, especially the primary endings of muscle spindles (2). In this re port l present evidence that vibration of muscle tendons can result in errors of position sense as great as 54* when the muscle is passively stretched. Further more. the size of this effect is not re stricted by the anatomically given limits of flexion and extension. Cat spindle primary endings are highly sensitive to periodic stretch of small am plitude while secondary endings are not (J). In humans, vibration of a tendon causes a predictable increase in the con tractile activity of (he agonist, caused by autogenous reflex excitation of the alpha motoneurons and reciprocal inhibition of the antagonist. This leads to involuntary movement (4)- When this movement is stopped by an external agent, the subject reports a persistent illusion of movement in the direction appropriate to extension of the vibrated, and contracting, muscle. This is associated with an error of posi tion sense, also in the direction of exten sion. the size of which has been reported as being between 5.5* 15) and 8* (2) when the biceps tendon is vibrated at 100 hertz. McCIoskey (5) argues that these positioo signals are not merely the in tegration of those responsible for the persistent movement illusion, for the size of the position error does not in crease with vibration time. Furthermore, procedures that lower or abolish the movement illusion do not similarly affect the size of the position error. This makes the existence of the position illusion of considerable theoretical importance, for it implies that some of the afference from the muscles could be used by the brain as a source of positional information, as distinct from the notion that vi bration merely biases position analysis by virtue of the volume of movement information. Some properties of the muscularly de rived position mechanism were studied in right-handed subjects 6 to 40 years of age. The majority were university stu dents and faculty. The apparatus con sisted of a vibrator with a piston 15 mm in diameter which was driven sinusoidal ly at 80 hertz with stroke, under load, of 2 mm. This piston was applied lo various sites on the left arm. Objective measure ment of the position of the left wrist or hand was achieved by asking the subject, whose vision was occluded, to make a mark with a pen held in the right hand on a vertically mounted Plexiglas sheet ad jacent lo the left arm. This task used only the position tense of the two aims. Pre cise localization of wrist or hand of the experimental arm was aided by the ex perimenter touching one or the other with slender pointed rod. Tha effect of rt 21129053 50 BFG10681 / Appendix IV MONITORING PLASTIC PIPE AND PIPING SYSTEM COMPONENTS Concern for health and environmental safety associated with appli cations for plastic piping system components is not new. Regula tory agency representatives at all levels of government - federal, state, and local - are aware of the voluntary standards and testing programs available through the National Sanitation Foundation (NSF), a private, not-for-profit organization chartered in 1944 under the Michigan law. NSF is dedicated to service, research, and edu cation, and operates through headquarter offices and laboratories in Ann Arbor, Michigan, with four regional offices in the U.S. and a European office in Geneva, Switzerland. Since 1951, it has adopted more than 50 consensus standards and criteria which are recognized and used throughout the world. Responsibility for safe drinking water in the U.S. rests offici ally with the U:S. Environmental Protection Agency (EPA) through the Safe Drinking Water Act (Public Law 93~523) and regulations relating to the Act. A Memorandum of Understanding (MOU), signed by EPA and the Food and Drug Administration (FDA), clarifies and assigns to EPA responsibility for regulating the quality of water in contact with pipe and other items which have the potential for contributing contaminants. Liaison between NSF and EPA is closely maintained. NSF Standard No. 14, adopted in 1965 and revised most recently in December 1980, relates to "Plastic Piping System Components and Related Materials." Currently 1368 products have been tested and listed by NSF for conformance with Standard 14. From 1956 to 1956, plastics were tested by NSF through contractural agreements with participating companies. Thus/ for 25 years, plastics used for potable water and drain, waste, and vent have been tested by NSF. When in complete conformance with the requirements of Standard 14, products are authorized to display the appropriate logo NSF-pw for potable water, and NSF-dwv for drain, waste, and vent. Me pip-ing *y*Zem component* OA pZumb-lng pAoducZ& altcAnaZ-Lve Zo plcutZc* have been *o Ze&Zed. Further, complete chemical formulations must be filed for all products included in this pro gram, and rigid additional testing is required for new or modified ingredients. The formulations are confidential and used only for decisions regarding the appropriateness and safety for proposed end use. The rigid test protocols include accelerated extraction testing for chemicals leached from the products, and animal feed ing studies for proposed new ingredients which have not received prior sanction from FDA for use in food contact. Listed products are sampled by regional personnel during unannounced annual visits (currently three or more) to production facilities. 51 BFG10682 These samples are shipped to Ann Arbor and tested in accordance with Standard 14. Established enforcement procedures require resampling and retesting of failed products. Repeated failures are cause for delisting. FEDERAL REGULATIONS Pertinent to Water Exposed to Plastic Pipe Public Law (PL) 93-523, known commonly as the Safe Drinking Water Act (SDWA), provides the basis for USEPA National Interim Primary Drinking Water Regulations (NIPDWR). (40 FR 59566, December 24, 1975; 41 FR 28402, July 9, 1976; 43 FR 5756, February 9, 1978; 44 FR 42246, July 19, 1979; 44 FR 68624, November 29, 1979; 45 FR 57332, August 27, 1980; and the final rule for control of trihalomethanes is published in 44 FR 68624.) The NIPDWR*s specify maximum contaminant levels (MCL) of specifi cally regulated inorganic and organic contaminants. The MCL established for total trihalomethanes (TTHMs) is 0.10 mg/1. (TTHMs are defined as the sum of the concentrations of bromodichloromethane, dibromochloromethane, tribromomethane, and trichloromethane (chloroform).) MCLs for carbon tetrachloride and tetrachloroethene are not included in the NIPDWR. Public Law 92-500, commonly called the Clean Water Act, is the basis for Water Quality Criteria (44 FR, 15926, March 15, 1979; 45 FR, 79318, November 28. 198(n . > BFG10683 52 21129055 Appendix V Letter on "The California HCD and ABS-DWV" DOW CHEMICAL U.S.A. February 16, 1981 FEB 2 0 198, midland. Michigan 48640 Jerilyn Church Plastic Pipe and Fittings Association 999 N. Main Street Glen Ellyn, Illinois 60137 Dear Ms. Church: RE: THE CALIFORNIA HCD AND ABS-DWV It is an extremely difficult task to reduce to meaningful numbers the potential for extraction or migration of trace contaminants from ABS-DWV into various waste streams. To project further towards estimating how these minuscule amounts of organic leachates might somehow persist through modes of waste treatment, diffusion, degradation, dilution, etc. and accumulate in local, regional, national, or world fresh water drink ing supplies in levels detrimental to life becomes extremely speculative. The plastic pipe adversaries will probably continue to persist in their efforts to establish guilt by implication. It is doubtful that they would be able to establish such guilt on a sound technical basis. There is a vast difference from developing data for potential migration from DWV systems vs. migration from closed transport systems into the transported media such as water pipes and drinking water. Domestic DWV systems are essentially open systems vented to the atmosphere. They only convey effluent sporadically and seldom if ever at full capacity. There are vapor trap components in the systems which do provide stag nant reservoirs for indeterminate periods of time but these would only constitute a very small fraction of the inside surface area of the entire effluent transport system. Typical residence time for effluent moving through a household.drain system would be only minutes or a fraction of a minute. I would not attempt to establish a practical method of assigning logical estimates of what might be construed as a typical concentration level of a particular trace contaminant leaching from an ABS-DWV system into effluent from a typical domestic residence into a larger outfall of similar effluent. For demonstrative purposes a theoretical worst case type of example might suffice to establish some perspective for the overall extremely limited potential for residential ABS-DWV systems to be contributory to contamination of fresh and salt water supplies. 9SW ZTTZ AN OPERATING UNIT OF THE DOW CHEMICAL COMPANY 53 BFG10684 Jerilyn Church -2- February 16, 1981 Basis for the example will be an established migration rate per 24 hour day of 55 ppb AN from ABS containing 65 ppm AN into water with a 10/1 volume to surface ratio (ml/sq. in.) at 120F. Assumptions used for benefit of the exaggerated example: Typical residence containing 50 ft. 4", 100 ft. 3", and 50 ft. 1 1/2" ABS-DWV. Total volume/surface ratio 13 ral/sq. in. 100 ppm residual AN present in the ABS pipe. Temp. 120F Time 24 hours The complete system (including vents) is filled with water for 24 hours at 120F. The system then is drained completely creating effluent containing 65-^ grams AN/liter. This exaggerated example would generate effluent which is significantly below the EPA Guidelines data for freshwater aquatic life protection of 130/: g/1 for 24 hour average and 300/ g/1 at any time. The same criteria for saltwater aquatic life is 130/g/1 as a 24 hour average and maximum concentration not to exceed 290./ g/1 at any time (Reference: Federal Register/Vol. 44, No. 191/Monday, Oct. 1, 1979/Notices. Remember, the example is based upon exaggerated average levels of residual AN, residence time, and temperature. Also, the assumption was made that the system was completely filled. I hope that this brief letter might be of some value in supporting the case of ABS-DWV piping. We certainly can provide more detailed arguments if needed. Best regards. J. E. Grybowski Plastics TS&D 433 Building (517)636-0840 sr 21129057 54 BFG10685