Document 37zy4Oq6djL6R5oXM267D2MdE

S DEPARTMENT OF HEALTH. EDUCATION. AND W ELFARE PUBLIC H EA LTH SE R VIC E N A TIO N A L IN S TITU TE S OF HEALTH September 22, 1978 NATIONAL INSTITUTE OF ENVIRONMENTAL HEALTH SCIENCES ZT109P .O . B O X 12233 R E SE A R C H TRIAMGUC PA RK . N.C. Dr. John F. Brown Manager, Life Sciences Branch Physical Chemistry Laboratory Bldg. K-l, Rm. 3B35 GE Company Research and Development Center P.O. Box 8 Schenectady, NY 12301 RECEIVED SEP ? s 1973 Dear Dr. Brown: The used and unused transformer fluids you provided have been analyzed and the detailed analytical data is included in the attached reports from Drs. Albro and Hass of our laboratories and Mr. Jack Weaver of the NC State nuclear services laboratories. The following summarizing conments are offered: 1. The total mixtures were analyzed in several ways including gas chromatography, infrared (IR), ultraviolet (UV) and nuclear magnetic resonance (NMR) spectroscopy, and neutron activation analysis (NAA) for gross characterization. 2. The gross characterization revealed that the unused fluid was a simple mixture of Aroclor 1254 and trichlorobenzenes. The used fluid on the other hand was an extremely complex mixture of chlorobenzenes, PCB's and other aromatics as determined by gas chromatographic techniques. The PCS mixture did not resemble any Aroclor suggesting that significant alterations and rearrangements have occurred during its use. A develop mental radioimmunoassay method for PCB's provided a fingerprint which most closely resembled that of an Aroclor 1260 standard. This type of assay may ignore much of the rearranged PCB's present. 3. The neutron activation analysis revealed that both mixtures were 7 approximately 60% by weight chlorine. Trace amounts (ppm) of bromine * -pwere found with the level in used fluid being about twice that in unused fluid. Trace amounts of iron found were also somewhat higher in used fluid. Tin was obscured in this analysis by the large concentration of chlorine and bromine and could not be accurately quantitated. 4. A fractionation scheme was devised based on our previous experience with these types of compounds, especially the Yusho Oil mixture. For both used and unused fluids the total recovery of starting materials accounted for in the fractions was greater than 80%. The fractions were 783260 GENP 010450 J% & Dr. Brown Page 2 subjected to combined gas chromatography-mass spectraMGC-MS) analysis for more specific structural information (only about ]10% of fraction 43 was submitted for analysis since this fraction contained most of the total material). h5. .omoAl sogoeuxspeccth. elbdo,riamnoast. etdfraarcotmiaot,nisc ahryedircoocmarpbl oenxsmi(/xitnudirifec_sa_ tionfg isomeric chlorine and scrambling) as out. l. i neda .in t. .h. e. ata .tachI ed1- report1.. WThl e major dI i f. f. e_ r_ !e__n__c__e___s____w___e__r_ --e it. Lhe. presence of a much higher level of chlorinated biphenyl e-t-h-e-r-s and a large amount of hydroxy triphenyl stannane in the used fluid. In addition, several other compound classes are represented |here albeit at much lower levels including straight chain and polynuclear aromatic hydrocarbons, brominated hydrocarbons, phthalates, thiazolesj chlorinated terphenyls, and methyl substituted chlorinated terphenyls (or chlorobenzylbiphenyls). No chlorinated quaterphenyls (biphenyl dimers) v/ere detected in either sample. 6. The presence of the stannane in used fluids is prjobably derived from the tetraphenyl tin additive used as stablizer some time ago, and as you pointed out, would suggest that this is a very old fluid indeed. 7. The finding of some chlorinated dibenzofuran level in the unused fluid is not surprising. The presence of high [levels of chlorinated diphenyl ethers which obscure the chlorinated dibenzofurans in the used fluid is somewhat surprising, but there may be a logical explanation. 8. One can only speculate on this at the moment, but it is likely that the diphenyl ethers present in the used oil are [derived from hydrolysis and/or oxidation and coupling of the various chlorobenzenes present since their formation from biphenyls would require breakage of the strong biphenyl pivot bond. Undoubtedly, there are some chlorinated dlbenzofurans present, but reactions leading to theiij formation would have to compete with those depleting available [oxygen sources to form diphenylethers. There is also evidence from other studies suggesting some thermal instability of the chlorinated dibjenzofurans. Therefore, the net result may be an attenuation of dibenzofuran [formation. If these mechanisms are*operating, one would also [expect chlorinated phenols and possibly chlorinated biphenylols as intermediates. Failure to detect these compounds would suggest their occurrence only in steady state concentrations. 9. In comparing the used transformer fluid with the used heat exchange mixture (Yusho Oil) with which we have some experience, there are some key differences. Apparently chlorobenzenes werje not added to the PCB mixtureused in this heat exchanger as is apparently the practice also for their use in capacitors. This eliminates the competing oxygen depletion reaction leading to diphenyl ethers an[d, therefore, one would expect enhanced dibenzofuran formation or at least greater ease in their 783261 Dr. Brown Page 3 detection. Model experiments involving heating (although at high tempera-, tures) of PCB mixtures or purified isomers in the presence of oxygen support this enhancement possibility. 10. The apparent absence of quaterphenyls or biphenyl; dimers in the used transformer fluid (would expect them to havje eluted in fraction 2A) may point out yet another difference in the two mixtures. There is probably much more surface area in heat exchangers which could encourage more metal catalysis such as with copper if coppjer tubing is used. This could also serve, to scavenge for oxygen, thereby) attenuating dibenzofuran formation while facilitating non-oxygen metal catalyzed free radical reactions such as dimerization of biphenyls to form quaterphenyls. We have confirmed the presence of large amounts of quaterphenyls in Yusho 011. i 11. In considering the more complex PCB pattern found in the used fluid, this may reflect a thermodynamic tendancy towarjd more syipetrical and structured PCB isomers having lesser degrees of ortho substitution; although there are probably both kinetic and thermodynamic influences on these reactions. There is no evidence to support this, but the alterations a_r_e__m_o_s_t l_i_k_e_l_y__t_o__o_c_c_ur t_h_r_o_u_g_h__d_e_c_h_l_or_i_n_a_t_i_o_n_s involving the more sterically crowded ortho chlorines. The more symmetrical and non-ortho s-u-b-s-t-i-t-u-t-e-d---P-C-B-'-s t-e-n-d--t-o--b-e--m-o-r-e---a-c-u-t-e-l,,y -to-x-i-c-;,,! the 3.,4,5,3'.,4',5'-hexa and 3^ ,A4,-33'I ,i4ll'-tetra compounds _r_e_p_r__e_s_e__nJt. _i_n_g_I jt, _w_o___e_x__t_r__e_m.e1s in thi^s- _r_e_g__a_r_d1 The PCB pattern in Yusho oil was similarly complex wilih isomer and homolog content primarily in the tetra to octa range. * 12. Toxicologically then the used transformer fluid nd the used heat exchange fluid (Yusho Oil) would be expected to have some similarities but yet some differences. Similarities would be expected with respect to the presence in both of the toxic chlorinated diben|zofurans and possibly symmetrical/non-ortho substituted PCBs. Differences would be expected with the relatively non-toxic chlorinated diphenyl ethers and the unknown (but probably predictable) toxicity of biphenyl dimers and certain chlorinated benzenes. 13. In addition to the hazard of handling used ^transformer fluids associated with some existing levels of chlorinated dibenzofurans present, the greater concern may be associated with increased l'evels from transforma t1on after disposal since dibenzofurans can readily be formed from diphenylethers under photochemical conditions and their (diphenylethers) further thermo- or photooxygenation could ultimately ijead to the even more toxic chlorinated dioxins. Of course, the real degree of hazard would depend (among other things) on the balance of reactions both forming and degrading these compounds. GP 01045 783262 9 Or. Brown 1 Pa9e 4 14. I think there is now evidence at least in support of considerable alteration/rearrangement of these mixtures under actual use conditions. It seems safe to say also that the general tendency i|s toward more oxygenated chloroaromatic content in addition to a much more comp!ex^ mixture of the non-oxygenated chioroaromatics, | This is almost certain to be a more biologically active mixture, both qualitatively and quan titatively as based on the many studies with the commercial mixtures and members of the individual compound classes without regard to their synergi stic properti es. 15. General population exposure would be dependent on the fate and distribution of these compounds in the environment eijther from accidental leakage or deliberate attempts at their disposajl in the environment. Fate and distribution studies will be further complicated by the necessity to deal with even more complex and difficult to simulate modified mixtures of this type. As I indicated in our recent telephone conversailtion (9/19/78) concerning this data, there are probably representative trends and patterns identified here which deserve publication. After you have| had an opportunity to review and evaluate the data in some detail, I would like to consider this matter further. In the review and evaluation process, if you should have any questions, please do not hesitate to contact me directly. Sincerely, Attachments cc: Dr. Moore, AD, RRP, NIHES Dr. Albro Dr. Hass Dr. Cox dUHeaa am3 /de1,s DPCU.hemMicsKitnrnyeyS,ectPiho.mDnh., EBCB GENP 010452 783263 &> M lVLUKAiN U UJM, i to : Drs. McKinney and H^ss M Mft A * l4M 4* * A M i * | M M M W 4 4 t W j 44 4 U PNUATBILOINICAL HINESATiITLUTTHE SEU.VICE OF HEALTH 9 L l * , t I 4 \ d a t e : March 3, 1978 FROM Or- Albro subject: Preliminary Examination of Transformer Fluids 1: GC Chromatograms, IR spectra, NMR spectra (proton), and UV spectra of the fluids have been obtained. 2. "New" transformer fluid appears to be a simple mixture of Aroclor 1254 and trichlorobenzene (mixture of 1,2,4- and 1,2,3-). No tetrachlorobenzene was found except a trace. 3. Neither of the fluids contain mineral oil or] silicone oil. 4. "Old" transformer fluid is an extremely complex mixture of mono-, di-, tri- and tetrachlorobenzenes, polychlorinated biphenyls and other aromatics. The PCB mixture does not resemble any Aroclor, although a mixture of 1242, 1254 and 1260 might come close, Even then one could probably not exactly simulate this pattern, and it appears more likely that alterations and rearrangements have occurred. Phillip W. Albro, Ph.D. ____ GENP 010453 783264 MEMORANDUM DEPARTMENT OF HEALTH, EDUCATION, AND WEL7ARJ PUBLIC HEALTH SERVICE NATIONAL INSTTTVTTJ OF HEALTH TO Head, Chemistry Section Group Leader, Specialty Instrumentation DATE: 8/21/78 FROM Group Leader, Anal. Biochem. and Immunochem. :s u b j e c t Possibility of Chlorophenols in Transformer Fluid By spiking transformer fluid with known amounts of 2,4,5-trichlorophenol, it was determined that it would easily be possible to detect chlorophenol in the fluid down to 1% by weight, using the infrared peaks at 2.8-2.9 and 7.75 y. Nevertheless, no chlorophenols were detectable in either ''new*' or "used" transformer fluid. Phillip W. Albro, Ph.D. Research Chemist GEhfp 783265 O o MEMORANDUM DEPARTMENT OF HEALTH, EDUCATION, AND WELFA PUBLIC HEALTH SERVICE NATIONAL IN tT IT U T Z J O F MCALTM *ro Head, Chemistry Section d a t e : August 4, 1978 Through: Research Chemist N Research Chemist fro m : Chemist subject : Transformer Fluid Analysis Ten samples of transformer fluid which had been fractionated were receive: from Dr. P. W. Albro. The fractionation scheme and sample weights were: T. F uid Silicic Acid Hexane V Fr 1 Alumina 3% CH2C12 'I' 3SCH2C12 tB F.N 2A 48 4C 5B 5C * <0.1 mg 20%CH2C12 58 Sample Wts. (mg) Old T.F. 14.3 ' 151.7 3.1 0.4 New T.F 1.6 170.4 2.3 40..67 20% CH2C12 2U 2 GENP 010455 IS /YJii+j 5 t( /.p < c 783266 -2The samples were analyzed by GC-MS on OV 17 100/8/280, scanning from 100-600 amu 0 1000 resolution. For each fraction a 10 ug aliquot was analyzed, except Old 5B - 5% of this sample was analyzed. The major differences between the two samples were: 1. Old T.F. contained a much higher level of chlorinated biphenyl ethers. 2. Old T ^ . 'contained a large amount of hydroxy triphenyl stannane in F.N. 4C, as compared to New T.F. Limited mass searching for the molecular ion cluster of chlorinated dibenzo furans and dioxins revealed the presence of several hexachlorodibenzofurans 1n one fraciton, New T.F. - 4 8 . Hexachlorodibenzofuran standards were not available for quantitation. However, comparison with 2,3,7,8 and 2,3,4,7,8 tetra and pentachlorodibenzofuran standards allows a crude estimate of 10 ppn, assuming a linear response and unity slope for different isomers. The old T.F. samples contained large amounts of chlorinated diphenylethers. Loss of two chlorines from a given chlorodiphenylether generates an ion of identical mass as a chlorodibenzofuran. This obscures the presence of chlorinated dibenzofurans and raises their detection level to the level of the chlorodiphenylethers. In the old T.F. samples, this was approximately the 0.2% level. 783267 GENP 010456 F.N. 2A Complex Mixture of Cl -Biphenyls and Cl -Benzenes # Isomers Component Old New CyHjgCl Tri Cl-Benzene Tetra-Cl-Benzene Biphenyl Mono-Cl-BP Di-Cl-BP Tri-Cl-BP Tetra-Cl-BP Penta-Cl-BP Hexa-Cl-BP Hepta-Cl-BP Octa-Cl-BP Hexa-Cl-BP ether Hepta-Cl-BP ether Octa-Cl-BP ether C10Hn 3 r3 isomers 0) (2) (2) 0) (2) (2) (7) (5) (4) (5) 0) (2) (3) (3) (3) - 0) - (2) - (2) (2) (4) (7) (7) (5) (2) (.2) - (2) (1) (2) Cl6H34 hydrocarbon large component GENP 783268 O O F.N. 4C Old New Two major components: 1) C^gH34 Hydrocarbon 2) Hydroxy Triphenyl Stannene ciaHi60Sn One major component: Ci6^34 Hydrocarbon Several PCB's - primarily^ and 6 Cl `s Comoonent Mono-Cl Biphenyl Di-Cl Biphenyls Tri-Cl Biphenyls Tetra-Cl Biphenyls Penta-Cl Biphenyl Hexa-Cl Biphenyls Hepta-Cl Biphenyls Octa-Cl Biphenyl Hexa-Cl-Biphenyl ether Hepta-Cl-Biphenyl ether Octa-Cl-Biphenyl ethers Phthalates W r3 cioHn Br3 # Isomers Old New a) (2) (6) (5) (1) (3) (2) (i) (2) (3) ' (2) (3) - - - 0) (3) (5) (6) (2) (1) - - - - (2) (2) Old Alkyl Thiazole (mw=155) Cl4Hio Hydrocarbons ^16^10 Hydrocarbons New Alkyl Thiazole (mw-155) ^14^10 Hydrocarbon ^18^14 HydrocarbQn B N p 010458 783269 o Both old and new were a complex mixture of Cl-Benzenes and Cl-Biphenyls. Component Di-Cl-Benzene Tri-Cl-Benzenes Tetra-Cl-Benzene Penta-Cl-Benzene Hexa-Cl-Benzene Di-Cl-Methyl Benzene Tri-Cl-Methyl Benzene Mono-Cl-8iphenyl Di-Cl-Biphenyls Tri-Cl-Biphenyls Tetra-Cl-Bi phenyls Penta-Cl-Bi phenyls Hexa-Cl-Biphenyls Hepta-Cl-Bi phenyls Octa-Cl-Biphenyls Hexa-Cl-BP ether Hepta-Cl-BP ether Octa-Cl-BP ether Nona-Cl-BP ether # Isomers Old New (i) (3) (2 ) 0) 0) - (1) (3) (5) (5) (5) (4) (5) (3) (2 ) (2 ) 0) 0) (2 ) (3) (2 ) - 0) (1) (2 ) (6) (6) (5) 0) - 783270 Old Major Component: Phthalate F.N. 5B Component Tri-Cl-Benzene Tetra-Cl-Benzene Tri-Cl-BP Tetra-Cl-BP Penta-Cl-BP Hexa-Cl-BP Hepta-Cl-BP Octa-Cl-BP Mona-Cl-BP Hepta-Cl-BP ethers Octa-Cl-BP ether ci2 Hi6 Hydrocarbon (Several (6) components to base peaks 163) CU H10 New Major Components: 4,5,6--Cl-PCB's # Isomers Old New - (2) - (1) (3) (5) (4) (3) (5) (4) (5) (3) (3) (3) 0 ) (1) (2) (1) - 783271 F.N. 5C Both samples were primarily (>90%) one component, a ^16^34 M r o c a r b o n . Other identified components were: CAH7B r 7 cioHn Br3 4 - Phthalates 2 - polynuclear aromatic hydrocarbons 1 - gH-j2 polynuclear aromatic hydrocarbons Don Harvan H 783272 GENP 010461 DHSU^PHS/NIH/NIEHS/'RRP/EBCB/SIG TOSS JPECTRQMETRY f a c i l i t y TO:HEAD , CHEMISTRY SECTION . ESCB THRU RESEARCH CHEMIST ^ =4 ^ -- FROM: CHEMIST SUBJECT:TRANSFORMER FLUID ANALYSIS FRACTION.2A CF THE TRANSFORMER FLUIDS (SEE MEMO OF Q / 4 ^ 3 FOR FRACTIONATION SCHEME) UEEE ANALYZED BY DIRECT PROBE ANALYSIS FOR TERPHENYLS AND QUATERPHENYLS THE SAMPLE OF CLD TRANS. FL. CONTAINED OCTA. NONA. DECA. UNDECA AND OODECA CHLCRO-TERPHENYLS. THE SAMPLE OF NEU TRANS. FL. CONTAINED HEPTA. OCTA. AND NONA- TERPHENYL. THIS SAMPLE ALSO CONTAINED MATERIAL WHOSE ELEMENTAL CCPPOSITIQN. AS DETERMINED BY EXACT MASS MEASUREMENT. LAS C19 H9 CL7. THIS UOULD CORRESPOND TO A METHYL-HEPTA CHLORO-TERPHENYL . OR A HEPTA CHLORO-BENZYL BIPHENYL. AN OCTA-CHLORO ANALOG OF THIS MATERIAL JA3 ALSO OBSERVED. NO EVIDENCE LAS FOUND FOR THE PRESENCE OF CHLORINATED QUATERPHENYLS IN EITHER SAMPLE. A SAMPLE OF OLD TRANS. FL. LAS BASE-EXTRACTED (J. CORBETT FOR DETAILS) IN ORDER TO CONCENTRATE ANY PHENOL ICS PRESENT. THIS FRACTION LAS ANALYZED SY DR. C.E. PARKER BY GC-MS FOR THE PRESENCE OF CHLORO-PHENOLS. IONS OCRRESPONDING TO EITHER 0 IPHENYLOLS OR DIPHENYL ETHERS LERE PRESENT. AND BECAUSE THEY FAILED TO SILYLATE . THEY LERE ASSIGNED TO EE CHLORO- !PHENYL ETHERS. DONALD HARVAN 9/18/1973 783273 GENP 010462 NUCLEAR ENERGY SERVICES ACTIVATION ANALYSIS REPORT CLIENT Dr. John McKinney National Institute Environmental Health Sciences Box 12233 Research Triangle Park, North Carolina 27709 P. O. No. Report No. Date of Report Phone PR-49S6E3-8 155091 4/04/78 \ EXPERIMENTAL PARAMETERS 1 min. and 4 hr. irrad. - 1.5 x 1013n/cm2-sec. J Monitored decay 100 to 2000 sec. count on an Ortec 24% Ge(Li) detector coupled to a computerize N02200 MCA System ANALYSIS RESULTS TABLE 1 Attached 783274 LOCATED AT: Q J #Issued by: 'Li&L / ack N. Weaver HHeead, Nuclear Services Labrate In n * T U M T W A T I k J I U l O t I T V I O A I Il > Element Chlorine Bromine Zinc Tin Arsenic Cobalt Iron Mercury Selenium Vanadium A1umi num Antimony Chromium Manganese Ti tanium TABLE 1 NAA Scan of Trace Elements Transformer Fluid* (ugrams element/gram sample) * 0 ^ / 0 / <3O NIEHS 1 NIEHS 2 NIEHS 3 644,523 58.03 2.09 <5 <1 <1 <25 <1 <1 <10 <10 <1 0.12 <0.5 <5 573,383 57.82 1.63 <5 <1 <1 <25 <1 <1 <10 <10 <1 <0.05 <0.5 <5 623,205 100.31 1.68 <5 <1 <1 <25 <1 <1 <10 <10 <1 <0.05 <0.5 <5 /.ox- NIEHS 4 576,373 108.24 1.30 <5 <1 <1 <25 <1 <1 <10 <10 <1 <0.05 <0.5 <5 Comments: /I *' * 1. An organic sample containing very high concentrations of chlorine can not be analyzed for trace quanti ti es of such elements as V, Al, Mn, Ti because the half-life of the isotopes of these elements are short as is the Cl-38 isotope. The high Cl-38 activity masks the much smaller activ- iti es of V-52, Al-28, Mn-56, Ti-51. 2. In a similar fashion, our high sensitivity to bromine and its 35 hr. half-life for 8r-82 will mask such isotopes as As-76, Hg-197, Se-75, Sb-124, Co-60, etc 3. In approximately 10 more days the Br-82 activity will be decreased sufficiently to provide real values for Se, Sb, Co, and ___ _ l------ * GENP fjiztis-/ pil{S - 1 <o . ~ o^ | O>-- * 4^ ON NUCLEAR ENERGY SERVICES ACTIVATION ANALYSIS REPORT CLIENT Dr. James D. McKinney National Institute Environmental Health Sciences Box 12233 Research Triangle Park, North Carolina 27709 P. O. No. Report No. Date of Report Phone PR-4S96:3- 155091-1. 7/28/78 EXPERIMENTAL PARAMETERS 4 hr. irradiation - 1.5 x 1013n/cm2-sec. Monitored decay 8000 sec. ct. on an Ortec 24% Ge(Li) detector coupled to a computerized NO 6:00 MCA ANALYSIS RESULTS Element Selenium Irpn Cobalt TABLE 1 Transformer Fluids (ugrams element/gram sample) NIEHS 1 <0.001 <2.0 .014 NIEHS 2 0.019 <2.0 0.024 NIEHS 3 0.015 20.4 <0.002 NIEHS 4 0.030 <4.5 .007 0-x0j GroO CT> LOCATED AT: \ Issued by: ack . Weaver Head, Nuclear Services Laboratory-