Document groZm0VR0LGjVzydn1rxBYBL
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DEPARTM ENT O F H EA LTH . ED UCATIO N . AND W ELFAR E
r'U JLiC H*''LTH SERVICE
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NATIONAL INal i TUTES O" mEALTH
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December 4, 1978
NATIONAL INSTITUTE OF ENVIRONMENTAL HEALTH SCIENCES
] P .O . B O X 1ZZ13 H C S E A R C H T n iA N C L E P A R K . N .C . STYOS
Dr. John F. Brown Manager, Life Sciences Branch Physical Chemistry Laboratory Bldg. Kl, Rm. 3B35 GE Company Research and Development Center P.O. Box 8 Schenectady, NY 12301
Dear Dr. Brown:
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I have just a few qualifying final comments ,.with regard to your sum marization of our data and views. -/ j
1) Perhaps some quantitative comparison of the chlorinated benzenes
present in such a used mixture with that in an unus|ed mixture (both
prepared by random chlorination of benzene in same way) should be made
before chlorine distribution in this class of compounds is assumed not
to occur. I think the possibility still remains that chlorinated
diphenyl ethers could- be formed by oxidative coupling of the highly
chlorinated benzenes (see below).
I
2) I can not accept the possibility that the chi orilnated jdiphenyl ethers were original contaminants of the chlorinated benzenes used since the levels are sufficiently high to have been easily mistaken for PCBs in gas chromatographic analysis. In addition, there a're substantial amounts of hepta and octachloro diphenyl ethers suggesting nvolvement of penta and above homologs of chlorinated benzenes.
3) While it would appear that the PCBs themselves are not substantially altered in use, this can only be said with any confidence with respect to PCBs found in Aroclor 1260. In addition, one can not]say that this is or is not the case with the other chlorinated components of the mixture.
4) The inability to detect the dibenzofurans in the used fluid is some-
what surprising in view of the data thatt is now appearing in the literature
on their formation from PCBs under "modl" conditions. However, this
suggest to me again that there are other significant oxygen depleting
reactions which are attenuating dibenzofuran formation (such as diphenyl-
ether formation).
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II 783219
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GENP 010408
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5) Finally, the diphenyl ethers are still a potential problem from a disposal viewpoint regardless of how they get therje. As pointed out in^ my previous letter of September 22, they can be converted both photolytically and thermally to dibenzofurans under certain conditions.
6) The raw data that I have enclosed is not all that we have, but it is representative and supportive of the conclusions drawn.
We trust that these comments and information meet[with your approval and thank you for our involvement in an interesting analytical chemistry problem.
Sincerely,
cc: Dr. Moore Dr. Albro
Dr. Hass
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James
D.
.,
McKinney,
PhV.JD.
Head, Chemistry Section
'783220
m?.?s i -- c t t c m i t t y f a c i l i t y
T O : HERD, CHEMISTRY S E C TIO N , E 5C3
THRU: F.ESSSRCH CHEM IST, SECS FROM: CHEMIST
SUB JECT: PCDF'S IN TR A N S FO R M FLU ID
IN RESPONSE TO P O IN T THREE CF MR. BROWN'S LETTER OF OCTOBER 17. 1373
EASE FIN D ENCLOSED SEVER*' P IE C E S OF D A TS, THERE ARE TTJO RECcjiSTRUCTED CKRGMATOGRAr
GUING L IM IT E D MASS SEARCHES FOR IONS FROM HEXACLDSF AT M/Z 372! 374. AND 37S
' OM FRACTION 42 ne CLT AND NEU TRANSFORMER F L U ID S . ALSO INCLUDED IS A MASS SEARCH
j'R M/Z 444. T -IE M+2 ISOTOPE OF OCTP CLDPE AND M^Z 410. THE M+2 OF HEPjTfi C LD PE.
iS OLD TRANSFORMER FL U ID HAS PEAKS FCR M^Z 374 AND 376. BUT NOT| A T 372. T H IS IS
'1D IC A T IV E OF CLD FE, NOT FURANS TriE NEU TRANSFORMER F L U ID HAS PEAKS FOR ALL
r:S ISOTOPE FSSKS OF THE K2XRCL5S F . WHICH IN D IC A T E S THE PRESENCE OF T H IS
IMPOUND. ONE SHOULD ALSO NC7E IN T riE OLD TRANSFORMER F L U ID THE LARGE PEAK
DR n/Z 444. U r H CORRESPONDING IONS A T rt/Z 372.374 AND 376. T H IS IS PPOSAELY THE
ES U LT CF LOSS OF TUO CHLORINES FROM AN O C T fi-C L D F E WHICH G IV E
I'SE TO IONS ID E N TIC A L TO THOSE OF HSXSCLD BF. T H IS D O E S N 'T MEAN T riA T ONE
ANNOT ANALYZE FCR THE HEXACLDSF. ONLY TH A T YOU MUST EE AUARE OF T H IS PC3S IS L E
RG2LEM . .PT-T MONITOR THE S IF H EN V L ETHER IONS AS WELL AS THOSE OF TriE FURfiNS.
HUS* FCR THE NEU TRANSFORMER FLUID. NO IONS AT M/Z 410 OR 444 WERE CcSERVED.
THEREFORE. THE PEAKS AT M/'Z 372. 374 AND 376 CAN BE ATTRIBUTED TO HEXA CLDBF.
IND NOT TC HSPTft CR COTA CLDPE.
ALSO INCLUDED ARE TLC MASS SPECTRA FROM THESE GC -MS RUNS.
THE DISPLAYS ARE DUAL FLCTS; THE UPPER SPECTRUM IS "ENHANCED". I . E . . THE
3ACKCROUW HAS SEEN SUCTEACTED. THE LOWER <INVERTED) SPECTRUM IS UNENHANCED 0 THAT ONE CAN SEE HOW INTERFERENCES CAN BE ELIMINATED BY TriE |W:PNCEM3NT 'RCCESS. SOFV #22; Z~ NS'.1 TRANSFORMER FLUID CLEARLY HRS IONS AT M^Z 372.
00t-toon00I
C74.37S. A**T 3~? - "HE `T-ICUL'.T ID!* ISOTOPE CLUSTER O F H E X R CL DC*. JCNO PFE
-.LSO OBSEiT.ET AT 337, 332 AND 34! AMD AT 2E-0-S2", ARISING FROM LOSS OF "NS AMD
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. TM f e c t :v z l w . sc a ;: 0312 o f t -:s c l ? t r a n s f o r m e r f l u i d a l s o h a s
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\z pr.r'is'f f c m Less c? c n e c h l o r i n e f r o m t h e h e p t a c l d p e p r e s e n t o e s o j r e
;j i;-:" F " TM " :cN o? t h s m a s s s p e c t r u m , t h u s , in t h e p r e s e n c e of l a r g e
t.-.NTITIES vc CLDFE'S, IT !S DIFFICULT TO ANALYZE FOR CLrEF'S.
7HSP.E IS NO DOUST THAT KEU TRANSFORMER R.UIS FRACTION 2A
INTO IKED CLDFE'S. THIS IS ESTABLISHED BY EXAMINATION OF THE MASS SFEO'R A
THE COMPONENTS. HOWEVER. THE LEVELS ARE FROM 5-50 TIMES LOWER THAN N THE
D TRANSFORMER FLUID. UM
1 . THE LEVEL OF KEXA CLD5F IN KEU TRANSFORMER FLUID FRACTION 42 U*S
jSTIMA7ED AT IE PPM. THIS VALUE REFERRED TO ITSCONCENTRATION IN THAT
1iACTION. SINCE THIS LAS THE ONLY FRACTION IN WHICH DIEENZOFURANS
]
IRE-OCSSERTED, UE MUST ASSUME THAT THEY WERE CONCENTRATED IN THIS FRACTION
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!I REGARDLESS C*F WHERE THEY SHOULD HAVE THEORETICALLY SEEN).
i J.U3, 10 FT* IN FRACTION 45 uDULD MEAN:
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(IS FPil) ClrS M3)
1.7 PPM IN THE ORIGINAL SAMPLE
! < .1003 MS) r
] HIS VALUE'IS IN REASONABLE CORRESPONDENCE UITH OTHER INVESTIGATORS ' ANALYSES
i ~ ARQCLORS FOR DI5SN2GFUEAN CONTENT.
I A.
I ALSO INCLUDED ARE THE RECONSTRUCTED CHROMATOGRAMS FOR EACH FRACTION. THESE
l EM0NS7RATE THE MUCH HIGHER LEVELS OF CLDPE'S IN OLD TRANSFORME[R FLUID! FRACTION
1 :A AND
RELATIVE TT HSU TRANSFORMER FLUID FRACTION 2A.
- <X\TVv-w DONALD HARVAN
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