Document 2J6g07652Yx8wrLypwD0a3R25
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s t a t u s 'r e v i e w FLUOROCHEMICALS IN BLOOD
5/22/79, PGG
On May 30, 1978, 3M informed Du Pont of findings of organic fluorocarbons in blood of employees exposed* to long-chain perfluoro surface-active materials. Organic fluoride blood levels of 1 to 71 ppm werefound. Higher
lavola viprp associatgd-withT-bperations_where
airborne mi-sts--or-dusts-generated-were-i-n-r-angfiL-of 4JB-sSl-ppm. 3M reports that some trace level of organic fluorine in humans is apparently normal, i.e. less than 1 ppm.
Du Pont Program and Status
Item Status
Communication
1. Inform affected C.W. employees of 3M information.
Complete 6/27/78
Toxicity
1. Haskell 10-Day Subacute Feeding Tests for MPD-5004 (homolog mixture of ammonium perfluoroalkyl carboxylates); perfluoroalkyl methacrylates (ZFM, TLF-1837); "Teflon" CSF Carpet Protector (TLF-4113-D); Zonyl BA (Telomer B Alcohol, TLF-1847); Zonyl FSC (TLF-3635C); Zonyl FSN (TLF-4714C); Zonyl FSD (TLF-3176); Zonyl Tela (Telomer A, TLF 4187).
Complete
2. Analysis of rat blood Medical Program
Done for rats fed Zonyl FSN and Zony BA.
1. Review all current operations and industrial hygiene controls to .insure that the potentials for exposures are properly controlled.
Complete
'2. Identify all employees who currently Complete work or have worked jobs in which there is or was potential for exposure to fluorochemicals.
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3. Review the medical records of all Complete
such persons still employed by
Du Pont, looking for consistent or
unusual health occurrences or trends.
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Status
4. Obtain blood fluorochemical levels on persons who have never had potential for occupational exposure to fluorochemicals to establish background levels for a baseline.
Complete
5. Obtain blood fluorochemical levels on representative employees with various potentials for exposures to various fluorochemicals.
Complete for 55 19 employees.
6. Review the physical findings of the workers examined for consistent or unusual health occurrences or trends.
Complete
7. If the period of potential exposure To be decided has been of sufficient duration and there is a sufficient number of employees, an epidemiologic study of the mortality of the cohort identified may be considered. A determination can be made of the. likelihood of having a meaningful study after the number of previously exposed employees is determined.
Program Cost to Date
Total $149, 400
1. Toxicity Testing
MR-3089 17, 000 MR-3187 27, 400
Total $ 44, 400
2. Blood Analysis (Additional blood analysis, $500 each)
$105, 000
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CHAMBERS WORKS FLUOROCHEMICALS IN BLOOD STUDY
(1) Re s u l t s of s t u d y - l e v e l s o f f l u o r i n e in t h e b l o o d of Ch a m b e r s Wo r k s e m p l o y e e s , (In o r g a n i c a n d l o w v o l a t i l i t y ORGANIC FLUORINE)
(2) In d u s t r i a l Hy g i e n e Su r v e y Ma n u f a c t u r e of Te l o m e r B a l c o h o l Ma n u f a c t u r e of Ze p e l Fl u o r o m o n o m e r , Zo n y l FSN, RP, FSE, FSP, UR
R. D. Ri c h a r d s o n /amb 18 Ma y 1979
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ORGANIC FLUORINE IN BLOOD
Group (s a m p l e s i z e ) 3M Data
General population Q06)
Plant o f f i c e w o rk er Plant worker - general Plant wo r k e r - long
SERVICE IN f/c AREA NEWER PLANT OLDER PLANT
ppm Organic Fluo r i n e *
0;002 to 0.13 CO.02]**
0.01 to 0.06 0.13 to 1.13
0.9 to 9,1 5.9 to 71
Du Po nt Da t a W ilmi n g t o n c o n t r o l g r o u p (25)
Ch a m b e r s Work s gro u p (55)
(23 of 25) 0 - 0,38 *** [0.094]
(54 of 55) 0 - 0.37 **** C0.15]
Co n c l u s i o n s
Chambers Works empl oyees do n o t have elevated levels of organic FLUORINE IN THEIR BLOOD AS WAS REPORTED FOR 3m WORKERS,
The m e a n v a l u e for Ch a m b e r s Wo r k s e m p l o y e e s was s l i g h t l y h i g h e r THAN THE WILMINGTON CONTROL GROUP C0.15 VERSUS 0,`094J> BUT ALL VALUES ARE CONSIDERED TO BE "NORMAL" (<1 PPM) EXCEPT ONE VALUE in t h e W ilmi n g t o n c o n t r o l g r o u p (10.6 p p m ).
* BY DIFFERENCE BETWEEN TOTAL AND INORGANIC FLUORINE
** [Media n v a l u e s ]
!
EXCEPT 2 VALUES 10,6;
0.78 EXCEPT 1 VALUE 0 ,`89 PPM
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CHAMBERS WORKS FLUOROCHEMICALS COHORT
Chambers Works empl oyees w e r e identified w h o (1) HAVE HAD JOB ASSIGNMENTS WITH POTENTIAL FOR EXPOSURE (2) ARE STILL ACTIVE OR ARE READILY AVAILABLE ON SITE
Blood samples taken at regularly scheduled physical examination
t
Jo b Assignment R8D
De v e l o p m e n t Ma n u f a c t u r i n g Ma n u f a c t u r i n g
Lo c a t i o n
Numbe r Id e n t i f i e d
Ja c k s o n La b . Te c h n i c a l La b .
50
Sp e c . Ch e m . West
36
Sp e c . Ch e m , Ea s t
84
Ot h e r
29
Nu m b e r Ch e c k e d To Da t e " 18 6 26
\5
(%) (36) (17) (31) (17)
199 55 (28)
& In f o r m a l c h e c k w i t h s u p e r v i s i o n i n d i c a t e d t h a t gr o u p (55) s a m p l e d was r e p r e s e n t a t i v e o f c o h o r t (199).
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CONCLUSIONS - INDUSTRIAL HYGIENE SURVEY
A) Telomer B Al c o h o l and ZFM Ma n u f a c t u r e 1) En v i r o n m e n t a l m o n i t o r i n g d a t a s u g g e s t e d c o n d i t i o n s in t h e MANUFACTURING FACILITIES TO BE NORMALLY <5 MG/M^ TBA (8 HRs.), Ho w e v e r ., e x c u r s i o n s t o r a i s e t h i s l e v e l to 30 to 10 m g /m 3 TBA (8 h r s .) h a v e be e n o b s e r v e d on MULTIPLE OCCASIONS, 2) Ad d i t i o n a l e n v i r o n m e n t a l m o n i t o r i n g r e q u i r e d to i d e n t i f y EXPOSURE SOURCES AND DEFINE POTENTIAL EXPOSURE LEVELS. CIn Pr o g r e s s ) 3) MOST PROBABLE EXPOSURE SOURCES ARE DRUMMING AMD DCDRUMMItfG FACILITIES/ AND TO A LESSER EXTENT SAMPLING EQUIPMENT AND PROCEDURES. 4) Dr u m m i n g , b e b w m m t n g a n d s a m p l i n g f a c i l i t i e s a r e of a low STANDARD FOR CONTAINMENT BY ENGINEERING CONTROLS, CNOT ENCLOSED, NO LOCAL VENTILATION) 5) A CONTRIBUTING FACTOR IS THAT THE FACILITIES ARE ENCLOSED IN A BUILDING, PROMPT ELIMINATION OF PROCESS LEAKS AND ~ MAINTAINENCE OF VENTILATION IS ESSENTIAL,'
B) Te l o m e r B Al c o h o l Use Areas Limited, available, environmental data suggest the POTENTIAL FOR EXPOSURE TO TBA (AND ZONYL FSN) TO BE LOW.
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RECOMMENDATIONS
1) D i s c o n t i n u e p r o g r a m to d e t e r m i n e f l u o r i n e in b l o o d V .
2) Ad v i s e e m p l o y e e s t h a t b l o o d a n a l y s i s p r o g r a m h as b e e n d i s c o n t i n u e d DUE TO UNIFORMLY FAVORABLE RESULTS.
3) Up g r a d e f a c i l i t i e s ,, if r e q u i r e d ,' t o m e e t h a s k e l l l a b o r a t o r y EXPOSURE LIMIT GUIDELINES WHEN THESE ISSUE.
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18 Ma y 1979
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JUMMAIIY OK SUIIACUTE TliSTS WITH. F'MJOIIOCIIKMICALS
riwmmihl TI.F-2654
N*|M*r(1 2lb-hit
"Zonyl" Rr
"7.onylM IF, ntaMuilH1l1Ina "ZoMinlylll"olRP,lo.wmIwSuSmWlltlwug "amyl" RIA
244-21 5-71 246-71 15/-76
"amyl" FSN
"Zonyl" FSC "Zonyl" FSC r "amyl"TKIA /
718-76
720-78 771-76 744-/8
(K/kt/diy 22WI
2250 2200 2200
450
4470
200 1400 5000
Mirtill|ty 0/5
0/b 0/6 0/6 06//1100
0/10
0/10 0/10 0/10
lHlHClV.ltlMSall |4IMVM
mdr1ieelgvldeeinrvgeesrariaabwttlerieiovgeehhnltntlteiurvlleclrtg1cihrankgiedsneychange* r1evleirvseribwleeiglihltatiiloglr liver changes r4evleirvesribwleeighhitstologic liverchange 4revleivresribwleeighhitstologic liverchange*
lNiaerv.itlimaat 2MUaya pf1erIIsnnisssteeevvederriittyy
preertsuirsnteeddInnorm! preertsuirsnteeddtonnrml ppeerrssiisstteeddwithonly slight recovery
ttrl.'hielyvvmeetrurr,sas,citbt,lelisentnsephsliemseatnrorloowgicchsnges litt
gprueenrtdsuirsnlitenedtdtIwonirttnHhnsrpolmnelltyerselciogvhetryrernvery
r1emvlaeirrvresoriwbwleaeingdhhltKtthuylmousglcclmsopglceesn, bne
preertsuirsnteeddtonoran1
noroapo.md-relatndefferta
nocompound-relatedeffects
1liverweight
partial recovery
nn11eeccsIplnrrrpimooolvisdseecuiiercssMntwreoaIfinm1ogdnwhghteetamrhnomydpmcoueistlehwtlyiesmciuwgsihctteshlls1sIpnerspmleen
praertturInneidrteoconveorrym'l nenrlycouplersrecovery
|Mrsl*lcd
4"tAtl/.iklr.l Imgti/ikMgi)
1100 2250
421
11,792 IIHI0
>25,MNI >25.INN)
Fluoroannoaer1617 747-78 MINI
1/10 11elriyvlehrrw|e8ioglhettlefoci Inspleen
praerttuiranledretroovnenrryml
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"Tellnn"CSF
778-76 5000
0/10 reversiblehlatolnglr liverchangra
PeyMral1l1liu:oarroiadI,kya1mroanrllwuiaa- M-U
110500 1//I100 hnr1eoe0muv1.o-eI1prrv.oeseivireebtwtrlreiasecicltghbhilstseytstotelemos,gtiiccluilcvaherrsndgeknsimdgnleeuiysnd
"Zonyl"BA
89W 00dfV
1-7
M18I75N00I0
1840///111000 hhr1lieassvltteeiovorvlelesrnorisggbllwilreceiogrhlthgiietasvsnettsroilccouhglaiancrgeccshhaannggeess In
Hlntty-DiiyFeedingStudywith"Zonyl"RPInRatH, Report 1190-65
Dietarylevels! 10(1,500or2500|i|Malor15doyam>I|ualedto100, 1000nnd5000p|aafnr45uaya
lUiMorvarImm*t 1fcf.l re......
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...
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ppaerrtsiiasltedrecovery
ppaarrttiiaall rreeccoovveerryy praerttuiranledretcoovnenrryml
II,INN)
,
ORGANIC FLUOROCOMPOUNDS IN BLOOD
In May, 1978, 3M informed Du Pont of findings of organic fluorocompounds in blood of employees exposed to long-chain `perfluoro-surface active materials. 3M reported airborne contaminant levels up to 81 ppm in their operations and organic fluorine blood levels of 1 to 71 ppm for exposed workers. 3M reports that some level of organic fluorine in humans is normal, i.e. equal to or less than 1 ppm.
Chambers Works makes.functional equivalents to the 3M fluorosurfactants and plant employees were informed of the 3M findings in June 1978. Also a program was initiated to define exposure potential in the Chambers Works fluorocompound manufacturing and use operations, review the medical records of employees assigned to these operations, determine organic fluorine levels in the blood of such employees and to gather additional toxicity information on selected plant fluorocompounds. Program results are summarized below:
Airborne contaminant monitoring results show that the highest potential for employee fluorocompound exposure to :be in the manufacturing facilities.
0 o Eight hour time weighted average measurements ranged j / r ^ from 0.3 ppm (5 mg/m3) to 2 ppm (40 mg/m3). The
drumming, dedrumming and sampling operations are major contributors to exposures above 0.3 ppm. Engineering control programs to reduce contaminant emissions from these scmrces is underway. Blood samples were taken from a representative sample of exposed employees and analyzed for organic fluorine. The mean organic fluorine value for Chambers Works employees was slightly higher than the Wilmington control group (0.15 ppm versus 0.094 ppm) but all values for exposed employees were less than 1 ppm. This program has been discontinued. A review and comparison of the medical records of active fluorocompound exposed plant employees with a control group showed no adverse health effects. However, while the difference is not statistically significant, the number of employees with abnormal liver function tests was notably higher in the exposed group (6 compared to 1). Medical surveillance will be continued with study update December, 1979.
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10-day subacute feeding tests carried out by Haskell showed compound related non-reversible effects for three of the eight fluorocompounds tested. Non-reversible liver and testes effects were noted in rats fed 4,470 mg/kg/day Zonyl FSN and 850 mg/kg/day Zonyl BA. Decreased sperm production was found in rats fed 5,000 mg/kg/day Zonyl Tela. The need for further toxicity testing is being studied.
A meeting is being arranged through Haskell Laboratory to inform 3M of -the results of our program.
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*
E. I. du Pont de N emours & Company
INCOPtPOAATED
Wilmington. Delaware 19898
CHEMICALS. DYES AND PIGMENTS DEPARTMENT
B. C. McKusick B. W. Karrh, ERD S. Pell, ERD F. J. Marascia, CW
Dade, F&F M. Shepherd, PPs Serenbetz, Elas. J. Raines, PP&R
PERSONAL & CONFIDENTIAL
June 20, 1979
TO: MEETING ATTENDEES
FROM: P. G. GILBY
^FLUOROCHEMICALS IN BLOOD 5/22/79 MEETING SUMMARY
This letter is to summarize discussions and decisions reached in the subject meeting. It was agreed that:
Item Responsible for Coordination
The Chambers Works program to determine organic fluorine blood levels will be discontinued.
Chambers Works employees will be informed of the results and discontinuance of the blood analysis program.
R. Richardson
Followup will be done in the
Dr. J. C. Bonnett (additional bl(
Wilmington control group employee whose blood sample was
sample has now been submitted fo: analysis)
analyzed at 10.6 ppm organic
fluorine.
Medical records review study of R. Richardson to submit updated
Chambers Works exposed and
tabulation to P. G. Gilby for
control group will be updated transmission to Dr. S. Pell.
December 1979. Update will
be limited to tabulation of
abnormal liver function tests.
%
o
-L.
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Item Responsible for Coordination
Blood analysis will be done
R. M. Shepherd, PP&R
.. for employees having potential
\\ for exposure to 3M's FC-143 at
\\ Washington Works. PP&R will
1 submit samples week of 6/18/79
to G. H. Patterson, CD&P,
Jackson Laboratory for analysis.
Engineering control programs to reduce Telomer B Alcohol airborne contaminant levels during drumming, dedrumming and sampling will be defined and projects initiated.
R. Richardson
Acceptable airborne contaminant exposure limits recommendations will be re quested for Telomer B Alcohol (Zonyl BA), Telomer A (Zonyl Tela) and ZFM.
W. Darnell (Request to Haskell submitted 6/12/79)
The need, if any, for (1) further toxicity testing of selected fluorochemicals, (2) MSDS revisions and (3) customer notifications will be determined.
R. E. Read
A meeting will be set up with 3M to review Du Pont toxicity, blood and health information.
F. E. French will coordinate through B. McKusick, Haskell
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Discussion Summary
Haskell completed 10-day subacute feeding tests and issued reports for the eight fluorochemicals submitted by CD&P for testing. Of the materials tested, compound related nonreysrsible-liver-and-testes--effects-werfiLjioted--in rats fed 4,470 mg/kg/day Zonyl FSN and #^-850 mg/kg/day Telomer (Zonyl) BA. Decreased sperm production was found in-rats fed 5,000 mg/kg/day Zonyl~,Tela.
The medical records of 221 active Chambers Works employees known to have potential for fluorochemical occupational exposure were reviewed and compared to a control group. The control group (221 employees) was randomly selected from Chambers Works employees and matched as to sex, age and A.S.D. No adverse health effects were noted. However, while-the difference is not statistically significant (P 0.05), the number of employees with abnormal liver function tests was notably higher in the exposed group (6 compared to 1). Continued surveillance is warranted.
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Blood samples were taken from a representative sample (55) of the Chambers Works exposed group and analyzed for organic fluorine. Du Pont Wilmington employees (25) having no (potential for fluorochemical occupational exposure were used (as the control group to establish base line levels. The `mean value for Chambers Works employees was slightly higher than the control group (0.15 versus 0.094 ppm organic fluorine), but all values are considered to be normal (&1 ppm) except one 10.6 ppm value found in the Wilmington control
group. A second blood sample from this individual will be taken and analyzed. Additional blood analysis of Chambers Works employees is not warranted in view of the low values found. An industrial hygiene survey of selected Chambers Works
fluorochemical manufacturing and use facilities was carried out. Fluorochemical exposure potential was found to be low in the use facilities. Airborne contaminant levels in the manufacturing facilities were normally 5 mg/m3 (0.26 ppm), 8 hr. TWA. However, levels up to 40 mg/m3 (2.1 ppm), 8 hr. TWA were measured and additional monitoring is being done to better define exposure sources. Most probable exposure sources are drumming, dedrumming and sampling operations (facilities are not now enclosed and have no local exhaust ventilation.) Engineering control programs to reduce airborne contaminants from these operations are being developed and projects will be initiated to improve these facilities. 3M's FC-123 fluorosurfactant is used at Spruance (TF) and Washington Works (PP&R). PP&R will submit employee blood samples for analysis. Textile Fibers have not yet reached a decision on whether or not blood analysis is warranted for their operations. For additional information, see attached meeting charts.
PGG/bam Att.
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000J.55
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Meeting Attendees J. C. Breckenridge F. E. French H. E. Hiestand R. N. Knowles W. H. Darnell S. B. Cupp L. Percival, PP&R A. A. Wright, TF J. C. Bonnett, ER R. D. Richardson, CW R. E. Read, Jackson Lab G. H. Patterson, Jackson Lab G. L. Thayer, Jackson Lab H. J. Trochimowicz, Haskell P. W. Schneider, Haskell
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