Document GKM50XDGzmBEzqzrj70N2Lbx4
iu fl ru rk c A. M. Mokhtar
P e rio d : March, 1981 - September, 1981 (P a rt Time) Reference: SA-195 P revious Reports: SpAR 79-3
T e x tile fib e rs Department Spruance
Process Control Development E. I . DuPont de Nemours & Co,, Inc,
Richmond, V ir g in ia
March, 1982
The in d iv id u a l to whom th is m e te ria i is issued is resp o nsib le f o r the s e c u rity o f the in fo rm a tio n . For those on the d is t r ib u t io n l i s t a t o th e r lo c a tio n s , r e s p o n s ib ilit y o f the document w i l l a u to m a tic a lly tra n s fe r to t h e ir successors. I f th e re is no f u r t h e r use fo r the docu ment, re tu rn to the above address. Do not leave exposed and unattended.
Company Sanitized. Does not contain TSCA CBI
INTRODUCTION
In 1978, the 31 Company n o tif ie d DuPont th a t th e FC-143 s u rfa c ta n t (am monium p e rflu o ro o c tan o ate ) sold to DuPont f o r use i n p o l y m e r i z a tio n may b e ^ e ra tp a e n ic . T h erefo re, i t was necessary t<7"monitor i t s le v e l in t h M H R | P r o c e s s and work environm ent. Work done in a pre vio us re p o rt tR e f. I ) , showed th a t i t was not present e it h e r in the work environm ent o r in s in te re d y a rn a t an eauipment lim ite d low er d e te c ta b le l i m i t o f 50 ppb. However, because o f a proposed TLV in a i r o f 0 .5 ppb,
jias^been necessary to m onitor the FC-143 le v e l through the complete [process w ith respect to th is low er le v e l.
OBJECTIVES
To measure the e x te n t, i f any, o f personnel exposure to FC-143.
To develop accurate methods f o r FC-143 in a i r , w a te r, y a rn and blood a t TLV le v e ls .
To deta rm ine _tfrei re a c tio n s and f in a l d is p o s itio n o f FC-143
in the1
process.
To determine the c o n d itio n f o r and by-products o f thermal tre a tm e n t to remove FC-143 from d is p e rs io n and y a m .
SUMMARY AND CONCLUSI' 3
The handling o f coated yarns o r d ir e c t co ntact w ith t h e M I H S d is pen sio n are the o n ly p o te n tia l areas th a t personnel can b e*exp o sed to s ig n if ic a n t le v e ls o f FC-143. The p erfluo ro o ctan o fc a d d o f FC-143 was not detected in the spinning a i r environment. The le v e l o f p e r ilu r o acid in the spinning wash w ater was 1-4 ppm, but no l i m i t has been defined end aoueous s o lu tio n s have not been considered a p o te n tia l means o f person
nel exposure. The p e rflu o ro acid was detected in yarn s coated w ith d is p e rs io n as in the case of yarns used f o r packing end uses. L e ve ls ranged from 200-700 ppm. With uncoated yarn s th a t come d ir e c t ly o f f the spinning machine, the le v e ls o f p e rflu o ro acid were nondetectable. Thus, the p o te n tia l fo r exposure o f personnel is v e ry lim ite d , and his was confirmed by the low le v e ls o f p e rflu o ro acid in blood. L e ve ls did not exceed 0.09 ppm, which were w e ll below th e 0 .4 ppm l i m i t ,
FC-143 is not found in the spinning area environm ent because o f two
r !S?nS' ~ ppr0* l a t e l y 10* *s washed o f f the y a rn on the wash re e l o r
module. The
decarboxylates, as the yarn goes over the heated
r o ii s , g iv in g o f f C02 and the 7 carbon p e rflu o ro monobydride. This has
? m " r C ni l r," ed J 1^ a n a ly s is o f FC-143 o f f gas as f t is heated up to 200 C, The monohydride forms ra th e r than the 7 carbon p e rflu o ro o le f in
saryUhydr5en her 3Urfact3nt present* Triton X100, provides the neces-
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3ecause o f the decarb o xylatio n a t 175-20QC, thermal trea tm en t is an e ffe c tiv e way to remove the FC-143. However, because o f d e le te rio u s e .fe c ts on y a rn p ro p e rtie s , thermal treatm ent is not co nsid o ^ d to be a route to it s removal. A m odined GC method wa- developed fo r h ig h e r s e n s it iv it y by usinq an
cr capture * * * * * and a new column packing. With these changes
p re c is io n o f ^ H ) ^ measured t0 0,3 ppb and in b,ood to u -02 Ppm w ith a
PATENT ACTION No patent ac tio n based on th is work is planned a t present.
PUBLICATION There are c u r r e n tly no plans to pub lish any o f th is work.
CODE LISTING FC*143 - Ammoni urn p e rflu o ro octanoate.
Prepared by: S'. S. ^Shelburne
Apprv ed by:
i\
' o s n -- ----------ocess Cbjptrol Development Supervi sor
M. A. Forte
-
.'i / / j/ / ' /
A. M. Mokhtar
Company Sanitized. Does not contain TSCA CBI
TABLE OF rONTENTS
I. Introduction
I I . Environmental Analysis; A. In - A ir B. Process Wash Water C. Yarn D. Blood E. D is p o sitio n in Process
I I I . Method Development A. In-A ir B. Yarn C. Blood
IV . Thermal Treatment V. References
V I. Appendi x V II. Abstract V ili. D istrib utio n
Paae 1
I 1 2 2 2
3 4 4 4 5 6 7 L a s t Page
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1. INTRODUCTION
V ^ H ^ ^ d i s p e r s i o n is shipped to Spruanc from the DuPont, Park-
irs b u rg , West V ir g in ia PPD P lrn t as a 60$ s c lid s /w a te r d is p e rs io n
th a t contains 5%T rito n k-100 and 1600 ppm FC-143 as s u rfa c ta n ts .
3M, the FC-143 vendor, n o tif ie d DuPont in May, 1978 th a t i t was a
p o s sib le teratogen. Therefo re, i t became necessary to measure the FC-143 le v e ls in the process and work environment to d e te r mine the le v e l o f personnel exposure, i f any. I n i t i a l work (R ef.
i ) was equipment lim ite d in s e n s it iv it y to a lo w er d etectio n
' .m it o f 50 ppb. W ith a proposed TLV o f 0.5 ppb, i t became acessary to redetermine it s le v e ls w ith increased s e n s it iv it y
and to determine i t s f in a l d is p o s itio n - whether i t is washed
o u t, decomposes or remains in the y a rn . Also , since thermal tre a tm e n t was a possible route to FC-143 removal from the d is persio n, the condition and byproducts o f thermal trea tm en t must be determined.
I I . ENVIRONMENTAL ANALYSIS A . In-A i r
A i r samples were taken a t e ig h t lo c a tio n s around Teflon
spinning machines 2 and 3 (F ig u re I ) , and a t fo u r lo c a tio n s
. . round the F inishin g Area induction d ryer. (Table I, Attach-
m :nt I ) Only one sample from in s id e tlK in d u c tio n d ry e r
'.tack i n le t had a d e ^ c ta b le
le v e l (3 ppb).
Since th is was
inside the duct, the" was no
personnel hazard
in vo lve d .The
lo w er d etection l i m i t f or in - " ir samples based on standards
i r 0.3 ppb. The lack of d etectio n precludes any personnel
exposure hazard since the exposure problem reported by 3M is
due to a i r borne contam ination.
B. Water
The FC-143 in r a B M H H d is p e rs io n is changed to the sodium s a lt afte : th e 'r in a l pn adjustment step a t Parkersburg. This
is converted to the acid form in the regeneration bath, but `.i s t i l l has some w a te r. sol u b il i t y . The wash water from the re e l machine (SM 3) and wash module (SM 2) has been analyzed.
Levels found are 1.3 ppm fo r SM-2 and 4.0 ppm f o r SM-3. The
d iffe re n c e s r e f le c t o iffe re n c e s in wash e f fic ie n c y due to d if f e r e n t equipment design. FC-143 in regenerated yarn from
SM-3 (60 ppm) and SM-2 (490 ppm) support the d iffe re n c e s in le v e l. Combined sewer samples were 2 ppn fo r SM-3 and 1 ppm f o r SM-3. FC-143 concentration in wat, a t these le v e ls does
not present an exposure hazard. (Table 1)
Company Sanitized. Does not contain TSCA CBI
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C. Yarn
S ln ie r e d y a r n h a d jw n - d e te c t a b le le v e ls o f FC-143. a n d B p B ^ m m B p r o d u c t s , where the yarn is d ip p e d in thed is p e rs io n and d rie d , had le v e ls ranging from 200-700 ppm. T h is v a r i a b i l i t y is due to the uneven appy c a t io n and to the probable adsorption of the F C - i4 3 B B | M its e l f. Soxhlet e x tra c tio n w ith methanol d id not s T g n T frc S n tly improve re covery (Ref. 2).
D. Blood
The TLV f o r FC-143 in blood is 0.4 ppm. No blood samples
from exposed personnel exceeded 0.02 ppm. Most had non d e te c ta b le le v e ls . Method lower d e te c tio n lim i t s was * 0.02 ppm.
E. D is p o s itio n in the Process
1
A n a ly s is has shown th a t *10% o f th e FC-143 is washed o f f the ya rn in spinning (Ref. 11. However, none is found on s in te re d y a rn . Previous work (R e f. 3) has shown th a t yarn
heated a t 175eC has no e; -actable FC-143 rem aining a f t e r 30 m inutes. A t 200C, th e re s none a f t e r 10 m inutes. T h is is because FC-143 can be removed th e rm a lly by d e c a rb o xyla tio n ,
i . e . , decomposition to C02 and the .p e rf1uoro^ptam onohydrida (R e f.. 4, 5 ). To c o n f in i^ J iis , '6 fe e t y a rn was p u lle d i n t o B 0 I ^ R t i ! b i n g which wa~s used as a GC
colum n. The GC o vtn was te m p e ra tu re programmed from
12S-250C. The tube was purged w ith n itro g e n and the off-gas analyzed by 1R in a 10 cm. c e l l. The N ic o le t, MX-1 I IR was
s e t to run r e p e t it iv e 1-minute scans. T h e ^ p M B t u b i n g I t s e l f was s ta b le a t these tem peratures.
Two absorbance peaks appeared "5 m inutes a f t e r the 150C oven tem perature was passed. The ho*lap tim e in the tub ing from the GC to the IR c e ll and it s o' un- was ~ 5 -minutes a t 20 m l/m inute N2 flow . A tw in geak at 2340 cm"1 (CO/,! and a s m a lle r C-F` peak a t " 1250 cm wers seen. These iaks in crease in size u n til a fte r ~ 5 minutes a t 250C, they begin to decrease. No carbonyl peaks a t 1700-1750 cm'r appear
which would have in d ic a te d evaporation o f the FC-143 (F ig u re
Although these scans show th a t d ec a rb o xyla tio n - not evapora tio n - occurs, they d id not show whether the p e rflu o ro by
product was the o le f in (p e rfluo ro h ep tene) o r the hyd rid e ( p e rflu o ro monohydride). Some concern was voiced over the p o te n tia l hazard from the o le f in . To determ ine the id e n t it y
o f the byproduct, an excess amount o f th e FC-143 sodium s a lt was mixed w ith T r ito n X-100 and poured in to t h e f lp B I Q I G C tube. The tem perature was programmed from 150-225C. me
scans show a peak a t 3010 cm"1, which is in d ic a t iv e o f the h yd rid e . There is no evidence o f the o le f in which would have absorbed a t 1790 cm (F ig u re 3 ).
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m
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In order to determine the completeness o f the decarLoxyla-
tio n , Draegsr tubes were used. The gas evolved from the
heating o f the FC-i43 sodium s a lt / T r it o n X-100 m ixtu re was
passed through the tube. This tu b ' gave a s p e c ific c o lo ri-
met. ic charge fo r COp. I t showed PO+% o f the th e o re tic a l CCL
e v o lu tio n .
2
I I I . METHOD DEVELOPMENT
The method u :.d in th is re p o rt f o r determ ining FC-143 le v e ls is s im ila r to th a t used in Reference I . The samples are extra c te d w ith methanol o r freeze d rie d , e s te r if ie d to get the v o la t ile e s te r w ith BF,, the re a c tio n quenched w ith w ater, the e s te r e xtra c te d in to "hexane and the hexane in je c te d in a GC. A new GC col linn packing (0V-202) was used to get b e tte r s e n s it iv it y .
FC-143 is not a pu-e compound and co n sists o f a t le a s t 5 id e n t i
fie d isomers (Ref. 6 ). The 0V-202 column consolidates these d if f e r e n t compounds in to one peak. A new Hewlett/Fackard 5380 GC
w ith a N Ig i e le c tro n capture d etecto r was used to increase the method s e n s it iv it y to the low ppb range. A ty p ic a l chromatogram is shown in F ig u re 4.
The fo llo w in g GC conditions were adopted fo r use
C a r r ie r Gas
Argon/Methane 5% (? 20 m l/M inute
In je c tio n Temperature
180 5C
Column Temperature
100C
Detector Temperature
300 C
Sample Size
2 pi
E xte rna l standards were used in each run and t h e ir peak ar|a in the c a lc u la tio n o f the sample c o n c e n tra tio n . P recisio n was 10?
fo r any sample (Table 2).
A. A ir Analysis
A ir samples were taken fo r one hour a t a ra te of 3 l i t e r s per hour in 10 ml o f w ater in an im pinger. One ml of water was freeze d rie d and 1 ml BFo/methanol added fo r e s te r if ic a tio n . A f te r heating insealed b o ttle s fo r 15 m inutes, the s o lu tio n is quenched w ith water and 1 ml hexane added. The e s te r is e xtracted in to the hexane and in je c te d in the GC. Twc micro l i t e r samples were used. Method was s e n s itiv e to 0.3 ppb le v e l, which is below the 0.5 ppb proposed TLV.
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9. Yarn
S in te re d ya rn a n d | f l ^ H O p arns wei*e analyzed id e n t ic a lly , r i v e ml o f methanUT was "5dded to one gram o f y a rn . A f te r
10-15 m inutes, one ml was removed, and one ml SF,/methanol e s te rfy in g reagent added. This was heated f o r la m inutes, w a te r quenched, e x t ra c te d w iih hexane and the hexane in je c te d
in to th e GC. T h e f lp H B ^ K y a r n s had co nsid e ra b le va ria n c e between samples, m is was due to th e r ypeven a p p lic a tio n o r to adsorption o f the f-'C on t h e p H B i t s e l f . S o xh le t
e x tra c tio n w ith methanol did not reduce t h is v a r i a b ilit y . (Ref. 2).
C. Blood
Blood was analyzes id e n t ic a lly to the w ater from the im pinger a i r samples. S. S ta ffo rd , o f PPD, prepared a s e rie s o f spiked blood samples as an in t e r la b check. These were analyzed w ith a precision o f - 10?. (Table 2} A se t o f spiked blood samples prepared a t PCD were run w ith good p re c is io n .
IV . THERMAL TREATMENT
Thermal tre a tm e n t can e f f e c t iv e ly remove the rC-143, b j t i t is
not the prime candidate because o f d e le te rio u s e t t e c t s o ^ y a rn
p ro p e rtie s . Previous work (Ref. 5) has shown t h a t H H B f t a r n s
heated a t 175 C fo r 30 minutes o r a t 2Q0C f o r 7 b minutes no
lo n g e r have any e x tra c ta b le FC-143. IR scans o f o f f gas from
yarn heated from 150 to 250eC confirm th e presence o f a f lu o ro
carbon gas by the auso rp tio n peak a t 1250 cm"*. The presence o f
the C02 peak a t 2350 cm'1 confirms CO e v o lu tio n , i . e . , the FC is
d e c a rb o x y la tin g . There is no carboxyl peak a t 1700-1750 cm
which would show evap o ratio n . F u rth e r study o f the gases evolved
from I50-200SC from T r it o n X-100/FC-143 sodium s a lt m ix tu re in a
5 : l, : a t 1 o . show the presence o f aC-H absorbznce peak 3 t 3C10
cm'L (F ig u re 3} T h is shows th a t the flu o ro carb o n y a rn evolved in
d e c a rb o xyla tio n is the p e rflu tn a n o s o h yd rid e . There is no e v i
dence o f an o le f in (C 55 C, 1790 cm"'1} which is a p o s sib le decom
p o s itio n p roduct. The T rito n sup p lies th e necessary hydrogen to
form the hydride (Ref.
5). .Analysis o f the completeness o f
the d e c a rb o xyla tio n was made by passing known amounts o f off-gas
through a Oraeger tube. The tube, s p e c ific fo r C0?f uses a c o lo r
change to v o lu m e tric a lly measure the CO evo lved . The amount was
90 - 10 o f the th e o r e tic a ., showing th a t no o th e r m ajor re a c tio n
occurs during thermal treatm ent.
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REFERENCES
1. F o rte , M. A. - SpAR 79-3.
2. F o rte . M. A., Mokhtar, A. M. - PCD M onthly, A p r il, 1981.
3. F o rte , M. A ., Mokhtar, A. M. - PCD Monthly, May, 1981. 4. LaZe-'te, J. D; JACS: 75, 4525 (1953).
5. Meschke, R. G. - PCRD-58-131.
6. S ta ffo rd , S. S. - PPD A n a ly tic a l Method, "D e te rm in a tio n o f C0
F lu o rr^ u rfa c ta n t in Water".
3
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APPENDIX
Table 1
FC-143 Samples
Table 2 Figure 1 Figure 2
GC P re c is io n ^ ^ m ^ S p i n n i n g in A ir Sampling lo c a tio n
IS Scans of I AT O ff Gas
Figure 3 Figure 4 Attachment I
FC-143 IR Scan GC Chromatogram L e t t e r , S. S. S ta ffo rd to M. A. F o rte , 12/17/81
Attachment I I GC Method FC-143 A n alysis
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i
TABLE I I . PINNING IN-AIR SAMPLES
LOCATION 1. SM-2 - R o ll 6 2. SM-2 - R o ll 23 3. SM-2 - R o ll 6 4. 3-1-2 - R o ll 23 5. O p e ra to r' s Desk 6. Between SM-2 and 3, R o ll 12 7. SM-2 - Between Bath and Wash Module 8. SM-3 - Between 3ath and Wash Module 9. SM-3 - R o ll 6 10. SM-3 - r o l l 23
LEVEL Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppbl Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detec tab l e (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb)
Samples taken a t estim ated p o s itio n o f o p e ra to r's head d u ring work.
PINNING FC-143 WATER/YARN LEVEL
Wash Water Sewer Regenerated Yarn Sintered Yarn
Wash Water Sewer Regenerated Yarn Sintered Yarn
1.2 ppm 1 ppm 49 ppm ND
4,0 ppm 2.0 ppm 60 ppm ND
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TABLE I I GC PRECISION
SAMPLE 5 ppm FC-143 1.0 ppm FC-143 0 .5 ppm 0.25 ppm
GC COUNTS /THOUSANDS 232.5, 241.0, 234.1 63.2, 62.3, 65.2, 61.6, 59.0 33.4, 34.3, 38.8, 39.5 17.5, 15.5, 19.1, 18.4
SAMPLE 1. 2
3 4 5 6 7
8 9
10
BLOOD SAMPLES ILC w ith PPO/S. S ta ffo rd
SPIKED LEVEL (ppm F) .50
1.5 81 ank
.027 0.17 1.0 31 anfc .054 .34 .054
MEASURED LEVEL (oom F) .56
1.9 .01
0.026 0.145 1.2
.009 .047 .314 .059
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? S a 7u
FIGURE 1
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(J0S.2S)
Iti/W G tS
3*wpk M\X m v C f l
Company Sanitized. Does not contain TSCA CB!
:IGURE 2
IfARN HEATED Iii GC u3LUMM IR 3F EVOLVED GAS id CM CELL - KRS-5 UINOOwS
j
8
3
a a
a
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3 3 N tfliiW S N fc i'd i %
ao
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Company Sanitized. Does not contain TSCA CBI
B
CONCORD. CA LIFO RN IA CHART NO. Z F -1 0 T
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FIGURE 4
GC RU?,' 3F FC-143 STAiiDARO 0 . 20b PPM
.2
-- p C W 3 fc /Z K
Gas XaTTS err T QBtO D e "TBGTBft S jtm pfe. "$/*&
-
fiO*c I9i> i300*0
aw
V*
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Company Sanitized. Does not contain TSCA CBF
45 WCV12*7
ATTACHMENT I
(iutusxtoiao* E uu Pcn t oe N em ours & C ompany
NCOAPORaTCO W i l m i n g t o n , D e l a w a r e 19398
POLYMER PRODUCTS DEPARTMENT E X P E R IM E N T A L STATION
ANALYTICAL REPORT
cc : A. J,. Dahl J J ,. Pana
w. c .. ? ~ r c i v a i K., u
a i P1D0
*c
----^ - 3- 2 _ ^2 ~
December 1 7 , l$ S l
SPEUA1JCE, TEXTILE FIBERS PJCHMCITD, VA.
DETEPiMIUATTON OF PEEFLUOEOOCTAHOATE IN AQUEOUS AIE -iPIDGEP SAJdPLZS (Jo b No. 6l l - o 0 1 ; PEAL .-io s. -1 - 2832- 2 6 3 5 ; Notebook No. S 26lb2 ;
As re p o rte d by phene 7 / 2/ 3 1 , the fo u r aqueous ai: 6 / 8l were an alyzed f o r p e rflu o rc o c ta n o a te (Cg; u s in g th e g; EB-TA9. r e s u lt s and sample id e n t if ic a t io n are as fo llo w s :
SasTJls PEAL .0
Id en tifica tio n
C-C A n a ly s is Date Analyzed
81-1532 31-2833 31- 2 =381-2835
H1 , S tack a t O u tlet
r 2 , Stack at In le t
,t 3 , O u tlet o f D ryer .?a, in le t to T e flo n
Induction Dryer
6/ 29- 7/ 2/31 tt
tt
M
pinger samples subm itted :rom atographic method
ug F C -lu g /:
V/SO''' n.i. n.d,
F C - lA ' (2M ammonium p e rflu o ro o c ta n o a te ) was used as c a lib r a t io n and Cg c o n c e n t ra t io n c a lc u la t e d as the s a l t . The low er U n i t fc was G .JC7 u g /a L .
(b ) Chromatograms f o r sample HI d if f e r e d s l i g h t l y in appearance from *3 , HU, and
the b la n k s; a lo n g e r a ir sem olina time n ig h t have aiven a d e tecta b le "evp~
o f Cft.
`"
'
.
L -'
;.ey novas:
?e r f i u c ro cc ta n ca t e
FC-ia3
A ir A nalysis
qq
There's 3 worfd ol things we're doing something bout
.
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m ATTACHMENT I I
METHOD TM-0405-32T
DATE 3/16/82 PAGE 1 OF 10
DU PONT FIBERS PRODUCTS FC-142 ANALYSIS
*
S. S. Shelburne Spruance F ib ers P la n t
I . duPont de Nemours & Co., Inc.
T e x tile Fibers Department Richmond, V ir g in ia 23261
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METHOD TM-Q405-32T
DATE 3 /1 6 /8 2 PAGE 2 OF iO
1. SCOPE
1.1 T h is method is used to describe sample p re p a ra tio n and GC a n a ly s is fo r FC-143 in a i r , w ater, blood and on y a rn .
2. PRINCIPLE OF METHOD
2.1 Samples from in a i r , water o r blood are f i r s t concentrated by fre e re d ry in g . Yarn samples are soaked in methanol to e x tra c t the FC-143. Then the FC-143 is e s t e r if ie d by heating w ith BFj/methanol to form the v o la t ile methyl e ster.
+ bf3 CF3 (CF2)C00' Me CH30 H -- CF3 (CF2 )6 COOCH.,
The re a c tio n is ouenched w ith w ater and the e s te r extra cted in to
hexane. The hexane s o lu tio n is snot in to a GC w ith an e le c tro n
capture d etec to r. The FC-142 co ncentratio n is determined based on
peak area comparison to standards.
.
3. SIGNIFICANCE AND USE
3.1 T h is method is used to determine F C - lA ^li and in blood. The ap p lic a b le ranges a r? f
arn, in a i r , in water
Yarn - 50 - 1000 ppm
A ir - 0.3 ppb - 1 ppm Water - 0.02 ppm - 25 ppm Blood - 0.02 ppm - 25 ppm
4. INTERFERENCES
4.1 Water must be removed from the samples to prevent re a c tio n w ith the e s te rfy in g agent.
5. APPARATUS
5.1 Gas Chromatograph - H ew lett Packard 5880 w ith N i63 e le c tro n capture d e te c to r and 5880 te rm inal H ew lett Packard Company.
5.2 Argon/Methane C a rrie r Gas 95/57 - 3 u rd e tt.
5.3 S yrin g e - Hamilton - 701 N - 10 pi - Supelco Co.
5.4 T elem atic A ir Sampler - T a y lo r P arker Co., N o rfo lk , V ir g in ia , Cat. No.
158.
.
5.5 B a tte r ie s , nickel-cadmium, 8.4 v o lts - T a y lo r P arker Co., Cat. No. 347a.
5.6 V i e i l s - 5 n l, glass - F is h e r Cat. *03-3288.
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METHOD TM -0405-82T
DATE 3 /1 6 /8 2 PAGE 3 OF 10
5.7 Erlenm eyer Flask - 250 ml Glass Stopperea - F is h e r Cat. No. 1C-C47C.
5.8 GC Column 10 g la ss , packed w ith 0V-202 on 100/120 Supelco p e rt Supelco Co.
5.9 Heater - F is c h e r #11-495-50 o r e q u iv a le n t.
5.10
Sand Bath w ith copper tubes - Spruance Process C ontrol Development.
5.11
P ip e ts 1 ml - F is h e r Cat. #!3-650B; 5 ml - F is h e r Cat. #13-650F.
5.12 5.13 5.14
Manometer - F is h e r Cat. #11-292 o r e q u iv a le n t. L y o p iliz e r - F is h e r Cat. #10-269-41 o r e q u iv a le n t. Freeze Or- Flasks (4 ), 350 ml - F is h e r Cat. #10-269-53.
5.15
Vacuum Pump - Two Stage Model D-25 - F is h e r C at. No. 01-183-31 o r e q u iv a le n t.
5.16
Pi pet A s p ira to r Bulb - F is h e r Cat. #14-0708.
5.17 5.18
Im pinger Tube - LG-6890-100 - S c ie n t if ic Glass Co., lin e rs - Supelco.
Vineland, N.J. '
5.19
Dewar F la s k , 1 q u a rt s iz e - F is h e r Cat. #10-195B.
5.20
Vacuum system tra p - LC-11025-102 - S c ie n t if ic Glass c o ., V in e la n d , N.J.
6. REAGENTS AND MATERIALS
6.1 BF./Methanol - P e s tic id e grade in g lass ampoules - Supelco C at. No.
3-3041.
'~
6.2 Methanol - F is h e r Cat. #A-936.
"
6.3 Hexane - F is h e r Cat. #tH-301.
6.4 D ry Ice - Richmond Dry Ice Company.
6.5 Acetone - F is h e r Cat. #A-17-5. PRECAUTIONS
7.1 8F3/Methanol - Hear le a th e r gloves when i n i t i a l l y breaking the glass ampoule. Wear rubber gloves when pouring o r p ip e tin g .
7.2 Wear rubber gloves when handling methanol o>' hexane. Keep away from
f 1ame.
7.3 Wear le a th e r glove' when handling v ia ls o r heater and sand bath.
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METHOD TM-0 405-82T
DATE 3 /1 6 /8 2
PAGE A c-F 10
7.4 Wear le a th e r g' ovrs when handling dry ic e .
7.5 Blood. Rubber gloves must be worn when handlina blood. When fin is h e d w ith bicod, heat w ith concentrated bleach in a hot oven a t ~ 90C fo r one hour, then flu s h down d ra in w ith w ater. Use bleach in "10:1 r a t io over blood. Rinse a ll p ip e ts , beaker and o th e r eouioment w ith bleach.
8. SAMPLING
.1 In - A ir
8.1.1 8.2
Place 10 ml D! w ater in an im pinger tube. Set tube in Telem atic and set tu rn e r fo r one hour. Flow should be set a t 3 1ite rs / m in o te . Set Telem atic in area to be sampled.
Yarn
8.2.1 8.3
No special sampling re a u ire d . Blood
.
8.3.1
Obtain the necessary blood samples from M edical. Store in r e f r ig e r a t o r u n t il ready fo r use. See 7.5 fo r d isp o sa l.
9. CALIBRATION AND STANDARDIZATION
9-1 FC-143 Standards
9.1.1 9.1.2
Weigh 0.1000 g of FC-143 in to a 100 ml vo lum etric fla s k . Make to volume w ith methanol. This is the 1000 ppm standard.
Take 1 ml o f 9.1.1 and d ilu te to 50 ml w ith methanol. This is the 50 ppm standard.
9.1.3
Take 5 ml o f 9.1 .2 and d ilu te to 10 w ith methanol. T h is - is the 25-ppm standard.
9.1.4 9.1.5
Take 1 ml o f 9.1.1 and d ilu te to 1000 ml w ith methanol. This is the 10 ppm standard. Take 5 ml of 9.1 .4 and d ilu te to 10 ml w ith methanol. T h is is the 5 ppm standard.
9.1.6
Take 1 ml o f 9 .1 .4 and d ilu te to 10 ml w ith meethanol. This is the 1 ppm standard.
9.1.7
Take 1 ml of 9.1 .5 and d ilu te to 10 ml w ith methanol. This is the 0.5 ppm standard.
9.1.8
Take 1 ml of 9,1 .6 and d ilu te to 10 ml w ith methanol. This is the 0.1 ppm standard.
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METHOD TM-0405-82T DATE 3/16/82 PAGE 5 OF !0
PROCEDURE (References Attachment I , GC C o n d itio ns and Attachment I I , L y o p b iliz e r Operation)
10.1
Yarn - S in te re d and M
10.1.1
F o r s in te re d y a rn , w e ig b O ^ g to O.COOl and put in to a glass v ia l.
Add 1 ml methanol. ForWkyarn, weigh 0.05 g y a rn to 0.0001 g, add
to a glass v ia l and ad d T ml methanol.
10. 1.2 Add 1 ml BFj/M ethanol. Heat in sand bath f o r 15-20 minutes a t sand
tem perature o f 65-70C.
10.1.3
Remove from bath and a llo w to co o l. Then add 1 ml DI and 1 m!
hexane. Then shake f o r 30 seconds.
i
10.1.4 A llo w la y e rs to separate and sheet sample on GC (See Attachm ent 15. FC-143 peak RT is "2 .9 m inutes.
10.1.5 Shoot standards (9 .1 ) th a t b racket the expected sample le v e l. --S in te re d - 0 .5 , 1.0, 5.0 ppm
0 - 10, 25, 50 ppm
1 0 .1 .o See 11.1 fo r c a lc u la tio n .
10.2
In - A ir Samples
10.2.1
10.2.2
P ip e t one ml o f the water from the im pinger tube in to a c le a n , g lass v i a l . C a re fu lly place i t in a Freeze Dry F la s k, put on th e rub b er top and hook i t to the L y o p h iliz e r (Attachm ent I I ) . Leave on the L yo p h i^ ize , u n t il a l l the water is gone ('2-3 h r s . ) .
Remove the v ia l from the fla s k and add one ml o f 3F,/Methanol bv p ip p t. Put a Teflon*5 gasket in the v ia l top, s c re w ^ it t i g h t and pi ace in the sand bath fo r 15-20 minutes a t 55-70*C.
10.2.3 Remove from the bath and a llo w to co o l. Then add i ml DI H-0 and l ml
Hexane. Then shake fo r 30 seconds.
10.2.4 Allow the la y e rs to separate and shoot the hexane la y e r on th e GC. (See Attachment I ) .
10.2.5 Shoot the standards th a t b racket the sample (0 .1 , 0 .5 , 1.0 ppm).
10. 2.6 See 11.2 fo r c a lc u la tio n .
10.3
Water
10.3.1 P ip e t 1 ml Of w ater in to a clean , g la s s v i a l. Then fo llo w 10.2.1 -
1 0 Z a5*
..
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METHOD TM -0405-32T DATE 3 /1 6 /8 2 PAGE 6 OF 10
10.4
Blood (See 7.5 f o r handling)
10.4.1 P ip e t 1 ml o f blood in to a cle .i, g lass v ia l, freeze dry and run as in 10.2.1 - 10.2.5.
11. CALCULATION
11.1
Yarn
A FC-143 ppm = F x C
11.2
A = Sample GC peak area B = Standard GC peak area C = Standard concentration, ppm D = Weight o f sample A i r , W ater, Blood
FC-143 ppm x c
;
A = Sample GC peak area B = Standard GC peak area
C = Standard concentration, ppm 12. PRECISION AND ACCURACY
12.1
P re c is io n is - 10%.
13. REFERENCE
13.1
PPD A n a ly tic a l Method - D ete rm ina tio n of Cfl F Iu o ro s u rfa c ta n t in Watur
GC, S. S. S ta ffo rd .
0
14. KEY WORD INDEX
14.1 14.2
FC-143 - in ya rn , w a te r, a i r and blood. GC a n a ly s is .
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METHOD TM-0405-82T DATE 3/16/82
PAGE 7 OF 10
C a r r ie r Gas In je c tio n Temperature Oven Temperature Detector Temperature Sample Size Cel umn Packi ng
ATTACHMENT I HP 5880 GC CONDITIONS
Argon/Methane
95/5
20 m l/m inute
180 C
100C 300 C
2 yl
6' Glass 1/8" OD
OV-202 on 100/120 Supelcoport
GC Term inal C o n d itio ns - Run tim e - 0.1 minutes Tan Skim. A tte n u a tio n 2 (a d ju s t as necessary fo r peak s iz e )
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METHOD TM -0405-82T
DATE 3 /1 6 /8 2 PAGE 8 OF 10
FREEZE DRYING SAMPLES
Equipment Setup
1. Put " 500 ml o f acetone in the ly o p h iliz e r tank.
2. C a re fu lly add enough dry ice to keep i t as a s o lid . Replace l i d .
3. Add " 50 ml acetone to vacuum tra p Dewar. Set the vacuum tra p in the Dewar and add dry ice to pack around i t .
4. Hook up heavy w a ll ru her tubing from the ly o p h iliz e r to the tra p to the vacuum pump. Tee in the manometer between the tra p and pump.
Sample Setup
1. Take the samples in the g lass v ia ls and dip them in the ly o p h iliz e r dry ice/acetone m ix tu re . Keep them immersed long enough f o r complete fre e z in g .
2. Place the frozen v ia ls in one o f the freeze d ry f la s k s . Put a f i t l e r in the top
o f the rubber top, place on the fla s k and connect to the ly o p h iliz e r w ith the...
metal neck.
'"
3. Open the connection to vacuum. Only those po rts being used can be open to vacuum. A ll o th e rs must be on vent.
4. Cut on the pump, open the manometer conenctions. Vacuum must be " 0.1 mm.
5. A f te r fre e z in g , shut o f f manometer, c a r e f u lly open sample ly o p iliz e r p o rt and cut o ff port.
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Pft.tJhK 1 - APPARATUS FOB FliKKy.lr.-l;]tYIH(i SAMPLES
y
_ | 1i
B rv ig i" Cluu-iiWr Manometei;
and
1*V' acuu--m----U-----
To pump ^
Dry Tee/ Acetone
Cold Trap (Mack-up) ib) y> e w * Port, Pry In,. Flask, and Sample
Valve (vacuum or -vent)
I>7 Ice/Acetone Cold Well, with 0-ring vacuum seul to lid
1* Vacuum Ports (12) for Prying Flasks
Prying Chamber
Stopper
Vacuum (Prying Chamber)
Vacuum Port Adapter (Vacuum port to flask)
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S-Iirem Vials, tissue over top
Prying Flask - Hubber top fils over glass bottom for a vacuum seal
Prosen Sample (1 mb aliquot)
TEST METHOD APPROVAL
FC-143 A n a lysis II -0405-82T
METHOD TN -0405-82T
DATE 3 /1 6 /8 2 PAGE 10 OF 10
S. S. Shelburne Author
S ite
A u th o rized By
For (Organization)
Spru'nce Si te
Date
Soruance Spruance Spruance ATM0Q1.7
S u p e rv iso r
/ /,;V . .
:/ 'H id
theirri s t
'
Supervisor
Process Control 3 '"O//<? 2_ Development
~
Process Control Development
:/_/./, t-
Process Control Lab
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7 ABSTRACT The FC-143 (aimtonium p e rflu o ro octanoate) s u rfa c ta n t used in p o ly m e riz a tio n process was a suspected te ra to g e n . Methods wei*e deve loped. and i t s le v e l measured in a i r , w a te r, blood and y a rn . In a i r , w ater and blood le v e ls were w e ll below T LV's. None was p resent on s in tered y a rn , b u t 1ST y a rn , which is coated w ith d is p e rs io n , has 200-700 gpm le v e ls . I t was shown th a t FC-143 d ic a rb o x y la te s when heated to 200C g iv in g ,, f f C02 and perfluoroseptam onohydride. IN0EXING SUBJECTS 1. Measurement o f p e rflu o ro o ctan o ic acid (FC-143) in a i r , w a te r, y a rn . 2. Ammonium perfluo ro o ctano ate d ic a rb o x y la tio n o f. 3. Sodiim p ert!uo ro o ctano ate d ic a rb o x y la tio n o f .
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COPY NO. 1
2
3
4
3 6 7 S3
9 & 10 11 i 12
13
DISTRIBUTION
G. B. F a ig le , J r . - R. D. Demarest R. C. Harper, J r . , - PCD F ile
R. F. J a n is , J r . - M. T. Waroblak PCD F ile
G. L. W atts - J. H. Fischer J. L. McDaniel
E. S. B rin t'" ' - E. K. Koffenberger PCD F ile
D. G. O 'D e ll
J. P. Yuk - PCD F ile
Research ib ra ry
Central Report Index
Patent Liaison F ile
S. S. Shelburne, M. A. F o rte , A. M. Mokhtar - PCD F ile
DSS001.27
LOCATION
Spruance
Sprnance
Spruance
Nemours-Wi 1mi ng to n Nemours-Wilmington Spruance Spruance Centre Road Centre Road
Spruance
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