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Report No. SpAR 82-1
Copy No. 9
Distribution - Last Page
FC--1143 IM THMfiVROCESS
S. S. Shelburne, Editor M. A. Forte
A. M. Mokhtar
Period: March, 1981 - September, 1981 (Part Time) Reference: SA-195 Proteus Seports; SpAR 79-3
Textile Fibers Department
Spruance Process Control Development
E. I. DuPont de Nemours i Co** Inc. Richmond, Virginia
March, 1982
The individual to whom this material is issued is responsible for the
security of the information. For thys on the distribution list at
other locations, responsibility of thg document win autanaticaTly
transfer to their successors. If there is ne further use for the docu
ment, return to the above address. Do not leave exposed and unattended.
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INTRODUCTION
In 1978, the 31 Company notified DuPont that the FC-L|3surfactant (am monium perfluorooctanoate) sold to OuPont for use in(pM(Hpolymeriza-
t-ion may be^eratoaenic. Therefore, it was necessary to monitor its
level in they------((Processand work environment. Work done in a pre
vious report (Ref. D, showed that it was not present either in the work
environment or in sintered yarn at an eouipment limited lower detectable
limit of 50 ppb. However, because of a proposed TLV in air of 0.5 ppb,
been necessary to monitor the FC-143 level through the complete [process with respect to this lower level.
OBJECTIVES
if To measure the extent, FC-143.
any, of personnel exposure to
To develop accurate methods for FC-143 in air, water, yarn and blood at TLV levels.
To determine _the reactions and final disposition of FC-143 in thep--------'process.
To determine the condition for and by-products of thermal treatment to remove FC-143 from dispersion and yam.
SUMMARYAND CONCLUSr 5
^
*9f
The handling of coated ya'-ns or direct contact with theHp----|disper-
slon are the only potential areas that personnel can be exposed to sig
nificant levels of FC-143. The perfluorooctanoic acid of FC-143 was not
detected in the spinning air environment. The level of perfluro acid in
the spinning wash water was 1-4 ppm, but no limit has been defined end
aaueous solutions have not been considered a potential means of person
nel exposure. The perfluoro acid was detected In yarns coated with
dispersion as in the case of yarns used for packing end uses. Levels ranged from 200-700 ppm. With uncoated yarns that ccme directly off the spinning machine, the levels of perfluoro acid were nondetectable.
Thus. the potential for exposure of personnel is very limited, and *his was confirmed by the low levels of perfluoro acid in blood. Levels did
not exceed 0.09 epm, which were well below the 0.4 ppm limit.
FC-143 is not found in the spinning area environment because of two reasons. Approximately 10% is washed off the yarn on the wash reel or module. The remainder decarboxylates, as the yarn goes over the heated rolls, giving off COy and the 7 carbon perfluoro monohydr'ide. This has
been confirmed by Iranalysis of FC-143 off gas as ft is heated up to
200S'C, The nionohydrids forms rather than the 7 carbon perfluoro olefin because the other surfactant present, Triton XIOO, provides the neces
sary hydrogen.
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Because of the decarboxylat-i'on at 175-200C, thermal tre-itment is an effective way to remove the FC-143. However, because of deleterious effects on yarn properties, thermal treatment is not consid"'"pd to be a route to its removal.
A modified GC method wa"' developed for higher sensitivity by using an electron capture detector ^nd a new column packing. Kith these changes, FC-143 in air can be measured to 0.3 ppb and in blood to U.02 ppm with a precision of - 10%.
PATENT ACTION
No patent action based on this work is planned at present.
PUBLICATION
There are currently no plans to publish any of this work.
CODE LISTING
FC-143 - Ainnom'um perfluoro octanoate.
^^^^----- Prepared by:
yiy.
{
S.
'"'Scheulb'ulrln,e..---''
w ^'a. M. A. Forte
Appr. ed by:
''^-S^ -^-^-^
v.';v.W\--------------
Process Control Development
Supervisor
A. M. Mokhtar
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TABLE OF fQNTEMTS
I. Introduction
II. Environmental Aneilysi's
A. In-Air
B. Process Wash Water
C. Yarn 0. Blood
E- Disposition in Process
III. t'ethod Development
A. In-Air
B. Yarn
C. Blood
IV. rhermat Treatment
V. References
VI.
VII. VIII.
Appendix Abstract
Distribution
1. INTRODUCTION
^tf^Hdispersion is shipped to Spruance from the DuPont, Park-
if ^rsbu^. West Virginia PPD Pifnt as a 60% solids/water dispersion
that contains 5% Triton X-lOO and 1600 ppm FC-143 as surfactants.
3M, the FC-143 vendor, notified DuPont in May, 1978 that it was a possible teratogen. Therefore, it became necessary to iTiessure
the FC-143 levels in the process and work "nvironment to deter
mine the level of personnel exposure,
any. Initial work (Rer.
i) was equipment limited in sensitivity to a lower detection
' ,mit of 50 ppb. With a proposed TLV of 0.5 ppb, it became
scessary to redetermine its levels with increased sensitivity
and to determine its final disposition - whether it is washed
out, decomposes or remains in the yarn. Also, since thermal
treatment was a possible route to FC-143 removal from the dis
persion, the condition and byproducts of thermal treatment must
be determined.
II. ENVIRONMENTAL ANALYSIS
A. In-Air
Air samples were taken at eight locations around Teflon
spinning machines 2 and 3 (Figure I), and at four locations
. ci"ound the Finishing Area induction dryer. (Table I, AttachTi-:nt I) Only one sample from inside th-^ induction dryer '.tgck inlet had a de^ctable level (3 ppb). Since this was
;nside the duct, ther- was no personnel hazard involved. The
lower detecT-ion limit ^or in""ir samples based on standards
' 0.3 ppb. The lack of detection precludes any personnel exposure hazard since the exposure problem reported by 3M is
due to air borne contc.nnnation.
B. Water
G--4 The FC-143 inM------dispersion is changed to the sodium
salt afte; thee-TTi'nnaal pffa, djustment step at Parkersburg. This is converted to the acid form in the regeneration bath, but
-.1 still has some water.solubility. The wash water from the
reel machine (SM 3) and wash module (SM 2) has been analyzed. Levels found are 1.3 ppm for SM-2 and 4.0 ppm for SM-3. The differences reflect oifferences in wash efficiency due to
different equipment design. FC-143 in regenerated yarn froni SM-3 (60 ppm} and SM-2 (490 pp-i) support the differences in level. Combined sewer samples were 2 ppn for SM-3 and 1 ppm for SM-;i. FC-143 concentration in wat'i at these levels does
not present an exposure hazard. (Table 1)
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C. Yarn
S1njred yarn had^pn-detectable levels of FC-143.
andH----UBUBproducts, where the yarn is dipped" In the"
dIspersTonanddrTed, had levels ranging from 200-700 ppm.
This variability is due to the uneven appUfation and to the
probable adsorption of the FC-l43Wg1tse1 F. Soxhiet
extraction with methanol did not sTgmfrcantly improve re covery (Ret. 2).
D. Blood
The TLV for FC-143 in blood is 0.4 ppm. No blood samples from exposed personnel exceeded 0.02 ppm. Most had nondetectable levels. Method lower detection limits was * 0.02
ppm.
E. Disposition In the Process
Analysis has shown that "10% of the FC-143 is washed off 'he yarn in spinning (Set. 1). However, none is found on sin tered yarn. Previous work (Set. 5) has shown that yarn heated at 175'C has no e; "actable FC-143 remaining after 30 minutes. At 200T, Inert s none after 10 minutes. This is
because FC-143 can be removed thermally by decarboxylation,
BI^BB i.e.,
(Ret..
decomposi:tion
4, 5). To
fto) COOyg and the perfl uoorroosjffttppttaammoononhoyhdvrd-ierjd^ coonnffirTmrmtthMis., '6 feet of^U--I^--------------BMl R
yarn was putted intoMQf^l^Hntttr'bing which was used as a GC
column. The GC ovenwas temperature programmed from
125-250"C. The tube was purged with nitrogen and the off-gas
analyzed by IR in a 10 cm. cell. The Nicolef.MX-l gIR was
set to run repetitive 1-nnnute scans. The
tubing
itself was stable at these temperatures.
--
Two absorb^nce peaks appeared "5 minutes after the 1WC oven
temperature was passed. The ho^-jp time in the tubing from
the GC to the IR cell and its o.-'-^.- -^as " 5 ,-ainutss at 20 ml/minute N3 How. A twin paak <? ?340 cm' (CO,) and a smaller C-F peak at " 1250 on wer-s seen. These peaks in crease in size until after " 5 minutes at 250"C, they begin to decrease. No carbonyt peaks at 1700-1750 on' appear which would have indicated evaporation of the FC-143 (Figure
2).
Although these scans show that decarboxylation - not evapora tion - occurs, they did not show whether the perfl uoro by
product was the oTefin (perfluoroheptene) or the hydride (psrftuoro monohydride). Some concern was voiced over the
potential hazard from the olefin. To determine the identity of the byproduct, an excess amount of the FC-143 sodium ia1t
was mixed with Triton X-100 and poured into t^------^|GC
tube. The temperature was programmed from ISO-Zzi'C.^'he scans show a peak at 3010 cm' , which is Indicative of the hydride. There is no evidence of tf.e olefin which would have absorbed at 1790 cm" (Figure 3).
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In order to determine the completeness of the decarLoxylation, Oraegsr tubes were used. The gas evolved from the heating of the FC-143 sodium salt/Triton X-IOO mixture was
passed through the tube. This tub' gave a specific colon-
met, ic charge for CO^. It showed P0+% of the theoretical CO.,
evolution.
II!. METHOD DEVELOPMENT
The method u-;d in this report for determining FC-143 levels is
similar to that used in Refer-ence I. The samples are extracted. with methanol or freeze dried, esterified to get the volatile
ester with BFq, the reaction quenched with water, the ester extracted intonexane and the hexane injected in a GC. A new GC colisnn packing (OV-202) was used to get better sensitivity. FC-143 is not a pu-e compound and consists of at least 5 identi fied isomer*; (Ref. 6). The OV-202 column consolidates these different compounds into one peak. A new Hewlett/Packard f880 GC with a NIgi electron capture detector was used to increase the method sensitivity to the low ppb range. A typical chromatogram is shown in Figure 4.
The following GC conditions were adopted for use:
Carrier Gas Injection Temperature
Argon/Methane 5% 180'C
@ 20 ml/Minute
Column Temperature
100C
Detector Temperature
300 "C
Sample Size
2 yl
External standards were used in each run and their peat: area in the calculation of the sample concentration. Precision was 10? for any sample (Table 2).
A. Air Analysis
Air ?amp1es were taken for one hour at a rate of 3 liters per
hour in 10 ml of water in an impinger. One ml of water was freeze dried and 1 ml BFo/methanol added for esterification. After heating ir: sealed 5ott1es for 15 minutes, the solution is quenched with water and 1 ml hexane added. The ester Is extracted into the hexane and injected in the GC. "''wo micro
Uter samples were used. Method was sensitive to 0,3 ppb
level, which i? below the 0.5 ppb proposed TLV.
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3. Yarn
and|fm/arns Sintered yarn
were analyzed identically.
Five ml of methanoT was "added to one gram of yarn. After
10-15 minutes, one ml was removed, and one ml 3F,/nicthano1
esterfying reagent added. This was heated for Is minutes,
water quenched, exti-actedwith hexane and the hexane injected
into the GC. Thej----B^lyarns had considerable variance
betwean samples, im s was due to ejtherupeven application
or to adsorption of the FC on thee----gitself. Soxhiet
extraction <ith methanol did not reduce this variability. (Set. 2).
C. B1opd
B1oo?< was analyze^ identically to the water from the impinger air samples. S. Stafford, of rPD. prepared a series of spike-l blood samples as an interlab check. These were analyzed with a precision of - 10?. (Tabia 2} A set of spiked blood samples prepared at PCO were run with good
precision.
Iv- TOER^L TREATMENT
Thermal treatment can effectively remove the FC-143, yt it is
not the prime candidate because of deleterious effectso^ yarn properties. Previous work (Ref. 3) has shown thatf----g^ams
heated at 175 "C for 30 minutes or at 200C for TO minutes no
longer have any sxtractable FC-143. IR scans of off gas from
yarn heated from 150 to 250^0 confirm the presence of a fluoro-
carbon gas by the ausorprion peak at 1250 cm"". The presence of
th-i COy peak at 2350 cm" deearboxylating. There
confirms CO, evolution, is no carboxyl oeak at
i.e., the
1700-1750
FC if cm"
which would show evaporation. Further study of the gases evol/ed
from ISO-ZOO^ from Triton X-100/FC-143 sodium salt mixture in a 5:'t.:^tio. show the presence of a C-H absorbz.ice peak at 3CIO cm (Figure 3} This shows that the fluorocarbon yarn evolved in
decarboxylation is the perflucn-omownydr'ide. There is no evi dence of an olefin (C " C, 1790 cm''1) which is a possible decom position product. The Triton supplies the necessary 'ivdrogen to
form the hydride (Ref. , 5). Analysis of the completeness of the cerarboxytation was made by passing known amounts of off-gas through a Draeger tube. The tube, specific for C0. uses a color change to voliimetricany measure the CO^ evolved. 'The amount was 90 - 10% of the theoretica., showing that no other major reaction
occurs during thermal treatment.
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REFERENCES
1. Forte, M. A. - SpAR 79-3.
2. FortP , M. A., Mokhtar, A. M. - PCD Monthly, Aprii, 1981.
3. Forte, M. A., Mokhtar, A. M. - PCD Monthly, May, l8l.
4. LaZe.-te, J. D; JACS: 75, 4525 (1953).
5. Meschke. R. G. - ^CRD-SS-m.
6. Stafford, S. S. - PPD Analytical nuorr'urfactent in Water".
Method,
"Determination of Co
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APPENDIX
Table 1
FC-143 Samples
Table 2 Figure 1 Figure 2
GC Precision
t6
1
|A----MSp1nnin^ in Air Sampling Location
n^^^^^^^~
IFl Scans of I&T Off Gas
Figure 3
FC-143 IR Scan
Figure 4 Attachment I
GC Chromatogram
Letter, S. S. Stafford to M. A. Forte, 12/17/81
Attachment II GC Method FC-143 Analysis
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TABLE I
PINNING IN-AIR SAMPLES
LOCATION
1. SM-2 - RoTi 6
2. SM-2 - Roll 23 3. SM-2 - Roll 6 4. 3-1-2 - Roll 23 5. Operator's Desk 6. Between SM-2 and 3, Roll 12 7. SM-2 - Between Bath and Wash Module 8. SM-3 - Between Bath and Wash Module 9. SM-3 - Ron 6
10. SM-3 - foil 23
LEVEL
Non-DetectabIe (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-DetectabIe (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-DetectabIe (<0.3 ppb) Non-Detectable (<0.3 ppb)
Samples taken at estimated position of operator's head during work,
PINNING FC-143 WATER/YARN LEVEL
SM-2 SM-3
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 NO
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TABLE II
GC PRECISION
SAMPLE 5 ppm FC-143
1.0 ppn PC-143 0.5 ppm 0.25 ppBi
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.
10
3LOOD SAMPLES ILC with PPD/S. Stafford
SPIKED LEVEL (ppro F)
.50 1.5
31 Mk .027
0.17 1.0 Blank .054 .34 .054
MEASURED LEVEL (ppm F)
.56 1.9
.01
0.026 0.145 1.2
.009 .047 .314 .059
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FIGURE 4
GC W", :3F FC-143 STAiiDARO J.2Cio ?Pf-'
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ATTACHMENT I
{S:A<uSrfZQtaiu
E. i. UU PCNT OE NEMOURS & COMPANY
NCORPQRATeO
WILM1NGTON, DELAWARE 19898
POLYMER PRODUCTS DEPARTMENT eXPERlMENTAI- STATION
ANALYTICAL 3?GR7
^lers^soBTE-^.
SPPL'AI-ICE, ?SXT;L3 FZ3EBS
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DT'P^I:?A?ION OF PSBFL'J'OROOCTAKOATE IN AQUEOUS A:? :MPI:;GZ? SAJ-iPLZS
(Job Mo. Sll-oOl; PRAL ;ios. 81-2832-233^; Notebook !So. 226-62;
As repcr-sed by phone 7/2'/3l, the foor aouecLiS air i^pir-ser sanples su'R'si'-T.e; o/8l -..-ere analyzed for perfluorooctanoate (Cs; -ising trie gas cr.rcsa^ogr'a'chic ^e^hod
" 2?--7^9. Sesolts and -saa-Dle identification are a3 fcllovs:
Saa-gis
C-C Analysis
gLAL ;io
Idanzification
3ate Analyzed.
_.g ?C-l-S/gL i'a.i
S1-&S32 31-2823
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Ctm^1
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'&} fC-l^S ^M a.'T'.'ncniua perfl-jorooctanoa-oe i was -.ised '1.3 calibration ;-,ari<;a-'i,
and Cg concentration calciulaied a.s ihe sal",. The Isver licit ^cr ';u&^;<,i'..a'-:':'l
V3.S 0,307 ug/al-.
,'b) Chrcnatosraiss for sample i?'! differed slightly in a-pp&ar&nce fron; ^3, ff1., and the 'blanks; a lone&r air san'o.i ina tise "light nave x-.'/en a detectable level ofCg.
^- ^-'V^. 2^-
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'?<-. r fluorccctanoat e
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I I ATTACHMENT
------------------
METHOD TM-0405-82T
DATE 3/16/82
PAGc. 1 OF 10
DU FONT FIBERS PRODUCTS FC-143 ANALYSIS
S. S. Shelburne Spruance Fibers Plant
E. I. duPont de Wemours A Co., Inc. Textile Fibers Department Richmond. Virgl'ifa 23261
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METHOD TM-0405-32T
DATE 3/16/82
PAGE 2 OF 10
1. SCOPE
1.1
This method is used to describe sample preparation and GC analysis for
FC-143 in air, water, blood and ori yarn.
?. PRINCIPLE OF METHOD
2.1
Samples from in air, water or blood are first concentrated by f-reeie
drying. Yarn samples an? soaked in methanol to extract the FC-143.
Then the FC-143 is esterified by heating with BF^/methanol to form the
volatile methyl ester.
CF.tCF^COO'Na
^3
CH,OH--w
CF^CFgIg COOCH,,
The reaction is ouenched with water and the hexane. The hexane solution is snot into a
capture detector. The FC-143 concentration peak area comparison to standards.
ester extracted into GC with an electron is determined based on
3. SIGNIFICANCE AND USE
3.1
This method is used to determ'ne FC-1-^l----^BBvarn. in air, in water
and in blood. The applicable ranges arcT
Yarn -
Air Water
Blood
50 - 1COO pom
0.3 ppb - 1 ppm - 0.02 ppm - 25 - 0.0? ppm - 25
ppm ppm
4. INTERFERENCES
4.1
Water roust be removed from the samples to prevent reaction with the
esterfying agent.
5. APPARATUS
5.1
6as Chromatograph - Hewlett Packard 5880 with Nig, electron capture
detector and 5880 terminal Hewlett Packard Company,
5.2
Argon/Methane Carrier Gas 95/57 - Surdett.
5.3
Syringe - Hamilton - 701 M - 10 pi - Supeico Co.
5.4
Telematic Air Sampler - Taylor Parker Co., Morfolk, Virginia, Cat. No.
1S8.
5.5
Batteries, nickel-cadmium, 8.4 volts - Taylor Parker Co., Cat. No.
8-4Ta.
5.6
Vicils - 5 ril, glass - Fisher Cat. s03-326B.
Company Sanitized. Does not contain TSCA CBI
^P
METHOD TM-04C5-82T
DATE PA6E
3/16/82
3 OF 10
5.7
Erienmeyer Flask - 250 nil Glass Stoppered - Fisher Cat. No. 1C-C47C.
5.8
GC Column 10 glass, packed with OV-202 on 100/12U Supeico pert -
Supeico Co.
5.9
"eater - Fischer ^11-495-50 or equivalent.
5.10 5.11 5.12 5.13 5.14 5.15
5.16
Sand Bath with copper tubes - Spruance Process Control Development. Pipets 1 ml - Fisher Cat. ff!3-650B; 5 ml - Fisher Cat. ?13-650F. Manometer - Fisher Cat. #11-292 or equivalent. Lyoplllzer - Fisher Cat. i?10-269"41 or equivalent.
Freeze iJr- Flasks (4), 350 ml - Fisher Cat. 10-269-53. Vacuum Pump - Two Stage Model D-25 - Fisher Cat. No. 01-183-31 or equivalent. Pi pet Aspirator Bulb - Fisher Cat. l4-070B.
5.17 5.18
Impinger Tube - LG-6890-100 - Scientific Glass Co.,
|fl^H||Cfp liners - Supeico.
Vineland, N.J.
5.19
Dewar Flask, 1 quart size - Ffsher Cat. '10-195B.
5.20
Vacuum system trap - LC-11025-102 Scientific Glass co., Vineland, N.J.
6. REAGENTS AND MATERIALS
6.1
BF,/Methanol - Pestlc-tde grade in glass ampoules - Supeico Cat. No.
3-3041.
'
~"
6.2
Methanol - Fisher Cat. <S^A-936.
6.3
Hexane - Fisher Cat. '^H-301.
6.4
Dry Ice - Richmond Dry Ice Company.
6.5
Acetone - Fisher Cat. #^LA-17-5.
7. PRECAUTIONS
7.1
BF^/Methanol - Wear leather gloves when Initially breaking the glass
ampoule. Wear rubber gloves when pouring or pipeting.
7.2
Wear rubber gloves when handling methand c- hexane. Keep away from
f1 ame.
7.3
Wear leather glove' hen handling vials or heater and sand bath.
Company Sanitized. Does not contain TSCA CBI
METHOD TM-0405-82T
DATE 3/16/82
PAGE A OF 10
7.4
Wear leather g''ov"s when handling dry ice.
7.5
Blood. Rubber gloves must be worn when handling blood, '/.'hen finished
wUh bicod, heat with concentrated bleach in a hot oven at "" 90C for
one hour, then flush down drain with water. Use bleach in "10:1 ratio over blood. Rinse all pipets, beaker and other eQuic-ment with bleach.
8. SAMPLING
.1
In-Air
8.1.1
Place 10 nil DT water in an impinger tube. Set tube ';n Telemaric and
set turner for one hour. Flow should be set at 3 liters/minute. Set
Tel emetic in area to be sampled.
8.2
Yarn
8.2.1
No special sampling reQuircd.
8.3
B^ood
8.3.1.
Obtain the necessary blood samples from Medical. Store in refrigerator until ready for use. See 7.5 for disposal.
9. CALIBRATION AND STANDARDIZATION
9.1
FC-143 Standards
9.1.1
Weigh 0.1000 g of FC-143 into ?. 100 ml volumetric flask. volume with methanol. This is the 1000 ppro standard.
Make to
9.1.2
Take 1 ml of 9.1.1 and dilute to 50 m1 with methanol. ppm standard.
This i; '.he 50
9.1.3
Take 5 m) of 9.1,2 and dilute to 10 with methanol.
standard.
This-is the 25-ppm
9.1.4
Take 1 ml of 9.1.1 and dilute to 100U ml with methanol.
10 ppm standard.
This is the
9.1.5
Take 5 ml of 9.1.4 and dilute to 10 ml with methanol.
ppm standard.
This is the 5
9.1.6
Take 1 ml of 9.1.4 and dilute to 10 ml with meethenol.
ppm standard.
This is the 1
9.1.7
Take 1 ml of 9.1.5 and dilute to 10 ml with methanol.
ppm standard.
This is the 0.5
9.1.8
Take 1 ml of 9,1.6 and dilute to 10 ml with methanol.
ppm standard.
This is the 0.1
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METHOD TM-Q405-82T
DATE PAGE
3/16/82 5 OF !0
10. PROCEDURE (References Attachment I, GC Conditions and Attachment II,
Lyophilizer Operation)
10.1 10.1.1
Yarn - Sintered andyij
For sintered yarn, weiglLO^ g to 0.0001 and put into a glass vial.
Add 1 ml csethanol. Forfyarn, weigh 0.05 g yarn to 0.0001 g, add
to a glass val and addTnn methanol.
50.1.2
Add 1 ml BF,/Methano'!. Heat in sand bath for 15-20 minutes at sand temperature of 65-70C.
10,1 3 10.1.4
Remove from bath and allow to cool. hexane. Then shake for 30 seconds.
Then add 1 ml 01 H and 1 mi
Allow layers to separate cnd shoct sanyle on QC (See Attachment 15. PC-143 peak RT is "2.9 minutes.
10.1.5 Shoot standards (9.1) that bracket the expected sample level.
m - _Sintered - 0.5, 1.0, 5.0 ppm 10. 25. 50 ppm
lO.l.o See 11.1 for calculation.
10.2
In-Air Saniples
10.2.1 10.2.2
it Pipet one ml of the water from the imp-.nger tube into a clean, glass
vial. Carefully place in a Freeze Dry Flask, pot on the rubber top
and hook it to the Lyophilizer (Attachment II). Leave on the
Lyophilize- until all the water is gone {"2-3 hrs.).
Remove the vial from the flask and add one ml of BFi/MfeShanol by
pippf. Put a Teflon1? gasket in tre vial top, screw it tight and place
in the sand bath for 15-20 minutes at SS-ZO'C.
10.2.3
Remove from the bath ard allow to cool. Hexane. Then shake for 30 seconds.
Then add I ml DI H0 and I ml
10.2.4
10.i.5 10.2.6
Allow the layers to separate and shoot the hexane layer on the GC.
(See Attachment I).
Shoot the standards that bracket the sample (0.1, 0.5, 1.0 ppm). See 11.2 for calculation.
10.3
Water
10.3.1
Pipet 1 ml of water into a clean, glass vial. 10.2.5.
Then follow 10.2.1 -
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METHOD TM-0405-82T
DATE 3/16/82
PAGE 6 OF 10
10.4
Blood (See 7.5 for handling)
10.4.1
Pipet 1 ml of blood into a cle .1, glass vial, freeze dry and run as in 10.2.1 - 10.2.6.
11. CALCULATION
11.1
Yarn
A
PC-143 ppm = B" x C
11.2
A = Sample GC peak area B = Standard GC peak area C = Standard concentration, ppm
0 = Weight of sample Air, Water. Blood
PC-143 ppm = ^.x c
A s Sample GC peak area B s Standard GC peak area
C s Standard concentration, ppm
12. PRECISION ANJ ACCURACY
12.1
Precision is ^ 10%.
12. REFERENCE
13.1
PPO Analytical Method Determination of Cg Fluorosurfactant in Wat^'r GC, S. S. Stafford.
14. KEY MOP.D INDEX
14.1 14.2
FC-143 - in yarn, water, air and blood.
GC analysis,
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METHOD TM-0405-82T
DATE PAGE
3/16/82
7 CF 10
Carner Gas Injection Temperature
Oven Temperature Detector Temperature Sa'sple Sl23
Cclumn Packing
ATTACHMENT I HP 5880 GC CONDITIONS
Argon/Methane 180'C
95/5
20 mi/minute
100C
300 C
2 y1
6' Glass 1/3" 00
OV-Z02 on 100/120 Supelcoport
GC Tennlnal Conditikins - Run time - 0.1 minutes Tan Skim. Attenuat-ion 2 (adjust as necessary for peak s-ize)
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FREEZE DRYING SAMPLES
METHOD TM-0405-82T
DATE PAGE
3/16/82
8 OF 10
Equipment Setup
1. Put " 500 ml of acetone in the lyophilizer tank.
2. Carefully add enough dry ice to keep it as a solid. Replace lid.
3. Adc ~ 50 ml acetone to vacuum trap Dewar. Set the vacuum trap in the Dewar and
add dry ice to pack around it.
4. Hook up heavy wall ru t-er tubing from the lyophilizer to the trap to the vacuum
pump. Tee in the manometer between the trap and pump.
Sample Setup
1. Take the samples in the glass vials and dip them -in the lyophilizer dry ice/acetone mixture. Keep them immersed long enough for complete freezing.
2. Place the frozen vials in one of the freeze dry flasks. Put a fitler in the top
of the rubbe* top, place on the flask and connect to the lyophilizer with the..
metal neck.
3. Open the connection to vacuum. Only those ports being used can be open to vacuum. All others must be on vent.
~
4. Cut on the pump, open the manometer conenctions. Vacuum must be 0.1 mm.
5. After freezing, shut off manometer, carefully open sample lyopilizer port and cut off port.
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PAGE 9 OF 10
'
Company Sanitized. Does not contain TSCA CBI
TEST METHOD APPROVAL
UHB- 1^
FC-143 AAnalysis" ^M-0-0440055--882T
S.S Shelburne
Author
Site
Authorized By
Spruance Spruance Spruance ATM001.7
^ - ^ SupeKyisor
&^'eiTrist
Supervisor
For [Organization)
Process Control Development
Process Control Development
Process Con+ro'! Lab
METHOD TN-0405-82T
DATF PAGE
3/16/82
10 OF 10
Spru;nce
Site
Date
3 /'3.//.?r
:/-'C/r ^-
Company Sanitized. Does not contain TSCA CBI
7 -
-
ABSTRACT
The FC-143 {aimionium perfluoro octanoate) surfactant used in the polymerization process was a suspected teratogen. Methods wer
loped, and its level measured in air, water, blood and yarn.
water and blood levels were well below TLV's. None was present tered yarn, but 1ST yarn, which is coated with dispersion, has
opm levels. It was shown that FC-143 dicarboxylates when heated 200 C giving .ft COgand perfl uoroseptamonohydn'de.
In air,
on sin 200-700
to
INOEXIHG SUBJECTS
1. Measurement of perfl uorooctanoic acid (FC-143) in air, water, yarn. 2. Ammonium perfl isorooctanoate dicarboxylation of. 3. Sodium perfluorooctanoate dicarboxylation of.
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COPY NO. 1
5 6 7 &8
9 & 10 11 & 12
13
DISTRIBUTION
G. B. Faigle, Jr. - R. D. Oemarest R. C. Harper, Jr., - PCD File
R. F. Janis, >Jr. - M. T. Waroblak PCD File
G. L. Watts - J. H. Fischer J. L. McDam'el
E. S. Brint'--' - E. K. Koffenberger
PCO File
D. G. O'Dell J. P. Yuk - PCD File Research ibrary Central Report Index
Patent Lfaison File
S. S. Shelburne, M. A. Forte, A. M. Mokhtar - PCD File
DSS001.27
LOCATION
Spruance
Spruance
Spruance Memo ur s-W i"t nn ng to n Nemours-Wilnn'ngton Spruance Spruance Centre Road Centre Road
Spruance
Company Sanitized. Does not contain TSCA CBI