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^4/2-226-/SS Report Mo. Sp/iR S2-1 Copy No. ) Q D is t r ib u t io n - Last Page FC-143 IN THE TEFLON PROCESS S. S. Shelburne, Editor M. A. Forte A. M. Mokhtar Period: March, 1981 - September, 1981 (P a rt Time) Reference: SA-195 Previous Reports: SpAR 79-3 T ex tile Fibers Department Spruance Process Control Development E. I . DuPont de Nemours & Co., Inc. Richmond, Virginia March, 1982 The individual to whom t h i s m aterial is issued 1s responsible for the se c u rity o f the information. For those on the d is tr ib u tio n l i s t a t other lo c a tio n s , r e s p o n s i b il it y of the document w ill autom atically t r a n s f e r to th e i r successors. I f there is no fu rth e r use for the docu ment, return to the above address. Do not leave exposed and unattended. 000083 SPR000310 EID714222 INTRODUCTION I n . 1978, the 3M Company n o tif ie d DuPont th a t the FC-143 s u r f a c ta n t fam monium perfluorooctanoate) sold to DuPont fo r use in Teflon polymeriza tion may be te r a to g e n ic . Therefore, i t was necessary to monitor i t s level in the Teflon Process and work environment. Work done in a pre vious rep o rt (Ref. 1), showed th a t i t was not present e i t h e r in the work environment or in s in te re d yarn a t an eauipment lim ited lower de te c ta b le l i m i t of 50 ppb. However, because o f a proposed TLV in a i r o f 0.5 ppb, j i t has been necessary to monitor the FC-143 level through the complete 'Teflon process with resp ect to t h is lower l e v e l. OBJECTIVES To measure the e x te n t, 1f any, o f personnel exposure to FC-143. To develop accurate methods for FC-143 in a i r , w ater, yarn and blood a t TLV l e v e l s . To determine the rea c tio n s and final d is p o s itio n of FC-143 in the Teflon process. To determine the condition for and by-products o f thermal treatm ent to remove FC-143 from disp e rsio n and yarn. SUMMARY AND CONCLUSIONS /The handling o f coated yarns or d ir e c t contact with th Teflon d is p e r sion are the only poten tia l areas th a t personnel can be exposed to sig n i f i c a n t le v e ls o f ^FCzlAl. The p e r f l uoroortanoic a rid of FC-143 was not d e tected in the spinning a i r environment! The level of p e rflu ro acid in the spinning wash water was 1-4 ppm, but no l im it hasbeen defined -and aqueous s o lu tio n s have not been considered a p o ten tia l means of person nel exposure. The perfluoro acid was d e tected 1n yarns coated with dispersion as in the case of yarns used for packing end uses. Levels ranged from 200-700 ppm. With uncoated yarns th a t come d i r e c tl y o f f the spinning machine, the le v e ls of perfluoro acid were nondetectable. j Thus, the p o ten tia l for exposure of personnel i s very l im ite d , and t h i s 'was confirmed by the low l e v e l s o f perfl uoro acid in blood. Levels did not exceed 0.09 ppm, which were well below the 0.4 ppm l i m i t . FC-143 i s not found in the spinning area environment because o f two reasons. Approximately 10 i s washed o f f the yarn onthe washreel or module. The remainder decarboxylates, as the yarn goes over the heated r o l l s , giving o f f CCU and the 7 carbon perfl uoro monohydride. This has been confirmed by IRT a n a ly s is of FC-143 off gas as i t i s heated up to 200C. The monohydride forms ra th e r than the 7 carbon perfluoro o l e f i n because the o th er su rfa c ta n t p rese n t, Triton XlbO, provides the neces sary hydrogen. 000034 SPR000311 EID714223 Because of the decarboxylation at 175-200C, thermal treatm ent is an e f f e c tiv e way to remove the FC-143. However, because of d e le te r io u s e f f e c t s on yarn p r o p e r tie s , thermal treatm ent i s not considered to be a route to its removal. A modified GC method was developed f o r higher s e n s i t i v i t y by using an e le c tro n capture d e te c to r and a new column packing. With these changes, FC-143 in a i r +can be measured to 0 .3 ppb and in blood to C.02 ppm with a precision o f - 10%. PATEMT ACTION No patent action based on t h i s work i s planned a t p r e s e n t. PUBLICATION There are c u rre n tly ro plans to publish any of t h i s work. CODE LISTING FC-143 - Arnioni un perfluoro octanoate. Prepared # / . q .. w M. A. Forte Approved by: Supervisor Development A. M. Mokhtar 000085 SPR000312 EID714224 TABLE OF CONTENTS I. Introduction I I . Environmental Analysis A. In-Air B. ProcessWash Water C. Yarn D. Blood E. D isposition inProcess I I I . Method Development A. In-Air B. Yarn C. Blood IY. Thermal Treatment V. References VI. Appendix VII. Abstract VIII. Distribution Page 1 1 1 2 2 2 3 4 4 4 5 6 7 Last Page 000086 SPR000313 EID714225 - 1- I . INTRODUCTION Teflon dispersion is shipped to Spruance from the DuPont, Park ersburg, West V irginia PPD Plant as a 60% s o lid s /w a te r d isp e rs io n t h a t contains 5% T rito n X-100 and 1600 ppm FC-143 as s u r f a 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 s ib le teratogen. Therefore, i t became necessary to measure the FC-143 le v e ls in the process and work environment to d e t e r mine the level of personnel exposure, i f any. I n i t i a l work (Ref. 1 ) was equipment lim ite d in s e n s i t i v i t y to a lower d e te c tio n l im it o f 50 ppb. With a proposed TLV o f 0.5 ppb, i t became necessary to redetermine its levels with increased se n sitiv ity and to determine I t s final d is p o s itio n - whether i t i s washed o u t , decomposes or remains in the yarn. Also, since thermal treatm ent was a possible route to FC-143 removal from the d i s persion, the condition and byproducts of thermal treatm ent must be determined. I I . ENVIRONMENTAL ANALYSIS A. In-A ir Air samples were taken a t e ig h t lo c a tio n s around Teflon spinning machines 2 and 3 (Figure U , and a t four lo c a tio n s around the Finishing Area induction dryer. (Table I , Attach ment I ) Only one sample from inside the induction dryer stack i n l e t had a detectable level (3 ppb). Since t h i s was inside the duct, there was no personnel hazard involved. The lower dete c tio n l im it for i n - a i r samples based on standards i s 0.3 ppb.. The lack of detection precludes any personnel exposure hazard since the exposure problem reported by 3M is due to a i r borne contamination. B. Water The FC-143 in Teflon dispersion is changed to the sodium s a l t a f t e r the final pH adjustment step a t Parkersburg. This i s converted to the acid form in the regeneration bath, but i t s t i l l has some water s o l u b i l i t y . 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 d iffe re n c e s r e f l e c t d iffe re n c es in wash e ff ic ie n c y due to d i f 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 ppm fo r SM-3 and 1 ppm fo r SM-2. FC-143 concentration in water a t these le v e l s does not present an exposure hazard. (Table 1) 000087 SPROO0314 EID714226 - 2- C. Yarn S intered yarn had non-detectab!e l e v e l s of FC-143. Teflon and Kevlar I and T products, where the yarn i s dipped in the disp e rsio n and d rie d , had le v e ls ranging from 200-700 ppm. This v a r i a b i l i t y i s due to the uneven ap p lic atio n and to the probable adsorption of the FC-143 Teflon i t s e l f . Soxhlet e x tra ctio n with methanol did not s i g n i f i c a n t l y improve r e covery (Ref. 2). D. Blood The TLV f o r FC-143 in blood i s 0.4 ppm. No blood samples from exposed personnel exceeded 0.02 ppm. Most had nond e te c ta b le l e v e l s . Method lower d e te c tio n l im it s was ~ 0.02 ppm. E. D isposition in the Process Analysis has shown th a t "10% of the FC-143 i s washed o f f the yarn in spinning (Ref. 1). However, none i s found on s i n tere d yarn. Previous work (Ref. 3) has shown t h a t yarn heated a t 175C has no e x tra c ta b le FC-143 remaining a f t e r 30 minutes. At 200C, th e re is n o n e -a fte r 10 minutes. This i s because FC-143 can be removed therm ally by decarboxylation, i . e . , decomposition to CO and the perfluoroseptamonohydride (Ref., 4, 5 ). To confirm t h i s , ~6 f e e t of Teflon I and T yarn was pulled into Teflon tubing which was used as a GC column. The GC oven was te m p e r a tu r e programmed from 125-250C. The tube was purged with n itrogen and the off-g a s analyzed by IR in a 10 cm. c e l l . The N icolet MX-1 FTIR was s e t to run r e p e t i t i v e 1-minute scans. The Teflon tubing i t s e l f was s ta b le a t these tem peratures. Two absorbance peaks appeared "5 minutes a f t e r the 150C oven temperature was passed. The holdup time in the tubing from the GC to the IR c e ll and i t s volume was ~ 5_jinutes a t 20 ml/minute N- flow. A twin peak a t 2340 cm"1 (CO) and a smaller C-F peak a t ~ 1250 cm 1 were seen. These peaks in crease in size u ntil a f t e r ' 5 minutes a t 250C, they begin to decrease. No carbonyl peaks a t 1700-1750 cm' 1 appear which would have indicated evaporation of the FC-143 (Figure 2). Although these scans show th a t decarboxylation - not evapora t io n - occurs, they did not show whether the p e rfluoro by product was the o le fin (perfluoroheptene) or the hydride (perfluoro monohydride). Scsne concern was voiced over the p o te n tia l hazard from the o l e f i n . To determine the id e n t it y of the byproduct, an excess amount of the FC-143 sodiun s a l t was mixed with Triton X-100 and poured into the Teflon GC tube. The temperature was programmed from 150-225C. The scans show a peak a t 3010 cm" , which i s in d ic a tiv e o f the hydride. There i s no evidence of the o le f in which would have absorbed a t 1790 cm"1 (Figure 3 ). 000088 SPR000315 EID714227 - 3- In order to determine the completeness of the decarboxyla tio n , Draeger tubes were used. The gas evolved from the heating o f the FC-143 sodium s a l t / T r i t o n X-100 mixture was passed through the tube. This tube gave a specific c o lo r i metric charge for C ^ . I t showed 90+% of the th e o r e tic a l CO evolution. IIT. METHOD DEVELOPMENT The method used in t h i s re p o rt for determining FC-143 l e v e l s 1s s im ila r to t h a t used in Reference I . The samples are e x tra c te d with methanol or freeze d rie d , e s t e r i f i e d to get the v o l a t il e e s t e r ,, w ith 8F ,, jth e ,, r e a c ti o n quenched with w jte r , the e s t e r e x tra c te d into nexane and the hexane in je c te d in a GC. A new GC column packing (0Y-202) was used to g e t b e t t e r s e n s i t i v i t y . FC-143 i s not a pure compound and c o n s is ts of a t l e a s t 5 i d e n t i fied isomers (Ref. 6). The 0V-202 column c o n solidates these d i f f e r e n t compounds into one peak. A new Hewlett/Packard 5880 GC with a Nlg^ e le c tro n capture d e te c to r was used to increase the method s e n s i t i v i t y to the low ppb range. A ty p ic a l chromatogram is shown in Figure 4. The following GC co n d itio n s were adopted for use: C a rrie r Gas Argon/Methane 5% @ 20 ml/Minute Injection Temperature 180C Column Temperature 100 C Detector Temperature 300 C Sample Size 2 pi External standards were used in each run and t h e i r peak ar^a in the c a lc u la tio n of the sample c o ncentration. Precision was - 10% fo r any sample (Table 2). A. A ir Analysis Air samples were taken for one hour a t a ra te o f 3 l i t e r s per hour in 10 ml of water in an impinger. One ml of water was freeze dried and 1 ml BFo/methanol added for e s t e r i f i c a t i o n . A fter heating in sealed B ottles for 15 minutes, the solution 1s quenched with water and 1 ml hexane added. The e s t e r is e x tra c te d into the hexane and in je c te d in the GC. Two micro l i t e r samples were used. Method was s e n s i t iv e to 0 .3 ppb l e v e l , which Is below the 0.5 ppb proposed TLV. 000089 SPR000316 EID714228 -4- B. Yarn Sintered yarn and I and T yarns were analyzed i d e n t i c a l l y . Five ml of methanol was added to one gram of yarn. A fter 10-15 m inutes, one ml was removed, and one ml BF-/methanol e s te r fy in g reagent added. This was heated for 1S> m inutes, water quenched, e x tra cte d with hexane and the hexane in je c te d Into th e GC. The I and T yarns had considerable variance between samples. This was due to e i t h e r uneven a p p lic a tio n or to adsorption of the FC on the Teflon i t s e l f . Soxhlet e x tr a c tio n with methanol did not reduce th is v a r i a b i l i t y . (Ref. 2). C. Blood Blood was analyzed i d e n t ic a l ly to the water from the impinger a ir - samples. S. S ta ffo rd , o f PPO, prepared a s e r i e s o f spiked blood samples as an in te rla b check. These were analyzed with a prec isio n o f - 10%. (Table 2) A s e t o f spiked blood samples prepared a t PCD were run with good precision. IV. THERMAL TREATMENT Thermal treatm ent can e f f e c t i v e l y remove the FC-143, but i t 1s not the prime candidate because of d e le te r io u s e f f e c t s on yarn p r o p e r t ie s . Previous work (Ref. 3) has shown t h a t I and T yarns heated a t 175'C f o r 30 minutes or a t 200C f o r 10 minutes no longer have any e x tr a c ta b le FC-143. IR scans o f o f f gas from yam heated from 150 to 250C confirm the presence of a flu o ro carbon gas by the absorption peak a t 1250 cm" . The presence of the CO- peak a t 2350 cm- i confirms CO- e v o lu tio n , i . e . , the FC i s decarboxylating. There is no carboxyl peak a t 1700-1750 cm"1 which would show evaporation. Further study of the gases evolved from 150-200C from T riton K-100/FC-143 sodium s a l t mixture in a 5:1. r a t i o , show the presence o f a C-H absorbance peak a t 3010 cm"1 (Figure 3) This shows t h a t the fluorocarbon yarn evolved in decarboxylation i s the perfluoromonohydride. There i s no e v i dence o f an o le f in (C = C, 1790 cm'1 ) which i s a possible decom p o sitio n product. The Triton supplies the necessary hydrogen to form the hydride (Ref. 4, 5). Analysis of the completeness of the decarboxylation was made by passing known amounts o f o ff-g a s through a Draeger tube. The tube, s p e c if ic for C0-, uses a color change to v o lu m etrically measure the CO- evolved. ` The amount was 90 - 10% o f the t h e o r e t i c a l , showing th a t no other major rea c tio n occurs during thermal treatment. OQOOin SPR000317 EID714229 - 5- REFERENCES 1. Forte, M. A. - SpAR 79-3. 2. F orte, M. A., Mokhtar, A. M. - PCD Monthly, A p r i l , 1981. 3. Forte, M. A., Mokhtar, A. M. - PCD Monthly, May, 1981. 4. LaZerte, 0. D; OACS: 75, 4525 (1953). 5. Meschke, R. G. - PCRD-58-131. 6. S ta ffo rd , S. S. - PPD A nalytical Method, "Determination o f C Fluorosurfactant in Water". 8 000091 SPR000318 EID714230 - 6- APPENDIX Table 1 FC-143 Samples Table 2 GC Precision Figure 1 Teflon Spinning in A1r Sampling Location Figure 2 IR Scans o f 1ST Off Gas Figure 3 FC-143 IR Scan Figure 4 GC Chromatogram Attachment I L e t te r , S. S. Stafford to M. A. F o rte , 12/17/81 Attachment II GC Method FC-143 Analysis 000092 SPR000319 EID714231 TABLE I i . TEFLON SPINNING IN-AIR SAMPLES LOCATION 1 . SM-2 - R o l l 6 2 . SM-2 - Roll 23 3. SM-2 - R o l l 6 4. SM-2 - Roll 23 5. O p e rator's Desk 6. Between SM-2 and 3, Roll 12 7. SM-2 - Between Bath and Nash Module 8. SM-3 - Between Bath and Wash Module 9. SM-3 - R o l l 6 10. SM-3 - ro ll 23 . LEVEL 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-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Oetectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Non-Detectable (<0.3 ppb) Samples taken a t estimated p o s itio n o f o p e r a t o r 's head during work. I I . TEFLON* SPINNING FC-143 WATER/YARN LEVEL Wash Water Sewer Regenerated Yarn Sintered Yarn 1.2 ppm 1 ppm 49 ppm ND Wash Water Sewer Regenerated Yarn Sintered Yarn 4.0 ppm 2.0 ppm 60 ppm ND 00005*3 SPR000320 EID714232 TABLE II 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 53.2, 62.3, 65.2, 61.6, 59.0 33.4, 34.3, 38.8, 39.5 17.5, 15.5, 19.1, 18.4 SAWLE 1 2 3 4 5 6 7 8 9 10 BLOOD SAMPLES ILC with PPD/S. S ta ffo rd SPIKED LEVEL (ppm F) .50 1.5 B1 ank .027 0.17 1.0 B1 ank .054 .34 .054 MEASURED LEVEL (ppm F) .56 1.9 .01 0.026 0.145 1.2 .009 .047 .314 .059 000094 SPR000321 EID714233 FIGURE 1 7 > / / / / I/ W i A A (.h .K S 3 I 0 k fflS M m o D U LS Ui/Ajoejes 0 M J/ts /f g s e -L 2*ee/Mf6 &//s '$*t) S/attss./^ foto fy*2J0 M/msxs 00009$ 0 .1 5Pmok MivhW/2. SPR000322 EID714234 FIGURE l Q sam ple N I CCILfET MX - 1 00 00005*6 SPR000323 EID714235 3 3 r.f iiiiN S N y 'ri % 0000^7 SPR000324 EID714236 FIGURE 4 GC RUN OF FC-143 STANDARD 0.205 PPM <'ZoS^fryn ---- P - C W 3 pf*< G a s A*ls%CJht Zomlj/tu-- 'X*rrr*c-r 7 /><: D6T0E73< SAmfks $/** .user* 000098 SPR000325 EID714237 y 45 CV 12*7* * ATTACHMENT I I5T iM S H C S ia O I E. I. du Po nt de N emours & C ompany INCOI) PO RATCO W il m in g t o n . Delaw are 19898 POLYMER PRODUCTS DEPARTMENT E X P E R IM E N T A L ST A T IO N ANALYTICAL REPORT cc : A. J . Dahl L . J . Papa W. C. P e r c iv a l T . K. Vu ? ra l F ile I.C . - 353 - 269 - 353 - 323 December IT , 1931 s-rzsmoEEE^. SPRUANCE, TEXTILE FIBERS RICHMOND, VA. DETERMINATION OF PERFLUOROOCTANOATE IN AQUEOUS AIR IMPINGER SAMPLES (J o b No. 8 1 1 -6 0 1 ; PRAL Nos. 8 1 -2 8 3 2 -2 8 3 5 ; N otebook No. E 26l62) As r e p o r t e d b y phone 7 / 2 / 3 1 , t h e f o u r aqueous a i r im p in g e r sa m p le s s u b m itte d 6 /8 l were an aly zed f o r p e rflu o ro o c ta n o a te (Cg) u sin g th e gas chrom atographic method ER-7 A9 . R e s u lts an d sam ple i d e n t i f i c a t i o n a r e a s f o llo w s : Sample PRAL Wo. - Id en tificatio n GC A n a ly s is Date A nalyzed Ufi FC-AB/m L (a ) S i-2 8 3 2 31-2833 31-233^ 81-2835 (uvsca^l #1, Stack a t O utlet ff2 , Stack a t In le t #3, O utlet o f Dryer A , In le t to Teflon In d u ctio n Dryer 6 / 29- 7 / 2 /8 1 II ft It n .d . (b) 0.032 n .d . n . d . - _____ (a ) FC-1 U3 (3M ammonium p e r f l u o r o o c t a n o a t e ) was u s e d a s c a l i b r a t i o n s ta n d a r d , an d Cg c o n c e n t r a t i o n c a l c u l a t e d a s t h e s a l t . The lo w e r l i m i t f o r q u a n t i t a t i o n was 0 .0 0 7 Ug/mL. (b) Chromatograms f o r sam ple #1 d if f e r e d s l i g h t l y in ap p earan ce from #3, A , and th e b la n k s; a lo n g er a i r sam pling tim e might have given a d e te c ta b le le v e l o f Cg. <T. S. S. S taffo rd jah Key W ords: Perflu o r ooctanoate FC-1U3 A ir A nalysis gn There's a world of things we're doing something about OOOOTO SPR000326 EID714238 ATTA C H M E N T II METHOD TM-0405-82T DATE 3/16/82 PAGE 1 OF 10 DU PONT FIBERS PRODUCTS TEFLON FC-143 ANALYSIS S. S. Shelburne Spruance Fibers Plant / E. I . duPont de Nemours 8 Co., Inc. T extile Fibers Department Richmond, V irginia 23261 O O O lO o SPR000327 EID714239 METHOD TM-0405-82T DATE 3/15/82 PAGE 2 OF 10 1. SCOPE 1.1 This method is used to describe sample preparation and GC a n a ly s is for FC-143 in a i r , w ater, blood and on yarn. 2. PRINCIPLE OF METHOD 2.1 Samples from in a i r , water or blood are f i r s t concentrated by freeze drying. Yarn samples are soaked in methanol to e x t r a c t the FC-143. Then the FC-143 i s e s t e r i f i e d by heating with BFj/methanol to form the v o la tile methyl e s te r. CF3 (CF2 )C00` + Na + CH3OH 0F3 -- * CF3(CF2 )g C00CH3 The reaction is quenched with water and the e s te r ex tra cte d into hexane. The hexane solution is shot into a GC with an e le c tro n capture d e te c to r . The FC-143 concentration is determined based on peak area comparison to standards. 3. SIGNIFICANCE AND USE 3.1 This method is used to determine FC-143 Teflon y a rn , in a i r , in water and in blood. The a p plicable ranges are: Yarn - 50 - 1000 ppm Air - 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 rea c tio n -w ith the esterfying agent. 5. APPARATUS 5.1 Gas Chromatograph - Hewlett Packard 5880 with Nig, e le c tro n capture d e te c to r and 5880 terminal Hewlett Packard Company. 5.2 Argon/Methane C arrie r Gas 95/57 - B urdett. 5.3 Syringe - Hamilton - 701 N - 10 pi - Supelco Co. 5.4 Telematic Air Sampler - Taylor Parker Co., Norfolk, V irg in ia , Cat. No. 158. 5.5 B a t t e r i e s , nickel-cadmium, 8.4 v o lts - Taylor Parker Co., Cat. No. 84Ta. 5.6 V icils - 5 ml, glass - Fisher Cat. #03-33. OOOIOl SPR000328 EID714240 METHOD TN-0405-82T DATE 3/16/82 PAGE 3 OF 10 5.7 Erlenmeyer Flask - 250 ml Glass Stoppered - F ish er Cat. No. 10-047C. 5.8 GC Column 10 g la s s , packed with 0V-202 on 100/120 Supelco po rt Supelco Co. 5.9 Heater - Fischer #11-495-50 or equivalent. 5.10 Sand Bath with copper tubes - Spruance Process Control Development. 5.11 P ip e ts 1 ml - F is h e r Cat. #13-65QB; 5 ml - F is h e r Cat. #13-650F. 5.12 Manometer - Fisher Cat. #11-292 or e q u iv a le n t. 5.13 Lyopilizer - Fisher Cat. #10-269-41 or equivalent. 5.14 Freeze Dry Flasks (4), 350 ml - Fisher Cat. #10-269-53. 5.15 Vacuum Pump - Two Stage Model D-25 - F ish er Cat. No. 01-183-31 or equivalent. 5.16 Pi pet A spirator Bulb - F is h e r Cat. #14-0708. -5.17 Impinger Tube - LG-6890-100 - S c i e n t if i c Glass Co., Vineland, N.J, 5.18 Teflon* cap lin ers - Supelco. 5.19 Dewar Flask, 1 quart s iz e - Fisher Cat. #10-195B. 5.20 Vacuum system trap - LC-11025-102 - S c i e n t i f i c Glass c o . , Vineland, N.J. 6. REAGENTS AND MATERIALS 6.1 BF,/Methanol - P e s tic id e grade in glass ampoules - Supelco Cat. No. 3-3041. 6.2 Methanol - F is h e r Cat. #A-936. 6.3 Hexane - Fisher Cat. #>1-301. 6.4 Dry Ice - Richmond Dry Ice Company. 6.5 Acetone - Fisher Cat. #A-17-5. 7. PRECAUTIONS 7.1 BFj/Methanol - Wear le a t h e r gloves when i n i t i a l l y breaking the glass ampoule. Wear rubber gloves when pouring or p ip e tin g . 7.2 Wear rubber gloves when handling methanol or hexane. Keep away from f 1 ame. 7.3 Wear le a t h e r gloves when handling v i a l s or h eater and sand bath. 000102 SPR000329 EID714241 METHOD TM-0405-82T DATE 3/16/82 PAGE 4 OF 10 7.4 Wear le a th e r gloves when handling dry ic e . 7.5 Blood. Rubber gloves must be worn when handling blood. When finished with blood, heat with concentrated bleach in a hot oven at ~ 90C for one hour, then flush down drain with water. Use bleach in '10:1 r a t i o over blood. Rinse a ll p i p e t s , beaker and other equipment with bleach. 8. SAMPLING 8.1 In-Air 8.1.1 Place 10 ml DI water in an impinger tube. Set tube in Telematic and set tu rn e r fo r one hour. Flow should be s e t a t 3 1ite r s /m in u te . Set Telematic in area to be sampled. 8.2 Yam 8 .2 .1 No special sampling required. 8.3 8.3.1 Blood Obtain the necessary blood samples from Medical. Store in r e f r ig e r a to r until ready for use. See 7.5 for d isp o sal. 9. CALIBRATION AND STANDARDIZATION 9.1 FC-143 Standards 9.1.1 Weigh 0.1000 g of FC-143 in to a 100 ml volumetric f la s k . Make to volume with methanol. This i s the 1000 ppm standard. 9.1.2 Take 1 ml o f 9 .1 .1 and d i lu t e to 50 ml with methanol. This i s the 50 ppm standard. 9.1.3 Take 5 ml o f 9 .1 .2 and d i lu t e to 10 w ith methanol. TMs-i-s the 25-ppra standard. 9.1.4 Take 1 ml o f 9.1 .1 and d ilu te to 1000 ml with methanol. This i s the 10 ppm standard. 9.1.5 Take 5 ml o f 9 .1 .4 and d ilu te to 10 ml with methanol. This i s the 5 ppm standard. 9.1.6 Take 1 ml o f 9 .1 .4 and d ilu te to 10 ml with meethanol. This 1s the 1 ppm standard. 9.1.7 Take 1 ml o f 9 .1 .5 and d i lu t e to 10 ml with methanol. This is the 0.5 ppm standard. 9.1.8 Take 1 ml o f 9 .1 .6 and d ilu te to 10 ml with methanol. This is the 0.1 ppm standard. 000103 SPR000330 EID714242 METHOD TM-Q405-82T DATE 3 /1 6 /8 2 PAGE 5 OF 10 10. PROCEDURE {References Attachment I, GC Conditions and Attachment I I , Lyophilizer Operation) 10 .1 Yarn - S intered and 1ST. 10. 1.1 For sintered yarn, weigh 0.5 g to 0.0001 and put into a glass v ia l. Add 1 ml methanol. For 1ST yarn, weigh 0.05 g yarn to 0.0001 g, add to a glass vial and add 1 ml methanol. 10. 1.2 Add 1 ml BF-j/Methanol. Heat in sand bath for 15-20 minutes a t sand temperature of 65-70C. 10.1.3 Remove from bath and allow to cool. Then add 1 ml DI hexane. Then shake f o r 30 seconds. and 1 ml 10.1.4 Allow la y e rs to separate and shoot sample on GC (See Attachment I ) . FC-143 peak RT i s ~2.9 minutes. 10.1.5 Shoot standards (9.1) th a t bracket the expected sample lev el. Sintered - 0.5, 1.0, 5.0-ppm 1ST - 10, 25, 50 ppm 10. 1.6 See 11.1 for c a lc u la t io n . 10.2 In-Air Samples 10. 2.1 Pipet one ml of the water from the impinger tube into a c le a n , glass v i a l . C arefully place i t in a Freeze Dry Flask, put on th e rubber top and hook i t to the L yophilizer (Attachment 11). Leave on the Lyophilizer until all the water is gone (~2-3 h r s .) . 10. 2.2 Remove the vial from the flask and add one ml o f BF^/Methanol by pipet. Put a Teflon gasket in the vial top, screw i t t i g h t and place in the sand bath for 15-20 minutes a t 65-70C. 10.2.3 Remove from the bath and allow to cool. Then add 1 ml DI HjO and 1 ml Hexane. Then shake for 30 seconds. 10.2.4 Allow the lay e rs to separate and shoot the hexane lay e r on th e GC. (See Attachment I ) . 10.2.5 Shoot the standards t h a t bracket the sample ( 0 .1 , 0 .5 , 1.0 ppm). 10. 2.6 See 11.2 fo r c a lc u la t io n . 10.3 Water 10.3.1 P ipet 1 ml of water into a clean, g la s s v i a l . Then follow 10.2.1 10.2.5. 000104 SPR000331 EID714243 METHOD TM-0405-82T DATE 3 /1 6 /8 2 PAGE 6 OF 10 10.4 Blood (See 7.5 fo r handling) 10.4.1 P ipet 1 ml of blood into a c le a n , g la s s v i a l , freeze dry and run as in 10.2.1 - 10.2.5. U . CALCULATION 11.1 Yarn A FC-143 ppm * i x C H A = Sample GC peak area B = Standard GC peak area C = Standard con c en tra tio n , ppm D = Weight o f sample 11.2 A ir, Water, Blood FC-143 ppm a x c A * Sample GC peak area B * Standard GC peak area C Standard c o ncentration, ppm 12. PRECISION AND ACCURACY 12.1 Precision is - 10%. 13. REFERENCE 13.1 PPD Analytical Method - Determination of Cfi F Iu o ro s u rfa c ta n t in Water GC, S. S. S ta ffo rd . 14. KEY WORD INDEX 14.1 FC-143 - in yarn, w ater, a i r and blood. 14.2 GC a n a ly s i s . 000105 SPR000332 EID714244 METHOD TM-0405-82T DATE 3/16/82 PAGE 7 OF 10 C a r rie r Gas Injection Temperature Oven Temperature Detector Temperature Sample Size Col umn Packing ATTACHMENT I HP 5880 GC CONDITIONS Argon/Methane 95/5 20 ml/minute 180C 100 C 300 C 2 M1 6 ' Glass 1/8" OD 0V-202 on 100/120 Supelcoport GC Terminal Conditions _-- - Run time - 0.1 minutes Tan Skim. - A ttenuation 26 ( a d j u s t as necessary for peak siz e ) 000106 SPR000333 EID714245 METHOD TM-0405-82T DATE 3/1 6/8 2 PAGE 8 OF 10 FREEZE DRYING SANPLES Equipment Setup 1. Put ~ 500 ml of acetone in the l y o p h il iz e r tank. 2. Carefully add enough dry ice to keep i t as a s o lid . Replace l i d . 3. Add " 50 ml acetone to vacuum trap Dewar. Set the vacuum trap in the Dewar and add dry ice to pack around i t . 4. Hook up heavy wall rubber tubing from the l y o p h iliz e r 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 v i a l s and dip them in the ly o p h iliz e r dry ice/acetone m ixture. Keep than imnersed long enough fo r complete fre e z in g . 2. Place the frozen v ia ls in one of the freeze dry f la s k s . Put a f i t l e r in the top of the rubber top, place on the flask and connect to the l y o p h iliz e r with the metal neck. 3. Open the connection to vacuum. Only those ports being used can be open to vacuim. All o th ers must be on vent. 4. Cut on the pump, open the manometer conenctions. Yacuum must be ~ 0.1 mm. 5. After fre e z in g , shut o f f manometer, c a re f u lly open sample ly o p il iz e r p o rt and cut off port. 000107 SPR000334 EID714246 FIGURE 1 - APPARATUS FOR FREEZE-DRYING SAMPLES >C (b ) Vacuum P o r t , D ry in g F la s k , and Sam ples 04 V alv e (vacuum o r -vent) Vacuum (D ry in g Cham ber) W >0 o 2-Dram V ia ls , o o tie s u e over top w to in F ro z e n Sam ple ( l mL a l i q u o t ) PAGE 9 OF 10 E ID 714247 TEST METHOD APPROVAL "Teflon - FC-143 Analysis" TN-Q405-82T METHOD TM-0405-82T OATE 3/1 6/8 2 PAGE 10 OF 10 S. S. Shelburne Author S i te Authorized By For (Organization) Spruance Site Date Spruance Spruance Spruance ATM001.7 _____________ Supervisor Process Control Development Process Control Development Process Control Lab 3 / 3 / A 2- " V * 11 o o o io y SPR000336 EID714248 - 7- ABSTRACT The FC-143 (ammonium perfluoro octanoate) s u rf a c ta n t used in the Teflon polymerization process was a suspected tera to g e n . Methods were deve loped, and i t s level measured in a i r , w ater, blood and yarn. In a i r , water and blood le v e ls were well below TLV's. None was p rese n t on sin tered y a m , but 1ST ya rn , which i s coated with d is p e r s io n , has 200-700 gpm le v e l s . I t was shown th a t FC-143 dicarboxylates when heated to 200C giving o f f COg and perfluoroseptamonohydride. INDEXING SUBJECTS 1. Measurement of perfluorooctanoic acid (FC-143) 1n a i r , w ater, ya rn . 2. Ammonium perfluorooctanoate dicarboxylation o f. 3. Sodium perfluorooctanoate d icarboxylation o f . f o o o iio SPR000337 EID714249 COPY NO. 1 2 3 4 5 6 7 &8 9 & 10 11 & 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 i s , J r . - M. T. Waroblak PCD F ile G. L. Watts - J . H. Fischer J . L. McDaniel E. S. Brinton - E. K. Koffenberger - _ PCD .File D. G. O'Dell J . P. Yuk - PCD F ile Research Library Central Report Index Patent Liaison File S. S. Shelburne, M. A. F o rte , A. M. Mokhtar - PCD Fi l e DSS001.27 LOCATION Sprnance Spruance Spruance Nentours-Wllmi ngton Nemours-Wi lmington Sprtfance Spruance Centre Road Centre Road Spruance O O O lli SPR000338 EID714250