Document DMONN0ZKQQe9Ok0qvymdavLoo

AR226-3330 Copy No. Distribution - Last Page IHIFC-143 IN THE] ROCESS M. A. Forte period: July, 1978 - March, 1979 Reference: Notebook No. SA-- 154 Previous Related Reports: None Textile Fibers Department Spruance Research Analytical Research Group E . I . DuPont de Nemours & C o ., Inc. Richmond, Virginia The individual to whom this material is issued is responsible for the security of the information. For those on the distribution list at other locations, responsibility of the document will automa t i c a l ^ transfer to their successors. If there is no further use of the document, return to the above address. Do not leave exposed and unattended. Company Sanitized. Does notconta/n TSCA CBI ' RECEIVED ' m m :ui 010 INTRODUCTION Based on information supplied by the 3M Company^, DuPont became aware that elevated organic fluoride levels were detected in the blood of 3M work rs exposed to certain fluorinated surfactants. Entry of the surfactant was felt to be related to e x p o s u r e airfefirne dust. A fluorinated surfactant is employed at Spruance in t h e g B B f j p r o c e s s . It is a component o dispersion which is purchased ??om P P ^ f Department. Based on ^ - 1 4 3 phy sical properties, the possibility existed for worker exposure at Spruance. Therefore, this study was undertaken to determine the extent of exposure, if any, and the ultimate fate of FC-143 in our process due to potential customer or environmental impact. OBJECTIVES To determine the fate of FC-143 in' t h e g ^ ^ W J p r o c e s s . Establish the extent, if any, of worker exposure to FC-143. To d e v e l o p s accurate analysis for FC-143 in air, water an d V H IH p i^o d u ct/in g red ien ts. SUMMARY AND CONCLUSIONS y_]_43 was not detected in operator breathing zones. Limit ttion was 50 ppb based on sample volume. Therefore, use of FC-143 in isper- sion is felt to lead to low, if any, airborne exposure of FC-143 was found to be 0.43 ppm in process wash water and less than 0.5 ppb in stack gas based on level in condensate. Therefore, the environmental impact is considered small with prese t production levels. It appears that 80-90/ of FC-143 is tightly bound i n H P * W ^ i n g polymerization at PP&R. FC-l^J was dejected at low levels in""lw Product, but was not detected in other products. FC-143 was measured by Gas Chromatography of the methyl ester with an elec tron capture detector. Esters of ether extracts were prepared with methanol/ BF-i rather than with diazomethane as recommended by 3M. ' Air samples were taken, as recommended by 3M, by scrubbing with methanol. Aqueous samples were ex tracted with ether and y a m samples were extracted with methanol. PATENT ACTION No patent action based on this work is planned at present. PUBLICATIONS There are currently no plans to publish any of this work. Company Sanitized. Does not contain TSCA CBI CODE LISTING FC-143: Ammonium perfluoro octanoate. Approved by: Prepared by: tyf, Jt<nZL M. A. Force Senior Chemist Research Supervisor Company Sanitized. Does not contain TSCA CBI TABLE OF CONTENTS I. rocess Measurements a . Background b. Fate of FC-143 in the Manufacture o II. Environmental Measurements a. Air Sampling in Spinning and Winding b. Process Effluents III. Method Development a. Background b. G. C. Analysis c. Preparation of Esters IV. Appendix I a. Analysis of FC-143 in Air b. Analysis of FC-143 in Ether or Methanol Extracts Appendix II - 3M Procedure for FC-143 Analysis in Air Appendix III - & [Off Gas Analysis . Page 1 1 4 5 5 5 7 10 15 19 23 not contain TSC A CBI Company SanlHamt. D063 & * j [PROCESS MEASUREMENTS Background [ ^ ^ ^ W M p o lapidai dispersion is mixed with viscose in the manu f a c t u r e of H f i b e r . The viscose is r e g e n e r ^ e d i r ^ n acid bath in s p ^ i ^ ^ a n d acts as a matrix to bind t h e ^ H f l i ^ H p a r t i d e s prior to sintering. Surfactants such as FC-I?^an<^Triton X-100 are added to the c o l l o i d a l ^ B B B | ^ J i i s p e r s i o n to prevent agglomeration of the particles. b. Fate of FC-143 in the Manufacture of FC-143 is added to dispersion at the 2200 ppm level by PP&R in polymerization. During polymerization most of ^ i s a n n a r e n t l y irreversibly absorbed on or incorporated in t h e B H H H p a r t i c l e s . This hypothesis is based on measurements of F C - M j in raw dispersion and on supernatant liquid from the PP&R polymerization. In order to understand the h y pothesises brief description of the polymeri zation is necessary. I f l ^ l H p o n o m e r (35%) is polymerized in water ('Vi 65%) in the p r e s e n c e o f FCL143 and other surfactants. The solids are increased to ^ 60% by decanting water off. If no other physical phenomenon were involved, one would expect t o f i n ^ 2 2 0 0 ppm FC-143 in the water associated with the r e m a i n i n g l B H I H ^ i s p e r s i o n and in the decantation water. This is not the case as can be seen from the data in Table I. TABLE I 6 Sample LEVEL OF FC-143 IN DISPERSION PROCESS SAMPLES FROM PP&R Cone, ppm Supernatant Liquid 220 Raw Dispersion - 35% Solids 100 Concentrated Dispersion 120 There |s additional supportive information for the absorption hypo thesis . Analysis of other surfactants used in polymerization at Parkersburg had given low recoveries. Attempts at analysis of FC-143 i n H H U I R p r o c e s s and yarn samples do not lead to a materials b a l a n c e b a s e d on amount added at PP&R. A schematic r e p r ^ e n t a ^ t o n of the process is given in Figure 1 to show the path o f B p H H M d i s p e r s i o n . The pertinent sample results are given in Table II. Company Sanitized. Does not contain TSCA CBI - 2- f *I . b. PROCESS MEASUREMENTS (Cont 'd ) Fate of FC-143 in the Manufacture o TABLE II FC-143 IN1 PROCESS Yarn Samples After Wash Reel Dried Yarn Sintered Yarn Cone, ppm 1.2 0.3 Not Detectable Aqueous Samples Regeneration Bath Wash Reel Water Not Detectable 0.43 FIGURE I YARN PROCESS Viscose 1 part Spinning 9 parts Dispersion 300 ppm FC 143 i^SO^ 6% ZnS04 Regeneration Bath Cpmpany Sanitized. Does not contain TSCA CBt Drying Sintering - 3- I. ROCESS MEASUREMENTS (Cont'd) Fate of FC-143 in the Manufacture of Based on the ratio of wash water to yarn, the level of 0.43 ppm is equivalent to ^ 70 ppm in yarn. Therefore, the majority of FC-143 must remain with yarn. Based on colloid c ^ g m i s t ^ ^ the FC-- 143 molecule would orient at the surface of t h ^ H m ^ H p a r t i c l e . pH of dispersion is adjusted with NaOH which conVferts the ammonium salt to the sodxum salt. The sodium salt would be converted to a carboxylic acid g r o u ^ i n the Regeneration Bath. The carboxylic acid would undoubtedly be decom posed in Sintering. Dispersion is also used to coat l ^ ^ ^ ^ l ^ H y a r n for pump packing end use. As can be seen from F i g u r e z ^ d ^ p e r s i o n is added to bleached yarn and dried in a dielectric oven. Thermogravimetric measurements made on FC-143 indicate it begins to volatilize at 120C. There was ome likelihood for FC-143 to volatilize in the oven. As can be seen from the data in Table III, this occurs on only a slight degree, probably due to its conversion to the sodium salt at pH adjustment- FIGURE 2 "I" YARN PROCESS Vent Dispersion Company Sanitized. Does not contain TSCA CBI Sr--NI*PROCESS MEASUREMENTS (Cont'd) b. Fate of FC-143 in the Manufacture o (Cont'd) TABLE III FC-143 IN INDUCTION DRYER SAMPLES Sample Cone,pom Coated Yarn Before Dryer 5 Coated Yarn After Dryer 5 Vent ResIdue 8 Fowder on Dryer Floor 117 Calculated on the basis of dispersion on the coated yarn, the level of FC-143 is v 10 ppm. This compares with 200 to 300 ppm on aqueous dispersion. Y a m s were extracted with methanol in which FC-143 is very soluble. Apparently, FC-143 became "locked" in dried disper sion. IT ENVIRONMENTAL MEASUREMENTS ^ S i n c e ^ t is difficult to prove the hypothesis of FC-143 entrapment in materials balance cannot be obtained. Since FC-143 acid ^ s v o l f f i l e it process temperatures, the possibility existed for FC-143 entry into the air. The possibility was considered low, however, since studies^ conducted in the past on the degradation products from sintering have not revealed the presence of any f' orinated hydrocarbons. a. Air Sampling in Spinning and Winding H B B B j y a r n is heated to remove cellulose in a sintering operation. *To ensure no exposure was taking place, air samples were taken in operator breathing zones. The results of this study given in Table show that operator exposure is very unlikely. The level of 50 ppb l b a s e d on detection limits of FC-143 and /olume of air sampled. Air samples were also taken at the dryer exit and above the dryer in the "I" process. These too showed less than 50 ppb FC-143. This is in part due to FC-143 conversion to the sodium salt. TABLE IV AIR SAMPLES TAKEN IN SM-3 AREA Location(1) Roll 2 . Approximate Temperature F 250 Level of FC-143 PF3 < 50 Company Sanitized. Does not contain TSCA CBI II. ENVIROiSMENTAL MEASUREMENTS (Cont'd) a. Air Sampling in Spinning and Winding (Cont'd) During a visit^ and examination of the "I" production facility, J. M. Morgan of Haskell Laboratory noticed that some of the equipment had a small amount of white dust on it. Since the material might conceivably have contained FC-143 from mechani cal introduction into the air, dust samples were taken and tested for FC-143 level. The dust sample testing showed that there was less than 1.5 x H T 10 FC-143 g/liter of air based on the detection limits. b . Process Effluents There are two process effluents which could contain FC-143. As was mentioned earlier, wash reel water was found to contain 0.43 ppm FC-143. This would eventually wind up in the James River. The other effluent which could contain FC-143 is oven exhaust. Measurements made on the condensate showed FC-143 level to be less than the detection limit of 0.5 ppb V/V. IJi. METHOD DEVELOPMENT a. Background The procedure for analysis of FC-143 in air (in Appendix II) was supplied by 3M. Their procedure was based on methyl ester pre paration with etheral diazomethane followed by gas chromatography and electron capture detection. We ultimately found their G.C. conditions and trapping method to be useful. Their ester prepara tion method was considered unsafe due to literature accounts of spontaneous explosions of highly toxic diazomethane. The literature5 indicated that methyl esters axe easily formed by two minute reaction in methanol/BF3. This reagent is available commercially from Supelco, Inc. b . G.C. Analysis A quantity of the methyl ester of FC--143 was prepared by refluxing - one gram of the material in 100 ml. of methanol to which 5 ml. of concentrated HC1 had been added. Upon addition of water, the ester separated as a heavy oily liquid. The ester product was confirmed by IR analysis as shown in Figure III. This material was employed as a standard to evaluate G.C. columns, for retention time measure ments, for detector linearity determination, and for partitioning studies. The retention time of the methyl ester was given as 11.1 minutes on the 20% DC-20, 10% Bentone 34 on Anakrom ABS column recommended by 3M. Company Sanitized. Does not contain TSCA CBI Company Sanitized. Does not contain TSCA CBI -7- III. fiLTHOD DEVELOPMENT (Cont'd) b- G.C. Analysis (Cont'd) Through suitable adjustments of initial temperature and tem p rature program, retention time on the 20% DC-2C, 10% Bentone 34 was reduced to % 7.0 minutes. Due to its high liquid S S L * ^ u n T t h a t h ^ r id? " d dlfficult Pack in a glass c o W ? * ^us tto^opaaickk a 10 glass col"uamtn.rial and -USing a vibratr enabled The electron capture detector is linear in response over only a sieiil L rah f i T Ct3in concentration no additional f o S d \ n bt if \ f detector on the Hewlett Packard GC was f s S i It-b 1 i rang f 600 t0 31>000 PPb of FC-143 ? h r - A pl0t of lntegrator counts vs. concentration flitlollowing conditions: ^ linearity study was made under the Carrier gas - Argon/methane - 95/5 Injection port - 150C Detector temperature - 250C Column SP 1000 - 10' glass Column temperature - 80C for 4 min Pulse interval - 150 then prog, at 8C/min to 180C Response is also a function of detector temperature. It was found that at 250C there was little change in response with temperature. c Preparation of Esters Pesticide grade methanol/BF3 was employed to prepare the FC-143 esteThe recommended procedure was to react the acid with mechanol/BF, and then add water to stop the reaction. Normally aliphatic acid esters could then be extracted with Freon or some other chlorinated solvent. Of course, in this case, a chlorinated solvent would flood the electron capture detector. Ether was found to be partially soluble m the water-methanol/ester mixture so a. good separation could not be obtained. It was found that a mixture of 80/20 cyclohexane/ether separated well if saturated KC1 was employed instead of water. A partitioning experiment showed that.the FC-143 methyl ester went completely to the ether cyclohexane phase. With these reaction conditions, 5 ppm of FC-143 could be detected _n the extracts. Solid samples were extracted with methanol. Liquid samples were acidified with HC1 if the FC-143 was- present as the ammonium salt. Ether or methanol extracts were evaporated almost to dryness in j 70-80C water bath with a stream of N? before re action with methanol/BF3 . ' Company Sanitized. Does not contain TSCA CB1 PPb FC 143 Methyl Ester Company Sanitized. Does not contain TSGA CBI - 9- REFERENCES 1. Rogers, L. B. - "Fluoro Surfactants in Blood", Employee Information Bulletin, July 12, 1978. 2. Hall, Linda - Parkersburg Analytical Research, Telephone Conversation, February 21, 1979. 3. Sarasohn, I. M. 23, 1975, Appendil^II. * f-Gas Analysis", Letter to Author, June 4. Morgan, J. M. - Visit to| Manufacturing Facility, March 20, 1979. 5. Metcalfe, T. D. and Schmitz, A. A. - Analytical Chemistry, Volume 33, No. 3, March, 1961, pages 363-364. Company Sanitized. Does not contain TSCA CBI D PONT DE NEMOURS AND COMPANY Incorporated Textil-' Fibers Department Industrial Fibers Division .SPRUANCE 10 Appendix la Section Method Page 1 PROCESS CONTROL - OPERATING PROCEDURE PLANT: SUBJECT: SPRUANCE FIBERS RICHMOND, VIRGINIA ANALYSIS OF FC-143 IN AIR CHANGES: NEW METHOD APPROVED BY: Prepared By:________________________ M. A. Forte I. INTRODUCTION FC-143 is absorbed in methanol in a Telmatic air sampler. Methanol is evaporated off and the methyl ester is prepared through reaction with methanol/BF3 . The ester is measured by GC with an electron capture detector. Detection limit is 0.05 ppm v/v based on a 40 liter air sample. ` CAUTION: The physiological properties of FC-143 methyl esters are unknown - handle with care to avoid exposure. II. REAGENTS AND EQUIPMENT A. Gas chromatograph equipped with an electron capture detector (Hewlett Packard 7620A with 3385A integrator)., B. Telmatic air sampler - Taylor Parker Co., Norfolk, Virginia, Cat. No. 158. C. Batteries, nickel-cadmium, 8.4 volts - Taylor Parker Co., Cat. No. 64TA. D. Methanol/BF3 , pesticide grade in glass ampoules - Supelco, Cat. No, 3-3041. Company Sanitized. Does not contain TSCA CBI - 11 - Section Appendix la Method Page OPERATING INSTRUCTIONS SAFETY INSTRUCTIONS II. REAGENTS AND EQUIPMENT (Cont'd) F. Chromatography Column 10' glass acked with: DC-200 20%, Bentone 34 10% on 1C0/120 mesh Anakrom ABS Supelco. G. FC-143 Methyl Ester Standard .1 Weigh 1.0 g. of FC-143 into a round bottom flask. Add 100 ml of dry methanol, 5 ml of concentrated HC1 and a few boiling beads. Perform these operations in a hood. 2. Connect flask to a reflux condenser and gently reflux .for two hours. 3. Cool the flask to room tem perature, then pour the con tents into a 500 ml. separ ating funnel which contains 300 ml. of DI water. 4. Stopper and shake. Allow the phases to separate. FC143 methyl ester separates as an oily liquid. 5. Drain this liquid into a serum stoppered vial. H. GC Standard .1 Fill a 10 ul syringe with 3 pi of FC-143 methyl ester. Weigh the syringe and its contents on a micro balance to 0.000001 g. . 2. Add 5 ml. of ether/cyclohexant 20/80 to a 10 ml volumetric flask. Inject 1.0 pi of FC143 methyl ester into ether/ hexane. 3. Reweigh syringe to 0.000001 g. Dilute to the mark with ether/ cyclohexane and label Solu tion '`A". Make a 1:10 dilu- Company Sanitized. Does not contain TSCA C B I | J V M yiyilijf Section Method IPP Appendix Za Page III. PROCEDURE OPERATING INSTRUCTIONS SAFETY INSTRUCTIONS A. Air Sampling 1. Add 15 ^ 0.2 ml. of methanol made basic to methyl red with 0.1N nethanolic KOH to a 25 ml. impinger tube. 2. Connect to Telmatic air pump with gum rubber tubing. ,J Set sampling rate at 2.0 liters per minute. 4. When ready to sample, turn air pump on and set timer to 20 minutes. 5. After sample has been taken, remove impinger and transfer contents with methanol rinse to a 150 ml. beaker. B. Sample Preparation 1. Evaporate the beaker contents almost Perform sample preparation steps to dryness on a steam bath. in a hood. 2. Transfer the beaker contents with methanol 10% concentrated HC1 rinsings to a 15 ml, tapered centri fuge tube. The tube contents should be acid to methyl red, add methanol 10% HC1 dropwise. Place the tube in a 70 - 5C water bath and evaporate the tube contents to about 1/2 ml. with a stream of N. - .. 3. Remove tube from bath, dry and add 1 ml. of methanol/BF3 from a freshly opened glass ampoule. 4. Stopper the centrifuge tube and put it back in 70 i 5C water bath. 5. Remove the tube after 2 * 0.1 minutes and quickly unstopper it. Cool to room temperature or slightly below. 6. Add 2 ml. of ether cyclohexane fol- Company Sanitized. Does not contain TSCA CBI III. PROCEDURE OPERATING INSTRUCTIONS B. Sample Preparation (Cont'd) 7. Allow the layers to separate until a clearly defined top layer of ether/cyclohexane appears or cen trifuge speed the separation. Prepare 15 ml. of an external stan dard containing 50 ppm of FC-143 in methanol the same way. C. Gas Chromatographic Analysis Column glass 2 mm i.d. x 10' packed with DC-200 20%; Bentone 34 10% on 100/120 mesh Anakrom ABS. Rejection port temperature - 150C. Argon/methane 95/5 flow race: 30 ml/min. Detector Settings: Pulse Interval Temperature Range Oven temperature 150 250C 103 Isothermal Program Integrator 3385A Attenuation Slope Sensativity 100C 4 min. 8C/min to 180C 26 0.50 . 4 min. reset baseline at all valleys NOTE: If air (oxygen) has entered the EC detector, it must be conditioned for two days at 100C with column installed and 15-20 nrl. of argon/methane flowing. Company Sanitized. Does not contain TSCA CBI - 14 - III. PROCEDURE OPERATING INSTRUCTIONS D. Sample Analysis 1. Inject a 2 pi sample of Standard "B"1 to check response and retention time. The FC-143 methyl ester should come out between 7 and 8 minutes. 2. Inject a 2 pi sample of external standard. 3. Record area counts for external standard. 4. Inject a 2 pil sample of prepared air sample. 5. Record area counts for air sample. IV. CALCULATIONS Let A = Sample peak area B = External standard peak area C = ppm v/v in external standard = 1.0 V = Volume of air sampled * 40 liters ppm FC-143 v/v = A Bx 0 Section Appendix la Method Page SAFETY INSTRUCTIONS =A B Example: A = < 3483 B - 69660 ppm < 3483 69660 pm a < 0.05 Company Sanitized. Does not contain TSCA CBI RIPB!S . I. D PONT DE NEMOURS AND COMPANY Incorporated Textil" Fibers Department - 15 Section Appendix lb Method Page 1 SPRUANCE _____ PROCESS CONTROL - OPERATING PROCEDURE PLANT: SUBJECT: SPRUANCE FIBERS RICHMOND, VIRGINIA ANALYSIS OF FC-143 IN ETHER OR METHANOL EXTRACT CHANGES: NEW METHOD APPROVED BY: Prepared By: M. a . Forte I. INTRODUCTION Liquid samples are acidified with 6N HC1 followed by extraction with ether. Solid samples are extracted with methanol. Extracts are evaporated almost to dryness and the residue is reacted with methanol/BF3 to generate methyl esters. The level of FC-143 methyl ester is measured by G.C. with an elec tron capture detector. CAUTION: The physiological properties of FC-143 methyl esters are unknown handle with care to avoid exposure. II. REAGENTS AND EQUIPMENT A. Gas chromatograph equipped with an electron capture detector - Hewlett Packard 7620A with 3385A integrator. B. Methanol/BFj, pesticide grade in glass ampoules- Supelco, Cat. No. 3-3041. C. Vials, glass stoppered, tapered 15 ml. - Fisher Scientific. D. Chromatography Column - 10' glass packed with: DC-200 20%, Bentone 34 10% on 100/120 mesh anakrom ABS - Supelco. r.E. FC-143 methyl ester standard - Prenare as in Ann^miiv 1= tt Company Sanitized. Does not contain TSCA CBI III. PROCEDURE m |i-5|Rp^PP^^^ Section Appendix Ib Method Page SAFETY INSTRUCTIONS_______. ___ A. Sample Preparation Dispersion 1. Pipet 1/2 ml. of dispersion into a 15 ml. tapered vial. 2. Pipet 1/2 ml. of 6N HC1 into the vial and mix. 3. Pipet 3 mis. of ether iuto the vial, stopper and shake well. 4. Add 10 ml. of saturated KC1 solu tion and shake well. 5. When the ether layer has separated, remove one ml. with a disposable pipet and put it into a graduated vial. 6. Place the vial in a 70C - 5C water bath and evaporate almost to dryness with a gentle stream of nitrogen. 7. Remove the vial from the bath and cool to room temperature. 8. Pipet 1 ml. of methanol/BF3 into the vial and stopper. 9. Put the vial in the 70C bath and react for 2.0 ^ 0.1 min. 10. Remove the vial from the bath and loosen the stopper slightly to orec a vacuum. 11. When the vial has cooled to room temperature a<td 2.0 ml. of 80/20 cyclohexane/ether and swirl to mix. 12. Add 9 ml. of saturated KC1,stopper and shake well. Company Sanitized. Does not contain TSC A CBI _ 17 - III. PROCEDURE OPERATING INSTRUCTIONS A. Sample Preparation (Cont'd) Solid Sample Methanol Extract 1. Add one drop of 30% NaOH to 200 ml. of extract to insure basic condition. 2. Evaporate almost to dryness on a steam bath. 3. Cool and add two drops of concen trated HC1. 4. Transfer the extract to a 15 ml. tapered vial with two 1/2 ml. wash ings of dry methanol. 5. Evaporate to 0.25 ml. with a stream of Nitrogen. 6. Pipet 1 ml. of methanol/BF3 into the vial and stopper. 7. Follow Steps 9-13 of dispersion preparation. 8. Prepare 15 ml. of an external stan dard containing 50 ppm of FC-143 in methanol the same way. B. G. C. Analysis . Follow Steps III C and D, Appendix la fo:1 G.C. checkout and sample analysis. IV. CALCULATIONS Let A Sample peak area ^ B = External standard peak area V = Volume of Teflon dispersion ml. W * Weight of solid sample grams. Section Appendix lb Method Page SAFETY INST' Company Sanitized. Does not contain TSCA CBI PROCEDURE OPERATING i n s t r u c t i o n s XV. CALCULATIONS (Cont'd) Dispersion ppm FC-I43 = 3 x A x S x M Weight/Volume VxB Solid ppm FC->143 Weight/weight -A x SxM BxW Example: A = 10,000 counts B = 15,000 counts S = 50 ppm M = ml. of external standard 3 = Volumetric factor Dispersion ppm FC-143 = 3 x A x S x M Weight/Volume VxB Solid ppm FC--143 = A x S K M Weight/Weight BxW Example: A = 10,000 counts B = 15,000 counts S = 50 ppm M = 15 ml. W = 5.0 g. ' Solid ppm = 10,000 x 50 x 15 * 100 15,000 x 5.0 Method Page SAFETY INSTRUCTIONS Comply SanWted-Doesno*contataTSCACBI Appendix II Interuflice Correspondence MCK!gII3gsro^ ._ . ^ ^ .t^ aSE^ ~ g?tM>g gjS g a Routing copy: .J. W. F euk - Med. - 2 2 0 - 2 E J. A. P e n d e r g r a s s - Med. - 220-2F. F. A. Ubel, M.D. - Med. - 220- 2 E Subject. J u n e 23, 1978 TO: R. A. P R O K O P - C O M M E R C I A L C H E M I C A L - 2 3 6 - 3 B FROM: D. F. H A G E N - C E N T R A L R E S E A R C H - 2 0 1 - l W S. D. S O R E N S O N - (3-7058) - M E D I C A L - IND. HYG. SERV. - 220-2E Attached is the sampling and analytical procedure for FC-143 as per your request. Please call if there are any questions. A 4DFH/SDS /mm ' Company Sanitized. Does not contain TSCA CBI Mr. R. A. P r o k o p June 23, 197 FC-143 Sampling Procedure I. F i l t e r M e t h o d : A. E q u i p m e n t 1. B a t t e r y o p e r a t e d p u m p c a p a b l e o f d r a w i n g 2 - 2 . 5 1pm t h r o u g h filter. Examples: M S A Model S, o r Bendix Super Sampler. ` 2. T h r e e p i e ce cas s e t t e filter holder. 3. N u c l e a r P o r e ^ 0 . 8 urn pdtfe size f i l t e r m e d i a . B. P r e p a r a t i o n . 1. P u m p f l o w r a t e should be c a l i b r a t e d u s i n g b u b b l e meter, wet test meter or similar method using standard industrial hygiene calibration techniques. 2. A s s e m b l e c a s s e t t e s u s i n g f i l t e r s u p p o r t o r s c r e e n u n d e r filter. It is desirable to wrap the cassette with vinyl tape (electrical tape). C. Procedure 1. R e m o v e c o l o r e d plugs f rom b o t h e n d s o f f i l t e r h o l d e r cassette. Attach cassette to end of sampling hose so that a i r flow is in right direction, e.g. filter support, or backup screen must be on pump side of filter. 2. I f a b r e a t h i n g zone or p e r s o n a l s a m p l e is de s i r e d , attach the cassette assembly to e mployees' lapel so that the inlet orifice is in a downward position. 3. T h e p u m p can b e a t t a c h e d to the e m p l o y e e s ' belt, generally in the back. . 4 . Turn on pump - record time. 5. C h e c k to see that the p u m p is at the d e s i r e d fl ow- ! rate. RechecX periodically. 6. R e c o r d time at end of s a m p l e per i o d . 7. R e p l a c e c o l o r e d plugs in e n d s o f c a s s e t t e . II. I mpinger Me t h o d , Alte r n a t e Method A. E q u ipment '. 1. B a t t e r y o p e r a t e d p u mps as d e s c r i b e d above. 2. A l l g l a s s m i d g e t impinger. - M e t h a n o l . G.C. grade p r e f e r a b l e , r e a g e n t g r a d e can be used. 4. T r a n S D O r t v i a l s - n l a e c 4-V> 1.--J ----- Company Sanitized. Does not contain TS C A C BI Mr. R. A. P r o k o p - 21 - J u n e 23, 1978 B. P r e p a r a t i o n 1. F l o w r a t e should be calibrated. 2. F i l l i m p i n g e r w i t h 15 m l me t h a n o l . C. Pro c e d u r e 1. S a m p l e at 2.0 liters per minute for 20 m i n u t e s Slower rate may be used for longer periods; at least 40 liters of air should be sampled. .2 Hand hold impinger in e m p l o y e e s b r e a t h i n g zone. <$> 3. At end of sample period, the impinger and s tem should be rinsed with methanol. The rinse should be added to the sample for analysis. 4. T r a n s p o r t vials should be tightly capped a nd sealed with tape. Analysis Procedures Trace analysis for FC-143 are performed via gas chromatography after formation of the methyl ester derivative. Dust samples which have been collected on filters are extracted wit#* of 0 1 N HCl. The acid solution is then extracted with J o r t i S U of diethyl ether. The diethyl ^ h e r extrects ere combined in a 10 cc volumetric flask. Two cc of diazomethane reagent* are added and the esterification allowed to proceed at room temperature for 25 minutes. behind safety shields and in efficient hoods. Pre cautions, as outlined by Aldrich Chemical Company, should be taken when using this reagent. Thi= 31 i r 2 L S a n e e asPe;< dt,,cefhyatheYl o ^ & \ 5 y e l I o ,, c o l ^ d The sSlStiln is then brought up to the 10 cc volume prior ?o I n k y s i s . A U q u I t s of this solution are injected into the gas chromatograph using the conditions outlined below. .^ In the alternate method, impingers containing IS cc of methanol 1 1 4- r s n a l s o b e u s e d for air s a m p l i n g a p p l i c a t i o n s . In ..this 501 iwS L i h J n o l in t h e impinger after sampling is t r a n s f e r r e d a 25 ct volumetric flask and diluted to volume. T t o % aliquat is ma d e basic with 1 dryness u n d e r a s t r e a m f t ^ to obtain a pH betwee n in a 10 cc v o l u m e t r i c flask. M t a * Ds notmain I S CM Mr. R. A. P r o k o p - 22 - June 23, 1978 G. C. Conditions C o l u m n : 12' tl/8" O.D. SS) 20% DC-200 + 10% Rentone 34 on 100/110 mesh ABS ,, .e . O v e n P r o g r a m : /0C (4 m i n u t e s ) to 180 C at 5 C / m m . Detector: Electron Capture r HP. 5840 clriier: Argon/Methane (95/5) at 45 cc/nunute Preparation of Diazomethane Reagent 4_. a ,,ohhnri for preparing the d i a z omethana regent is given in the D ? A Z A L D R l i t e r a t u r e f r o m A l d r i c h C h e m i c a l Com p a n y , Inc.; 940 West St. Paul Avenue; Milwaukee, Wisconsin. The Aldiich Chemical Company's procedure for "Preparation of Ethereal-Alcoholic Solution of Draromethane" from D I A Z A L D is detailed below. 1 Preparation of ethereal-alcoholic solutions of diazomethane: * Ethanol (95%, 25 ml) is a dded to a solution of potassium h v d r o x i d e (5 g) i n w a t e r (8 ml) in a 100 ml d i s t i l l i n g flask fitted with dropping funnel and an efficient condenser s e ^ d o w n w a r d for distillation.. The condenser is connected to two receiving flasks in series, the second of which contains 20-30 ml ether. The inlet tube of the seond receiver dips below the surface of the ether, and both receivers are cooled to 0.C. The flask containing the alkali solution is heated in a water bath to 6 5 > a n d a solution of 21.5 g (0.1 inole) of DiazaldR in about 200 ml of ether is added through the dropping funnel in about 25 minutes. The rate of distillation StoSld L o u t equal the rate of addition. When the dropping funnel is empty, another 40 ml of ether xs added ji^wly an the distillation is continued until the distilling ether is colorless. The combined ethereal distillate contains about 3g of diazomethane and must be stored in the freezer com ' partment of a refrigerator (shelf life is about 2 weeks or until weakly yellow). Diazomethane is not only exceedingly toxic, but its solutions have been known to explode quite unaccountably. Hence, ALL WORK WITH DIAZOMETHANE, regardless of hov it is generated, SHOULD BE CARRIED OUT BEHIND SAFETY SHIELD IN EFFICIENT wnno; U s e T E F L O N s l e e v e s on all g r o u n d g l a s s joints. Company Sanitized. Does not contain TSCA CBI R .I2004 REV. S -S - 23 - mm> APPENDIX III K ST U U SM IO Jt U E. I. d u P o n t d e N e m o u r s & C o m p a n y (conroAATCo W i l m i n g t o n , D e l a w a r e 19898 ce: R. G. Parrish J. Trotman File PE-3 TEX TILE FIBERS DEPARTM ENT Pioneering Research Division ' Experimental Station Wilmington, Delaware June 23, 1975 TO: M. A. Forte Spruance Plant Richmond FROM: I. M. Sarasohn OFF-GAS ANALYSIS The purpose of this memorandum is to summarize our data concerning analysis of cff-gases from a sintered Teflon yarn submitted by you to this laboratory a number of weeks ago (M. A. Forte to I. M. Sarasohn, memorandum, May 8, 1975) This pyrolysis experiment was carried out in a hot quartz tube in flowing air. The sample was heated rapidly from room temperature to 305C (.^20-30 min); the temperature was then slowly increased to 315C over a two hour period in a simulation of your process. The resulting effluent was swept into a collection trap at -78C and the stripped air was collected in a Saran gas bag which was sampled at the end of the run and analyzed by mass spectrometry to insure the absence of significant quantities of an untrapped gas; only air and COg were detected in the gas bag. . Condensed liquid from the cold trap was injected into a gas chromatograph for separation prior to mass spectro scopic analysis, G.C. conditions being chosen to emphasize lower molecular weight materials. The effluent from the G.C. .column was split into two streams, one going to the flame ionisation detector (FID) for rough quantitation, the other going directly into the mass spectrometer using suitable oressure-dropping and enriching devices. Concentration levels vrere estimated from FID peak areas using the measured response factor for n-heptane. These levels are reported at the bottom of each table in terms of \Lg n-heptane/jil injected and (ig nheotane for the entire tran a s s u m i n g u n i t fipnsitv fnr -the trn Company Sanitized. Does not contain TSCA CBI l ^ ^ ^ f t r t e ^ ' ' ' " " ' '."vr"""" ^.. _ 24 -..... June 23* 1975 contents. Apparently, the trap and side arm condensate contained at least 90% water, based on these figures. Except for water, CO, COg, and formaldehyde which exhibit no FID response, calculated amounts should be in error by no more than a factor of 5 or 10 depending on the nature of the specific material in question and can be reasonably estimated from published values of FID response factors by consulting the literature. Measured weight gain of the trap is recorded in Table I, but some material condensed in the gas transfer line upstream of the trap (l.e., trap side arm), preventing precise quantitative measure of material evolved by the sample. The condensation collected from the trap side arm was analyzed separately (Table II). This work was charged to 8416-05502-2210-002. IMS:rkc attachments Company Sanitized. Does not contain TSCA CBi - 25 - TABLE I SanpletUMW?' Sample w ^ . : 1.6676g Sanrple Wgt. Los s: 0.093og Trap Wgt. Gain: 0.01592 ^ Temperature: R.T. to 305 (1/2 hr) 305 to 315 (2 hr) Air Flow Rate: 6 ml/mln S t a t i v e Identification rater, CO, C02, Formaldehyde lethanol tcetaldehyde Sthanol Acrolein Acetone \cetic Acid Propionaldehyde 1,3-Dioxolane Methyl Vinyl Ketone? 2-Methyl-l 3-Dioxolane + IiiCTOtonaldehyde or 2,5-Miydrofuran p -Dioxane Methylfuran Furfural Furfural Methyl Ketone 5-Methyl-2-Furaldehyde G.C. Area N.R. 06 .66 .03 .05 .34 .0 2 .01 .04 .05 .24 .25 1.09 .04 3.41 .09 .53 ft (A/Aj .8 9.1 0.5 0.7 4.6 0.3 0.2 0.6 0.7 3.4 3-4 15.0 0.6 47.5 1.3 7.4 _ , - r r Area 7.244 mv-min (1.6 H-l iuj) w.e 9 <entire trap> 1 Peak Unidentified l-2ft (A/A) Company Sanitized. Does not contain TSCA CBI - 26 - ^iiiliiiM MU TABLE II Side Arm Condensate 15 1*>1 Recovered Tentative Identification . - G.C. Area HgO, CO, C02> Formaldehyde Acetaldehyde Formic Acid Pyruvaldehyde Acetic Acid H y droxy-2-P rop anone N.R. .02 Trace .13 2.02 .25 (a /a ) .4 .1 1-9 29.9 37 Total G.C. Area 6.770 mv-min (1.4 jil) Equiv. Organics 43.6 jig/iil or # 1 3 0 0 p.g (entire sample*) 11 Peaks Unidentified 1-18# (A/A) * Assumes 50# recovery of side arm condensate Company Sanitized. Does not contain TSCA CBI - 27 INDEXING APPENDIX Abstract A survey of potential exposure sites for FC-143 in th e | B B ^ ^ l M i u ^ ^ l i r i n g facility is presented. The fate of the fluorosurfactant in t h e Q p | P d > r o cess is also shown. It was concluded from the study that employee exposure to the material is negligible. Analytical method development for measurement of FC-143 via gas chromatography of methyl esters and detection by electron capture.detector is discussed. Methods for FC--143 in air, on solids and in iispersion are given. Indexing Subjects 1. Perfluorooctanoic acid (FC-143) in air. 2. perfiuorooctanoic.acid (FC--143) physical properties. 3. Gas chromatography of perfluorooctanoic methyl ester with electron capture detection. Company Sanitized. Does not contain TSCA CBI Copy No. 1 2 3 4 5 6 7 8&9 LO & 11 12 & 13 14 15 16 - 28 DISTRIBUTION G L. Watts G. B. Faigle, Jr., J. W. Williams R. F. Janis, Jr. H. J. Sampson - H. Sheppard J. P. Yuk - Analytical Research File D. G. O'Dell M. R. Warden - S. M. GxJings - A. A. Wright . Research Library Central Report Index Patent Liason File R. L. Cook M. A. Forte J. M. Morgan Spruance Spruance Spruance Spruance Spruance Nemours-Wilmington Nemours-Wilmington Spruance Centre Road Centre Road Spruance Spruance Haskell Laboratory nol contain TSC A C B l Sanitized. Does Comply