Document DMeOvpkNok5DLVQNqa4nM8zKa

AR226-3330 TRipmP Copy No. \^) _ Distribution - Last Page FC-143 IN THE 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 & Co., 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 tically transfer to their successors. If there is no further use of the document, return to the above address. Do not leave exposed and unattended. CompanySanitized. Does not contafn TSCA CB1 fswsisacwsy^^issy.ns'wtuRaesw'wiff-ft-i^^-'if^. ^ RECEIVED - - | '. i^n\' :;n 1Q7Q 1 INTRODUCTION Based on information supplied by the 3M Company , DuPont became aware that elevated organic fluoride levels were detected in the blood of 3M workers exposed to certain fluorinated surfactants. Entry of the surfactant was felt to be related to exposure^oairborne dust. A fluorinated surfactant is employed at Spruance in theg------Qprocess. It is a component ofHH dispersion which is purchased from PP&R Department. Based on FC-143 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" theM^------------ process. Establish the extent, if any, of worker exposure to FC-143. To dgvelop^n accurate analysis for FC-143 in air water I f and^B------Blproduct/ingredients. -- SUMMARY AND CONCLUSIONS FC-143 was not detected in operator breathing zones. Limit^fdete^tion was 50 ppb based on sample volume. Therefore, use of FC-143 injBHRiisper- sion is felt to lead to low, if any, airborne exposure of personnel 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 of c F onsi C-14 d 3 e re is d t small ightly wi b th ou n p d r esentproduction levels. inQ------Qduringpolym e r It iza t app ion ea a r t s P th P& a R t . 80-90% FC-143 ira.3 detected at low levels in^T' Product, but was not detected in other aroducts. 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/ BF3 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 yarn 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 CB CODE LISTING FC-143: Ammonium perfluoro octanoate. Prepared by: Approved by: /T/^'PJ. ^<!^.'/^^_________ Wialytica^ Research Supervisor Y^ Q. \^<rCL M. A. Forte Senior Chemist Company Sanitized. Does not contain TSCA CBI TABLE OF CONTENTS 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 10 b. Analysis of FC-143 in Ether or Methanol Extracts 15 Appendix II - 3M Procedure for FC-143 Analysis in Air 19 Appendix III - [Off Gas Analysis . 23 ^,--------,.^n.,^nTSCACe, PROCESS MEASUREMENTS a. Background Ii^J^^^^^B^^^BMp:ooUUooiiddaall^^iispersion is mixed with viscose In the mmanu rfaaccture offjl^^Hfiber. The viscose is regeneratedin^^nn acid bath in sp^i^gand acts as a matrix to bind the^fll^^DDppar ti cdlees prior to sintering. Surfactsnts such as FC-T^TannddTTrriton X-100 are added to the colloidal^fffffllspersio'D. to prevent agglomeration of the particles. b. Fate of FC--143 in the Manufacture FC-143 is added to dispersion at the 2200 ppm level by PP&R in polymerization. During polymerization most of ^isansarently irreversibly absorbed on or incorporated in theJHRjparticles. This hypothesis is based on measurements of FC-K3 in raw dispersion and on supernatant liquid from the PP&R polymerization. In order to understand the hypothesis^a brief description of the polymeri zation is necessary. ^HP----^ionomer(35%) is polymerized in water (^ 65%) in the presen?eof FC-143 and other surfactancs. The solids are increased to ^ 60% by decanting water off. If no other physical phenomenon were involved, one would expect to find^2200 ppm FC-143 in the water associated with the reinaining^BBBB|dispersion and in the decantation water. This is not the case as can be seen from the data in Table I. TABLE I LEVEL OF FC-143 IN DISPERSION PROCESS SAMPLES FROM PP&R Sample Cone. ppm Supernatant Liquid 220 Raw Dispersion - 35% Solids 100 Concentrated Dispersion 120 There is 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 inHUM|process and yarn samples do not lead to a materials balance based on amount added at PP&R. A schematic representat^n of the process is given in Figure 1 to show the path ofglBB^dispersion. The pertinent sample results are given in Table' II. Company Sanitized. Does not contain TSCA CB1 2 - PROCESS MEASUREMENTS (Cont'd) b. Fate of FC-143 in the Manufactureo TABLE II FC-143 IN 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 9 parts 7J Spinning Dispersion 300 ppm FC i43 H^SO^ 67, ZnS04 Regeneration Bath Company Sanitized. Does not contain TSCA CB ROCESS MEASUREMENTS (Cont'd) Fate of FC-143 in the Manufactureof 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 yarr,. Based on colloid ''Jipm-taf-T-y- che FC-143 molecule would orient at the surface of th^lBJ^Rparticle. pH of dispersion is adjusted with NaOH which converts the ammonium salt to the sodxum salt. The sodium salt would be converted to a carboxyiic acid groupvi-n the Regeneration Bath. The carboxyiic ac-Ld would undoubtedly be decom posed in Sintering. Dispersion is also used to coat^^^fjyam for pump packing end- use. As can be seen from Figured, dispersion is added to bleached yarn and dried in a dielectric oven. Thermogravimetric measurements III, made on FC-143 indicate it begins to volatilize at 120C. There was cnne likelihood for FC-143 to volatilize in the oven. As can be seen from the data in Table 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 Induction Dryer Dispersion Company Sanitized. Does not contain TSCA CBI I. jj^^^Ba PROCESS MEASUREMENTS (Cont'd) w - b. Face of FC-143 in the Manufacture of^^^^B^I (Cont'd) ---------------u -^ T&BLE III FC-143 IN INDUCTION DRYER SAMPLES Cone. pom Coated Yam Before Dryer 5 Coated Yarn After Dryer 5 Vent Residue 8 Powder on Dryer Floor 117 Calculated on the basis of dispersion on the coated yarn, the level of FC-143 is ^ 10 ppm. This compares with 200 to 300 ppm on aqueous v e r ydispersion. Yams were extracted with methanol in which FC-143 is soluble. Apparently, FC-143 became "locked" in dried dispersiou. IT ENVIRONMENTAL MEASUREMENTS , is difficult to prove th hypothesis of FC-143 entrapment in [a materials balance cannot be obtained. Since FC-143 acid Is volatile -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 revaaled the presence of any f orinaced hydrocarbons. a. Air Sampling in Spinning and Winding ^arn is heated to remove cellulose An a sintering operation. Co ensure no exposure was taking place, air samples were taken in "perator breathing zones- The results of this study given in Table .' show that operator exposure is very unlikely. The level of 50 ppb i.; based on detection limits of FC-143 and volume 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 Roll 2 . Approximate Temperature OF 25U Level of FC-143 PF3 < 50 Company Sanitized. Does not contain TSCA CBI II. ITI. ENVIRONMENTAL 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 ccnceivably 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 10~10 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. 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 chroma tography 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 litera ture indicated that methyl esters are easily formed by two minute reaction in methanol/BFi. This reagent is available commercidlly from Supeico, Inc. b. G.C. Analysis A quantity of the methyl ester of FC-143 was prepared by refluxing - one grain of the material in 100 ml. of methanol to which 5 ml. of concentrated HC1 had been added. Upon addition of water, the ester III. separated as a heavy oily liquid. by IR analysis as shown in Figure The ester product was confirmed This material was employed as a standard Co 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 ^9sa^^%K^^T^^"!^s^!E^!s^ii^^^^^i^^^*S^ M 0 ^ Company Sanitized. Does not contain T8CA CBI - 7 III. rILx-HOD DEVELOPMENT (Cont'd) b. G.C. Analysis (Cont'd) Through suitable adjustments of initial temperature and tem perature program, retention time on the 20% DC-2G, 10% Bentone 34 was reduced to ^ 7.0 minutes. Due to its high liquid loading, this material is sticky and difficult to pack in a glass column. I fcund that chilling the material and using a vibrator enabled us to pack a 10' glass column. The elep.tron capture detector is linear in response over only a specific range. Above a certain concentration no additional signal is obtained. The detector on the Hewlett Packard GC was found to be linep.L- in the range of 600 to 31,000 ppb of FC-143 ester in ethe-. A plot of integrator counts vs. concentration is shown in Figure IV. . The linearity study was made under the following conditions; Carrier gas ~ Argon/methane - 95/5 Injection port - 150C Detector temperature - 250C Column SP 1000 - 10' glass Column temperature - 80C for 4 min. then prog. at 8C/nin to 180C Pulse internal - 150 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/BFn was employed to prepare the FC-143 ester. The recommended procedure was to react che acid with me;'nanoi/BF3 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 in the watermethanol/ester mixture so. a. good separation cculd not be obtained. It was found chat 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 in 'the extracts. Solid samples were extracted with methanol. Liquid samples were acidified with HC1 if the FC-143 waa- 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 i.iethanol/BF3. Company Sanitized. Does not contain TSCA CBI FIGURE IV Company Sanitized. Does not contain TSCA CB1 - 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. ^ ^a 3. Sarasohn, I. M. -U^UqOff-Gas Analysis", Letter to Author, June 23, 1975, AppendilRlT.---- ^ --> 4. Morgan, J. M. - Visit to^fH Manufacturing Facility, March 20, 1979, 5. Metcaife, T. D. and Schmitz, A. A. - Analytical Chemistry, Volume 33, No. 3, March, 1961, pages 363-364. Company Sanitized. Does not contain TSCA CBI I. 3U FONT DE A'EMOUSS AND COMPANY Incorporated Textil" Fibers Department Indus trial Fibers Division SPRUANCE 10 Appendix la Section Method Page 1 PROCESS CONTROL - OPERATING PROCEDURE PLANT: SUBJECT; SPRUANCE FIBERS RICHMOND, VIRGINIA ANALYSIS OF PC-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 ppia 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 - Supeico, Cat. No, 3-3041. Company Sanitized. Does not contain TSCA CBI ^^^i^'^^B^^^^^^^^^^^^^S^^^^^^-^^S^^^^^^^^^^^^B'^!^^??^^!'^" ggi^o^ 'Appendix la Method Page OPERATING INSTRUCTIONS SAFETY INSTRUCTIONS II. REAGENTS AND EQUIPMENT (Cont'd) F. Chromatography Column 10' glass lacked with: DC-200 20%, Bsntone 34 10% on 1CO/120 mesh Anakrom ABS Supelco. G. FC-143 Methyl Escer 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 mi. of ether/cyclohexan^ 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 father^ cyclohexane and label Solu tion "A". Make a 1:10 dilu Company Sanitized. Does not contain TSCA CBI ^lAt^a^u1!^^^ Section Method Appendix la Page PROCEDURE OPERATING INSTRUCTIONS SAFETY INSTRUCTIONS A. Air Sampling 1. Add 15 0.2 ml. of methanol made basic to methyl red with O.lN nethanolic KOH to a 25 ml. impinger Cube. 2. Connect to Telmatic air pump with gum rubber tubing. 3. 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 ainost to dryness on a steam bath. 2. Transfer the beaker contents with methanol 10% concentrated HC1 rinsings to a 15 ml. Capered 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 N5. Perfonn sample preparation steps in a hood. 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 * 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 13 - III. PROCEDURE OPERATING INSTRUCTIONS Section Appendix la Method Page SAFETY 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 tAspeed the separation. 8. 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 . Injection port temperature - 150C. Argon/methane 95/5 flow race: 30 ml/min. Detector Settings: Pulse Interval Temperature Range 150 250C 103 Oven temperature Isothermal 100C 4 min. Program 8C/min to 180C Integrator 3385A Attenuation 2" . Slope Sensativity 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 irl. of argon/methane flowing. Company Sanitized. Does not contain T5CA CBI -'14 III. PROCEDURE OPERATING INSTRUCTIONS D. Sample Analysis 1. Inject a 2 pi sample of Standard "B"l 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 pi 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 x C Section Appendix la Method Page SAFETY INSTRUCTIONS = A B Example: A = < 3483 B = 69660 ppm = < 3483 69660 prja. a < 0.05 Company Sanitized. Does not contain TSCA CBI I . ::;. 3U FONT 3E XEMOURS AND COMPANY Incorporated Textil" Fibers Department SPRUANCE - 15 Section Method Page 1 Appendix Ib ^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. i-'orte 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/BF3, pesticide grade in glass ampoules- Supeico, Cat. No. 3-3041. C. Vials, glass stoppered, tapered 15 ml. - Fisher Scientific. D. Chromatography Column - 10' glass pac^rid with: DC-200 20%, Bentone 34 10% on 100/120 mesh anakrom ABS - Supeico. E. FC-143 methyl ester standard - Prensre as in Annon/Hy la TT r: i-'; Company Sanitized. Does not contain TSCA CBI ^^ww^^ --..-;-- .. .:-.......,,,-.,.,,-.-.--.....;..---..,. ..._..^_... . .-. . ............. ..... g ^ ^ Method Appendix Ib Page III. PROCEDURE OPERATING INSTRUCTIOMS SAFETY INSTRUCTIONS A. Sample Preparation Dispersion 1. Pipet 1/2 ml. of dispersion into a 15 ml. capered vial. 2. Pipet 1/2 ml. of 6N HC1 into the vial and mix. 3. Pipet 3 mis. of ether i^Co 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 pat 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 tc 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 prev-i c a vacuum. 11. When the vial has cooled to room temperature add 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 nol contain TSCA CB1 - 17 Section Appendix Ib Method 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. capered vial with two 1/2 ml. wash ings of dry methanol. 5. Evaporate to 0.25 mi. with a stream of Nitrogen. 6. Pipei: 1 ml. of methanol/BF^ 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 PC-143 in methanol the same way. B. G. C. Analysis III Follow Steps C and D. Appendix la fo G.G. checkout and sample analysis. IV. CALCUIATIONS Let A = B = Sample peak area xBp External standard peak area V = Volume of Teflon dispersion ml. W = Weight of solid sample grams. Page SAFETY INST';.""T'TO : Company Sanitized. Does not contain TSCA CBI "-"ra^ III. PROCEDURE OPEBATING INSTRUCTIONS IV. CALCULATIONS (Cont'd) Dispersion ppm PC-143 ss 3 x A x S x M Weight/Volume Vx B Solid ppm FC-143 Weight/weight = A x Sx M Bx W 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 M x^ Weight/Volume Vx B Solid ppm FC-143 = A x S x M Weight/Weight Bx W 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 15,000 x 5.0 3S 100 Section Appendix Ib Method Page SAFETY INSTRUCTIONS Company SanWied. Does nol contain TSCkCBl " ' InlertjOice Correspondence Appendix II w^v -., h kJ^.J' ^.MsassssmiffsssxaeR^w'^^tXia'sw.aasta^^ '^ Houtiny copy; J. VI. Feuk - Med. - 220-2K A. Pendergrass - Med. - 220-2F. j.F. A. Ubel. M.D. - Med. - 220-2E Subject June 23. 1978 TO: FROM: R. A. PROKOP - COMMERCIAL CHEMICAL - 236-3B D. F. HAGEN - CENTRAL RESEARCH - 201-lW S. D. SORENSON - (3-7058) - MEDICAL - 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. ^. Q DFH/SDS /nun Company Sanitized. Does not contain TSCA CBI FC-143 Sampling Procedure I. Filter Method: A. Equipment 1. Battery operated pump capable of drawing 2-2.5 1pm through filter. Examples: MSA Model S, or Bendix Super Sampler. 2. Three piece cassette filter holder. 3. Nuclear Pore^'0.8 urn pd^e size filter media. B. Preparation 1. Pump flowrate should be calibrated using bubble meter, wet test meter or similar method using standard industrial hygiene calibration techniques. 2. Assemble cassettes using filter support or screen under filter. It is desirable to wrap the cassette with vinyl tape (electrical tape). C. Procedure If 1. Remove colored plugs from both ends of filter holder cassette. Attach cassette to end of sampling hose so that airflow is in right direction, e.g. filter support, or backup screen must be on pump side of filter. 2. a breathing zone or personal sample is desired, attach the cassette assenibly to employees' lapel so that the inlet orifice is in a downward position. 3. The pump can be attached to the employees' belt, generally in the back. 4 . Turn on pump - record time. 5. Check to see that the pump is at the desired flow- ! rate. RechecJ; periodically. 6. Record time at end of sample period. 7. Replace colored plugs in ends of cassette. II. Impinger Method, Alternate Method A. Equipment 1. Battery operated pumps as described above. !.. All glass midget impinger. ^. Methanol. G.C. grade preferable, reagent grade can be used. 4. TranSDOrfc Vials - niaee Li'-h -^n^ i.-.-.a -.---- Company SanHized. Does nol contain TSCACBl Mr. R. A. Prokop - 21 - j^^ ^ ^g^g B. Preparation 3 1. Flowrate should be calibrated. 2. Fill impinger with 15 ml methanol. C. Procedure 1. Sample a'-. 2.0 liters per minute for 20 minutes Slower rate may be used for longer periods; a^r least 40 liters of air should be sampled. 2. Hand hold impinger in employees' breathing zone. < 3. At end of sample period, the impinger and stem should be rinsed with methanol. The rinse should be added to the sample for analysis. 4. Transport vials should be tightly capped and sealed with tape. Analysis Procedures Trace analysis for FC-143 are performed via gas chromatography after formation o'f the methyl ester derivative. Dust samples which have been collected on filters are extracted witMp<&j cc of 0.1 N HC1. The acid solution is then extracted with three 2 cc portions of diethyl ether. The diethyl ether extracts are 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. WARNING - Diazomethane is extremely toxic and its solutions have been known to explode. All work should be carried out behind safety shields and in efficient hoods. Pre cautions, as outlined by Aldrich Chemical Company, should be taken when using this reagent. This solution is then placed under a dry air jet co drive off the excess diazomethane as evidenced by the loss of the yellow color ation. The solution is then brought up to the 10 cc volume prior to analysis. Aliquats of this solution are injected into the gas chromatograph using the conditions outlined below. In the alternate method, impingers containing 15 cc of methanol \^ solvent can also be used for air sampling applications. In this case, the methanol in the impinger after sampling is transferred quantitatively to a 25 cc volumetric flask and diluted to volume. A 10 cc aliquat is made basic with 1 N KOH and evaporated to near dryness under a stream of nitrogen. Five cc of distilled water .is added and 1 N HC1 is added dropwise to obtain a pH between 1 and 2. the resultant acidic solution is extracted with three \ \ 2 cc portions of diethyl ether. The ether extracts are combined in a 10 cc volumetric flask. Comttnv Salted. Does nol contain TSCA CBl Mr. R. A. Prokop - 22 - June 23, 1978 G. C. Conditions Column: 12' (1/8" O.D. SS) 20% DC-200 + 10% Bentone 34 on 100/110 mesh ABS Oven Program: 70C (4 minutes) to 180 C at 5C/min. Detector: Electron Capture - HP. 5840 Carrier: Argon/Methane (95/5) at 45 cc/minute Preparation of Diazomethane Reagent * The method for preparing the diazomethana regent is given in the DIAZALD11 literature from Aldrich Chemical Company, Inc.; 940 West St. Paul Avenue; Milwaukee, Wisconsin. The Aldrich Chemical Company's procedure for "Preparation of Ethereal-Alcoholic Solution of- Diazoir.e thane" f^om DIAZALD is detailed below. 1. Preparation of ethereal-alcoholic solutions of diazomethane: Ethanol (95%, 25 ml) is added to a solution of potassium hydroxide (5 g) in water (8 ml) in a 100 ml distilling flask fitted with dropping funnel and an efficient, condenser set downward 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 second 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 65^ and a solution of 21.5 g (0.1 mole) of Diazald11 in about 200 ml of ether is added through the dropping funnel in about 25 minutes. The rate of distillation should about equal the rate of addition. When the dropping funnel is employ another 40 mi of ether is added slowly and 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). it Diazomethane is not only exceedingly toxic, but its solutions have been known to explode quite unaccountably. Hence, ALL WORK WITH DIAZOMETHANE, regardless of ho'-' is generated, SHOULD BE CARRIED OUT BEHIND SAFETY SHIELD IN EFFICIENT HOODS. Use TEFLON sleeves on all ground glass joints. Company Sanitized. Does not contain TSCA CB1 B.12004 REV. B-0 APPENDIX III UTUUUIOMU E. 1. DU FONT DE NEMOURS 5t COMPANY INCOHPOaATtO WiLMINGTON, DELAWARE 19898 cc; R. G. Parrish J, TrOtlHEU'1 File ^-3 TEXTILE FIBERS DEPARTMENT Pioneering Research Division Experimental Station Wilmtngton, Delaware June 23, 1975 TO: M. A. Forte Spruance Plant Richmond FROM: I. M. Sarasohn ^^i^KOFF-GAS ANALYSIS IB 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 305 C (^20-30 min)i the temperature was then slowly Increased to 315" C 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. . colusn 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 ^^ ores sure-dropping and enriching devices. Concentration levels were estimated from FID peak areas using the measured response factor for n-heptane. These levels are reported at the bottom of es-ch table in terms of ng n-heptane/ul injected and (xg nh6T3"i;c.r.5 for the entire tran assuraina- nm'-h rfpnsi'-i-.v fr>r' h'ho +.i-r> Company Sanitized. Does not contain TSCA CBI contents. Apparently, the trap and side am condensate contained at least 90^ water, based on these figures. Except for water, CO, CQ^f and formaldehyde which exhibit no FID response, calculated amounts should be in error by no more than a factor o.f 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 (i.e., trap side am), 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 nol contain TSCA CBI 25 TABLE I fI^^IBHHL^^f1c '1'11 Sample: Sample wgl.: 1.6676s Sample Wgt. Loss: 00938g Trap Vgfc. Gain: 0.0159g Temperature: R.T. to 305 305 to 315 Air Flow Rate: 6 ml/min (1/2 hr) (2 hr) Tentative Identification "Water, CO, COg, Formaldehyde Methanol G.C. Area N.R. .06 .66 % (A/A) -- .8 9.1 Acetaldehyde Ethanol Acrolein Acetone Acetic Acid Propionaldehyde .03 0.5 .05 0.7 .3^ ^^ .02 0.3 .01 0.2 .0^. 0.6 1,3-Dioxolane Methyl Vinyl Ketone? - .05 0.7 .24 3.4 Blacetyl? 2-Methyl-l,3-Dioxolane + Mixture-. Crotonaldehyde or 2,5-Dihydrofuran p-Dioxane Methylfuran Furfural Furfural Methyl Ketone 5-Methyl-2-Furaldehyde .25 1.09 .04 3.41 .09 .53 3.4 15.0 0.6 47.5 1.3 7.4 Total 5.0. Area 7.244 mv-min (1.6 649 ^.1 inj) (entire Organic Equiv. 40.8 ng/p.1 or (A/A) p.g 1 Peak Unidentified 1-2^ trap) Company Sanitized. Does not contain TSCA CB1 TABLE II Side Arm Condensate 15 VLL Recovered Tentative Identification G.C. Area HoO, CO, COo, Formaldehyde Acetaldehyde Formic Acid Pyruvaldehyde Acetic Acid Hydroxy-2-Propanone 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 (il) Equiv. Organics 43.6 p.g/t.H or s?1300 ug 11 Peaks Unidentified l-l8^ (A/A) (entire sanple*) * Assianes 5Q% recovery of side am condensate Company Sanitized. Does nol contain TSCA CB1 27 INDEXING APPENDIX Abstract A survey of potential exposure sites for FC-143 in the|^BII^BpIanufacturing facility is presented. The fate of the fluorosurfactan? in theflpU|firocess 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 ^apture_detector is discussed. iispersion are given. Methods for FC-143 in air, on solids and in Indexing Subjects 1. Perfluorooctanoic acid (FC-143) in air. 2. Perfluorooctanoic.acid (FC-143) physical properties. 3. Gas chromatography of perfluorooctanoic methyl ester with electron capture detection. ^- CompanySanitized. Does not contain TSCA CBI 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. Gluuings 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 Comply ^ d . o ^ 0 ^ 9 ^