Document yrbnDwew8ae9DgpjZbEgwaaL2

PHOTODEGRADATION EFT7-2 TEST SUBSTANCE Identity: Perfluorooctanesulfonate; FC-95. (1-Octanesulfonic may acid, also be referred to as PFOS or 1,1,2,2,3,3,4,4,5,5,6,6.7.7.8,8.8- heptadecafluoro-, potassium salt, CAS # 2795-39-3) Remarks: Testing is in progress. 00211 PHOTODEGRADATION TEST SUBSTANCE Identity: PFeCr-f9l5u.or(o1oc-tOacnteasnuelsfuolnfaotnei;c macaiyd,a1l,s1o,2b,e2.r3e,f3e,r4r,e4d,5t,o5a.s6,P6.F7.O7S.8o.r88heptadecafluoro-, potassium salt, CAS # 2795-39-3) Remarks field: The test substance is a white powder. The test substance used was C labeled (285 dpm/ug). Purity of the test substance is not described. This testing is currently being repeated using current procedures and best available practices. METHOD Method/guideline followed: Procedure as described in the Federal Register (Volume 43, No. 132-Monday, July 10, 1978) by the U.S. Environmental Protection Agency. Type (test type): Simulated sunlight GLP (Y/N): No YLeiagrh:t S1o9u7r8ce: General Electric F-40BL fluorescent black light Light Spectrum (nm): Max output at ~360 nm and essentially no output below 300 nm. Spectral energy characterized from 290-600 nm. Intensity: [Wav29e0l-3e00ngth| Watts0.R0a9d0iated : 310-320 [0285| [320-330|" iat0 340-360 [foto| 336800--430800 [237.61 80 0| 400 - 500 |2300| 500 - 600 `Spectrum of substance (max lambda, max epsilon and epsilon 295): Not determined. Remarks fold: - Test medium (air, water, soil, othe-r specify): Distilled water - Duration: 30 days - Positive Controls: None - Negative Controls: None 000212 aPhnodto3l0yzdaatyse.saSmapmlpelsewsewreerceolalneacltyezdeadftuesriinrgraadiLaitqiuonidinStceirnvtaillsatoifo0n,C3o,u7n,te1r5, (LSC), TLC-Autoradiograph and Gas Chromatography. RESULTS Concentration of Substance: 50 mg/L Temperature C: 23+3C Degradation %: 0% ater 30 days iRnetmhaisrsktsudfyi.eldE:ssNeontipahloltyotdheegrsaadmateioannaolfystihse rteessutlstsubwsetraencoebtwaainseddeftoercttheed s3a0m-pdlaey.photolyzate sample (no photoproducts formed) as the 0-day Radiocarbon assays at 0 of product was volatilized adnurdi3ng0 tdhaeysstauldsyo. indicate no significant amount CONCLUSIONS sNuonlpighhott,odinedgircaadtaintgiotnheprteosdtucstusbswtearnecededtoeecstendotinutnhdisersgtuodpyhoutsoilnygsissi.mulated Submitter: 3M Company, St. Paul, Minnesota, 55133 Environmental Laboratory, P.O. Box 33331, DATA QUALITY cRuerlrieabnitlliytayv:aiKliaibmliespchrorcaendkuirnegs2.anPdhobteosltyspriascsttiucedsy uissibneginagsraemppelaetewdituhsing characterized purity. REFERENCES S3UMNTLeIcGhHnTic.a"l JR.eWpo.rTto"dFdC,-P9r5o/jePcHtO9T7O7L6Y7S5I0S20S2T,UJDanYuaUrSyI9N,G19S7I9MULATED owWER 000 Last changed: 5/2/00 00213 SUMMARY OF PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT ON THE POTASSIUM SALT OF PERFLUOROOCTANESULFONIC ACID ExposureConditions `This study was performed on the potassium salt of perfluorooctanesulfonic acid as described in Federal Register (Volume 43, No. 132-Monday, July 10,1978) by the U.S. Environmental Protection Agency. The test solution contained 50 ppm of "C labeled potassium perfluorooctanesulfonate (285 dpm/ug) in2 liters ofD.L. water. The specific activityofthe solution was 14,250 dpm/ml (0.0064 ' uC/ml). The photoreactor contained a General Electric F-40BL fluorescent black light with a maximum output at about 360 nm and essentially no output below 300 nm. The temperature of the reactor was controlled at 23 + 3 C by circulating tap water. Photolyzate samples were collected after irradiation intervals of 0, 3, 7, 15, and 30 days. Collected samples were removed through the reactor drain port and were refrigerated until analyzed. AA 100 ml aliquot ofthe0and 30 day photolyzate sampleswereconcentrated with a rotary vacuum evaporator and a water bath to dryness, redissolved in 3 mlof methanol, and transferred with two 3 ml `washings into Kuderna-Danish concentrator tubes. Each solution were further concentrated to 1 ml. A 10 ul aliquot of each sample (equivalent to 1 mlof the original photolyzate solution) was transferred onto a Thin Layer Chromatography (TLC) plate using a 10 ul syringe. "Each plate was developed two-dimensionally with ethyl acetate/acetic acid (95/5) followed by ethyl acetate/chloroform/formic acid/water (65/20/10/5). After air drying, the spots were scraped and quantified for radioactive carbon. AnalysisofPhotoproductsby GasChromatography : Photolyzate samples from days 0 and 30 were analyzed by acidifying 2.0 ml of each in a 4-dram vial with 0.2 ml of concentrated HCI and extracting with two 2 ml portions of diethyl ether. The combined extractsofeach sample were concentrated to 0.1 ml in a 10-ml Kudera-Danish concentrator tube using a nitrogen purge. The concentrated samples were methylated with 0.4 ml of diazomethane `methylating solau ndmtixiedowelnl. Using a 10 ul syringe, 6 ul of sample (equivalent to 1.5 ug of the compound of interest) was injected, via on-column injection at 150 C, into a Model 7620 Hewlett-Packard gas chromatograph with a. 6 ft X 1/8 in. OD. stainlesssteel packed column with 5% OV-17 silicone onChromosorb G support. The. GC column oven was temperature programmed from 60 to 150 C at 15 C/min. Analytes were detected. with a microwave sustained helium plasma detector from Applied Chromatography Systems Limited, Luton, England. The detector was operated in the fluorine and sulfur modes simultaneously with outputs 10 a dual-pen recorder. Results No`photodegradation products were detected in this study. Similar radiocarbon assays (with good analyte recoveries) and similar gas chromatograms were obtained from the 0 and 30 day samples. 000214 Tiy22,19% 3: TECHNICAL REPORT SUMMARY 70: TECHNICAL COMMUNICATIONS CENTER -- 201:2CN "Important I port sprinontbeotdh siodfpaepesr, and wocopietso TCC.) TM 1-9-79 Commercial Chemicals Division - Agrichemicals Project 3068 Service to TOSCA 9776750202 FC-95/PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT 001 R. A. Prokoj w= J. W. Todd Agrichemical Request 888 4395=3 13 SecOMTYD (LO0,Contamia) oiiunaranion | "hE > Suedetogernd TEhCmreSuigroemnoaumer |CUIRnRvENeTsotRiEgTaItVeE!the photolylic stability of FC-95 as a function sopieatiewine) of irradiation time and identify any major photo products. ctoom/pRoasdiitoigornaphy vsi=rCohnrmoemnattograph YrEarp/hCyhromato=T |RES PORT ABSTGRrAoCeT:n R0a02:60word Thssoerac formation Gerbumdb a TechnicalCommunicationsContr 1 otolysis Shanes Irradiation of a 50 ppm aqueous solution of FC-95 for 4 t30hinda-ylsayerre-scuhltreodmotinogrnaophdye/treacdtieodaupthoogtroapprhoyd,uctasndonbyagnaaslysis by cphlraosmmaotadgertaepcthoyr.of dTheeriviartriazdeidatisoanmplseosurcuesinpgrodaucmeidcro3w0a0venm and longer wavelength light to simulate natural sunlight. -- nite ded 000215 . FC-95/PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT INTRODUCTION It is generally acknowledged that manufactured chemicals may find their way into the environment in various degrees and by various means. Once in the environment they may be destroyed or chemically altered by the action of sunlight (Crosby and Li, 1969). This study investigated the possible photodegradation of FC-95 in distilled water on exposure to simulated sunlight (Kohler, 1965). This study was conducted essentially as recommended by the Environmental Protection Agency (Federal Register). EXPERIMENTAL ' 1. Sample Materials FC-95 1s the potassum salt of perfluorooctanesulfonic acid. CgFy7505K The major component is the straight-chain Cg but some branched. chain isomers and other homologs also are present. FC-95 Water Solution. A 50 ppm solution of FC-95-1%C (285 dpm/pg) was prepared by dissolving 100.0 mg of FC-95 in 2 liters of distilled water. The resulting solution had a specific activity of 14,250 dpn/ml (0.0064 uC/ml). 2. Analysis Instruments/Materials : Liquid Scintillation Counter (LSC) Nuclear-Chicago Mark I Rotary Evaporator Blichi Rotovapor R Kuderna-Danish Concentrator R1e0flmu1xcocnocleumnntrator tube -= KKoonntteess NNoo.. K-K-557609025501 Heated water bath coz16 :: NEARER =2- Thin-Layer Chromatography (TLC) plates M1EstRCKdevSeilloipciangGelso6l0venFt-25-4,eth0y.l25amcmetatthei/cakcneetsiscanadcid209x5/520 cm size 2nd developing solvent - eatchiydl/waatceert,ate6/5c/h2l0o/1r0o/f5orn/formic X-Ray Film KODAK NS-5T, 8 x 10 inch size Gas Chromatography System (GC) GCaolsumcnhromatograph -- H6ewftlet1t/-8Paicnkaordd sMtoadienlles7s620steel : packed with Column temperature- 56%0 OtVo-11750siplriocgornaemmeodn CHROMOSORB G at 15C/min. support. IDnejteeccttoorr -- omni-ccroolwuamvne astust1a5i0neCd helium plasma from Applied Chromatography Systems Limited, Luton, England DIAZALD DIAZALD is Aldrich Chemical Company's trade name for N-methyl-N-nit- roso-p-toluenesulfonanide. It is used to prepare diazomethane, an analytical reactant chemical. Diazomethane solution - Alcohol Free. Diazomethane (DAM) was used to convert acidified FC-95 into its corresponding methyl sulfonate ester just prior to gas chromato- graphic analysis. - CgF17SOsH + CH Np ----> CgF,SOCHy + wT - (FC-95 acid) (DAM) (FC-e9s5temre)thyl The DAM reagent used must be free of alcohols or the desired reaction product will not: form or will degrade after it has formed. The alcohol-free DAM was prepared essentially as recommended by Aldrich: A solvent mixture consisting of 35 ml of 2-(2-ethozyethoxy)-ethanol and 20 ml of diethyl ether was added to a solution of 6 grams of potassium hydrozide dissolved in 10 ml of water. This mixture was 000217 . a ae placed in a 100 ml long-necked distilling flask fitted with a dropping funnel, an efficient condenser and a water bath at 70C. As the distillation of the ether started a solution of 21.5 g of DIAZALD in about 200 ml of ether was added through the dropping funnel over about 20 minutes. The etheral DAM solution was collected in a 250-ml Erlenmeyer flask cooled in an ice bath. The flask contents were transferred into a bottle, sealed with a TEFLON-lined cap and stored in a freezer. 3. Irradiation The preparative photoreactor used (Crosby and Tang, 1969) is illustrated in Figure 1. The lamp employed was a General Electric F-40BL fluorescent black light with maximum output at about 360 nm and essentially no output below 300 nm (Table I, Genral Electric Co.). The temperature was controlled at 23 + 3C by circulating tap water through flexible plastic tubing wrapped around the reaction chamber. Nitrogen was passed through the photolysis solution at 20 ml/min to provide mixing. The exit port was connected to a vapor trap. The trap consisted of a 6 x 3/4 in. glass tube containing first XAD-2 resin and then charcoal. The photolyzate was sampled after irradiation intervals of 0, 3, 7, 15 and 30 days. The samples were removed through the reactor drain port and were refrigerated until analyzed. : 4. Radiocarbon Recovery The photolyzate samples were assayed for radiocarbon by LSC to deternine radiocarbon recovery as a function of irradiation time. Similar results were obtained for all samples. Results for the 30 and 0-day samples are presented in Tables II and III, respectively. 5. Investigation for Photoproducts by TLC-Autoradiography Aliquots of the 30 and 0-day photolyzates were reduced in volume 100-old before TLC analysis. First a 100-ml aliquot of each sample was concentrated to about 5 ml using a rotary vacuum evaporator with a 40-50 C water bath, 50 ml of acetonitrile was added and the rotovac'ing continued to just dryness (Acetonitrile was added to expeditiously re- move remaining water as an azeotrope and thereby minimize possible loss of radiocarbon). 00218 The sample solids were dissolved in 3 ml of methanol and quantitatively , itp: tm transferred into a Kuderna-Danish concentrator tube with two additional 3-ml washings. Reflux tubes were attached and the concentrator tubes were immersed in a 65-74C water bath. The tube contents were concentrated to exactly 1 ml. | A 10.0 pl aliquot of each sample concentrate (equivalent to 1.0 ml of the original photolyzate solution) was transferred onto a TLC plate using a 10 pl microsyringe. Each plate was developed two-dimensionally, first with ethyl acetate/acetic acid (95/5) and then with ethyl acetate/chloroforn/formic acid and water (65/20/10/5). The air-dried TLC plates were then.radioautographed. Figures 2 and 3 are pictures of the 30 and 0-day radioautographs, respectively. Various component spots and areas on each TLC plate were quantitated for radiocarbon by carefully scraping the silica gel from the plate and LSC counting. The results are presented in Tables II and III. 6. Investigation for Photoproducts by Gas Chromatography Sulfonate salts as FC-95 are not analyzable by gas chromatography. Recent work has shown that FC-95 is analyzable if acidified, isolated from the water matrix and methylated with DAM. The 30 and 0-day + photolyzate samples were analyzed by this method (3M Central Research Laboratory). The procedure used is summarized below: Two ml of the photolyzates were pipetted into 4-dram vials. Each sample was acidified with 0.2 ml of concentrated hydrochloric acid and the resulting acids were quantitatively extracted with two-2 ml portions of diethyl ether. The combined ether extracts were concentrated 0 0.1 ml in a 10-ml Kuderna-Danish concentrator tube using a nitrogen purge. The concentrated extracts were diluted to 0.4 ml with DAM solution and mixed well. Using a 10 pl microsyringe,6 nl sample portions (equivalent to 1.5 pg of FC-95) were injected into the gas chromatograph for analysis. The microwave plasma detector was operated simultaneously in the fluorine and sulfur modes with outputs to a dual-pen recorder. The chromatograms for the 0 and 30-day photolyzate samples are presented in Figure 4. 00219 ni 5 This analysis method is unique in that 1) there are only a few microwave plasma detectors in this country and 2) methyl esters of sulfonic and fluorosulfonic acids generally have been considered to be too unstable for gas chromatographic analysis. The analysis results here demonstrate that FC-95 indeed can be analyzed by gas chromatography. Several less obvious paramaters also are important: The DAM solution should be freshly prepared, preferably the same day it is used. Excess DAM is necessary in the analyzed sample solution and its presence is evidenced by a characteristic yellow color. Several injections of sample may be necessary to passivate the column before accurate and repeatable results are obtained. Presence of diazomethane in the analyzed sample produces interfering peaks when the more conventional flame ionization and electron capture detectors are used but does not interfere with the microwave plasma detector used here. RESULTS No photodegradation of FC-95 was detected in this study. Essentially the same analysis results were obtained for the 30-day photolyzate sample (no photoproducts formed) as the 0-day sample. Similar radiocarbon assays were obtained. (Tables II and III). Therefore no significant amount of radiocarbon was volatilized during the photolysis and so the contents of the vapor trap were not analyzed. Similar TLC-radioautographs were obtained indicating no change in composition in the 30-day sample compared to the 0-day sample (Figure 2'and 3). Quantitative measurement of radiocarbon in various TLC spots and background areas show similar radiocarbon distribution and good recoveries (Tables II and III). Similar gas chromatograms were obtained further confirming the same `composition of the 30 and 0-day samples (Figure 4). LI. 7hA J. W. Todd ER 000220 rl -6- REFERENCES Crosby, D.G. and Li, M. 1969. Herbicide Photodecomposition, Chapter 12:321-363 in Degradation of Herbicides, Kearney, P.C. and Kaufman, D.D. (ed), Marcel Dekker Inc. New York, 394 p. General Electric Company, Information from their Lamp Division, F4OBL black light bulb. 1 Koller, L.R. 1965. Ultraviolet Radiation, 2nd Ed. Wiley, New York. 312 p. Federal Register, Volume 43. No. 132-Monday, July 10, 1978. Crosby, D.G. and Tang, C.S., J. Agric. Food Chem., 17, 1041 (1969). 3M Central Research Laboratory, Analytical Request A-70732. ad 000221 em 7 \ 7 rg \N| ER : 2 YN 000222 Table I - Spectral Energy Distribution for a GE F4OBL Black Light Bulb Wavelength 290 - 300 310 - 320 320 --340 340 - 360 360 - 380 380 - 400 400 - 500 500 - 600 : ] Watts Radiated 0.090 0.235 1.410 I 2.3100\. intensity At about 360 nm 1.680 2.300 0.340 a 000223 Figure 2 - 3P0h-oDtaoygraFpCh-95ofPhToLCtolRyazdaitoeautograph, -- 05-2 ----> 2ESTCOPY AVAILABLE bs-1 || R59 efpegrenocfe FSCa-m9p5l-e1s4.C p1o4t,35p0hotpeowl,yzed @ Fe-95 orig&in BE ackgo round es spots 1 and 2) DS-1 = Developing Solvent #1, ethyl acetate/acetic acid,95/5. DS-2 = Daceivde/lwoaptienrg,6S5o/l2v0e/n1t0/#52., ethyl acetate/chloroforn/formic 00224 Figure 3 - 0P-hDoatyogrFaCp-h95 ofPhoTLtColyRzaadtieoautograph, --_-- DS-2 --> Reference Samples. 59 14u,g300ofDPFMC,-95:14C not phototyzed, DS-2 | ~~ @ re-95 @ origin @ Background (All area less spots 1 and 2) DS-1 DS-2 = Developing Solvent #1, ethyl acetate/acetic acid,95/5. = Developing Solvent #2, ethyl acetate/chloroform/formic acid/water, 65/20/10/5. 000225 Table II - Radiocarbon recovered in 30-Day Photolyzate Solution and TLC Plate Scrapings (FIGURE 2) Sample Solution TLC Plate Scrapings DPM/ml Relative % 14,430 [fod Area Description 1 Fe-95 2 origin. | DPM(per m1)* 13,873 49 %Recovery 9 0.3 3 "Background" 1,276 9 " Total 15,198 103 * The amount of 4c radioactivity on the plate is equivalent to 1 ml of the original photolyzate solution. Table III - Radiocarbon recovered in 0-Day Photoyzate Solution and TLC Plate Scrapings (FIGURE 3) Sample Solution DPM/ml Relative % 1,425 [log . Area 1 2 3 TLC Plate Description Fe-g5 Origin. "Background" Total Scrapings DPM(per ml)* 13,485 26 1,600 15,091 % Recovery 93 - 0.2 11 104 * The amount of 1%C radioactivity on the plate is equivalent to 1 ml of the original photolyzate solution. C0026 ot "" Cu RE "= Sinore 4 Wispousys Fasne Gan Chromatogram of Derivatized Photolyzate Samples. ` 0-Day Sample Lob! o Flort i |!1 t : fe i v } i.:; | : RR I Ixy) =| iim pd i i 1" . 30-Day Sample . ced| e | ;{ a: li, Fluorine Xa) ley :: faA-f| vrSe I} il A S pot T sie a" IH | 4 t io! WZ Co ee] + . So Gb J fl i } i Raia Beis I cogil| obi 18 eli l18 Ls fol Lo - i i i peal iWw i. ki en 1 1[5hege) d| 8 IM : $ Bj iin io ; [ood 18 iHm i lli le ul 12d Iie i a Aft i] i$ DC 7 Ep fe fe rh MUA LN AU : fd lord appr nel) 4 2 o 4 &-- Peak Retention Time in Minutes 2 0 00227