Document B84pL3QggogkrqjDxMy1go5qX

PHOTODEGRADATION TI ESTe SUBSo TANCT E SUB 00S0 T0A 0 NCE Identity: PPeFrOflAuoarmoomcotnaniouimc ascailtd,, Aammmmoonniiuumm psaelrtf;lmuaoyroaolcstoanobaeter,efPeFrrOe,d FtoC-as a11m6m,oFnCi-u12m6s,alFtC,-C1A69S,#or38F2C5--12463-.1)(Octanoic acid, pentadecafiuoro Remarks: wTahes tneostt ssuufbfisctiaenntcley cuhsaerdacwtearsiz"eCd, ltahboeulgedh (c3u5rr8ednptmi/nufgo)rm.atIi'osnpurity . 3in.d5i%caCtse,s iCt7i,saanmdixCtsupreerofflu9o6r.o5a-na1l0o0g%uefecsotmspuobusntdasn.ceThainsdt0es--ting is currently being repeated using current procedures and best available practices. Me MeEwThHODO:: e M(eVtohloudmieg4u3i,deNloi.n1e3f2o-lMloonwdeady:, PJruloyce1d0u,r1e9a7s8)debsyctrhiebeUd.Si.n tEhneviFreodnemreanltaRlegister Protection Agency. TGyLpPe((YtNes)t:typNeo): Simulated sunlight Year complete1d97:9 Light Source: General Electric F-40BL fluorescent blacklight bLeiglhotwS3p0e0cntmr.umSp(encmt)r:alMaenxeorugtypcuhtaartac~t3e6r0iznedmfarnodm e2s9s0e-n6ti0a0llnym.no output Intensity: [Wavelength|Watfs Radiated 290 - 300 [8fo=%0T0235 | [32[ 0-3s 40 Tt |at iso o to || [Se0-380 [2310 | [400-500[2300 | . [s00-s00T0340 | Spectrum of determined. substance (max lambda, max epsilon and epsilon 295): Not The test solution was created by dissolving 140.0 mgofthe test substance in 2.8 liters of distilled water. The resulting solution had a specific activity of 17,320 dpm/mL (0.0078 pCi/ml). 03652 Remarks: -= TDuersattmioend:i3u0m:daDyisstilled water -- NPoesgiattiivveeCCoonnttrroollss::NNoonnee (aPLhnSodCt)o3,l0yTzdLaaCty-seA.suatSmoaprmalpdeliseowsgerwraeperhceaolanlndeaclGtyaezdseadCfthuersroiimnragrtaadoigLaritiqaoupnihdyin.Stceirnvtialllsoatfio0n,C1o,u3n,te7,r15, R0 ReEsSUwL0 tTSs 0000000000 TCeomncpeenrtartautrieonCo:f2S2u+b2stCance: 50 mg/L Degradation %: 0% after 30 days tRheismastrukdys.fiEeslsde:nNtioalplhyotthoedesgarmadeaatniaolnysoifstrheestuelstts swuebrsetaobnlcaeiwnaedsfdoerttehcete3d0-idn ay photolyzate sample (no photoproducts formed) as the 0-day sample. pRraoddiuocctarwbaosnvaolsastaiyliszeadt d0urainndg 3t0hesdtauydsya.lso indicate no significant amount of c0 oCOnNcClLuUsSI0 iOoNnSs 02000 sNuonlpihghott,odiendgircaadtaitngiotnheprteosdtucstusbswtearnecededtoeecstendotinutnhdisersgtoudpyhoutsoilnygsissi.mulated Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 b0 DaAtTAa0 QQUuALAI0 bTYY 000000000 Reliability: Kimisch ranking 2. Testing meets the criteria for quality testing at the time it was conducted. However, sample purity was not properly characterized. RREEFFEERREENCCEESS ~~~00 3M Technical 2S,U1N9L7I9GHT." JR.epWo.rtToFdCd-,1P4ro3jePctHO97T7O6L7Y50S2I0S2,STReUpDoYrtUnSuImNbGerS0I0M2U,LFAebTrEuDary o0 OR THER 00000000 Last changed: 5/24/00 03653 Form arir ica < TECHNICAL REPORT SUMMARY TO: TECHNICAL COMMUNICATIONS CENTER ~ 201.20H {important ~ Ifreportispinta onboth ides ofpaper,sn twocopies t0TCC.) 2x Commercial Chemicals Division - Agrichemical Project Service to TOSCA FC-143 PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT R. A. PROKOP 3068 9776750202 002. J. W. TODD 43953 Agrichenical Request 994 scurvy Dom BS nerion | "hSET > ---13 Komonos, cummin oaxcrive: gamete ar:Suggest other oIfnveisrtriagdaitaetiotnhetipmhoetoalnydic'idensttiafbyiliatnyy moafjFoCr-1p4h3otoasproadufcurnec'tior cutoom/pRoasdiitoigornaphy aavsi-rCohnrmoemnattograph ayhgoertrao/plChyhysriosmato- SEtITorAS5STCRAoCTm. (Fp25r0G250 ori)This sn formation +dbamdb 3 ToeSomeonesrons So acdifnottirlalacteiron b2Iy0rrtdaahdyiisant-irloeansyuelortf-ecdahroi5n0matnpopomgdreaatpqeyuc/etroeauddsicpsahouolttuootgiproranopdhuoycf,tsFaCn-odn143baynafloyrsis lsciohgurhrotcmeattooprgsoridamupuchleyadtoef300dnaetrnumirvaaaltndizseuldnolnigsgaehmrtp.lweasv.elenTgheth iurlrtardaiyaitoigioaenst ten ve 03654 - --FC-=143=/PH1OTO2LYS3IS / SSTTUPUDDYHUUSSO IINGTSSIIOMMUULL LAATYED SSSUUNNTLLIGSHHTT INTRODUCTION wIaty isingtoenetrhealleynviarcoknnmoewnltedgiendvatrhiatousmadneugfraecetsureadndchbyemivcaarlisousmayme.afnisn.d their Once in the action environment of sunlight they may be (Crosby and destroyed or chemically altered by the Li, 1969). This study investigated the Possible photodegradation of FC-143 simulated sunlight (Kohler, 1965). in distilled water on exposure to This study was conducted essentially as recommended by the Environmental Proection Agency (Federal Register), EXPERIMENTAL 1. sample Materials FC-143 1s the ammonium salt of perfluorooctanoic acid. CF, 5C00NH, isomTheersmaajndorotchoemrponheonmtoloigssthaelsostarraeighptr-ecsehnati.n C; but some branched chain FC-143 Water Solution: A 50 pom 140.0 mg of FsCo-l1u4t3ioninof2.8FCl-i1t4e3r-s1Cof (d3i5s8tidlplme/dug)watwears. preThpearerdesublytidnigssolving solution had a specific activity of 17,320 dpu/ml (0.0078/uC/n1). 2. Analysis Instruments/Materials Liquid Scintillation Counter (LSC) Nuclear-Chicago Mark I Rotary Evaporator Biichi Rotovapor R Kuderna-Danish Concentrator R10eflmlux ccoonlcuemnntrator Heated water bath tube -- KKoonntteess NNoo.. KK--356790205510 03655 : -2- : `Thin-Layer Chromatography (TLC) plates M1EstRCKdevSeilloicpaingGelsol60venFt-2-5e4t,hyl0.a25cetmantet/hmiectkhnaensosl/awnadte2r0, x7250/15c/m10size 2nd developing solvent-methyl ethyl ketone/chloroform/acetic acid, 55/30/15 X-Ray Fila KODAK NS-2T, 8 x 10 inch size Gas Chromatography System (GC) GCoalsumCnhromatograph =- 26H0e%wftleDCt1t/8-20P0aicnksaiordldicsoMtnoaedi/enlll0es%5s84B0sEtNeTeOlNEpa34ck| eodn with CCoalrurminertgeamsperature --AA8rN0gAoKCnR/OmMfeotrAhBa4Snem(,i1n0u90t5/e/1510promgersha)med to 180 at 5C/min. DSIeantmjepeclctetoiroinnjepcarttion --- eo1nlpelcctorvliuoamnn,1c0ap1pt8lu0reCm,icr3o0s0yrCinge . DIAZALD DIAZALD is Aldrich Chemical Company's roso-p-toluenesulfonanide. It is used to trade name for N-methyl-Nonitprepare diazomethane, an analytical reactant chemical. Diazomethane solution - Alcohol Free. Diazomethane (DAM) was corresponding methyl ester used just to convert acidified FC-143 into its prior to gas chromatographic analysis. C7F1sQO0H + CN, ------ cP coocn, + ow, 1 (FC-143 acid) (DAM) (FC-143 methyl ester) The DAM product reagent used must be free of alcohols or the desired reaction 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-ethoxyethosy)-ethanol and 20 ml potassium of diethyl ether was added to a hydrozide dissolved in 10 ml of solution of 6 grams of water. This mixture was C03656 "de : placed in a 100 ml long-necked distilling flask fitted with dropping funnel, an efficient condenser and a water bath at a 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 solution was funnel over about 20 minutes. The etheral DAM collected in a 250-ml Erlenmeyer flask cooled in an ice sealed bath. with a The flask contents were transferred into a TEFLON-lined cap and stored in a freezer. bottle, 3. Irradiation illuThsetraptreedpariantiFviegurpehot1.oreaThcetorlamupsedemp(lCoryoesdbywaasndaTaGnegn,era1l969E)lec1tsric F-40BL fluorescent and essentially no black light with output below 300 maximum output at about 360 nm nm (Table I, General Electric Co.). Tthheroutgehmpefrlaetxuirbelewapslasctoinctrotlulbeidngawtra2p2pe+d2aCroubnyd ctihreculraetaicntgiontacphawmabteerr. Air was passed through the photolysis solution at 10 ml/min for oxygenation and mixing. The trap consisted of a The exit port was connected to a 6 x 3/4 in. glass tube containing vapor first trap. XAD-2 resin and then charcoal. The photolyzate was sampled after irradiation intervals of 0, 1, 3, 7, 15 and the reactor drain port and were 30 days. The samples were removed refrigerated until analyzed. through 4. Radiocarbon Recovery The photolyzate samples were assayed for radiocarbon by LSC to determine radiocarbon recovery as a function of irradiation time. aSnidmil0a-rdayressualmtpslesweraereobptraeisneendtedforinalTlablseasmplIeIs.and ReIIsIu,ltsresfpoercttihveel3y0. . IP nvesh tigao tiont foropro byd TLC-u Autoc radit ogras phy 100-Al0i1qduotbsefoorfe thTeLC 3a0naalnydsi0s-.dayFiprhsottoalyz1a0t0e-smlwearleiquroetducoefdeaicnh voslaummpele was concentrated to about 5 ml using a rotary 40-50C water bath, 50 ml of acetonitrile vacuum evaporator was added and the with a rotovac'ing continued to just dryness (Acetonitrile was added to expeditiously re- move remaining water as an azeotrope and of radiocarbon). The sample solids were thereby minimize possible loss dissolved in 3 ml of methanol and 03657 . "tm quantitatively 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. of 410.0 pl aliquot of each sample concentrate (equivalent the original photolyzate solution) was transferred onto a to 1.0 ml TLC plate using first a 10 with yl microsyringe. Each plate was developed ethyl acetate/methanol/water (75/15/10) and two-dimensionally, then with methyl ethyl ketone/chloroforn/acetic acid (55/30/15). 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 plates and LSC. The results are presented in Tables II and III. 6. Investigation for Photoproducts by Gas Chromatography Perfluorocarboxylic salts as FC-143 are not directly analyzable by gas chromatography but can be analyzed if acidified and methylated with DAM. The 30 and 0-day photolyzate samples were analyzed by this method (34 Central Research Laboratory). The procedure used is summarized below: Four ml of photolyzate solution was pipetted into a 4-dram vial and acidified with 0.4 ml of concentrated hydrochloric acid. The resulting samples acids were quantitatively extracted with two 2-ml portions of diethyl ether. The ether extracts were combined in a calibrated 10'ml centrifuge tube. One ml of DAM solution was added and the sample allowed to react for 15 minutes. Excess DAM was then removed by purging the tube contents with a nitrogen jet until the yellow DAM color was almost gone. The sample solution was then diluted to exactly 5 ml with diethyl ether, and analyzed immediately to minimize possible degradation due to any instability of the sample derivative. The chromatograms for the 30 and 0-day photolyzate samples are presented in Figure 4. C03658 .. -5- However several less obvious parameters are important: The DAM soultion should be freshly prepared, preferably the same day it is used. Several injections of sample may be necessary to passivate the column before accurate and repeatable results are obtained. RESULTS No photodegradation of FC-143 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. The 30 and 0-day photolyzates had similar radiocarbon assays (Tables II and III) so no significant amount of radiocarbon was volatilized during the photolysis and so the contents of the vapor trap were not analyzed. Radiocarbon recoveries after sample concentration were good for the 30-day photolyzate (99%) but less desirable for the 0-day sample dure to physical loss (86%). A repeat concentration of the 0-day sample was not done since it is important only as a TLC reference. Similar TLC-radiocautographs were obtained indicating no change in composition of the 30-day sample compared to the O-day sample (Figures 2 and 3). Quantitative measurement of radiocarbon in various TLC spots and background areas show similar radiocarbon distribution and good recovery for the 30-day sample (Tables IT and III). Similar gas chromatograms were obtained further confirming the same composition of the 30 and 0-day samples (Figure 4). J. W. Todd 03659 . 6 REFERENCES Crosby, D1.2G:.321a-nd363Li,inM.Deg1r96a9d.atioHnerboifciHdeerbiPchiodteosd,ecoKemapronseiyt,ionP,.C.Chaanpdter Kaufman, D.D. (ed), Marcel Dekker Inc. New York, 394 p. Crosby, D.G. and Tang, C.S., J. Agric. Food Chem., 17, 1041.(1969). Federal Register, Volume 43. No. 132-Monday, July 10, 1978. General Electric Company, Lamp Division, Cleveland, OH .44112. Koller, L.R. 1965. Ultraviolet Radiation, 2nd Ed. Wiley, New York. 2 p. 3M Central Research Laboratory, Analytical Request A-70732. 03660  [7 inter . 7 | 7 Ni ` A Pyrex gloss aro Z .|7 2 2 03661 3 = Table I - Spectral Energy Distribution for a GE F4OBL Black Lignt Sulp davelengen Watts Ragiated 290 - 300 310 - 320 320 = 340 340 - 360 360 - 380 380 - 400 400 - 500 500 - 600 0.090 0.235 1.400 1.920 _~ Maximus intensity an A% about 360 ne 1.680 2.300 | 0.340 ~ gr 03662 : -9- ! Table II - aRnaddiToLcCarbPolnatereSccorvaepriendgsin (3F0I-GDUaRyE P2)hotolyzate Solution Sample Solution Dft/ol Relative % Ares TLC Plate Scrapings Description DPMiper ml) % Recovery 17,320 [lod 1 Fe-143 16,643 97 2 3 origin. | "Background 66 288 0.4 17 Total 16,997 99.1 * 1Th'emlaomfounttheoofri1g%iCnarladipohaocttoilvyziattyeonsoltuhteiopnl.ate is equivalent to Table III - aRnaddiToLcCarbPolnatereSccorvearpeidngsin `0F-IDGaUyREPh3o)toyzate Solution Sample Solution DP/l Relative % Area TLC Plate Scrapings Description DPM(per ml)* Recovery 16,643 [10g 1 Fe-143 14,493 84 2 origin. 3 3 "Background" 222 0.2 1.3 Total 14,758 85.5 * 1Themlaomofunttheofori4gcinarladipchaocttoilvyziattyeonsoltuhteiopnl.ate is equivalent to es 03663 . -10- Figure 2 - 3P0hoDtaoygraFpCh-14o3f TPLhCotoRlaydziaotaeutograph --_ | | 8aa | 052 -- setarance sanpies 50 pg FC-143-14c 7,300 dpm, jot photolyz. NN@ Fe-143 origin Background (A11 areas less spots 1 and 2) DS-1 = 7D5e/v1e5l/o1p0ing Solvent #1, ethyl acetate/methanol Mater, DS-2 = aDceivde,lop5i5n/g30/S1o5lvent #2, methyl ethyl ketone/chloroform/acetic 03664 . -1- Fgiure 3 - 0P-hDoatyogrFaCp-h143ofPThLoCtolRyazdaitceautograph --_-- 052 ----y | i R5e0feprgenFcCe-14S3a-m1pl4eCs i| > 1o7t,30p0hotdoplmyzed 27 | || NQ@ Fe-143 |-- @ origin @ Background (R11 area less spots 1 and 2) DS-1 = D75e/v1e5l/o3p0ing Solvent 1, ethyl acetate/methanol/water, DS-2 = Developing Solvent #2, methyl ethyl ketone/chloroform/acetic acid, 55/30/15 03665 Figure 4 - Gas Chromatogram of Derivatized Photolyzate Samples : e ~ , if o8 tevontion Tine tn Minutes ----p 2a 2 : sii ) Retention Tine fn Minutes -- 3 =