Document VJR11ERk0QQbLMYXqLa54mdjo

PHOTODEGRADATION (AQUEOUS) TEST SUBSTANCE Identity:N-ethylperfluorooctasnuelfonamidoethanolm;ay alsobe referredto as N-ETFOSE Alcoholor FM-3422. (1-OctanesulfonamideN,-ethyl1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-N-(2-hydroxyethyl)-, CAS # 1691-99-2) Remarks: Materialisan off-whitwea,xy solidT.he testsubstanceused was 14C labeled(220dpm/pg). Purityofthetestsubstanceisnot descdbed. Thistestingiscurrentlbyeingrepeatedusingcurrent proceduresand bestavailablperactices. The followingsummary isabbreviateddue to thefactthata new study is pending. METHOD Methodiguidelinefollowed: Procedure"essenfiallays"describedinthe FederalRegister(Volume 43, No. 132-Monday,July10,1978) by theU.S. EnvironmentalProtectioAngency. Type (testtype): Simulatedsunlight GLP (Y/N):No Year: 1981 LightSource: GeneralElectdcF-40BL fluorescenbtlacklight LightSpectrum (nm): Max outputat-360 nm and essentiallnyo outputbelow 300 nm. Spectralenergycharacterizefdrom 290-600 nm. Intensity: 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 1.910 2.310 1.680 2.300 10.340 Spectrum of substance (max lambda, max epsilonand epsilon295):Not determined. Remarks field: Testmedium (airw,ater,soilo,ther-specify)6:0/25/1s5olutionf waterlmethanol/acetonitrirleespectively - Duration: 31 days - PositiveControls: None - Negative Controls: None RESULTS Concentration of Substance: 50 mg/L Temperature *C: 22+2*C Degradation %: 0% after31 days Remarks field:No photodegradation of the testsubstance was detected inthis study. Essentiallythe same analysisresultswere obtainedforthe 31 -day photolyzatesample (no photoproductsformed) as the 0-day sample. Radiocarbon assays at 0 and 31 days also indicateno significanatmount of product was volatilizedduring the study. CONCLUSIONS No photodegradation productswere detected inthisstudy using simulated sunlight,indicatintghe testsubstance does not undergo photolysis. Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul, Minnesota, 55133 DATA QUALITY Reliability:Klimischranking 2. Photolysisstudy isbeing repeated using currentlyavailableprocedures, improved analyticamlethods, and best practices using a sample withcharacterizedpurity. REFERENCES 3M Technical Report "FM 3422 PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT." J.W. Todd, Project97767502, Report Number 004, August 11, 1981 OTHER Last changed: 5/18/00 . .... TECHNICAL REPOT [A IY A RY 8-11-81 TO TECHNICAL COMMt)t4lCATIONS CENTER - 201-2CN os ED AUrzi@ (1111f;rIjtfrirl,lji)ts(,pritriltoen(II)ostih(olfepsai)seetr,tivcfclopiteosTCCISev"GulI(I foCroeyti)iet,oiait ivailjflr)elI),t..i.f.or,L,;,j,i,so;orTO,C,,C,f35545). AGRICULTURAL PRODUCTS PROJECT-LIFE SCIENCES SECTOR SERVICE TO TOSCA FM-3422 PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT, AL) 3068 1'97767502 t 004 R. A. PROKOP Author(s) J. W. TODD NOI&Ix)ok R*fwonce AGRICHEMICAL REQUEST 1008 SECURITY 10, r-Io,,, U Closed 3M CHEMICAL ih. (ContWyConfidetnial) 4SpeciAaulthorization) REGISTRY "Waal/so he, s 43953 No, of 1.2_ P"es inclucs-n C sb"t B Now ChemicaRlesported 0 Yes sa No KEYVVORDS: IncludLeahCode Pt@%9-t L--4c-m AUTO/RADIOGRAPHY DECOMPOSITION ENVIRONMENT GAS-CHROMATOGRAPHYI PHOTOLYSIS RADIOTRACER CURRENT OBJECTIVE: Investigate the photolytic stability of FM-3422 as a function of irradiation time and identify any major photoproducts. REPORT ABSTRACT: This&bstract infornution is tlislrii)uted by the Techn-cal Commun.r-ations CorrtpoRn&yD. ItisCompany-lonfidenmtaitaelr.ial. Center to alert 3M*"s to Trradiation of an aqueous solution of FM-3422 for 31 days resulted in no detected photoproducts on analysis by thin- layer chromatography/radioautography and by gas chromato- graphy. The irradiation source produced 300 nm and lcnger wavelength ultraviolet light to simulate natural sunlight. J. W - TODD REPORT #004 FM-3422 PAOTOLYSIS 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 inve.stigated the possible photodegradation of FM-3422 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 FM-3422 is 1-octanesulfonamide, N-ethyl-1,1,2,2,3,3,4,4,5,5, 6,6,7,7,8,8,8 - heptadecafluoro-N-(2-hydroxyethyl)-. It is also identified by the Environmental Protection Agency (EPA) as CAS 1691-99-2. CSF17SO2N -'- C2H5 C2H40H The major component is the straight-chain Ca compound but some other liomologs, branched-chain isomers and other impurities may be present. FM-342@" - 14 C Aqueous Solution: A worki-ng solution was prepared by dissolving 140 mg of FM-342214C (220 dpm/jag) in 2800 ml of 60/25/15 water/methanol/acetonitrile mixture. FM-3422 Analytical Standard: obtained from Chemical Resources Division, 3M Co. (St. Paul,MN) it is tised to prepare the gas chromatographic calibration standards. J. T. TOE-D -2- REPORT #004 2. Analysis Instruments/Materials/Conditions Ultrasonic Bath Mc>del 8845-4 from Cole Parmer- Liquid Scintillation Counter Beckman LS 8000. Rotary Evaporator Buchi Rotovapor R. (LSC) Thin-Layer Chromatography (TLC) plates MERCK Silica Gel 60 F-254, 0.25 =a thickness and 20 x 20 cm size, ,Ist developing solvent-75/25 hexane/acetone. 2nd developing solvent-97.5/2.5 chloroform/methanol. X-Ray Film KODAK NS-2T, 8 x 10 inch size. Photographic Print 4 x 5 Film Type 55 from Polaroid Corp. Gas Chromatography Parameters. a) Gas chromatograph Varian model 3700. Sample injection 5 )alof photolyzed 10,Flmicrosyringe. solution via Injection port Column on column, 3000C. 6 ft. glass 6% SP 2250 on GAS CHROM Q, 80/100 mesh. Col-amn temperature 1550C. Detector Flame photometer operated with: temperature hydrogen flow 320*C. 140 ml/min. air #1 flow air #2 flow optical filter 80 ml/min. 170 ml/min. sulphur-specific J - W. TODD Report 1011 Electrometer -3- operated with: input range output attenuation -10 10 amps FS. square root mcde (linearized). x 2'56. Data system 3. Irradiation spectra - Physics 14odel 4100 computing integrator in peak height mode. operated The preparative photoreactor used (Crosby and Tang, 1969) is illustrated in Figure 1. The lamp employed was a naw General Electric F-40BL fluorescent black light with maximum output at about 360 nm and essentially no output below 300 nm (Table 1, General Electric Co.). The temperature was controlled at 22 + 2*C by circulating tap water through flexible plastic tubing wrapped around the reaction chamber. Air was passed through the photolysis solution at 10 ml/min for oxygenation and mixing. The exit port was connected to a vapor trap. The trap consisted of a 6 x 314 in. glass tube containing first Y.AD-2 resin and then charcoal. The photolyzed samples were sampled after irr&liatia intervals of 0, 1, 3, 7, 15 and 31 days. The samples were removed through the reactor drain port and were refrigerated until analyzed. a) Except for Figure 6 (impurities profile analysis) where: Sample introduction Column temperature Electrometer output 10 ul 75.0-A;75 at 20*C/mtn,4nd_h4ild 5 mn. a im: ..zr normal mc>de. Electrometer attenuation X16. J. W. '.L'ODD -4- REPORT t004 4. Radiocarbon Recovery The photolyzed samples were assayed for radiocarbon by LSC to determine radiocarbon recovery as a function of irradiation tir.ie. The results are presented in Table II. 5. Investigation for Photoproducts by TLC-Autoradiography Aliquots of the 0 and 31 day photolyzed samples were effect- ively reduced in volume 10--fold before analysis by two-dimensional TIZ/radioautography: A 50-ml aliquot of each sample was quantitative'Ay extracted with consecutive 50 ml portions of chloroform, the two chloroform extracts were combined and evaporated to near-dryness using a vacuum rotary evaporator with a 350C water bath. Then 10 ml of acetonitrile was added an& the evaporationwas continued to just-dryness (acetonitrile was used to expediciously remove any water as an azeotroop- and thereby minimize possible loss of sample). The sample solids were dissolved in 5.0 ml of chloroform and a 100 )il portion of the sample concentrate (equivalent to 1 ml of the original photolyzate solution) was "spotted" onto the TLC plate using a 100)11 mic-rosyringe. The plate was developed two- dimensionally, first with hexane/acetone (75/25) and then with chloroform/methanol (97.5/2.5). it was air dried and then radioautographed. Figures 2 and 3 are pictures of the 0 and 31 day radioautographs, respectively. 6. Investigation for Possible Photoproducts by Gas Chromatography The 0 and 31 day photolyzed samples were directly analy-zed for *non-phototyzed FM 3422" by gas chrcmatography using flane photometric detection. Known.concentratio-.% solutions of analytical standard FM 3422 were used for external standard calibration. The results are presented in Tabl* III and the sar,iplechromatograms in Flquro 4. The calibration chromtograns J. W. TODD -5- REPORT # 004 are presented in Figure 5 and the linear calibration plot in Figure 6. Possible photoproducts were further investigated by reanalyzing the 0 and 31-day photolyzed samples at greater detection sensitivity (x 16 attenuations) and over a wide temperature range (75 to 275*C column temperature). The resulting chromatograms are presented in Figure 7. DISCUSSION OF RESULTS No photodegradation of FM-3422 was detected in this study. Neither TLC/radioautography (Figures 2 and 3) nor temperature-prc>gramed gas chro-@aatography (Figure 7) showed any components in -,he 31-day sample which were not present in the 0-day initial sample. Gas chromatographic assay analysis of the samples showed FM3422 concentration of 49 ug/ml (49 ppm) in the 0-day sample and 44.ug/ml (44PPm)in the 31-daysample (TableIII).This 10% relative decrease was also substantiated by radiocarbon assay (Table II). The cause of the 10% relative decrease in Fm 3422 concentration during the 31 day photolysis is unknown. Possible loss t@r&,rough volatilization was investigated by analyzing the photolyzex vapor trap for radiocarbon but only a negligible amount was found 140.01%). The most plausible explanation is the loss by precipitation in tk-.e photoreactor. The solubility of FM 3422 in the 60/25/lS water/ methanol/acetonitrile photolysis solvent is apparently only marginal although inilial studi@ushad indicated adequate solubility (and this in turn was & modification of a previous 70/30 water/methanol solvent which wes found inadequate). Also the 10 a!/minute air aveep through the photolyzer would preferentially volatilize the organic solvent J. W. TODD -6- REPORT 1 004 components and thereby would cause a decreasing solubility for FM 3422 in the remaining sample solution. After the study was completed, the photoreactor was cleaned but the washings were not analyzed for radiocarbon content. Marginal solubiluty of FM 3422 in the photolyzate was further substantiated by the tuzb'idity and white solids which formed when the collected samples were refrigerated. Before analysis the samples were warmed to 35*C and sonicated until the precipitate was resolublized. The samples were then cooled to ambient temperature and analyzed. A water/acetonitrile solvent system is recommended for any future phototysis studies on FM 3422. Methanol is a relatively poor solvent and its inclusion would be of dubious value. 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. Crosby, D.G. and Tang, C.S., J. Agric. Food Chem., 17, 1041 (1969). Federal Register, Volur-e 43. No. 132-14onday, July 10, 1978. G@--neralElectric Company, Lamp Division, Cleveland, OB 44112. Koller, L.R. 1965. 312 p. Ultraviolet Radiation, 2nd Ed. Wiley, New York. Submitted by% 0 - v. -190a J. W. To(ld, Senior /ml Research Specialist J. W. TODD -7- REPORT #004 Table I - Speutral Energy Distributicn for a GE F40BL Black Light Bulb Wavelength 290 - 300 310 - 320 320 - 340 340 - 360 360 - 380 380 - 400 400 - 500 Soo - 600 Watts Radiated 0.090 0.235 1.410 1.910 2.31q0 l< Maximum intensity at about 360 rm 1.680 2.300 0.340 J. W. TODD REPORT # 004 Table II - Radiocarbon Found in Photolyzed Solution as a Function of Irradiation Time Sample Irradiation -ime in Days 0 1 3 7 15 31 Radiocarbon Observed Disintegrations/Kin. Percent Recovery 10,984 10,822 10,940 10,958 10,786 9,896 [100.01 98.5 99.6 99.8 98.2 90.1 J. W. RL'ODD -9- REPORT #004 Table III. Quantitative Gas chromatographic Analysis Result3 for F.143422: Calibration Standards and Photolyzed Samples. SamiRle Description 20 pg/ml standard 40 60 so 0 - day sample 31 - day sample FM 3422 Analysis Results Peak Height I!g/mi conc.(ppm) I 117 (201 272 1401 451 [601 573 [801 344 49 315 44 iabu.'aLT ury 1:notor@vactur intot Pymx glass oj,gtv.stopo F-408L bulb J. T. TODD REPORT -;004 F@-gure 2 Photograph of TLC Radioautograph, O-Di.y FM 3422 Photolyzed Sample. DS-2 > DS-1 Reference Samples, 50 pg of FM 3422-14C, 10,984 DPH, not photolyzed. FM 3422 DS'l = Developing Solvent 11, hexane/acetone 75/25. nS-2 = Developing Solverit #2, chloroform/methanol 97.5/2-5. + = origin (where samples were spotted) J. W. TODD REPOR'N t004 Figure 3 Photograph of TLC Radioautograph, 31 Day FM 3422 Photolyzed Sample. Ds-2 DS-1 Reference Samples, 50 ug of FM 3422-14 c 10,984 DPM, not photolyzed FM 3422 DS-1 = De-.;elop4LngSolvent #1, hexane/acetone 75/25. DS-2 = Developing Solvent #2, chloroform/methanol 97.5!2.5. + = origin (where samples were spotted). Figure 4 Quantitative Gas Chromatograms for FM 3422 Photolyzed Samples O-Day 31-Day ?A CIO) r. c 0 0 04 04 m rA 4J cz w CD It In 04 U't -4 LL; ul $tu.i.-]H 0 to 4 Hinxite Retention Times (as indicated on each chromatogram) J. W. TODD REPORT -1"004 Figure 5 Gas Chromatograms for FM 34"12 External Calibration Standards 20,pg/ml 40 ug/ml 60 ug/ml 80. uq/ml Solvent Pea 0 M 3422 cu re CD ct ul ut w 0 to 4 Minute Retention Times Cb ut Lu CL- W ir NO. 34LJ-10 DIICTZGCM GRAPH 113 X 113 PER INCH PAPCR lftk R.PC).RAT 10 N dok e_ T 1 -T p--Ca bration- Plot or* F M- -142@ t t i-4 L.. . . . . . . . . . . . . .. . t 7 t-4 . . . .. . . .. .. .. . . . . . . . . .. . . .. . .. .... .... ... ..... ... .... (49 d Sam lp (45',l J2 Al . . . . . . 20 40 60 80' Concentration of FM 3422 111 pg/ml Figure 7 Impurity Profile Gas Chromatograms for FM 3422 Photolyzed Samples 0 Day Sample cr, 31 Day Sampl.--,, r4 0 Solvent tn FM 3422 Ila ao IDA V. ul ul 0 to 15 Minute Retention Times (in indicAteM on each chromatoarams) DISTRIBUTION LIST S. -9'%.BANDAL ........................o..o..230-B R. L. BOHON .....................2.1-02W R. A. PROKOP ............................23.6-2B E. A. REINER ............................21.-02 D. R. RICMR ............................5.3-04-02 TECHNICAL COMMUNICATIONS ................2.01-2S