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A R U G O 363 PHOTODEGRADATION (AQUEOUS) TEST SUBSTANCE_________ Identity: N-ethylperfluorooctane sulfonamidoethanol; may also be referred to as N-EtFOSE Alcohol or FM-3422. (1-Octanesulfonamide, N-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: Material is an off-white, waxy solid. The test substance used was 14C labeled (220 dpm/pg). Purity of the test substance is not described. This testing is currently being repeated using current procedures and best available practices. The following summary is abbreviated due to the fact that a new study is pending. M E T H O D ______________________________________________________________ Method/guideline followed: Procedure "essentially" 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 Year: 1981 Light Source: General Electric F-40BL fluorescent black light Light Spectrum (nm): Max output at -3 6 0 nm and essentially no output below 300 nm. Spectral energy characterized from 290-600 nm. Intensity: Wavelength 290 - 300 3 1 0 -3 2 0 320 - 340 340 - 360 360 - 380 3 8 0 -4 0 0 400 - 500 500 - 600 Watts Radiated 0.090 0.235 1.410 1.910 2.310 1.680 2.300 0.340 Spectrum of substance (max lambda, max epsilon and epsilon 295): Not determined. Remarks field: 006446 - Test medium (air, water, soil, other - specify): 60/25/15 solution of water/methanol/acetonitrile respectively - Duration: 31 days - Positive Controls: None - Negative Controls: None RESULTS__________________________________________________________ Concentration of Substance: 50 mg/L Temperature C: 22+2C Degradation %: 0% after 31 days Remarks field: No photodegradation of the test substance was detected in this study. Essentially the same analysis results were obtained for the 31-day photolyzate sample (no photoproducts formed) as the 0-day sample. Radiocarbon assays at 0 and 31 days also indicate no significant amount of product was volatilized during the study. CONCLUSIONS No photodegradation products were detected in this study using simulated sunlight, indicating the test substance does not undergo photolysis. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 DATA QUALITY_________________________________________________________ Reliability: Klimisch ranking 2. Photolysis study is being repeated using currently available procedures, improved analytical methods, and best practices using a sample with characterized purity. REFERENCES_________________________________________________________ 3M Technical Report "FM 3422 PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT." J. W. Todd, Project 97767502, Report Number 004, August 11, 1981 OTHER________________________________________________________ ____ Last changed: 5/18/00 006447 ' '' TECHNICAL REPO 8-11-81 TO; TECHNICAL COMMUNICATIONS CENTER - 201-2CN (Im portant If report is printed on both sides o f paper, send two copies to TCC ) See "Cuidelings fo r ConipletiOi:u^iT>clctiP t r ftl: S um m ary" .iv jiljh /e from Inform ation Liaison or TCC 13 5545). ( I A U U j v) AGRICULTURAL PRODUCTS PROJECT-LIFE SCIENCES SECTOR " "" - SERVICE TO TOSCA Mapof"t~r"Tiln FM-3422 PHOTOLYSIS STUDY USING SIMULATED SUNLIGHT, UC-, 3068 97767502 PojjC* t turrit 004 To R. A. PROKOP A u th o r(t) J. W. TODD E^ nptvaa N u rn h tH i" 43953 N otebook Reference AGRICHEMICAL REQUEST 1008 SECURITY ^ D Op*n (Company C onlideniiall 153Cloied (Special A u th o riza tio n ) 3M CHEM ICAL t , REGISTRY w N o of P'Qt In clu d in g Cp4trtfi ^ \&(3] New Chemicals R epoited Yes J No KEYWORDS: Include Lab Code CHfA AUTO/RADIOGRAPHY DECOMPOSITION ENVIRONMENT GAS-CHROMATOGRAPHY PHOTOLYSIS RADIOTRACER CURRENT OBJECTIVE: Investigate the photolytic stability of FM-3422 as a function of irradiation time and identify any major photoproducts. | REPO R T A B S T R A C T : This abstract in fo rm a tio n is d is trib u te d by the Technical C om m unications Center to alert 3M*ers to j C om pany R & D . It is C om pany c o n fid e n tia l m aterial. i Irradiation of an aqueous solution of FM-3422 for 31 days resulted in no detected photoproducts on analysis by thinlayer chromatography/radioautography and by gas chromato graphy. The irradiation source produced 300 nm and longer wavelength ultraviolet light to simulate natural V/ sunlight. i HlItI1m \, 006448 J. w. TODD REPORT #004 -1- FM-3422 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 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. C 8F17S02N < ^5o h The major component is the straight-chain Cg compound but some other homologs, branched-chain isomers and other impurities may be present. FM-3422 - 14 C Aqueous Solution: A working solution was prepared by dissolving 140 mg of FM-3422!4c (220 dpm/^jg) 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 used to prepare the gas chromatographic calibration standards 006449 J. T. TODD REPORT 004 BEST COPY AVAILABLE -2- 2. Analysis Instruments/Materials/Conditions Ultrasonic Bath Model 8845-4 from Cole Parmer. Liquid Scintillation Counter (LSC) Beckman LS 8000 . Rotary Evaporator Buchi Rotovapor R . Thin-Layer Chromatography (TLC) plates MERCK Silica Gel 60 F-254, 0.25 rom thickness and 20 x 20 cm size 1st 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: Gas chromatograph Varian model 3700. Sample injection 5 pi of photolyzed solution via 10 pi microsyringe. Injection port Column on column, 300C. 6 ft. glass 6% SP 2250 on GAS CHROM Q, 80/100 mesh. Column temperature 155C. Detector Flame photometer operated with: temperature 320C. hydrogen flow 140 ml/min. air #1 flow 80 ml/min. air #2 flow optical filter 170 ml/min. sulphur-specific 006450 J. W. TODD Report 1004 BEST COPY AVAILABLE -3- Electrometer Operated with: input range = 10 amps F S . output - square root mode (linearized) . attenuation x 256. Data system 3. Irradiation Spectra - Physics Model 4100 computing integrator operated in peak height mode. The preparative photoreactor used (Crosby and Tang, 1969) is illustrated in Figure 1. The lamp employed was a now General Electric F-40BL fluorescent black light with maximum output at about 360 nm and essentially no output below 300 nm (Table I, General Electric C o .). The temperature was controlled at 22 + 2C 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 3/4 in. glass tube containing first XAD-2 resin and then charcoal. The photolyzed. samples were sampled after irratiatin 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 10 jil. Column temperature Electrometer output normal mode. Electrometer attenuation X16. 006451 J. W. TODD REPORT #004 BEST COPY AVAILABLE -4- 4. Radiocarbon Recovery The photolyzed samples were assayed for radiocarbon by LSC to determine radiocarbon recovery as a function of irradiation tine. The results are presented in Table II. 5. Investigation for Photoproducts by TLC-Autoradioqraphy Aliquots of the 0 and 31 day photolyzed samples were effect ively reduced in volume 10-fold before analysis by two-dimensional TLC/radioautography: A 50-ml aliquot of each sample was quantitatively 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 35C water bath. Then 10 ml of acetonitrile was added and the evaporation was continued to just-dryness (acetonitrile was used to expediciously remove any water as an azeotrooe 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 pi microsyringe. The plate was developed twodimensional ly, 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 analysed for "non-phototyzed FM 3422" by gas chromatography using flame photometric detection. Known concentration solutions of analytical standard FM 3422 were used for external standard calibration. The results are presented in Table III and the sample chromatograms in Figure 4. The calibration chromatograms 006452 J. W. TCDD REPORT | 004 BEST COPY AVAILABLE -5- 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 275C column temperature). The resulting chromatogrsuns 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-programmed gas chromatography (Figure 7) showed any components in the 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 pg/ml (49 ppm) in the 0-day sample and 44pg/ml (44PPm) in the 31-day sanple (Table III).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 through volatilization was investigated by analyzing the photolyzer vapor trap for radiocarbon but only a negligible amount was found XD.01%). The most plausible explanation is the loss by precipitation in the photoreactor. The solubility of FM 3422 in the 60/25/1S water/ methanol/acetonitrile photolysis solvent is apparently only marginal although initial studios had indicated adequate solubility (and this in turn was a. modification of a previous 70/30 water/methanol solvent which was found inadequate). Also the 10 mi/minute air sweep through the photolyzer would preferentially volatilise the organic solvent 006453 J. W. TODD REPORT | 004 BEST COPY AVAILABLE -6- components and thereby would cause a decreasing solubility for IW 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 turbidity and white solids which formed when the collected samples were refrigerated. Before analysis the samples were warmed to 35C 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, Volume 43. No. 1^2-Monday, July 10, 1978. General Electric Company, Lamp Division, Cleveland, OH 44112. Roller, L.R. 1965. Ultraviolet Radiation, 2nd Ed. Wiley, New York 312 p. Submitted by: J. W. Todd, Senior Research Specialist /ml 006454 J. W. TODD REPORT #004 BEST COPY AVAILABLE -7- Tabie I Spectral Energy Distribution for a GE F40BL 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 1.910 2.310 1.680 2.300 0.340 Maximum intensity at about 360 nm 4 006455 J. W. TODD REPORT t 004 1 S T COPY AVAILABLE - 8- Table II - Radiocarbon Found in Photolyzed Solution as a Function of Irradiation Time Sample Irradiation Time in Days Radiocarbon Observed Disintegrations/**in. Percent Recovery 0 10/984 [100.0] 1 10/822 98.5 3 10,940 99.6 7 10,958 99.8 15 10,786 98.2 31 9,896 90.1 006456 J. W. TODD REPORT 1004 BEST COPY AVAILABLE -9- Table III. Quantitative Gas Chromatographic Analysis Results for FM 3422' Calibration Standards and Photolyzed Samples. CD O Sample Description 20 fag/ml standard 40 SO 0 - day sample 31 - day sample FM 3422 Analysis Results Peak Height ^tg/ml Cone, (ppm) 117 [20] 272 [40] 451 [60] 573 [80] 344 49 315 44 006457 BEST GORY AVAILABLE -- jLwibox'a'cury i n o t o i v a c t o r 006458 J. T. TODD REPORT "004 nFST COPY AVAILABLE Figure 2 - Photograph of TLC Radioautograph, O-Dc.y FM 3422 Photolyzed Sample. DS-2 ------ > A DS-l Reference Samples, 50 fig of FM 3422-14C, 10,984 DPM, not photo lyzed. FM 3422 DS-l = Developing Solvent 41, hexane/acetone 75/25. PS-2 = Developing Solvent 42, chlorofora/methanol 97.5/2.5. + = Origin (where samples were spotted) 006459 J. W. TODD REPORT #004 b est co py AVAILABLE Figure 3 - Photograph of TLC Radioautograph, 31 Day FM 3422 Photolyzed Sample. DS-2 ------ ;> A DS-l Reference Samples, 50 ug of FM 3422-14C 10,984 DPM, not photolyzed FM 3422 t DS-l = Developing Solvent 11, hexane/acetone 75/25. DS-2 = Developing Solvent #2, chloroform/methanol 97.5/2.5. + = Origin (where samples were spotted). 006460 BEST COPY AVAILABLE Figure 4 - Quantitative Gas Chromatograms for FM 3422 Photolyzed Samples 0-Day 31-Day <Vj iru ITJ % i Peak Height Response t l fv I CNi If*" r-' 1rvC. ir* o. <V' U: Cb U1 t Va c o a. Ua)) II J0ZH s <0 in IX UI If' O'. <s> ui X ru tui. 0 to 4 Minute Retention Times -- > (as indicated on each chromatogram) 006461 J. W. TODD REPORT j?004 BEST COPY AVAILABLE Figure 5 - Gas Chromatograms for FM 34.72 External Calibration Standards 20 pg/ral H 40 jug/ml 60 pg/ml M ri 8*0s*^uq/ml Pea? '{eight Response Solvent Peak 1*. o rIn I- 0Tl IV CP. cr aU ' O' u: ^J Ui CM <r. CD u; s C UJ 0 to 4 Minute Retention Times a *. IT ; CD d w a. a. ad a<*. cI-' a~ in - mJt*- c. Z *- A 006462 Concentration of FM 3422 in ^g/ml a. .V, '. <T> m a> - f - ................ _ ; . 006463 BEST COPY AVAILABLE Figure 7 - Impurity Profile Gas Chromatograms for FM 3422 Photolyzed Samples 0 Day Sample 31 Day Sampl. i 4M J t- 0 to 15 Minute Retention Times -- ^ (an Indi cated on each .ehromnt.orjrnms) 006464 BEST COPY AVAILABLE DISTRIBUTION LIST S. X. BANDAL............................... 230-B R. L. BOHON ............................... 21-02W R. A.PROKOP ............................ .236-2B E. A. REINER ..... ...................... 21-02 D. R. RICKER ..............................53-04-02 TECHNICAL COMMUNICATIONS ................. 201-2S 006465