Document 1QLrQkkG3aw82bMkm6XRG8rYq

BACK TO MAIN m 'ijy i TECHNICAL REPORT SUMMARY Ootu _ 1/7/80 TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN (Im portant -- Ifreport is printed on both sides o f paper, send two copies to TCC.) NOV i 3 1980 Division ' EE & PC (Environmental Laboratory - Bldg. 2-3E) Proloct RupoFrtl^Tuitolerochemical - Commercial Chemicals Photolysis of FM3925 in Aq ue ou s Solutions, To mh^r t Dale Author(t) Bacon - EE ~& PC^,:_rB.lr.dr.gg-.:--2-1---2--W---0-4--- ept. KJumber 0535 ProjectNumber .R.e.po9rt9.N7u.mQb.e01r2.600__ 0U5 Employee Number(i) James Gagnon, Notebook Reforence C. H. Schrandt - Envir. 51567 CFrii-iiTV^P. 52692 LR #4649S (CoOmppeanny Confidential) C(S3peCcilaolseAduthorization) Lab 2-3E 3MRECGHIESMTIRCYAL ^r 213531. 1TS452 No. ofRegesInclydtTTj-Goy^rsheet 21 (.3 ) New ChemicalsHeportep/ Q Yes C3TTO KEYWORDS: ISelect terms from 3M Thesaurus. Suggest other applicable tormi.) ebC & T pc -- BfW-:-- Irab- CURRENT OBJECTIVE: 1) Determine if FM3925 is d e gr ad ed by ph ot ol ys is and identification of major products. 2) Construct a th re e- ch am be r p h o t o r e a c t o r and compare results with a Crosby-Tang photoreactor. E -N V !liC H n iL ft f t|L- Fluorochemicals Octylsulfonyl fluorTcTe REPORT A B STR A C T: (200-250 words) This abstract inform ation is distributed by the Technical Communications Center to alert 3 M 'ars to Company R & D . It is Company confidential material. Introduction : Object : Summary : cc : A.Mendel-2-3E-y D.Ricker-53-4N Experimental : 1. Sample materials. 2. E q u i p m e n t : A. Single chamber photoreactor. B. Triple chamber photoreactor. C. Gas chromatograph. 3. Procedure: A. Pr eparation and ph ot ol ys is of FM3925 solutions. B. Extractions: 1) Carbon filter. 2) FM3925 solutions and blanks. 3) Solvent blanks. C. Analysis: 1) Thin layer chromatography. 2) Gas chromatography. 3) Gas ch ro m a t o g r a p h y / m a s s spectrometry. information Liaison Results and Discussion: Recommendation for Future Work; References: - -Iii BACK TO MAIN rK!r> PhotoLysis - JI3G/CIIS p.iqo 2 Movo;nbor 7, 190 0 Introduction: Chemical' .troduced into the environment may be destroyed or p h o t o L y 1 1 >'ly altered by the action of sunlight. Co ns eq ue nt ly , photolysis tudics on such chemicals are now required by the United States Environmental Protection Agency (EPA). Laboratory photomactors produce predictable and reasonably constant irradia tion intensity and are not subject to the perturbation effects of natural sunlight. The Crosby and Tang photoreactor was specif ically designed to simulate sunlight photolysis and has been/is being used in our la bo ra to ry for such s t u d i e s . 1 A v a r i a t i o n of the Crosby and Tang photoreactor, consisting of 3 stackable individual sections, was designed to allow for simultaneous photolysis of a compound of interest, a reference compound, and an actinometer. Object: The object of this study was to d e te rm in e if FM-3925 was photolyzed under laboratory conditions. A second experiment was conducted to compare the photolysis products from a triple versus single chamber photolysis unit. Summary: comparison of the ph ot ol yz ed sample (Figure 7) with the co n t r o l sample (Figure 5) by el ec tr on capture gas c h r o m a t o g r a p h y (EC/GC) showed no ph ot ol ys is products after 30 days. C o m p a r i s o n of the above samples (Figures 12 and 13) by flame io ni za ti on d e t e c t i o n (FID) showed two possible ph ot ol ys is products later id en ti fi ed by gas chromatography/mass spectroscopy (GC/MS) as acetic acid, n-propyl acetate and/or ethanol. Repeat of the experiment in the 3 chamber photolysis unit produced similar results by EC/GC - no observable difference. GC/MS identified two possible photolysis products from the second experiment as a fluorocarbon amine and M- me th yl p e r f l u o r o h e x a n e s u l f o n a m i d e (C 6 F1 2 S O 2 N C N 3 ) Carbon filters on the photolysis units showed insignificant amounts of FM-3925 was volatilized during the experiment. The three-chamber photolysis unit will be useful for preliminary photoLysis information whereas the preparative single chamber unit will be useful for isolating and identifying photolysis products, especially of compounds with low water solubility. Ex per imejatal: 1. Sample Materials: FM-3925 is N - m e t h y l p e r f l u o r o o c t a n e s u l f o n a m i d e - N - e t h y l a l c o h o l : C 8 F 1 7 S O 2 - N - C H 2 CII2 OH CH3 BACK TO MAIN FM-3925 Photolysis - JEG/CHS Paqo 3 No ve mb er 7, 1980 Analytical standard-grade material^ (Lot 505) was obtained from Don Ricker q 3M Commercial Chemicals Division. C a l i b r a t i o n standard samples from 1 to 50 ppm FM-3925 in methanol (ethyl acetate) were prepared by volumetric dilution of a 100-ppm standard (10 mg in 100 mL of methanol (ethyl acetate)). Deionized water was obtained by passing St. Paul city water through beds of activated carbon, macroporous resin, 2-mixed bed deio ni ze rs , a 5 and 0.2 urn filter. Final r e s i s t i v i t y was g r e a t e r than 18 megohms. Carb on for traps was W i tc ar b grade 950 , 8 x 30 mesh av ai l a b l e from Witco Chemical Corporation, New York, NY 10017. Methanol and dichloromethane were reagent grade while the ethyl acetate was chromatography grade ("LiChrosolv"-available from MC/B Manufacturing Chemists, Inc., Norwood, ON 45212). Th in -l ay er ch ro matography (TLC) plates were silica gel, with 254 nm fluorescent indicator, precoated onto glass plates to a thickness of 0.25 mm. Plates available from EM Laboratories, Inc., 500 Executive Boulevard, Elmsford, NY 10523. 2. Equipment: A ,, S i n g l e - c h a m b e r photoreactor, Figure 1, was that originally described by Crosby and Tang2 . B. T r i p l e - c h a m b e r photoreactor, Figure 2, was a m o d i f i e d v e r s i o n ( o r i g i n a l l y d e s c r i b e d in 3M T e c h n i c a l N o t e b o o k 52692-14) of the Crosby and Tang unit. C. Gas c h r o m a t o g r a p h s were a H e w l e t t - P a c k a r d (H-P) Model 5713 (electron capture) and an H-P 5750 (flame ionization detector) with a H-P 3380A integrator-printer. The above are available from Hewlett-Packard Company, 150 Page Mill Road, Palo Alto, CA 94304. 3. Procedure: A. P r e p a r a t i o n and photolysis of FM-3925 solutions A saturated solution of FM-3925 was prepared by magnetically stirring an excess of the sample in water for 6 hours. The resulting solution was filtered (What.man-GF/F) and the clear filtrate used in the following studies. 11 i* 1I j" l , i BACK TO MAIN FM- 3925 Photolysis- JEG/CHS Pagc '1 ' 'Jovember 1, 1980 The saturated FM-3925 solution was added to the ohotolysis unit (Figure 1) and lab air was bubbled through the solution for 10 m i n u t e s . - 1 A c a l c i u m chloride drying tube filled with carbon/glass wool^ was then placed' in the addi ti on port. The temperature was maintained at 35C (95F) by passing an air stream between the fluorescent; tube and inside wall of the unit. The unit was then wrapped in aluminum foil to minimize extraneous effects. A glass amber bottle filled with saturated FM-3925 solution for a control, was placed in the dark at room temperature. The ex pe ri me nt was run for 30 days. The above procedure was used for the triple chamber (Figure 2) unit with the following variations: 1) Chamber 1 (top) filled with water, chamber 2 was empty, and the bottom chamber filled with the FM-3925 solution; 2) temp er at ur e was ma i n t a i n e d at 21+3C (70+5F) by passing water through latex tubing (3/16" i.d., 3/32" wall) that was wrapped around the outside of photolysis unit. B. Extraction 1. Carbon The carbon from the calcium chloride traps was So xhlet e x t r a c t e d (1 cycl es per 30 minutes) for 5 hours wi th d i c h l o r o m e t h a n e (C H2 C 1 2 )- The extract was then concen tr at ed to 1.0 mL with a Kuderna-Danish (K -D ) co nc en tr at or . A p p r o x i m a t e l y 10 m L of m e t h a n o l was added and sample r e c o n c e n t r a t e d to 1.0 mL in the K - D . The carb on was then r e - e x t r a c t e d (1 cycles for 30 minutes) with meth an ol for 5 hours and the methanol extract concentrated to 1.0 mL with the K-D concentrator. 2. FM-3925 (photolyzed and controlled) and water blank. 100 mL of solution was pipetted into a 250-mL separatory funnel. Sample was extracted 3 times (15,5,5 mL) with ethyl acetate (EtOAc). The extracts were added to a 25-mL volumetric flask and diluted to mark with ethyl acetate. For the second experiment, the aqueous samples were extracted 3 times (10,10,5 mL) with dichloromethane. The extracts were combined and concentrated to 1.5 mL with the K-D concentrator and then diluted to mark with methanol in a 25 mL vo lu me tr ic flask. 1035 ''hot.olysis - JHG/CHS P5 Movember 7, 1900 ' 5. Solvent blanks Appropriate solvent blanks were prepared by taking solvents, eq ui va le nt amounts as in. above extractions, and subjecting to the same concentration schemes. C . Analysis 1. Th in -l ay er c h r o m a t o g r a p h y (T L C ): Plates were predeveloped with methanol and samples were c h r o m a t o g r a p h e d in paper-lined glass tanks using 95/5 ethyl acetate/ethanol as the solvent. Visualization was with New Fuchsin^ (0.05% aqueous solution) or Rhodamine 6G. 2. Gas c h r o m a t o g r a p h y (GC): Elec tr on ca pt ur e (E C )-rJi^-and flame ionization detection (FID) was employed for analysis of all samples. A six-feet, 1/8 inch o d , stainless steel column packed with 10% CW20M on 60/80 mesh Chromasorb W - A W was used. Injection (5 ul) was on -c o l u m n at 200C with detection port at 300C. Carrier flow was 95.5 Ar g o n / M e t h a n e (He for FID) at & 40 cc/minute. Tw o temp er at ur e programs were used: 1) 180C isothermal; 2) 165C initial (with a 16 minute hold) then to 235C at a rate of 8C/minute with an upper limit hold so total run time was 1 hour. 3. Gas c h ro ma to gr ap hy/ ma ss sp ec tr os co py (GC/MS): After optimizing GC conditions sample concentrates were submitted to Central Research Lab (Joe Schroepfer) for GC/MS identification. . $ Results and Discussion: Preliminary TLC indicated four spots (Rp =: 0.06 , 0.20, 0.64, 0.76) with Mew Fuchsin in both the control and ph ot ol yz ed samples while Rhodamine 6G detected only one spot (Rp = 0.76) in the same samples. Mew Fuchsin and Rhodamine 6G indicated only one spot (Rp = 0.57) for the FM-3925 standard. Additional TLC on ethyl acetate extracts of water, FM-3925 (control, photolyzed sample, and standard), and a blank indicated the spot at Rp = 0.76 to be an impurity in the ethyl acetate. More detailed work by GC showed methanol as the only solvent containing an impurity (Figures 3, 4, and 11). A methylenechloride extracted water blank (Figure 10) showed no impurities. GC shows 78% of the FM-3925 to be unreactive over a 30-day period (Table 1 ). BACK TO MAIN ''M~ i*J:ir> Photolysis - JFG/CHS I', b :lovember 7, 1980. TA BLR 1 electron Capture GC Results of FM-3925 Photolysis Sample . Concentration _FM23925 Figure ' (mg/V ' McOM blank RtOAc blank FM-3925 Control FM-3925 Std. FM-3925 Photolyzed Carbon filter CT1p C 12 extract MeOfl extract ND* NO 4.9 15.7 3.8 0.1 pg/g carbon ND 3 4 5 6 7 8 9 *ND = Not detected. The 22% Loss is either caused by v o l a t i l i z a t i o n (not d e t e c t e d in the carbon trap), 2) formation of si mi la r prod uc ts in large qu an ti ti es as in the control (Figures 5, 12), 3) s o r p t i o n of FM-3925, or degradative products, onto the walls of the photolysis unit, 4) formation of c o mp ou nd s (e.g., FC-95 C^FiySOgM), which cannot be analyzed by GC. TLC did not detect FC-95 in the photolyzed sample indicating that if formed it was present in very small quantities. Th e c o m p o u n d s p r e s e n t in the photolyzed sample were also present in the control indicating d e gr ad at io n other than ph ot ol ys is is oc curring^. GC (FID) shows an enrichment of the early peak (TR = 6.2 minutes) with almost complete loss of the late eluting peak (TR = 8.3 minutes) when compared to the FM-3925 standard "triplet" (Figures 12 i. 14). A. l a t e e l u t i n g p e a k ( b y EQfcJC) t e n t a t i v e l y i d e n t i f i e d ( b y G C / M S ) as o c t y l s u l f o n y l f l u o r i d e , OSF, {C8 F 1 7 S O 2 F) w a s p r e s e n t in the control and photolyzed samples. Further work indicated OSF formed rapidly in aqueous solutions. The presence of OSF could be a ranid hydrolysis product or a very water soluble impurity^ in the standard. Sample work-up (solvent interactions or thermal degradation) was shown to be an unlikely cause for formation of OSF. Methylene chloride extracts of the carbon filter showed a small amount of FM-3925 (Table 1, Figure 8), wi th no o t h e r m a j o r peaks present. FM-3925 was not present in the m e t h a n o l e x t r a c t e d carbon but a late eluting peak (TR = 6.6 mi nutes, Figure 9) was detected but not identified. Small amounts of this late eluter were present in the methylene ch lo ri de e x t r a c t e d carbon photolyzed and control samples. Since FM-3925 was not present in the methanol extracted carbon, m e th yl en e c h l o r i d e e x t r a c t i o n is sufficient for determining loss of FM-3925 from solution. BACK TO MAIN '1-192') Photolysis - JEG/CHS P.<l- 7 November 7, 1980 Recommendations for Future Work: 1) Dete rm in at io n of origin and i d e n t i f i c a t i o n of late eluting peak in the met'hanol extracted carbon. 2) Cause of the appa re nt en r i c h m e n t of the early el u t i n g oeak in the FM--3925 "triplet" and loss of the late eluter. 3) More de tailed id en ti fi ca ti on of p r od uc ts formed in the control sample. 4) De te rmination of exact cause of f o r m a t i o n of OSF. 5) Determine if hy dr ol ys is plays a larg er ro le in d e gr ad at io n than photolysis. NOTES AND REFERENCES 1. Technical Report Su mmary "E valuation of a Laboratory Ph ot or ea ct or for Si m u l a t i n g S u n l ig ht Ph otolyses," by Je r r y W. Todd, 20 July 1979. Dept. 3068, PM 9776750202, Report #3. 2- Crosby, D. G. and Tang, C. S., J. A g r i c . Food C h e m . , (1969) 17, 1041. 3. Private co n v e r s a t i o n of A. Mendel with R. G. Zepp of the U.S. CPA, Athens, GA. 4. The carbon trap would co ll ec t v o l a t i l e c o m p o u n d s le av in g the test solution. These compounds could then be desorbed and quantitated. 5. Kwapniewski, Z.; Cichon, R. M i c r o c h emical J o u r n a l C1979), 24, 298-299. '" " "" 6 . f m - 3925 is a mixture of at least three components, va r y i n g in branching and/or chain length. 7. C. R. 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