Document 3NJYwonGzv8dmEMwnYaoG3BvD

BACK TO MAIN 35?7a7*u.A T E C H riid & fe R e p o r t s* . i , TO: TEC H N IC A L COMM UNICATIONS CENTER - 201-2CN ' su m m a r y . ( I m p o r t a n t -- I f re p o r t is p r in t e d o n b o th sides o f p a p e r, sen d tw o co p ie s to T C C . D ato 8/6/80 A U U 2 ^ 1980 D iv is io n Environmental Engineering Projoc t "Pni-r' r- . FI nnrnphpmi pair. R oport Titlo Phnt.ndpo-rndation S tu d v on To and P o llu t io n C o n tro l . ... 0535 Project Num bor ... ------------------- 997OO1260.0 Report Number FM-3925._f:in ; r- 4_i:_)--? ^ ---------------- :------- )1 043 D. L. Bacon A u th o r(s) Arthur Mendel. . Connie N o teb ook Reference 51050, 51567 SECURITY Q Ooen (Company Confidential) H. S c h r o n d i. 13 Closed (Special Authorization) 3M CHEMICAL REGISTRY w Employoo Num bor(j) 043939^ N o. o f lnc\u ding Cov^rshoot 9 (2V Now Chemicals Reported Yes Q No KEYWORDS: (Select terms Irom 3M Thesaurus. Suggest other applicable torms.) CURRENT OBJECTIVE: EE^&.PC - Div. (Env. Lab) Final Report. Fate Degradation P h o to ly sis REPORT ABSTRACT: (200-250 words) This abstract information is distributed by the Technical Communications Center to alert 3M'ersto Company R&D. It is Company confidential material. A supersaturated aqueous solution of FM-3925 was subjected to sunlight to determine if the compound undergoes photolysis. GC/MS indicates isomerization possible. Informntio Initial*: 73 BACK TO MAIN FM-1925/AM Page 2 August 6, 1980 OBJ LCT1VE; The purpose of this first pilot photolysis study was to examine the feasibility of subjecting chemicals in water to long-term intense sunlight simulating "real world" conditions. The work site chosen was the Bird Corporation, a 3M subsidiary, located in the sunlight-drenched desert of Palm Springs, CA. RESULTS: Four aqueous mixtures were subjected to nearly seven months of natural sunlight (Palm Springs, CA) FM-3925, FM-3925-acetophenone (activator), DDT (reference), and water blanks. Respective light-protected retains served as controls. Gas chromatography (GC) and GC/MS (mass spectroscopy) of the laboratory processed mixtures indicated that FM-3925 did not undergo any major photolysis (and/or hydrolysis) other than possible isomerization (MS). The sunlight and climate at the Bird Corporation location (Palm Springs, CA) make this an ideal site for conductiog "real world" simulated photolysis studies. Further, many valuable lessons jere learned (see Discussion). DIS 'ION: In-, se photolysis studies have been done in the Environmental Laboratory. Such work tries to simulate natural conditions, r.. G. Zepp1 suggested that aqueous photolysis studies be done but subjecting candidates in water to natural sunlight. He further pointed o-ut that use of natural waters, e.g., those from a nearby river, approximates the "real world" better than in-house studies using pure water. Accordingly, the "Fate of Fluorochemicals" project was dovetailed with this initial photolysis project to provide experience in this area for future laboratory protocol. The fluorochemical chosen in this investigation was FM-3925 (N-Methylperfluorooctanesulfonamj.de) . The overall plan for thi.s study was to place an excess of candidate chemicals in fish tanks, add water, seal the tanks, and expose them to sunlight in a suitable location (e.g., roof) for a given length of time. The tanks' contents were to be returned to the Environmental Laboratory for processing. The overall plans were executed and the following lessons were learned: 1. Nearly seven months' sunlight exposure led to clean materials, i.e., the tanks and contents were not discolored, choked with algae or other organisms. BACK TO MAIN FM-3925/AM Page 3 August 6,1980 \ 2. We cannot rely on a local (California) source of supply for all-glass fish tanks or other accessories. In future work, the Environmental Laboratory must purchase, ship, and supply all items to test site. 3. Better sealing of glass lids onto aquarium tanks, better pressure-equalization regulators on sealed tanks, and an improved method to support tanks during testing are needed (see Observations, Table I). 4. Teflon-lined or an inert material-lined caps should be used in place of aluminum foil to seal containers such as retains, controls, blanks, and the like. 5. The personnel at Bird Corp. were cooperative^, they provided us with excellent written observations, kept in communication, and were a key help in the close-out stages of the experiment. 6. Bird Corporation's Palm Springs, CA, location is ideal since (1) the over experiments were successful, (2) the sunlight conditions are ideal, (3) no security or confidentiality problems, and (4) cost effective (3M subsidiary). Briefly, an excess of chemical or chemicals were added to water contained in a fish tank. It was then sealed and sunlight exposed for nearly seven months. One tank served as a blank. Another tank eontained FM-3925 and a third tank contained FM-3925 plus acetophenone, an activator. It was thought that if FM-3925 does not undergo photolysis, it may be induced to do so in the presence of an activator. A reference material, DDT, was photolyzed in a fourth tank to serve as a reference since its photolysis is documented^. A duplicate set of experiements was prepared in case of an accident, e.g., breakage or leakage of a tank, breakage of a sample dur in g`shipment back to the Environ mental Laboratory, etc. This foresight proved of value (see Table I). Similarly, control samples were kept in the dark for the duration of experiments. All samples and controls were returned to the Environmental Laooratory where they were processed. It was shown by GC/MS that FM-3925 did not undergo any major photolysis and/or hydrolysis other than branching4 . As expected, the reference DDT sample . underwent nearly complete decomposition during this photolysis study. See Experimental for details. BACK TO MAIN FM-3925/AM Page 4 August 6, 1980 EXPERIMENTAL : This work is filed under request 4920S and recorded in notebooks 51967 and 51050. At Bird Corporation's facilities^, eight (5-gal.) aquarium tanks were filled to within c a . 25 mm from the top with distilled water (two of the aquaria did have some plastic parts). Two tanks were then set aside and labeled blanks while four were supersaturated with FM-3925 (c a . 0.5 to 1 g). Twenty drops (ca . 1 ml) of acetophenone, a photoactivator, was added to each of two of the FM-3925-containing tanks. The remaining two tanks were supersaturated with DDT (0.5-1 g, Aldrich Chemical Co.). About 150 ml, representative of each tank, was transferred to a respective jar which was then sealed with an aluminum foil-lined lid and then stored in the dark for the entire study. These retains were laoeled controls. Each aquarium, whose water level was marked, was covered with glass and sealed with Dow Corning silicone sealant^1. An 18-gauge syringe needle was positioned and imbedded through the sealant to serve as a pressure equalizer between the inside of the tank and the atmosphere. The tanks were then exposed to sunlight and observations were recorded of the outside temperature, water level and general physical conditions throughout this investigation. (Table I). At the end of the experiments, samples from all the remaining aquaria, including blanks and controls, were transferred to amber bottles, capped (TedlarR-liners) and shipped to the Environmental Laboratory. When received, some of the control samples looked turbid and it was thought that was due to the aluminum foil used tc cover the tanks**. One sample from each group of controls and photolyzed samples were extracted three times each with dichloromethane. The combined extract of each was concentrated to <1 ml with a Kuderna-Danish (K-D) concentrator. This concentrate was then diluted to 25 ml with methanol. . . The methanol solutions for the water blanks, FM-3925 samples, and FM-3925 plus acetophenone samples were analyzed on the HP5713 gas chromatograph under the following conditions: Oven temp: 150C Detector temp: 300C Injection port temp: 200C Detector: Ni 63 Flow: 35 cc/min. of Ar/CH4 , 95/5 ; i\ ;i* ji '1 ,, ; .; j I I ; ; BACK TO MAIN FM- 39 25/AM Page 5 August 6, 1980 | Following is a description of the column used: Column material: stainless steel Dimension: 6 1 x 1/8" OD Liquid phase: 10% Support: 60/80 mesh Chromasorb W, acid washed. One major peak was in both the control and photolyzed samples, which did not appear in a freshly prepared standard. See Table II for results, which were obtained by direct area comparison with a known standard. The methanol from the DDT extracts was also analyzed on the 1IP5713 gas chromatograph under the following conditions: Oven temp: 200C Detector temp: 250C Injection port temp: 200C Detector: Ni 63 Flow: 40 cc/min. of Ar/CH4 , 95/5 The following column was used: Column material: glass Dimensions: 6 ' x 1/4" OD Liquid phase: SP2250 and SP24G1 Loading: 1.5% and 1.95%,. respectively Support: 100/120 mesh Supelcoport Concentration of the control was 4.9 mg/1 DDT and concentration of the photolyzed sample was 0.09 mg/1 DDT. These results were also obtained by direct area comparison with a known standard. The methanol extract from the photolyzed FM-3925-acetophenone sample was concentrated on a K-D unit and the concentrate was a n a l y z e d by G C / M S (Central R e s e a r c h 'A P R L La b R e q u e s t C55135) which indicated branching of the fluorochemical (isomerization) only. ' T3WaOBS2HB BACK TO MAIN l'M-3 9 25/AM Page 6 August 6, 1930 TABLE I REMARKS ON THE PHOTOLYSIS EXPERIMENTS Date Time Temp Observations . j 6/26/79 7:30 AM 80F Original placement of tanks ! 7/1/79 7:30 AM 65F Tanks 6 and 7 cloudy; no dis coloration in remaining tanks. , 7/9/79 8:00 AM 80F Replaced aluminum foil tops on Tanks 6 and 7 with glass; some contamination with foil and silicone. I 7/17/79 7:30 AM 85F Small hole in sealant of Tank 1; otherwise no change. : 7/24/79 7:30 AM 85F Tanks were subjected to severe rain storm; all tanks shown an elevation of fluid level. 8/1/79 11:00 AM 95F No change from 7/24/79. 8/14/79 2:30 PM HOOF Tanks were subjected to addi tional rain s:orm; all tanks above original fluid level; visible cracks in sealant; will repair after fluid level has dropped somewhat by evaporation. 8/27/79 8:30 AM 750F Tank 1 is low; tanks 2, 4, 8 elevated;, remainder of tanks show approximately normal fluid level. 9/7/79 4:00 PM 120F Resealed tanks 1, 8, 5, 2, 4; Tank 1 is low; fluid level in remainder of tanks is elevated. 9/24/79 7:30 AM 550f No change from 9/7/79. 10/12/79 7:45 AM 50F No change from 9/24/79. FM-3925/AM Page 7 August 6, 1980 Date 10/30/79 Time 8:00 AM 11/6/79 7:30 AM 12/9/79 1/9/80 7:30 AM 7:30 AM I TABLE I (continued) BACK TO MAIN Temp 52F 50F 55F 50F 1 Observations No change from 10/12/79, except Tank 1 is markedly low. IMPORTANT: Tank 1 appears to have lost its fluid content through a leak in the base of the tank and not via evaporation. No change from 10/30/79. IMPORTANT: Contents from Tank 1 transferred to glass jar; some particulate contamination (glass, foil); sample stored with controls in the dark. No change from 11/6/79. Tanks subjected to severe rain storm; Tanks 4, 8, 2 damaged structurally; total contents of Tank 2 lost; small amounts of contents of Tanks 4 and 8 recovered; degree of contamination to contents of Tanks 4 and 8 is uncertain; recovered ` samples from Tanks 4 and 8 stored with controls in dark. REMARKS: Experiment terminated on 1/15/80. Tanks 5 and 3 structurally damaged. There was no algal growth in any of the tanks for the duration of the experiment. There was no discoloration of the samples for the duration of the experiment, with the exception of the tanks lined with aluminum foil (Tanks 6 and 7). . |i| |;j J! ** j |r : j j j| j| j I BACK TO MAIN FM-3925/AM Paye 8 August 6, 1980 i TABLE II ANALYTICAL RESULTS OF SAMPLES CONTROLS Description Amount Extracted (ml) FM-3925 mq/1 #8 Blank 205 <0.06 #1 FM-3925 380 (2 jars) 0.4 If3 FM-3925 340 (2 jars) plus acetophenone 0.3 PHOTOLYZED SAMPLES #8 Blank 490 <0.02 #1 FM-3925 975 7.9 #3 FM-3925 ' plus acetophenone 1,000 2.7 New Peak* (mq/1) <0.06 0.1 0.1 <0.02 0.7 0.7 * Assigned to isomers of FM-3925 based on GC/MS data. BACK TO MAIN FM-3 9 2 5 /AM Page 9 August 6, 1980 NOTES AND REFERENCES 1. Phone conversation of A. Mendel with R. G. Zepp, Environmental Research Laboratory, USEPA, Athens, GA. _ : 2. The assistance especially of Mr. David F. Wirt, Bioengineer, Bird Corp., Palm Springs, CA, is greatfully acknowledged. 1. R. G. Zepp, N. L. Wolfe, J. A. Gordon, and R. C. Fincher, J. Agric. Food Cham., 24, 727 (1976). 4. GC/MS identified acetophenone, oC-methylbenzylalcohol, a hydroxy-substituted acetopnenone and possible tolualdehyde in the FM-3925-scetophenone photolysis product in addition to fragments attributed to FM-3925 and its branched chain isomers. Only one and the same sample of FM-3925 was used throughout this study. 5. The Environmental Laboratory is indebted to Mr. A. u. Dressier who set up these experiments at the Bird Corp. 6. Two of the aquaria from a local (California) supplier had some plastic parts. The aquaria, covered with aluminm foil, served as backups and were not needed in final processing.