Document 10Dj5BorxGnEa2Oz4nB4230RK

Fdrm 6 7 4 7 - 1 l . A BACK TO MAIN Oiv ision -Proioct Ropurt I I O 'c~lr. Oopt. Numbor Prolect Numbor 9970012600 Report Number 04 3 n . 1., Bacon Author(5) Arur N otobook Rdoren:o i e H . oc c h r u d t -- 51050, SECURITY 51567 0 Ooen (Company Confidential) - II!Closed (Special Authorication) KEYWORDS: :URRENT OBJECTIVE: ( S c l c a terms from 3M Thesaurus. Suggest other applicable tormr.) E ~ I P ~ ~-. PG ci v . (Env. Lab) Final 3M CHEMICAL REGISTRY Report. i Now Chemicals Reported ta Yes E4 No Fate Degradation Photolysis - . - - IEPORT ABSTRACT: (200-33words) This abstract information is distributed by the Technical Communications Center to lert 3M'ers to Company R&D. It i s Company confidential nraterial. A s u p e r s a t u r a t e d a q u e o u s s o l u t i o n of FM-3925 w a s s u b j e c t e d t o s u n l i g h t t o d e t e r m i n e if t h e compound u n d e r g o e s p h o t o l y s i s . GC/MS i n d i c a t e s isomerization possible. b b0 inforrnotio Liairor, initinis: BACK TO MAIN 'The p u r p o s e of this f i r s t p i l o t p h o t o l y s i s s t u d y was t o C!Xainlne the f e a s i b i l i t y of s u b j e c t i n g chemicals i n water t o J.ong-term i n t e n s 2 s u n l i g h t s i m u l a t i n g " r e a l world" c o n d i t i o n s . The work s i t e c h o s e n was t h e B i r d C o r p o r a t i o n , a 3M s u b s i d i a r y , l o c a t e d ir. the s u r . l i g h t - d r e n c h e d d e s e r t of Palm S p r i n g s , CA. , F o u r aqueous m i x t u r e s were s u b j e c t e d t o n e a r l y s e v e n m o n t h s of n a t u r a l s u n l i g h t (Palin S p r i n g s , CA) FM--3925 FM-3925-acetophenone ( a c t i v a t o r ) , DD'l ( r e f e r e n c e ) , and water blanks.. R e s p e c t i v e light-protected r e t a i n s served as contirols. Gas chromatography ( G C ) a n d GC/MS (mass s p e c t r o s c o p y ) of t h e l a b o r a t o r y p r o c e s s e d m i x t u r e s i n d i c a t e d t h a t FM-3925 d i d n o t u n d e r g o a n y lnajor photolysis (and/or hydrolysis) other than poss.ible isomerization iMS). The s u n l i g h t and climate a t t h e Bird Corporation l o c a t i o n (Palm S p r i n g s , C A ) make t h i s a n i d e a l s i t e for c o n d u c t i o g " r e a l w o r l d " silriulated p h o t o l y s i s s t u d i e s . F u r t h e r , many v a l u a b l e l e s s o n s dere l e a r n e d (see D i s c u s s i o n ) . - D I . S '- I O N : In-, ie p h o t o l y s i s s t u d i e s h a v e b e e n (done i n t h e E n v i r o n m e n t a l Labo~?:Lory. Such work tries to siinulate n a t u r a l conditions. r.. G . Z e p p l s u g g e s t e d t h a t a q u n o u s p h o t o l y s i s s t u d i e s be d o n e b u t s u o j e c t i n g c a n d i d a t e s i n water t o n a t u r a l s u n l i g h t . He f u r t h e r p o i n t e d o u t t h a t use of n a t u r a l waters, e.g., those from a n e a r b y r i v e r , approximates t h e "real world" better than in-house studies using pure water. A c c o r d i n g l y , t h e " F a t e of Fluorockiernicals" p r o j e c t was d o v e t a i l e d with t h i s i n i t i a l photolysis project t o provide experience in t h i s area f o r f u t u r e laboratory protocol. The fluorochemical c o h c o t s a e n n e s i u n 1 f t o h n is ani i i d n e v ) . e s t i g a t i o n was FM-3925 (N-Methylperfluoro- 'Th? o v e r a l l p l a n f o r t h j , s s t u d y was t o p l a c e a n e x c e s s o f c a n d i d a t e chemicals i n f i s h t a n k s , add water, seal t h e t a n k s , and expose them t o s u n l ' i g h t i n a s u i t a b l e l o c a t i o n ( e . g . , r o o f ) f o r a g i v e n l e n g t h af time. T h e t a n k s ' c o n t e n t s were t o be r e t u r n e d t o t h e E n v i r o n m e n t a l Laboratory f o r p r o c e s s i n g . 'The o v e r a l l p l a n s were e x e c u t e d a n d t h e f o l l o w i n g L e s s o n s were l e a r n e d : 1. N e a r l y s e v e n m o n t h s ' s u n l i g h t e x p o s u r e l e d t o c l e a n materials, i . e . , t h e t a n k s and c o n t e n t s were not d i s c o l o r e d , choked w i t h algae or o t h e r organisms. BACK TO MAIN FPl- 3 3 2 5/nn Page 3 August 6, 1980 2 . We c a n n o t r e l y o n a l o c a l ( C a l i f o r n i a ) source o f s u p p l y f o r a l l - g l a s s f i s h t a n k s o r other accessories. I n f u t u r e work, the E n v i r o n a e n t a l L a b o r a t o r y must p u r c h a s e , s h i p , a n d s u p p l y a l l iteiiis t o t e s t s i t e . 3 . Better s e a l i n g of g l a s s l i d s o n t o aquarium t a n k s , better pressure-equalization r e g u l a t o r s on sealed tanks, and an iiiiproved method t o support tanks during t e s t i n g are needed (see Observations, Table I ) . 4 . T e f l o n - l i n e d o r a n i n e r t m a t e r i a l - l i n e d ca,?s s h o u l d be u s e d i n place of aluminum f o i l t o s e a l c o c t a i n e r s s u c h a s r e t a i n s , controls, blanks, and the like. 5 . T h e p e r s o n n e l a t a i r d Corp. were c o o p e r a t i v e 2 , t h e y p r o v i d e d us w i t h excellent written observations, kept in c o m m u n i c a t i o n , a n d were a k e y h e l p i n t h e close-out s t a g e s o f the experiment. 6 . Bird Corporation's Palm Springs, CAI location is ideal zince (1) t h e o v e r e x p e r i m e n t s were s u c c e s s f u l , ( 2 ) t h e s u n l i g h t conditions are i d e a l , (3) no s e c u r i t y or confidentiality prooleins, and ( 4 ) cost e f f e c t i v e (3M subsidiary). B r i e f l y , a n excess of chemical o r chemicals were a d d e d t o water c o n t a i n e d i n a f i s h t a n k . I t was t h e n s e a l e d a n d s u n l i g h t exposed f o r n e a r l y s e v e n months. One t a n k s e r v e d as a blank. A n o t h e r t a n k c o n t a i n e d FM-3925 a n d a t h i r d t a n k c o n t a i n e d F?l-3925 p l u s a c e t o p h e n o n e , a n a c t i v a t o r . I t was t h o u g h t t h a t i f FM-3925 d o e s n o t u n d e r g o p h o t o l y s i s , i t may be i n d u c e d t o d o s o i n t h e p r e s e n c e o f a n a c t i v a t o r . A r e f e r e n c e material, DDT, was p h o t o l y z e d i n a f o u r t h t a n k t o s e r v e as a r e f e r e n c e s i n c e its p h o t o l y s i s i s d o c u i n e n t e 2 3 . A d u p l i c a t e s e t of e x p e r i e m e n t s was prepared i n case o f a n a c c i d e n t , e.g., breakage or leakage of a t a n k , breakage of a samgle d u r i n g ' s h i p m e n t back t o the Environm e n t a l L a b o r a t o r y , e t c . T h i s f o r e s i g h t proved of v a l u e ( s e e T a b l e I ) . S i m i l a r l y , c o n t r o l s a m p l e s were k e p t i n t h e d a r k f o r t h e duration of experiments. A l l s a m p l e s a n d c o n t r o l s were r e t u r n e d t o t h e E n v i r o n m e n t a l L a o o r a t o r y w h e r e t h e y were p r o c e s s e d . I t was shown by GC/MS t h a t FM-3925 d i d n o t u n d e r g o a n y iiiajor p h o t . o l y s i s a n d / o r h y d r o l y s i s o t h e r t h a n b r a n c h i n g 4 . A s e x p e c t e d , t h e r e f e r e n c e DDT s a m p l e underwent n e a r l y complete decomposj.tj.on d u r i n g t h i s p h o t o l y s i s s t u d y . See Experimental f o r d e t a i l s . BACK TO MAIN 12N- 3 92 5/AM Page 4 August 6, 1980 This work is f i l e d under request 4920s and recorded i n notebooks 51567 and 51050. A t Bird Corporation's f a c i l i t i e s s , eight (5-gal.) aquarium tanks were f i l l e d t o w i t h i n - c a . 2 5 mm f r o m t h e t o p w i t h d i s t i l l e d water ( t w o o f the a q u a r i a d i d h a v e some p l a s t i c p a r t s ) . Two t a n k s were t h e n s e t a s i d e and l a b e l e d b l a n k s w h i l e f o u r were supersaturatcd w i t h FM-3925 (- c a . 0 . 5 t o 1 9 ) . Twenty d r o p s (-c-a . 1 m l ) o f a c e t o p h e n o n e , a p h o t o a c t i v a t o r , was added t o e a c h of two of t h e FM-3925-containing t a n k s . T h e r e m a i n i n g two t a n k s were s u p e r s a t u r a t e d w i t h DDT (0.5-1 g , A l d r i c h Chemical C o . ) . About 1 5 0 n i l , r e p r e s e n t a t i v e o f e a c h t a n k , was t r a n s f e r r e d t o a r e s p e c t i v e j a r w h i c h was t h e n s e a l e d w i t h a n a l u m i n u m f o i l - l i n e 2 l i d and then stored i n t h e dark f o r t h e e n t i r e study. These r e t a i n s were l a m l e d c o n t r o l s . Each aquarium, whose water l e v e l was m a r k e d , was c o v e r e d w i t h g l a s s a n d s e a l e d w i t h Dow C o r n i n g s i l i c o n e s e a l a n t 6 . An 1 8 - g a u g e s y r i n g e n e e d l e was p o s i t i o n e d a n d iiwedded through t h e s e a l a n t to serve as a pressure equalizer between t h e inside o f t h e tank and t h e atmosphere. The tanks were t h e n e x p o s e d t o s u n l i g h t a n d o b s e r v a t i o n s were r e c o r d e d o f t h e o u t s i d e temperature, water l e v e l and general physical conditions throughout t h i s investigation (Table I). A t t h e e n d of t h e e x p e r i m e n t s , s a m p l e s fro:n a l l t h e r e m a i n i n g a q u a r i a , i n c l u d i n g b l a n k s a n d c o n t r o l s , were t r a n s f e r r e d t o amber bottles, capped (TedlarR-liners) and shipped to the Environmental L a b o r a t o r y . When r e c e i v e d , some of t h e c o n t r o l s a m p l e s looked t u r b i d arid i t was t h o u g h t t h a t was d u e t.o t h e a l u m i n u m f o i l u s e d tc cover t h e tanks6. One sample froin e a c h g r o u p of controls and p h o t o l y z e d samples were e x t r a c t e d t h r e e times e a c h w i t h d i c h l o r o m e t h a n e . The c o m b i n e d e x t r a c t of each w a s c o n c e n t r a t e d t o (1 ml w i t h a Kuderna-Danish (I<-D) c o n c e n t r a t o r . T h i s c o n c e n t r a t e w a s then t d i l u t e d to 25 in1 w i t h methanol. T h e m e t h a n o l s o l u t i o n s f o r t h e water b l a n k s , FM-3925 s a m p l e s , a n d FM-3925 p l u s a c e t o p h e n o n e s a m p l e s were a . n a l y z e d o n t h e tIP5713 g a s chroitiatograph under t h e following condit,ions: Oven temp: 150oC Detector temp: 300OC I n j e c t i o n p o r t temp: 200OC Detector: N i 63 Flow: 35 cc/min. o f Ar/Cklq, 95/5 BACK TO MAIN Following i s h d e s c r i p t i o n of the column Iuscd: I Colum inaterial: stainless s t e e l Dimension: 6 ' x 1/8" OD Liquid phase: 1 0 % Support: 6 0 / 8 0 mesh Chroinasorb W , acid washed. O n e major peak was i n both the c o n t r o l and photolyzed samples, which d i d not appear i n a f r e s h l y prepared s t a n d a r d . See 'i'able I I f o r r e s u l t s , which were obtained by d i r e c t a r e a comparison w i t h a known s t a n d a r d . The inethanol from the DDT e x t r a c t s was a l s o analymzcd on the 111~5713gas chromatograph under the following c o n d i t i o n s : 3ven temp: 2 0 0 O C Detector temp: 250OC I n j e c t i o n p o r t temp: 2 0 0 O C Detector: N i 63 F l o v : 40 cc/min. of Ar/C114, 95/5 ! 'The following column was used: I Column i n a t e r i a l : glass Diinens'ons: 6 ' x 1 / 4 " OD L i q u i d phase: S P 2 2 5 0 and SP24C1 Loading: 1 . 5 % and 1.95%; r e s p e c t i v e l y Support: 1 0 0 / 1 2 0 mesh Supelcoport Concentration of the c o n t r o l was 4 . 9 mg/l DDT and c o n c e n t r a t i o n o f the photolyzed sample was 0 . 0 9 mg/l DDT. These r e s u l t s were a l s o obtained by d i r e c t a r e a comparison w i t h a known s t a n d a r d . r T h e iiie ttlanol e x t r a c t from t h e photolyzed FM-3925-acetophenone sample was concentrated o n a K-D u n i t and t h e c o n c e n t r a t e was analyzed by GC/'MS ( C e n t r a l Research'APRL Lab R e q u e s t C55135) which i n d i c a t e c branching of t h e fluorochemical ( i s o m e r i z a t i o n ) 0111~4. i BACK TO MAIN TABLE I lIEMAl<l<S ON THE PlIOTOLYSIS EXPERIMENTS D a tc 6/26/79 Time 7:3a AN -T-emp 800F O- b s e r v a t i o n -s O r i g i n a l placement of t a n k s 7/1/79 7/9/79 7:30 AM 650F Tanks G and 7 cloudy; no d i s - coloration i n remaining tanks. t! .i 1 8:OO AN 800F R e p l a c e d a1::minuln foil t o p s o n T a n k s 6 a n d 7 w i t h g l a s s ; some contamination with f o i l and 1 silicoce. !; 7/17/79 7 : 3 0 AM 850F Small h o l e i n s e a l a n t of Yank 1; otherwise n o c h a n g e . 7/24/79 7:30 AM 8SoF T a n k s were s u b j e c t e d t o s e v e r e r a i n storm; a l l t a n k s shown a n e l e v a t i o n of f l u i d l o v e l . 1 1 : O O AM 9 50F No c h a n g e f r o m 7 / 2 4 / 7 9 . T a n k s were s u b j e c t e d t o a d d i - t i o n a l r a i n szorm; a l l tanks above original f l u i d level; visible cracks in sealant; w i l l repair a f t e r f l u i d l e v e l has dropped somewhat by 11 < evaporation. 8/27/79 - 8:30 A M 7 50F T a n k 1 i s low; t a n k s 2 , 4 , 8 e l e v a t e d ; - r e m a i n d e r of t a n k s show approximately normal fluid l e v e l . 4:OO PLY 1200F Reseale2 t a n k s 1, 8 , 5 , 2 , 4; Tank 1 is low; f l u i d l e v e l i n remainder of t a n k s is elevated. 9/24/79 7:30 AM 550F No c h a n g e from 9/7/79. 10/12/79 7:45 AM SOoF No c h a n g e froin 9/24/79. -~ i BACK TO MAIN 'TABLE I (continued ) Date T i me Temp Observations 1O/3 0/7 9 8 : O O Ai4 520F No c h a n g e from 1 0 / 1 2 / 7 9 , e x c e p t Tank 1 i s m a r k e d l y low. - IMPO- RTANT: 'Tank 1 appears t o have lost its fluid content through a leak i n the base of t h e tank and not via evaporation. I:/ 11/6/79 7 : 3 0 AM 50OF No c h a n g e f r o m 10/30/79. '1 I;, - IMPOR- TANT: C o n t e n t s f r o m Tank 1 transferred to glass jar: some p a r t i c u l a t e c o n t a m i n a t i o n ( g l a s s , f o i l ) : sample s t o r e d with controls i n the dark. 12/9/79 7:30 AN 550F No c h a n g e f r o m 1 1 / 6 / 7 9 . 1/9/80 5 7:3C AN 5 OOF Tanks subjected to severe rain storm; Tanks 4, 8, 2 damaged structurally; total contents of Tank 2 l o s t ; small alnounts of c o n t e n t s of Tanks 4 and 8 recovered: d e g r e e of contami n a t i o n t o c o n t e n t s of Tanks 4 and 8 is uncertain; recovered ' samples from Tanks 4 and 8 stored with controls i n dark. REMARKS: Experiment terminated on 1/15/80. Tanks 5 and 3 s t r u c t u r a l l y damaged. T h e r e was n o a l g a l grotcrth i n a n y of t h e t a n k s for t h e d u r a t i o n of t h e experiment. T h e r e was n o d i s c o l o r a t i o n of t h e samples f o r t h e d u r a t i m of t h e e x p e r i m e n t , w i t h the e x c e p t i o n of t h e t a n k s l i n e d with aluminum f o i l (Tanks 6 and 7). BACK TO MAIN b"-3925/API Page U A u g u s t 6, 1 9 8 0 I TABLE I 1 ANALYTICAL RESULTS O F SAMPLES Description #8 Blank CONTROLS Amount E x t r a c t e d ( m l ) ---- 205 FM-3925 mg/l <O. 06 New Peak* (mq/l) <0.06 #1 FPl-3925 380 ( 2 jars) 0.4 0.1 113 L'M-3925 340 ( 2 j a r s ) plus acetophenone 0.3 0.1 PHOTOLYZED SAMPLES I {IS U l a n k 490 <0.02 (0.02 I #1 FN-3925 975 7.9 0.7 # 3 FM-3925 plus acetophenone 1,000 2.7 0.7 * A s s i g n e d t o isomers of FM-3925 based o n GC/MS d a t a . BACK TO MAIN c FP1-3925/APl I Page 9 August 6, 1980 NOTES AND REFERENCES i 1. Phone conversation of A . M e n d e l ' w i t h R. G . Zepp, Environmental Research L a b o r a t o r y , USEPA, Athens, GA. i 2. The c s s i s t a n c e e s p e c i a l l y of Mr. David F. d i r t , B i o e n y i n e e r , Bird Corp., Palm S p r i n g s , CA, is g r e a t f u l l y acknowledged. i 3 . li. G. Zepp, N. L. W o l f e , J . A. G o r d o n , a n d R . C . F i n c h e r , J . Acjric. Food Chzin., - 2 4 , 7 2 7 ( 1 9 7 6 ) . I 4 . GC/MS i d e n t i f i e d a c e t o p h e n o n e , o ( , - m e t h y l b e n z y l a l c o h o l , a hydroxy-substi2uted acetopnenone and possible tolualdehyde i n 1 t h e FM-3925-acetophenone p h o t o l y s i s p r o d u c t i n a d d i t i o n t o ! f r a g m e n t s a t t r i b u t e d t o FM-3925 a n d i t s b r a n c h e d c h a i n isomers. O n l y o n e a n d t h e same s a m p l e o f FM-3925 was used throughout this s t u d y . 5 . 'l'hc C n v i r o n m c n t a l L a b o r a t o r y i s i n d e b t e d t o Mr. A . It. i j r c s s l e r wt1o s e t u p t h e s e e x p e r i m e n t s a t the D i r d C o r p . 6 . Two o f t h e a q u a r i a from a l o c a l ( C a l i f o r n i a ) s u p p l i e r h a d some p l a s t i c p a r t s . T h e a q u a r i a , c o v e r e d w i t h a l u m i n m f o i l , s e r v e d a s b a c k u p s a n d were n o t n e e d e d i n f i n a l p r o c e s s i n g .