Document BRdjqKEOyojwjnYEzbxRjZKgm

BIOACCUMULATION (ANALYTICAL ONLY) TEST SUBSTANCE Identity: Perfluorooctanoic acid, ammonium salt; may also be referred to as PFOA ammonium salt, Ammonium perfluorooctanoate, FC-116, FC-126, FC-169, or FC-143. (Octanoic acid, pentadecafluoro-, ammonium salt, CAS # 3825-26-1) Remarks: The 3M production lot number was 37. The test sample is FC-143. It's purity was not sufficiently characterized, though current information indicates it is a mixture of 96.5 -1 0 0 % test substance and 0 - 3.5% Ce, C7, and C9perfluoro analogue compounds. METHOD Method: Devised by 3M Company to determine if bluegill sunfish bioaccumulate fluorochemicals from 3M's Decatur, AL plant effluent (See Remarks) GLP (Y/N): No Year completed: 1978 Remarks: The following method was devised and used: 1. Two lots of 30 fish each were used. 2. One lot was exposed to Decatur plant effluent from Oct. 5 to Oct. 25. The other lot was exposed to Tennessee River water only from Oct. 3 to Oct. 25. 3. Twelve fish from the effluent exposed lot were collected dead (died in test) and the remaining eighteen fish were sacrificed in Decatur. The river water exposed fish survived through the exposure period and all were sacrificed in Decatur. 4. Effluent-exposed and river water-exposed fish were all preserved and shipped in dry ice to the 3M Environmental Laboratory in St. Paul, MN for analysis. 5. Fish were homogenized using a Tekmar Model SDT tissuemizer. 6. Two 2 g. portions were weighed and extracted. One portion using ethyl acetate and toluene on the other. 7. Samples were analyzed by GC, TLC, and GC/MS. RESULTS Analytical Observations: The effluent-exposed fish weighed 25.7 grams. The river water-exposed fish weighed 33.0 grams. 003667 GC/MS analysis of ethyl acetate and toluene extracted fish exposed to plant effluent contained no detectable amounts of ammonium perfluorooctanoate. No fluorochemicals were detected in the river water-exposed fish. Remarks: Study was conducted because 3M's Decatur plant manufactures fluorochemicals. Water used in manufacturing is later treated and the treated effluent discharges eventually into the Tennessee River. CONCLUSIONS No reliable conclusions can be derived from this study. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133- DATA QUALITY Reliability: Klimisch ranking 3. Study was conducted at the manufacturing facility rather than at 3M's Environmental Laboratory. Effluent concentrations of subject fluorochemicals were not characterized and the specific protocol for exposure of the fish was not found. There was also no information on analysis of the Tennessee River water or effluent used in the study (e.g., NH3N in effluent is known to cause death during NPDES testing, or low DO, high TDS). Additionally, it is not known if there was any opportunity for depuration of the fish prior to sacrifice. Presence of the test substance could have been a normal function of the fish concentrations homogenizing with the effluent concentrations. No explanation is attempted as to what was the cause of the 12 dead fish in the effluent-exposed group. No differentiation was given to whether the subject chemical was actually accumulated in the fish or simply sorbed on the surface of the fish body. Sampling locations were not described. REFERENCES 3M Technical Report "Analysis for Fluuorochemicals in Bluegill Fish" G. A. Vraspir / Arthur Mendel, Project 9970612600, Fate of Fluorochemicals, Report Number 14, May 1, 1979 3M requested expert overview, "Bioaccumulation Studies", Dr. James Gillett, Cornell University, March 8 ,1 99 3 OTHER Last changed: 5/25/00 C03GS8 I -IV* TECHNICAL REPORT SUMMARY TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN rti S/l/79 (important - / / report sprintati on both das o fpapm, sand two copasto TCCJ Oivition Dapt. Numbar Proiact Environmental Laboratory (EE fc PC) Req. No. 48765 0535 rrafact N um bar Fate of Fluorochemical8 Haport fitta 9970612600 R ^ o rt Mumtar Analysis for Fluorochemicals in Bluegill Fish Vo 014 Authorial D. L. Bacon employ Numborft) G. A. Vraspir/Arthur Mendel Notebook Roforoneo 48838-18 SECURITY ^ G Ooan fit aM i m CHEMICAL REQISTRY 76416/43939 No. o f Papai i f r t i M C o o n h M t 7 Nm Chamicala Raponad Ya* SB No a(TKSphEapalYlaaiWaccuatOrbtualRaar.mDtoSSarum:fgrago..am)tt 3M Othar CURRENT OBJECTIVE: Status Report REFORT A RETRACT: 120O-2B0 word) Thia abatract inform ation ia diatrlbutad by th# Taehnical Communication Cantor to art 3M'ra to Company RAO. cc:R.A.Prokop-236-3 3 V .Pothapragada-2 36-3A A.N.Welter-21-2W R.L.Bohon-21-2W InformationLiaiaop Initiale (' I 003669 FC (Req. 4876S)/GAV/AM -2 5/1/79 OBJECTIVE The purpose of this Investigation was to determine if bluegill fish, after exposure to our Decatur plant effluent, bioaccumulated fluorochemicals. SUMMARY Extracts from bluegill fish exposed to Decatur plant effluent (PE) contained 10 ppm (yg/g) of FM 3923 and 7 ppm of FM 3422. TLC indicated the presence of FC-95, while FC-143 and FC-128 were not detected. Extracts from bluegill fish exposed to river water (Hf) contained ethanol, ethyl etherr ethoxyethyl acetate, toluene, and xylene. No fluorochemicals were detected. A copy is attached of CRL report 7124 which detailed GC/MS experiments. INTRODUCTION The uptake and clearance of specific radiolabeled fluorochemicals by fish were reported (1). The current report details the analyses for fluorochemicals in fish previously exposed to our Decatur plant effluent and in fish exposed only to Tennessee River water (2). Thin-layer chromatography (TLC), gas chroma tography, and gas chromatography/mass spectroscopy (GC/MS) were used. DISCUSSION Our Decatur plant manufactures fluorochemicals. Water used in manufacturing is later treated and the treated effluent discharges eventually into the Tennessee River. Bluegill fish, chosen for these bioassay experiments, were exposed to P.E. Another lot of fish were exposed only to the Tennessee River water (2), The fish were then analyzed for fluorochemicals by an involved three-route procedure as outlined in Flow Diagram 1 and detailed in the experimental section. Briefly, fish were homogenized, and some of the homogenate was extracted with toluene (Route 1), while some of the homogenate was extracted with ethyl acetate (Route 2). A portion of the latter extract was concentrated Route 3) for GC/MS and TLC. Results are given in the summary section. C03670 '3 - FLOW DIAGRAM 1 ANALYSIS OF BLUEGILL FISH 30 Fish (1) Weigh (2) "Tissuemize" (1) Weigh 2 g. (2) Extract (ETOAc) (3) Centrifuge (4) Isolate ETOAc Layer GC For FM 3923 FU 3925 FM 3422 Route 3 "1 Concentrate * GC/MS TLC For FC-95 FC-128 FC-143 (3) Extract (Toluene) (4) Centrifuge (5) Isolate Toluene Layer (6) Methylate I GC/MS GC For FC-143 (Ester) 003671 FC (Req. 4876S)/GAV/AM -4 5/1/79 EXPERIMENTAL Two lots of thirty fish each, wrapped in aluminum foil, respec tively, and shipped in dry ice, were received on November 3, 1978, by the Environmental Laboratory. The fish were kept frozen until analyzed (Nov. 3, 1978). The effluent-exposed lot (Oct. 5 to Oct. 25) weighed 25.7 g. Twelve fish were collected dead and eighteen fish were sacrificed in Decatur. The river-exposed lot (Oct. 3 to Oct. 25) weighed 33.0 grams and were all sacrificed at Decatur. To simplify, the experimental one lot is discussed. The other was analyzed in exactly the same manner. The following codes were used: River Water Holding Tank Exposed Fish - ethylacetate extract (R.W.-EtAc) River Water Holding Tank Exposed Fish - toluene extract (R.W.-Tol.) Plant Effluent S-l Exposed Fish - ethylacetate extract (P.E.-EtAc) Plant Effluent S-l Exposed Fish - toluene extract (P.E.-Tol.) The fish were homogenized using a Tekmar Model SDT tissuemizer. Two 2 g. portions were weighed into separate polyethylene centrifuge tubes. Two ml'8 of pesticide grade ethylacetate were added to one and 2 ml cone. HC1 plus 2 ml of AR grade toluene were added to the other. Each sample was mixed approximately 1 min. on a Vortex Genie mixer. The samples were centrifuged for 15 min. at 10,000 rpm's. The ethylacetate and toluene extracts were drawn off and placed in glass vials, respectively. The ethylacetate extract was examined using the following GC conditions: Instr. HP 5713 with Ni electron capture detector. Column - 6'x 1/8" S.S. 10% Carbowax 20 M on 60/80 mesh Chromosorb W-AW, Ini. Port Temp - 200 C., Def. Temp - 300 C., Oven Temp - 150 C isothermal, Flow - 40 cc/min. Argon/Methane (95/5). After GC analysis of EtAc extract, a portion was concentrated under N,, purge for two dimensional TLC analyses. The following TLC conditions were used. The concentrated EtAc extracts were spotted alongside standards of FC-95, FC-143, and FC-128 on E. Merck silica gel plates. They were first developed in 10% EtQH in EtAc and dried. Then the plates were turned 90 and developed in 50% EtQH in EtAc. The dried plates were visualized by spraying with 0.01% New Fuchsin in water (3). The toluene extract was methylated with diazomethane and then examined using the following GC conditions: Instr. HP 5713 with Ni electron capture detector. Column - 12'x 1/8" S.S. 20% DC-200 and 10% Bentone 34 or 80/90 mesh Anakrom PA. Inj. Port 200 C. Det. temp - 300 C., Oven - 110Q C Isothermal, Flow 40 cc/min. Argon/Methane (95/5). The ethylacetate and methylated toluene extracts were submitted to Central Research Analytical for GC/MS analysis (Req. No. C-50687). See attached CR Report No. 7124 for GC/MS conditions. 603672 FC (Req. 4876S)/GAV/AM -5- 5/1/79 PE/EtAc extract showed approximately 10 yg/g of FU 3422. RW Ei PE-Tol. showed no difference. No FC-143 or FC-128 was detected by TLC of the PE EtAc, but a spot was noticed whose Rf was that of reference FC-05. REFERENCES (1) a) M. T. Elnabarawy, "Bioconcentration of FM 3422 in Bluegill Sunfish and In Channel Catfish," EE & PC Report, 5/17/77. b) A. N. Welter, "Aquatic Fate of A Fluorochemical, FU 3422," EE & PC Report, 10/14/77. (2) Decatur Effluent Fish Toxicity Test Protocols, dated Oct. 18, 1978 and Feb. 5, 1979; M. T. Elnabarawy. (3) J. Sliwiok and A. Uacioszczyk, MicrochfilBlfigl Journal 23, 121 (1978). GAV/AU/cen Attachment 0Q3673 CENTRAL ANALYTICAL LABORATORY Report N o . . I 1**........................... O o U -- J 979.......... Subject: Oecatur Fish B lo tssy. Dept. Nome . X !S ............... Proj. N to J im i!* * * R e q u e st N o . . " 2 5 *1 .............. Datod .JttSSfclt ... R e p o rt: INTRODUCTION Samples were received from the requestors from a f i s h b io a ssy taken a t the Decatur Plant. F is h w areexposed to two d iffe r e n t water system s: the Tennessee River which flow s Just o u tsid e the p la n t and the p la n t e fflu e n t running Into the riv e r. Ethyl acetate e xtracts o f the f is h ware analysed using the 6C/NS system. Toluene e x tra cts o f the f is h ware methylated w ith dlazomathane and analyzed. DISUCSSION The samples were labeled R.W. #1 and P .E . #1 (methylated toluene e x tra c ts ) and R.V. 12 and P.E. #2 (e th y l acetate e x t r a c t s ) . Samples R.W. f t and P .E . f l were analyzed u sin g c o n d itio n s fo r column A below and samples R.W. #2 and P .E . #2 were analyzed u sin g co n d itio n s fo r column B below. instrument: V a ria n 2720 gas chromatograph Column A: 12' S .S . 202 DC-200 + 102 Bentone 3k on Anakrom PA Oven: I1 0 aC isotherm al fo r I I minutes then I10-170*C a t 10*C/min. In je c to r: 165*C Column B: 6* S . S . CW 20H 152 on Chromosorb W Oven: 50 - 225*C a t 10*C/min. In je cto r: 220*C Detector: V a ria n flame io n iz a tio n a t 290*C C a rrie r Gas: Helium a t 25 cc/m ln. Instrument: duPont 21-2)1B mass spectrometer Source: Chemical io n iza tio n Mode: a l l samples were run in E le ctro n Io n iz a tio n , sample P.E. #2 was a ls o run In Chemical Io n iz a tio n w ith NH. g a s Mass Range: 18 - 617 m/e * Helium Separator: S in gle Stage Jet M u ltip lie r: Bend!x Channeltron C03674 / Rii|*or l No. y I 2ll * ik .r u i <.0 >.i/> RESULTS SampUs R.W. #1 and P. E. I t showed by GC/MS o n ly tha so lv e n ts used In e x tra ctin g and m ethylating: ethanol, ethyl ether, ethoxy eth yl acetate toluene and xytenee. I t was necessary to a i r concentrate the e th yl acetate e x tra ct In order to o b tain s u f f ic ie n t data to In te rp re t the mass sp ectra. The Tennessee River exposed f i s h ethyl acetate e x tra c t contained numerous G.C. peaks none o f tdtlch appeared to co n tain flu o r in e . The components appear to correspond to references o f 2-methyl~3"OCtanone, a c e t ic a c id , a phthalate, and high m olecular alkanes from about C|j to a t to a st C ^ . The p la n t e fflu a n t exposed f i s h ethyl acetate e x tra c t contained compounds which appear to correspond to references o f 2-msthyl-S-octahDHOk d o s tlc a cid , fluorochem icats whose highest mass fragments seen were 483 m/e and 582 m/e, n itro gen c o n ta in in g fluorocahm icals (whose h ig h e st mess fragments seen were 448 m/e and 584 m/e^ FH 3923 (FOSE amide) and PM 3822 (FOSE a lc o h o l). SUMMARY T h is f is h b io a ssy s howed th at extracts from the f i s h exposed to the Tennessee River water contained such compounds as eth ano l, eth yl e th e r, ethoxy ethyl acetate, toluene and xylene. The e x tra c ts from the f i s h exposed to the Decatur p lan t e fflu e n t contained FOSE amide, a lc o h o l, oth er re la te d flu oroch em tcals, 2~methyl~3~octanone, and a c e tic acid. /ch 003675 fi) "fi)(filbOO PROJECT N a ^ _ X L ' I. Subject: , oAr i F/*-" 6i 3M TECPN IC AJX N O T E B O O K 4 1 1 m J b + m + l /v* ^''i NO. 41947 tes l f ^ h i t , PAG! 21 Object: Reference: 4 ^ t' <>'>iv^iCLC/ Tl*'** * T k f e c q < V u f S o f 5"- Ccfrh^U 4<5v* '%C'*JU<> 4 Qcr\jYol u/0l4 i 4 0 0 ^ *<v*t*l *\ (YV\* /(*/. FVft*^ 477 -M 00** <iPVlXU<i v* IO rvsavU^S i* /(^j Tvvfc c *T^- -fr^t o f - k v _ 3 7 < t a y -<fltPSA^'e v*t*< <dK/^df *f tu W -S w 15 0 p 25 Y .10 35 fl,nftiftLl 4* (5ct 477^ 7 ^ + f l r ^ f 5" IdA) u*jf > uj*t* *. iroH 7fC 4.- I Ut. J 'ri< .a-e^+,4^<ciS . <^ >cCl mu-^cpUU ss cu<i-f 'Trf'--?tfnl d<i fhw/hfcf JLy * e4 u / W L f * 1 W ~ c i ^ o J CLCW r Pm 'T 4 ^ ' --------------- wtff* ** ? 5 * Tfr 4q ^ $ 0 * 1 vX i t I^ * f l A*'k fff /0*tl f l c W ) ' - a /s o 4r ^/I (^. C**4 S-^- C I ( 1 f~?b ^icA'tfcW ^6-^ys/j, '"/'O ^fW</ L &f-r ,- * a / l F W - 3 4 Z 2 Ca^4ir0 1 - AA.' ^ Ac~e'h* - AA ^ F * - 3 * 7 z - o > n ^ u P**t < fu * - d<"**d ft*4 CCh'Uro f - d f O o I V ! A'c-fjam^ - OkQfiQiVN.ly R *l-*? 4 7 7 - f l U l G03676 Signature. ii T ir Date:- l h ? Ot -tI PROJECT N O . _ 5 J ^ f^ ^ 00 1 Subject: Object: 3M TECHNICAL N O T E B O O K NO. Date: Reference: L R *3114- iu \/ir:tf H * uj^ i< \k X c U rl-e r^ tp X^- ^0 00 *(H -feu*4 W. erf ( PAGE 3 3 J0* < 0 * * f ? W - Tv,4 Ujl-Ur f/jOOijapvrv) f /-N n r ^ A g u lU i u A P iik 0 - 3 . 7 U i F * 4 (S 2. 5^ 9 T ^ X u->a^~W 5**\fU (AJte^ tX-a^ Ia>( $ c X I0**f i?0 F s k wu-^T'f , n /d*t c, n{ ?0%(eO{\ ioa A Xo *V 5'0C * / ^r. T > w + d ~ r * i Q & ^ * A /0*3 0tr, P ^JvTAti 6 Sa * mX-^rcoUr iVpeA'i 0 4 3 - $ 4 6 '3 0$ 7>A 4>8k*^Lf i Fat* (f) - <j{ Pstt 0 ' 0,24 j/| - " ' 30 F 'i L 0 - a 4 (" l f t ' '* " '* 'T&f 'b$l oJa.4^r UJ*A t"fari*f ^H*tvh A At>(t.fOor* "AXA* ^v.eT &sfil lo&4r sd-vac-L-of tM> Z ~ t cX. G>.* 35 /r"4gra'4*. 0 4 ^ ~ OS*l y i+tef tO lf * y l * G03677 Signature- : i~pC_ D ,.:-? > /Z ! PROJECT Subject: NO... r\,i l Q 1* 1? b 00 3 M TECHNICAL N O T E B O O K NO PAG Object: Reference: 114 T h s*ro *d c>a *4 o*^ -^ -t--tm---cV--C 1I ^ Srt *'A Arn' "fi"* ^ *>-./ c5J-- fLt**. /K 10 Q A ci -fo**- <i^4v- -ft' \S ' H H p h i * 6foa$ux~ H Ffr-XrL1 0 ~f*~k C (j> A *. It e , 1 flAVAp L'-^'5 *}U ine Iffe? - C o^ S itqI l O f t A r I kJaS-er Ic UkSer (VAtjl FtsA fl C o *S *o f f-<$k ^ -Aft f V potici /v-V<jrA/ 2*' Jib P r m k *u~ttacf Cut. 4,h\ ' 8l "S X ^ A/ftyO f v i f i * ^ 06,1 5 ^tri^-r ti*'/ tXfcf (K tt S /0*l 0 C< ^ v * * p k fa]' (^, < < / y> W cf Q**ro ( UJo. 0(*(~ C(*3 0,O f/*jjt/ kU r - 0,013%# / f C- 1 OtdOO^w^f^, 10 c - z ' W O 7 ^ *-/ 0 , 0 2 e! r - ' 2' 0,0 3/ * 15 G03678 Signature. Date: 3 /ft/ 78_____ -*1 f i PROJECT NO Subject: Object: Reference: PAC 3M TECHNICAL N O T E B O O K NO. Date: 44947 4: 3/5/77 BESTCOPY AVAILABLE 3 '4*j*k Sy * 1**1* IS ^ U j I* -** 3&vfi#S rwrUfci ir K ^ / f cb ji* VU1' ^ < ^ u .4 (D& * s^ 8 D 8 7 - ^ 0 g*iM ? Jiqti-Ui L m q I // -f A SiUvjO^S 8 ^(r<J -fii* /#/$ fi/s#c/ 6sA #?77^# ^OL-Ur ScutMoUv -iis.t* Sa*pl/s oy\ "5 / h / / 7 " AUjp <?f poseur. iule-e* A*k*i 3//1/77 -3Ak U^.` M3lj. ^pos/4 V*/77 - st lL*M 7?j. f r i k 5A*plii ufr^ fJtifVuW o *t H \ 2 - /(W G*S*Q *^Ct\ tfnf **2 ~ l0\*1 OlC'4ur*^/ e/ oj-^ 4* 2 ? C> ftjijI'W it*U ztM*f>lr u>c3 p/r aijiA^ef ^r A g r c0b(. fo p t f 7 -g ^a^p i-fs >54 *Svilfs i - Oo \ocictrOU^ T<j{*( fcj(</r*l-{A fvik 8d*4fS T/b/ll" ToUf m*. f f ^ ai * 0* ^4pes^ F'H M do^5 "bftfjn ' f,I72j* ^1 f3?| * F*t S ip , re___ _______________________________________ ~ ........ M T L * Kn *>,.h S r* $4 ty 2 M * y D M - l i l i h ' 7-- C036S0 _ PAGE 3M REPORT: BIOACCUMULATION STUDIES March 8, 1993 4. Report No. 14 (5/1179) 'Analysis of Fluorochemicals in Bluegili Fish' aalrceophAroellstehoncotcueugdrhsintihnaistvhreeerypeomnrvtaiorrgfofinnearmsliezsnoedtmme danetnaeirl.edItexgipvleasnathtieonimopfraensasliyotnictahlaptrdoccse-d(huyredsro, xthyectshayml)patlieosnooufrcNes-EalnFdOdSatEa 3 003682