Document MGkY2Lz0kOgVxVLDR7vbYV5R7

BIOACCUMULATION (ANALYTICAL ONLY) TEST SUBSTANCE Identity:Perfluorooctanesulfonylamido(ethyl)acmeatyatael;sobe referredtoas PFOSAA, FC-128 oras themajor component of FC-127, FC-129, FC-109,or FC-109-X. (Glycine,N-ethyl-N[(heptadecafluorooctyl)sulfopnoytla]s-s,iumsaltC,AS # 299151-7) Remarks: The testsampleisFC-128.Currentinformatioindicateistis a mixtureof 86% testsubstanceand 14%C4-C7fluoroalkylcarboxylate compounds. METHOD: Method: Devised by 3M Company todetermineifbluegilslunfish bioaccumulatefluorochemicalfsrom 3M's Decatur,AL plant effluen(tSee Remarks) GLP (Y/N): No Year completed: 1978 Remarks: The followingmethod was devised and used: 1 . Two lotsof30 fisheach were used. 2. One lotwas exposed to Decaturplanteffluenftrom Oct.5 to Oct. 25. The otherlotwas exposed toTennessee Riverwater onlyfrom Oct.3 to Oct.25. 3. Twelve fishfrom theeffluenetxposed lotwere collecteddead and the remainingeighteenfishwere sacrificeidnDecatur.The river water exposed fishsurvivedthroughthe exposure periodand all were sacrificeidnDecatur. 4. Effluent-exposeadnd riverwater-exposedfishwere allpreserved and shippedindryicetothe3M EnvironmentalLaboratoryinSt. Paul,MN foranalysis. 5. Fishwere homogenized usinga Tekmar Model SDT tissuemizer. 6. Two 2 g.portionswere weighed and extractedusingethylacetate on one and tolueneon theother. 7. Samples were analyzedby GC, TLC, and GC/MS. RESULTS AnalyticalObservations: The effluent-exposefdishweighed 25.7grams. The riverwater-exposed fishweighed 33.0 grams. GC/MS analysisof ethylacetateextractedfishexposed to planteffluent did not detectthe presence of FC-128. No fluorochemicalswere detectedinthe riverwater-exposed fish. Remarks: Study was conducted because 3M's Decatur plant manufactures fluorochemicals.Water used inmanufacturingislater treatedand the treatedeffluendtischargeseventuallyintothe Tennessee River. CONCLUSIONS No reliablceonclusionscan be derivedfrom thisstudy. Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 DATA QUALITY Reliability:Klimischranking3. Study was conducted atthe manufacturingfacilitryatherthan at3M's EnvironmentalLaboratory. Effluentconcentrationsofsubjectfluorochemicalswere not characterized and the specificprotocolforexposure ofthe fishwas notfound. There was also no informationon analysisofthe Tennessee Riverwater or effluentused inthe study (e.g.N,H3-N ineffluentisknown to cause death duringNPDES testingo,r low DO, highTDS). Additionalliyt,isnot known iftherewas any opportunityfordepurationofthe fishpriortosacrifice. Presence ofthe testsubstance could have been a normal functionofthe fishconcentrationshomogenizing withthe effluenctoncentrations.No explanationisattemptedas towhat was the cause ofthe 12 dead fishin the effluent-exposegdroup. No differentiatiwoans given towhether the subjectchemicalwas actuallyaccumulated inthe fishor simplysorbed on the surfaceofthe fishbody. Sampling locationswere notdescribed. REFERENCES 3M TechnicalReport "AnalysisforFluorochemicalsinBluegilFlish"G. A. Vraspir/ArthurMendel, Project9970612600, Fate of Fluorochemicals, Report Number 14,May 1,1979 3M requestedexpertoverview,"BioaccumulationStudies",Dr.James GilleftC,ornellUniversityM,arch 8, 1993 OTHER Last changed: 5/18/00 '13M Forp 6747-11 -A TECHNICAL REPORT SUMMARY Dow 5/l/79 TO: TECHNICAL COMMUNICATIONS CENTER - 2M-2CN timporan-tIfreporitsprintoondbothsUm ofpmpw,sondtm copantoTCC.) Division Proiwt Report Tige Environmental Laboratory (EE & PC) Reg. No. 48765 Fate'of Fluoro'chemicals Analysis for Fluorochemicals in Bluegill Fish Dept Numbw 0535 fleclecNtumbw 9910612600 report r4urnbw 014 Author(sl D. L. Bacon G. A. Vraspir/Aithur Notetwok Rofer*nco 48838-18 Mendel SECURITY lo. 0 Open Closed (CompanyConfidential)(SpeciAaulthorkadon) 31ACHEMICAL REGISTflY KEYWORDS: (Selot"ermsfrom3M Thomrus.Sugpstadw awlicablteorml) CURRENT OBJECTIVE: Status Report ]Enwuovw Humber(s) 76416@43939 N4L of Pagn inciucing4;ovenoswt 7 .. .... Now ChernimisWorted 13yes M No REPORT ABSTRACT: (200-25w0arcw Thisabsbacinformatiiosndkukxnedby theTachnW Conwnuni=tionCsenterto aler3tM'*rstoConparvvR&D. ItisCongmy confidentrimwtwim. -c:R.A.Prokop-236-3B V.Pothapragada-236-3A A.N.Welter-21-2W R.L'.Bohon-21-2W InformationLiajAo Initials: FC (Req. 4876S)/GAV/AM -2- 5/l/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 ef fluent (PE) contained 10 ppm (Ug/g) of FU 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 (RW).contained ethanol, ethyl ether, etboxyethyl 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 ef f luent and in fish exposed only to Tennessee River water (2). Thin-layer chromatography (TLC), gas chromatography, 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 fiomogenate was extracted withtoluene (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. -3FLOW DIAGRAM 1 ANALYSIS OF BLUEGILJJ FISH 30 Fish (1) Weigh (2) "Tissuemizell e 0 e (1) Weigh 2 (2) Extract (ETOAC) (3) Centrifuge (4) Isolate ETOAC Layer Route 3 GC For. FM 3923 FM 3925 FM 3422 Concentrate GC/MS TLC. For FC-95 FC-128 FC-143 (1)Weigh 2 g. (2)Acidify (3)Extract (Toluene) (4)Centrifuge (5)Isolate Toluene Layer (6) Methylat6 pGC/MS GC For FC-143 (Ester) FC (Req. 4876S)/GAV/AM -4- 5/l/79 EXPERI MENTAL Two lots of thirty fish each, wrapped in aluminum foil, respec- tively, and shipped in dry lee, were received on November 3, 1978, by the Environmental Laboratory. The fish were kept frozen until analyzed (Nov. 3, 1678). 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 River Plant Plant Water Holding Tank Exposed Fish - ethylacetate extract (R.W.-EtAc) Water Holding Tank Exposed Fish - toluene extract (R.W.-Tol'.) Effluent S-1 Exposed Fish-- ethylacetate extract (P.E.-EtAc) Effluent S-1 Exposed Fish - toluene extract (P.B.-Tol.) The fish were homogenized using a Tekmar Model SDT tissuemizer. Two 2 g. po' rtions were weighed into separate polyethylene centrifuge tubes. Two ml's of pesticide grade ethylacetate were added to one and 2 ml cone. HCI 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.rpmls. The ethylacetate and toluene extracts were drawn off and placed in glass vials, respectively. The ethylacetate extract was exagned using the follow,ing GC conditions: Instr. HP 5713 with Ni electron capture detector. Column - 6,1,x1/811 S. 10% Carbowax 20 M on 60/80 mesh 0 Chromosorb W-AW.' Ing. PO.;rtTemp - 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 con itions were used. The concentrated EtAc extracts were spotted alongside standards of FC-95, PC-143, and FC-128.on E. Merck silica gel plates. They were first developeg in 10% ETOH in EtAc and dried. Then the plates were turned 90 and developed in 50% ETOH 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 exeined using the following GC conditions: Instr. HP 5713 with Ni electron capture detector. Column - 12'x 1/811 B.S. 20% DC-200 and 10% Bentone 3 or 80/90 mesh Anakrom PA. Inj. Port 0 9 200 C. Det. temp - 300 C., Oven - 110 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. FC (Req. 4876S)/GAV/AM -5- 5/l/79 PE/EtAc extract showed approximately 10 Ug/g of FM 3422. RW & PE-Tol. showed no difference. No FC-143 or FC-128 was detected by TLC of the PH EtAc, but a spot was noticed whose Rf was that of reference FC-95. REFERENCES (1) a) M. T. Elnabarawy,."Bioconcentratibn of FM 3422 in Bluegill Sunfish and In Channel Catfish," BE PC. Report, 5/17/77. b) A.-N..Welter, "Aquatic Fate of A Fluorochemicali FM 3422111 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. Macioszczyk, Uii-rne-hpmie-klTniirnjtl, 23', 121 (1978). GAV/AM/cen Attachment 2643 CENTRAL ANALYTICAL LABORATORY Report 7,24 Date._ March 28, 1979 subject: Decatur Fish Sloossy. RequeiBtorG:'---V*r-a-s-p-i-r-. -A.--H-e-r-4o-l Reques t No. -------- Report: INTRODUCTION Dept. Na3no _EE PC Dated_ Novembo r 16 1978 F@r0j. No. 915016190404' SwVles were received from the requestori from a fish bloassy taken at the Decatur Plant. Fish were'exposed to two different water iyat4m: the -TennesseeRive'rwhich flows just outside the plant -and-ttsi-plont@e'ffluont running Into the river. Ethyl acetate*extracts of the fi.sh.wereanalyzed udisaiznogmetthheanGeC/aMnSd saynsatleymz.ed.Toluene -extracts of the.fish were mothylato,dwith DISUCSSION The samples were labeled R.W. 11 and P.E. 11 (mothylatedtoluene extracts) and' R.W. 12 and P.E. 12 (ethyl acetate extracts). S&Wl*s R.W. 11 and P.E. 11 were analyzed using conditions for column A below and swples R.W. .12 and P.E.#2 were analyzed using conditions for column 8 below. instrument: Varian 2740 gas chromatograph Column A: 121 S.S. 20% OC-200 + 10% Benton'e 34 on Anakrom PA Oven: 110*C Isothermal for 11 minutes. then 110-170'C at 10*ClWn. Injector: 165*C Column 6: 6' S.S. CW 20M 15% on Chromosorb W Oven: 50 225*C at 10*C/min. Injector: 220*C 'Detector: Varian flame Ionizationat 290*C .CarrierGasi. Helium at 25.cc/min. Instrument: dupont 21-491B mass spectrometer Source: Chemical Ionization Mode: all samples were run In Electron Ionization, sample P.E. 12 was also run In Chemical Ionization with UN gas Mass Range: 18 - 617 m/e 3 Helium Separator: Single Stage t Multiplier: Bandix Channeltron RclbtirtNo. 4u, iii-, RESULTS Samples R.w. ii and P. E. 11 showed by SC/MS only the solvents used In extracting and mthylating: ethanol. ethyl other, othoxy ethyl acetate toluene and xylones. it was necessary to air concentrate the ethyl acetate extracts In order-to obtain sufficient data tb Interpret the mass spectra. The Tennessee River *Wsed fish ethyl *estate "tract,.contained-oupetrso,us t.C. Oeaks none of which appeared to contain fimrins. The appear to correspond to references of 2-mthyl@3-octancoes phthalate, and hig'h molecular alkanes from &bout c to a-t.-limst C.e*, The plant effluent exposed.fish ethyl watate extract con" which appear to correspond to references of 2-m*thyl-3-"t a -nds acid, fluorochomicals whose highest mass f ralim "n %or* we 582 m/e. nitrogen containing fluorocahmicals (Izs:hloh"t i7, "a nts seen were 448 mle and 584 m/s@ Fm 3923 (FOSE ara'dlo) and FM 3422. Sf. alcohol)-* SUMMARY This fish blossty showed that extracts from the fish exposed to the Tennessee River water co'ntained such compounds as ethanol$ ethyl other, othoxy ethyl acetate, toluene and xylone. The extracts from the fish exposed to the Decatur plant effluent contained FOSE amide, alcohol, other related fluorai.-h*micals, 2-mathyl-3-octanone, and acetic acid. N. Schroop@e@r /ch