Document dQnMMdjNj2jx5Mx6eXxgdBXqe

BIOACCUMULATION TEST SUBSTANCE Identity:N-ethylperfluorooctanseulfonamidoethanol;may also be referredto as N-ETFOSE Alcoholor FM-3422. (1-Octanesulfonamide,N-ethyl1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-N-(2-hydroxyethyl).-, CAS # 1691-99-2) Remarks: Materialisan off-whitew,axy solidofuncharacterizedpurity. METHOD: Method/guideline followed: None given forsampling ofthe organisms. Extractionand analysisprocedureswere devised by 3M. Type: Analysisoftissueforfluorochemicaflrom indigenousfishcaught inthe Tennessee Riverabove and below the Wheeler Dam. GLP (Y/N): No 'Year: 1979 Remarks field:There isno informatioonn samplingproceduresofthe organisms from theTennessee Rivernear the manufacturingfacility. Four fishwere caught and utilizeads samples; Two channelcatfishcaught above Wheeler Dam, one white bass caught below and one white crappiecaught above Wheeler Dam. Wheeler Dam isapproximately26 nauticalmilesdownstream from the 3M Decatur Planteffluendtischarge.Itwas notnoted in-thereporthow many milesabove and below the dam the fishwere caught. A ten ppm standardof FM-3422 (N-ETFOSE alcohol)was preparedby dilutinIg ml ofa 100 ppm standard(inethylacetate)to mark withethylacetateina 10 mi volumetdc flask. One whole channel catfishwas homogenized to createone sample. The other channel catfiswhas dissectedand the variousindividuaplartswere homogenized tocreateindividuaslamples. The white bass had a 6.3 cm i.d.dinkerdiecore sample takenjustoffthe lateral linebehind the gilpllatemaking up a 20.591 g sample containingskin,filets,mall partofthe backbone, reproductiveorgans,partofthe kidney,and rectum. The white crappiehad a dinkerdiecore sample taken behind the gilpllateto createa 16.684 gram sample containingfiletv,ertebrae,skinand bile. Allsamples were homogenized inknown volumes of Di water and dividedinto fivealiquotseach. Samples were centrifugede,xtractedwithethylacetate,and analyzed by GC for organicand inorganicfluoride. Itwas noted thatFM-3925 (N-MEFOSE alcohol)and FM-3422 (N-ETFOSE alcohol)could notbe distinguishewdithGC withelectroncaptureparameters. The resultsare thereforea combined value. RESULTS N-MEFOSE alcohol/N-ETFOSE alcoholConcentration InTennessee RiverFishby GC N-MEFOSE alcohol& Sample N-ETFOSE alcohol Water blank EthylAcetateblank (ppm) N.D. N.D. Whole ChannelCaffish 0.73 WhiteBass coresample 3.31 White Crappiecoresample N.D. Channel CatfishGills 0.80 Channel CaffishLiver 0.38 Channel CaffishParts* 0.43 Channel CatrishMuscle N.D. Channel CaffishFat ** 6.12 Channel CaffishGallBladder 0.74 Upon completionofGC analysist,herewas concern thatthevalues were not definitiveA.dditionaalnalysisof ethylacetatehomogenate extractwas then done usingCapillaryGas Chromatography withElectronCapture and GC using a Microwave SustainedHelium Plasma Detector. Qualitativaenalysisofthe fishextractsusing CapillaryGas Chromatography with electroncapturefailedtoidentiftyhe presence of N-ETFOSE alcohol.This was furthersupportedby analysisby a Microwave Sustained Helium Plasma Detector where again,no evidence ofany fluorochemicalwsere detectedand specifically no N-ETFOSE alcoholand no N-ETFOSA (F-6309)were detected.The results obtainedby themicrowave plasma detectoron spikedsamples indicatedthatNETFOSE alcohol,ifpresent,could have been detectedfrom itsfluorinecontentat 0.1 ppm intheethylacetateextracts.No referencewas made to N-MEFOSE alcoholexcept forthegeneralstatementmade "No fluorocarbonpeaks were observed intheactualsamples." Remarks: The originarleport(5/22179)referenceda sample forFM-3923. Itwas broughtup afterthe reportwas generated thatFM-3923 and FM-3422 are both the same coumpound (N-ETFOSE alcohol).Analyticawlas conducted to vedfy its identitaynd itwas found tobe N-ETFOSA (F-6309).The attachedreport("AR No. 7238 - Determinationof FluorinatedAlcoholsinFishExtracts"1,0/23/79)still refersto FM-3923 when infactthe sample labeledas FM-3923 isF-6309. This reportalsohas inconsistenciesT.he lastparagraph indicatesthe abilittyodetect fluorinecontentat0.1 ppm level.However, a reviewofthe procedureused indicatesa detectionlimiotf0.5 ppm. The firsrteport(5/22/79)describesanalysisofethylacetateextractsoffish homogenate by gas chromatography (GC) withelectroncapturedetection.The analysisshows the presence of materialsinfishtissueextractsthathave GC retentiontimes identicatlo both N-MEFOSE alcoholand N-ETFOSE alcoholand to N-ETFOSA. The GC retentiontimesof N-MEFOSE alcoholand N-ETFOSE alcoholstandardswere thesame (notresolved)by the method used inthe first report.The firsrteportindicatesthe presence offluorochemicalsinthe fish extracts,but electroncapturedetectionisnot specififcorfluorochemicalsT.hus the resultsreportedinthe firsrteportwere not a specificidentificatioofn fluorochemicaldsetectableby GC. (ReportI alsohas errorsincolumn 4 of Table 1.Inthe 1B row,0.40 should be changed to4.13,and inthe 2A row,0.004 shouldbe changed to0.06.) The second report(12/28/79)shows a misinterpretatiionnthefirsrteport.It includesa descriptioonf GC analyses ofethylacetateextractsoftwo ofthe samples describedinreport1 samples 1B and 3A. The work describedinreport 2 used electroncapturedetectionand referencesa reportusingmicrowave sustainedhelium plasma detection(MSHPD) inthe fluorinaend sulfurmode. In fluorinemode, MSHPD method isspecififcorfluorineT.he MSHPD resultsshow no fluorochemicalsinthe ethylacetateextracts.The resultsare interpreteads indicatintghatF-6309 and N-ETFOSE alcohol(FM-3422) are presentinthe ethyl acetateextractsatlessthan 0.1 ppm. Inthe firsrteport,N-ETFOSA (F-6309)and N-MEFOSE alcohol(FM-3925) /N-ETFOSE alcohol(FM-3422) had appeared to be presentrespectivelayt0.82 and 3.31 ppm insample IB and at 1.48and 0.80 ppm insample 3A. Thus, the GC-able compounds seen inthe firsrteportappear notto have been fluorochemicalsand thus could nothave been N-MEFOSE alcohol,N-ETFOSE alcoholor N-ETFOSA. The firsrteportshows the presence ofunidentifieodrganicfluorinaend of inorganicfluorinienthe fishtissue.Thiswas not re-evaluatedinthe second report. CONCLUSIONS No reliablceonclusionscan be derivedfrom thisstudy. Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul, Minnesota, 55133 DATA QUALITY Reliability:Klimischranking3. Withoutan understandingofthe sampling design inrelatiotnothe ouffalalnd sampling points,verifiabldeata on the actual concentrationsoffluorochemicalsinthe riverfrom both the manufacturingfacility and from naturalsources,activitiiensthe manufacturingfaciliptryiorto sampling, any applicablenvironmentalconditions(e.g.rainevents),and a clear understandingof how longthe sampled fishwere inthe sampling area,thereis litttloe be concluded. Additionalltyh,e analyticadlata conflictsI.tcannot,be definitivecloyncludedwhich analyticadlata setiscorrect.Extractionand analyticamlethodology were notvalidated.Stateunitsofresultsisppm. Itisnot correlatedto mg analyteper kg body weight. Identitaynd purityof reference compounds was not establishedthereforestatedanalyteconcentrationshave no basisinfact. REFERENCES 3M TechnicalReport "Bioaccumulationof FluorochemicalsinTenn. RiverFish." James E. Gagnon, Project78-2740, Decatur,Alabama - Tennessee River Fish, Report Number 001, May 22,1979 3M TechnicalReport"AR No. 7238 - Determinationof FluorinatedAlcoholsin FishExtracts."D. F. Hagen, ProjectA000007, EnvironmentalEngineeringand PollutioCnontrol,Report Number 238, October 23, 1979. 3M TechnicalReport "FluorochemicalsinTennessee RiverFish."James E. Gagnon, Project78-2740,Decatur,Alabama - Tennessee RiverFish,Report Number 100, December 28, 1979 3M requested expertoverview,"BioaccumulationStudies",Dr.James Gilleft, CornellUniversityM,arch 8, 1993 OTHER Last changed: 5/18/00 3MFoM 4747-11 -A T14 )tI@EPORT S LOM M A R Y TO:TECHNICALCO&MMWAnow cEiffEi-tm-mm (imporant - lf,wom I itarinswen aoo awn of~. Now rAe, .0, wrce-) 5/22/79 @(%90 1979 t k, A. pI Environmental Laboratory (ZE & PC) Decatur, Alabama - Tennessee River Fish DWL kwobbw 0222 ptaimi mw"w 78-2740 Bioaccuoulation of Fluorochemlcals In Tenn. To Awdwwid D. L. Bacon %&%@be" Ja"s N I -- 1. Gagnon 51568 Lob Request#4871 ncumrvlo. ConfkbwMU cood Ube" AwdnnWAMW NAcoduam nommv River Fish 001 213531, of r4w 1 10 ftM CMWA=K 0 V" Pi@';W E fte owiiww EL & PC Decatur tmmmTOIAcTM'Qualitative and quantitative determination of P 6309, PH-3925. and FV-3422 in fish taken from the Tennessee River above and below Wheeler Dam at 3M*s Decatur plant. Analyze for organic and inortanic fluoride in the maim wamples. @T AW=ACT Ulow UM*dWA dMm Wdwmeftn6dmftmd 6WSo TOMEW Cemftampow4Comm a don3brom a Omom FAWX ItIsGoomw ndtaomw amwiml Ethyl acetate extracts of a Channel catfish (Ictoluruspunctatus). white bass (Roccus chrysops), mw %Altocrimio (to--W-7xis annularis were analyzed by gas chraomatography. cc: D.Ricker-236-21 A.Wolter A.Mendel Tenn. River Fish/JEG 5/22/79 INTROMCTION It is known that 3M's Decatur, Alabama plant effluent has high organic fluoride levels, 10.9 Ippo(1)(2). It has also been shown fluorochosicals can bloaccusulate In fish in a laboratory onvi- ron"nt (3)(4). With these combined factors, the next step was to 800 if fish caught in the Tennessee River near the Decatur plant had detectable levels of flu--rochomicals. LIIUL RESULTS AND DISCU33ion Table 1 list& the concentration, in ppm, in fish of compounds which have the*aaao retention time an the three fluorochouleals of interest (7-6309, PM-3925. and YM-3422). Analysis of the results for the dissected channel catfish, Sample 3A, shown that the fluorochomicals bloconcentrate to a greater extent In the gastrointestinal tract, reproductive system, and.fat. It can also be seen that the muscle layer was found not to bioaccuoulate the three fluorochmicals of interest. These results agree with earlier reports (3)(4). When comparing the total fluoror-homical content (TPC) for the two whole fish samples. the larger channel catfish cont,,i6inemdore than twice the fluorochosical content, 2 74 pps vs..1.13 ppo. Since both fish were caught In the same ire&, a reasonable explanation for this way be related to the high partition coorricients for channel catfish. Fluorochemicals bioaccumlato in fatty tionuo, and since more fatty tissue is present in the larger fish, more fluorochomicals would be expecied. P-6309 Is present at higher ec.acentrations in the dissected channel catfish, sample 3A, thun other samplem. tion rates have not been determined for F...309 for the higher concentrations c-anbe offered. Since bioaccumulano explanations The two fish samples which had cores taken from them will not be rigorously compared to whole fish amples. The reason for this is that the core samples may not have representative concentrationa of fluorochemicals (whole fish values may be higher or lower). Since core wampi5s were taken from the approximate same loc&Ltion, the results can be rigorously compared. The white bass from below Wheeler Dam. ample IB, had a whole fish TPC of 0.40 ppm. while the white crappie from above Wheeler Dan, m"ple 2A, had a whole fish TFC of 0.004 ppe. With such small mtatintical samples. it would be difficult to may that the larger TFC is due only to the white bass living In the presence of higher fluorochemical concentration. downstream from the plant. Ot!iarpossible explanations for the higher TFC could be the following: Tenn. River Fish/JEG 5/22/79 TA13LX I FLUOROCIIEMICAL CONCENTRATION IN TENNESSEE RIVZR FISH (PPO) samplo C,A - Whole fish 1B - Core (3) 2A - Core (5) ("--3-A Gills 3A - Liver 3A - Parts (7) 3A - Mumele 3A - Fat (8) 3A - Gall bladder Water blank Ethyl acetate blank F-6322 0.40 0.82 0.06 1.45 2.17 1.33 N.D. 13.85 1.57 N.D. N.D. YU-3923 ym-3422 (1) 0.73 3.31 N.D. (6) 0.60 0.38 0.43 N.D. 6.12 0.74 N.D. Total Combined PC if(Fish (opp) (2) 1.13 0.40 (4) 0.004 (4) 2.74 (9) pootautes to Table 1: (1)Fm-3925andPM-342c2annotbe resolvewdithGC parameters used;thereforea,comblaev4aluein reported. (2)BiLmodon frozen weight of the fish. (3)Samplecore,3.61en,id containes,dkin,filet,reproductive organs,anepartsof kidney,rectum andb&cW)oae. (4)Assumesthattheconcentratioonbstaineidn thecareare representative of the rest of the fish. (5)Sample core, 3.61 em ld contalood filot, vertebrae. mkin. and bile. (6)N.D. - Not detected. (7)Consisted of muscle, skin, blood, bone. and cartilage. (9)Consisted of gastrointeatiual tract. reproductive s7st". and fat. (9)Basedon theactualweightof amWIe used,10.8%lessthan frozen weight. and weight percent of each part. lnto,mm.en Tenn. River Fish/JEG 3M CONFIDENTIAL -4- 5/22/79 1. Longer river residence time, older fivii. 2. Longer location residence time. 3. Different species a) Different f**ding and life style* b) Contains larger w*ight percent of organs which tend to bioaccusulate fluoruchenicals c) Larger fluarocb*aical partition coefficients If the core samples are representative of whole fish concentrations, then It can be postulated that channel catfish bioaccusulato fluorocb@leals to a greater extent than either white bass or crappi*. Reasons for this arc the same as listed above. Table 2 9(1;Is 140 results of the organic (RF) and Inorganic fluoride concentration, in pps, in the flab samples. IA 2A 18 Water TADLZ 2 (5) ORGANIC (RF) AND INORGANIC (PO) FLUORIDS OONCZNTILATIONS (ppe) R2 9.7 16.2 10.5 N.I. 24.6 13.3 6.2 0.01 Jon Soliale points out that tht high Inorganic fluoride valucmm soon r&Lber surprising. Uig OF-IY OXPI&O&tiUG Wan that fish flour previously analyzed, for a difloreat requester, van obwa to have lnorgania fluoride values higher than orgaale fluorid*. Joe also states that high inorganic fluaride values would sake It difficult to calculate low levels of organic fluoride. Comparison of the organic and Inorganic fluoride cost*at shows that wa"luu frus &Wvo Whoolur Dm have just an back, I[ out higher, values thaa for %be amele frm below the dm. Tbtre uv no clear cut explanations for Lbis observation. An earlier analysis of T*aaeesoo River water @bowed blglk orvolo tluoride concentrations upstrna frm the plast. At that tLm, It was thought the suoles way have been stalaboled. With thou* results, bJcis Tenn. River Fish/JEG 5/22/79 it would seen to indicate that the concentration of fluorocht@micals may actually be lose below Wheeler Dan. This may be caused by volatilization of the fluorochemical when going over the dam (1). settling of fluorochemicals before the dam. Comparison of organic fluoride values from Tables 1 and 2 show no correlation. For exmple, the highest organic fluoride value. 16-.2 ppa for ample 2A, had the lowest TFC, 0.004 pps, for the fluorochomicals analyzed. A possible are organic fluorides present In very were not analyzed for individuillly. highest filtcontent, channel catfish, explanation In that there high concentrations which The species which had the had the lowest organic fluoride concentrations. With limited &ample population (2 fish of one species and one of each of two other species), it in diffleult to drom any meaningful conclusions. The only definite conclusion In that the fluorochemicals studied do appear to bioaccu@late in river fish under natural conditions. EXPZRIIMTAL 1. Sangle materials Fish IA Small chilnnel catfish (lotaturus punotatme), caught above Wheeler D@ in "aenaesae* River. 1B White bass (Rocaus ohi-yeops), caught below Wbeele7r. D" In Tennessee River. 2A - Whit* crapplo(Ponoxis annutarie), caught above Wheeler Dan in Tennessee Rivej-. 3A - largo channel catfit4h (rt-triturultlt&otijt.st-ioat).caukht above Wheeler D@ La lannommee Rive'r. Standards F-6309, VU-UI)25. and VU-3422. Ton ppm standards of 7-6309, VII-3925, and YU-3422 were prepared by diluting I al of a 100 pps vtaa"rd, in ethyl acetate, t,3mark with ethyl &estate In separate 10 al volumetric flanks. 2. Analysis Instrumnts/l%terials Blender: Waring Co@relal bleader, S"el 091-263, available from Waring Products Divisios, tiouto 44. Now Hartford. CT 06057. following:. Tenn. River Fish/JEG 5/22/79 Tissuemizer: Model #SDT, available from Tek=r .37202. Cincinnati, 09 45222. Company, P. 0. Box Dinker Die: 3.61 ca id AISI-02 high carbon steel cutting die @de by Jerry Guthrie in Central Research Labs, described in 3M Technical Notebook #51568-35. Mixer: "Vortex Genie" Model #K-550-G, available from Scientific Industries, Inc., Bohemia, NY 11716. Centritup Damm-IZC liodel #9-20A, available from Dawn-INC Corporation, Needham Heights, KA. Four-ounce widemouthed clear glass bottle sealed with aluminum foil and aluminum foil-lia*d cap&. 125-ml linear polyethylene (LJ?Z)plastic bottle with polymeal Cape. Gas Chromatocraph: Chrowatograph -Hewlett-Paci-ard Model 5723 CoC. Integrator - Hewlett-Packaj-d Model 3380A intogralor- printer. Both of the &Wvo avallablt: from Rowlett-Packard 150 Page Mili Hoad, Paiu Aito, CA 94304. Cn.. Column - 3ix-foot, 1/8 inch OD, stainless steel. packed with 10% CV20M on 60/90 Chrommorb N-AW. Col@ Temperature - loathe I ISO 0 C. Injector - On-column at 2009mc. 0 Detector - glactron Capture at 300 C. Flow - @,40 cc/slaute of Argoa*Methane (95/5). Sthyl Acetate: "LL Cbrooolv" ebromatograplay solvent available from MC/O Manufacturing Cb@ints, 2909 Mighland Avesue, Norwood, Olf 45212, as Catalog #WO&"&M. and fit. (9) Based on the actual weight of sample used, 18 .817 less than frozen weight, and weight iorcent of each part. Tenn. River Fish/JEG 5/22/79 iater, Deionized water. 3. -Procedure (6) Procedures used below. except for minor toodifications were obtained from earlier 3H Technical Report summaries (7). Sample* 1A through 3A and 1B were removed from the freezer and placed in large aluminum pans, in a fuse hood. and allowed to thaw. A whole channel catfish, sample IA, was cut into 5 sections and homogenized in a blender with 200 al water. Sample 18 had a dinker die core sample taken just off the lateral line behind the gill plate. Contents of the 20.591 gr@ sample were skin, filet. small part of backbone, reproductive organs, part of kidney. and rectum. Sample 2A had a dinker die core sample taken behind the gill plate. The 16.684 grm wasple contained filet, vertebras, skin, and bile. Sample* 1B and 2A were homogenized with 10 =I of water in a -Itianumizer.11 Sample 3A was dissectodand the various individual parts were homogenized with water. Individual parts v*lgbing more than 25.0 gra@ were homogenized in a blender, while those of lesser weight were homogenized In a "tissumizer.10 Table 3 list* tLe sample, sample weight, and amount of water added for homogenizit.g each sample. All of the above amples. &&fter homogenization, wore divided into five aliquoto and placed in preciesned bottles. (dichromate/seld. water riiino,dry. toluano, dry). Three aliquot* were placect LU LPS DOLULOW. WbIL6 the other two were plac:d inogl"s bottles. S&Mles were stored in a refrigerator a 4.5 C. until needed. Samples &"alyzod for P-6309, PH-3925. and YU-3422 were prepared *ccording to the following procedure. See Table 4 for,moight of ample and milliliters of ethyl acetate used for =tractions. A previously homogenized sample, stored La a glass battle. was weighed (so larger than 4.00 S) and added to a 30-al preclemed glass centrifuge tube. A vol%@ of otbyl acetate was added at the rate of 1.0 al ethyl "otate pur grm of bomogenate. The ethyl aestate/flob boso"aate were mixed for 1.5 minutes in a mixer at a speed settle$ of 3. The sa"leo were removed and centrifuged at ISW rpm at Tenn. River Fish/JEG 5/22/79 21 0 C. for 10 minutes. After centrifuging. the ethyl &estate layer was separated, by use of a pipet, and placed In a vial. Five ul of sample (standard) was injected for gas chromatographic analysis. S&Mles IA, 2A, and ID bono"natoo, plus a water blank. in LPZ bottles, were sent to Joe golisl* of the Central Research talmrstary for organic and Inorganic fluoride analysis. REVERENCZS (1) 3M to ,Pato*f Technical Report guomry, August 30, R. L. Bobon, nuorochosicals 1976, Arthur Mandel Project - Progress Report.$' (2) Central Research Laboratory Report Number 6902. April 20, 1978, Jon Belisle. (3) "niocoticantration of PH-3422 In 13lueltill.4&unfixhand in Channel Catfish," U. T. glaabaravy to A. M. V*Itor. May 17. 1977. (4)3M TIA. August 16, 1978, A X. Welter to D. L. Bac". "Zvaluation of the SloconeAstration Potential of YU-3422." (5) Central Research Laboratory Report os lkequent OA72199 by Joe Belisle, May 7, 1979. (6) Zxperisental work done in cooperation with A. X. Welter of the Zavlro@stal Laboratory (Zt & PC), wbo performed the diametions and bonogenizatiose. (7) 3H TtichniCgRLulixieSLunwmry,MovanberIfo,1977.A. Unofi4-1 to D. L. bmeas,"AnalyticaMlethodologoym VS-3422." G/con Tenn. River Fish/JIG -9- 5/22/79 FISH WEIGHTS TABLE 3 &ND WATER VOLUMCS USED FOR HOMOGENIZATION Sample Description 1A 2A 1B 3A - Muscle 3A - Gall bladder 3A - Liver 3A - Fat 3A - Parts 3A - Gills Initial Whole Frozen Weicht 146.0 g 266.5 g 210.0 g 752.0 g 752.0 g 752.0 g 752.0 g 752.0 g 752.0 g Actual Sample Weight Used ml Water Used Whole fish (1)(2) 200 16.684 g (3) 10 20.591 g (3) 10 209.93 g 200 1.378 g 10 5.949 g 10 52.2:,10g 100 321.57 g 300 19.38 g 100 Footnotes: (1)A fish hook. with no apparc3t rurt or lin(,,,wnsroin(iin ribh aud wum ruwvud btifurtl.iumugo-,uizaLiutt. (2)The fish appeared to be slightly dehydrated (possibly due to constant air flow over L-urfaceof fish) so the actual weight of fish used may have been less than frozen weight. (3)Sample core 3.61 em id. Tenn. River Fish/JEG 5/22/79 TABLE 4 FISH WEIGHTS AND ETHYL ACETATE 'USED FOR EXTRACTIONS VOLUMES Sample Description 3A - Gall Bladder 3A - Liver 3A - Muscle 3A - Fat 3A - Parts 3A - Gills Water Blank 1A in 2A Weight of Fish % Water Romogenate in (Era=) Romocenatt 1.20 87.9 2.20 62.7 2.40 48.8 2.40 65.7 3.00 48.3 3.00 83.8 2.40 100.0 2.40 57.8 2.40 32.7 2.40 37.5 Actual Fish Wt. Extracted (me) 145.2 820.6 1228.8 823.2 1551.0 486.0 -- 1012.8 1615.t 1500.0 ml ETOAC 1.2 2.2 2.4 2.4 3.0 3.0 2.4 -2.4 2.4 2.4 F., n 6747 11 A TECHNICAL F-C- AMPORT SUMMARY TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN (Important - If report isprinted on both sidesofpaper, sendtmcopiesto TCC.) Environmental Laboratoxy (EE Project -Aep-ort f itie Decatur, Alabama - Tennessee Fluorochemicals in Tennessee To - D., L.-Bacon Author(s) James E. Gagnon Notebook Reference 51568 Lab Request #4871 SECURITY 100 0 Open (Company Confidential) ZI Closed (Special Authorization) KEYWORDS: (Select terms from 3M Thesaurus. Suggest other applicable terms.) CURRENT OBJECTIVE: Progress Report. & PC) River Fish River Fish 3M CHIEMICAL REGISTRY P' EE & PC Decatur (Cr 2/28/79 D;t. Number 222 Project Num b*r 78-2740 Report Number 100 EmpioV@ 1 Numbgr(s) 21353 No. Of PMOI Including 3 Covershost Now yeChsemicals Reported ag No REPORT ABSTRACT: (200-250 words) This abstract information isdistributed by the Technical Communications alert3M'ors to Company R&D. It isCompany confidential ffetwisi. Center to The microwave sustained helium plasma detector system and capillary column with electron capture were utilized to examine fish extracts for fluorocarbon alcohol levels. cc: D.Ricker-53-4 A.Welter A.Mendel :n,ftitj)irsrnatioLn n @'&@ -2- Introduction: Previous work 1 indicated a need for more definitive answers to the presence of volatile fluorochemicals. Capillary gas chromatograpliy with an electro-.ic,.,,)turdeetector (CGCEC) and microwave sustained helium plasma detector (MSHPD) were used to analyze ethyl acetate extracts of fish taken from the Tennessee River, near 3M's Decatur, Alabama plant. A Minnesota brown bullhead ,sample, extracted as previously describedl, was also analyzed as a background check. Results: 1. Capillary Gas Chromatography with Electron Capture No compounds were detected in the Minnesota brown bullhead (sample IM) having retention times close to the fluorochemical standards (Table 1). Except for a peak at 6.14 minutes, and solvent peaks, the chromatogram was very clean. In comparison, samples IB and 3A (bass and catfish from below and above Wheeler Dam, respectively) showed more than 25 peaks. A peak with retention time similar to F-6309 was detected in samples 1B and 3A (Table 1). TABLE 1 QUALITATIVE ANALYSIS OF FISH EXTRACTS FOR FLUOROCHEMICALS Sample Retention Time (Minutes) 10.84 12.68 1B im 3A FM-3422 Std. F-6309 Std. N.D. N.D. N.D. N.D. N.D. N.D. N.D. = Not detected = Very small amount = Peak Area less than standard, = 10 ppm standard but greater than 2. Microwave Sustained Helium Plasma Detector: (MSHPD) The above samples were also analyzed by MSHPD in the fluorine and sulfur detection modes. The results obtained by the microwave plasma detector on spiked samples show that FM-3422 and F-6309, if present, could have been detected from their fluorine content at the 0.1 ppm level in the ethyl acetate extracts. No fluorocarbon peaks were observed in the actual samples.2 -3- Discussion: The above results indicate that no volatile fluorocarbnng wprp pErEe6@s@e@-@nl-t@@,n@@es@ @i c aI@-rarf-;,@-aarit-;uo,o@unn ss@oo roo@rggaann@cc @u u-(orine ffientioneidn the original report are due to the presence of nonvolatile fluorochemicals (NVFC). Thin-layer chromatography for NVFC,s (e.g., FC-95) was hindered by an overabundance of -nterferring compounds. Integrity of the Standards: 1, After the initial report it was brought up that FM-3923 and 3 FM-3422 are both the same compound (N-ethyl FOSE alcohol) . The compound used for our FM-3923 standard had given a different retention time, by gas chromatography, than FM-3422. Samples of FM-3923(a new sample),FM-3923(theold "standard"),FM-342a2n,d FM-3925 were sent to Commercial Chemicals Analytical Lab for verification. It was determined that the old FM-3923 standard had been improperly labeled before being sent to us. In reality, the sample was F-6309 (N-ethylperfluorooctanesulfonamide: c F so NHET). 8 17 2 As of 27 August 1979, the new FM-3923, Lot 518, will be used for preparation of standards (identification verified ) and the old FM-3923 has been properly labeled as F-6309. References: Gagnon, James E., 3M Technical Report Summary "Bioaccumulation of Fluorochemicals in Tennessee River Fish," 22 May 1979. 2 Hagen, D. F., 3M Technical Report Summary "AR No. 7238 Determination of Fluorinated Alcohols in Fish Extracts," 23 October 1979. 3 Personal Communication with A. Mendel. 4 Winter, L. D., Commercial Chemicals Analytical Lab Request No. 14998, 24 August 1979. @G/cel 3M REPORT: BIOACCUMULATION STUDEES March 8, 1"3 6- ReportNo. 001 (5122179')Bioaccumuladonof Fluorochemicalisn Tenn.RiverFish,and ReportNo. loo (1212,817"9F)luorochemtcailnsTennesseeRtverFtsh., Thispairofpapersisquiteconfusingl,argelbyecauseof incorrecsttandardsc,onfusedidentitoyf labelasnd verityof contents,and the difficulotfyactualdeterminations.When theseare combined with a lackof clear samplingdesignin relationto outfauand samplingpoints,the resultadd littlteo our understandingof the problem These papers make an excellentexample of hcyw a Uttlelmawledge can be dangerous. 6 --form 6747.1 I-A TECHNICAL REPORT SUMMARY TO: TECHNICAL COMMUNICAR ICPJP*Lr-2CD Ic 4y (Import-anItfreporitsprintoendbo6sideosfpapers,endtm copietsoT:CC.) 0 ofm October 23, 1979 Deipmcumner- CENTRALRESEARCHI.ABORATORIESA,nalyticaland PropertiesResearchLaboratory 0502 Project Project Number Environmental Engineering and Pollution Control Report Teti* A000007 H*Port Number AR No. 7238 Determination of Fluorinated Alcohols in Fish Extracts 238 To J. E. GAGNON Author(%) D. F. HAGEN Notebook Reference 209-lS 201-lS Employee Numberts) 042608 N oict pages In)d'sng Covershout RI SECLJR ITY 10- El Open (Company KEYWORDS; (Select terms from 3M Thesaurus. Suggest other applicable terms.) Confidential) Closed tspecial Authorization) CURRENT OBJECTIVE' Request No. A73154 REGISTRY Now rh6.-e Reportofl Yes No Central Research Analytical Report Requestor - J. E. Gagnon Project No. 91500600 Chemical Analysis REPORT ABSTRACT: (200-250 words) This abstractinformation isdistributedby the Technical Communications Center to alert3m'ers to Convany R&D. itisCompany confidentialmaterial. The microwave sustained helium plasma detector system ind capillary column with electron capture detection were titil!zed to eximine fish extracts for fluorocarbon alcolinilevels. formation Liaison In room 2643-C PWO CENTRAL ANALYTICAL LABORATORY Report No ------3.230---------- Date-------Orr.-<Lh2g3T.--1.99-9- Subject: Determination of Fluorinated Alcohols in Fish Extracts Reque stor: -qzl&rLc!L--- Dept. Diamel--EE&PC ------- Reque at No. _ A73154 -------- Dated _-August-S, -1979------ Proj. No. 91500600 Report: Introduction The microwave sustained helium plasma detector (MPD-850)-chromatographic systems and capillary column chromatography with electron capture detection were utilized to examine fish extract samples for the pre"senceof fluorocarbon alcohols FM-3923, FM-3925. and F@1-3422. Discussion and Results The helium plasma detector yields atomic line spectra for the elements present in the chromatographic peak as it elutes from the column. One can therefore monitor specifically for fluorine and sulfur to allow for the detection of specific compounds such as the fluorocarbon alcohols. Detection levels are intermediate between FID and EC detectors. In this type of sample, the lower detection limit is somewhat dictated by the sample matrix. If large non-fluorine containing peaks are present they will overload the plasma activating a "bypass mode" to prevent carbon buildup or-the quartz cavity tube. This presents little difficultyif the non-fluorine interference peaks are 3de@quatelyseparated from the fluorine containing peak of interest. The lower level 6f the fluorocarbon alcoliolsdetectable in these ethyl acetate fish extracts is about 5 nanograms/101ilinjection. Additional sensitivity was obtained by concentrating 1001ilof the solution as received to 20Liland injecting 10iiIof this concentrate for analysis. Operating conditions for the MPD-850 are listed below. Column Svstem A - 6', 6% CW-20M-TPA on 80,1100 mesh Chrom C. H.P. programmed from 100 tt)2000C at 15*C/min. Helium carrier at 25cc/min. with purge rate to MPD of 50 cc/min. Forty percent of the column effluent is split to the FID on the HP-7620 gas chromatograph and 60% is transferred to the MPD-850 plasma cavity via a heated 1/16" capillary line ac 180*C. The cavity head temperature is held at 200*C and the plasma is sustained by a 100 watt microwave power supply operating at 2.450 gi ahertz. The emission lines used for fluorine and sulfur were 6856.0 and 5453.9 @ respectivelv. Approximately 0.5 ml/min. of oxygen is used as the sctvenger gas to prevent carbon buildup on the quartz plasma reqctor tubes. The above samples were also examined on a capillary column system with electron capture detection in an attempt to lower the sensitivity level.sfor the compounds of interest. Operating conditions for the capillary system are listed below. Column Svstem B - 30 meter glass capillary column wall coated with CW-20.4. Initial column temperature was 60*C and it was programmed at 10*C/min. to 2400C. Split mode of injection was utilized with 99% of the injected sample (lVl) being vented to the AR No. 7238 October 23, 1979 Page 2 atmosphere. Column flow was approximately I cc He/min. and an auxillary flow of 41 cc/min. of 95-5 Argon-methane was utilized to purge the electron capture detector. This purge flow is added at the exit Of Lhe column system on the HP-5840. System A - Chromatogram 10-10-79-1 illustrates the fluorine and sulfur responses for a lowl injection of a 10 ppm solution of FM-3923 or CGF17SO2N(CH3) C2H%OH. Note that three fluorine peaks are observed with the major at 6.5 min. The sulfur response lags the fluorine response by 0.5 min. to prevent pen overlap. Chromatogram 10-10-79-2 results from a 1OUl injection of sample 1-H (ethyl acetate extract of a brown bullhead from Minnesota. Note the absence of fluorine containing peaks. Chromatogram 10-10-79-3A illustrates the res(ults for a lftl injection of sample 3-A (ethyl acetate extract of a channel catfish above Wheeler Dam). At those points where an overload is shown, the effluent peak which is non-fluorinated is bypassed around the plasma cavity tube. Clear areas do exist however where the fluorocarbon alcohols elute and they appear to be absent. Chromatogram 10-10-79-4 shows the response obtained for a Iftl injection of the ethyl acetate extract of sample 1-B (bass below Wheeler Dam). Chromatogram 10-10-79-5 illustrates the response obtained for a 5 rold concentrate of sample 1-B. Chromatogram 10-10-79-6 shows the response for a 1OUl injection of a 5 fold concentrate of sample 3A. Chromatograms 10-10-79-7 and 10-10-79-8 illustrate the responses obtained for the injection of llilof 10 ppm sblutions of F?-t-3923and FH-3925 respectively. %*ote the F@t-3925 C8Fl7SO2N homolog. (C?.Hs) C2HY.OH elutes approximately 2 minutes after the u-cethyl These levels correspond to 10 nanograms injected and I expect one could detect a 5 nanogram level. Chromatogram 10-10-79-9 illustrates the sample of 1.4which has been spiked with known levels of these homologs. In this case 20 ng of each species was added to 10OUl of sample 1-A and this was concentrated via evaporation to 2.ftl. 10al were then injected for the analysis. System B - Chromatograms 10-12-79-1, 10-12-79-2, and 10-12-79-3 illustrate the -clectma capture response for samples 3-A,.l-@t, and 1-B respectively. .140tethe laritenuv+.er of capture sensitive peaks. These are not neces;.-trilyhalogenited npecies In that a number of compound classes give a degree of EC reponse. The arrow,.%point out those areas where the alcohol homologs will elute as illustrated In chromtogr=to 10-12-79-4 and 10-12-79-5. The capillary column-electron capture results indicate that souple I.-Mumld have to contain less than 0.05 ppm based on the attenuations for tht sn=ple Va. referxece solutions. Samples 3-A and 1-B would also contain very little of the FX-3925 or AR No. 7238 October 23, 1979 Page 3 F-4-3422 species. These latter two samples do have a peak at the retention tim of F7@1-392m3ajor isomer but the isomer distribution14;not evident in the sa=ple chrom.itogram.Lower levelsof detectionvia electron capture would requireadditional sample cleanup prior to chromatography. The results obtained bv the microwave plasma detector on spiked samples show that these alcohols if present could have been detected from their fluorine content at the 0.1 ppm level in the ethyl acetate extracts. No fluorocarbon peaks were observed in the actual samples. D. F. Hagen DFH/rs c: B. W. Nippoldt 201-lS 3M CONFIDENTIAL 3 Cl-.L'3 BORATORIES ANALYTICAL RESEARCH RequestNo. DivJDept. ProjectNo Date Chemi st A -7 C143 slo ti IN lo Z: LABORATORIES ANALYTICAL RESEARCH RequesNto. A - -7-3/ -T Div./Dept. lr-gc=,A- p@-ProiectNo. 9,P S---*Js@Eo 0 Date Chemist F7C ----------!L ;YSA ANALYTICAL RESEARCH Reque stNo. DivJDept. ProjectNo. Date Chemist A--i3i 4 'Se/ 4210, r it t Ij FORM 1944-0 77,!- i KBORATORIES ANALYTICAL RESEARCH Request No. DivJDept. ProjectNo.9/-45'L2fZ-4T--00 Date Chemist .O%WV4 FORM 2644.0 i ANALYTICAL RESEARCH Request No. ivJDept. ProjectNo. 490,e Olate 4 7,* Iola - F)c FORM 2044-0 ....... !J: f '79- RIES ANALYTICAL Requ estNo. DivJDepL ProjectNo. Date Chemist RESEARCH rL o .9 cv E FORPA 2644-0 I %H LABORATORIES lox to ANALYTICAL RESF-ARCH Request No. DivJDePL projectNo. Date + -0 0 aA AV.&V ift-t-3 cl so C. ti C@: L -FORM 2644-0 ITi7- @;ES ANALYTICAL RF-SEAFICH Request No. DivjDept. ProjectNo.. Dat Chemist A34 li IF tA C S40 5A iR;OP,441 I pr*ftm 2644.0 it: 7 i-, pk )RIES I. davw@ ANALYTICAL RESEARCH Request NO. A- DivJDept. 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