Document KGGqwVdYN0Vb9gpg8G2Jb3z2r

BIOACCUMULATION TEST SUBSTANCE Identity:N-methylperfluorooctanseulfonamidoethanolm;ay alsobe referredtoas N-MEFOSE Alcohol,FC-790, or FM-3925. (1Octanesulfonamide,N-methyl-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-N-(2-hydroxyethylC)A-S, # 24448-09-7) Remarks: Materialisan off-whitew,axy solidofuncharacterizedpurity. METHOD Method/guideline followed: None givenforsampling ofthe organisms. Extractionand analysisprocedureswere devised by 3M. -Type:Analysisoftissueforfluorochemicaflrom indigenousfishcaught in the Tennessee Riverabove and below the Wheeler Dam. GLP (Y/N): No Year: 1979 Remarks field:There isno informatioonn samplingproceduresofthe organisms from the Tennessee Rivernear the manufacturingfacility. Four fishwere caught and utilizeads samples;Two channel catfishcaught above Wheeler Dam, one white bass caught below and one whitecrappie caught above Wheeler Dam. Wheeler Dam isapproximately26 nautical milesdownstream from the 3M Decatur Planteffluendtischarge.Itwas not noted inthereporthow many milesabove and below the dam thefish were caught. A ten ppm standardofFM-3925 (N-MEFOSE alcohol)was preparedby dilutin1gml ofa 100 ppm standard(inethylacetate)tomark withethyl acetateina 10 ml volumetricflask. One whole channel caffiswhas homogenized to createone sample. The otherchannel catfishwas dissectedand thevariousindividuaplartswere homogenized tocreateindividuaslamples. The whitebass had a 6.3cm i.d.dinkerdiecoresample takenjustoffthe lateralinebehind the gilpllatemaking up a 20.591 g sample containing skin,filets,mallpartofthe backbone, reproductiveorgans,partofthe kidney,and rectum. The whitecrappiehad a dinkerdiecore sample taken behind the gilpllate to createa 16.684 gram sample containingfiletv,ertebrae,skinand bile. Allsamples were homogenized inknown volumes of DI waterand divided intofivealiquotseach. Samples were centrifugede,xtractedwithethylacetate,and analyzed by GC fororganicand inorganicfluodde. .Iwtas notedthatFM-3925 (N-MEFOSE alcohol)and FM-3422 (N-ETFOSE alcohol)couldnotbe distinguishewdithGC withelectroncapture parameters.The resultsarethereforae combined value. RESULTS N-MEFOSE alcohol/ N-ETFOSE alcoholConcentration InTennessee RiverFishby GC Sample N-MEFOSE alcohol& N-ETFOSE alcohol Water blank (ppm) N.D. EthylAcetate blank N.D. Whole Channel Catfish 0.73 Whfte Bass core sample 3.31 Whfte Crappie core sample N.D. Channel CaffishGills 0.80 Channel CatfishLiver 0.38 hannel CatfishParts* 0.43 Channel CatrishMusde N.D. Channel CatfishFat 6.12 Channel CatfishGallBladder 0.74 Upon completionof GC analysist,herewas concern thatthevalueswere notdefinitivAed.ditionaalnalysisofethylacetatehomogenate extractwas then done usingCapillarGyas Chromatography withElectronCapture and GC usinga Microwave SustainedHelium Plasma Detector. QualitativaenalysisofthefishextractsusingCapillaryGas Chromatography withelectroncapturefailedtoidentiftyhepresence of NETFOSE alcohol.Thiswas furthesrupportedby analysisby a Microwave SustainedHeliumPlasma Detectorwhere again,no evidenceofany fluorochemicalwsere detectedand specificalnloy N-MEFOSE alcoholand no N-ETFOSA (F-6309)were detected.The resultsobtainedby the microwave plasma detectoron spikedsamples indicatedthatN-ETFOSE alcohol,ifpresent,couldhave been detectedfrom itsfluorinceontentat 0.1ppm intheethylacetateextracts.No referencewas made to NMEFOSE alcoholexceptforthegeneralstatementmade "No fluorocarbon peaks were observedintheactualsamples." Remarks:The originraelpor(t5/22/7r9e)ferenceadsampleforFM-3923. Itwas broughtup afterthereportwas generatedthatFM-3923 and FM3422 are both thesame coumpound (N-ETFOSE alcohol).Analyticawlas conducted toverifyitsidentitaynd itwas found tobe N-ETFOSA (F-6309). The attachedreportC'AR No. 7238 - DeterminationofFluorinated AlcoholsinFishExtracts"1,0/23/79)stilrleferstoFM-3923 when infact the sample labeledas FM-3923 isF-6309. Thisreportalsohas inconsistenciesT.he lastparagraph indicatetsheabilittyo detectfluorine contentat0.1 ppm level.However, a reviewoftheprocedure used indicatesa detectionlimiotf0.5 ppm. The firsrteport(5/22f79)describesanalysisofethylacetateextractsof fishhomogenate by gas chromatography (GC) withelectroncapture detection.The analysisshows the presence ofmaterialsinfishtissue extractsthathave GC retentiotnimes identicatloboth N-MEFOSE alcohol and N-ETFOSE alcoholand to N-ETFOSA. The GC retentiontimes of NMEFOSE alcoholand N-ETFOSE alcoholstandardswere thesame (not -resolvedb)y the method used inthefirsrteport.The firsrteportindicates the presence offluorochemicalsinthefishextractsb,ut electroncapture detectionisnotspecififcorfluorochemicalsT.hus the resultsreportedin thefirsrteportwere not a specificidentificatioofnfluorochemicals detectableby GC. (Report1 alsohas errorsincolumn 4 ofTable 1.Inthe 1B row, 0.40 should be changed to4.13,and inthe2A row,0.004 should be changed to0.06.) The second report(12/28/79)shows a misinterpretatiionnthefirsrteport. Itincludesa descriptioonf GC analysesofethylacetateextractsoftwo of the samples describedinreport1 samples IB and 3A. The work describedinreport2 used electroncapturedetectionand referencesa reportusingmicrowave sustainedhelium plasma detection(MSHPD) in the fluorinaend sulfurmode. Influorinmeode, MSHPD method isspecific forfluorine.The MSHPD resultshow no fluorochemicalisnthe ethyl acetateextracts.The resultsare interpreteads indicatintghatF-6309 and N-ETFOSE alcohol(FM-3422) are presentinthe ethylacetateextracts at lessthan 0.1 ppm. Inthe firsrteport,N-ETFOSA (F-6309)and NMEFOSE alcohol(FM-3925) /N-ETFOSE alcohol(FM-3422) had appeared to be presentrespectivelayt0.82and 3.31 ppm insample 1B and at 1.48 and 0.80 ppm insample 3A. Thus, theGC-able compounds seen inthe firsrteportappear nottohave been fluorochemicalasnd thuscouldnot have been N-MEFOSE alcohol,N-ETFOSE alcoholor N-ETFOSA. The firsrteportshows the presence ofunidentifieodrganicfluorinaend of inorganicfluorinienthefishtissue.Thiswas notre-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 designinrelatiotnothe ouffalalnd sampling points,verifiable data on theactualconcentrationsoffluorochemicalsinthe riverfrom both the manufacturingfaciliatnyd from naturalsources,activietsinthe manufacturingfacilitpyriortosampling,any applicableenv' ironmental conditions(e.g.rainevents),and a clearunderstandingof how longthe sampled fishwere inthe sampling area,thereislitttloebe concluded. Additionalltyh,eanalyticadlata conflictsI.tcannot be definitively concludedwhich analyticadlata setiscorrect.Extractioannd analytical methodology were not validated.Stateunitsofresultsisppm. Itisnot correlatetdomg analyteper kg body weight. Identitaynd purityof referencecompounds was not establishedthereforestatedanalyte concentrationshave no basisinfact. REFERENCES 3M TechnicalReport "Bioaccumulationof FluorochemicalsinTenn. River Fish."James E.Gagnon, Project78-2740, Decatur,Alabama Tennessee RiverFish,Report Number 001,May 22, 1979 3M TechnicalReport "AR No. 7238 - DeterminationofFluorinated AlcoholsinFishExtracts."D. F. Hagen, ProjectA000007, Environmental Engineeringand 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 requestedexpertoverview,"BioaccumulationStudies",Dr.James GilletCto,rnellUniversityM,arch 8, 1993 OTHER Last changed: 5/18/00 3M REPORT: BIOACCUMULATION STUDEES March 8,1"3 -------- ------- 6. Report No. 001 (5122179) abioaccumuladon of Fluorochemicals in TentL River Fish- and Report No. loo (12128179) "Fhiorochemwah in Tennessee River FisiL II& pair of papers is quite confusing, largely because of incorrect standards, confused identity of labels and verityof contents,and the difficulotfy actualdeterminations.When theseare combined with a lack of dear samplingdesignin relationto outfau and samplingpoints,the resultadd littlteo our understandingof the problem. These papers make an excellentexample of how a littllemowledge can be dangerous. 6 ,3,m. Form 6747 11 A TO: TECHNICAL TECHNICAL FtEP'CrRT SUMMARY COMMUNICATIONS CENTER - 201-2CN (Important - Ifreport isprinted on both sidesofpaper, sendt"copiesto TCC.) C),v,%iO.I% Projtct Environmental Laboratox-y (EE & PC) Decatur, Alabama - Tennessee River--Fish Fluorochemicals To D. L. Bacon Author(s) ' James E. Gagnon Notebook Ref*r*nco 51568 Lab Request SECURITY 10, 0 Open (Company Confkkntial) in Tennessee #4871 C3 cloud (SpeciaAluthorization) KEYWORDS: (Select*rrmfrom 3M ThesaurusS.uggestother applicable terms.) CURRENT OBJECTIVE: Progress Report. River Fish M4 CHEMICAL REGISTRY EE & PC ? Decatur CCRD r"12/28/79 Dept Number 0222 rrol*ct Number 78-2740 We-pa-r-t-Wu--mg;r 100 F-rnplayse Numbor(s) 213531 No. of Pages Including Covershe*t 3 P4sw ChwnicalsReported 0 Yo No REPORT ABSTRACT: (200-250 words) This abstract information isdistributed by the Technical Communications alert3M'ors to Company R&D. It isCompany confidential material. Center t. The microwave sustained helium plasma detector system and capillary column with electron capture were utilized to examine fish extracts for fluoro- carbon alcohol levels. cc: D.Ricker-53-4 A.Welter A.Mendel :n.lortnatioLn n tiait: @'ER) -2- Introduction: Previous work 1 indicated a need for more definitive answers to the presence of volatile fluorochemicals. Capillary gas chromatograpliy with an electron ca,)ture detector (CGCEC) and microwave sustained helium plasma deteztor (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 bullbead (sample 1M) 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 1B 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 doected 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, but greater than = 10 ppm standard 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 fluorocarhnnm wprp - e-itin c I.arFr-, oun s o organ c uorine aT mentioned in 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 @M-3422 are both the same compound (N-ethyl FOSE alcohol) 3 . 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 (the old "standard"),FM-3422, and FM-3925 were sent to Cominercial 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-ethylperfluorooetanesulfonamide: c 8 F 17 2 NHET). -),P. 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: 1 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. ,A C v@GG/cel 3FMed4747,IIA T14 *"f.PORT SL"MARY To. TECHNICAL COUMTJPIWATICM CEOffER - M-XN timpo-rIarfnetpiwWsriRwanbooSWNopfww=,9N4o,No1'0rcc.) c@M.06" p2 lggwt,yw TO Environmental Decatur, Alabama Bioaccusulation D. L. Bacon Laboratory (ZZ & PC) - Tennessee River of Fluorochosicals Flab In Tenn. - River Flab DEL, 2 DWL N4mbw 0222 F-ie-mt maxbbw 78-2740 W40wiWwmbw 001 mo"oo" Ja"s getwom 1. Gagnon 213531-1 "4L Orr I. UCUMTY sissa 00 12 n.. Emio-Ww ewomo*o Lob Request #4871 0 cund I*mw Aw*AnieftW 30 C3dmCAL ogaunv 10 - Chous" C3 va E me KEVWCMUML%ism urm fmn 3M romommulboom mokamearoal LE & PC Decatur cum""T O"cTml Qualitative and quantitative determination or F 6309. FM-3923, and FY-3422 in fLab taken fr,3m the Tennessee River above and b*low Wbc-clor D@ at 3M'u Decatur plant. Analyze for organic and inorianic fluoride in the samw mumples. T ANTRACT: 93mmawol WA o@ kwonefte Isdwowd dw Won a Comeow OMM k a coomw Meadow omwi& IVso Toomw CoommanOW4 amm a Ethyl acetato extracts of a Channel catfish (ictolurws pumtstus), %Alto bass (Roccus chrv$&Sis &rW a white crapple (Famoxis annularls) war* analyzed by gas chromatography. cc: D.Ricker-236-21 A.Welter A.M*odel Tenn. River Fish/JEG 5/22/79 INTROMCTION It is known that 3M's Decatur, Alabama plant effluent has histh organic fluoride levels. 10.9 ppm (1)(2). It has also been whuwn fluorochonlc&lg can biolecumulate In fish in a laboratory onviron"nt (3)(4). With the** combined factors, the next stop was to see If fish caught in the Tennessee River near the Decatur plant had detectable levels of flu--rochomicals. LliaL RESULTS AND DISCUSSION Table 1 list& the concentration, in ppm, in fish of compounds Which have the'a*Ae retention time as the three fluorochosicals of interest (7-6309, PM-3925. and rM-3422). Analysis of the results for the dissected channel catfish, Sample 3A. &bows that the fluorochomicals bioconcentrate 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 bio&ccumulate the three fluorochanicals of interest. These results agree with earlier reports (3)(4). When comparing the total fluorochomical content (TFC) for the two whole fish samples, the larger channel catfish cont.;Linedmore thin twice the fluorochosical content, 2.74 ppe vs.. 1.13 ppm. Since both fish were caught in the same area. a reasonable explanation for this may be related to the high partition coorficientai for channel catfish. Fluorocheaicals bioaccumulat* in fatty tianuo, and since more fatty tissue is promont in the larger fish, mure fluorochomicals would be expected. P-6309 is present at higher cc.neentrations in the dissected channel catfish, sample 3A, thun other samples. Since bionecuoula- tion rates have not been determined for F-6309 for the higher concentrationsi c-an be offered. so oxplanationu The two fish aamjples which had cores taken from then will not be rigorously compared to whole fish samples. The reason for this in that the core samples may not have representative concentrations of fluorochemicals (whole fish values may be higher or lower). Since core samp!5s weru taken from the approximate manu locution, the results can be rigorously compared. The white bass from below Wheeler Dam. sample 1B. had a whole fish TFC of 0.40 ppm, while the white crappie from above Wheeler Dam, umple 2A, had a whole fish TFC of 0.004 ppe. With such small ntatintical samples, it would be difficult to say that the larger TFC is due only to the white bass living in thu prowunce of higher fluorochesical concentration, downstream from the plant. Ot!ier possibl* explanations for the higher TPC could be the following: Tenn. River Fish/JEG 5/22/79 TABLE I FLUOF*A[EMICAL CONCENTRATION IN TBNNZSSZZ RIVZR FISH (PPO) Sample C,A - Whole fish 1B - Core (3) 2A - Core (5) ('--3-A Gills 3A - Liver 3A - Parts (7) 3A - Muscle 3A - Fat (8) 3A - Gall bladder Water blank Ethyl acetate blank F:U22 0.40 0.82 0.06 1.48 2.17 1.33 N.D. 13.85 1.57 N.D. N.D. YU-3923 YU-3422 (11 0.73 3.31 N.D. (6) 0.30 0.33 0.43 N.D. 6.12 0.74 N.D. N.D. Total Combined PC io Fish (Vpp) (2) 1.13 0.40 (1) 0.004 (4) 2.74 (9) Footnut a_ to Table 1: (1) Fm-3925and FM-3422cannotbe resolvedwithOC parameters used;therefore&, ecabinecv4alu*in reported. (2) Based on frozen weight of the fish. (3) Samplecore,3.61 em, id coat&Laeds,kin,file%,reproductive organs,ane partsof kidney,rectum Lad backbone. (4) Assume that tb* concentrationosbtainedin the core are representativoef the rest of the flab. (5) Sumplecore,3.61 em id containedfilet,vertebrae.mkin. and bile. (6) N.D. - Not datectod. (7) Conainted of muscle, skin, blood. bone. and cartila" (8) Consisted of gantrolatestiual tract, reproductive system. and fat. (9) Basedon the actualweightof sampleused,le.8%losethan frozen weight, and weight percent of each part. 3PACONFIDENTIAL Tenn. River Fish/JEG -4- 5/22/79 1. Longer river residence time, older lisli. 2. Longer location residence time. 3. Different species a) Different fo*dlng and life styles b) Contains larger weight percent of organs which tend to bioaccuoulate fluoruchenicalm c) Larger fluorochosical partition coefficients If the core samples are representative of whole fish concentrations, then it can be postulated that channel catfish bioaccuoulato fluoroebasicals to a greater extent than either white bass or crappi*. Reasons for this arc the same an listed above. Table 2 giv fluoride t4a results of the organic (RF) and Inorganic camcentration, in ppa, In the fish samples. S!Ml* 1A 2A to Water TABL& 2 (5) ORGANIC (RF) AND INORGANIC (70) FMRIDR CONCZNTUTIOKS (ppa) R7 9.7 16.2 10.5 24.6 13.3 6.2 0.01 Jon Belisle points out that tho high Inorganic fluoride valu" woos rather surprising. His orly explanation wan that fish flour previously analyzed, for a dillereat roqueetor. mm shows to have Inorganic fluoride values higher than orgesic fluoride. Jon &Igo states that high inorganic fluoride values would swlke it difficult to calculate low levels of organic fluoride. Comparison of the organic and Inorganic fluoride contest ohn that mamlow fnm UWVQ Whoolor D@ have junt am big%, kr so% higher, values %has for the amele from below the dm. There &" no clear cut explanations for this observiltios. As earlier analysis of Tennessee River water @bow" high orvole fluoride concentrations upstrom from the pl&st. At that time. it was thought the OSAPIOG may have bees siolooled. Vith tb"* results, e Lie- z-Igo Tenn. River Fish/JEG 5/22/79 it would seem to indicate that the concentration Of fluoroch(@micals may actually be less below Wheeler Dan. This may be caused by volatilization of the fluorochemical when going over the dAm settling of fluorochemicalsbefore the dam. Comparison of organic fluoride values from Tables 1 and 2 show no correlation. For example, the highest organic fluoride value. 16-.2pps for ample 2A, had the lowest TFC, 0.004 ppm, for the fluoroeb@icals analyzed. A possible explanation in that there are organic fluorides present In very high concentrations which were not analyzed for individually. The species which had the highest fat content, channel catfish, had the lowest organic fluoride concentrations. With limited sample population (2 fish of one species and one of each of tvo other species), It in diffIcult to dr= any meaningful conclusions. The only definite conclusion is that the fluorochemicalsstudied do appear to biosecumlate in river fish under natural conditions. EXPZRI MENTAL 1. sawle materials Fish IA - Small channel catfish (lotaluruspunatatum).caught above Theelor Dm In "&ennesaeeRiver. 1B - White bass (Rocaus ah@-yeope), caught b*low Wbeele-r. Dan In Tennessee River. 2A - White crapple(Ponosis an"mtarie), caught above Wheeler Dm in Tennessee Rives-. 3A - largo ch&Lnnelcatfimh (re-tsituriwas &Wve Wheeler Dam in leanqmuee VAva-r. caulghl Standards F-6309, YU-JU25, aud VU-3422. Too ppm standards of P-6309. tli-3925, and FM-3422 were prepared by diluting I ml of a 100 pps utaa"rd, to ethyl acetate, to mark witb Otbyl acetate In separate 10 al valmetric flanks. 2. Analysis Inotrumnts/l%ter3 &)-a Blender: Waring Co@rcial blender. *miel 091-263. available true Waring Products Divisloo, liout*44, Now Hartford, Cr CMST. following:- Tenn. River Fish/JEG 5/22/79 Tionuemizer: Model #SDT. available from Tekmar Company, P. 0. Box .37202, Cincinnati. OH 45222. Dinker Die: 3.61 ca id AISI-02 high carbon steel cutting die made by J*rry Guthrie In Central Research Labs, described In 3M Technical Notebook #515619-35. Mixer: "Vortex Genie" Model #K-550-G. availablo from Scientific Industries, Inc., Bohemia, NY 11716. Contrituee: Damn-IEC Model #9-20A, available from Dawn-llC Corporation, Weedhm Hoights, MA. nottlog%: Four-ounce widemouthed clear glass bottle sealed with aluminum foil and aluminum goil-lined caps. 125-al linear polyethylene (LPZ) plastic bottle with polysoal caps. Gas Chromatocraeb: Chrosatoffraph -lic.-wic-tt-PactardModel 5713 CoC. Integrator - Hewlett-Pack&3-d Model 3380A intogralar- printer. Both of the above availablt: from Howlett-Packard 150 Page Mill Road, Palo Aito. CA 94304. Cn.. Column - Six-foot. 1/8 inch OD. stainless steel. picked with 10% CV20M on 60/80 Chromaorb W-AW. Col@ Te"erature - Isothe 1 Igo a C. &M- Injector - On-column at 200 C. 0 Detector - Zlectron Capture at 300 C. Flow - %40 cc/minuteof Argoa:Notbane(95/5). Rthil Acetate: "Ll Chrosolv" chromatograptsy solvent available from MC/9 Manufacturing Cbminte, 2909 gichlaod Avenue. Norwood, ON 45212, am Catalog #6008"90. and fat. (9) Based on the actual weight of aLmPI e used, 18.8' less than frozen weight, and weight ;.ercent of each part. Tenn. River Fish/JEG 5/22/79 iater: Deionized water. 3. -Procedure (6) Procedures used below, except for minor modifications. were obtained from earlier 3H Technical Report summaries (7). S&Wl*s 1A through 3A and IB more removed from the freezer and placed in large aluminum pan*, in a fuse hood. and allowed to thaw. A whole channel catfish, sample LA. was cut Into 5 sections and homogenized in a blender with 200 ml water. Smple ID had a dinker die core sample taken just off the lateral line behind the gill plate'. Contents of the 20.591 gram sample were skin, filet. small part of backbone, reproductive organs, part of kidney, and rectum. Sample 2A had a dinker die core sample taken bohind the gill plate. The 16.684 grm sample contained filet, vertebras, skin, and bile. Samples 18 and 2A were homogenized with 10 ml of water in & -*tissumizer.11 Smple 3A was dionectedand the vrlrious individual parts were homogenized with water. Individual parts weighing more than 25.0 grams were homogenized In a blender. while those of lesser weight were hmogenized In a "tisou"iser.11 Table 3 lists tLe sample. sample weight. Lad amount of water added for homogenizis.g each sample. All of the above s=ples. &&fter homogenization. were divided into five aliquots and placed In preclessed bottles. (dichro@te/acid, water riitxo.dry, toluene, dry). Three aliquoto ware placed %a LPS DoLties, while the other two were placed inoglass battles. Samples wore stared in & refrigerator at 4.5 C. until needed. Samples analyzed for F-6309, YU-3925, and FN-3422 were prepared *ccording to the following procedure. See Table 4 for weight of smpl* and milliliters of ethyl acetate used for extractions. A previously homogenized sample. stared La a glass bottle, was weighed (no larger than 4.00 g) and added to a 30-al precleaned glass centrifuge tub*. A volume of *tbyl acetate was added at the rate of 1.0 al ethyl acetate per grm of bowgoa&to. The ethyl @4*tats/fishbanogesatewere mixed for 1.5 minutes in a mixer at & speed settiag of 3. The sm*loa were removed and centrifuged at ISW rpm at Tenn. River Fish/JEG 5/22/79 210 C. for 10 minutes. After centrifuging. the ethyl acetate layer was separated, by use of & PIP*T, and placed In a vial. Five ul Of 8=Pl* (standard) was injected for gas chromatographic analysis. 3&mpl*o IA, 2A, and 12 hoo"eaates. plus a water blank, In LIPZbattles, were sent to Joe Belisle of the Costral Research Laboratory for organic and Inorganic fluoride analysis. REFNRENCES (1)3H Technical Report Summary, August 30, 1978, Arthur Mandel to R. L. Bobon, "Fate of Fluorochosicals Project - Progress Report. (2)Central Research Laboratory Report Nmber 6902. April 20, 1978, Jon Belisle. (3)'IntocasicontroaftPiSo-n3422InBluc%lgSiulnlfishand in ChannelCatfish,U". T. Zla&barawtyo A. U. Welter, May 17, 1977. (4)3MTES,August16,1978.A M. W*Iterto D. L. Bacm. "Zvaluation of tho SloconeAstratPiootnentiaolf PM-3422." (5)Central Research Laboratory Report on Request OA72199 by Joe Belisle, May 7, 1979. (6)Zxpori@stal work dome In cooperation with A. M. Welter of the Zavlro@stal Laboratory (U & PC), who performd the dla"ctloas and bomgoalsatloss. (7)3MTt2chniCRSuLiIxorgLuamry.NnvcmboIrfo. 1977. A. Unoml4-l to D. L. bacon, "Analytical Methodology oa YU-3422." G/coa Tenn. River Fish/JEG -9- 5/22/79 FISH WEIGHTS AND WATER TABLE 3 VOLUMES USED FOR HOMOGENIZATION Sample Description 1A 2A 1B 3A - Muscle 3A - Gall bladder 3A - Liver 3A - Fat 3A - Parts 3A - Gills Initial Whole Frozen Weiffht 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.,'0g 100 321.57 g 300 19.38 g 100 Footnotes: (1)A fish hook, with no apparcat rust or linc,,wa.,;rotin(in fiath uAd wam rc.-muvud bq@fors. humugt.,uizaLiuii. (2)The fish appeared to be slightly dehydrated (poanibly due to constant air flow over *urface of fish) so the actual weight of fish used may have been less than frozen weight. (3)Sample core 3.61 en Ld. Tenn. River Fish/JEG 5/22/79 TABLE 4 FISH WEIGHTS AND ETHYL ACETATE USED FOR EXTRACTIONS VOLUMES B&Mle Description 3A - Gall Bladder 3A - Liver 3A - Muscle 3A - Fat 3A - Parts 3A - Gills Water Blank 1A in 2A Weight of Fish Romogenate (cram)- Actual % Water Fish It. in Extracted Romogenate (me) 1.20 87.9 145.2 2.20 62.7 820.6 2.40 48.8 1228.8 2.40 65.7 823.2 3.00 48.3 1551.0 3.00 2.40 83.8 100.0 486.0 -- 2.40 57.8 1012.8 2.40 32.7 1615.t 2.40 37.5 1500.0 ml ETOAC 1..2 2.2 2.4 2.4 3.0 3.0 2.4 -2.4 2.4 2.4 Orm $74 7-11-A TECHNICAL REPORT TO: TECHNICAL COMMUNICA I LCOO Lr-2CD SUMMARY tlmportant - If report is printed on both sides of p8per, send tv.,o copies to T.CC.) 0818 October 23, 1979 Division CENTRAL Project RESEARCH LABORATORIES, Analytical and P operties Environmental Engineering and Pollution Control FqopoftTit[* Research Laboratory AR No. 7238 Determination of Fluorinated Alcohols in Fish Extracts OOPE Number* 0502 Project Number A000007 R*port Number 238 J. E. GAGNON Authar(s) D. F. HAGEN Notebook Reference 209-lS 201-lS SECURITY III- 0 Open (Company Confidential) Closed (SpecialAuthorization) 3M CHEIFSAICAL f'@ R@ECGHISTR Y KEYWORDS: (Selecttermsfrom 3M Thesaurus. Sugg*st other applicable terms.) CURRENT OELJECTIVE: Request No. A73154 Central Research Analytical Report Requestor - J. E. Gagnon Project No. 91500600 Chemical Analysis Employee Number(%) 042608 No. of Pages In 18 . ding Coversh*et ) Now Chelicbl-sR Ported 0 Yes N. REPORT ABSTRACT,. 1200-250 Ywords)This abstract information isdistributedby the Technical Communicatinns start3M'ers to Convany R&D. ItisCompany confidentialmaterial. Center to The microwave Sustained helium plasma deteCLor system -indcipill.-iry column with electron cipture detection were titilizedto eximine fish extracts for fluorocarbon ilcoliollevels. Information Liaison ronu 2643-c Pvo CENTRAL ANALYTICAL LABORATORY Report No ------3;3B---------- Date -------Ort.(akp2-3r.--:L%-7-@-9- Subject: Determination of Fluorinated Alcohols in Fish Extracts Reque stor: -qil&rLCTL --- Reque st No. - A73154 -------- Dept. Name EE&PC ------- Dated -August 8, -1979 ------ Report: Introduction 91500600 Proj. No. 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'sence of fluorocarbon alcohols FM-3923, F',-1-392@. 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 difficulty if the non-fluorine interference peaks are adequately separated from the Fluorine containing peak of interest. The lower level of the fluorocarbon alcohols detectable in these ethyl acetate fish extracts is about 5 nanograms/lOUl injection. Additional sensitivity was obtained by concentrating 10OP1 of the solution as received to 20ul and injecting loul of 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/mtn. 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 at 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 R respectively. Approximatelv 0.5 ml/min. of oxygen is used is the scavenger 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 levels for the compounds of interest. Operating conditions for the capillary system are listed below. Column System 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 240*C. Split mode of injection was utilized with 99% of the injected simple (lUl) being vented to the AR No. 7238 October 23, 1979 Page 2 atmosphere. Column flow was approximately 1 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 101il injection of a 10 ppm solution of FM-3923 or COF17SO2N(CH3) CZH40H. Note that three fluorine peaks are observed with the major at 6.5 =in. 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 red'ults for a 1OUl 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 loul 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 fold concentrite of sample 1-B. Chromatogram 10-10-79-6 shows the response for a 10ol 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 lijlof 10 ppm solutions of F'@t-3923and F,'1-3925respectively. \'ote the F@1-3925 C 9F I7SO ZN (C2HS) C2H40H homolog. elutes approximately 2 minutes after the u-nethyl 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 IM which has been spiked with known levels of these homologs. In this case 20 ng of each species was added to 100ul of sample 1-A and this was concentrated via evaporation to 2NI. IOUI were then injected for the analysis. System B - Chromatograms 10-12-79-1, 10-12-79-2, and 10-12-79-3 illustrate the elcctt= capture response for samples 3-A,.I-I-t,and 1-B respectively. tnote the lar.Reaumiher of capture sensitive peaks. These are not neces,.trily halogenated species In th-it a number of compound classes give a degree of EC reponse. The artow point out those areas where the alcohol homologs will eluto as illustrated In chroutogrmvm 10-12-79-4 and 10-12-79-5. The capillary column-electron capture results indicate that sample I.-"wmld have to contain less than 0.05 ppm based on the attenuations for tht ammle vs. refer~e solutions. Samples 3-A and 1-B would also contain very little of the YM-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 F@1-3923major isomer but the isomer distribution Is not evident In the is le chrotmitogram. Lower levels of detection via electron capture would require addl.tional 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 eth.vl acetate extracts. No fluorocarbon peaks were observed in the actual samples. D. F. Hagen DFH/rs C: B. W. Nippoldt 201-IS ran !944-0 3M CONFIDENTIAL F*M-*39-L3 I ce*--It BORATORIES ANALYTICAL RESEARCH RequestNo. A DivJDetpt. 4r-dc+-PCM PfoiecNto.- 91!5rO V-V'-O'D Date PZ 7,t or nit 9'-so JU F,x I LABORATORIES ANALYTICAL RESEARCH Request No. DivJDept. ProiectNo. Date Chemist *7 -3 lE4E: 9,f S-"^ !V--@:00 oco1/0 alt 70e F7(i FORM 2644-0 ,IAI OFSA '00@ '1:-'IATORIES ANALYTICAL RESEARCH Reques tNo. DivJDept. ProjectNo. Date ichomist A-073 IS7 el E. d 4 4 r 41 A FORM 2644-0 r j 77,! i %BORATORIES ANALYTICAL RESEARCH Rewest No, DivJDept ProjectNo. Date Chemist 2/4-q-92fZ->'00 64LU 1 i is )4! LA FORM 2444-0 ANALYTICAL RESEARCH I nequesi NO. 4--31 DivJDept. 4- PC ProjectNo. '@tt 45-00 Date Chemist-A.IL-S. F)ci LLil ..I..: FORM ZG44-0 3A ...... ............ RIES ANALYTICAL RESEARCH Requen No DivJDept. ProjectNo. -'Wf Da e Chemist '-lq"440/4Z'O 10 FORM Z944-0 1 /0:-179 . .. .. ..... -.HLABORATORIES ANALYTICAL RESEARCH Request No. DivJDePL ProjectNo. Dat Chemist C/ + PC 00 *7 A3rv so V-3 014 .;.r: Aj Ct, I. :lit -FORM 2644-0 I;ES ANALYTICAL RESEARCH Request No. DivjDept. ProjectNo. 91 !C'12 :V-V-"O 0 Date Chemist IF tA -set-ZC 7 :(Or: )RIES ANALYTICAL RESEARCH Request No. A DivJDept. P ProjectNO. !TL S: Date Chemist 7- FPt 3ci lb 4.L- S*l *zo c @T' :7-7. t4 t L4.63 1'5. 2 7 L6.63 16.87 16.99 t 7..2 3 L7.53 17.99 HP RUN 0 46 AREA P. T LO.74 S -rtoo.at) OCTelae?g T)PF-A Tinra L2%42134 1.47 a. 92 3.26 2.48 rj 37*,Z"5. 6.14 CD a) 8.74 R 10.37 10.64 I L.87 12.34 L2.68 12.94 4 36 14:54 at le 4 RTTH 2t 1 0 13.38 L4.139 16.46 HP RUN* 1* 43 IDS33376-1363 FIRFA % RT 1.47 t.52, 95 -29 37. 'P.4* . OCT 12.*79 aFtEn a477.. 380 LZL608 13 ILGLIS 141311 ARER % B.a44 8*373 La.4*s . 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