Document Raomwd07OqLBerNN3nN8D7DZV

BIOACCUMULATION TEST SUBSTANCE Identity:N-EthylperfluorooctanesIufonamide;may also be referredto as U1464, ETFOSA, ETPOSA, F-6309, or FX-12. (1Octanesulfonamide,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-N-ethylC-A,S # 4151-50-2) Remarks: Materialisa white solidofuncharacterizedpurity. METHOD Method/guideline followed: None givenforsampling ofthe organisms. Extractionand analysisprocedures were devised by 3M. Type: Environmentalsampling ofindigenousfisharound a 3M fluorochemicalmanufacturingfacility. 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 whitebass caught below and one white crappie caught above Wheeler Dam. Wheeler Dam isapproximately26 nautical milesdownstream from the 3M DecaturPlanteffluendtischarge.Itwas not noted inthe reporthow many milesabove and below the dam the fish were caught. A ten ppm standardof FM-3422 (N-ETFOSE alcohol)was prepared by dilutin1g mi of a 100 ppm standard(inethylacetate)to mark withethyl acetateina 10 mi volumetricflask. One whole channel catfiswhas homogenized to createone sample. The otherchannel catfishwas dissectedand the variousindividuaplartswere homogenized to createindividuaslamples. The white bass had a 6.3cm i.dd.inkerdiecore sample takenjustoffthe lateralinebehind the gilpllatemaking up a 20.591 g sample containing skin,filets,mallpartofthe backbone, reproductiveorgans,partofthe kidney,and rectum. The white crappiehad a dinkerdiecore sample taken behind the gilpllate tocreatea 16.684 gram sample containingfiletv,ertebrae,skinand bile. Allsamples were homogenized inknown volumes of DI water and divided intofivealiquotseach. Samples were centrifugede,xtractedwithethylacetate,and analyzed by GC fororganicand inorganicfluoride. RESULTS ETFOSA Concentration InTennessee RiverFishby GC Sample @Water-bIank EthylAcetate blank WholeChannelCatfis@--White Bass core sample White Crappie core sample ETFOSA (ppm) N.D. N.D. 0.40 0.82 0.06 Channel CaffishGills Channel CaffishLiver 1.48 2.17 Channel CatfishParts* 1.33 (5han-neClatfishMuscle Channel CatfishFat N.D. 13.85 Channel Caffihs Gall ladder 1.57 Consisted ofmuscle,skin,blood,bone, and cartilage. Consistedofgastrointestintarlactr,eproductivesystem,and fat. Upon completionof GC analysis,therewas concern thatthevalueswere notdefinitiveA.dditionalanalysiswas then done using CapillaryGas Chromatography with ElectronCapture and a Microwave Sustained Helium Plasma Detector.Resultsfrom onlythe whitebass core sample and the catfishgill-samplweere describedinthisreport. Qualitativaenalysisof thefishextractsusing CapillaryGas Chromatography withelectroncapturefailedto quantitateETFOSA. However, the whitebass core sample showed a peak witha retentiotnime similarto ETFOSA. This peak area was lessthan the ETFOSA standard, butgreaterthan thatseen inthe channel catfishgillsw,hich was described as a "verysmallamount". Analysisby a Microwave Sustained Helium Plasma Detectorfound no fluorocarbonpeaks. The resultsobtainedby the microwave plasma detectoron spikedsamples indicatedthatNETFOSA, ifpresent,could have been detectedfrom itsfluorinceontentat 0.1 ppm intheethylacetateextracts. Remarks: The originalreport(5/22/79)referenceda sample forFM-3923. Itwas broughtup afterthe reportwas generated thatFM-3923 and FM3422 are boththe same coumpound (N-ETFOSE alcohol).Analyficawlas conducted toverifyitsidentitaynd itwas found to be N-ETFOSA (F-6309). The attachedreport("AR No. 7238 - DeterminationofFluorinated AlcoholsinFish Extracts"1,0/23/79)stilrlefersto FM-3923 when infact the sample labeledas FM-3923 isF-6309. This reportalsohas inconsistenciesT.he lastparagraphindicatesthe abilittyodetectfluorine contentat0.1 ppm level.However, a reviewofthe procedure used indicatesa detectionlimiotf 0.5 ppm. The firsrteport(5/22/79d)escribesanalysisof ethylacetateextractsof fishhomogenate by gas chromatography (GC) withelectroncapture detection.The analysisshows the presence ofmaterialsinfishtissue, extractsthathave GC retentiotnimes identicatlo both N-MEFOSE alcohol and N-ETFOSE alcoholand to N-ETFOSA. The GC retentiontimes of NMEFOSE alcoholand N-ETFOSE alcoholstandardswere the same (not resolved)by the method used inthe firsrteport.The firsrteportindicates the presence offluorochemicalsinthe fishextractsb,utelectroncapture detectionisnotspecififcorfluorochemicalsT.hus the resultsreportedin the firsrteportwere nota specificidentificatioofnfluorochemicals detectableby GC. (Report1 alsohas errorsincolumn 4 ofTable 1.Inthe 1B row,0.40 shouldbe changed to4.13,and inthe 2A row,0.004 should be changed to0.06.) The second report(12/28/79)shows a misinterpretatiionthe firsrteport. Itincludesa descriptioonf GC analyses ofethylacetateextractsoftwo of the samples describedinreport1 samples 1B and 3A. The work describedinreport2 used electroncapturedetectionand referencesa reportusingmicrowave sustainedhelium plasma detection(MSHPD) in the fluorinaend sulfurmode. Influorinemode, MSHPD method isspecific forfluorine.The MSHPD resultsshow no fluorochemicalsinthe ethyl acetateextracts.The resultsare interpreteads indicatintghatF-6309 and N-ETFOSE alcohol(FM-3422) are presentinthe ethylacetateextracts atlessthan 0.1 pp'm. Inthe firsrteport,N-ETFOSA (F-6309)and NMEFOSE alcohol(FM-3925) /N-ETFOSE alcohol(FM-3422) had appeared to be presentrespectivelayt0.82 and 3.31 ppm insample 1B and at 1.48 and 0.80 ppm insample 3A. Thus, the GC-able compounds seen inthe firsrteportappear nottohave been fluorochemicalsand thus could not have been N-MEFOSE alcohol,N-ETFOSE alcoholor N-ETFOSA. The firsrteportshows the presence ofunidentifieodrganicfluorineand of inorganicfluorinienthe fishtissue.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:Klimisch ranking 3. Without an understanding of the sampling design inrelationto the outfalalnd sampling points,verifiable data on the actualconcentrationsof fluorochemicalsinthe riverfrom both the manufacturingfacilitaynd from naturalsources,activitieisnthe manufacturing facilitpyriorto sampling, any applicableenvironmental conditions(e.g.rainevents),and a clearunderstandingof how long the sampled fishwere inthe sampling area,thereislittlteo be concluded. Additionallyt,he analyticadlata conflicts.Itcannot be definitively concluded which analyticaldata set iscorrect. REFERENCES 3M Technical Report "Bioaccumulationof Fluorochemicalsin Tenn. River Fish."James E. Gagnon, Project78-2740, Decatur,Alabama Tennessee RiverFish,Report Number 001, May 22, 1979 3M Technical Report "FluorochemicalsinTennessee River Fish."James E. Gagnon, Project78-2740, Decatur,Alabama - Tennessee River Fish, Report Number 100, December 28, 1979 3M requested expert overview,"BioaccumulationStudies",Dr. James GilleftC,ornellUniversityM,arch 8,1993 OTHER Last changed: 5/18/00 3M REPORT: BIOACCUMU"LATION STUDUES March 8, 1"3 6- Report No. 001 (5122179)'Bioaccumulationof F7uorochenticalisn Tenm RiverFish,and Report No. loo (12126179)*Fluorochemicalisn TennesseeRiverFisIL" This pairofpapersisquiteconfusingl,argelybecause of incorrecsttandardsc,onfusedidentitoyf labelsand verityof contents,and the difficultoyf actualdeterminations.When these are combined with a lackof clear sampling design in relationto outfau and sampling points,the resultadd littlteo our understandingof the problem. These papers make an excellentexample of how a littlkenowledge can be dangerous. 6 3MFo"% S747 11 A Te -AiEp()RT Sti@AMARY 5/22/79 TO: TECHNICAL CO&U"ICATIONS CENTER - M-3CN (imporont- IfmooffisP*Wd D.wo*. Environmental an bo* slatosfpww, owd fm Laboratory (BE go'110TCC) PC) Decatur, Alabama - Tennessee River Fish Bioaccumulation of Fluorochemicals in Tenn. River Fish E%r9@)1971) OGOLW.-I-ow 0222 w,cm t U.,Mbw 78-2740 lwopI@Rw-..bw 001 D. L. Bacon J&aeo 9. Gatnon GG 213531-1 51568 Lab R*quest #4871 "CUIUTY 00 92 a..- Em;;-.w caowm*w 0 cwww lumw Awowmowj am CNN"CAL "ONTRY Now awousm pi@,@ C3 Ym xavvsorjm- L%Lwwmo iON3m ThunwrSwALMM "W %raw) EL PC Decatur CM"OffO"CTM: Qualitative and quantitative determination of F 6309. FM-3925, and YU-3422 in fish tilken fram the Tennessee River above and below Whccler Dam at 3M'ti Decatur plant. Analyze for organic and inorganic fluoride in the uuj*c-mumplou. 004=T ANTRACT:C3W3@*wnrdTd%Wobwm wawasom isdmftwwd mign 3Wen a Congo" PAW)L It InComemeW maidbdwmw SeWi@L bv dwregadw camftommbowa comw m Ethyl acetate extracts of a Channel catfish (Ictolurus punctatus). %Alto bass (Roccus chryscos , and a white cr"ple (Pamoxis annularls) @;re-analyz*d by gas chr*satography. cc: D.Ricker-236-21 A. W4olter A.Mondel :mfwwmo.oo 't.aft L Tenn. River Fish/JEG 5/22/79 INTROMCTION It is know that 3M's Decatur, Alabama plant effluent has high organic fluoride levels, 10.9 ppm (1)(2). It has also been tihuwn LIIUL fluorochemic&ls can bioaccumulate in fish in a laboratory envirommat (3)(4). With these combined factors, the next step was to 400 if fish caught in the Tennessee River near the Decatur plant had detectable levels of flucrc>chemicals. RESULTS AND Dlscussrom Table 1 list& the concentration, in ppm, in fish of compounds which have th**sano retention time as the three fluorochosicals of interest (7-6309, YU-3925, and PH-3422). Analysis of the results for the dissected channel catfish, Sample 3A, shows that the fluorochemicals 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 bioaccumulate the three fluorochemicals of interest. These results agree with earlier reports (3)(4). When comparing the total fluorochemical content (TFC) for the two whole fish samples, the larger channel catfish cont.@ined more than twice the fluorochomical content, 2.74 pps 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 coerricient6 for channel catfish. ]Pluorochemicals bioaccumgulat* in fatty tissue, and since more fatty tissue im promonl in the larger fish, more fluorochomicals would be expecied. IP-6309 in present at higher cc.acentrations in the dissected channel catfish, sample 3A, thun other samples. Since bioaccumula- tion rates have not been determined for F-6309 for the higher concentrations (-.Labe offered._ no explanationu The two fish samples which had cores taken from them will not be rigorously compared to whole fish samples. The reason for this is that the core samples may not have representative concentrations of fluorc>chemicals (whole fish values may be higher or lower). Since core mampl@@s were taken from the approximate uaml- loculion. the results can be rigorously compared. The white bass from below Wheeler Dam, sample 1B, had a whole rish TPC of 0.40 ppm, while the white crappie from above Wheeler Dam, mample 2A, had a whole fish TFC of 0.004 ppe. With much small "tatintical samples, it would be difficult to say that the larger TPC is duu only to the white basm living in the pruul:nzo of high*r fluorochemical concentration, downstream from the plant. Ot!ier possible explanations for the higher TFC could be the following: Tenn. River Fish/JEG 5/22/79 TABLE I FLUOROCIIENICAL CONCENTETATION IN TENNESSEE RIVER FISH (ppm) Sa.mple 1A - Whole fish 1B - Core (3) 2A - Core (5) 3A - Gills 3A - Liver 3A - Parts (7) 3A - Muscle 3A - Fat (8) 3A - Gall bladder Water blank Ethyl acetate blank F -63 09 0.40 0.82 0.06 1.48 2.17 1.33 N.D. 13.85 1.57 N.D. N.D. FM-3925 & TV-3422 (1) 0.73 3.31 N.D. (6) 0.80 0.38 0.43 N.D. 6.12 0.74 N.D. N.D. Total Combined PC ig Fish (ppo)(2)_ 1.13 0.40 (1) 0.004 (4) 2.74 (9) Footnotes to Table 1: (1)FM-392a5ndFM-342c2annotbe resolvewdithGC parameters used;thereforae,eosblnev4alueis reported. (2)Bused on frozen weight of The fish. (3)Sample core, 3.61 am. id cuatain*d skin. filet, r*productive organs, ane parts of kidney, rectum. Lad backbone. (4)Assumsthattheconcentrallonbstaineidn thecoreare representatoifvetherestof the fish. (5)Sumple core, 3.61 co id cobtalood filet. vertebrae. skin. and bile. (6)N.D. - Not detectc!d. (7)Cunwisted of muscle, skin, blood. bone, and cartila". (8)Consisted of gistraintestiual tract. reproductive mystes. and fat. (9)Bas*don theactuawleightof sampleused,16.9%lossthan frozewneighta,ndweightpercenotf suchpart. 3M CONFIDENTIAL Tenn. River Fish/JEG -4- 5/22/79 1. Longer river revidence time, older fikill. 2. Longer location residence time. 3. Different species a) Different feeding and life styles b) Contains larger weight percent of organs which tend to bioaccusulate fluorochemicalm c) Larger fluorochosical partition coefficients If the core samples are representative of whole fish concentrations, then it can be p(mtulat*d that channel catfish bioaccumulato fluoroebasicals to a greater extent than either white bass or crappie. Reasons for this alro the same an listed above. Table 2 gi a t',aresults of the organic (RF) Lad inorganic fluoride (;$) c@"ocrebnt ration, in yps, in the fish samples. S!Mle 1A 2A 1B Water TABLE 2 (5) ORGANIC (RF) AND INORGANIC (F FLOORIDZ CDNCENTRATIOKS (ppe) R2 9.7 16.2 10.5 24.6 13.3 6.2 0.01 Jon Belisle pointx out that th# high inorganic fluoride valuc44 woos rather surpriving. His or.ly explanation was that flub flour previously analyzed, for a diftereat r*qu"tor. was show to IL&" inorganic fluoride values high6r than organic fluoride. Joa also states that high inorganic fluoride valu@ would make It difficult to calculate low levels of organic fluoride. Comparison of the organic &ad inorganic fluoride costest sh that oaaplub from &Wvo Wheelur D@ have just am high, ir not higher, values than for the asaple from below the dam. There are no clear cut explanation* for this obe*rvatioa. An earlier analysis of Tennessee ]Liverwat*r obow*d highiorganic fluoride concentrations upstr"a from the plant. At that tim, it was thought the BUOIGG my have bass mislaboled. With these results, tk)C e, Tenn. River Fish/JEG 5/22/79 it would seem to indicate that the concentration Of fluorocii(-mical@, May actually be loom below Wheeler Dm. 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 I and 2 show no correlation. For example, the highest organic fluoride value, 16-.2 pps for sample 2A, had the lowest TFC, 0.004 ppm, for the fluorochemicals analyzed. A possible are organic fluorides present in very were not analyzed for individually. highest fat content, channel catfish, explanation is that there high concentrations which The species which had the had the lowest organic fluorido concentrations. With limited samplo population (2 fish of one species and one of each of two other species), it is diffleult to draw any Meaningful conclusions. The only definite conclusion Is that the fluorochemicals studied do appear to bioaccusulate in river fish under natural conditions. EXPERIIMTAL 1. Sample materials Fish 1A - Small chilanel catfish (lotalurus punotatus), caught above Wheeler Dan in -Lannessee River. 1B - White bass (Rocous oh@-yoops), caught below Wheeler Dan in Tennessee River. 2A - White crappie(Ponoxis aR"Ul4riS), caught D@ in Tennessee Rivea-. 3A - largo eh&Lnnel catrip4h (rt-Lrilurmis above Wheeler I)am in '4ennousee Rive@r. above Wheeler CaUghL Standards F-6309, YM-UU25, and VM-:1-122. Ton ppm standards of F-6309, @11-3925. and YU-3422 were prepared by diluting 1 ol of a 100 ppe btandard, in ethyl acetate. to mark with otbyl acetate in separate 10 al valmeetric flanks. 2. Analysis Instru@nts/V%terigAIS Blender: Waring C4@rcial blender, liodel #91-263, available from Wartng Products Division. I&oute 44. Now Hartforid. CT W057. following: Tenn. River Fish/JEG 5/22/79 Tissuemizer: Model #SDT, available from Tek=r .37202, Cincinnati, OH 45222. Company. P. 0. Box Dinker Die: 3.61 cm id AISI-02 high carbon steel cutting die made by Jerry Guthrie in Central Research Labs, described in 3M Technical Notebook #51568-35. Mixer: "Vortex Genie" Model #K-550-G. availablo from Scientific Industries, Inc., Bohemia, NY 11716. Centrifuge: Damien-IEC Model OB-20A, available from Damon-IEC Corporation, Needham Heights, MA. not tIcft: Four-ounce widemouthed clear glass bottle sealed with aluminum foil and aluminum foil-lined cap&. 125--ml linear polyethylene (LPZ) plastic bottle with polyneal caps. Gas Chromatogral2h: Citro&atograph -lic.-wiett-Paclard Model 5713 r.C. Integrator - Hewlett-Packaj-d Model 3380A integrator- printor. noth of the above availablt: from Hewlett-Packard 150 Page Niii Road, Paiu Aito. CA 94304. (@n.. Column - Six-foot, 1/8 inch OD, stainless steel. packed with 10% CV20M on 60/80 Chromanorb W-AV. 0 Column Temp*rature - luothosml 180 C. Injector - On-column at 200 C. 0 Detector - glectron Capture at 300 C. Flow - 40 cc/minute of Argon:Motban* (95/5). Sthyl Acetate: "Ll Chrosolv" chromatograpity solvent availablo from MC/9 Manufacturing Ch@istb, 2909 Highland Avenue. Norwood, OR 45212, am Catalog 06008648M. and fat (9) Based on the actual weight of sLmPI e used, 18.8' frozen weight, and weight percent of each part. less than Tenn. River Fish/JEG 5/22/79 Water: Deionized water. 3. Procedure (6) PrOCedures used below, except for minor modifications, were obtained from earlier 3H Technical Report summaries (7). Samples 1A through 3A and 1B were removed from the and placed in large aluminum pans, in a fuse hood. allowed to thaw. freezer and A whole channel catfish, sample 1A, was cut into 5 sections and homogenized in a blender with 200 ml water. Samplo 1B had a dinker die core s@ple 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 behind the gill plate. The 16.684 gram u&mple contained rilet. vertebras, skin, and bile. Samples 1B and 2A were homogenized with 10 ml of water in a -Itissu@izer.11 SLmple 3A wLs dissectedand the vtlrious 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 homogenized in a "tissu@izer.11 Table 3 lists tLe sample, samplo weight. and amount of water added for homogenizit.g each s@ple. All of the above ample*. ufter homogenization, war* divided into five aliquot& and placed in precloanod bottles. (dichromate/acid, water riiina.dry. toluono. dry). Three aliquots were placed in LPIS ootliew, wbilu the other two wore placed in glass bottles. S&Mles in a refrigerator at 4.5 0 C. until needed. were stored SmWles analyzed for F-6309, FM-3925, and FN-3422 were prepared &ccording to the following procedure. So* Table 4 for weight of ample and milliliters of ethyl acetate used for extractions. A previously bonog*aiz*d sample, stored in a glass bottle. was weighed (no larger than 4.00 S) and added to a 30-al precloan*d glass centrifuge tub*. A volume of *tbyl acetate was added at the rate of 1.0 al ethyl m4etato per gram of homogenate. The ethyl ac*tate/fish hanogesato wore mixed for 1.5 minutes In a mixer at a speed mettiag of 3. The samples were removed and centrifuged at ISM rpm at Tenn. River Fish/JEG 5/22/79 21 0 C. for 10 minutes. After centrifuging, the acetate layer was separated. by us* of a pipet, placed in a vial. FIVO ul of gsmpl* (standard) injected for gas cbromatographic &AglYBis- ethyl and was So,npl*s 1A. 2A, and 1B bogo"ust0s, plus & water blank# in LPZ bottles, were sent to Jon Beli&lg Of the Central Research Laboratory for organic and inorganic fluoride analysis. REYERENCES (1)3H Technical Report Summary. August 30. 1978, Arthur Mandel to R. L. Bobon, "Pat* of Fluorochanicals Project - Progress Report." (2) Central Research Laboratory Report Number 6902, April 20, 1978, Jon Belisle. (3)"niocotkcantration of TV-3422 In nluegill Runfisth and in Channel Catfish," U. T. gln&blrawy to A. M. Walter. May 17. 1977. (4)3M TVA, August16, 1978.A M. Welterto D. L. 13&cAm. "Evaluatioonf the SlocomeAstratiPoontentialof YU-3422." (5)CentralR"ea"b laboratoryReporton RequestfA72199 by JoeBelisle,May 7, 1979. (6)Zxperimental work dome in cooperation with A. M. Wolter of the Zaviromwntal L&boriLtor-y (ZZ & PC), who performed the dimmetions and homogealzatioas. (7) 3M TtichniCiLl RUIX)rt SUNMMry, Nnvcmbtr Ifs, 1077. A. Mosele-I to D. L. bacon, "Analytical Methodology on VS-3422." G/con Tenn. River Fish/JEG -9- 5/22/79 FISH WEIGHTS TABLE 3 AID WATER 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 WeijLtlt 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 9 10 52 .2..'0g 100 321.57 g 300 19.38 g 100 Footnotes: (1)A rishhook,withno apparict rustor Iin(-w...-trsotini(ni fij:utnhdw" rl@muvobduturlliumoguaiizuliuti. (2)The fish appeared to be sl@ghtly dehydrated (possibly due to constant air flow over t@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 -10- 5/22/79 TABLE 4 FISH WEIGHTS AND ETHYL AUTATE USED FOR EXTRACTIONS VOLUMES Sample Description 3A - Gall Bladder 3A - Liver 3A - Muscle 3A - Fat 3A - Parts 3A - Gills Water Blank 1A 1B 2A Weight of Fish % Water Homogenate in (crazm)- Romoirenate 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 (mg) 145.2 820.6 1228.8 823.2 1551.0 486.0 -- 1012.8 1615.@ 1500.0 ml ETOAC 1.2 2.2 2.4 2.4 3.0 3.0 2.4 2.4 2.4 2.4 TECHNICAK REPORT SUMMARY T& -RECHNICAL commuNicATiomsCENTER - 201-2CN (Imporont- ifreportiiprkmd on boo jidao(p*w, ond tbw caPAn to TCC.) Divi"n Project -ffii;cw-Ttitle Environmental Laborato2p,y (EE & PC) Decatur, Alabama - Tennessee Fluorochemicals in Tennessee River Fish River Fish D. L. Bacon Authorls) Jmes.,E. .,Gag4oiL Not*book Ref*fence 51568 Lab Request SECURITY 0- [:] Open (Company Confidsntial) #4871 f] Liosed ispeewi Authorization) KEYWORDS: - (Sais" wms from Thaeurus. Sugpst appiiemble terms.) 3M other CURRENT OBJECTIVE: Progress Report. 3M CHEMK :AL b, REG98TRY EE & PC Decatur 2-L 1'*12/28/79 Dealt.Numbw 0222 lpraiect Numbw 78-2740 PROPO" Numbw 100 Employft mumbefisf 213531 -wo- OTF'O-@I-nc"luding Coweroleat 3. Now ChwnkeliRtomrted [3 Ym a No REPORT ABSTRACT: (200-2SO words) This sbsumct information is dktrbuted owt 3M'wo to Company R&D. it iscoffomy confidentw rmuwiai. by the Tochniml CmmwnicationCsentetro The microwave sustained helium plasma detectbr system and capillary column with electron capture were utilized to examine fish extracts for fluoro- carbon alcohol levels. c: D.Ricker-53-4 A.Welter A.Mendel information Ligison N -2- Introduction: Previous work 1 indicated a need for more definitive answers to the presence of volatile fluorochemicals. Capillary gas chromatography with an electron,ca.pture detector (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 1M) having retention times -cTo-sw-To--th-e-fluor-o- chemical 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 bq5.ll)eo-aw.-Masna.d aWbovneeaWwtwhtiheelireDerDtaemnmtroens etcmcetEtvi-vsee,-:lLy-T-sWowe'dmore than 2 5 pea s. pea with retention time similar to F-6309 was detected in samples 1B and 3A (Table 1). TABLE 1 QUALITATIVE ANALYSIS OF FISH EXTRACTS FOR FLUOROCREMICALS Sample Retention Time (Minutes) 10.84- 12.68 1B im 3A FM-3422 F-6309 Std. 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 Discussion: The above results indicate that no volatile fluorocarbons were present in samples. The large atounts of organic fluorine mentioned in the original rer)ort 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 interferring compounds. Integrity of the Standards: After the initial report 1 , 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 (the old "standard"),FM-3422, and 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 P-6309 (N-ethylperfluorooctanesulfonamide: c F 8 17 so 2 NHET). As of 27 August 1979, the new FM-3923, Lot 518, wall be used for preparation'of standards (identification verified ) and the old FM-3923 has been properly labeled gs,F-6309, References: 1 Gagnon, Jams E., 3M Technical Report Summary "Bioaccumulation of Pluarochemicals in Tennessee River Fish,"' 22 Mp-y 1979.'' 2Hagen, D. F., 3M Technical Report Summary "AR Determination of Fluorinated Alcohols in Fish 23 October 1979. 3Personal Communication with A. Mendel. No. 7238 Extracts," 4Winter, L. D., Commercial Chemicals Analytical Lab Request No. 14998, 24 August 1979. J GG /cel 3m --Po rn 6 747-1 1-A TECH NICAL.REPORT SUMMARY Date October 23, 1979 TO- TECHNICAL COMMUNICA It C T 4@t -2C (Importan-tIfreportisprinteodn bothsideosfpaper,sendtm copiestoTCC.) Oi@ision CENTRAL RESEARCH LABORATORIES, Proi*ct Environmental Engineering and Report Title Analytical and Properties Pollution Control Research Laboratory AR No. 7238 - Determination of Fluorinated Alcohols in FisliExtracts To @i()V 0 7 Depr Number' 0502 P, oioc t N um to, A000007 Report Nurnt@*r 238 IOFIQ J. E. GAGNON - 209-lS AuthorIS) D. F. HAGEN - 201-lS Notebook Reference Lmploy@ Number(s) 042608- No. of Pros InCfUd.ng Co@erstioet 18 SECURITY 100- 0 Open (Company Confidential) Closed (SpecialAuthor, t7lo.)7 3M CHEMICAL REGISTRY New Ch'emic@'rs Reported C] Yes E) No KEYVVORDS: (Select terms from 3M Thessuru&. Suggest other applicable terms.) Central Research Analytical Report CURRENT OBJECTIVE: Request No. A73154 Requestor - J. E. Gagnon Project No. 91500600 Chemical Analysis REPORT ABSTRACT: alert3M'ers to Company (200-250 words@ This abstract information is distributed by the Technical Communicaiinns R&D. it isComr)any confidential n@3terial. Center to The microwave sustained helium plasma cletector sv,.-;tenIind cipilliry column with electron capture detection were titilizedto ex;imine Fish extracts for fluorocarbon alcoliollevels. limnfiotrimaalt$,oo L.a,son FURM ?643-c Pwo CENTRAL ANALYTICAL LABORATORY Report No ------2;35---------- Date -------Qctqb-u2-3.-:L@-.-7---9 Subject: Determination of Fluorinated Alcohols in Fish Extracts Reque stor: - f -- --- Request No. - A73154 -------Report: Dept. Name --EE&PC-------Dated _-August-8, -1979------ Introduction Proj. No. 91500600 The microwave sustained helium plasmi 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, F,1-1-3925,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 fluorineand sulfur to allow for the detection of specificcompounds such as the fluorocarbon alcohols. Detection level.sare 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 btiildup or,the quartz cavity tube. This presents little difficultyif the non-fluorine interference peaks are adequately separated from the fluorine containing peak of interest. The lower level 'ofthe fluorocarbon alcoilolsdetectable in these ethyl acet,itefish extraccs is about 5 nanograms/1001 Injection. Additional sensitivity was obtained by concentrating 100@ilof the solution as received to 20wl and injecting 101ilof this concentrate for analysis. operating conditions for the MPD-850 are listed below. Column Svstem A - 61, 6% CW-20M-TPA on 80,1100 Tnesh Chrom G. H.P. programmed from 100 tt)2000C at 15*C/min. lieliumcarrier at 25ce/min. with purge rate to MPD of 50 cc/min. Forty percent of the column effluent is split to the FIT)on the HP-7620 gas chromatograph and 60% is transferred to tile@4PD-850 plasma cavity via a heated 1/16" capill.-trlyine a: 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 @,i@ahertz. The emission lines used for fluorine and sulfur were 6856.0 and 5'453.9 respectivelv. Approximately 0.5 ml/min. of oxygen is used as the sctvenger gas to prevent carbon buildup on the quartz plasma rec(ctortubes. 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 C14-20@t.Initial column temperature was 60*C and it was programmed at 10OC/min. to 2400C. Split mode of injectionwas utilized with 99% of the injected simple (1@ll)being vented to the AR tio. 7238 October '@3, 1979 Pag(? 2 atmosphere. Column flow was approximately 1 cc He/min. and an auxiliary flow of 41 --c/min.of 95-5 Argon-methane was utilized to purge the electron capture detector. Thi:3 purge flow is added at the exit Of Lhe column system on the HP-5840. Sys,-em 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 CSF17SO2N(CH3) C2.HUOR. Not,a that three fluorine peaks are observed with the major at 6.5 min. The sulfur res@3onse lags the fluorine response by 0.5 min. to prevent pen overlap. Chri)matogram 10-10-79-2 results from a 10111 injection of sample 1--M (ethyl acetate extract of a brown bullhead from Minnesota. Note the absence of fluorine containing pea<s. ChrDmatogram 10-10-79-3A illustrates the res'ults for a 10111injection 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 1OP1 Injection of the ethyl acetate extract of sample 1-B (bass below Wheeler Dam). Chromatogram 10-10-79-5 illustrates the response obtnined for a 5 fold concentrate of sample 1-B. Chromatogram 10-10-79-6 shows the response for a 10ol injection of a 5 fold concentrate of sample 3A. Chtomatograms 10-10-79-7 and 10-10-79-8 illustrate the responses obtained for the injection of llilof 10 ppm solutions of F@1-3923 and T--,1-392r5espectively. '.%ote thE!F,,1-3925C8Fl7SO2N (C2Hs) C2H[.OH elutes approximately 2 minutes tfter the n-methyl horiiolog. ThE@Se levels correspond to 10 nanograms injected and T expect one could detect a 5 Tianogram level. Chi7omatogram 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 101)ljlof sample 1-A and this was concentrated via eviporation to 2NI. IOUI vere th,aninjected for tne analysis. System B - Chromatograms 10-12-79-1, 10-12-79-2. and 10-12-79-3 illustrate the clcctron capture response for samples 3-A,.l-@t, and 1-B respectively. Note tile lar@.qneurt@er of capture sensitive peaks. These are not neces;nrily halogenated species In tb@it a number of compound classes give a degree of EC reponse. The irro". point out those areas where the alcohol liomologs will elute as illustrated In chromtogrimm 10-12-79-4 and 10-12-79-5. The capillary column-electron capture results indicate that sanple I-M %oculd h3ve to contain less than 0.05 ppm based on the attenuations ror the!somrle ". reference solutions. Samples 3-A and 1-B would also contain very little of the FM-3925 or A AR No. 7238 October 23, 1979 Page 3 F,4-,3422species. These latter two samples do have a peak at the retention tijae of F'@1-392m3ajor isomer but the isomer distribution is not evident in the sample chi-omatogram. Lower levels of detection via electron capture would require additional saniple cleanup prior to chromatography. Thc! results obtained bv the microwave plasma detector on spiked samples show that the!sealcohols if present could have been detected from their fluorine content at thc!0.1 ppm level in the ethvl acetate extracts. No fluorocarbon peaks were observed In the actual samples. D. F. Hagen D I-'Iir-, c: B. W. Nippoldt 201-lS ltititmit u-@ L @a,s,ln In,I-als FOR !644-0 F)4 3M CONFIDENTIAL F'm -39-L73 I I BORATORIES ANALYTICAL RESEARCH Request No. D iv./0 ep t. Projec:tNo. Date Chemist A '7 !9 'ZIOI -7 -LA4 ri@A F)c I FF'Y LABORATORIES ANALYTICAL RESEARCH Request No. Div./Dept. ProieciNo. 91S--6SIS--00 Date Chemist 9. /0 4zo! A!@@ - FORM 26411-0 i SA L ---@-'IATORIES ANALYTICAL RESEARCH Request No. .4-&7 s- Div./Dept. ProjectNo. Dat e Che 24 A.^ @AlJv@IMI FORM Z64-1-0 77,!- i KBORATORIES ANALYTICAL RESEARCH RequestNo. Div./Dept. ProjectNo. 2/q 40 5Z 00 Date Zell Chemist RORM ::644-0 10 -'7 ANALYTICAL RESEARCH RequesNto. Div./Dept. ProjectNo. Date Chemist t4- -131,-t;(- -dF 4 - PC S:6 7,* )P.@- 4.m c.- Oil F)c FORM 26&,I-C RIES ANALYTICAL RESEARCH Request No. DivJDept. 3A ProjectNo. cy/9740 Dat /7.9 Chemist FORM Z644-C) H LABORATORIES 46- ANALYTICAL RESEARCH Request No. Div./Dept. ProjecNto. Date Cherriist Ac )PC cl1:5:@@ -z- CIA C.,IAY 0 7 C-1 FORM 2644-9) ES ANALYTICAL RESEARCH RequestNo. Div./Dept. P,,iec-.No. Date Chemist S43 @k FORM 2644-Cl -7 7! RIES ANALYTICAL RESEARCH Request No. Div./Dept. A ProjectNo. 4qt 4ir4n Cyr Date Chemist -39 7- _,SL z c@ -4@ 20 0 0 g Fr@ -6ctz-3 t ..L' C). -0 4 I 16.87 17.23 17.53 17.9@? 18.74 Hp RUN ID 535 TIREA ;,0O_Clg4o6 PT OCTeIZ/79 i4REA k)pr,t) TIME 12142234 VL 1.47 1.95 3.29 2.48 c'6 rj 5.33 923.213 8.74 6.14 I.C=) cr) I k3.37 10.84 11.87 12.34 12.68 12.94 14 36 14:54 at le 15.84 ATTK at 1 0 13.58 14.09 16.86 HP RUN 0 43 OCTet2e79 BREA X RT 1. 47 1.52' 1.95 2..26 FiFtER 2477.. 3808 1216013 16110 126708 FKRER % 0.244 B. 37Z '1.392 ti- 4*0 TIME 11902134 i@ r T ri @t DELETI: Mlli- 1 4 4 -iT I VL 1.72 311 2.76 3.30 2.49 4.41 4.65 5.39 5 95 6: 15 6.65 7.49 8.13 8.36 8.96 9.1921_262 l@:9;49.469 9.62 10.70 12.01 12.34 12.52 7.12 7.78 B-73 10.37 11.87 p 9.91, 10.135 11.39 12.92 30 13. 4 13 r@?@02 14. L7 14. Ag. 37 15.27197 15.54 4))33 16.331 23 16.977 17.-1 23 t 7. !-'3 -r t1.77.7.99 'a 93 18.7-499-5 14.98 Ll,! 4 EIIP 1 300 60 6! TEm YL rj L@4 Z_1.477 2-.020 2.53 4. @3 4. 85 C) Flo.: 4_- t 3.62 .22 11.78 13.58 14.06 ttIW2 2 o a 15.35 15.05 10.86 ISTOP TE;IP 1 TEMPI TEMPI T E M PW YL 700 300 60 66 300 tio 60 23_.95L 2.977 3e 4.00 2.29 5.93 3.74 9.00 R't Li.88 4 2 96 723713.2171 13. t59 13.82 114-44.-8.09 14.54 15.35 15.85