Document b9Ln4Jwnk3QXYZBdmep5jNgk

A R a % '0 3 7 l BIOACCUMULATION TEST SUBSTANCE Identity: N-methylperfluorooctane sulfonamidoethanol; may also be referred to as 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-hydroxyethyl)-, CAS # 24448-09-7) Remarks: Material is an off-white, waxy solid of uncharacterized purity. METHOD Method/guideline followed: None given for sampling of the organisms. Extraction and analysis procedures were devised by 3M. Type: Analysis of tissue for fluorochemical from indigenous fish caught in the Tennessee River above and below the Wheeler Dam. GLP (Y/N): No Year: 1979 Remarks field: There is no information on sampling procedures of the organisms from the Tennessee River near the manufacturing facility. Four fish were caught and utilized as samples: Two channel catfish caught above Wheeler Dam, one white bass caught below and one white crappie caught above Wheeler Dam. Wheeler Dam is approximately 26 nautical miles downstream from the 3M Decatur Plant effluent discharge. It was not noted in the report how many miles above and below the dam the fish were caught. A ten ppm standard of FM-3925 (N-MeFOSE alcohol) was prepared by diluting 1 ml of a 100 ppm standard (in ethyl acetate) to mark with ethyl acetate in a 10 ml volumetric flask. One whole channel catfish was homogenized to create one sample. The other channel catfish was dissected and the various individual parts were homogenized to create individual samples. The white bass had a 6.3 cm i.d. dinker die core sample taken just off the lateral line behind the gill plate making up a 20.591 g sample containing skin, filet, small part of the backbone, reproductive organs, part of the kidney, and rectum. The white crappie had a dinker die core sample taken behind the gill plate to create a 16.684 gram sample containing filet, vertebrae, skin and bile. 006558 All samples were homogenized in known volumes of Dl water and divided into five aliquots each. Samples were centrifuged, extracted with ethyl acetate, and analyzed by G C for organic and inorganic fluoride. It was noted that FM-3925 (N-MeFOSE alcohol) and FM-3422 (N-EtFOSE alcohol) could not be distinguished with GC with electron capture parameters. The results are therefore a combined value. RESULTS N-MeFOSE alcohol / N-EtFOSE alcohol Concentration ________In Tennessee River Fish by GC________ N-MeFOSE alcohol & S am p le N-EtFOSE alcohol (ppm ) W ater blank N.D. Ethyl Acetate blank N.D. Whole Channel Catfish 0.73 White Bass core sample 3.31 White Crappie core sample N.D. Channel Catfish Gills 0.80 Channel Catfish Liver 0.38 Channel Catfish Parts* 0.43 Channel Catfish Muscle N.D. Channel Catfish Fat ** 6.12 Channel Catfish Gall Bladder 0.74 Upon completion of G C analysis, there was concern that the values were not definitive. Additional analysis of ethyl acetate homogenate extract was then done using Capillary Gas Chromatography with Electron Capture and G C using a Microwave Sustained Helium Plasma Detector. Qualitative analysis of the fish extracts using Capillary Gas Chromatography with electron capture failed to identify the presence of NEtFOSE alcohol. This was further supported by analysis by a Microwave Sustained Helium Plasma Detector where again, no evidence of any fluorochemicals were detected and specifically no N-MeFOSE alcohol and no N-EtFOSA (F-6309) were detected. The results obtained by the microwave plasma detector on spiked samples indicated that N-EtFOSE alcohol, if present, could have been detected from its fluorine content at 0.1 ppm in the ethyl acetate extracts. No reference was made to NMeFOSE alcohol except for the general statement made "No fluorocarbon peaks were observed in the actual samples." 0065 Remarks: The original report (5/22/79) referenced a sample for FM-3923. It was brought up after the report was generated that FM-3923 and FM3422 are both the same coumpound (N-EtFOSE alcohol). Analytical was conducted to verify its identity and it was found to be N-EtFOSA (F-6309). The attached report ("A R No. 7238 - Determination of Fluorinated Alcohols in Fish Extracts", 10/23/79) still refers to FM-3923 when in fact the sample labeled as FM-3923 is F-6309. This report also has inconsistencies. The last paragraph indicates the ability to detect fluorine content at 0.1 ppm level. However, a review of the procedure used indicates a detection limit of 0.5 ppm. The first report (5/22/79) describes analysis of ethyl acetate extracts of fish homogenate by gas chromatography (GC) with electron capture detection. The analysis shows the presence of materials in fish tissue extracts that have G C retention times identical to both N-MeFOSE alcohol and N-EtFOSE alcohol and to N-EtFOSA. The G C retention times of NM eFOSE alcohol and N-EtFOSE alcohol standards were the same (not resolved) by the method used in the first report. The first report indicates the presence of fluorochemicals in the fish extracts, but electron capture detection is not specific for fluorochemicals. Thus the results reported in the first report were not a specific identification of fluorochemicals detectable by GC. (Report 1 also has errors in column 4 of Table 1. In the 1B row, 0.40 should be changed to 4.13, and in the 2A row, 0.004 should be changed to 0.06.) The second report (12/28/79) shows a misinterpretation in the first report. It includes a description of GC analyses of ethyl acetate extracts of two of the samples described in report 1 samples 1B and 3A. The work described in report 2 used electron capture detection and references a report using microwave sustained helium plasma detection (MSHPD) in the fluorine and sulfur mode. In fluorine mode, MSHPD method is specific for fluorine. The MSHPD results show no fluorochemicals in the ethyl acetate extracts. The results are interpreted as indicating that F-6309 and N-EtFOSE alcohol (FM-3422) are present in the ethyl acetate extracts at less than 0.1 ppm. In the first report, N-EtFOSA (F-6309) and NM eFOSE alcohol (FM-3925) / N-EtFOSE alcohol (FM-3422) had appeared to be present respectively at 0.82 and 3.31 ppm in sample 1B and at 1.48 and 0.80 ppm in sample 3A. Thus, the GC-able compounds seen in the first report appear not to have been fluorochemicals and thus could not have been N-MeFOSE alcohol, N-EtFOSE alcohol or N-EtFOSA. The first report shows the presence of unidentified organic fluorine and of inorganic fluorine in the fish tissue. This was not re-evaluated in the second report. 006560 CONCLUSIONS No reliable conclusions can be derived from this study. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 DATA QUALITY Reliability: Klimisch ranking 3. Without an understanding of the sampling design in relation to the outfall and sampling points, verifiable data on the actual concentrations of fluorochemicals in the river from both the manufacturing facility and from natural sources, activities in the manufacturing facility prior to sampling, any applicable environmental conditions (e.g. rain events), and a clear understanding of how long the sampled fish were in the sampling area, there is little to be concluded. Additionally, the analytical data conflicts. It cannot be definitively concluded which analytical data set is correct. Extraction and analytical methodology were not validated. State units of results is ppm. It is not correlated to mg analyte per kg body weight. Identity and purity of reference compounds was not established therefore stated analyte concentrations have no basis in fact. REFERENCES 3M Technical Report "Bioaccumulation of Fluorochemicals in Tenn. River Fish." James E. Gagnon, Project 78-2740, Decatur, Alabama Tennessee River Fish, Report Number 001, May 22,1979 3M Technical Report "A R No. 7238 - Determination of Fluorinated Alcohols in Fish Extracts." D. F. Hagen, Project A000007, Environmental Engineering and Pollution Control, Report Number 238, October 23,1979. 3M Technical Report "Fluorochemicals in Tennessee River Fish." James E. Gagnon, Project 78-2740, Decatur, Alabam a-Tennessee River Fish, Report Number 100, December 28,1979 3M requested expert overview, "Bioaccumulation Studies", Dr. James Gillett, Cornell University, March 8,1993 OTHER Last changed: 5/18/00 006561 3M REPORT: BIOACCUMUIATION STUDIES March 8,1993 6. Report N o. 001 (5/22/79) *Bioaccum ulation o f Fluorochem icals in Term. River F ish * and Report N o. 100 (12/28/79) *Fluorochem icals in Tennessee R iver Fish.* This pair o f papers is quite confusing, largely because o f incorrect standards, confused identity o f labels and verity of contents, and the difficulty o f actual determinations. W hen these are combined with a lack o f dear sampling design in relation to outfall and sampling points, the result add little to our understanding o f the problem. These papers make an excellent example o f how a little knowledge can be dangerous. 6 006562 Form 6 747 I t A F i ' u 'F > " w ' F C - - ( t>/Wj ? .,~c Fvtv TECHNICAL ffEPORT SUMMARY f i o 12/28/79 TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN (Im portant - I f report is p rin te d on both sides o f paper, send two copies to TCC.) D ivision Environmental Laboratory (EE & PC) P roject R epo rt Title Decatur, Alabama - Tennessee River Fish Fluorocheraicals in Tennessee River Fish To D. L. Bacon A u th o r(s ) James E. Gagnon N otebook Reference 51568 Lab Request #4871 ^c c n m i T V ^ ScCUni ry Open Closed {Company Confidential) (Special Authorization) 3M CHEMICAL w REGISTRY ^ KEYWORDS: (Select terms from 3M Thesaurus. Suggest other applicable terms.) - ^ A- i L CURRENT OBJECTIVE: Progress Report. EE & PC Decatur \ b p t. N um bar 0222 P rolact N um bar 78-2740 R eport N urn bar 100 E m ployee N um ber(s) 213531 No. o f Pages In c lu d in g C oveisheet 3 New Chemicals Reported Yes |S No REPORT ABSTRACT: (200-250 words) This abstract information is distributed by the Technical Communications Cente alert 3M'ers to Company R&O. It is Company confidential material. The microwave sustained helium plasma detector system and capillary column with electron capture were utilized to examine fish extracts for fluoro carbon alcohol levels. *` v , fl r - ^ - ^ c c : D. Ricker-53-4 A.Welter A.Mendel \In fo rm a tio n L ia is o n lnitiaii z>Khu COPY AVAILABLE 006563 -2 - Introduction: Previous work* indicated a need for more definitive answers to the presence of volatile fluorochemicals. Capillary gas chroma tography with an electron capture 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 csample, extracted as previously described1 , 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 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 defected in samples IB and 3A (Table 1). ' .X . TABLE 1 \ QUALITATIVE ANALYSIS OF FISH EXTRACTS FOR FLUOROCHEMICALS Sample IB 1M 3A FM-3422 Std. F-6309 Std. Re1te.n4t-i-o--n---T.i.m.e..(.M.i1n2u?t;es) - ** 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 * = 1 0 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 s a mples.2 best copy m u m 006564 -3 - Discussion: The above results indicate that no volatile fluorocarhnng wsrp present in sajnnies~ The large amounts of organic fluorine mentioned in the original report1 are due to the presence oi 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 report1 , it was brought up that FM-3923_and FM-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-3 4 2 2 , 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 F-6309 (N-ethylperfluorooctanesulfonamide: C8F1 7 ^ 2 1IHEt>' 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. ^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. 006565 F m * 7 4 7 11 A TECHj l M t pEPORT SUMMARY 0w 5/22/79 TO: TECHNICAL COMMUNICATIONS CENTEN - 201-SCN (Im portant - H ro p o rt n p rtn to d on b o lt dototpopor, tm d tw o copit TCC.) DEC 20 1979 DkiiUM *MCI WspsrtTins T* Environmental Laboratory (EE k PC) Decatur, Alabama - Tennessee River Bioaccumulation of Fluorochemicals D. L. Bacon Fish in Tenn. -A River Fish ' Dopt.Nwmtoer 0222 FraattP>> 78-2740 WapMMNeMUr 001 h E. O n B o n 2 1 3 5 3 3 -- _________ We sifip>iNsJKyqn ntfiiii 51568 sacuMTY^ Lab Raquast 0*871 asasntv -- ul@ t y 83 m* _ |3M CUAMMT ECTivt! Qualitative and quantitative determination of P 6309, FM-3925, and FM-3422 in fish taken from the Tennessee River above and below Wheeler Dam at 3M's Decatur plant. Analyze for organic and Inorganic KK k PC fluoride in tbe saaie sample. Decatur ITRACT:13001 neo. K*ca Cm Ethyl acatata extracts of a Channel c a tfis h (Ictalurus punctatus). white bass (Roccus chrysoos). and a white crapple (Pcmnxls annularis) were analysed by gas chromatography. ce : D.Rlcker-236-2) A.Welter A.Mendel Iwlwnem <*>* ^ U ) 006566 Tenn. River Fish/JEG -i- 5/22/79 INTRODUCTION BEST COPY AVAit/lBiE It is known that 3lf's Decatur, Alabama plant effluent has high organic fluoride levels, 10.9 ppm (1)(2). It has also been shown fluorochemicals can bioaccumulate in fish in a laboratory envi ronment (3)(4). With these combined factors, the next step was to see if fish caught in the Tennessee River near the Decatur plant had detectable levels of fluorochemicals. that RESULTS AND DISCUSSION Table 1 lists the concentration, in ppm, in fish of compounds which have the'same retention time as the three fluorochemicals of interest (7*6309, 7M-3925, and FM-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 contained more than twice the fluorochemical content, 2.74 ppm 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 coefficients v for channel catfish. 71uorocheaicals bioaccumulate in fatty tissue, and since store fatty tissue is prosont in the larger fish, store fluorochemicals would be expect e d . F-6309 is present at higher ccncentrations in the dissected channel catfish, sample 3A, than other samples. Sinco bioaccumulution rates havo not been determined for 7 -6309 no explanations for the higher concentrations can be offered. The two fish samples which had cores taken from them will not bo rigorously compared to whole fish samples. The reason for this is that the core samples stay not have representative concentrations of fluorochemicals (whole fish values may be higher or lower). Since core samples wore takon from tho approximate same location, the results can be rigorously compared. The white bass from below Wheeler Dam, sample IB, had a whole fish T7C of 0.40 ppm, while the white crappie from above Wheeler Dam, sample 2A, had a whole fish TFC of 0.004 ppm. With such small statistical samples, it would be difficult to say that tho larger TFC is due only to the white bass living in tho presence of higher fluorochemical concentration, downstream from the plant. Other possible explanations for the higher TFC could be the following: 006567 Tenn. River Fish/JEG 5/22/79 TABLE 1 PLUOftOCHEMICAL CONCENTRATION (ppm) IN TENNESSEE RIVER FISH Sample F-6309 C \ k - Whole fish 0.40 IB - Core (3) 0.82 2A - Core (5) 0.06 ("'3A - Gills 1.48 \ 3A - Liver 2.17 / 3A - Parts (7) 1.33 !1 3A - Muscle | 3A - Fat (8) N.D. 13.85 1 3A - Gall bladder 1.57 Water blank N.D. Ethyl acetate blank N.D. FM-3925 k FM-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 FC iff Fish (PE*? -- 1.13 0.40 (4) 0.004 (4) 2.74 (9) BEST copy AVAILABLE Footnote to Tablo 1: (1) FM-392S and FM-3422 cannot be resolved with GC parameters used; therefore, a combi net, value is reported. (2) Bused on frozen weight of the fish. (3) Sample core, 3.61 cm, id contained skin, filet, reproductive organs, and parts of kidney, rectum, and backbone. (4) Assumes that the concentrai Iona obtained in the core are representative of the rest of the fish. (5) Sumpic core, 3.61 cm id contained filot, vertebrae, skin, and bile. (fi) N.D. Not dotcctnd. (7) Consisted of muscle, skin, blood, bone, and cartilage. (8) Consisted of gastrointestinal tract, reproductive system, and fat. (9) Based on the actual weight of sample used, 18.8% less than frozen weight, and weight percent of each part. 006563 ln<ormion LW w n, \ <CkJ u Tenn. River Fiah/JEG BEST COPY AVAILABLE 3M CONFIDENTIAL -4- . 5/22/79 1. Longer river rewldenco Line, older fish. 2. Longer location residence time. 3. Different species a) Different feeding and life styles b) Contains larger weight percent of organs which tend to bioaccumulate fluorochemical* c) Larger fluorochemical partition coefficients If the core samples are representative of whole fish concentrations, then it can be postulated that channel catfish bloaccumulato fluorochemicals to a greater extent than either white bass or crappie. Seasons for this aro the same as listed above. Table 2 fives the results of the organic (RF) and inorganic fluoride (F*) concentration, in ppm, in the fish samples. Sample 1A 2A IB Water TABLE 2 (5) ORGANIC (RF) AND INORGANIC (F) FLUORIDE CONCENTRATIONS (ppm) R? 9.7 16.2 10.5 N.I . F 24.6 13.3 6.2 0.01 Jon Bolisle points out that th< high inorganic fluoride values seem rather surprising. Ills or.ly explanation was that iish flour previously analysed, for a dlflereat requestor, was shows to have Inorganic fluoride values higher than organic fluoride. Jon also states that high inorganic fluoride values would make it difficult to calculate low levels of organic fluoride. Comparison of the organic aad inorganic fluoride coateat shows that samples from above Wheeler Dam have Jusl as high, ir sot higher, values than for the sample from below the dam. There are no clear cut explanations for this observation. As earlier analysis of Tsaassaee River water showed high organic fluoride concentrations upstream from the plant. At that time, it was thought the snsiplss may have been mislabeled. With these results. 006563 '*/* )% > BEST COPY AVAILABLE Tenn. River Fish/JEG # 5/22/79 it would seem to indicate that the concentration of fluoroeheraieals may actually be less below Vheeler Dam. 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 example, the highest organic fluoride value, 16.2 ppm for sample 2A, had the lowest TFC, 0.004 ppm, for the fluorochemicals analyzed. A possible explanation is 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 fluorido concentrations. With limited sample population (2 fish of one species and one of each of two other species), it is difficult to draw any meaningful coecluslons. The only definite conclusion is that the fluorochemicals Studied do appear to bioaccumulate in river fish under natural conditions. EXPERIMENTAL 1. Sample materials Fish 1A - Small channel catfish ( l o t a l u r u a p u n o t a t u a ) , caught above Wheeler Dam in Tennessee River. IB - White bass (Rooaua o h s y s o p ), caught below Wheeler Dam in Tennessee River. 2A - White crappie {Pomoxia a n n u l a r i ) , caught above Wheelor Dam la Tennesseo River. 3A - I<urgo chan n el R a t f i s h ( Tt* l a l u r u a p uu */.I itj , c a u g h t above Wheeler Dam in Tennessee Uivo'r. Standards F-4309, FM-U`J25, aud KM-3'122. Ten ppm standards of F -4309, 1*11-3925, and FM-3422 woro prepared by diluting 1 ml of a 100 ppm standard, la ethyl acetate, to mark with ethyl acetate la separate 10 ml volumetric flasks. 2. Analysis Instrumswta/Materiala Blender: Waring Commercial blender, Model #91-203, available from Waring Products Divlaloa, (touts 44, New Hartford, CT 060ST. 006570 following: BEST COPY AVAILABLE Tenn. River Fish/JEC --- 5/22/79 Tisauemizer: Model #SDT, available fron Tekaar Company, P. O. Box 37202, Cincinnati, OH 45222. Pinker 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: Damon-IEC Model #B-20A, available from Damon-IKC Corporation, Needham Heights, MA. Bottles: Four-ounce wldesrouthed clear glass bottle sealed with aluminum foil and aluminum foil-lined caps. 12S-ml linear polyethylene (LPB) plastic bottle with polyseal caps. Gas Chromatograph: Chromatograph - Hewlett-Pacl ard Modol 5713 fiC. Integrator - Hewlett-Packard Model 3380A intogrator- printor. Both of the above available from Hewlett-Packard Co., 150 Page Mill Hoad, Palo Aito, CA 94304. Column - Six-foot, 1/8 inch OD, stainless steel, packed with 10% CW20M on 60/80 Chromasorb V-AV. Column Temperature - Isothermal 180 C. Injector - On-column at 200 C. A pi Detector - Hlectron Capture at 300 C. Flow - v|0 cc/minute of Argon:Methane (95/5). Kthvl Acetate: "Li Chrosolv" chromatography solvent available from MC/B Manufacturing Chemists, 2909 Highland Avenue, Norwood, OH 45212, as Catalog #60086888. 006571 U Q Vi- j 1O D0 1 l (9) Based on the actual weight of sample used, 18.8 less than frozen weight, and weight percent of each part. BEST COPV AVAILABLE Tenn. River Fish/JEG - 5/22/79 Water: Deionized water. 3. Procedure (6) Procedures used below, except for minor modifications, were obtained from earlier 3M Technical Report summaries (7). Samples 1A through 3A and IB were removed from the freezer and placed in large aluminum pans, in a fume hood, and allowed to thaw. A whole channel catfish, sample 1A, was cut into S sections and hoaMgenized in a blender with 200 ml water. Sample IB 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 behind the gill plate. The 16.684 gram sample contained rilet, vertebrae, skin, and bile. Samples IB and 2A were homogenized with 10 ml of water in a 'tissuemizer.'* Sample 3A was dissected, and the various 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 "tissuemizer." Table 3 lists the sample, sample weight, and amount of water added for homogenizing each sample. All of the above samples, after homogenization, were divided into five aliquots and placed la precleaned bottles, (dichromnte/acid, water rinse, dry, toluono, dry). Three aliquots wore placed m U*k bottles, while the other two were placed in glass bottles. Samples were stored in a refrigerator at 4.5 C. until needed. Samples analyzed for F-6309 FM-3925, and FM-3422 were prepared according to the following procedure. See Table 4 for weight of sample and milliliters of ethyl acetate used for extractions. A previously hoamgenixed sample, stored in a glass bottlo, was weighed (no larger than 4.00 g) and added to a 30-ml precleaned glass centrifuge tube. A volume of ethyl acetate warn added at the rate of 1.0 ml ethyl acetate per gram of homogenate. The ethyl acetate/flah homogeaate were mixed for 1.5 minutes la a mixer at a speed setting of 3. The samples were removed and centrifuged at 1500 rpm at 006572 cST COPY AVAILABLE Tenn. River Fish/JEG 5/22/79 21 C. for 10 minute. After centrifuging the ethyl acetate layer as separated, by use of a pipet. and placed in a vial. Five til of sample (standard) was injected for gas chromatographic analysis. Samples 1A, 2A, and IB homogsnatss, plus a water blank, in IPS bottles, vers sent to Jon Belisle of the Central Research Laboratory for organic and inorganic fluoride analysis. REFERENCES (1) 311 Technical Report Summary, August 30, 1978, Arthur Mendel to R. L. Bobon, "Fate of Fluoroehemicals Project - Progress Report." (2) Central Research Laboratory Report Number 8902, April 20, 1978, Jon Belisle. (3) "Rtocoiicontration of PM-3422 in Blucgill Sunftnh and In Channel Catfish," M. T. Slnabarawy to A. N. Velter, May 17. 1977. (4) 3M TRS, August 18, 1978, A N. Welter to D. L. Bacon, "Evaluation of the Blocoacatratioa Potential of FM-3422." (5) Central Research Laboratory Report on Request PA72199 by Jon Bellsle, May 7, 1979. (8) Experimental work done in cooperation with A. N. Velter of the Environmental Laboratory (EE fc PC), who performed the dissections and homogenisations. (7) 3M Tcichnir.nl Ruporl Summary, Novowbor If, 1977, A. Mosel*I to 0. L. Bacon, "Analytical Methodology on FM-3422." ///*' <-v'MJUtK wSC/cea 006573 BEST COPY AVAILABLE Tenn. River Fista/JEG -9- 5/22/79 TABLE 3 FISH WEIGHTS AND WATER VOLUMES USED FOR HOMOGENIZATION Description 1A 2A IB 3A - Muscle 3A - Gall bladder 3A - Liver 3A - Fat 3A - Parts 3A - Gills Initial Whole Frozen Weight 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 ml Water Weight Used Used Whole fish (1>(2) 200 16.684 g (3) 2 9 . 5 9 1 g (3) 10 10 209.93 g 200 1.378 g 10 5.949 g 10 52.230 g 100 321.57 g 300 19.38 g 100 Footnotes: (1) A fish hook, with no apparent rust or lino,v was found in lash uml was removed 'before homogeuizuliou.' (2) The fish appeared to be slightly dehydrated (possibly due to constant air flow over burface of fish) so the actual weight of fish used may have been less than frozen weight. (3) Sample core 3.61 cm id. 006574 Tenn. Hiver Fiah/JEG 10 * 5/22/79 TABLE 4 FISH WEIGHTS AND ETHYL ACETATE VOLUMES USED FOR EXTRACTIONS Sample Description 3A - Gall Bladder 3A - Liver 3A - Muscle 3A - Fat 3A - Parts 3A - Gills Water Blank 1A IB 2A Weight of Fish % Water Homogenate in (grams) Homogenate Actual Fish Wt. Extracted (mg) 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 83.8 486.0 2.40 100.0 -- 2.40 57.8 1012.8 2.40 32.7 1615.2 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 BEST COPY AVAILABLE 006575 3B3 *Trm 8747-11-A TECHNICAL REPORT SUMMARY TO: TECHNICAL COMMUNICA'llONSJCSSITeB ^ < iT -2 C i Oata October 23, 1979 (Im portant -- I f report sprinted on both sides o f paper, send two copies to TCCJ Oivifion \ tffpcKumfa1 1~ (' CENTRAL RESEARCH LABORATORIES, Analytical and Properties Research Laboratory 0502 Project ProjectNumber Environmental Engineering and Pollution Control RpOrt Title A000007 Report Number AR No. 7238 - Determination of Fluorinated Alcohols in Fish Extracts To 238 J. E. GAGNON - 209-1S Author(s) D. F. HAGEN - 201-1S Notebook Rfrnc E m ploy N um beirU ) 042608 No. of^eaetIncludingCoveriheet SECURITY O Opn (Company C onfidential! 3 Closed (Special A u th o riza tio n ) ' 3M C HEM ICAL i REGISTRY 1 KEYWORDS: (Select terms fro m 3M Thesaurus. Suggest oth er applicable terms.) Central Research Analytical Report CURRENT OBJECTIVE: Request No. A73154 Requestor - J. E. Gagnon Project No. 91500600 Chemical Analysis New Chmicfs Reported Yes g ) No REPORT A B S T R A C T : 1200-250 words) This abstract in fo rm a tio n is d is trib u te d b y the Technical C o m m u n ica tio n s C enter to alert 3M ` ars to Company R & D . It is C om pany c o n fid e n tia l m aterial. The microwave sustained helium plasma detector system and capillary column with electron capture detection were utilized to examine fish extracts for fluorocarbon alcohol levels. Infotm adon Lauon Inmalt w orgy i 006576 . FORM 2 6 4 3 -c Po C E N T R A L A N A L Y T IC A L LA B O R A T O R Y BEST COPY AVAILABLE R ep ort N o . _________7.2.32_______ ________ D a te ----------- Qc to.h.<yr_23* A9_72_ Subject: Determination of Fluorinated Alcohols in Fish Extracts R e q u e sto r: _ A -_ A _?iS .n__n. ____ Request N o. _ A 7.3.1^ .................... Report: Introduction D ep t. N am e _ _ A A _ C____________ Dated _ A UA U_S5 _? i A 9-7.9. ............ P r o j. N o. _9A ?P i?^^ 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 presence of fluorocarbon alcohols FM-3923, FM-3925, and FM-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/lOyl injection. Additional sensicivity was obtained by concentrating lOOyl of the solution as received to 20ul and injecting lOyl of this concentrate for analysis. Operating conditions for the MPD-850 are listed below. Column System A - 6', 62 CW-20M-TPA on 80/100 mesh Chrom G. H.P. programmed from 100 to 200C at 15C/min. Helium carrier at 25cc/min. with purge rate to MPD of 50 cc/mln. 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 180C. The cavity head temperature is held at 200C and the plasma is sustained by a 100 watt microwave power supply operating at 2.450 gigahertz. The emission lines used for fluorine and sulfur were 6856.0 and 5453.9 A respectively. Approximately 0.5 ml/min. of oxygen is used as the scavenger gas to prevent carbon buildup on the quartz plasma reqetor 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-20M. Initial column temperature was 60C and it was programmed at 10C/min. to 240C. Split mode of injection was utilized with 99% of the injected sample (lyl) being vented to Che 006577 AR No. 7238 October 23, 1979 Page 2 BEST COPY AVAILABLE atmosphere. Column flow was approximately 1 cc He/min. and an auxiliary 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 che column system on the HP-5840. System A - Chromatogram 10-10-79-1 illustrates the fluorine and sulfur responses for a 10yl injection of a 10 ppm solution of FM-3923 or CsFj7S02N(CH3) C2 H i,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 lOyl injection of sample 1-M (ethyl acetate extract of a brown bullhead from Minnesota. Note the absence of fluorine containing peaks. Chromatogram 10-10-79-3A illustrates the results for a lOyl 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 lOyl 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 concentrate of sample 1-B. Chromatogram 10-10-79-6 shows the response for a 10yl 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 lyl of 10 ppm solutions of FM-3923 and FM-3925 respectively. Note the FM-3925 CaF17S02N (C2H5) C 2Hi,0H elutes approximately 2 minutes after the n-methyl homolog. 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 1M which has been spiked with known levels of these homologs. In this case 20 ng of each species was added to lOOyl of sample 1-A and this was concentrated via evaporation to 20ul. 10yl were then injected for the analysis. System B - Chromatograms 10-12-79-1, 10-12-79-2, and 10-12--79-3 illustrate the electron capture response for samples 3-A,^1-M, and 1-B respectively. Note the large nmnfrer of capture sensitive peaks. These are not necessarily halogcnated species In that a number of compound classes give a degree of F.C reponse. The arrow point out those areas where the alcohol homologs will elute as Illustrated In chromatogram 10-12-79-4 and 10-12-79-5. The capillary column-electron capture results Indicate that sample 1.-H would have to contain less than 0.05 ppm based on the attenuations for the sample vs. reference solutions. Samples 3-A and 1-B would also contain very little of the FN-3925 or 006578 AR No. 7238 October 23, 1979 Page 3 BEST COPY AVAILABLE FM-3422 species. These latter two samples do have a peak at the retention time of FM-3923 major isomer but the isomer distribution is not evident in the saaple r chromatogram. Lower levels of detection via electron capture would require additional sample cleanup prior to chromatography. The results obtained by 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. Nlppoldt - 201-1S 006579 I" ini()rm<inu" In io tlt BORATORIES H- Rquest No. - ^ * l l j s - t . Div./Depi. Project N o .._ _ g / s r e v s r o * Date Chemist__ C ti . H i OVA BEST COPY AWMABIE 006580 JC-IO -T*?'-- '2- L A B O R A T O R IE S / y i /-M A NA LYTIC AL RESEARCH Request No. Project N o .__^ / c ^*` V S * O 0 D a te ___ U o q ? . Chemist B* i / M a* Cy, `\ * 006581 I o 1AT0RIES ANALYTICAL RESEARCH Request No. DivVDept. Project No. A - n s is < / + / ? C . 9 / <~<3 */<T<TO D a te ___ -- a w / * 4 7 ? Chemist 3A m 4 L 4 a j iJ $ L $*7 F O R M 2144*0 pTT'n- :]T / a - a - 7 < l > \ - y I U30RAT0RIES i; IB A NALYTICAL RESEARCH Request No. A - * 1 3 / S V D iv ./D e p t.. Project No---- 9 / g * 0 /S~fl0 D a ----- Chemist -- >,V ~ i | , I " (5 C a U4lAA m 3I K A CO 00653 BEST COPY AVAILABLE RIES ANALYTICAL RESEARCH Request N o .. A - + T 3 / g / D iv V D e p t.. 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