Document 1QRXOYrjox60omNy5kv3nL6KZ

/H U 7 t03M3> BIOACCUMULATION TEST SUBSTANCE Identity: N-Ethylperfluorooctanesulfonamide; may also be referred to 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-ethyl-, CAS # 4151-50-2) Remarks: Material is a white solid of uncharacterized purity. M E T H O D _______________________________________________________ Method/guideline followed: None given for sampling of the organisms. Extraction and analysis procedures were devised by 3M. Type: Environmental sampling of indigenous fish around a 3M fluorochemical manufacturing facility. 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-3422 (N-EtFOSE 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. 006086 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 GC for organic and inorganic fluoride. RESULTS_____________________________________________ EtFOSA Concentration In Tennessee River Fish by GC EtFOSA Sample (ppm) Water blank N.D. Ethyl Acetate blank N.D. Whole Channel Catfish 0.40 White Bass core sample 0.82 White Crappie core sample 0.06 Channel Catfish Gills 1.48 Channel Catfish Liver 2.17 Channel Catfish Parts* 1.33 Channel Catfish Muscle N.D. Channel Catfish Fat ** 13.85 Channel Catfish Gall Bladder 1.57 * Consisted of muscle, skin, blood, bone, and cartilage. ** Consisted of gastrointestinal tract, reproductive system, and fat. Upon completion of GC analysis, there was concern that the values were not definitive. Additional analysis was then done using Capillary Gas Chromatography with Electron Capture and a Microwave Sustained Helium Plasma Detector. Results from only the white bass core sample and the catfish gill sample were described in this report. Qualitative analysis of the fish extracts using Capillary Gas Chromatography with electron capture failed to quantitate EtFOSA. However, the white bass core sample showed a peak with a retention time similar to EtFOSA. This peak area was less than the EtFOSA standard, but greater than that seen in the channel catfish gills, which was described as a "very small amount". Analysis by a Microwave Sustained Helium Plasma Detector found no fluorocarbon peaks. The results obtained by the microwave plasma detector on spiked samples indicated that NEtFOSA, if present, could have been detected from its fluorine content at 0.1 ppm in the ethyl acetate extracts. 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 ("AR No. 7238 - Determination of Fluorinated 006087 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 GC retention times identical to both N-MeFOSE alcohol and N-EtFOSE alcohol and to N-EtFOSA. The GC retention times of NMeFOSE 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 NMeFOSE alcohol (FM-3925) / N-EtFOSE alcohol (FM-3422) had appeared to be present respectively at 0.82 and 3.31 ppm in sample IB 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. CONCLUSIONS__________________________________________________ No reliable conclusions can be derived from this study. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 006088 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. 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 "Fluorochemicals in Tennessee River Fish." James E. Gagnon, Project 78-2740, Decatur, Alabama - Tennessee River Fish, Report Number 100, December 28,1979 3M requested expert overview, "Bioaccumulation Studies", Dr. James Gillett, Cornell University, March 8,1993 O T H E R _______________________________________________ Last changed: 5/18/00 006089 3M REPORT: BIOACCUMULATION STUDIES M arch 8, 1993 6. R eport N o. 001 (5122179) *B ioaccu m u lation o f F h toroch em icals in Term. R iver F ish " an d R eport N o. 100 (12/28/79) *F lu orochem icak in T ennessee R iver Fish." This pair of papers is quite confusing, largely because o f incorrect standards, confused identity of labels and verity o f contents, and the difficulty of actual determinations. When these are combined with a lack o f clear 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 006090 Porm74? 11 A t T^CHSI PORT SUMMARY o<w 5/22/79 TO: TECHNICAL COMMUNICATION CENTER - 20V X N (Important- Itraporth printson bo* sMtaofpaper,mnd twocopm toTCC.I DEC 201979 Ptmmi Environmental Laboratory (EE A PC) Decatur, Alabama - Tennessee River Fish WlSSftTiSS Bloaccumulatlon of Fluorocbemicals in Tenn. River Flsb % A .. - . - D. L. Bacon 0S<-Nanas 0222 FftiMlNMSkfl 78-2740 001 51568 Itmrnm ttom S tt HU Ik Deca Lab Raquast # b 8 7 1 213531 'revn Mawmv V gj Ms c u u m n t ouctivc:Qualitative and quantitative determination of P 6309, FM-3925, and PH-3422 in fish taken from the Tennessee River above and below Vhcoler Dun at 3U's Decatur plant. Analyze for organic and inorganic fluoride in tbe musk.* wuaplos. ins .WMCa INrWafa Ethyl acetate extracts of a Channel catfish (Ictalurus punctatus). white bass (Roccus chrysoos). and a trfilte crapple (Powoxls annularis) were analyzed by gas chroaatography. -- -- -- BEST Cl Ice: D.Rlcker-236~2p A.Velter A.Mendel ImiMM 006091 Tenn. River Fish/JEG 5/22/79 INTRODUCTION BEST COPT AVAILABLE It la known that 3 M 's Decatur, Alabama plant effluent has high organic fluoride levels, 10.9 ppm (1)(2). It has also been shown lliui 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. 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 (F-6309, FM-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, Fluorochealcals bioaccumulate in fatty tissue, and since more fatty tissue is present in tho largor fish, more fluorochemicals would be expected. F-6309 is present at higher concentrations in the dissected channol catfish, sample 3A, than other samples. Sinco bioaccumula tion rates have not boon determined for F-309 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 sasples. The reason for this is that the core samples may not have representative concentrations of fluorochemicals (whole fish values may be higher or lower). Since core samples wore takon from tho approxiaalu same location, the results can be rigorously compared. The white bass from below Wheeler Dam, sample IB, had a whole fish TFC of 0.40 ppm, while the white crapple 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 thu presence of higher fluorochemical concentration, downstream from the plant. Other possible explanations for the higher TFC could be the following: 006092 ' Tenn. River Flsh/JEG 5/22/79 TADLE 1 BEST COPY AVAIL FLUOROCHEMICAL CONCENTRATION (ppm) IN TENNESSEE RIVER EISB MB Sample 1A - Vhole fish l 1B - Core (3) 2A - Core (5) r 3A - Gills .^2.0?, 0.40 0.82 0.06 1.48 \ 3A - Liver 2.17 -/ 3A - Parts (7) 1.33 i 3A - Muscle 3A - Fat (6) N.D. 13.85 3A - Gall bladder 1.57 Water blank N.D. Ethyl acetate blank N.D. FM-3925 k FM-3422 (11 0.73 3.31 N.D. (6) 0.80 0.38 0.43 N.D. 6.12 0.74 N.D. N.D. Total Combincd FC inr Fish iSS*) i2)_____ 1.13 0.40 (4) 0.004 (4) 2.74 (9) Footnote to Tablo 1: (1) FM-3925 and FM-3422 cannot be resolved with GC parameters used; therefore, a combine* value is reported. (2) Bused on frozen weight of the fish. (3) Sample core, 3.81 ca, id contained skin, filet, reproductive organs, an<* parts of kidney, rectum, and backbone. (4) Assumes that the concentrations obtained in the core are representative of the rest of the fish. (5) Sumplo core, 3.61 ca id containod filot, vertebrae, kin, and bile. (0) N.D. Not detected. (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, 18.6% less than frozen weight, and weight percent of each part. 006093 InformationLMon. . J '" <T,IC.UJ Tenn. River Fish/JEG BEST COPY MM i 3M CONFIDENTIAL -4- . 5/22/79 1. Longer river residence tine, older fish. 2. Longer location residence tine. 3. Different species a) Different feeding and life styles b) Contains larger weight percent of organs which tend to bioaccuaulate fluorochenical* c) Larger fluorocbenical partition coefficients If the core sasples are representative of whole fish concentrations, then it can be postulated that channel catfish bioaccuaMlato fluorochenicals to a greater extent than either white bass or crappie. Reasons for this aro the sane as listed above. Table 2 gives the results of the organic (RF) and inorganic fluoride ( F ^ concentration, in ppn, la the fish saaples. TABLE 2 (5) ORGANIC (RF) AND INORGANIC (F) FLDORXDB CONCENTRATIONS (ppn) Sample 1A 2A IB Water R7 9.7 10.2 10. N.I . F 24.0 13.3 0.2 0.01 Jon Bollsle points out that th high inorganic fluoride values soon rather surprising. Uis or.ly explanation was that fish flour previously analyzed, for a dlflerent requestor, was shows to have inorganic fluoride values higher than orgaalc fluoride. Jon also states that high inorganic fluoride values would sake it difficult to calculate low levels of organic fluoride. Comparison of the organic and inorganic fluoride contest shows that saeplos from above heeler Dae have Just as high, it sot higher, values than for the sastple froe below the dae. There are no clear cut explanations for this observation. An earlier analysis of Tennessee River water showed high organio fluoride concentrations upstrean from the plant. At that tins, It wan thought the nasties nay have bees sislabsled. With these results, 006094 BEST COPY AVAILABLE -/'Wtfz) Tenn. River Fish/JEG 5/22/79 it would seen to Indicate that the concentration of fluorochemicals may actually be leea 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 fluoride 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 conclusions. The only definite conclusion is that the fluorochemicals studied do appear to bioaccunulate in river fish under natural conditions. EXPERIMENTAL 1. Sample materials Fish 1A - Small channel catfish (letalurua punotatua), caught above Wheeler Dam in Tennessee River. IB - White bass (Roooua ohsyaopa), caught below Wheeler Dam in Tennessee River. 2A - White crappie (Pomoxia annularia), caught above Wheeler Dam in Tennessee River. 3A - (.urge channel catfish (TrLnlurutt fUMfl-nlmt), caught above Wheeler Dam in "jenneeeee Rivor. Standards r-4 309, FM-UD2 5 . aud KM-UaMM. Ton ppm standards of P4J09, PM-392S, and FM-3422 wore prepared by diluting 1 ml of a 100 ppm standard, in ethyl acetate, to mark with ethyl acetate la separate 10 ml volumetric flasks. 2. Analysis Inatrumenta/Matenale Blender: Waring Commercial blender, Model #01-263, available from Waring Products Division, Itoute 44, New Hartford, CT 0A0S7. ^06095 following:. M M COPY AVAILABLE Tenn. River Fish/JEC --- 5/22/79 Tlasuemizer: Modal #SDT, available from Tekmar Company, P. 0. 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-5S0-G, availablo from Scientific Industries, Inc., Bohemia, NY 11716. Centrifuge: Damon-IEC Model #B-20A, available from Damon-IEC Corporation, Needham Heights, MA. Bottles: Four-ounce widemouthed clear glass bottle sealed with aluminum foil and aluminum foil-lined caps. 125-ml linear polyethylene (LPB) plastic bottle with polyseal caps. Gas Chromatograph: Chromatograph - Ilowlott-Pacl ard Model 5713 GC. Integrator - Hewlett-Packard Model 3380A intogrator- priator. Both of tho 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% CV20M on 60/80 Chromasorb V-AV. Column Temperature - Isothermal 180 C. Injector - On-column at 200 C. Detector - Electron Capture at 300 C. Flow - M O cc/mlnute of Argon:Methane (95/5). Ethrl Acetate: "Li Chrosolv" chromatography solvent available iron MC/B Manufacturing Chemists, 2909 Highland Avenue, Norwood, OH 45312, as Catalog #6008688M. and fat. (9) Based on the actual weight of sample used, 18.8* less than frozen weight, and weight percent of each part. Tenn. River Fish/JEG 5/22/79 Water: Deionized water. BEST COPY AVAILABLE 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 5 sections and homogenized in a blender with 200 ml water. Sample IB had a dlnker 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 dlnker die core sample taken behind the gill plate. The 16.684 gram sample contained filet, vertebrae, skin, and bile. Samples IB and 2A were homogenized with 10 ml of water in a `'tlssuemlzer." 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 "tlssuemlzer.'' Table 3 lists the sample, sample weight, and aawunt of water added for homogenizing each sample. All of the above samples, after homogenization, wsre divided into five aliquots and placed la precleaned bottles, (dichromate/acid, water rinse, dry, toluono, dry). Three aliquots were placed m Uk d o itlew, 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 homogenized sample, stored la a glass bottlo, was weighed (no larger than 4.00 g) and added to a 30-nl prec leaned glass centrifuge tube. A volume of ethyl acetate was added at the rate of 1.0 ml ethyl acetate per gram of homogenate. The ethyl acetate/flsh hoengeaate were nixed for 1.5 minutes in a mixer at a speed setting of 3. The samples wsre removed and oentrifuged at 1500 rpn at 006097 Tenn. River Flsh/JEG 5/22/79 21 C. for 10 einutee. After centrifuging, the ethyl acetate layer as separated, by use of a plpet, aad placed ia a vial. Five yl of sample (staadard) as injected for gas chromatographic aaalysis. Samples 11, 2A, aad IB homogenates, plus a water blaak, la LPB bottles, ere seat to Jon Belisle of the Central Research Laboratory for organic aad inorganic fluoride aaalysis. REFERENCES (1) 3M Technical Report Summary, August 30, 1978, Arthur Mendel to I. L. Bobos, "Fate of Fluorochemicals Project - Progress Report." (2) Central Reeearch Laboratory Report Number 6902, April 20, 1978, Joa Belisle. (3) "lUoconcontration of PM-3422 in Dluogill Stinflnh and In Channel Catfish," M. T. Blaabarawy to A. N. Veltsr, May 17, 1977. (4) 3M TRS, August 16, 1978, A N. Welter to D. L. Bacon, "Evaluation of the Biocoactatration Potential of PM-3422." (5) Central Research Laboratory Report on Request WA72199 by Joa Belisle, May 7, 1979. (6) Experimental work done la cooperation with A. N. Welter of the Environmental Laboratory (BB % PC), ho performed the dissections aad homogenisations. (7) 3M Technical noport Summary, November If*, 1977, A. Mend*I to 0. L. Bacon, "Analytical Methodology on KM-3432." 006098 Tenn. River Fish/JEG -9- 5/22/79 TABLE 3 FISH WEIGHTS AND WATER VOLUMES USED FOR HOMOGENIZATION Sample 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) 10 29.591 g (3) 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.^was round in fiali and w u m removed bdi'ori homogenization. (2) The fish appeared to be slightly dehydrated (possibly due to constant air flow over surface of fish) so the actual weight of fish used may have been less than frozen weight. (3) Sample core 3.61 cm id. b e s t m ai 006099 Tean. Hiver Fieh/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 (crams) 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 EtOJ 1.2 2.2 2.4 2.4 3.0 3.0 2.4 2.4 2.4 2.4 BEST COPY AYiLB 006100 i1 in * TECHNICAL REPORT SUMMARY , TOi TECH N ICAL COM M UN ICATIO N ! C EN TER - 201-2CN {Important - If raportIsprinted an both sidasofpopar, sendtwo coplas to TCC.I i1 f m v i 2'*- *2/28/79 D ivision Environmental Laboratory (EE & PC) P ro je c t Decatur, Alabama - Tennessee River Fish R eport T itla Fluorochemicals in Tennessee River Fish T D. L. Bacon Author(s) James. >E. ^ Gagnon^*..# Notabook Rafaranea 51568 Lab Request #4871 rai iBiTv ^ s e c u r it y ^ LJ OpiA fJ Gond (Company Confidential) (Spoetai Authorization) 3M CHEMICAL ^ REGISTRY W KEYWOROS: (Salact tarm* from 3M Thesaurus. Suggest other appliesb<a tanra.) CURRENT OBJECTIVE: Progress Report. h p t Number 0222 Proiaet Num bar 78-2740 Report Num bar 100 employ NumbartaJ 213531 No. of Pagas including Coveraheat 3 Naw Chemicals Reported Yes QB No EE & PC Decatur REPORT ABSTRACT: (200-250 words) This abstract Information Is distributed by the Technical Communications Cantar to alert 3M*ars to Company RBD. 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 BEST COPT AVAILABLE D.Ricker-53-4 A.Welter A.Mendel Infnrrmirinn1 *nn \ * 006101 - - -- -- *3* Introduction: -a- best m m IIPS F 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 sample, extracted as previously described*, 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 xo tne 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; snowed more than 25 peaks. A peak with retention time similar to F-6309 was detected in samples IB and 3A (Table 1). TABLE 1 QUALITATIVE ANALYSIS OF FISH EXTRACTS FOR FLUOROCHEMICALS Sample IB 1M 3A FM-3422 Std. F-6309 Std. TRet7eSnt3-i-o-n---T-ime (Minutes) ** 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 006102 BEST COPY m Discussion: The above results Indicate that no volatile fluorocarbons were present in samples. The large amounts of organic fluorine mentioned in the original report4' are due to the presence of nonvolatile fluorochend cals (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 Fli-3422 are both th 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), IK-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 F-6309 (N-ethylperfluorooctanesulfonamide: C8F17S02NHEt)* As of 27 August 1979, the new FM-3923, Lot 518, will be used for preparation'of standards (identification verified4 ) 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,,r 22 May 1979.* 2Hagen, D. F., 3M Technical Report Summary "AR No. 7238 Determination Of Fluorinated Alcohols in Fish Extracts," 23 October 1979. 3Personal Communication with A. Mendel. 4Winter, L. D . , Commercial Chemicals Analytical Lab Request No. 14998, 24 August 1979. 006103 Form 8747-11-A TECHNICAL REPORT SUMMARY r\ fsr TO: TECHNICAL C0 MMUNlCA-Q0 N3 CE&TEfe Osto October 23, 1979 (Im portant -- I f report sprinted on both sides o f paper, send two copies to TCCJ Oivision i CENTRAL RESEARCH LABORATORIES, Analytical and Properties Research Laboratory 0502 Project ProjectNumber Environmental Engineering and Pollution Control Report Titift A000007 Report Number AR No. 7238 - Determination of Fluorinated Alcohols in Fish Extracts TO 238 J. E. GAGNON - 209-1S AuthOr(i) D. F. HAGEN - 201-1S Ktotibook Rtrnc Employ* Numbir(i) 042608 No. ofPasInetWdingCov#r*ht SECURITY D Opn (Company Confidential! 3 Closed iSpecial Authorization) 3M CHEMICAL w REGISTRY w 18 ( / New Chmicis Reported Yes 0 No KEYWORDS: (Select terms from 3M Thesaurus. Suggest other applicable terms.) CURRENT OBJECTIVE: Request No. A73154 Central Research Analytical Report Requestor - J. E. Gagnon Project No. 91500600 Chemical Analysis REPORT ABSTRACT: (200-250 words) This abstract information is distributed by the Technical Communications Center to alert 3M'ers to Company R&D. It is Company confidential material. The microwave sustained helium plasma detector system and capillary column with electron capture detection were utilized to examine fish extracts for fluorocarbon alcohol levels. COPY AVAILABLE Information Liaison Initials A >hi.: 006104 . FORM 2 6 4 3 -C P0 CENTRAL ANALYTICAL LABORATORY R ep o rt N o . ______ 7223____________ D a te ---------Octoker. 22 .X9J2-____ "EST COPY AVAILABLE Subject: Determination of Fluorinated Alcohols in Fish Extracts R e q u e sto r : _ _J_ * _ _ ^ & n_0_n_ ___ R e q u e st N o. .A 7.3.1^ ................. R ep ort: Introduction Dept. Nam e ________ D a ted _ A UAU_S5 _ i A 9.7.9. .......... P roj. No.A^P?? 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/lOul injection. Additional sensitivity was obtained by concentrating lOOyl of the solution as received to 20ul and Injecting 10pl of this concentrate for analysis. Operating conditions for the MPD-850 are listed below. Column System A - 6', 6% 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/min. Forty percent of the column effluent is split to the FID on the HP-7620 gas chromatograph and 60% is transferred to the MPD-850 plasma cavity via a heated 1/16" capillary line 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 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-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 (lpl) being vented to the 006105 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 deteccor. 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 lOyl injection of a 10 ppm solution of FM-3923 or CaFj7S02N(CH3> C2Ht,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 10ul 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 10yl 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 lOyl 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 CgF^SOzN (C2Hs) C 2H i,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 IM which has been spiked with known levels of these homo logs. In this case 20 ng of each species was added to lOOyl of sample 1-A and this was concentrated via evaporation to 20pl. lOyl 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 number of capture sensitive peaks. These are not necessarily hnlogcnatcd species in that a number of compound classes give a degree of F.C reponse. The arrows point out those areas where the alcohol homologs will elute as Illustrated In chromatograms 10-12-79-4 and 10-12-79-5. The capillary column-electron capture results indicate that sanplc 1-fl 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 FH-3925 or 006106 mamm m AR No. 7238 October 23, 1979 Page 3 FM-3422 species. These latter two samples do have a peak at the retention tine f of FM-3923 major isomer but the isomer distribution Is not evident In the sample : 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. Nippoldt - 201-1S 006107 BEST COPY AVAILABLE BORATOFUES ^* ANALYTICAL RESEARCH Request No. - ^ * * 7 3 ; S ' * / D iv./D ep t.___ ' '+ - P C L Project N o ..^ < 9 / * r a * / s r a * D a te __ Chemist ,c H 3 S o, 00GJ.08 BIST COPY AVAILABLE o /6~to 1 /*yJ^ / - * LABORATORIES ANALYTICAL RESEARCH Request No. ^ ^ * f D iv ./D e p t.____ ^ Project N o .__^ t c ? ~ ^ V S * Q O Date______ / Q j Joi/ZyZ^ 2 _ _ Chem ist____ / U * <t^v & * + J l ^ S 4 r y J a 7 * t t s%\ M F*1 i I r i t -2i I I 00G109 DATORI ES ANALYTICAL RESEARCH Request N o .. A -*7 3 1STV D iv./D ep t.___ * - / ? c T Project No. . q / . < r o v < r o o D a te __ Chemist j" 1* Jl li^ ^ J K ^ (L-^ctoif I* III `I l i I 1 JL*'-*e l IJ I I i i I .. II \ \ I I I 00G110 f BEST COPY AVAILABLE ; VBORATORIES A NALYTICAL RESEARCH Request No. OivVDept. _ Project N o .. D a te ___ C hem ist. A - * 7 3 / S '? ' 9/Ca</5"oo *\ lV4AA i i I i toVuJLla^ ' Q o ^ . 4 i fI I O \i ii 006111 rONM 2(44*0 BEST COPY AVAILABLE i1I:>! \! j i::j ;;I: "7 I: i:` !; \ a - / o ~ 7 9 - iT !I : : ,*;i I{!` | M-f i. --- S X/ ANALYTICAL RESEARCH Request N o .. f t - T 3 t s 4 DivVDept___^ - h ______ Project No. ? / * T A * / ~ O O D ate----------A / a / /s i / 7 i Chemist. t 20yJL . flJ AA-l-VS. '*>o>A r V0y j J ijyrW h i` I; ;| ;--a' :I F * i \\\ffi. ... i ^ i i i i i J i . l 2 .iJA.LL- j. i 006112 % BEST COPY AVAILABLE RIES ANALYTICAL RESEARCH Request No. DivVOept. Project No. D a te __ Chemist ^/jS~oV-<ro o fe" *z*^JL. `I'l i iii I L t 006113 FORM 2(44-0 I j : h la bo ra to ries ; :! II : i! ANALYTICAL RESEARCH Request No. Div./Dept. _ Project No. D a te _____ C h e m is t__ i \jj*jl I I.;I \o II Q . (T S O ^ Ki c a ^ oH ;I : J . ... r !f ,i i * r : : II : .i ! : fI i .h .O' .: If t 006114 I: ANALYTICAL RESEARCH Request No. . / l - T Z l h t f Project N o .. 9 1 C f l v r - g a Date _______ / * y / } / > 7 Chemist V * *1 \ 0 tv ^ ^1 S *- * 006115 iii -- U.-. FORM 2*44-0 BEST COPY AVAILABLE ,0 - )R IE S ANALYTICAL RESEARCH Request No. A - ic V Div./Dept. _ Project N o .. > V < T <7 > D ate________ / O / / o / 7 T _______ Chemist-------, Q m * ,, ------ --- A t="M. - 3 S 2-S' LO-sA - wQ JB "f e \-- f\ . vO-*- "2.0^>-Sl .... SP 1 ^ > M)-e A,,v^ a^ o. - ^ T M / ~rv^ o .\ A>- kft. jjtS pt w i[v. *1 - -iLuJk^ " v^ !"-'!! - i : ^ ! ! (; I : 'Jj 0G6116 --4 J-LI.IJ :T. JLI OJJ. : M i .1 I ..L . .o : BEST COPY AVAILABLE i HP RUN 4 6 ID >3W O -O B 0 HRER \ r OCTV1 2 / 7 9 HUE* rtRErt i, T in e 12*42*34 VL BEST COPY AVAILABLE 1.47 1.95 (J I -- 2.48 S. 38 6 . 14 O CD "14.36 14.34 BTTH 2T 1 0 13.38 1 4 .8 8 16.86 HP RUN 43 JS'33370-000 'BREA % O C T / 12/79 RT BREB BREB X 1.47 - 2477.. 1.32' ' 3888 1.93 121608 2.28 * 16118 . 2.37. , . ..14130 . ?. 1*26780 ` >.8.244'.. 8.373 11.977 V.387 . . ..392 12.488 TIME 11102134 006118 \+r$.. M , ; . rtrTu f - DELETE NIM" I * 3 8 . 13 3 .3 6 fi 7 0 1 8 .7 3 9 . 9 V* 10.85 11.39 13.58 14.90 ro m!. 00 6 1 1 9 ' 0 1 r1 T| t I -t VN _o N -c VX 4 [ Q STOP 06120 TEMPI TEMPI TEMPI TE"TT vu 300 300 0 300 60 66 60 1:4 .01 2.97 3.33 4.00 2.29 i/j y t -- BEST COPY AVAILABLE 5.93 | N> - J5 0 A <7 OGO l J \ 12.68 \ 006121 )