Document vypmqnd0KnQOd7Lb2GJrZavOw

AR2z26 - 1050 SELECTED FLUOROCHEMICALS IN THE DECATUR, ALABAMA AREA 5 om 22 Prepared for: am St.Paul, Minnesota Prepared by Entix, Inc. John P.Gicsy, PhD, Join L. Newsted, PhD. East Lansing, Michigan Projet No. 178401 June, 2001 1 & 1 EXECUTIVE SUMMARY A monitoring study was conducted 10 determine the concentrations of selected fluorochemicals in biotic and abiotic phases within the Tennessee River in the vicinity of the 3M Decatur, Alabama Facility. Surface water, sediments, clams and fish were collected from locations upstream and downstream of the 3M facility and analyzed for four fluorochemicals: perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (FOSA), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (FHS). Surface waters and sediments were collected from five primary locations. These areas consisted ofa location near the point of discharge oaf combined industrial effluent (3M. and a neighboring industrial facility) (Outfall), a stream that receives this combined effluent (Bakers Creek), a location about five miles downstream (Fox Creek), a location upstream of 3M Facility but below the City of Decatur Drinking Water Treatment Plant and adjacent to the Decatur Wastewater Treatment Plant, and a reference location upstream of Guntersville Dam. Clams were collected from the Guntersville location and the Fox Creek location. Fish were collected from the Outfall and from the Guntersville location. All samples were collected according to standard procedures and analyzed for fluorochemicals according to 3M Environmental Laboratory methods. Results from the monitoring study indicate temperature and conductivity differed from the reference location only in the immediate vicinity of the Outfall Dissolved oxygen and PH did not differ from te reference location. Average surface water PFOS concentrations ranged from 0.009 10 151 ug/L for Guntersville and Outall, respectively. Average PFOS sediment concentrations ranged from 0.180 to 5930 ig/ke (wet weight) for Guntersville and the Outall, respectively. However, while fluorochemical concentrations in sediments and surface waters were greater in locations downstream of the Outfall, the downstream sample locations within the main stem of the Tennessee River (Fox Creek) were not statistically greater than those upstream (WWTP and Guntersville). Only samples collected from the Outfall and Bakers Creek locations were significantly greater than those in the reference location. From these results, it can be. concluded that the effluent from the combined industrial Outfall does not significantly 2 7 affect fluorochemical concentrations in sediments or surface waters in the main stem of the Tennessee River. Fluorochemicals were detected in all fish collected from both the Guntersville reference area and Outfall. The least luorochemical concentrations were observed in fish collected from Guntersville while the greatest concentrations were observed in fish from the Outfall. For instance, at Guntersville, average whole body concentrations for PFOS, FOSA, PFOA, and PFHS were 59.1, 943, 117 and 7.50 ugk, (wet weight) respectively. For fish from the outfall, average whole body concentrations for PFOS, FOSA, PFOA and PFHS were 13320, 20.1, 1064, and 86.9 pkg, (wet weight) respectively. While there were species specific differences in the accumulationof the selected fluorocarbons into fish collected from either Guntersville or Outfall locations, these differences were not statistically significant due to the small sample size and among-individual variability. Concentrations of FOSA md PFOA in clams collected from the Outfall were greater than concentrations observed in clams collected from the `Guntersvlle reference site. However, PFOS and PEHS issue concentrations in Outfall clams were not greater than concentrations in clams collected from Guntersville, In conclusion, fish downstream of the Outfall contained greater concentrations of fluorochemicals than did fish from the Guntersville area but the significance of these differences is difficult o assess due to the small sample size and variability. 3 g 2 INTRODUCTION Entei, Inc. (ENTRIX) is providing a report on activities to assess the impactofeffluents `containing fluorochemicals from the combined industrial Oufal in Decatur, Alabama to the Tennessee River. Water, sediment, clams and fish were collected from upstream and downstream locations of the 3M Facility and were used to evaluate the magnitude of eleases of target compounds from the Facility to the Tennessee River. The objectives of the research are to determine concentrations of selected fluorochemicals in abiotic and biotic phases of the Tennessee River system in the vicinityof the 3M Facility at Decatur, Albama. ~~ Fluorochemicals selected for evaluation in this study included: perfluorooctanesulfonate~~ (PFOS), perfluorooctancsulfonamide ~~ (FOSA), perfluorooctanoate (PFOA) and perfluorohexane sulfonate (PFHS) (Append A). 3 FIELD SAMPLING 31 SiteDescription Four primary locations were selected for the field investigation (Figure 1, Appendix B). These areas consisted ofa location near the point of dischargeof a combined industrial effluent (3M and a neighboring industrial facility) labeled Outal, a stream that receives this combined effluent (Bakers Creek), a location about five miles downstream (Fox Creek),a location upstreamof 3M Facility but below the City of Decatur Drinking Water `Treatment Plant and adjacent 0 the Decatur Wastewater Treatment Plant, anda reference location upstream of Guntersville Dam. Specifically, samples were collected adjacent to the Outfal (includes Outall and Bakers Creek) that coresponds to River miles 301-302. Samples were also collected downstreamof the 3M Facility near the mouth of Fox Creek (River miles 296-297). Sediment and water were collected upstream adjacent to the Decatur Wastewater Treatment Plant (approximately river mile 303.5). Finally, fish, clams, sediment, and water were collected from a reference site above the Guntersville Dam (approximately river mile 370). To better evaluate the impact of the effluent from the Outfall, the Bakers Creek location was divided into twosub-locations, Bakers Creek1 included Stations 1, 2 and 3 that were collected near the Outfll and within Bakers 4 9 Creek. Stations 4, 5 and 6 were collected near the interface of the mouth of Bakers Creek and the Tennessee River and are identified as Bakers Creek-2. s 10 N | Bakers Crk - 5 / DeTcartiurmWeanstePwaantter Sunerile Chatanooga a Decatur _-- Decor Drainking Wate \ | \ | Tennessee River expen am a fo DiFrliowon Dicion Figure 1. Teese River ad sampling ocatonscvalsod during sy. GRuesnertvoeirr . i" Fox Creek sampling locations were also divided into two sub-locations. Fox Creck-1 included Stations 7, 11, 12 and 26/27 that were collected from the mouth of Fox Crock. Fox Creek-2 included Stations 8,9, and 10 that were collected on the northern side of the Tennessee River across from the mouth of Fox Creek. Locations and sample codes for samples collected from the Tennessee River are given (Table 1). 3.2 Field Sampling Logistics Sampling at selected sites on the Tennessee River was initiated on June 19, 2000 by ENTRIX. Collection of water and sediment samples continued until June 21, 2000. During the collection of sediments, clams were also collected. Fish collection was initiated on June 21 and continued through June 22, 2000. Water, sediment, clams and fish were collected as outlined in Enix sampling protocols (Appendix C) 3.3 SAMPLE COLLECTION 33.1 Water Collection Water samples were collected using ENTRIX sampling protocols froma total of 26 locations (Table 1, Appendix B). At each location, water quality parameters were measured using YSI Model 63 and 95 meters. Six samples were collected from the areas surrounding the Outfall, the City of Decatur wastewater treatment facility and the upstream reference location. Seven water samples were collected from the area near Fox Creek. In addition to these 25 samples of surface water, water was collected from the combined industrial effluent stream. All sampling locations were documented using TRIMLBE PRO-XRS Global Positioning Satelite technology and these locations were recorded on topographic maps. Samples were properly labeled, stored on ice at 4C, and delivered to the 3M Environmental Laboratory, St. Paul, MN. 3.3.2 Sediment Collection Sediment samples were collected from the same location, as were the water samples (Table 1, Appendix B). A total of 25 grab samples were collected from the Tennessee River. Six samples were collected from areas surrounding the Outall, the City of Decatur's wastewater treatment facility, and the upstream reference location using either a Petite PONAR dredge. Seven samples were collected from the downstream area in the 7 12 vicinity of Fox Creek. All sampling locations were documented using TRIMLBE PROXRS Global Positioning Satelite technology and these locations were recorded on topographic maps. Sediments were collected by use ofaPONAR dredge following standard protocols. Sediments were placed into labeled 250 mi wide-mouth LDPE containers, stored on ice at C, and shipped to the 3M Environmental Laboratory, St. Paul, MN. f`Traobmleth1e. TLeoncnaetsisoeneanRidviedrenitnifAilcaabtiaomnaof sediment and water samples collected Water Sample SW-01 Sediment Sample Location SED-01 Bakers Creek Sublocation Code BCRI sW-02 SW-03 SED-02 SED-03 BBaakkeerrss CCrreeeekk BBCCRRII SW-04 SW-05 SED-04 SED-05 Bakers Creek Bakers Creek BCR2 BCR2 SW-06 SW-07 SED-06 SED-07 Bakers Creek Fox Creek BCR2 FCRI SW-08 SED-08 SW-09 SED-09 Fox Creek Fox Creek FCR2 FCR2 SW-10 SW-11 SED-10 SED-11 FFooxx CCrreeeekk FFCCRR12 SSWW--1132 SSEEDD--1132 FDoecxaCtruereWkWTP WFwCRTIP SSWW--11s4 SSEEDD--1145 DDeeccaattuurr WWWWTTPP WWTP WWTP SW-16 SW-17 SED-16 SED-17 Decatur WWTP Decatur WWTP WWTP WWTP SW-18 SW-19 SED-18 SED-19 GuDnetceartsuvrilWlWe TP WwTP GTVL SSWW--2210 SSEEDD--2210 GGuunntteerrssvviillllee GGTTVVLL SsWw--2232 SSEEDD--2232 GuGnutnteerrssvviillllee GTVL GIVL SW-24 SW-25 SED-24 SED-25 Guntersville Outfall GTVL OUTF SW-26 SSWW-2277 SSEEDD-2277 Fox Creek FoFxoxCrCreeeekk FCR1 FCFCRR1I 3.3.3 Clam Collection Samples of the Asian clam (Corbicula fluminea) were targeted for collection from a location downstream of the 3M Facility and from a location upstream of Guntersville 8 13 Dam. Historically, various state and federal agencies have used clams in monitoring programs for organic and inorganic pollutants in aquatic systems, as a result, they were also included h this study. Furthermore, due to their ubiquitous distribution in the Tennessee River and their sessile behavior, they provide site-specific. information conceming the potential accumulation of fluorochemicals into aquatic biota. Due to the habitat requirements of C. fluminea, clam samples were not co-located with water or sediment samples. Clams were collected usaiPnetgit PONAR dredge. However, due to difficulties in locating clam beds as well as interference of substratum with the PONAR dredge, the collectionofclams was limited to two composite samples from locations in the vicinity of sediment samples. One sample (approximately 25 clams/sample) was taken from a location downstream of the 3M Facility (SED-08, -09, -10) and one upstream sample was collected from the Guntersville location (SED-20, - 21,- 22, -23, 24). Clams from each location were placed into labeled plastic bags and shipped on ice to the MSU-ATL (Michigan State University-Aquatic Toxicology Laboratory), East Lansing, M1 3.3.4 Fish Collection Fish were collected from two locations (Table 2). One location was in the vicinityof the Outfall and the other was located within the reference area upstream of Guntersville Dam. The fish samples were collected using both hook and line as well a gill nets. Gill nets (passive gear) were placed in the lower energy environments where concentrations of fish were generally greater. Due to the techniques employed for collection of fish, all fish caught in cachofthe sampling locations were retained for analysis. Collected fish were removed from the nets, measured (total length), weighed, and immediately wrapped in aluminum foil and stored in plastic bags. Samples were labeled placed on ice, and shipped to the MSU-ATL (East Lansing, MI) for processing. 4 CHEMICAL ANALYSIS Water and sediment samples were collected from the Tennessee River and analyzed by the Centre Analytical Laboratories, State College, PA (CLA, Report No. 023-0140; Appendix D). The analytical methods used for the water samples were validated by Centre. 9 I The methods were modified for the analysis of sediment samples but were not fully validated for this matrix. Fish livers and clam samples were extracted and processed at MSU-ATL. LOMS/MS characterization of fluorochemicals was conducted at 3M Environmental Laboratory. Summariesofeach protocol are given: TTeanbnleess2.ee SRaivmeprl.e identification and location of individual fish collected from the TSharmplelD oe _T_oGucnerasitlleionLargemouth bass SpeMicropiens uta Largemouthbass~~ Micropterus smalomomidses SSHHAADD!? ouutlal SSkkiippjjaacckk HHeerriinngg AAlloossaa cchhrryyssoocchhiioorriiss SSHHAADD3 SHADS Ouuatllll Outll SSkkiippjiaacckk HHeemrtriinngg ~~ lAloossa cchhrryyssoocchhllrriiss Skipjck Hering~~ Alosa chrysochloris SSHHAADDS? Ouulilll SSikdippjiacckk HHeerriinngg~~ AAlloossaacchhrryyssoocchhiloorriiss WSPHIADS We2 uuttaa SkiWphiiatcek PHeerrcihng AMloorsoancehraymseorcihcloarnias Oudall White Perch Morone americana CCcAATT!2 GuGnunetresrivillllee: CCaattffiisshh IIccttaalluurruuss ppuunnccttaattuuss CCAATTSS Qouuitlal CCaattffiisshh GARI Guntersille Gar tIeatualruunuss ppuunnccttaattuuss Lepisoseus sp. GGAARRY2 GGuunnetresrwviillllee: GGaarr GARd Gunrsille Gar LLeeppiissoosstceuuss sspp. Lepisosteus sp. GGAARRGS sB1 OOuuttalll Guntersvlle GGaarr Striped Bass LLeeppiissoosstteuuss sspp.. Morone sats S8823 sB4 GGuunnttressivlillee: Guntersville SSttrriippeedd BBaassss Striped Bass MMoorroonnee ssaaxaatillss Morone saxailis sSB8s6 S87 GuGnutneterrssiillllee: Guntersvile SSttrriippeedd BBaassss Striped Bass MMoorroonnee ssauxxaattllss Morone saxatls B8Y8 GGuunnetresrvsivllllee SSttrriippeedd BBaassss MMoorroonnee ssaaxxaaitllss SBBIIO GGuunnteerrsvviilllee SSttrriippeedd BBaassss MMoorroonnee ssaaxiaillss sBB1I23 GGuunntteerssviillllee: SSttriippeedd BBaassss MMoorroonnee ssaaxaattillss SSBBIM Guunmterrsiwlillee SwStpreipdedBBuassss MMoowrnoensswaaitlss 10 1s 41 Water Analysis Water samples were initially treated with 200 pl of 250 mg/L sodium thiosulfate to remove residual chlorine. Solid phase extraction was used to prepare the samples for LC/MS/MS analysis. A fort-millliter portion of sample was transferred to a Cig SPE. cartridge and the cartridge was cluted with S ml of 40% methanol in water. The eluate was discarded and the SPE column was eluted with $ ml of 100% methanol. The eluate was collected for analysis by LC/MS/MS. This treatment resulted in an cight-fold concentrationofthe samples. 4.2 Sediment Analysis For sediment samples, a 5g portion was extracted into ml methanol. The extracts were filtered and diluted to final volume of 40 ml with ASTM Type I water. The diluted extracts were then treated in the same manner as the water samples, beginning with the solid phase extraction. Sediment and water extracts were analyzed by use ofa Hewlett-Packard HP1100 HPLC system coupled to a MicroMass Ultima MS/MS. Analysis was performed using selected reaction monitoring (SRM). HPLC conditions and MS/MS methods used for analysis and instrument parameters are given in the procedure described below. 4.3 FishLiver Analysis Fluorochemical surfactants were extracted from fish livers using an ion pairing reagent and methyl-rert-butyl ether (MBE). Details of the analytical procedure have been outlined in 3M Environmental Laboratory (St. Paul, MN) standard operating procedures of the analysis of fluorochemicals in tissues. The title of the SOP is: ETS-8-60, "Extraction of Potassium Perfluorooctanesulfonate or other Fluorochemical Compounds. from Liver for Analysis using HPLC-Electrospray/Mass Spectrometry". Briefly, fish were thawed and livers were removed, weighed and then homogenized in HPLC grade water. An aliquot of liver homogenates were spiked with a sumogate standard and then 05 M tetrabuyl ammonium hydrogen sulfate (TBA) and 025 M sodium carbonate/sodium bicarbonate was added to each sample. Five ml methykert-butyl ether was added to cach tube and the sample was capped and shaken for 20 min. The samples were then centrifuged for 25 min at 3500 rpm and 4.0 mi of the organic layer was n 6 transferred to a fresh tube. The extracts were evaporated under nitrogen gas to dryness then reconstituted in methanol. The methanolextracts were then passed through 0.2 ym nylon fillers into glass autovials for chromatographic analyses. 4.4 Whole Body Fish Analysis Perfluorochemicals and other fluorochemical surfactants were extracted from whole fish tissues using an ion pairing reagert and methykert-butyl ether (MBE). Detailsof the analytical procedure have been outlined in the 3M Environmental Laboratory (St. Paul, MN) standard operating procedures for the analysis of fluorochemicals in tissues. Briefly, whole fish were thawed and then homogenized in a Hobart grinder. The homogenates wee placed in kChenTM bottles and stored at -20C until chemical analysis. Whole fish homogenates were weighed and then further homogenized in HPLC grade water. Aliquots of tissue homogenates were spiked with a sumogate standard and then 0.5 M tetrabutylammonium hydrogen sulfate (TBA) and 025 M sodium carbonate/sodium bicarbonate was added to cach sample. Five ml methyktert-butyl ether was added to cach tube and the sample was capped and shaken for 20 minutes. Following the shaken period, the samples were centrifuged for 25 minutes at 3500 rpm and 4.0 mi of the organic layer was transferred 10 a fresh tube. The extracts were evaporated under nitrogen gas to dryness then reconstituted in methanol. The methanol extracts were then passed through 0.2 pm nylon fillers into glass autovials for chromatographic analysis. 45 ClamTissue Analysis Clam tissues were extracted with acetonitrile followed by a solid phase column cleanup ofthe extract. Briefly, frozen clam tissues were thawed and the tissues were composited and homogenized in an Omni homogenizer. A S gram sample was weighed a 50 mi polypropylene tube and 15 mi acetonitrile was added. Samples were shaken for 30 min and then centrifuged for 30 min at 3500xg. The supematant was passed through a column of Florisil and activated charcoal and the eluate was collected in 50 mi polypropylene tube. The column was eluted with 15 ml methanol and both eluates were 2 17 combined. Two drops of octanol were added 10 the cluate and then the sample was. reduced to near dryness under a flow of nitrogen gas. The sample was resuspended in 1 ml methanol and passed through a 0.2 um nylon filter into autovials forchromatographic analysis. 5 QAQC Standard operating procedures for sample collection and preparation were maintained during the entire project. Proper QA/QC samples, as required by 3M, were collected in the field (Appendix C). Two field matrix spikes and two field control samples were collected. water and Field spiking mwaittrhix20soprke1s00soullutofioans10weprpempsrteopcakresdolubtyiocnolcloencttaiinnginognePFliOte,r of site FOSA, PFOA, and PFHS to yield 200 and 1000 ppt solutions, respectively. The same procedure was followed samples. All to spike ome samples were liter of shipped distilled water under ENTRIX to prepare the field spike chain of custody forms and control a field book was used to document conditions and activities. A field camera was used to document all locations and to provide a visual recordofthe conditions of the sit during the sampling events. In addition, ambient water quality parameter, such as temperature, conductivity, salinity, pH and dissolved oxygen were measured at cach location during. each sampling event. Since the method detection limit (MDL) and limit of quantification (LOQ) are analyte and matrix specific, method and matrix blanks along with matrix spikes were used to determine accuracy and precision of the extractions and final chemical determination matrix spike recoveries Woartefroranpdursietdyimoefntthceoncfeunotrroacthieomniscwaelrestnaontdacrodrsr.ecteFdisfhor either tissu fluorocarbon concentrations were reported as wet weight and were not converted toa dry weight basis. 6 STATISTICAL ANALYSES SUtSaAti)s.ticaGlenaenraallyselsinewaerremodperlesfor(mPeRdOCwitGhLMS)ASwer(eVeursseidonto8,teSstASforIndsitfitfuetree,ncCeasraymoNnC,g locations for all endpoints measured in the study. If values of F tests indicated a significant difference, Tukey's HSD test for multiple comparisons was used to compare meansof the different locations a 8 7 RESULTS 7.1 Water qualityparameters Water quality parameters Appendix E and F: figures of 1a, river water 1b, Ic, and from each location are reported (Table 3, 1). Dissolved oxygen and pH were variable within the study, however there were no significant differences observed between values measured in waters collected from the Outfall or Bakers Creeks and those from upstream or downstream locations. Conductivity and temperature measured at the Outfall and within Bakers Creek (BCRI) were significantly different from the upstream and dfioowmnstBraekaemrssaCmrpelceklo2catisoanms.pleHsowaenvder,thothseerecwolalsecntoedsigfnriofmicaenittdheirffetrheenceupbsettrweeaemn that and downsiccam sampling locations. This result indicates that the effect of the combined industrial effluent on water quality parameters was limited to a small area near the Outfall. TRiavbelre, i3n. thWeaDteecratquuralAitlyabpaamraamearteear.s Vfoarluseasmpalreesrecpoolrlteecdtedas fmreoamnsthaenTdenStnaensdsaered deviations Location DO (mg/L Conductivity (umhos/cm) Temperature CQ) pH Gu Guntersville 76 192.8 29.0 82 wwrp 038) (54) 03) (04) 100+ 1847 203 88 wy) G4) 3) 02) Outal 65 4650+ 32+ 72 Bakers Creek-1 (7i.7)5 (11874439.30)+ 3[0)7% 73.7) Bakers Creek2 0960) (41603890) 2606) o5n0 Fox Creek-1 08.1 1@799.)0 02278) 83.2) Fox Creck-2 a838) 1612)7 2738) 532) Signy Wren om Gamer Reso WR 00 9 A 7.2 Fiuorochemicals in Surface waters Fluorochemicals were detected in all surface waters collected from the sample locations in the Tennessee River (Table 4) (Appendix F: figures 2a, 2b, 2c, and 26). The least concentrations of all measured fluorochemicals were observed in samples taken at Guntersville while the greatest concentrations were observed at the Outfall. In increasing order, the concentrations of PFOS, FOSA, PFOA and PFHS in surface water was as follows: GTVL < WWTP < FCRI < FCR2 < BCR2 < BCRI < Outfall, Concentrations of surface water florochemicals at only the Oufall and Bakers Creek 1 locations were significantly greater than those measured at Guntersville Reservoir. TTeanbnleess4e.e RMiveearn incontcheentDreactaitounr,ofAlfalbuaormoachaermeiac.alsCoinncesnutrrfaatceionwsatemresanosf atnhde standard deviations Location (FgFLO)S FGOgS)A PFOA Gl) TRIS el) Guntersville 0000029) 00.00024) 0.008 0.005 wwe 00o5133) 00001256) 00.002068) 00.00066) Outta 150.500 778) 7.985% 148) 190000 00) 4270 (1.697) Bakers Creek-1 ~~ 82260% (56.672) S420 G.o74) 103600 T1264) 23740 (14665) Bakers Creek-2 @133.s8n3)8 L0129414) 612198.327)5 4034 (0575) Fox Creek-1 [052) 00.012629) 2661447) [1022) Fox Creek-2 01.11709) 0003535) L4o4o1t) 0.111648) * LcSiomnticteaontmfraeqtuiyaonntAsafrfteeiprooenrnttoedrfbolelmlohGworutohncehtLeOmeiQrcaalResesewseatritvmeaatreDsa.t02350.p0L5. All forochemical Additional statistical analyses were conducted on fluorochemicals in surface waters to further examine the difference between sample locations (GTVL, WWTP, BCR2, FCRI, Js 40 and that FCR2) located within the Tennessee both the Outfall and BCR could be River. Resul influencing th t s from results the of fist analysis th statistical showed analyses by acting in a manner similar to that of an outlier. For instance, the concentration of PFOS at the respectively, Outfall and BCRI were approximately than the concentration observed at the 17,000-fold and 9,700-fold, greater, Guntersile locaton. Removal of the Outfall hypothesis and that BCRI samples there were no from the analysis allowed for the statistically significant differences evaluation ofthe in fluoochemical concentrations within the main channel and near shore locations within th river. Results from the second analysis (Table 5) show that for water concentrations of PFOS and PFOA, only BCR2 was statistically greater than Gunersville Reservoir concentration. Furthermore, while the concentrations of FOSA and PFHS at BCR? and FCRI were significantly greater than Guntrsville, they were not significantly diffrent from the furthest downstream location. Thus, at FCR2, the furthest downstream locaton, the concentration of targeted fluorochemicals was not significantly diffrent from that observed at Guntersville Reservoir, which was selected as an. upstream reference location. "Table 5. Tukey's range test results for surfuce water fuorochemieals taken from within or near the main channelofthe Tennessee River* Sie PROS FOSA PFOA PRIS BCR FCRI AA 8 B aA a 8 B FeR2 B BC B c wwe B c B c GTVL B c B c Siteswiththe sameTeer aenor igmeantyGeren ta 005 From these results, it can be concluded concentrations of uorochemicals further that the Outfall does not downstream than FCR2. significantly In addition, affect there were no statistically significant differences in the concentrations of fuorochemicals 21 2 within the main channel of the river immediately below Bakers Creek as compared to those measured at the reference location. 7.3 Sediment concentrationsoffluorochemicals Fluorocarbons were detected in all sediments collected from the study sites (wet weight Appendix F-figures 3a, b,c, d and dry weight: Appendix F-figures 4a, b, c, d). Er 22 TLoacbatiio6nMesnconcenPtOrSioTnWoeflfwoFOrSsuAchmmsemciPosOncAeenmmeonksemnSrom he TpenrnoesssDreyRwiveeiFrgOnhStshAeediDmeentccaPRoAOnbNcbaesntsesP"ES | Gumerle GOhI n w0eld oon G0%k om G0e0Fo g0eBl) om) G0emd Goehko 00 o0em oo wwe 008%) 00s0 0o0m) 0o0m) 1)m e0%h 0o0l ooios { out SO0H)0 0200) 618055)00 IGS20O)N 1G6e0e00)0 2o550m00 SG 000 o 287500 BnCrokl SOSELT) 230602) G2a0ss0) @4R1000y W(iGs2e)r OSsmiI) s(rieey Teesrn | BienCosk2 9112200) GS6039) E6 BON 0l8e ammeets (mooly Gmlaorw (eios) | Face w2sn a0 w mem eomm easm aame aane oomm) FxCrk2 0%000o9s 0omm) TS em Gate eros ost 020m 0os oiim opp CLoimtconrqainagrensinentwianba s htsons0308ashghegsntsigh, Al aes pad lo fe LOGwesos "3 Le Least concentrations of fluorochemicals in sediments were observed at Guntersille vRiecsienrivtoyoifrtwhheilOeuttfhaellgr(eTaatbelset 6c).oncentrations were observed in sediments collected in the Concentrations of fluorochemicals in sediment decreased in the following order: GTVL. < WWTP < FCR2 < FCRI< BCR2< BCRI< OUTF. For PFOS and FOSA, only concentrations in sediments at the Outfall and BCR locations were significantly greater than those collected from the reference location in Guntersville Reservoir. In addition, concentrations of PFOA and PFHS in sediments at the Outfall, BCR1 and BCR2 were significantly greater than concentrations in sediments from Guntersville Reservoir. However, the fluorochemicals in sediments at BCR? were not significantly different from concentrations measured at WWTP, FCRI or FCR2. When sediment concentrations of targeted fluorochemicals were evaluated on a dry weight basis, only concentrations at the Outfall and BCRI were significantly different from those measured at Guntersville Reservoir. As was done with the surface water data, statistical analyses were conducted that examined only the Tennessce River channel sample locations (GTVL, WWTP, BCR2, FCRI, and FCR2). Results from the second setofanalyses showed that only the BCR2 concentrations of targeted fluorochemicals were greater than those observed at Guntersville Reservoir reference location on both a wet and dry weight basis. Thus, `while concentrations at the Outfal and within Bakers Creek were statistically greater than the reference location, concentrations in sediments downstream of the 3M Facility were not statistically greater than those measured at the upstream reference location. The resultsofboth of these analyses indicated that that there is litle accumulation of the target fluorochemicls in sediments downstreamof the Outfal, 7.4 Fish Mean length, whole body weight and liver weight data for all fish species collected from the Tennessee River in the Decatur Alabama area are given (Table 7, Appendix G), 2U " S `tSThaaembpTlelene7n.IeDse sMeeeaRnivleerna (g(CtCoho,llllweeeccittgeehddtr o,onnan00dT66/e2l2n1i1vg//eh00re 00w--e0i60/g62h22tW/2e0f0i0o0gr)e h)'ft.is_h collLet citveedrwfirom C EE Location (d cm) @ Ouall 2 ast 202 SHAD outa 3 6) 352 [2] 195 0985) wel Outall 168 76 042 cat Guntersville: 036) 2s 3a7n6 0506% Outall en) as an) 6592 18) 68 GAR Guntersville 20 G1 84 765 6 64 Outall 625 a7) @3) 483 4607 36 sB Guntersvlle 63) A704) 23 168 9) Lot --_a--ls src means with standard deviationsa(iin p)arenthe0 ses)556) 0 034) Due to the small sample size and large amount of variability in the endpoints, there were no statistically significant differences between the sites for species common to both the Outfall and Guntersville locations. 7.4.1 Concentrationsof PFOS, FOSA, PFOA, AND PFHS infish livers Fluorochemicals were detected in all livers removed from fish collected at both the `Guntersville and Outfal locations (Table 8, Appendix H). The least liver concentrations for all measured fluorocarbons were observed in fish collected from the Guntersville location while the greatest concentrations were observed in Outfall fish. Average for PFOS, FOSA, PFOA, and PFHS liver concentrations for all fish collected from the Outfal were approximately 19-fold, 340-fold, 109-fold and 710-fold greater than those observed in Guntersvile fish, respectively. 5 A Average liver concentrations for PFOS, FOSA, PFOA, and PFH for all fish collected at the Guntersill site were 1036, 22.0, 22.1 and 3.79 g/kg, wet weigh, respecively. TTeanbnlees.seeLiRvievrercoinnctehnetrDaetciaotunro,fAslealbecatmead afrleau.or*ocarbon in fish collected from the GSupenctieerssvile Nekm)os TSGekAD) mo ke)A GAem Catfish 2 @872.23 52003) 18.8" 3.75" Gar 4 (2189539) 2(019645) 188 (415658) SwipedBass 9 1736330)0 219 a0) 27 76) 378" Largemouth Bass 1 643 188 188 375" OuCtattafnish 2 10085 uLs 2529 302 Gar CTY) 09) 13) 2 18920 S090 1935 ese 2565 Shad GOL) G79) E27) 99) 5 os2 4400 99 129.1 Whitpech (132522) @0473) 2 492850 174030 @90) 16285 (453) 20695 Largemouhbass | GI6577) (4695) (12282) 271430 24560 375 (1941.0) 16 $7CRoenkscuelnfttorrwaetPriHeonSrsp.aorrAltrlcedtpoharsetrhevdealiuemmsiebaoenflsqouwandathneotLniOd:Gaa1e8d.3seukvagatkse.fdovPuFeOsS, FOSA, PFOA and 3.75 "Numberoffish nalyzed. Differences in liver fluorochemical concentrations were also observed between fish species collected at Guntersville, Liver concentrations for the selected fluorocarbons increased in the following manner: PFOS Catfish < Gar < Largemouth bass < Striped bass FOSA: (Largemouth bass)< Catfish < Gar < Striped bass PFOA: (Catfish = Largemouth bass) < Gar < Striped bass PES: (Striped bass = Catfish < Largemouth bass) < Gar 26 2 The fish in Except for parentheses indicate PROS, there were liver fluorochemical concentration below no statistically significant differences in the LOQ. flurochemical liver concentrations between fish species collected at Guntersville, For a 160-fold difference between catfish that had the least concentration PFOS, there and striped was. bass with the greatest liver concentration. FOSA, PFOA, and PFHS liver concentrations in rfeissuhltfsroamndGuantterruseviulnldeerwsetraendaillngleosfs tthheanmtahgenirirteusdpeecotfivteheLoObQsse.rveTdhedisfifgenriefnicceasnacte hoifsthseistee are unknowna this time du to the variability in the data and small sample size. Average liver concentrations for PFOS, FOSA, PFOA, and PFHS for all fish collected from the Outfall location were 15.692, 7,195, S81, and 384 spectively. As was observed at the Guntersvill site, differences in pgkg wet weight, liver fluorochemical concentrations were also observed between fish species collected at the site. Liver concentrationsofthe selected fluorochemicals at Outfall site increased as follows: PFOS: FOSA: PFOA: PFHS: Shad < Catfish < Gar < Largemouth Bass < White Perch Largemouth Bass <Shad< Ga<r Catfish < White Perch Largemouth Bass < Shad < Catfish < White Perch < Gar Largemouth Bass < Catfish < Shad < Gar < White Perch Except for PFOA, there were no statistically significant differences in species specific liver concentrations of the selected FOSA, and PFHS there were 5.4, fluorocarbons for 7.1 and 178-fold fish from the Outfall. ForPFOS, differences between the least and eratest liver concentrations. However, due 0 the smal sample size and large amount of variability observed in the data, these differences were not statistically significant. For PFOA liver concentrations, therewas a S16-Tod difference between the least and greatest concentration. However, oly shad and gar liver concentrations were significantly different. Largemouth bass was not included in the analyss due to the fact that there was only a single value for this species. The magnitude and significance of these differences is unknown a his time due tothe variability in the data and small sample size. 27 = F7l.4u.o2.rochWehmoilceaflisshwecroencdeenttercatteidonisnoafllPfFiOshSc,olFlOeSctAe,d PfFroOmA,boathndtPheFGHunStersville and Outta locations (Table 9, Appendix 1). Table 9. Whole body concentrations (wet weight) ofselected fluorochemical in fish collected from the Tennessee Rimveor sin the Tosa Decatur Alabama arema,o*R mE Species Guntersville NE (pg/kg) (ug/g) (g/kg) (g/kg) Catfish 2 75 wr 201 78 Gar 4 (1155.21) " 201 " StripedBass. 14 65.6 10.4 8.03" 1.8 @32) (0.96) Largemouth Bass 1 230 8.76 8.03 7.5 OuCtattfaish Gar Shad 2 1190 (170) 2 1863 (1679) 8 ND Whiteperch 2 ND ND 1196 14 ND (140.6) (5.52) 1545 355 ND (40.3) (25.0) 540 389 @2) 02) ND 275 405.5 (69.3) (129.4) Largemouth bass 1 ND 557 201 7.5 Concentrations are reported as means and standard deviations. "*fNoNDRruesPsmiurbgloetansir.fowiefsriehchrteatnphaeloycrzoaetmsdptehodeunldimiitorefsqeunanttibfiucaotitonq:7.u5 agn/dkgdafeo r PFOS, FOSA, PFHS, othe dota no meting 8.0 us 3 ug h kg . contol err. The least fluorochemical concentrations were observed in fish collected from the `Guntersill location whi the greatest concentrations were observed in fish from near the Outall. Mean POS, FOSA, PFOA and PFHS concentrations for all fish collected 28 2 from those the Outfall were approximately 23-fold, measured in Guntersville fish, respectively. 2fold, 9fold and 12-fold greater than Mean whole body collected from the concentrations Guntesvile site for PFOS, were $9.1, FOSA, PFOA 9.43, 11.7 and and 7.50 PFHS g/kg for wet all fish weight, respectively. observed with Species differences in whole body concentrations increasing as follows: concentration at the sie were also PROS: Cat<Gfari<Stsriphe bas<s Largemouth bass FOSA: Catfish= Gar < Largemouth ba<Ssripsed bass PFOA: Largemouth bass = Striped bas<s Catfish < Gar PHS: All species cqual due to being at LOQ wDhuoeletobtohdeyscmaolnlcesnatmrpalteiosnizfeo,r tthheerespweecrieesncoolslteacttisetdicaatlltyhissigsniitf.icaFnutrtdhiefrfmeorrenec,esexbceetptwefeonr PROS, there fuorochemical was less than concentration a in 3-fold difference between the species being evaluated in the this least study. and greatest For PFOS, there was a concentrations. 30-fold difference between the catfish and the largemouth bass Mean whole body concentration for PFOS, FOSA, PFOA and PEHS for fish caught at he Outfall were 1332.0, 20.1, 106.4, and 86. 9 ng/kg wet weight, respectively. As observed at the were Guntersville also observed location, between dsipfefceireesnccesauignhtwhoonlesitbe.odyWhflouloerobchoedmyiccaolncceonntcreanttiroantsioonfs fluorochemicals in Outfall sit increased as follows: PFOS: FOSA: PFOA: PFHS: Gar < Catfish (Shad, White perch, Largemouth bass) Largemouth bass (Gar, Catfish, Shad, White perch) Largemouth bass < Shad< Catfish < White perch Largemouth ba<Castfissh= Sh<Wahidte perch 29 2+ The species listed in the parentheses were not quantified during the analyses and could notbeevaluated in this report. As with the Guntersville fish, small sample size precluded any statistical analysis of the data to evaluate differences between species at the Outfall location. Thus, while these data show that there are differences between locations and between fish in cach location, the small sample size precludes an evaluation of the significance and magnitudeofthese differences. 7.5 Fluorochemicals in Clam Tissues Fluorochemical concentrations were also measured in clam tissues collected at both sites (Table 10, Appendix H). PFOS concentrations did not differ between the sites and ranged from 15.6 pkg to 14.1 ugg wet weight at Guntersville and the Outfall, respectively. In contrast, there was a 428-fold difference in FOSA clam tissue concentrations with 25.1 ughkg and 1074 pgke, wet weight, being measured at `Guntersville and Outfall locations, respectively. There were no significant differences in the concentration of PFOA and PFHS in clam tissue collected at cach of the two sites "The results of the clam analyses reflect the areas from which the samples were collected. Due to substrate problems, Outfall clams were collected at the Fox Creek location. This location had surface water and sediment fluorochemical concentrations that were statistically similar to those observed at the Guntersville location. Thus, these results indicate that for at least clams, the environmental concentrations of fluorochemicals downstreamofthe Outfal are comparable to background levels in the Tennessee River. 30 Ls cToalblleceted10.fromTitshseuTeemcnoenscseneteraRtiivoenrsinoftheseDleeccatetdurfAlluaobroacmhaemairceaa.ls in clams ~ PROS FOSA PFOA PFS Location Guntersville (ugk) 156 (nee) BI (ugke) oF (nghke) 09367 Outfall a143.1% 1A037594) 8(.74.1288) 005337) TTCoCnoLcniemcniettnrsraatotifoinoqsnuasentppirotaerteiimodin:ebel13os8wmeLauOngQshsgsanedfsosratniPdmFaaOtrSed.ddFveaOvlSiuAeos,nsP.FOA, 375 ugg for PFHS. 8 REFERENCES Hans(ePnF,OS)K,J.perafnlduorHoOo.ctanJeohsnuslofno,nyl2a00m0i.de Determination (FOSA), and peorfflpueorrfoloucotraonoocattaen(ePFsuOfAo)naitne m`waastesrsbpyecltirqouimde-tsroyli(dHePxLtrCa/cMtSio/nMaSn)d. hi3gMh-EpnevrifroornmmanecnetalliqLuaibdocrhartoomryatmoegtrhaopdh,y/ntuamnbdeemr ETS-8-154.0. 3M Environmental Laboratory, St. 1958, E01-0520. Paul, MN. LIMs Report numbers: E00-2361, E00- 26 31 9 APPENDICES AppendiAx. mStornuicttourreed ainndwatcehre,misceadlimecnhtaraacntderibsitoitcas ofoftheseTleencnteedssefeluRoirvoecrheimnictahles Decatur Alabama area. Appendix B. Water and Sediment locations within the Tennessee River study areas Appendix C. Water, sediment, clams, and fish sampling protocols Appendix D. fCleunotrroecAhneamliyctailcsalinLwaabtoerrataonrdiessedainmaelnytt.ical report for the characterization of Appendix E. Water quality data collected at sample locations. Appendix F. TMoapposgraipnhcilcudemapwsaotefr sqaumapllietylodcaattai,onswaitnetrheoTrensneedsismeeentRivfeurorsotcuhdyemairceaa.l concentrations for sample locations Figure 1. Water quality parameters FFiigguurree 32.. FFlluuoorroocchheemmiiccaallss iinn ssuerdfiamceentwsa,tewrest weight Figure 4. Fluorochemicals in sediments, ry weight Appendix G. Physiological data for fish collected from the Tennessee River. Appendix H.. fFlruoomrtohceheTneincnaelssseceonRcievnetrraitniotnhse Diencafitsuhr lAilvearbsamanadarccla.am tissues collected Appendix I. W`TheonlneessbeeodRyivefrluionrtohceheDmeiccaatlurcoAnlcaebntarmaatiaorncas. in fish collected from the 2 32 APPENDIX A StheeleTcetnendesfsleuoeroRicvheerm,icDaelcsatmuorniAtloarbeadmainarweaat.er, sediment, clams, and fish collected from Chemical Name: MMoolleeccuullaarr siotnr:ucture: Perfluorooctanesulfonate C9aF9irSOy QI CoFpS--0 0I PFOS Chemical Name: Molecular structure: Molecular ion: Perfluorooctanesulfonamide CsFisSO;NH; 498 q I CaFip--NH, 0 FOSA Chemical Name: Molecular structure: Molecular ion: Perfluorooctanoate CHFisC00 a3 Cro? n PFOA MCohleemciuclaalr Nsatrmuec:ture: Molecular ion: Perfluorohexanesulfonate [ER 399 0I CaFS--0" o PEHS 33 APPENDIX B LRiovceart,ioDnecaantduridAelntaibfaimcaa.tionof water, sediment and clam samples collected from the Tennessee Water Samples Sediment Samples Clam Samples Locations -- Latitude/Longitude Sswwat SESEDD-0021 SW.03 SED.03 BaBkiekerrssCCrreeeekk Bakers Creek NNIE3I822898410624690"" WWE7T0012 93.701B9T905"" NI 38 20.53395" WAT 01 7.65374" sSwWo0s1 SSEEDD-0s4 Swaos SED.06 BBaakkeerrssCCrreeeekk BakersCreek NNI3E338 22868462840801"" WWEETT0011 75.44526378639"" NAF40 3340841" WAT020033515" SswWaAo07DUP SESDE0D.706DUP SWox SED.08 Mussels. BFaokxerCsreCerkeek Fox Creek NNIIPE 440133593.007540870"" WWEST 0066 03234.03920077"" sw.09 SED-09 oMuusenls- Fox Creek NIEAI ILT6T67" WET05 $7.66518" sw-10 SED-10 oMususells. Fox Creek NEI 2878044" WET05 49.7688" swt SED-11 oul SWIIIPMSI SED1IFMSI FFooxx CCrreeeckk NI 40 14.5485" WET 06 3.16910" sSwWARMS? sep12 SW-2DUP SED.12DUP FFooxx CCrreeeekk Fox Creek NIE 40 2397538" WET 060831686" Sswwaiy SSEEDD-1134 Swiis SEDI DDeeccaattuurr WWWWTTPP)) Decatur (WWTP) NN33#&3377 2391783324688"" WWETT 0000"00207358163181"" N3# 37 3267310" WT" 00 05.3064" sswwae7 SSEEDD--11T6 swag SED18 DeDcecaattuurr ((WWWWTTPP)) Decatur (WTP) NN334#3377 351.8116009786"" WWTA" 0000" 0088..946650957"" N337" 7.13274" WS 00 14.65060" SRWa-InSDUP SEDSE-D1.9IS.DUP sw2o SED-20 Mussels- GDuencaetrusrei(lWeWTP) Guntrsille NNIEC 330022048483365553"" WWAGG"" 1100 41823074420393"" swai sep-21 GMuunstseelssi-ll|e? Guntesville Guntersvill N30 2328174" WE105161750" swaz sep22 GMuusnseerlssi-le? Guntesville NI 302020578 WEE" 10 54.9906" swas sep.23 GMuusnsteelrss-ile? Guntersville NI 30 16.66486" WEG" 10 56.85539" swas seD24 GMuussnetlse-r? Guntersille NIE I0ISISIIS" WAG 10 5436650" sswwaes sesEpD2-275 F3MoxOuCrteaelkl Fox Creek NNIIEE348029233239007905"" WWATT 0052 40362298159493"" NIE 40 1380610" WET 05 4403756" SSWW.SFSCCsS2 SW-FB0L Qa/C Qnnaiec * MMuusssseellss ccoolllleecctteedd ffroomm tthhee vViiceiniittyyooffaeacchh sseeddiimmeennttUswaamtpelre,sampling Tocation downstream of SVT OWE 34 APPENDIX C StSanMDdaerWtdaeptererSsSauimmopplgiiPnnrggocTeidpure TLhoerpuRorossoEfissSandu periProce (SOsboprovidedecalsfore cllcion ionsSftCehwOaeetPresErupessingeria MoawsftooerrrckcFpalllexcsiapenordisoQtfalwttiicpsuesmpnamoerps.ioPmSaepctecocmipeparsnabpp leiunnite . Thiss Se OP.`outlis nesthe S`cWbeoaivtmneepgrsapalrrmopeeplrerrsiias.toeeTfdhleoesrsiiehgenussenddweerip iiiapehSreileplt.uOypTsohhiPmbepbdlaesdokieevlifgceewssvtbiatMicansottemrssehnoopp innpt oo uorspyme Acaosbsriheinsoegnhwledlrtdseiopeislvupmecrooonvmtarehsehcehihnattecubroelinyhece.yvwcTesirheeelseheiudanvatblc is.nohpAcstomodewospwonrsriomonemtostfsn rveeopeBse oo nhinan Se Wilh achamps omiesn kofcomet EiEpQOmUneIenPoMtnEuNdTsasnplipn rcsepderdmeaiypncpslde,fbltlacrie n tee rheeFod dllow:ice vt le + eDmipnrea,sDo0,peyoaieddtlrsuYlSyMcamapingbrns caple of cing + SaM mpleca oinss andposl lssmeiti chowmtpn rFeorsnipl se + imekmsredsidsn,1hFldoCemcOhCosmoehn,m,diencdolttteodn tbihiaevndne1 asse lev fo ship, ig: R+E Peron PrtciveEqpentFFE ---- iedby escHs nd eet Offic, ae lrobyrrtctodtdtr hehceacwctheodrye .tlquaSlloioftgyniepefsoendidewpiaatremrssectasphrEs,sdpdtlicfootrnemd.feTdhmiaetseeswidlbeeedneeplsoeyedito be Werte Tempore) + Dietoxygen) + Conic (mbosm) MS Word 97 , 5 Seliiy C1) PG rIneqsuiormeed.iWnasttaencregs,ultihetyclmlceiotn0eocfoarldledscotnasd!dviantse) pqauraalimteytpearrsamwieltlerbse amddyedbessvernrdteedd or P1.R`OOWbCotrEakiDnPUtaRhneE.SsThuimspmalyobcaetionnitnhfeorfmoartmioonf afnoamctiuatlecrootrdhinsactoepeo-rofa-dweosrckr,iwpotrikonuotfltihne,oenrtehre 2. aPlsoawsmatpyolsinnwtgohlreokscaatmfipoolnimntghbeumrgosotrdboowantsotvreeratmheloscealtecitoend1samtphleemlootsitonu.psTtrheamfiellodccaroenwshlouelsds 3. Olontohcceaertywoionsuedaedviireeccataetdtitohenpsroepneriiloecdatoonntmeeassaumrpelianngdlroegc.orddepth ofwaterandrecordsample 45..MsMaaetkaeesliustreuesrtthyehstsaamlaptllndiaentrgaemclsooh)rcedaettsoacnmospmlrieenscpootnoedrbtieonsttahatevcoeansoiartbheleesseaacmmphpllniilnnogggilyofc(agtolnobal positoring. 6. Aacnofldlrercewtceaodrrdamendud.pTaanhnyedodcteahlpeitrbhrraeotfqiuroienraedomifentnhgtesssofhifoeluhdlemdesrtteeeflrsespctwechaeirdeeqwpoutrhaky1pwlaphna.ircnhtweartsewsialmpbleemseaes.sed 7. 8. TWthuaebtisenprgedcseiapfmiepcnledtssypwoeinlatlnhtdehdseeabepeofcbooflilseacnmtpedfloeusisnagbmepalnciosnlplgpercsothpeodruilsdtbeepoubtpaiwnietd.h pre-leaned tubing The leoafthis 9. Wheeaadvies tchoetmuebliyngsttuahedrthoduesggnithed lot on the pump. Make sue thtthe peril: 10. 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Obs anewsection of MS Word 97 8 36 `PSettSaitndPeaornddaOrp3eiordraStEmiocnklgaeaSPaurnmonpcDelrditeundrggee Forthe 3MDecaturSampling Trip 10 PURPOSE oTsefahtmesapupllruifanhapgecodesgeseevenidoecirfemasetl.iasmAteslSttbhiaoonudndsgaehrredtqOheupierreednaiePn0secgcooPfrPlsoatcaemsdprulfroeeccE(eoSclOlskPeec)tiisnoDnewoonidpslgrpoebvi.iedPesrdowctienlg orpteuotlocetiosn hr of dcueossncirinigipeotinitsohne,rscosofftteihqeunsisepmpmeeetnchtto,dosf.esldupproececdoulrleesc,tionndcduocbuemesnatantdiroinzdc.teTfshseosnec1peoobecyesgfpeisncs 20 scope PTtlthheeeiePsePtavoenbnaPadreodrabdrloiosomdywsied.sewliyIlulssoeesdtipwenocbrioakl.yTfuhreeesPlhaandrsssatx,wsagetaievreslf,ocrocnlsioloedsmedaitmeontssafyomesnofnt 0 nniitwceoimgehstisnacopnptraocxtimwaitheltye5s5ikg.m. Thesample re fwcliotshiohgssuaimptles15h.t1f5eceasnwhem TjyEhescleltk.EemTmcashktnemDhaaurtenihDdtargiveseedhtgyiepgihciaeldleymsliuogwnseerdoetfdodcoeotblhrlieescbtostmrtpooclkmeyvsibonatsaomfs,fitnheelsy dnitvisdepdileotrysboriss,kIn lXin1e5comarreaotefesesdpilrmienngtc,lodaeddoeors.The doorswedepsiegnnedd cmoesssege,sensctomer15 sTahmipslSiOnPgdweivlilcecsovaerdthheecsqpiepcimfeinctprreqoucirhede10tchotlaleectfsoilelnet,samplesusin ithe ofthese 30 EQUIPMENT E+auPietmietnetPaonnadssaupdplEiescckedmDedraemdangyenla,but re otlie oeFlowing + SStaibnleesbosteoplmilxiangctbonatroagieners + * FSiSuetmlapdildneectsosnbetealitnssepor(oanptsrefojreqchutalosiptemyciocfhigce)meainnsdesic,ezodeilinmeeennrtwgsidthtwestheif)orsample stage + Chuinofcustodyforms MSWord 97 37 + sehimpsmennets,dneddi0dnogc:umceanmtedras,talcmol,lefciteilodnnactoivtitieesbpaenondso(fowkriat,belsinamhpelreacionatnadinSehrasroix), `samplelabelscustodyseals: + oPregrasoincalvaprpootremcteitoenresquVipMmSen)targued bythestHeath andSfetyOfficer,including. `Deconeqtuipamemntsipecnifiac fotrthie porojnect 40 SAMPLECOLLECTION PROCEDURE Suprrofcaecduersees:dimentcolton usingthePoraorDredge samplers will ivolvethe following 1. `OWboirsknPtlhaens.Tuhmipsemacyabtieoinnitnhfoerfmoatmioonfafrnoamctiuhaelcootrhdeicnaotpeeoorafwdoerskcr,wipotrioknooufttlihneeg,noctahael sampling location. 2.sPeodsiimieontnst,htshaemfpileidncgrbeawrgsehourldbosuitvoavysewthoekeflreocmtedhesammopsltedocwainns.eaWmhleocnastaomnploitnhgemest upstream location unlessotherwisedirected. 3. Wthhernesapmopilnitngisdeodwinme(nt2.ndspeuedpowaltse)r.s,Tahits wtiltroovetitdheesboemreesianipllaycefwoitthheeiptlhetrforwmo andcau that theplatformcossnotdriftwhilesapling. 4.lOoncacteioynoudaenviefcaatttohn pasroepnetliofceadtoonnmheesssuarmspalnindgrleocgo.rddep ofwaterand recordsale S. Makesure thatalldaashescorrespond to thecore sampling location. 6.sMaetaeslux shyesseamm)plnidngrekcoocradtsoanmupsliencgotohredbiensatteasvoanitlbhleesatmepchlnionlgogoyg(. .globalpositioning. 87.. MOabkse suhreedtehcaonthteadmriendagteedorrpedaeorpeoatrhe(odpepeennpdssoinitohnensedismieonwtlsyulboswetrtteetryspeo)v.erthe ssliidgehotfytsheubbmoeatr.gTeh,iesilsstoprheevemnatntdheItutsherfroumllpr0emhaetbuoretcloosfet.eOsnycsetetmhyeonuiasreare sampling in.The weigofhthte units should force tem noth sdimeat boom. 9. thfuesiineg).thPeuElclkhmealninDerteadugtea,dmarkeelesausreetthhetmtesesenigeir.sOunpcriegthhteomnetshseebntgteormrel(ecagselisgthhtleyon doors, pul the itoffthe botomandslowlytrough he wer ote ost 10.dFoorrtsheoPpoennatro,rehleeafseo.reThoefrtehfeourneiwthietninygouhpeasledtihmeelnitneshhooludlidncgatuhseeutnhie,ptihnehdoolduinsgwtilel lose: (collethcestamiplne)g. 11. sOtnecelemtihxeiunngictosnnsteherb.oaUts,epaldaececaolnahmeicnoantteen,tanoolosnseosfeethsepdoeocnon0thaomminoageedsniitlzheeess sediment. 12.prOoncpeerhsaomplmecoontgauiensetrnh.eitstsazcnlreeiscsadlstt,eh sthepsaotmopoplleancbe seuffocreintsssaammpplleebveolpuamceesdnotnothhee i`ncoinatasineorf.thAevpaermsionniscmoulml,echtiisnga,abnedsyhpoueldocfaonanlaysnitshfeosratmipslseamDp,ldea.te, imecollected, MSWord57 38 13. pCoellienctweorskparn.itQAIQCsamples utind heQAPPachedtothere 115.. PCllcfoltlsmawhmeeptlpehsaiilnnokhfeeeppsrtootpdseasmfaepomlmpelsesh3ipepcinmgpoerngsofco4nCtsint,ewhipc sbhyolhdecMopenrtnary: sSraimigpnhlgticnmogodl.ialfniedccaw.tiiTlonhlsbemeauieyndblceoewioilwlhievsnaphsechaevlrd,edagepiemnkdeiinnnggsnuopaowbnldhreittyopf.eooAfenscyaqmipcplmehetanhtaitpsin1s Sohrocthsanagedselhlatern t cede edfrsei prin.gspecificsyst holdbeScum elddt MSWor9d7 39 UsingFNieth,SSameplaiOngerTsra,ps GeneraIlMSDteacnadtaurrdOSpaepraltiinngg PTriopcedures `ob1hec0efkoplilPspocUwoesRmdpRfloOoefrStheEhdseSfcoCSlrOoplaPcdrtiEaioannlOlopfelfrlahtinwgiPfrnhoceheewTrenk(nsSeOsPrs)eeRtiveoedrwefiainnhedSahMse.oecAtnlecdipnrsoces T0is sciriltol ebemspiebrfiocornfomtenhadedstsoeismniectheohoredtmnasi.onptArlchcsocgobfhltseeapcltuhcolldloedcitsinongaptsbsesicuon,derwniiledlls eTneaherdnby cr`2o0"oletdEQicshU.IihAPlvbMleaEdpeNcteTirdrplf)ogornsasmiuopsflpioenagpmrmeecrnhtaop,efrsyecdwrilcbeesa,dansdldoow,mheowever ecoyc Exliopwoienngt obwed ing hecoleion offs sy node, tis otmed ore ++ GSSialumlpnldirntgsmeviiensmeseaalwnptdrsiradanndu.bpiont nilstveinvis) FFiWiedlmaeievasenisdsbiogbynoswg(hor ltost) +J -- Blciicsca PSlFaiamesltpdilciebdcucoeknseitsnsnedarnstdlworosenloeimyhis bs +++ lneBeusbl(tatledowcrnopyve)rs ++ + SVPaualsepiperZodoiefnamifabikocgiastnognpeaabseltags To3h0pe.rfooFplIoiwSeiHsnCguOmsLpelLneEgnCTcpItuiOeoNtne.s wll flowed collin ishsples rome GGidillleeNtaestebsemosrmtlsyiswhesenl.wThiesndeepsloycesdpciJleyni halnlowvcatnehWbhywmheenrie aosscoionssid Gil tsofvain entsand comprisedofvarios mesh zs (6 10, 1 0, 25 130 er 4o `ian1r.y3c3.t.e5md,eshahn.sdiz4cw.h0ei1t)lirsle yq,pucpaNleeldsywuairellseel.deFwdoeig0hhtcissopnnsdatforofmateidhennvpeeedssoopptSi02g.amitltlceitosnnwi,th Jeisltceaalpnlyrfioonttphaesbwowveerighhecsob,loautnmda ui1.yvaiieeds cdweioplllaobtyemrewiingttgh,ebdhoteaobtmowoiemthhof1)-2eTfehettewwiistlhwlbieelSsbpuepmndcehedra irenixfvteipgnarcleietwceaeearicvgahhysli,odcbeaotfiyoolsnlwfoiwilenngdogeibplelsoley.tmTenhsae.vsiTegodaceboplmlepolcyymhewnaitnthc.ehTdheies esbuooisilrnegenrnsettmgeiyronaoslr pinssfiilioovoicenegd soyfsttehm).etfnnctehsewaactye,rgciollluemtstwhirthoaulgehntaitnheg imelshcsees(1mwaoyrbkeiansd1. inaglyfed Gainigdlhlteevasiovdweilhdlebcheaetdfceohplrlleoovyweiidnvpgemeopmheeinnlgi,lcaolsvrpirogadcsethiyocrawbidlleli.bGnerneherealert,epasrheecrsoeovnnt-ocfacspyrecviseesidonoihvngesn wriegtuilnaibeissewsa.rDnueridn.gThdieslowyilmlend,eiciadeydbeidseedonebentptrotfecshieocnkailn dheg1mtosfmaeld Thefollowinger]proces wilbe followed orcolinfishwithilets. 231..PoAesinttitocntnhdehvceoavseeawciith,hodboeoitsg)ahtwehsertnoesyrhceleeaeitlsfl,teoxpsousesbdsesrsndtw.b,oaodm kndelgcls,iepcih ilof 4.NDoehptelveeosyhseegtliilwmlheesetnrpdehrecpanetenidomniiigofhattobcstecdooepmlreocyamaegntefindodmbuldonfwgoo-dfSevpkle.oye whi vse sn vee. 56. RMeaatlieenvseugrditlplhunltltlbhatefoheerotdhwnesdfoleheeseoyginilten. ceevatlh.eArpresin pceeeoaFnochorheedcdeol,wednd 7&PlShaeacnekettfihhepgcuiallpllettdurnoeudtoiofthhceeowelaetneroo,rwacslhan,inecloel,obroGineg igiht,ecar,lyrseloendcolfeh),as. .10.sIdafmeapdlieiqn,gutmeveeaanmn.b,iasnodrprpoecessos shehair otspaclifliidesiheepWeirhckelilrl etfor cr TTdruiamwvesnabgcolslheactpedshe. tThteamteasrehdsriaegwgeddbywibloltbehdoepgehnewoaeecfhoamgoedonfogoon collection.Tra tswillbo epeyed dingcoyhightpos. "Tefollwinggeneralprocedureswilbe olefo clltin ishwithvals. 1. lots,rolls, andlorweights ilbetachedtote rlaspproprine MS Word 7 2 Leoweetd aceo ieovo Coo mBiodefhset, obort 43.. NOhonGtEdtiSesowd dbmyennddo sdfiorncdoeoawrn:yi ta eddibctk.opriis &5ENuiprobepotp osesim ong vee dal SB S7s.anIdeentta ify,meaisr utre,iacne delotrporoncib etisshstheofo nisgfhaescspdn eciifviedwlientaehenWor,kTPloaen.oporife eti KhShretmroelrSoaeewtlsyyvptograuecots nBnSlgnoeowlotrnessslpyo esete eEwe t. -- helio rent ocd ilelw flinwigi 32J . TSThoesieSnwsilelenctenoienb gbr hd trkpee-- pebse lomoy aEon 4. Ey AN0antehnpaogdorewdtnseinoteseihos n ogc he noired ls i cn k 5, sd 1. ferened,mse, psbehpiedfn Wok i BaSittmeniTnMhiosnyowyskTcaapnse Coneseao orbyetsBchec enlmnhos1orliolv esstSsFnse ectnort. -- yvliarslremwptipnegedgwhiysdon eaotlto opmrotoeenbs mton vleog Telin nn cocalled fr leiwihinn ps. 1. P[lrcehcaet t mshi ron honk dhe oofeo, Ah wisn e 23..a{NLhcooewtheletrterdhiu0terdapatrotnedhttoletoehcieiwtnoatontheferufvsrppoemcreatnlbheoboseyi.cmdeeonafttbhsueobhyoeeatid,dmkadskoiedgnbrglsoeukry.ee tdhvaittlheetroanpsssecturelyof 4. yAEonlfplnrygce acph ppwofe phren-lepas lesp,darrholdiingcheonti. inl ol)bysoy 6. deny,mess, dor rocks hes seid neWorkPl. lTotroogtltieneeastypiccalhredwiswceiagnhtss ohn ecascbhoetdonnddudeliingashabredehdoceks,Aocdice isa oluumgeha,ndTvheeroioiftefychanbe pce ioshoutsn ates dyandcacolts re Thefollowin ener proceswill elves orcolin 5 ih oie: 21. bLBuoeovtyehtreothcbeocnoehsotetnhehdrevwooaeefl.solomntg ehe thfhe. Athweightnd cofbsbos,malin re hens tor ecely 3. sNooucthcrbeeo.fibAmleealvowrdheonaehsoifhnoekeeodceaepnobbymreeacnnt.nAdeeonFyeelsddlhoognubdebkeienas visheoe 4S. ASfihtrianttenpepcepd<pfanhdieoeledbieygpvlci,onrngsoeetro.fnoeiw.adeacoded)ing hebout. Poce 6 deny esas, dorprocessehpsi noWork ls Fi4e0sl_hsoeSl.cAtMiePhdLfcEoHor ldAtifaotrNisonoAeoDNrpDolLyPpRlEiIsSnhEsRNvVAybeTsGIlsOhNooulddbpeadteinibegdsneledkby dping sishteeipsoinpaaiinodnessnupldmepfjolsringpedno.esnCtlodetlphcraeeicdeodisorhnnvwieAltllebmeatciavfe sdciivfeiigom1keliddlisel tcsooemsilnlomfppohlvaeirn e libero.nh vetke. flrsampleproces, llhrpocedonve fe xd ped MS ord? ud APPENDIX D PART | - REPORT =e Analytical Report Fluorochemical Characterization of Water and Sediment Samples MSU-Entrix (Tennessee River) FACT-GEN-037 (E00-1958) Centre Analytical Laboratory Report No. 023-0140 (Revision 2) Revision Date 6/28/01 -- - ero Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 16801 000 3M Environmental Laboratory Contact Kent R. Lindstrom Bldg. 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 Phone: (651) 778-5352 - Requester Dale Bacon Ph.D. 3M Environmental Technology& Safety Services Bldg. 2-3E-09 St PaPu.lO,. MBNox53531333313331 YH macerare 1 Introduction RCsoaonmsipurlloessAanwraeelryreteicpcaoolrltleeLcdatbeofrdoarfttorhroeimesat,nhaelITnyces.nsn(oeCfsenastersooe)rRiiefvseoromfawntahdetear3reMapnadErntsvoiefrdoi3nmMmeennPtrtoasjlaemcLtpalbEeo0sr0a-tr1oe9rc9ye8.i,vedTThhbeey. `Centre study number assigned fo the projects 023-014. `(SLpCecIiMfSicIMfuSo)rowcahsemriecqaulesciheadrafoctearlizsaatmipolnbesy.liAqutiodacl hofr6o6 msaamtploesg/wrteaarnepdrheemyceimvaedssfosrpaencatlyrsotmsetry The samples were prepared and analyzed by LCIMSIMS for the following ist of fuorochermicals: + Table 1: Target Analysis Porfluorooctane Sufonate Pros Perfiuorooctane Sulfonviarmide [PerfuB orchexae ne ruSufo _ona_tr s_ o --o--cp to anaTcn ear--tie s|| Tahned arnealsyutiscaalrmoetohnodfisleuwsiehdfoCrewntartee.r sTahmepimoestwheordosvwaleirdeatemdobdiyfCieendirfeo.r tThheesevdaliimdeanttionsapmroptloacsol hhiogwheevsterqtuhaelprdoacteadauvraeisahbaleveatnottibetemn.fully validated fortis matrix. Data presented here is the 2 Sample Receipt wTinehdroievsidacumoalplllseecastmepwdleerbeectoswnuetbaeminniet6re/sd1w8ie1n0ri0endraienvcidediuv6ae7ld2.2p/l0aSs0t.aimcpCclhoaenistnawi-onoerfrecsursaetncodediywvaeidrneofonnrom7ta/t2pi6ro/en0s0e.irsveTpdhr.eesseSainxmttpeyld-essii.xn Atachment C. 3 Holding Times wTehreeanraelcyetiicvaeld maefttheotdheu1s4e-ddwayashovkaliindgatteidmea.gaHionwsaavtemr,axitismhuomuhdolbdeinngottiemdeothfa1f4iedladyos.rtSfcaamtpiloenss ilnonwgaetrerthaannd1o4thdaeyrs.maticshaveshown accoplabie recoveries at 100 and 1000 ng. for periods. Pace20F6 4 Methods - AnalyticalandPreparatory 44114 SLaCmpMleSPMreSparation for LCMSMS Analysis LrWeCamIorMvSeIsMarmeSspialdneuaalsylswicesh.roeriAnienf.oarSlyo-ltmdriapltheeardsepwoirettxhitor2na0co0ifousnLam(oSpfPl2Ee5)w0wamassLtr.uasnessdofdetirouepdmrfatophaairoeyssutlhStePesEsaomclpaulrietonsnifgtoeor mdTiehstochaacrandroetlrdiwdaganesdwctaohslelreScstPteEduftcoeorldaunmwanliyhswia5ssmbtyLhoaLnfCMo0Sl%IteMdSm.ewtihhaTnho1ils00tn%rewamatetmteehrnatnsoorllue.tsounlA.od5TihmnLea.nlpoaosirgitohn-wfao9sfd concentration ofthe sampls pric to analyss. w5Famotrietroh.fe msTeehtdheiamndecinlu.tteaTdmhpeelxetexrsta,rcatacsetswpowrreeesreetnhftoianeirrveeedaplaoontddidoinniotfehsedams0palmaee (nm5aalgnvrnaomors)alwsoaufts4hefm0wtmeaeLlxtewriastchatmeTdpylnpet|eso begiming with the sold phase extraction. 41.2 Sample Analysis by LOMSIMS. cInolHuPmLnC., Baansealdiouonttohfeeaxftiratcyt oifitnhjeecatneadlyatnedfoprasthseedsttathiroonuagrhyaphlaisqueidin-pthhaesecochlruommnatroeglraatpehitco oHhrPegLalnCiiqcusiedcpoamrmoapbtoiiuolnn,dpshEa,sMien,Sctuhdpoirnoagvinldoearsoacihsrearmpeiitdacilansne.dd afEocrlceaucrtcraothseaprmraaeycatnisesgrfesonraeamrnoaaullnyotzpionefgratatimewed.iadteFrorelallnoagwtoionlogyf Kmiodontemupreorcahtuermeisc;amloslearceuloebssearrveeidonainzdedq,uafnrtaigtmaetnetdeadg,aiannsdt sdteatnedcatredds.. lons characters of (aASnHRaoMlw)yl.zeetWtat-htPeearcsksaaamrmpdplleHePsew1x1etr0ra0cetsHe.xPtLArnCaacltsyeysdsiotsnemw8acsou/ppleaer2ndfdoor8.1ma3ed0M0i0ucasr0ionnmgdasassnealUellcyttzieemdda brMyeSaMcItMiSoSnSwmaosauntstweoondentngo a8b/ny3d/M0iS0nIsatMnrSdum8eb/ne1tt7/wp0ae0re.anmSBee/td8oi/rm0s0ecnaatnnsdbae8m/pf1lo7eu0sn0d.weinTrhAeeteaxHctPhraLmceCtnetdasn8d/D4Ma0Sn0/daMEnSd m8e/1t0h1o0d0saunsdewderfooraannaalyyzsoids 5 Analysis 51 ACa-lpiobirnattciaotnraton for ihe compounds ocfuirnvteerewsat.s Tahnaelyczaeldbratatohn pboaignitnsnwinegreanpdroepnadreodf tahte0.ana2l5y,t5ic0a,l s1e00q,ue2n5c0e, ce5oa0e0cf,fhiacpinoednnt,1(010)U0sainnndggLcno(aepftri.iteTenhsooifinodsenitreuirmemhnitn1arteosnwpoa(ng)seiwnveegrresvudseotidahreempicn.oandcr.oniorAactciaoenlowrpnaadtsocnpolcruoartvteoonr `acceptable fr >.0.985 (> 0.970). Galbraton standards aro prepared using tha same SPE procedure used for sample. pacesors 36 `tCcaholrniocbuergnahttoriauottniocnthsheeacrkeasnwtaialtnhydisanisr+d/s-swe2eq0ur%eenofcaent.ahelayczCteoudmappllovriaialonduciecealliys (aovbetrayintehdreeIftotihvee ssatamnpdlaerdi.njeacntailoynis)s For the resus reported here, calbation criteriaweremet. 52 EBxltaacntkiosn `xracton bbllaannkkssswheourlednproephaarveed aannyd taanrageltyzaendalwyitths epvreesreynetxtartaocrtiaobnovbaetcthheocfonscaomnptlreast.ioTn hof the low-ovel calbraton standard. For these samples,theextraction blanks were compliant. hIlenavsvetelrucamanleybnrtattbairloganentksstaaninnadltayhrtede,fs oapnmrodesfaefnleteraaktnnomorewtanhbahonivogehliltsohovolovlelnostawm-wpoelvreeesl.aclasAiogbaraaintnai,loyntzheesdtbaanafdntaekrrds.esvehrFoyourhditgphhoe-t `samples presented hero the instrument banks are compliant. 53 `SSuurrrrogoagteastpeiskes are not a componentofthe LCMSIMS analytical method. 54 Matrix Spikes sMpaitkiexrescpoivkeersiewserareepgrievpeanriendAftoarcehvmeernytfi&e.ld sample using al compounds of interest. Matrix trFiheeeclofdvieesrlpdiieskspeiskaerw,oeiarnledsiocsauitbinncmgliuttdehedad twinhietArhtetowanacehsmseendptirmoBeb.nlteTmahnweidtshoetndhieemsesunertcfiasmcaaenmtwaeftieelsrdhssoapwmiepkdilneg.noprrFoiececeloddvuesrrpeyikoef `Fsiaelmdplceosntrsohlowseadmplreecsovsepriikeesd AtachmentB. batet2w0e0enpp7t0anadnd1010300%p.p wTahree sruesbumlittseda.re Talhseo fiinecdlucdoendtroIln 55 ADlupfilelidcsaatmepsles were analyzed in duplicate. in Atachment A. Rosuis are given along with the sample results 56 FLoarbLoCrIaMtSoIrMyS aCnoanlytsreos,lMSiallmpwalteorswas spiked with al compoundsofinterest at 25 and 250 `negalcLhdLuCrSi.ngReeascuhltesxatrragctiivoennsaelt.onAglwlirtehctohveerriaews fdoartaallincAotmipaocuhmnednstsweDraenbdetE.ween 70-130% in 57 S"Tahemrepalree nRoeoltahetresdamCpolemrmeleatnetd csomments for tis data set 6 Data Summary aPrloearsoeposreteedAitnapcahrtmsenpetrAtfroorna (Gpept)a(indglLl).siSngedoifmethnet asnaamlyptliecalresreuslutlstsa.reSurrefpaorcteewdaitneprarrtessuplotrs bilion (pb) (ug)onbothanas-1o00ived andcry weight basi. Pacesors 7. DatalSampleRetention {oaSdaaocmriposlneimscaarGietnadeisidpsoabsryecCdhaiovfneodtneonmorntitehvaabfleathmrocrieaparnd hsaudedcouplyesrespotrhtasravivseSespreecdifided,sAll 8 Attachments 81 Atachxm:Reontst 82 AachmentMae pheRocovoris 83 AtachmentC: ChoafCuistondy 84 tachment: LOMSIMS RawAnalyticalOat (SuracoWaterSamples) 85 AtochmentE: LOMSMS Raw Anatcal Dat (Sediment Samp) 9 Signatures Toh Faber, Operators Manager ow eKe-- vein 3 ie yo,Vicae Presi-- dent --Da-- te Other Lab Members Conibuting to Data Karen Smith Pacesors ne APPENDIX E-1 collectebdy Entrix, June 2000. Sample ID Conductivity| Salinity | Temperature gL) | (umhosiem) | (oloo) C) [SW-or1-60 T [SWeo2 T77271 aise 2540 | 19 | 35 | 10 | 313 172 | | 74] [[SWWoosdT T7787 10 505[0 |0022| | 1 229956 4 || 5s1i]] [SW0s 17041 540 [Sw-o6 1861 38 | 02 | 300 | 81] | 02 | 291 |75| [[SWw-o08rT1o 78s0 1 T1v 7% T|oorr | | 280 284 |75| | 87] [sweoo [SWero 1784Tiss T7777 Tiss Toi [276 Tod[275 | si| | 77] Wn [wn 1758TvTor | T7778TmTor | 280 276 | 84| | 82| [[WWiidsTT soT7 7187T T6 o or r| |1 229971 8 ||8040|] [SWeis [SWeis 177o565TT7i1s80s[|ooir| | 22944 | 87 | | 88| [[SSWW-isT1o70o5T177718sTToorr| | 228090 | 8s | | ss | P[SWW2D0TT7o73s5 TT7w7o18sT To or r | | 96 287 | 89 | | so | [SWalT7735 T7196 [Sway 7701 7ioe |o1 | 280 Toi | 288 | 80 | | 80 | [SWas [Sw2d T7727T7106 T1773Tia of| Tor| 289 | 80 | 2001&1| [SWas 176514650 [Was TT %6[18 |20| 332 |75| 1 or | 216 | 85| wq APPENDIX E2 dWoawtnesrtqrueaalimtoyfptahreamWehteeerslefrorDasamm.pleSsamcpollleesctweedrefocomlltehceteTdenbnye3ssMeeanRdivPearce AWnaatleyrtical Laboratory. DO. Conductiviy Temperature pil Sample WDD0S (gL) 73 @mhosicm 170 CC 53 Gu 70 WWDDDDO0?G 7785 117700 22s0 7721 WWDDDD00S9 18052 117600 2243505 7774 WWDDDDIILO 110s4 116600 2250 7818 WDwoDDII32 1n0z5 116600 22305 8813 WWDDDDII4S 19024 116600 22300 8729 wrt 90 160 230 75 SabemingefurTthoecstadtowinuossgtnirsveaemn.nWATpIpeinWdateBr_ TrWeDatDmen+WthIentealkeerneDaarmWiDlieonmDamrewin WoD $0 FhadEXe E e by wisti=e i p C - E he E oy E SeEfe E EST ER Ey | eo a || | |Zelsl a2mSa Ns| g Tom ur7 o a be | [BEp=I] lDRrES zEe i c e i JIC| a SEA n51E , O3L2 m TE ee teeNN l o a he E aw || a rH lm RRR, ) r 2 J2 RE 5 ~ p55 7 tcneoanT=d1s8r0 ATU SEZS R s T E SRMR ohNNoZ oA= o|| IiN TcoUJ lleBRtESeer8dEe HSe R0R I OB TE ns : a.| EARN. | gl posit, IN ND get z es 35. 5 TMHy L--ecen: 1 St okey at CeSe = CR igroweer a StesNma NO RN | RmEeEr | 7 T= T EEHS Treate, reSmRTee * | TT git of Ee wi | | Soogtin La "gl 2 oh a x hi | Wf JF ma gs iVta pch savor sa anme TM EY 3 SB Al 1 EE SINT] Sez " wa Rom Cond. = m 230 I=eAS :: A - 1) NR ons 3 f Te Si gear ] ES CSIEE ) = amma TIES EE 4 | = iE SMA 2 BN iE T= LR | | EE EJn E T hEQt FiE= A | Le 2 oo) Hoe, os 19 | | | | | 5 ce JbooBy. ESSi| des S2EENNEBERh=SS,S HJ(il=hlTNN\N s e Te, | A SPN EE No A | Soy |v WER | wGgmEnT. LN ------ nN rr] 3 | CREPE) 07 -- PETEI. a SRLa (8 ceonn=,19s0 C ZT l ovary TemSRA ee, EE Lei NASER wo" Fe Fm | B LeI moe e HGOEE TC le | CON romeo200 Tf gs Ey Ra R MReIiSTe Dggs ePne,l a Ror ECRaE oesion Tee SBCAR LpAesey E PNRS En, EhBN | REC ay 7a cee GRE A | 2M PEA RBA da ae VA SE Na zh SH | PE eeS terFyEMarySeB erlCee | | RE ee EE EE Er | AEE Jad7 ik Xl | LaoelEa AE EEAe eoea h: 2 I. | TALcEormrecd ETEoRS T E NIRCK S, | ro e), SaE UE NTRi EEE 2 SR OTR AGG E I CITES| ks | |= . Se, ee | == NOAYr ST 6 || P Na Nl r E, Neg Za 4 | oeEe mmm i z hl [ N LS *. 20 | B ims faa NT Te CrONhr| Ta | doen BE. \o.. wu FA = pa WlmmN 1 CEE PRS | (5s Be | 7 | 2D 2 5 | eu | a7-e2.ITWE ronson: ae--" ----" |r 6% | WVlamssn J TomPFm T mm aei : n | 6 a Aly YT ea | SVEN NST A Sowa nfs C balye ETE ae C an Wf wi eel $8 BLE EE.grUaeeT on TE e me Pleo aE RE, LGC EE E| EEWe eie | bil) fo EE TE he] bp 8 (mie, SEER Bo &= | SAEEEge TalsohR SR aT n eEein Xd | EN Ce in SheJET iE TRL a | H FET [Ro iher bE NIN lees 1 |= ey ee| | Fale IslandCabin SieAren BY i ol i se| fren SEE Se BEEN CNY Sle REECT r | | ies Rg rE ~ | as) EE -- Ge SONIm NNDMEr= oTme mmm=TS Nal| A | 60 | NONEE or See | [| paflits | | 2N er - Low wos =a er 4 --y > _ 1 S| feRdes oo motarioms no, | mmo, tes a TP NNgE FE d LT TM %. RN | ETpl a risie Far NiERs hd 2, | KN=U EaetES N NoD O e23 N[| rroEmosrN Ease L \oe l = . AA RE ZN i % i "NO N. \ i Shas | prosssas T _ = bath E Jig mraA z eam i Fass < mi ~... -- dedeTn S bd 6l SE DS = hey.. Li] PEORVRo NEANTwbll olT7 2 Zz 7 A pik7 e aEE=E~||| EE irk ei EPIC. ronan 7)ra Sie | {5 ka we o v CediEo s =a EL Tn | ed & 1resarom re ee | | a. = oy waits 7am Aro de gag x| fo re ----~-- | W a k a ge Am er , ol re x | 18 Bre EEE Pm =] = Loo dhe ps aa] fai | Fe FS omit Cowie i Shee BiESha(f{dra?s 2) I\REPE ER PSR sa XT Ne || RE MlioLTilo ese Re EN-- | | Lon fp i Asa man Wem SC 1 ES Ra PAP es pg 34 wn = 7 ee | 3 i er EEN | ( pz phe Se | COO, ERE ET PNTT | Ne aa 1 a En Tre are Nee 2 ) om an rena& Aefo ||CL TN, E,Rm| IEE| proasz20 0 mee | | |: a 1i%2 n > e 20 | B L Em EN EENIOSS. 1I> lm N%Nh ON Te *e ` | Ee Bad 200 | morse me | Riot Cl & LEVie 22 i NS |RESETha rera = fe J EE Si < Rl mmm TOA or > i mane TO romom Salat [ Ho FN 7 Es ETE nS Ee E ma e, agPremsoie obe o | . | | | ii i= ael ev -- | 13 - APPENDIGX cLoelnlgetcht,edwferiogmhtt,hecTonedninteisosneefaRcitvoerr.and liver somatic index. for Sample LengthWeight Thew 2 oTMIe m52 1@55 ast TKo! 13855 137 292 SSHHAADD!? 352 SHAD3 36 S0672 0076s53 969 oss; 0mn87 343 SSHHAADDS4 SHADG a3s 3 590639 o07s6e 344 09017 11382 2 SSHHAADD?S 221s wel 17 91%54 0190835666 sl 16487 mm 044 CwArTH cAT2 1365 2796 0195983068 34 re List 05379 55 CCAATT4S i 1M03548 o08s79e6 a9478 GGAARRI: 465 89095 003374m7 1208772 GGAARRY4 GARS 55 377 00x366 ws 02 0361 924415 ass sGBA1Re 30 S1419 2 o12a24n6 202579 ssBB32 2265 216611 L1a6a6s 019022 sSB845 27 21%4 1L2i3e1s0 os1219 $$8867. 2215 113104 1112431130 1L0i4s S$B8S9 S810 2i5o 120038 1153031172 006893 25 rs ar 069 sBsaii12 sB13 22% 1913 T13a4r3n0 017768 23 137 Lars 081 SBla 25 153 TTCondition factor (Rcy waas comemsdKe 12027 Vx OO 12 nLiaviernsootmaaptpilcicianbdleexi(nLSc1)twhasvecaelcwualsatoedtarseLmSovIed(Lfirvoemr swaimtpolael wi) x100 individual fish 0L6s76?7 0061453324 08m612 0042653867 06TM46 05m432 0159445933 1L2a175099 0092106m1 1152165024 0L3a8s6i4s 0033996006 0055474114 0o7d10o5 0L8os0s0 0063699990 0054361652 0049103832 03416 67 (Gem042 Arts esl: Fish Liverand Clo Tis APPENDIX H i[eUE ImERm ~ SV Bj1t)orm=s FE tr n A mr oSieme---------------- Oepl maA.,Con, oe 68 GHEe3 RIE i httisonngd Ry nr oT boWt W WOH T 1] IFisoa LU ppm y Cle T eST See] i 1] i Eel Jerre ll erty Co hiA ; i 1 BLe H Ce iss 1fy, Eup i S si ALiF A eeEa LEE Ll | LiIlili pghsipL ikmf bi{e4d iid 3 i fEENRERG i | Jt HEF bl er AH ATT mbeblA ily pang ih ob EH | yp{ [topo] ma MIT TA ma Shannan Ml fet EI Wh LdAigAItpIosriitnn,g 1 Edu | B 4m HHT {AIT UaII[rrElCiMeIEEsIEEiCCiEIEvIEhEy Pl BE itpd T{RL]} bPiined I Gen-042 Analytical Results: Fish Liver and ClamTissues i HIIf pheyo Co He | EO lLiyd Hi 1 i " X| lett) i i oiLl] Ih ll fhirg g ht al i iy bl 1h | HmH ith dle | 1 76 i iii] Ji) pater lH Eo pd N AJodi iil eH iH Al gt i 77 i aitihf i , Fits hi ht ial) 1 i lf hi ih Calle i 7% i Hi mi ill nh ll HH Ta ai da FH Laill Tpi het) | 29 i flihili fH ! ha i fpeHrt i yf:hiiA iHl l[hho e LEH | 80 oo Analytical Data Summary: 3M FACT-G0EN0-502505 Environmontal Lab Appendix | Quaniative Analysis Analytical Laboratory Report Title of Fiuorochemicals in Environmental Samples Obtained from Entrx (Decatu-r Tennessee River Samples) on 03/30/2001 Data Requirement Not Applicable Author 3M Environmental Laboratory. Analytical Phase Completion Date atsigning Project Identification 3M Study Number: FACT-GEN-055 3M Laboratory LIMS No. 00-0520 Page 1019 gl Summary of Findings AnAnoayiicsaODtotaaSSuummmmaarryy:: uEEnnvviFirAroonCmnTemGnatnE0at0Nle00LL8Soo0pSb. FISH (wroLesobY) AaQlumlaenortfiittchaeatinsoanSmihpnal5deso-u(Pl1Fo=Of88S).aanndPdF4POoFAuOaSonAdf8wPesFraHemSpmleweaessruorremesepdeaacsibuvorevoleyd.tahbeomvietthoef qmuiatntoifation in Csaamtpfliessh.samples. PPFFOOSAaannddPPFFOHSSA wweerree mmeeaassuurreedd aabboovvee tthhee ilimmiitooffqquuaannttiiattatiioonn nin 12 oouutt oof4f4 `sPaGFmAOpRSleA-s,P. OPFSOAw,asanmdePasFuHrSedwearbeovmeeatshuerleimditaobfoqvueanttheatiimoinoifn q3uaonuttitoatf6iosnanmpl2eosu.t of 6 QLinuaabrnogitoiha-otMfiootunhteihnsBaamnapyslseosf-.tPhFePOsFSaOmapAnldaensPdFPOFSHASwwereermneoatsmueraesduarbeodvaebtohveelitmiht omfiqtuaonftitation StqhtueraisnpaiemadplBloeanssis(nn-a=nPyF14Oo).fSthaPenFdsOaPAmFpalOneSdsAPwFeHrSo wmeeraesunroetdmeaabsouvreetdheabmoivteotfhqeuaInmiitiaotfion in all of WofhithteesPaemrpclhesQuantitation in (PnF=2O).S_ anPdFPOFAOaSnAdwPeFrHe Smewaesruerenodt anyof the samples ambeoavseurtheed iambioovfe qtuhaenifimtiattioofn in both Refer tothe atached spreadsheets for more information. D-- Meo tho-- d Su-- mmari-- es ---------------- uFsoleldowdiunrginsg tahibsrstiuddye.scriptionofthe 3M Environmental Laboratory analytical methods 3M Environmental Laboratory PrepARATORYMETHODS + EFSlpTueSoc8rto:rc6oh0me,meit"crEaxyltrCaoctmipoonuonfdPsotrasosmiuLmivePrerfforloArnoaolcyisainseussuilnfgonHaPtLeGo.rEtlhecetriosprayMass ApannrilttoirnoopngeaenrdieinvngafoproMeraBagEteo.nrtuwTntaihlsdearxyd.tdraeEcdatctwhoatesxhterrasancatsmtpwelaresraarne(dc0o.t3nhseciaaunnliaeflduygithei1ot.nu0bpmoatainowdfatpsuht aonnto, aglnadssthaeuntofviiatiesr.ed through a 3ccplastic syringe attached (a 0.2 ym nylon itr nto Page 2019 8Y Analytical Data Summary: 3m FACT.0G0E.N0-502505 Environment Lab ANALYTICAL METHODS + EFlTuSo8r-o7c.h0e,mi"cAanlaslyisniLsiovferPEoxttarsascitsumUsPienrgfuHoProLoCc-tEalneecsturiofsopnraatyeMoarsosthSeprectrometry" Tperxhiaemmaaprnlyael,iyomsnoeclsheawcruealrctaeerrpiieosrntfi4co9ro9mf,eadsepbalyretcmitocenudliatarosrlitonhrgeoacprhsieimmnagirlcyeailpornuosdfiourncgtPHFioPOnLSsGe(-lCeEacSFtMeSdSOIfsrMo)Sm.aFor apnraoldyuscits,iowna9s9fwraagsmemonntietdofruedrtfohreoqruapnrtoidtautcieveioanna9ly9si(sF. SO. The characteristic ANALYTICAL EquiENT "oTfhtehifsolsltuodwyi.ng are representative ofthe actual setings used during the analytical phase ALniaqluyitdicCahlrcoomluamtno:grKaepysht:oHneewiBsettt-aPsaicTMkaCr,d2S4e5r0iemsi1m1(050pLmi)quid Chromatograph system `MCaobliuemnptheamspeercaotumrpeo:neAnmtbsi:ent CCoommppoonneenntt AB:: 2memtMhaanomlmonium acetate FInljoewctriaotne:vo3l0u0mep:Li1m0inul Solvent Gradient: 16.0 minutes Time (0m0inutes) ~~ 0%%8 6100 010%% 0130 1o00n% MQuaasdsruSppoelcetrsoymsetteemr:_Micromass APIMass Spectrometer Quattro I" Triple SCoofntewaVroel:taMgaes:s30Ly-n6x"0 V3.4 CMooldlei:sioEnleGcatsroEsnperraoyyN:e2ga5t4iv5e eV SEloeucrtcreodBel:oZc-ksTpermapyerature: 150C +10C Analysis Type: Multiple Reaction Montoring (MRM) Page dors 8% Rso ane Tle.Tarotons Monkordin LaboratoryAnstysen [roPronx [| 7% | ___--eros |r| wm | B TEDatria Qrupaaliittsy eOebrjeectiE rvesusamnFddoDartaatInttuegerniteydm-- se permeston Linearity: The coefficient of determination (r%) equal to or greater than 0.980. + + cYopoienProciin: Limits of Quantitation (LOQ): The rss LOQ is equal to tora 5% the lowest `acceptable ortht standard rBlanket S ---- ssur-- ostomai-- xarks must hve pkae< 4hpesk rn _ A Sosqty et fr . Data Summary, Analyses, and Results Suomemaryof Quly ontoAnts ReuitaforPEGS, PFOSA, PFOA,a ~ Ctaealbnlrtact:oSTnihSetcawnodfoaierctsi:nGoa cfuodtleataaisnef, ooe mianogtf.yeo oSsroahros oaccnotrSrayvtrneeotwoOaronin21tns0.t250a.r Se ga Ls ssHiro bobs cemy bon Piena mloe iadheas?aaia oCgamnoobraamaay sroveebeaerSggsnfccarrtey aapforrt rar 84 Analytical Data Summary: 3M FACT.G0E0N--005S205 Environmental Lab wrCaealasicbtrbiaoatnsi-eomdnonsoitntaotnrhdieanrgrdemssopwdoeenrosefeoptrfheeopanirenesodtrrtumomorerunnet,s(upsneedceiilfAuiptcepdpe,rnoaddpiupxcrtCo,xniAsmnaa)tleyultsiyicwanilgthMtiehntehtmohudelsti)in,pelear range of the instrument (approximately 5-100 ng/g). LiaimnnitdhtsescoaatlfilbQerauasattniottniwtocauttriivmoeens((dteLhfOeiQna)en:dalTayhsteeaLpseOtaaQkndiaasrreedaqwduietahttielonctteh3de0li%nowtoehfsettshauecrtcrhoeegpoatrtaeetbilmceaatlsrtviaaxlnudea)r,d biaslpaipnmrkpose.xriamtaBiteveecaLtuhOastQetlfhooerwseelaeccvrheiltsaeonifaalftyohtreeLtianOrQegaetdcehatnemaralmtyirtnieaxstsiaorlneisbutebedioqobunsiettrohvueesdrn,estuThltheselsabuomrmataorryy, it table, BlTblahaennkkwss.el:lAM-lacllhrabiraxa/ncstkuesrrriwozegeradtemeabmiearltiorxiwoxtfbhrelaablnbikimitstiwoveferrqeuwa<antsi%tuatstheieodnlaefvsoerlstuohrfertochgoeamtLepOoiGus.nsdues foofrimnatetrreisxt, Prweicthiisnitohne,cIonsutrorufmtsehnietsals:tuIdnys.trIunmeontthaelr,psriemciilsaironivwearsfinsostuespsetcuidfiiecsa,lliyndsettreurmemnitnaeld precision has been determined to be better than 7% for all target analytes. MaedtiafrcehirextnytSppelieokvfeeltssi:sfsWourheeefanrcohpmotseysapicebohlfet,fyiapstehl.oefaMsaatntioimnaxel;sspteiytkpeoisfcamwlaletyrrseipxipskrpeesipkawereserdw,eaapsfrtepeprraearpneadrineafdtiatflowro ssbpceirtkeweeenseitnnudg1ieo0sf-.3t5he00sangm/pgl.esP,laetasapepsreopertihaeteatletvaeclhsed(ussuuamlmlyaary"htiagbhl"eafnordr"elsouwl"tsleovfelt)h,e iMnadtirciaxtisnpgiktehartescoovmeerioefstwheermeatnroitcaelswcahyasllweitnhgiendtthheeeaxnpaelycttiecdalrmaentgheod(.+/-A3l0%t)h,ough smoamyesiSlpibkee rceocnosviedreyrerdestuoltssupwpeorret waitsheimniq+u/a-n5t0i%toaftitvheeientxeprapcrteteadtivoanluoefs,theanddattah,uas few mraetsrtixsscpainkbees cwoenrseirdeecroevderteodboeuqtusiadleaotfitvheiosnlrya.nge. For these tissues, the presented Tproevpearrieyd tihnerasbtbaittusivoefr.theMaetxrtirxacstpiiokne asntuddaineaslyctoincdalucstyesdteimnsr,abmbaittrwixersepiakllesacwceerpetaabllseo (and+f-ish3fmao0trti%hxoss)peikaensa.lytical runs used when reporting data for the fish homogenates fPirsihorhotomothgeenexattreasctwioenreanedxtarnaacltyesdisbyofEtnhierxfisphertsiossnuneesl buysi3nMg,asnaamlptlerensatoifvteheextsraacmteion `mmeattrhioxds.p3ikMe csotunddiuecstceodntdhuectaneadlyosnisthoenEEnnttirxi-xp-rperpeapraerdedseaxmtpralcetss.arReespurlotvsidoefdtihnean attached summary table for comparison. + DchermoomnasttorgartaipohincorfeStpeenctiifoinctiitmye: aSnpedcmiafcstsysfpoercatnraallydtaeuigdhetnteirfiicoanticohnarwaactserdiezmaotinosnt.rated by Amdadsistosnpaelcctornofmiertnrayto(rEyStMesStMs Sw)erseyspteermf,otrhmee4d9fo9r DPaF~O>S.80InDtahetreanlseicttiroonscpraany ptraonvdideema stinhttereoranfngoaerlerynsstiiwsgnaoafsltptirhseassuneetnshteaim4np9tl9heesD4ac9o9-l>lDe9ca9tDe>daf8tr0roamDnssaiottimroaennossifpttieohcnei.eAPslFotfOhoaSungiahnmaaltlyhssi,issai.nntHruofnweirdoeevnnettri,ifsiiend ra9r9eDlyaobtrsaenrsviteodn,. to ensure complete selectivity, quaniitation was based on the 489 Da > Page 5019 85 Analytical Data Summary: 3M FACT-EG0E0N.-0055250 Environmental Lab `7Tq0ouanvnetigrtfayt(iitvvheeearoigdrreonetteihmteyeornftttitshoseuwedi)et,htiaentctl+ee-ad3s0atn%2a.ltyrtaTeny,spiiitcnaislolnaysm,wp4el9ree8s>md9oe9ntieatrnomdrien4de9da9nt8od0csohntrtoaawnisenidtPioFnOs wSeraet.> q`mousnaainmtipoilraeetdwi.vaesaOrgner-etahenemaloeycnzcteadwsiimtoohnntsithtehoarritentpgohretthseeed4td9wa9ot>at1rf3arn0ostimrtatinohsneist4di9iofn3f.5e9rTe9hdidsbeytthemirromdrirnoaatnthisoafnnio3n0s%,hotwheed Statement of Data Quality trIiatmdsei,onlomatabtperolisexsdisrbpelifekeetroestnvuecdreiitemysa,tteriruniedarilec.catToevheethroaytnoltfyhemendeadatosaguecnraoneumbseeanorntefaplaoyrctteceufdrrawocimtyhtaiavsassiutleaastbelwdeitaahtcoctuhutirsacy sofuemimtaherry+1ta-b3l0e%,re+g-ar5d0i%n,godraqtuaalqiutaalityi.ve only. Please see the values in the attached E References e, E`ETnCSvo-im8rp-oo6nu.mn0ed,nts"aEflxrtLoramabcLotirivaoetnroroffyo,rPAoSntt.aalsPysasuiilus,muMsPNie.nrgflHuPoLrCo-oEclteacntesruofsopnraatye/MoarsosthSeprecFtlruoomreotcrhy"e.nic3aMl LEiTvSe:r8-E7xt.r0a,ct"sAnUasliynsgisHoPfLPCo-tEalsesciturmosPperrafyl/uMoraososctSapneecsturiofmoentartye".or3oMthEenrvFilruoonrmoecnhtearlnicals in Laboratory, St. Paul, MN Kis Hansen, PAI Date Page 6019 86 Ein COT L TEEe E Aap OnaSurry: 4Enron Cn renin Teme Tomoe[omme fom] -- EHHEiITEE:EEEsE E eEEl a E - EE EE EF erp iE J 8 ra OotSny EnvFaicrrooeonoionssg sacromess Cotmactpptas aPnROS cost Guess . C e = ig zon nege a Somrena | ! IdopT e ofeepikests 29 fe