Document QkOkgOQYoGGVp4Dyab8GB0mgL

AR226TM1732 A SURVEY OF SELECTED FLUOROCHEMICALS IN THE DECATUR ALABAMA AREA ~ 2002 SAMPLING Bo Revised Report 11/3/03 a2 es Preparedfor: 3M St. Paul, Minnesota Prepared by: Entrix, Inc. John P. Giesy, Ph.D. John L. Newsted, Ph.D. East Lansing, Michigan Project No. 178401 November, 2003 TABLE OF CONTENTS 1 EXECUTIVE SUMMARY worms4 2 INTRODUCTION css6 EIR 4 10 ETN 2DLc---------------------- 3.1 SITEDESCRIPTION... r-- -- 32 FIELDSAMPLINGLOGISTICS -- cml 33 SAMPLECOLLECTION. r-- wn 33.0 Water and SedimentCollection............ 33.2 Fish Collection............ ---- erin 8 ---- 33.3 FishFillet Processing and SamplePreparation. r---- 8 4 IDENTIFICATION AND QUANTIFICATION OF FLUOROCHEMICALS 11 41 WATER ANALYSIS corns omnes 1) 42 SEDIMENT ANALYSIS... cms 1 43 FISHFILLET ANALYSIS ccc p-- A 6 STATISTICAL ANALYSES won 13 7.1 WATER QUALITY PARAMETERS... cnm-- 7.2 FLUOROCHIN ESUMRFIACCE ALS WATERS... 7.3 SEDIMENT CONCENTRATIONSOF FLUOROCHEMICALS... 7 nis BY I. 7.57.4C.1OMPAFiRsIhSFOilNleTtOc2o00n0cDeEnCAtTrUaoRtfMiPOoFNOInSTs,ORFIONSGA, PFOA, PSF TUDaY.n.H .d...P.FcSBvcSc.ne.m.sm.s.ne.m.en.nov... 16 18 750 SULfACE WEP. 752 Sedment......... -------- --------. 8 0 753 Fh. em-- nn 20 REFERENCES... 2 EI 200 ------ - | 9.1 APPENDIAX cm------ 92 APPENDIBX. -------- css 93 APPENDIXC...... ---- I 9h ARREHDIKD.rnensssssmsmsmsmmmsmsmsssmmmsmsmsst wa 35 LE 9.6 APPENDIX F. cS ---- A 9.7 APPENDIX Goce p---- I 2 TABLES Table 1. Location from the and identificationofsediment and Tennessee River in Alabama...... water samples collected rs---- Table 2. Sample identification and locationofindividual fish collected from the TENNESSEE RIV. cen 10 Table 3. Water quality parameters for samples collected from the Tennessee River, in the Decatur Alabama area. Values are reported as a single `Table 4. Concentration of fluorochemicals in surface watersofthe Tennessee. RIVer in the Decatur, AlaDAMA ATCA. vrs 14 Table 5. CionntcheentDreactaitounro,ffAlLuoAroAcheATmCiAc.alo s in sedimr entsofthen Tennessee: River 15 `Table 6. MTeeannnelsesnegethR,iwveeirg(hCto,lalencdtecdonodnit0i4o/n15fa/c0t2o-r0f4o/r18f0is2h).collec cted fc rom thes 16 Table 7. Fillet concentrations (wet weight) of selected fluorochemicals in fish collected from the Tennessee River in the Decatur Alabama arca. ............ 17 `Table 8. Mean concentrationoffluorochemicals in surface waters of the `TennesseeRiver nearDecatur, AIBDAMA. .......o.covccerrrcs 19 `Table 9. Mean fluorochemical concentrations in sediments ofthe Tennessee RICVarDeECAUrT, AIDA. +... 20 `Table 10. Mean tissu fluorochemical concentrations in fish sampled from the `Tennessee River Nar DECAU ALAIN... 22 FIGURES Figure 1. Tennesse River and sampling locations evaluated during the study. .........7 3 1 EXECUTIVE SUMMARY A monitoring study was conducted to determine the concentrations of selected fluorochemicals in fish, water and sediments within the Tennessee River in the vicinity of the 3M facility in Decatur Alabama. Samples were analyzed for five fluorochemicals: perfluorooctancsulfonate ~~ (PFOS), perfluorooctanesulfonamide ~~ (FOSA), perfluorooctanoate (PFOA), perfluorohexanesulfonate ~~ (PFHS), and perfluorobutanesulfonate (PFBS). Three primary locations were sampled during the survey. These included a location upstream of the 3M facility (LOC-3) near river mile 307.5,a location across the River from the 3M facility near river mile 301 (LOC-2), and a location downstreamofthe 3M facility near river mile 296 (LOC-1). All surface water, sediment and fish samples were collected according to standard procedures and analyzed for fluorochemicals according to 3M Environmental Laboratory methods. The results presented in this report have been revised from a previous report Conductivity and pH were greater in surface waters from the downstream location (LOC1) when compared upstream locations (LOC-3 and LOC-2). However, these differences were minor and fell within the range of water quality parameters previously measured in the Tennessee River near Decatur, AL. Surface water concentrations of targeted fluorochemicals wer less than limits of quantitation (<LOQ) at LOC-2 and LOC-3. In contrast, PFOS, FOSA, PFOA, PFHS and PFBS were detected in surface water collected downstreamofthe 3M facility (LOC-1) but were less than 0.6 pg/L. In sediments, PFOS concentrations ranged from 0.42 pg/kg t0 3.1 pg/kg (wet weight) for LOC-3 and LOC-1, respectively. In addition, concentrations of FOSA, PFOA, PFHS and PFBS in sediments were also greater at the downstream location (LOC-1) when compared to measured concentrations at LOC-2 and LOC-3. However, due to the small sample size (N=1), statistical analyses were not conducted to evaluate the differences between sample locations. In general, concentrations of fluorochemicals in water and sediment were greater downstream of the 3M facility as compared to concentrations measured across (LOC-2) or upstream (LOC-3) of the 3M facility. The concentration of fluorochemicals in surface waters remained relatively constant or decreased slightly between the 2000 and 2002 sampling seasons. However, due to differences in sample locations, small sample 4 sizes, and analytical methods, no conclusions about temporal trends for surface water could be made. While differences were observed in sediment fluorochemical concentrations between 2000 and 2002, these changes were not great (less than 2-fold) and due to differences in sample size, analytical methods and variability in the data, conclusions concerning temporal trends could not be made. Fish collected from LOC-1 contained quantifiable levels of PFOS and FOSA in fillets while at LOC-2 and LOC-3, the only quantifiable fluorochemical in fish fillets was PFOS. The least concentration of fluorochemicals were observed in fish fillets from LOC-2 and LOC-3, actos from and upstream of the 3M facility while the greatest concentrations were observed in fish filles collected downstreamofthe facility, at LOC1. For instance, in fish fillets from LOC-3, the average concentration of PFOS was 7.6 ng/kg while FOSA, PFOA, PHS, PFBS concentrations were <LOQ (wet weight). For fish collected at LOC-1, average fillet concentrations for PFOS and FOSA were 305 ng/kg and 32 pghkg (wet weight), respectively. However, concentrations of PFOA, PFHS and PFBS in fish fillets from LOC-1 were <LOQ (wet weight). While differences in the concentrations of fluorochemicals were observed between catfish and largemouth bass at the different locations, due to among individual variability and small sample sizes, these differences were not statistically significant. While fish previously have been sampled in the Tennessee River near the 3M facility, a comparison between the previous `monitoring study could not be done du to differences in sampling locations, fish age and size, and the types of fish tissues analyzed in each ofthe studies. Therefore, a trend analysis was not conducted with the fish fluorochemical data 5 2 INTRODUCTION Entrix, Inc. (ENTRIX) is providing a report on activities to assess the distribution of fluorochemicals in the Tennessee River in the Decatur Alabama area. The results of this study are part of a larger effort to ascertain the spatial and temporal behavior of fluorochemicals in the Tennessee River that may have been discharged from the 3M Decatur Alabama Facility. The resuls of the 2002 sampling season were compared qualitatively to the results the 2000 sampling season to examine any potential trends in the distribution and magnitude of the fluorochemicals in water, sediment and biota. `Water, sediment, and fish were collected from three locations upstream, across and downstream of the 3M Facility. Fluorochemicals selected for evaluation in this study included: perfluorooctanesulfonate (PFO), ~ perfluorooctanesulfonamide (FOSA), perfluorooctancate (PFOA), perfluorohexancsulfonate~~ (PFHS) and perfluorobutanesulfonate (PFBS) (see Appendix A) 3 FIELD SAMPLING 3.1 SiteDescription The sampling locations selected as part of the 2002 sampling program were representative of arcas used by recreational and commercial fishermen. At cachofthree locations selected for this field investigation, water, sediment, and fish samples were collected. Sampling arcas consisted oaf location across the River from the 3M point of discharge, a location downstream of the 3M facility, and a location upstream of the 3M facility. The Riverwalk Marina (Marin) located on the northeast side of the river at approximately river mile 305 was used for river access. The downstream sampling location (LOC-1) was in the vicinity of Fox Creek (approximately river mile 296). The sampling location across the river from the 3M facility (LOC-2) was located approximately at river mile 301 while the upstream location (LOC-3) was at river mile 307.5 (upstream ofthe 3M discharge, the city of Decatur, and the Highway 31 bridge) (Figure 1; also see Appendix B). 6 ee 2 oe Hi be Noh i HE iH + RAE K aTee ToS s SRM PRM tere : Ls NEEL oc Ue =(2 i go oh br 5 gLLadlBe /rLEHeAReS1| dy aETSS F-- ig] SA A -- ag i NY Horai aed Hi LEG ser i Coad Ey. 3.2 FieldSampling Logistics Sampling at selected sites on the Tennessee River was initiated on April 15, 2002 by ENTRIX. Collection of water and sediment samples continued until April 16, 2002. Fish collection was initiated on April 15 and continued through April 18, 2002. Water, sediment, and fish were collected as outlined in the General Project Outline (GPO) provided by 3M. 3.3 Sample Collection 3.3.1 Water andSediment Collection Water samples were collected using standard sampling protocols from a total of 3 locations (Table 1: also see Appendix C). At cach location, water quality parameters were measured using YSI Model 63 and 95 meters. One sample was collected from each of the locations. All sampling locations were documented using TRIMLBE PRO-XRS Global Positioning Satelite technology and these locations were recorded on topographic maps. Samples were labeled, stored on ice at 4C, and delivered to the 3M Environmental Laboratory, St. Paul, MN. Sediment samples were collected from the same locations as the water samples (Table 1). A total of 3 grab samples were collected from the Tennessee River. Sediments were collected by use of a PONAR dredge following standard protocols (Appendix C). Sediments were placed into labeled LDPE containers, stored on ice at 4C, and shipped to the 3M Environmental Laboratory, St. Paul, MN. `thTeabTleen1n.esLsoeceatRiiovneranidn Aildeanbtiafmiacationofsediment and water samples collected from Water Sediment Location Sample Sample River Mile Code SW-01 SED-01 SW-02 SED-02 Downstream Across River 296 301 LOC-T Loc2 SW-03 SED-03 Upstream 3075 Loc 8 3.3.2 Fish Collection Fish were collected from three locations (Figure 1). These three locations were in close proximity to where water and sediments were collected. Fish were collected using a boat mounted Smith-Root type VI-A electroshock device (Appendix G). According to the GPO, a minimumofsx bass (preferably largemouth) and six catfish were to be collected from each of the three sites. For this investigation, only the desired fish species caught at each of the sampling locations were retained for analysis. Collected fish were measured (total length), weighed, and immediately wrapped in aluminum foil and placed in Ziplock storage bags (Table 2). Samples were labeled, placed on ice, and shipped via ovemight FedEx to the ENTRIX office in East Lansing, Michigan, and then transported immediately to freezer facilities in the Aquatic Toxicology Laboratory (ATL) at Michigan State University. Upon completion of sampling activities, the Alabama Department of Wildlife and Freshwater Fisheries was notified that sampling was complete and their required notification form was completed and mailed to them, 3.3.3 Fish Fillet Processing andSample Preparation ENTRIX conducted the fish processing and preparation of filles. Procedures described in the 3M GPO and the Alabama Department of Environmental Management Standard Operating Procedures Volume ITT were followed in fish fillet preparation (USEPA 2000) Fillets included the tissue from behind the head to the tail on both sides of each fish. Each fillet was removed from the fish and the skin removed using a fillet knife. The rib bones were cither avoided during filleting or removed from cach filet so that only edible portions of the fillet remained. The carcass of each fish, the skin, and rib bones from each fillet were then wrapped in aluminum foil (dull side to fish), labeled with its sample location and ID number, placed in a pre-labeled Ziploc bag and stored at -20C. The fillet was cut into smal pieces to expedite the grinding process. A hand grinder was used for the larger fish and a stainless steel blender for samples with less tissue. In all cases, the ground tissues were thoroughly mixed with stainless steel spatulas and mortar and pestle to ensure adequate homogenization. Once homogenized, the tissue was massed to the nearest hundredth gram and placed in Nalgene HPDPE containers. A label detailing the sample location, ID number, date processed, sample identity (bass or catfish) and 9 mass of the tissue was placed on each container. All containers were placed in prelabeled Ziploc bags and stored in coolers at -20C. All tools and homogenizers were washed with detergent and warm water, then rinsed with methanol followed bya deionized water rinse to avoid cross contamination between cach fish sample. `Table 2. Sample Tennessee River. identification and location of individual fish collected from the Sample 1d SLoI.LMOT Location `Downstream (Near Fox Creek) Fish Type Largemouth Bass SSLLOOLILLMMOO23 `DDoowwnnssttrreeaamm ((NNeeaarr FFooxx CCrreeeekk)) LLaarrggeemmoouutthh BBaassss SSLLOOII--LLMMOOS4 DDoowwnnssttrreeaamm ((NNeeaarr FFooxx CCrreeeekk)) LLaarrggeemmoouutthh BBaassss SLSLOOIIL-CMAOTGOL DDoowwnnsstirrecaamm ((NNeeaarr FFooxx CCrreeeekk)) CLaatrfgieshmouth Bass SSLL00II..CCAATTOO32 DDoowwnnssttrreeaamm ((NNeeaarr FFooxx CCrreeeekk)) CCaattffiisshh SSLLO0II--CCAATTOOSS DDoowwnnssttrreeaamm ((NNeeaarr FFooxx CCrreeeekk)) CCaaitffiisshh SSLLOOI-CLAMTBOO6L DAcorwonssstrReiavme(fNreoamr3FMo.x Creek) CLaairfgieshmouth Bass SSLLOO22--LLMMBBOO23 ``AAccrroossss RRiivveerr ffrroomm 33MM LLaarrggeemmoouutthh BBaassss SSLLOO22-LLMMBBOOLS ``AAccrtoosss RRiivveerr ffrroomm 33MM LLaarrggeemmoouutthh BBaassss SSLLOo22.-CCAATTOOL2 ``AAccrroossss RRiivveerr ffrroomm 33MM CCaattffiisshh SLSOL022--CCAATTOO43 ``AAccrroossss RRiivveerr ffrroomm 33MM CCaattffiisshh SSLL0022--CCAATTOOS6 ``AAccttooss RRiivveerr ffrroomm 33MM CCaattffiisshh SSLL0O23--CLAMTBOO?L U`ApcsrtorsseaRmiver from 3M CLaatrfgieshmouth Bass SSLLOOSL-MLMBBOOY2 UUppssttrreeaamm LLaarrggeemmoouutthh BBaassss SLSLOO-3LLMMBBOOSS UUppssttrreeaamm LLaarrggeemmoouutthh BBaassss SSLLOO33--LLMMBBOOG7 UUppssttrreeaamm LLaarrggeemmoouutthh BBaassss SSLLOO33.SCMAOTOL! UpUspsttrreeaamm CSamtaflilshmouth Bass SSLLOO33..CCAATTOO32 UUppssttrreeaamm CCaattffiisshh SLSLOO33..CCAATTOOSS UUppssttrreeaamm CCaattffiisshh SLO3-CATOS Upstream Catfish 10 4 IDENTIFICATION AND QUANTIFICATION OF FLUOROCHEMICALS Water and sediment collected from the Tennessee River were analyzed by the 3M Environmental Laboratory (Study No. 02-0443). The analytical methods used for the analysis of water samples were validated by the 3M Environmental Laboratory. HPLCElectrospray/Mass Spectrometry (HPLC/ES/MS) characterization of fluorochemicals was conducted at the 3M Environmental Laboratory. Summariesofeach protocol are given: 4.1 Water Analysis Solid phase extraction was used to prepare the samples for HPLC/ES/MS analysis. A forty-millilter portion of river water was passed through a preconditioned Cis SPE cartridge and the column was allowed to dry for at least 3 min. The cartridge was eluted with 2 ml of methanol into autovials. The eluate was collected for analysis by LC/MS. Water extracts were analyzed by use of a Hewlett-Packard HP1100 HPLC system coupled to a Hewlett-Packard Series 1100 APIMass Spectrometer Detector. HPLC conditions and ES/MS methods were based on ETS-8-155.1 "Analysis of waste stream, `water extracts or other systems using HPLC-Electrospray/Mass Spectrometry". 4.2 SedimentAnalysis For sediment samples, a 20 g portion was extracted into 35 ml of 1% acetic acid in capped centrifuge tubes. The samples were shaken for 60 min and then centrifuged. The aqueous solutions then passed through pre-conditioned SPE cartridge and the eluate was discarded. Methanol was then added to the sediment and the mixture was shaken for 30 `min and centrifuged. The methanol was passed through the SPE cartridge and the eluate was discarded. The SPE cartridge eluted with 4 ml methanol and the collected methanol was then added to approximately 200ml of ASTM Type I water. This solution was then passed through a new pre-conditioned SPE cartridge and the aqueous cluates were discarded. The analytes were eluted from the SPE cartridge with 2.0 ml methanol into autovials for analysis. The extracts were analyzed by use ofa Hewlett-Packard HP1100 HPLC system coupled to a Hewlett-Packard Series 1100 APUMass Spectrometer Detector. HPLC conditions and ES/MS methods were based on ETS-8-155.1 "Analysis of waste stream, water extracts or other systems using HPLC-Electrospray/Mass Spectrometry". n 4.3 FishFilletAnalysis Fluorochemicals were extracted from fish filets using a solid phase extraction (SPE) method. Briefly, 2 g homogenized fillet tissues were diluted with ASTM Type I, mixed and aliquoted into triplicate samples. Matrix spikes were prepared and cach sample was spiked with 10 uL of a 100 ug/L spike solution of cach targeted fluorochemical. Acetonitrile was used to extract the fluorochemicals and to precipitate proteins that can interfere with the analysis. After mixing and centrifugation, the supernatant was then passed through a pre-conditioned Cis SPE cartridge. Finally, the analytes were eluted from the SPE cartridge with methanol into autovials. The extracts were analyzed by HPLC-ES/MS. Details of the analytical procedure have been outlined in the 3M Environmental Laboratory (St. Paul, MN) standard operating procedures (ETS-8-231.1) for the analysisoffluorochemicals in tissues. 5 QaQC Standard operating procedures for sample collection and preparation were maintained during the entire project. QA/QC samples were collected in the field as required by 3M (Appendix D). Fieldblanksand trip blanks were collected and shipped with the samples. Field matrix spikes and field control samples were collected at each location along with a field duplicate. Field matrix spike solutions were prepared by collecting one literofsite water and spiking with a stock solution containing PFOS, FOSA, PFOA, PFHS and PFBS. The same procedure was followed to spike one liter of distilled water to prepare the field spike control samples. All samples were shipped under ENTRIX chain of custody forms and a field book was used to document conditions and activities. Photographsofall locations were taken to providae visual record of the conditions of the site during the sampling events. Since the method detection limit (MDL) and lowest limit of quantification (LLOQ) 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. Data quality objectives were also established for each sample matrix (river water, sediment, and fish). In general, the Data Quality Objectives were: (1) all samples were analyzed in triplicate and the %RSD should be < 25%, (2) matrix spikes should be 30% of expected value, (3) water blanks should be less than < % LLOQ for cach analyte, and (4) extraction blanks should be < % 2 LLOQ. Water and sediment concentrations were not corrected for cither matrix spike recoveries or for purity of the fluorochemical standards. In addition, ambient water quality parameters, such as temperature, conductivity, salinity, pH and dissolved oxygen `were measured at each location during each sampling event, 6 STATISTICAL ANALYSES Statistical analyses were preformed with SAS (Version 8, SAS Institute, Cary NC, USA). Where relevant, General linear models (PROC GLM) were used to test for differences among locations for all analyte concentrations in fish measured in the study. If values of F tests indicated a significant difference, Tukey's HSD test for multiple comparisons was used to compare meansofthe different locations. All fish samples were included in the statistical analysis. For samples where fluorochemicals concentrations were less than their limit of quantitation, the limit of quantitation was substituted as a conservative estimateofthe fish fluorochemical concentrations. 7 RESULTS A letter report summarizing field activities associated with the Tennessee River field sampling effort in 2002 was provided to 3M by ENTRIX, Inc (see Appendix F). The letter report included information relative to sample locations and a photograph log of sampling activities on the Tennessee River. The result sections below summarize this information along with analytical results from water, sediment and fish that were collected from the Tennessee River. 7.1 Water quality parameters Surface water quality parameters from each location are reported (Table 3). Dissolved oxygen, pH, conductivity, and temperature were relatively constant for the Upstream (LOC-3) and Across (LOC-2) locations. However, at the downstream location (LOC-1), PH and conductivity were slightly greater than those recorded at the other locations. These minor differences may be due to the fact that sampling locations LOC-2 and LOC3 were within or near the Tennessee River channel whereas LOC-1 was located in the mouth a small bay at the mouth of Fox Creek. As result, LOC-1 most likely was influenced by the water quality of the creek. Regardless, all values fell within historical 3 water quality parameters measured in the Tennessee River in the Decatur Alabama area (Giesy and Newsted, 2001). Table River, 3. in Water quality parameters the Decatur Alabama area. for samples collected from Values arereportedas asingle the Tennessee value * Location DO (mg/L) Conductivity Temperature S) co pH Gu) Upstream (LOC-3) 107 139.4 18.1 72 Across River (LOC-2) ~~ 9.36 1389 210 73 Downstream (LOC-1) ~~ NC 1623 218 9.4 Mefarnosm aeancdhsltoacnadtairodn.deviations could mot be determined since only 3 Single sample wasconesed NC meansnotcollected 7.2 Fluorochemicals in Surface waters Fluorochemicals were quantifiable in surface waters collected from one sample location in the Tennessee River (Table 4) (Ellefson, 2003). At LOC-2 and LOC-3, surface water concentrations of PFOS, FOSA, PFOA, PFHS, and PFBS were less than the limit of quantitation. In contrast, PFOS, FOSA, PFOA, PFHS, PFBS were quantified in surface waters collected from LOC-1, downstream of the 3M facility. However, in samples where fluorochemicals were quantified (LOC-1), the concentrations were less than 0.6 g/L. Duc to the small sample size (N=1), statistical analyses of the data was not conducted to evaluate differences among the sample locations. R_ iTRiavvbeelrre_ iinn4t.thheeC_ DoDenecccaeattnutu_ rrr,a,tAAilloaan_ bbaoafmmaafalar_ ureoeara.oc*he_ micals_ in su_ rface w_ aters_ of the_ Tenne_ ssee Location PFOS (gL FOSA GEL) PFOA gl) PFHS _ PFBS (gl) (uel) Upstream (LOC-3) S037 <0025 <005 <0.005 <005 AcrossRiver ~~ <013 (Loc2) <0025 <005 <0.025 <005 Downstream (LOCI) 049 0.025 0.5 020 0.08 SAilnlcvealouesndaesnliontgyeldewsiatmhpl(<e)waaesrcoelplaeoFrlcoermtseseattchdahenltohdceaiioini,tmoofSquaTntistartiieon pcortsed. 1 7.3 Sediment concentrationsoffluorochemicals Some targeted fluorochemicals were quantified in sediments collected from all three locations within the study site (Table 5). Least concentrations of fluorochemicals in sediment were observed at LOC-3, upstream of the 3M Facility while the greatest concentrations were observed in sediments collected at LOC-1, downstream of the 3M facility. While there was insufficient data to conduct a statistical comparison among the sampling locations, these data indicate that concentrations of fluorochemicals. in sediments were greater downstream of the 3M facility as compared to the upstream or across the river locations in the Tennessee River. ttThhaeebDlDeeeccaa5t.tuurCr,o,nAAcllesantbbraaammtaaiosanrreeoafa..f*l"uorochemicals in sedimentsof the Tennessee River in Location PFOS Gohe) GeFkOSoA) (PoFkOoA) GPoFkHS) (ePkFBeS) Upstream (Loc) 042 0.068 013 <0.10 045 Across River (LOC-2) 0.46 0.14 <0025* <0.10 044 Downstream (LOC-1) 313 144 073 013 0.58 Mefarnomscnacdh sltocaantdiaorn.d dAlelconvcenictoruaaltdioontstbrieepodroetteednromisnaewndestinwceeigohntlby3asSi.gle ample was coleci All values denoted with (9)ar reported as les than thie limitofquantitation 7.4 Fish `The fish species that were targeted in this study included largemouth bass (Micropterus `salmoides) and channel catfish (lctalurus punctatus). However, two other fish species were collected during the field sampling from LOC-3 and included one smallmouth bass (Micropterus dolomiex) and one yellow catfish, also known locally as a flathead catfish (Pylodictis olivaris). Statistical analysis of fish weight, length and condition factor was conducted using only the data for largemouth bass and channel catfish. There were no significant differences in weight or lengthofeither fish species among the three locations (Table 6; also sce Appendix E). Condition factors were calculated for each species and are given (Table 6). The conditionfactoris a measureof the overall physiological health of a fish that is measured asa ratio of weight to length. Statistical analysis of the 1s condition factors showed no significant differences in fish health between the three locations for either fish species. `fTraobmleth6e.TeMneneasnseleenRgitvhe,rw(eCioglhlte,ctaenddonco0n4d/i1t5i/o0n2-f0a4c/to1r8/f0o2r),fi*sh collected Sample ID Length Weight Condition Targemouth Location Upstream (LOC-3) (em) 363 ) 30 Factor 1305 Bass Across (LOC-2) @m 35.4 9 647 2 1432 Downstream (LOC-1) ~~ 348.5) G5291) (10421068 @o) am) Cafish Upstream (LOC) 55.1 2386 126) 1.468 Across (LOC-2) ay 1099) (0598) 56.5 1942 1.049 Ga) Downstream (LOC-1) ~~ 61.4 6) 2020 010) 1.166 Smallmouth Upstream (LOC-3) 30) as) 25 563 (0192) L640 Bass "* CVondaitaliornuemfaeecatonsrscwailtchusltaatneadsdar(dWdeeivgihattixo1n0s0(YiLepanrgetnhth"eses). "Catfish datafromthis sit includesboth channel nd yellow catfish 7.4.1 Fish Fillet concentrations ofPFOS, FOSA, PFOA, PFHS andPFBS Some fluorochemicals were quantified in some fish fillets collected at all three locations (Table 7). The least concentrations of fluorochemicals were observed in fish collected from the upstream location (LOC-3) while the greatest concentrations were observed in fish collected from the downstream location (LOC-1). For all three locations, the fish fillet concentrations of PFOA, PFHS and PFBS were less than the LOQ. PFOS was quantified in fillets of some fish collected from all three locations. However, FOSA was `quantified only in catfish which were collected from the downstream location (LOC-1). `The mean concentration of PFOS for fish fillets collected at LOC-1 was approximately 3.5-fold greater than that measured in fillets collected from LOC-2 and 40-fold greater than that measured in fillets from LOC-3. In the smallmouth bass collected at LOC-3, all monitored fluorochemicals were less than their limit of quantitation (LOQ). Since there 16 `was no apparent difference between the concentration of fluorochemicals in channel and yellow catfish collected from LOC-3, the data for both species was combined. `Table 7. collected Fillet concentrations (wet from the Tennessee River weight)ofselected fluorochemicals in the Decatur Alabama area. in fish Species PROS Nek) FOSA PFOA eke (wke) PFHS PBS eke) (uke) UpStream (LOC-3) Catfish 6 (1154.20) <25% <50 <25 <50 LargemouthBass 7 <50 <50 <50 <10 <25 SmallmouhBass 1 <25 <50 <50 <10 <25 Across (LOC-2) Catfish 7 <25 <25 <50 <25 <s0 Largemouth Bass 4 169 <50 <50 <10 <25 (55) Downstream (LOC-1) Catfish 6 m3 "sn 61 eo <50 <25 <50 LargemouthBass 6 553 <50 <50 <10 <25 @1) TT No`uCmonbceenrtoraftfiiosnhsE aanralryeE zpeordtedEssTmeans snd standarde deviations. Means caleulated with LOG values. CAalsvhaludeastadefnrootmedthwiistsht(<i)nacleudreespobrottehdachaennsesltahnand ytehlelioiwictatofifshquantaton PFOS concentrations were significantly greater (p <0.05) in both catfish and largemouth bass fillets collected from LOC-1 (downstream) as compared to fish from collected from across the river (LOC-2) or upstream (LOC3) of the 3M facility. While largemouth bass from LOC-2 had PFOS concentrations that were greater than those measured in fish from LOC, the difference in concentration was not statistically significant due to the variability in the measured concentrations in fillets from LOC-2 (Coefficientof variation 152%). The relatively great variability observed at LOC-2 was duc to PFOS concentrations in largemouth bass fillets that ranged from <LOQ to 550 pkg, wet weight. Similarly, there was an apparent difference in catfish concentrations between 17 LOC-2 and LOC-3 but it wasn't statistically significant because of the variability in the measured concentrations in catfish fillets from LOC-3 (<SLOQ to 37.4 ke, wet weight). In catfish, FOSA concentrations were significantly greater (p <0.05) in fish from LOC-1 than in catfish collected from LOC-2 or LOC-3. The mean concentration of FOSA in catfish from LOC-3 was not statistically different from those measured in catfish from LOC-2. Concentrations of FOSA in largemouth bass were not statistically different among any of the locations. Since all fillet concentrations were less than the LOQ for each analyte, no statistically significant differences were observed for PFOA, PFHS or PFBS concentrations in either catfish or largemouth bass among LOC-1, LOC-2, LOC-3 sampling locations. 7.5 Comparison to 2000 DecaturMonitoring Study To evaluate trends in fluorochemical concentrations in the Tennessee River, data from the 2000 and 2002 sampling programs were compared (Giesy and Newsted, 2001). However, while fluorochemical concentrations in sediment and surface water can be directly compared among years, concentrations in fish could not be compared due to differences in experimental design. In 2000, the study design was intended to evaluate the distribution and magnitude of fluorochemicals in biota of the vicinity of the 3M facility and asa result ish concentrations were measured in whole body homogenates. In 2002, the objectiveofthe study was to provide information on the potential exposure to humans consuming sport-caught fish and as a result, ish concentrations were measured only in homogenized fillets. Thus, a direct comparison of fluorochemicals in fish can not `be made based on the different tissue targeted for analysis. 7.5.1 Surface water The concentration of fluorochemicals in surface waters remained relatively constant or decreased slightly between the 2000 and 2002 sampling seasons. (Table 8). For locations where a direct comparison could be made, WWTP to LOC3 and Fox Creek 1 to LOCI, the concentrations of fluorochemical in surface waters in 2002 were equal to or less than 18 those measured in 2000. For instance, concentrations of PFOS, FOSA, PFOA and PFHS were 9%, 85%, 80% and 65% less at in surface water collected at LOC-1 than that collected at Fox Creck 1, respectively. However, a direct comparison of fluorochemical concentrations between 2000 and 2002 was complicated by the fact that in 2000, the LOQs for all target analytes were approximately 2-fold less than those reported in 2002. `This was due to the fact that different analytical methods were used in each sampling event to quantitate fluorochemicals in river water. Thus, if one used the greater LOQs from 2002, a decreasing trend in fluorochemical concentrations is observed for surface waters above and below the 3M facility in Decatur. However, due to the small sample size in 2002,a statistical comparison could not be made for surface water fluorochemical concentrations in the Tennessee River. Finally, it is important to note that all concentrations of fluorochemicals in surface water collected in 2002 were less than 1.0 Hg/L (ppb). Ri`RTviaveberlrnenc8e.oarrMDDeeeaccanattucuror,n,cAAenlltarabaabtmiaao.nmo*af'fluorochemicals in surface waters of the Tennessee River PFOS FOSA PFOA FFAS Y20e0u0 SGuunttoernsville Mi37l0e (<e00l25) Ge<0.l02)5 Ge<0l02)5 (g<0n.0)25 2000 WWTP 3035 0053 <0025 0.028 <0.025 2000 BakersCr-2 301302 14 12 130 40 2000 FoxCr-1 296 0.54 017 27 0.57 2000 Fox Cr.2 296 018 0.055 1.00 017 2002 LOC3 2002 LOC2 307.5 <013 <0025 <005 <0.025 301 <013 <0025 <005 <0.025 2002 LOCI 296 049 s7 Alul rfwaterconcentrations repossrmtenevdalue <0025 055 020 *Concentrations giavselens than (<ar) essthan theilimitofquantitation (LOG). 7.5.2 Sediment Concentrations of fluorochemicals in sediments upstream of the 3M facility (LOC3, WWTP and LOC?) did not differ greatly between the 2000 and 2002 sampling events. PFOS and FOSA concentrations at LOC-3 were approximately 0.42 -fold less than those. measured at WWTP. In contrast, sediment PFOA concentrations at LOC-3 were 1.4-fold 19 greater than those measured at WWTP. While differences in sediment fluorochemical concentrations of FOSA, PFOA and PFHS were observed between the three upstream sites (WWTP, LOC-3 and LOC-2), these differences were less than 1.5-fold and most likely are indicative of the variability in fluorochemical concentrations in the Tennessee River in the Decatur Alabama arca. However, downstream of the 3M facility, concentrations of fluorochemicals in sediments were more variable. The mean concentration of PFOS and FOSA was approximately 2-fold greater at LOC-1 than that `measured at Fox Creek 2 but were similar to those measured at Fox Creek 1. In contrast, no trend was evident for concentrations of PFOA or PFHS in sediment among these three down stream locations. Overall, the temporal differences in sediment fluorochemical concentrations did not differ greatly and due differences in sample locations, analytical methods, and small sample size in 2002 (1 sample per location),a trend in fluorochemical concentrations could not be statistically evaluated upstream or downstream of the 3M facility. `Table 9. DeDeccsatwurr, AAMlleabbaaanmwafa.lu*orochemical concentrations in sedimentsofthe Tennessee River near Year Station River ~~ PFOS Mile (gg) FOSA (pk) PFOA (eke) PFHS (wks) 2000 Guntersville 2000 WWTP 370 <020 3035 098 <020 <020 <020 <2 <020 <020 2000 BakersCr2 301302 192 2000 Fox Cr. 296 258 54.1 170 238 181 is 022 2000 FoxCr.2 296 093 044 080 <020 2002 LOC3 2002 LOC2 3075 042 0.068 013 <0.10 301 046 04 <025 <010 2002 LOCI 296 313 AM sedimentconcentrationsTeporedssmean value, 144 073 013 *Coawnceetntwreaigihotnsbagsi,ivaselenss than (<) ae lesthan therlimit ofquantitation (LOQ). Al datareporteodn 7.5.3 Fish Concentrations of fluorochemicals were less in fish collected upstreamofthe 3M facility as compared to fish collected at the two downstream locations. However, comparisons 20 between sampling events is difficult due to differences in the tissue type analyzed cach year and to the fact that fish were collected from different locations in the Tennessee River. Taking these differences into consideration, the mean concentration of PFOS was less in fish collected from Guntersville, LOC-3 and LOC-2 than that observed in fish from the Outfall or LOC-1. This same general trend was also observed for FOSA, PFOA and PFHS where concentrations in fish downstreamofthe 3M facility were greater than those measured in fish upstreamofthe facility. However, in largemouth bass collected in both years, concentration of PFOA and PFHS were less than their LOQ while FOSA was only quantified in fish collected from the Outfall in 2000. In catfish, PFOA and PFHS were not quantified in fish collected from Guntersville, LOC-3, LOC-2 and LOC-1. In addition, PFOS and FOSA were not quantified in fish collected from Guntersville, LOC3, and LOC-2. Only the Outfall had quantifiable concentrations of all targeted fluorochemicals in catfish (2000) while LOC-1 had quantifiable concentrations of PFOS and FOSA (2002). The statistical significanceofthese differences can not be determined due to the fact that whole body homogenates were analyzed in 2000 while fillet homogenates were analyzed in 2002. Finally, for both 2000 and 2002, some concentrations of fluorochemicals were different between species sampled at all locations. For PFOS, the concentrations in largemouth bass were greater than those `measured in catfish. However, for FOSA, PFOA and PFHS no species differences were discerned due several factors including variability in the data, small sample size and the fact that for PFOA and PFHS, all concentrations were less than the LOQ. Table 10. Mean tissue fluorochemical concentrations in fish sampled from the `Tennessee River near Decatur Alabama. PFOS FOSA PFOA PFHS Species Location gke) (eke) (uke) (uke) Largemouth Bass Guntersville 230 83 <80 <15 Loc3 <s50 <50 <50 <10 Loc2 170 <50 <50 <10 Outtall* NQ 560 <20 <75 Loc-1 550 <50 <s0 <10 Catfish Guntersville*~~ <7.7 <15 <20 <15 Loc-3% <50 <25 <50 <25 Loc2 <25 <25 <50 <25 Outtall* 1200 NQ 120 n Loc-1 110 61 <50 <25 TFishecolle ected nn2002 CAatlfivsahludeastdaefnrootmedthwisitshit(<)inacrleudreespboorthteachdanlneeslhaannd yheelilolwimciattfoifsqhuantiation 'ANlQdisatnorteqpuoarntiedfioenddauweettodweaiaghntobtamsie.ting quality control criteria 8 REFERENCES Ellefson, ME. 2003, Tennessee River Valley Samples. 3M Environmental Laboratory Study No. E02-0443. p. 276. Giesy, JP. and J.L. Newsted. 2001. Selected fluorochemicals in the Decatur Alabama Area. Report to 3M. Reagferno,m WbKio.l,ogi2c0a0l2.maStroilcieds.pha3seMexEtnrvaicrtoinomneanntdalanLaalbyosriastoofryflMueotrhoocdhe,miNcuamlbceormpEoTuSn-d8s2311. US EPA. 2000. Guidance for Assessing Chemical Contaminant Data for Use in Fish AEdnvviisroorniemse.ntalVoPlroutmeecti1o:n FAigsehncSya,mpOflfiincgeoafndWaAtnearl.ysEiPs,A 832"3-EBd-i0ti0o-n0.07.United States 2 9 APPENDICES 23 9.1 APPENDIAX Selected Perfluorocarbons monitored in water, sediment and fish Collected from the Tennessee River, Decatur Alabama. Chemical Name: Molecular structure: Molecular ion: Perfluorooctanesulfonate CsF17805 499 o I CeF1r$--0 0I PFOS Chemical Name: Molecular structure: Molecular ion: Perfluorooctanesulfonamide CafFyiSONH; 498 Chemical Name: Molecular structure: Molecular ion: Perfluorooctancate CiF1sC00" 413 Chemical Name: Molecular structure: Molecular ion: Perfluorohexanesulfonate CeFiSOy 399 Chemical Name: Molecular structure: Molecular ion: Perfluorobutanesulfonate CiFsSOy fi Rl 0 FSOA f CrF1sCO PFOA Cfg 0 PFHS CRO" PEBS 2 9.2 APPENDIX B `Water, sediment and fish sampling locations for the 2002, 3M Tennessee River Project Water and Sediment [Eas|tNi orthn ing g| Tr 1 Downstream- Sample Location 1 Across 3M- Sample Location 2 490208 498946 3836096 38357705 Upstream- Sample Location 3 505470 3827825 rr rr 1 ---- [FishLocatons | Easting | Northing | 491386 3836210 3834205 3836283 Across 3M end 498483 505306 3836387 3827660 [Upstreamend@ | 504900 3824585 [Upstreamstart(0) | 505466 3828685 [Upstreamend 0) | 506967 3827705 rr _-- 1 Coordinate System- UTM- Zone 16 North-NAD 1927 25 Standa`rWdaOtpeerrSaatmipnlgiPnrgo,cedure 3MDecaturSampling Trip "1Th0epPuUrpRoPsOeSoEfthisStandardOperatingProcedure(SOP)istoprovidedealsfo thecollection ogfenwearial purosciendaugrMeassftoescFolelxlpeericosttfawliatiotcepnusmapmoplfess.omSepecciofmipcasraambplleinungite. tThlissShOouPldoubtelionuetsltihneed iSnCtOhePsE.ite-wsorpkeplacnaindfquialicty assuraneeproject lanfo eachindividualproject. ``cWoamtpearsaabmlpeluensic.olTlheectseedsuanmdpelrerthsiasrSOfPialryestiombpelteadkeveincweitthhaatMcaosntseicstFloefatpuebriinsgtaplutimcppuomrspamned. tSuebvienraglarolplerpsarrefdoersoitghnpesdpwerictihfiiincptsrhoejeepctu.mTphheetaudbionrgoflitsowvietrhtihne ugbreoonvewciltohciknwtihsepfuamshpiohne.ad. Asbithnegaronldledrissmpoelvsetooventrhteeottuhbeertsihdeey.cTrhaetseeuavnaicsuaurme tophtitmdarlafwosrtshuerwfactewtautpetrhsraompulgihntghien. cpbaoesruetssieowdnhowefirttehhieeptaiucihmmppscoarmotpmalenesttotmihniatncoionmltiayzctehweiastneyhlehrcietsskeoadfmtcupoblnietn.agmcAionnameteiwsoipno.nrctoinotnaocftwpirtheth-e<slampelbeai.nngNecoadn E`EQquUiIpmPeMntEaNnTdsuppliesneeded may include,butar not limitetod the following: + Onebos orsamplingbargeorthepurposeofcolctng isitparametersand suf watersamples + Dteimrpecrtaetuarde,aDnOd, pprHo,pecornldyucctailviibtrya,tneddwsaatleiriyqu(aYlSi1tyMsoamdpeli6ln3g0idns9t5r)uments capable of recoding + Masielextubingpumporsomecomparabuliet + Samplecontainersandcovers with wet ce forsamplesorage + Field datasheets, COCforms,andrelatedmatecisls + ceammesrn,efeidle,dfteokddoncoutmeebnotodk,ptensc,olslaecmtpiloen abtevlt,ecsusatnoddy0sebaelsl samplears for shipment, inclding: + PersonaProtectiveEquipment PPEasrequiedby th sieHeathsodSaftyOfficer, + Decontamination equipment Prmieoasruoretthhecwoaltleerctiqouanoliftysuprafraacmeewtaetresrasaemapclhessu,mdpilreesctta-teiaodn.iTehdedmierteecrtsrieald biendsetplroyuemdwetionlltbse cmaalyibriantcelduedaecbhudtaayr.e pSoutglgiemsitteeddfpoa:rameters targetedformeasurement a each sampling station + Wate depth m) J-- + Dissolvedoxygen(mg) Conductivity (umboslem) MS Word 97 7 2 + Sely Cl) pew) TInesquoimeedn.aWantcee,utnhietyomlleeecirontoocfodlliecotnadeiiwonaaelpqaaraimceytpearrsawmieltebresdmeaydbeawnasdredd. oe P1.ROObCtaEiDntURhEsSamplelocatoninformation rom eetescapeof-wrk,wok aulo ,the sWaomprlkiPnlganl.ocTathisonm.aybeinthefom ofancualcordate or 8description of hegeneral 2. aPloswiatyisonwtohreksafmrpolmintghbearmgeesotrdoowsntsatvreeratmheloscealetcitoend(s0amtphleemloscattiuopns.tTrheaemfleodcactroenwsuonulelsds obervisedicted. 3. lOoncacteiyonodueatmificeasttiohnepodpeenlioecadtoinotnmheasasmuprlianngdoegc.arddepth ofwarand recordsample 4. Makesure thatlldatashctscorespond othesortsamplinglotion. 5. SMaealslureestyhsetseamm)splnidnrgelcoocradtsoinmupsliengctoerbdeastteavaoniabheleseamcpolliongg1y5(3.globalposining. 6. aAnfdterrewcaorrdemdu.pTahneddceaplibfraodiofnghesiheodumderteeflresc,wahteedqeahliaypwahriacmhevtaertseislalmpbelmesearseured Collcidndanyotherrequirementsofthesespecificwok pla. 7. Watesampleswil enbecllcted singa spprpristpumpwithpre-clened bing 8. tTuhbiensgpecdiefpiecnydpseonatnhde dieepofowfsianmgpfloe tsoabmeplcianglslheoudld beobined.Thelegthiofs 9. bWeeaavdescheomeilnygtiharodu.ghtheessedsokonthepump.Makesethat he pestalic 10i.Ltooweprritmheeeneldfo.fthetoe ntothewate otedesireddep.Tur hepumpon ndvai for 1.TRubuinnwgat(ecraltehruoauegdhbtyheatkbineguhelryaodusaovfechoempblientgeadnad tshesltenrgtehvoTlIuPm.e additionsofthe 12 yOoncuesasmpplper.oimaerloyevolumeadditions haveruntrohuetugbinhg, begincollecting 13.aSnamspllaetceodntacineors nwilotlfbecisoeoanrl.edwiththeappropiatecas,labeled,andplacedonwetce in 14. SAppepcriofpirciQaAtPePC.OCdocumentationwill cotmhesapmpleasaenuieydby thepres: 15.TuAbfitnergcaolnldecntaivoingoaftethoestaemprleex,rseammoplvietnghlocbationng.nddiscard.Obi new ectionf MS Word 97 5 2 Peti`t SPoaearadnodriSEomiclSekamnmpDlriatendgnge FoSrttahneda3rMdDOepceartautriSngaPmropceldiuTrrneigp 10 PURPOSE odTefhtsaeipclutrhepeogsseeendoeifrmteainmtsesSttuhasoindndsgarreeidqtOuhpieerrendPien0cgtotPlrlPoeccoteudsuuorrefEa(cceSksOemFda)iinmseDnrtepdsrgaomevp.ildPeersodwceiteandigulsrfeeostroetureotcfoilhdleebcsetelioonw s`dceaosmncpdrliitipintogindos,nesveoicfreeasq.uniaApslpmelecontutsgofhfietslhudenpdprelotceaecidollusolreefcsst,aiamoanpdcldeaoccabulmeeesncttiaanotdniaworindlinlzeecbdee.sTsnhafrelysoen1pcercodolbclyeescidstuee-rgspdeeesciifsic sing iterofthesemethods. 20 scope "PrTehetePelePtaointthaPariorndvbaoretitlowmiysd.eIlytuisseedspiecbioalyfurseesfhalidnssaanldt,wtgerarvsef,occonoslolleisdtaitnegdsmedsilmeontlsfyrobmosoofmtsto. `wnnhiiettrwceoesmgaehnstdiiesncdaopndptrraeocdxgiewmsiawttiheltllyheos5t5ekdwgio.mrekn.tT.hTehPeosoaamrpilseasreelsfw-ictlohsithnigsswamiplier1th5atr1e5leranseaswndhteeth. `ETychsketmEemcaskntmDhaartnehdDargveeedgheigihsadmeosuingtnsedof0dceoblrliescotrsarmopclkeysbeitsoomfs,,fitnheelsyeduniivtisdetdypiicralalywbioltltoomtsw,oIrnk ti`Xw1nel5.tcoTrhelemeuaiseaottifhsseetrsdyppiimrceeainltnl.ygl-olwoeradedodoetrodst.hTehbeodtooomrvsaiardersoipgeaneddtoamcelsosseaUggehr,einsecatodmopwanstshi8e.1n5g. * saTmhipsliSnOgPdweivlilcecsoavenrdtthheeeqsupeicpimfeinctprroecqeudiurreedsttohcotllaercetfsoleldoiwmeedn.tsamples singeterof these 30 EQUIPMENT Equipmentadsuppliesneededmay clade,butwenotlimitedtothe following: + + PSettaibtleePboortaorarnpdlEacfkboarnDgrmaeegne + + SSaltesssleeelmasipxoionlngsfcoosrnthaiosnemrsogensiedziimenntgs + + FSieemlpdldeatcaosnhteaeitnser(swaptreorjeqctuspelciifict) ayndccohgleeenresrmwaliidtahstwsettheyief,to)rsamplestorage + Chainofcustodyforms MSWord 97 2 `sheimpsmenet,sidncthoidnogc:ucmeanmtera,taico,lilckinnaoctteibvoiotke,s pnends1(vbieelisnaemplaeco4ndveSrharfpoie), samplelabels, custody seals: oPregrasnoincavparpootrecmteitoenresqu(iOpVmMesn)tas reqiredby hesicHeathodSafety Officer,inching + Decontequaipmmentispnecifatortiheporent 40 SAMPLE COLLECTIONPROCEDURE. Surfs iment olcion singthe PonaorDredgesamplers wll svlvethefollowing procedures: 1. OWboirsknPtlhaens.aTmhplsemaloycbaetonntihnfeofromartmioofnfaroamcetthaecrotohrsiontpee-ooawdoersckr,iwpteironkouflhien,geaatle samplig locaton. 2. Pseodsiimieontnst,hethseamipelidncgrboawrsgheooulbdaovsavyesrwtohreksefloecmtedthseammopltedoawtsitone.aWrhleoncastaimopnlointhge. most upstream location nessxherwise rected. 3. 1W0h1ensapmopilinntgesdedimoent iwnsduendpwpaot,lesr)s.,Taittsemwpitlto sreotvtihcebsaormeesianipllce fiotrhheitphleatfaotrmwo 4. aOnndceenysourueamhitvetahtetphaetpiroopedrooccsatniootndmieaswuirleaensadmrpelcionrgd.detofwateandrecordsample Jocationdentais dfeifiiedcoahtsamiplinog nog. 5. Makesuretatalldtshets comespond othecorrecsamplinglotion. 6.sMetaslurestysetseamm)pslidngeccoadtisoanmpsliegctoohredbiensatteasvaoniatbeleseacmphlliongglyg(.5, globalpoioing 817..MOabkaensutreedtheactotnhieadmriedngaetdodrrpeodngaeroarornahedaeppeennpdsioontnhesnedfislmoewlnysulbotwearttehteympae)v. rte slsighiotfytsdhuebbmeoeartg.eTdh,irseilsea0se tpreevmenatntdeunittesmffomlpretmeatburoetcsouofrt.eOsystnetmhyeeoauisserw:e sampling.Theweigh ofth unisshouldforce the ifthesedimentboro. 9. Ihesiinn)g.hPeuEclktreolanoDreadtgea,nmarkeleeauseeteamtesheengneirt.sOunpcreighttheomtheebsotetomne(lguegecighrhet on doors,pul he unitoftebotomsndslowlyhoughthewater othebot. 10. FdortohopPeonoosretlheasfso.reTohfetehleourneitwhietninygotuhpesleldhiemenltnshhooludidncgtaseeunthiep,tihnehdoolrdisnwgtihle ose (coltecsaimplge). 1.sOtncletmihxinngciosntianitnehresb.otU,seplaadc alehecconotentnssnnoaeosnmesofeith5e7nd0e0c0son0thaiomminoeagteenddiszen,tehes sediment. 12.pOrnocpeerhsoammogpelneicoznetda,iunseerst.heIstnscesasetlastoheosnatmopllescabesulfffiocrietnstssaammpplleebvoelpulmaecsedtoontthee: icnonttalieosf. hAetpaermsionssmcaalltiinsg,aabedlstoypuekocfoannatliysitshfosramipslseaImDp,ldea.t,timecollected, MS Word97 29 13.sCpeoclifeitctwoerpkpprloapnr.steQAIQCsamplesasoutlinedinthe QAPPaachedtotheproject 16. Completethechainofcustodyform. 15.`Psluaffciecailelntswaemtplie 1i0nkteheepprtohpesrasmapmlpelseashitpepmnpge/rsaotruargeocfon4taCuinelr,wrhecieciptsbhyotulhdecloanbotraaitnory. beSilingghtcmoodlilfcitceadt.iTonhsemfaiyebdcerreewquwiireldsianythse fhiaevde, dewpoernkdiinnggknpoowolehdegetyopfetohfeseuqmupilpemteanttpsrior10 `osarmcphlainngge,sathdawtialrlebneefediedlfraswaimtphltihnegssppeecicfiifciresqyusiireemmssehntosuolfdtbheedporcojuemcet.nAtendyinmfoideifdidcaattaions sheetsandreflected ithe finalreport. MSWord 97 30 2/8] ole a EEE8E8 RE|gEE2E8R|EeEElHE Slee [slsldg [S]5)5 8 23] [22(E(E (2I2(E18 121855 EE EE E EEEa EEE EE EasaE Sama]2(3(S(S|8]21821(3 S5(3S|3 =z le ee ee 5 ESEER EEI EIEE EES EE Iara PEF H FEET :5 ||H22E50R58E32 FEERD 5 1548 258 85g el5 x22 =5| SE EE E ZE E E EEE Ee = R|&|81&|8 c[3 FBFsEEF55EEEEEREEIEEEIE EEEsSE gE| | RE2E3/2/2825 2R[2sR (2 5 S |3zlzzlz2 5588 55122 5122 9.5 APPENDIXE mtr otn | Coes[| |e] rr rr Date Fish TLenT gth [SLOI-LMOI |Downstream [4/15/02 |LargemouthBass| 41 | 872| [SLOI-LMO3 |Downstream [SLOI-LM04 |Downstream |4/16/02 |4/16/02 |LargemouthBass| |LargemouthBass| 31.4 33.2 | | 450 | 535 | [SLOI-LMOS |Downstream |4/16/02 |LargemouthBass| 44.5 |1181| [SLOI-CATOI|Downstream [SLOI-CATO2 |Downstream [4/16/02 |Catfish [4/16/02 |Catfish [SLOI-CATO3 |Downstream [4/16/02 |Catfish | 61 |2000| | 62.5|3150| | 62.1|2785| [SLOI-CATOS |Downstream [SLOI-CATO6 |Downstream [4/16/02 [4/16/02 |Catfish | 55 |17a4| |Cath____| 53.5 | 1575 | [SLO2-LMO1__|Acrossfrom 3M |4/18/02 |LargemouthBass| 30 | dso_| [SL02-LM03_|Acrossfrom3M |4/18/02 |LargemouthBass| 33 | 506 | [SLO2-CATOS|Acrossfrom3M[4/18/02 |Casish | _64 |3206| [SLOS-LMOL |Upstream [SLO3-LMO3 |Upstream [SLO3-LM04 |Upstream [4/17/02 |LargemouthBass|305 | 450 | 4/17/02 |4/17/02 |LargemouthBass| |LargemouthBass| 38 41.2 | | 675 956 | | [SLO3-SMO1 |Upstream [SLO3-CATOT[Upstream [SLO3-CATO2 |Upstream [SLO-CATO4 [Upstream [SLO3-CATO6 |Upstream |4/17/02 [4/17/00 | Largemouth Bass| [Catfish | 32.5 | 322| 563 | 816 | [4/17/02 |Cash | 57 |3516| [4/18/02 |Catih | 61.5 |2081| [418/02 |Catfish | 605|2278| 2 9.6 APPENDIX F Letter Report and Photographs of water, sediment and fish sampling efforts in 2002 on the Tennessee River. 33 eEmxtTTerki sie 20 Ormeax April 24,2002 Mr. Dale Bacon 3M Environmental Technology and Safety Services Building 2-3E-09 P.O. Box 33331 St. Paul, MN 55133-3331 Soe 1 Eine elo Re: 2002 Tennessee River Sampling - Fish, Sediment, and Water, Decatur, Alabama (ENTRIX Project 178401) Dear Dale: investigation. ENTRIX, Inc. (ENTRIX) is providing this letter report summarizing field activities associated with the Tennessee River field-sampling effort conducted April 15 -- 19, 2002 in Decatur, AL for 3M. To satisfy project deliverables, surface water, sediment and fish (fcaacitlfiitsyh oanndthleaTregnenmeosustehebRaisvse)r.werTehecoolbljeecctteidvefroofmthtihsreefefolrotcawtaisontsoicnoltlheectarreeaproefsetnhteat3ivMe samples for the measurement of selected perfluorinated compounds (PFCs). Samples were collected by Barry Gillespie, Matt Barczyk, Ramsey Redman, and Ryan Holem of ENTRIX. The General Project Outline (GPO) and Sampling Protocols provided by the 3M Analytical Technologies Group were followed by ENTRIX in the conductofthe field Sampling reviewed locations were determined previously by ENTRIX and 3M personnel and by the ENTRIX field team prior to sampling. The 2000 sampling event provided the necessary site river conditions and specific reconnaissance to site locations. The allow ENTRIX to sampling locations familiarize itself with were representative of areas used by for this field recreational and commercial fishermen. investigation, water, sediment, and fish At eachofthree locations selected samples were collected. Sampling areas consisted of a location across the River from the 3M point of discharge, a location downstream of the 3M facility, and Riverwalk Marina (Marina) located on a location upstream the northeast side of of the 3M the river at facility. The approximately river mile 305 was used for river access. The downstream sampling location was in the vicinity of Fox Creek (approximately river mile 296), the sampling location across the river from the 3M facility was located approximately at river mile 301, and the upstream location was the Highway at 31 river mile 307.5 bridge) (Figure (upstream 1). of the 3M discharge, the city of Decatur, and 34 FIELD SAMPLING T20h0e2.ENETqRuiIpXmefnietldansdamspulpipnlgiecsrweewrearlriovaeddedatonthea sampling site 16" sampling the morning barge in the of April morning 15, and Atepsrtiilng15o,f20fi0e2ld(Meqounidpamye)ntanpdraoccteievdietdi.es weArcetucaolmpslaemtpeldinogn cthoememveennciendgofthAepraiflte1m8o,o2n00o2f c(Tohnutrisnduaeyd).unCtiolllAepcrtiilon16o,f2w0a0t2e.r aFnidshsecdoilmleecnttiosnamwpalsesincitoimatmeednocnedthoenevAeprniilng15o,f2A0p0r2ilan1d5 and continued through April 18, 2002. Water and Sediment Collection Water, sediment, and the QA/QC samples General Project Outline (GPO) provided by for 3M. water were collected according to the The boat was navigated to the selected location and a Garmin GPS 12 sampling location (Table 1a). Global Positioning System was ~All sampling locations have used to document the been recorded on a topographic map (Figure then calibrated and used 1). to mWeaatseurrequaplHi,tydmiestseolrvsed(YoSxIygMeond,elte9m5pearantdurMeo,desalli6n3i)tywaenrde conductivity according to (Table the 3M 1b). GPO, Once surface water and they were properly labeled, sediment stored on samples were ice at 4C, and collected delivered to the 3M environmental and accompanying water laboratory in Minnesota QA/QC samples were via FedEx courier. delivered (priority All water, overnight) sediment to 3M in Minnesota on April 16, 2002 dSutrainndgartdheoepnetriarteinprgojpercto.cedPurroepserfoQrAs/aQmCplseamcpollleesctfioornwaatnedr,parsepraerqautiiroend wbeyrtehema3iMntGaiPnOe,d wcuesrteodcyolfloecrtmesd, ainndthaeffiieellddd(aTtaabbloeo2k).wAalslussaemdpltoesdowceurmeesnhticpopneddituinodnesraEndNTacRtiIvXiticehs.ain of Fish Collection aFibsohveweurseincgoallbeocattedmforuonmtetdheSmthirtehe-RsoaomtplteypleocVaIt-ioAnsel(eTcatbrloesh1oackainngd dFeivgiucree (1s)eeidaetnttaicfhieedd sPihxotcoatLfoigs)h.weArcecotrodbiengcotloltehceteGdPfOr,oma mcaicnhimoufmthoeftshirxeebassiste(s,preiffeproasbsliybllea.rgeAmtoubtoht)h atnhde upstream fish was and downstream collected (ic., six sampling bass and locations, the minimum number six catfish). However, while the of cach species of minimum number oRfepceaattfeisdh aatctreomspstsftroomcotlhleect3tMhefarceimlaitiyniwnagstcwaoptbuarsesd,reosnullytedfoiunr nboascsapwteurree. coFlloercttehdi.s investigation, retained for only the analysis. desired fish Collected species caught at each fish were measured of the (total sampling length), locations weighed, were and immediately wrapped Samples were labeled, ipnlaacleudmoinnuimce,foailndansdhipplpaecdedviain ziplock overnight storage FedEx bags (Table 3). to the ENTRIX tohffeiAcequiantEiacsTtoLxaincsoilnogg,yMLiacbhoirgaatno,ryan(dAtThLe)n transported at Michigan immediately to freezer State University. facilities in 35 UFrpeosnhwactoemrpleFtiishoenrioesf swaamsplniontgifiaccdtivtihtaiets,satmhepliAnlgabwaamsa Department of Wildlife and complete and their required notification form was completed and mailed to them. Fish Processi&ng Sample Preparation Fish remained personnel (Mr. frozen in MSU freezer Ryan Holem) conducted facilities until processing began. the fish processing and preparation ENTRIX of fillets MPraoncaegdeurmeesntdesSctrainbdeadrdinOptehreat3iMng GPProOceadnudretsheVoAlluambeamIaII DweepraertmfeonlltowoefdEninvifriosnhmetinstsaule preparation. Parnidorwtaorpmrowcaetsesrintgh,enallcowvoerrkeidngwistuhrfaalcuesmiinnutmhefoMilS. UAnlaybourtaetnosriylswuetrielizweadsihnedthewiftihllsetoianpg amentdhahnoomlo-rgiennsiezdatifoonllopwreodcesbsy were first washed a de-ionized (DI) with soap and water rinse. warm water, All utensils then were decontaminated between fish to avoid `was wrapped (dull side out) around the cross-contamination. handlesofboth fillet In addition, aluminum foil knives. Nitrile gloves were `worn throughout the process. to avoid cross-contamination. This process was repeated before cach new fish was started FEialclehtsfiillnectlwuadesdrtehmeovtiesdsuefrformotmhebefhiishndantdhethheeasdkintortehmeovtaeild ounsinbgotah fsilildeetsknoiffee.acThhefisrhi.b bones were portions of cither avoided during fillting or the fillet remained. The carcass removed of each from fish, each fillet so the skin, and that rib only edible bones from eloaccahtifoilnleatnwdeIreD nthuemnbwerraapnpdedplianceadluinmianpurme-floaible(ldeudllzispildoectboafgi.sh)W,hleabnelpeodsswiibtleh,ictsarscaamspslees were kept placed in in their portable original coolers foil and before stored being placed in at -20C. The ziploc bags. fillet was cut Carcasses into small were then pices to `steexepledibtleetnhdeergrfionrdinsgampprloceesss.witAhhalensds gtriisnsduee.r waIsn uasleld cfaosrest,he tlhaergegrrofiusnhdantdisasusetsaiwnleerses thoroughly mixed homogenization. with Once stainless steel spatulas and mortar and homogenized, the tissue was massed pestle to the to ensure adequate nearest hundredth glorcaatmioann,dIDplancuemdbeirn, 3daMteapprporcoevsesdedN,aslagmepnlee ciodnetnatiinteyrs(.bassAolrabcealtfidseht)aialnindgmtahsessoafmptlhee tissue was placed on cach container. bags and stored in coolers at -20C. All containers were placed in pre-labeled ziploc Upon 20C, completion of processing, placed in portable coolers samples were removed from the coolers operated at and covered with wet ice. Original Chain of Custody forms (or copies notebook pages in of originals), a ziploc bags were sample placed isn uemamcharcyoolserh.eet,Taapned copies was used of to laboratory secure the lids and at 3M's EdnrvaiinrsoonfmealnltaclooLlearbso.ratCooroyleirnsMwiennreessohtiap.ped priority overnight mail to Sue Beach ENTRIX have any qiusepslteiaosnesdplweiatshetchoentoapcptormteunaitty71t3o-6c6o2n-d1u9c0t8.this sampling effort for 3M. If you 36 Sincerely, W. Barry Gillespie, Jr. Project Scientist Ce: Dr. John Giesy 37 Photo L0g:2002 3M, Tennessee River Sampling Effort Photograph 1: Downstream sampling location (mouth of Fox Creek) Photograph 2: 3M facility near outfall (sample location across river from this facility). 38 Photograph 3. Upstream sampling location. -12 Ii| Photograph 4: Collection ofsurface water. 39 i oP. 3 v [a ~ yo prt Ls 7 A - BY 3 > Photograph 5: Collectionofsediment using Ponar sampler. h . LN - i] |A PY ad po a a Photograp6h: Electroshocking device mounted onto 16" pontoon boat. 0 Photograph 7. Site across the river from the 3M facility. a1 -------------------------------------------- 9.7 APPENDIXG Felieschtwroesrheocskaemr.pleThdifsrcolmecetarcohshloocckaetriocnawnitbhe ausSemdiitnh-lRarogoetbToydpieesoVfI-wAatheeravliykdeultaykeSskaWnd rTievnernse.ssEeleecRtirvoesrhwoecrkeoptearkaetninfgropmrotcheeduSrmeisthf-oRlolootwemdaninuatlhes cTohlelescetiionncolfudfeisthhefrfoolmlotwhieng: 1. 2. Type Type VI-A VI-A Operation Manual. Parts Identification. January 1994, pp4. December 1994, pp 10 3. 4. EElleeccttrrooffiisshhiinngg MSaafneutayl,.JaJnuunaery1919949,4p.ppp9.3 Smith-Root, Inc. V1a4n0c1o4uNveEr,SaWlAmo9n86C8r6e.ek Avenue Phone: 360-573-0202 Fax: 503-286-1931 a2 ---- ee --