Document oDmvdGK7Q70G3YgB8oq13zpQg

Ar226 -- 1109 SELECTED FLUOROCHEMICALS IN THE DECATUR, ALABAMA AREA e 22 =z 3258 2=R - CONTAIN NO CB! 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 June, 2001 000422 1 1 EXECUTIVE SUMMARY A monitoring study was conducted to assess the current extent, status, and magnitude of fluorochemical concentrations from a 3M Facility near the Tennessee River in the Decatur Alabama area. The objectivesofthe study were to determine the concentrations ofselected fluorochemicals in biotic and abiotic phases withinthe Tennessee River in the vicinityofthe 3M 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 (PFE). Surface waters and sediments were collected from five primary locations. These areas consisted ofa location near the 3M pointofdischarge (Outfal), a stream the receives the 3M Facility effluent (Bakers Creek), a downstream location (Fox Creek), a location upstreamof3M Facility but below the CityofDecatur (DWTP), and a reference location upstreamofGuntersville Dam. Clams were collected from the Guntersville location and the Fox Creek location. Fish were collected from the 3M Outfall and from the Guntersville location. All samples were collected according to standard procedures and analyzed for fluorochemicals accordintgo 3M Environmental Laboratory methods. Results from the monitoring study indicate that the while the effluent from the 3M Outfall did cause changes in some water quality parameters within Bakers Creek, it did not cause any statistically significant changes in water quality parameters at the farthest downstream location, Fox Creek. Average surface water PFOS concentrations ranged from 0.009 to 151 ug/L. for Guntersville and Outfal, respectively. Average PFOS sediment concentrations ranged from 0.180 to 5930 pg/kg (wet weight) for Guntersville and the 3M Outfall, respectively. However, while fluorochemical concentrations in sediments and surfacewaterswere greater in locations downstreamofthe 3M Outfal, the downstream sample locations within the main stemofthe Tennessee River (Fox Creek) were not statistically greater than those upstream (DWTP and Guntersville) of the 3M Outfall. Only samples collected from the 3M Outfall and Bakers Creek, locationsthatare in the immediate vicinity the 3M Outfall, were significantly greater than those in the 000423 2 reference location. From these results, it can be concluded that the effluent from the 3M Outfall does not significantly affect fluorochemical concentrations in sediments or surface watersinthe main stemof the Tennessee River. Fluorochemicals were detected in al fish collected from both the Guntersville reference area and 3M Outfal. The least fluorochemical 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, 9.43, 11.7 and 7.50 ugg, (wet weight) respectively. For fish from the outfall, average whole body concentrations for PFOS, FOSA, PFOA and PFHS were 1332.0, 20.1, 106.4, and 86.9 pg/kg, (wet weight) respectively. While there were species specific differences in the accumulationofthe selected fluorocarbons into fish collected from either Guntersville or 3M Outfall locations, these differences were not statistically significant due to the small sample size and among-individual variability. Concentrations of FOSA and PFOA in clams collected fromtheOutfall weregreaterthanconceonbst ervr edianct lai msco olln ectsedfromthe `Guntersville reference site. However, PFOS and PFHS tissue concentrations in Outfall clams were not greater than concentrations in clams collected from Guatersville. In conclusion, fish downstream of the 3M Outfall contained greater concentrations of fluorochemicals than did fish from the Guntersville area but the significance of these differences is difficult to assess duetothe small samplesizeand variability. 000424 3 2 INTRODUCTION Entrix, Inc (ENTRIX) is providing a report on activititeos assess the impactofeffluents containing fluorochemicals from the 3M Facility in Decatur, Alabama to the Tennessee River. Water, sediment, clams and fish were collected from upstream and downstream locationsofthe 3M Facility and wereusedto evaluate themagnitudeofreleasesoftarget `compounds from the Facility to the Tennessee River. The objectives ofthe research are to determine concentrations of selected fluorochemicals in abiotic and biotic phases of the Tennessee River system in the vicinity of the 3M Facility at Decatur, Alabama. Fluorochemicals selected for evaluation in this study included: perfluorooctanesulfonate: (PFOS), perfluorooctanesulfonamide (FOSA), ~perfluorooctanoate (PFOA) and perfluorohexane sulfonate (PHS) (Appendix A). In addition, trifluoroacetic acid was also evaluated in water and sediment samples taken from the Tennessee River. 3 FIELD SAMPLING 3.1 SiteDescription Four primary locations were selectedforthe field investigation (Figure 1, Appendix B). These areas consisted of a location near the 3M point of discharge (Outfall), a downstream location, a location upstram of 3M but below the City of Decatur, and a reference location upstream of Guntersville Dam. Specifically, samples were collected adjacenttothe 3M Facility Outfall (includes Outfall and Bakers Creek) that corresponds River miles 301-302. Samples were also collected downstreamof the 3M Facility near the mouthof Fox Creek (River miles 296-297). Sediment and water were collected upstream of the 3M Facility 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). Tobetterevaluatethe impactofthe effluentfromthe 3M Outfall,the Bakers Creek location was divided into two sub-locations, Bakers Creek-1 included Stations 1, 2 and 3 thatwerecollectedneartheoutfallandwithinBakersCreek.Stations4, 5 an6dandwere collected near the interfaceofthe mouthofBakers Creek and the Tennessee River and are identified as Bakers Creek-2. 000425 . | N | BakersCreek DecaetusrpWVaastcewater RGeufineenrcilSete Chattanooga FoxCreek Decatur DecaturDrPiaknitng Water i "TennesseeRiver GunteDrasvmille, " a DFirleoctwion Direction | Figure 1TeeRisverasnsaplinglocations evlusted rin study. GRuesnertvoeirr | 000426 $ Fox Creek sampling locations were also divided into two sub-locations. Fox Creek-1 included Stations 7, 11, 12 and 26/27 that were collected from the mouth of Fox Creek. Fox Creek-2 included Stations 8, 9, and 10 that were collected onthe northern sideofthe `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 FieldSampling Logistics `Sampling at selected sites on the Tennessee River was initiated on June 19, 2000 by ENTRIX. Collectionofwater 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 Entrix sampling protocols (Appendix C). 3.3 SAMPLE COLLECTION 3.3.1 Water Collection Water samples were collected using ENTRIX sampling protocols from a totalof26 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 3M Outfall, the City of Decatur wastewater treatment facility and the upstream reference location. Seven water samples were collected from the area `downstreamofthe 3M Facility near Fox Creek. In addition tothese25 samplesofsurface `water, water was collected from the 3M Facility effluent stream. All sampling locations were documented using TRIMLBE PRO-XRS Global Positioning Satellite technology and these locations were recorded on topographic maps. Samples were properly labeled, stored on iceat 4C, and deliveredtothe 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 3M Outfal, the City of Decatur's wastewater treatment facility, and the upstream reference location using either a Petite PONAR and/or Eckman dredge. Seven samples were collected from the 000427 6 downstream area in the vicinity of Fox Creek. All sampling locations were documented using TRIMLBE PRO-XRS Global Positioning Satellite 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 4C, and shipped to the 3M Environmental Laboratory, St. Paul, MN. `Table 1. Location and identificationofsediment and water samples collected from the Tennessee River in Alabama Water Sample _ Sediment Sample _ Location Sublocation/Code SW-0 SED-01 `Bakers Creek, BCRI SW-02 SED-02 Bakers Creek BCRI SW-03 SED-03 Bakers Creek BCRI SW-04 SED-04 Bakers Creek BCR2 SW-05 SED-05 Bakers Creek BCR2 SW-06 SED-06 Bakers Creek BCR2 SW-07 SED-07 Fox Creek FCRI SW-08 SED-08 Fox Creek FCR2 SW-00 SED-09 Fox Creek FCR2 SW-10 SED-10 Fox Creek FCR2 SW-11 SED-11 Fox Creek FCRI SW-12 SED-12 Fox Creek FCRI SW-13 SED-I3 . Decatur WIP WWTP SW-14 SED-14 Decatur WWTP WWTP SW-15 SED-15 Decatur WWTP WWTP SW-16 SED-16 Decatur WWTP WWTP SW-17 SED-17 Decatur WWTP WWTP SW-18 SED-18 Decatur WWTP WWTP SW-19 SED-19 Guntersville GTVL oswao SED-20 Guntersville GTVL sw-21 SED-21 Guntersville GTVL sw-22 SED-22 Guntersville GTVL sw-23 SED-23 Guntersville GTVL SW-24 SED-24 Guntersville GTVL SW-25 SED-25 3M Outfall OUTF SW-26 Fox Creek FCRI Sw-27 SED-27 Fox Creek FCRI 3.3.3 Clam Collection Samples of the Asian clam (Corbiculafluminea) were targeted for collection from a location downstream of the 3M Facility and from a location upstreamofGuntersville 7 000428 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 in this study. Furthermore, due to their ubiquitous distribution in the Tennessee River and their sessile behavior, they provide site-specific information concerning the potential accumulationoffluorochemicals into aquatic biota. Due to the habitat requirementsofC. fluminea, clam samples were not co-located with water or sediment samples. Clams were collected using aPetit PONARdredge. However, due to difficulties in locating clam beds as well as interferenceofsubstratum with the PONAR dredge, the collectionofclams was limited to two composite samples from locations in the vicinityofsediment samples. One sample (approximately 25 clams/sample) was taken from a location downstream of the 3M Facility (SED-0, -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, MI 3.3.4 Fish Collection Fishwere collectedfromtwo locations (Table 2). One location was in the vicinityofthe 3M Outfal and the other was located within the reference area upstreamofGuntersville Dam. The fish samples were collected using both hook and line as well as gil net. Gill nets (passive gear) were placed in the lower energy environments where concentrations offish were generally greater. Due to the. techniques employed for collection of fish, all fish caught in eachof the 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, 000429 8 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. LC/MS/MS characterization of fluorochemicals was conducted at 3M Environmental Laboratory. Summariesofeach protocolaregiven: Table 2. Sample identification Tennessee River. pySample ID. LGoucntaetrisoinle M2 3M Outfall SHAD1 3M Outfall SHAD2 3M Outfall SHAD3 3M Outfall SHAD4 3M Outfall SHADS 3M Outfall SHAD6 3M Outfall SHAD? SHADS 3M Outfall 3M Outfall WPL 3M Outfall WP2 3M Outfall CAT1 CAT2 Guntersville Guntersville CAT3 3M Outfall CAT4 3M Outfall GARI Guantersville GAR2 Guntersville `GAR3 Guntersville GAR4 Guntersville `GARS 3M Outfall GARG 3M Outfall SBI Guntersville SB2 Guntersville SB3 Guantersville SB4. Guntersville SBS Guntersville SB6 SB7 Guntersville Guntersville SBS Guntersville SB9 Guntersville: SB10 Guntersville SBI Guntersville SBI12 Guntersville sSpBuId3 GGuunntteerrsvviillllee and locationofindividual fish collectedfromthe Largemoutibass|SpeciMeiscropters samoides Largemouth bass Micropterus salmoides Skipjack Herring Alosa chrysochloris Skipjack Herring Alosa chrysochloris Skipjack Herring Alosa chrysochloris Skipjack Herring Alosa chrysochloris Skipjack Herring Alosa chrysochloris Skipjack Herring Alosa chrysochloris `Skipjack Herring `Skipjack Herring Alosa chrysochloris Alosa chrysochloris `White Perch Morone americana `White Perch 'Morone americana Catfish Catfish Ictalurus punctatus Ictalurus punctatus Catfish Ictalurus punctatus Catfish Ictalurus punctatus Gar Lepisosteus sp. Gar Lepisosteus sp. Gar Lepisosteus sp. Gar Lepisosteus sp. Gar Lepisosteus sp. Gar Lepisosteus sp. Striped Bass 'Morone saxatilis Striped Bass Morone saxatilis Striped Bass Morone saxatilis Striped Bass Morone saxatilis Striped Bass Morone saxatilis Striped Bass Striped Bass Morone saxatilis Morone saxatilis Striped Bass Morone saxatilis Striped Bass Morone saxatilis Striped Bass `Morone saxatilis Striped Bass Morone saxatilis Striped Bass Morone saxatilis SStrriippoeddBBaassss MMoorroonneessaaxxaaitilliiss 000430 41 WaterAnalysis `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 forty-millilter portionofsample was transferred to a Cig SPE cartridge and the cartridge was eluted with mi of 40% methanol in water. The eluate was discarded and the SPE column was eluted with S ml of 100% methanol. The eluate was collected for analysis by LC/MS/MS. This treatment resulted in an eight-fold concentrationof the samples. 4.2 SedimentAnalysis Forsediment samples, a 5 gportion was extracted into 5 ml methanol. Theextracts 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 FishLiverAnalysis Fluorochemical surfactants were extracted from fish livers using an ion pairing reagent and methyl-tert-butyl ether (MtBE). 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-8-6.0, "ExtractionofPotassium 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 surrogate standard and then 05 M tetrabutyl ammonium hydrogen sulfate (TBA) and 025 M sodium carbonate/sodium bicarbonate was added to each sample. Five ml methyl-fert-butyl ether `was added to each 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 ml of the organic layer was 000431 10 transferred to 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 filters into glass autovials for chromatographic analyses. 4.4 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 5 gram sample was weighed a 50 ml polypropylene tube and 15 ml acetonitrile was added. Samples were shaken for 30 min andthencentfror3i0mfinuatg35e00xdg. The supewamspaassted tahrnougtha column of Florisil and activated charcoal and the eluate was collected in 50 ml polypropylene tube. The column was eluted with 15 ml methanol and both eluates were combined. Twodropsofoctanolwereaddedtotheeluateandthenthe samplewas reduced to near dryness under a flowofnitrogen gas. Thesamplewas resuspended in 1 mi methanol and passed throu20g.h2 um nylon filter into autovials for chromatographic 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. Field matrix spikes solutions were prepared by collecting one liter of site water and spiking with 20 or 100 ul oaf 10 ppm stock solution containing PFOS, FOSA, PFOA, and PHS to yield 200 and 1000 ppt solutions, respectively. 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. A field camera was used to `document all locations and to provide a visual recoofrthde conditionsofthe site during the sampling events. In addition, ambient water quality parameters, such as temperature, conductivity, salinity, pH and dissolved oxygen were measured at each location during each sampling event. Since the method detection limit (MDL) and limitofquantification (LOQ) are analyte and matrix specific, method and matrix blanks along with matrix o00acz spikes were used to determine accuracy and precision of the extractions and final chemical determination. Waterand sediment concentrations were not corrected for either `matrix spike recoveries or corrected for purityofthe fluorochemical standards. Fish tissue fluorocarbon concentrations were reported as wet weightandwere not converttedo a dry weight basis. 6 STATISTICAL ANALYSES Statistical analyses were preformed with SAS (Version 8, SAS Instiute, Cary NC, USA). General linear models (PROC GLM) were used to test for differences among 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 meansofthe different locations. 7 RESULTS 7.1 Water quality parameters Water quality parameters of river water from each location are reported (Table 3, Appendix E and F: figures la, 1b, 1c, and 1d). Dissolved oxygen and pH were variable `within thestudythere were no significant differences observed between values measured inwaterscollectedfrom the 3MOutfall orBakersCreeksandthosefromupstream or downstream locations. Conductivity and temperature measured at the 3M Outfall and within Bakers Creek (BCRI) were significantly different from the upstream and downstream sample locations. However,therewas no significant difference between that fromBakersCreek 2 samplesand thosecollectedfrom eitherthe upstreamand downstream sampling locations. This resultindicatesthat the effectofthe effluent from the 3M Facility on water quality parameters was limited to a small area near the 3M Outfal, 000433, Table 3. Water quality parameters for samples collected from the Tennessee Rdievveira,tioinnsthe Decatur Alabama area. Values are reported as means and standard Location (DmOg) C(ounmduhcotsievimt)y Temperature pGu)H `Guntersville 786) 16942)8 293.)0 824 DWTP 1030)* 1(8344.)7 02933) 8238) Outfall 6.5 4650 * 332% 72 Bakers Creek-1 a1745 (118473435.*0) 3(10.74)% 1 3) " Bakers Creek-2 9.0 0.6) 463.0 (108.9) 29.6 (0.6) 8.0 .1) Fox Creek-1 (8.41) 1@799.)0 2278) 832) Fox Creek-2 8.8 162.7 278 82 3) @1) (0.5) (0.5) Smet;Gl omGee Sea00 72 Fluorochemicals 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 2d). The least concentrations of all measured fluorochemicals, were observed in samples taken at Guntersville while the greatest concentrations were observed at 3M Outfall In increasing order, the concentrationsof PFOS, FOSA, PFOA and PFHS in surface water wasas follows: GTVL < DWTP < FCR1 < FCR2 < BCR2 < BCRI <Outfall. Concentrationsofsurface water fluorochemicals at only the 3M Outfall and Bakers Creek 1 locations were significantly greater than those measured at Guntersille Reservoir Trifluoroacetic acid (TFA) concentrations were elevated in 3M Outfall (mean =1420 4/1), Bakers Creek (mean = 680 ug/L) and Bakers Creek 2 (143 gL) samples but `were less than the reporting limit of 100 ug/L in water samples collected from the other 000434 3 sampling locations. This result indicates that the effectofthe effluent from the 3M Facility on TFA water concentration was limited to a small area near the 3M Outfall. Table 4. Mean concentrationoffluorocarbons in surface watersofthe Tennessee River in the Decatur, Alabama area. Concentrations in means and standard deviations PFOS FOSA PFOA FFAS Location (ug/L) (ug/l) (ug/L) Gel) `Guntersville 0.009 0.004 0.008 0.003 (0.002) (0.002) DWTP 0.053 (0013) 0.016 0.025) 0.028 (0.006) 0.006 0.006) Outtall 15050 7.985% 1900.00% 42.704 @.778) (0.148) (0.00) (1.697) Bakers Creek-1 ~~ 82.260% 5.424% 1023600 22374* (56.672) 3.074) (71264) (14.665) Bakers Creek2 13.838 1191 129375 4.034 (2351) 0244) (31.892) 0.575) Fox Creek-1 0.54 0.169 2.647 0.566 05) 002) 6149) (.102) Fox Creek-2 0.179 0.055 1.001 0.168 .110) 0.033) 441) 1149) *TLSiimgniitfoicfaqnutalnyiGaitfieorneftorFralolmGluuaotreorcshvelmliceaRlessweartveoriirsat0.0=250.g0/5L. Allluorochemical `conrcepoertendbetlowrthae LtOQiareeostinmatses. Additional statistical analyses were conducted on fluorochemicals in surface waters to further examine the difference between sample locations (GTVL, DWTP, BCR2, FCRI, and FCR2) located within the Tennessee River. Results from the first analysis showed that both the 3M Outfall and BCRI could be influencing the resultsofthe statistical analysesbyactingin amannersimilartothatofanoutlier. For instancteh,e `concentrationofPFOS at the 3M Outfall and BCR1 were approximately 17,000-fold and 9,700-fold, greater, respectively, than the concentration observed at the Guntersville Tocation. Removalofthe 3M Outfall and BCR1 samples from the analysis allowed for the evaluationofthe hypothesis that there were no statistically significant differences in 000435 1 fluorochemical concentrations within the main channel and near shore locations within the river. Results from the second analysis (Table 5) show that for water concentrations of PFOS and PFOA, only BCR2 was statistically greater than Guntersville Reservoir `concentrations. Furthermore, while the concentrations of FOSA and PFHS at BCR2 and FCRI were significantly greater than Guntersville, they were not significantly different from the furthest downstream location. Thus, at FCR2, the furthest downstream location, the concentrationoftargeted fluorochemicals was not significantly different from that observed at Guntersville Reservoir, which was selected as an upstream reference location. `Table 5. Tukey's range test results for surface water fluorochemicals taken fromwithinor nearthemain channelofthe TennesseeRiver" Site. PFOS FOSA PFOA PFHS BCR2 A A A A FCR1 B B B B FCR2 B BC B c WWTP B Cc B c GTVL B Cc B c From these results, it can be concluded that the 3M Outfall does not significantly effect concentrations of fluorochemicals farther downstream than FCR2. In addition, there were no statistically significant differences in the concentrations of fluorochemicals within the main channelofthe river immediately below Bakers Creek as compared to thosemeasuredatthereference location. 7.3 Sedimentconcentrationsoffluorocarbons Fluorocarbons were detected in all sediments collected from the study sites (wet weight: Appendix F-figures 3a, b, c, dand dry weight: AppendixF-figures4a, b, c, d). oooaze Table6 Mean concentratioWnoetfwfeoirgohchseendiicmaelnsticosnecinmrenatosnsake rom Location POs' FOSA POA BEES he TennesDsereyRwievigehnttsehdeimDeecnattcuorncAenltrbataiornss' BROS FOSA PFOA pS Tg Galan Gg (007) o1 on) (020) (0.04) (0) 09) pwr 0o@ss) ols Eomm 0om) 01%m) eoms 0o0l) 0o0u) oust SQ0s0)0 1@20400)00 I0S6SS000)T DGS2)O IGZeENsO)0C 2L55m0)00 3e950a00% 208179)0 BeCrkl ODsOiS)E (ZTeIz) G82S0R0)0 (Q20I9 W(I2S79E GSeMaT) I(SreAyT (Tseesr) BheaCrsk2 19200 S zmer wa mes mol mar lem 9127) (3633) (283.01) (8.08) @1905) (303) (41079) (1191) FCs a25m% a1mm o1m8 o0m2 a4smt e2%m aane ooms FoxCok2z 09 0o0w) o0n%) oof 022m eosos 1smw ort RLSS pitl-- yarGcl--aneo-- ramGce-- trero--nRen-- mt--0025-- 0gvetweight.Allo ond lowtsLOQi ies | 000437 1 Least concentrations of fluorochemicals in sediments were observed at Guntersville Reservoir while the greatest concentrations were observed in sediments collected in the vicinity of the 3M Outfall (Table 6). Concentrations of fluorochemicals in sediment decreased in the following order: GTVL < DWTP < FCR2 < FCRI< BCR2< BCRI< OUTF. For PFOS and FOSA, only `concentrations in sediments at the 3M Outfall and BCR1 locations were significantly greater than those collected from the reference location in Guntersville Reservoir. In addition, concentrationsof PFOA and PFHS in sediments at the 3M Outfall, BCR1 and BCR2 were significantly greater than concentrations in sediments from Guntersville Reservoir. However, the fluorochemicals in sediments at BCR2 were not significantly different from concentrations measured at DWTP, FCR1 or FCR2. When sediment concentrations of targeted fluorochemicals were evaluated on a dry weight basis, only concentrations at the 3M Outfall and BCR1 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 Tennessee River channel sample locations (GTVL, DWTP, 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 concentrationsattheOutfall and within BakersCreekwerestatisticallygreaterthan the reference location, concentrations in sediments downstreamofthe 3M Facility were not statistically greater than those measured at the upstream reference location. The results of both of these analyses indicated that that there is little accumulation of the target fluorochemicals in sediments downstreamofthe 3M Outfall. Sediment trifluoroacetic acid (TFA) concentrations were not significantly different between the sampling locations within the main channel of the Tennessee River. TFA concentrations for all sample locationsexceptthe 3M Outfall werelessthanthe reporting. limit of500 pg/kg, wet weight. The 3M Outfall sediment TFA concentration averaged 000438 v 510 pg/kg. This result indicates that the effluent from the 3M Facility only alters sediment concentrations in the immediate vicinity of the 3M Outfall, but does not significantly affect sediment TFA concentrations within Tennessee River. 74 Fish `Mean length, whole body weight and liver weight data for al fish species collected from the Tennessee River inthe Decatur Alabama area are given (Table 7, Appendix G). Table 7. Mean length, weight, and liver weight for fish collected from the Tennessee River (Collested on 06/21/00-06/2200)', ED) Length Weight Liverwi TMI GLunotceartsivolnle (2c6m5) 129)5 138)7 3M Outall 2 54 292 SHAD wei 3M Outtall 34 352 195 6) (160) 0385) 3M Outil 13668) [27 0.02 04) CAT Guatersville e32n.)5 a37)6 15.6 8) 3M Outfall 40.5 2.0) (6$55931.22) 363388) GAR Guntersville 58.4 765 64 3M Outall 542353) 116700.)7 @336) 63) (704) as SB Guntersville 2a3i3n (5156.86) 13.091) `valuesare meanswithstandarddeviations(inparentheses) Due to the small sample size and large amountofvariability in the endpoints,therewere no statistically significant different between the sites for species common to both the Outfall and Guntersville locations. Physiological condition factors were calculated for each species and are given (Table 8, Appendix G). Statistical analysisofboth condition factor and LSI showed no significant differences between sites for the species collected from both locations. The lack ofany statistical significance was influenced by large amount variability in the data and by the 000439 18 small sample size. The small sample size was due the fact that only a few species were collected at both locations. Furthermore, replicate fish samples were only collected for catfish and gar at both Guntersville and the Outfall location while largemouth bass, only a single fish was collected at both locations. `fTorabfliesh8.colSlpeecctieedsfraonmdtlhoecatTieonnnsepsesceiefiRcicvoenrdiinttihonefDaecctaortu(rK)Alaanbdalmiaverarseao.matic index (LST) Species Location K ST Largemouth Bass 3M Outfall 13855 292 Shad `White perch Catfish Largemouth Bass 3M Outfall 3M Outfall 3M Outfall Guntersville 08207 1224) 1.6146 (0.0481) 0.8724 (0.0102) 1.0478 04772 (02877) 0.5463 (0.0043) 1.1935 (03923) 0.6769 Catfish Guntersville 1.0743 1142) 1.5826 (05186) Gar Guntersville 03815 0.8649 (0.0180) 6137) Striped Bass Guntersville 12004 (0.1207) 0.6241 0.1902) "Data presenteasdmeanand scandard doviation -- 2LCiovndeirtsioomnatfiacctionrd(ex)(wLaSsDcwalacsuclaaltceudalasteKd=a(s WLiSIx=1(L0i0ve1rwiAotalw)x100 7.4.1 ConcentrationsofPFOS, FOSA, PFOA, ANDPFHS infish livers. Fluorocarbons were detected in all livers removed from fish collected at both the Guntersville and Outfall locations (Table 9, 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 Outfall were approximately 19-fold, 340-fold, 109-fold and 710-fold greater than those observed in Guntersville fish, respectively. 0004420 19 Average liver concentrations for PFOS, FOSA, PFOA, and PFHS for all fish collected at the Guatersville site were 1036, 22.0, 22.1 and 3.79 pg/kgwetweight, respectively. `Table 9. Liver concentrationsofselected `Tennesse River inthe Decatur, Alabama afrleau.or*ocarbon in fish collected from the PFOS FOSA PFOA PRS Species (ugk) (gk) (eke) (uke) Guntersville Catfish 873 203 188" 375" 222) 5.0) Gar 2493 20.95 18.8" 4.58 (859) 64) (163) Striped Bass, 1(373603.)0 (2130..109) 72.4.67) 3.75" Largemouth Bass 643 18.8" 18.8" 3.75 Outtall Catfish Gar Shad White perch Largemouth bass 10093.5 G78) 138920 GOB 91952 32522) 492850 G76577) 271430 145215 (2009) 50800 (7392 44200 @0473) 174030 (146795) 2456.0 2529 (173) 19345 627) 96.9 @90) 16285 (12282) 375 302 (286) 256.5 (#99) 120.1 (453) 2069.5 (1941.0) 16 *RCeosnucletnstwraatsiroenpsoartredraespotrhteed 2mimteoafqnusanatnidtasttiaonnd:a1r8d:d8epvigationfso.rPFOS,FOSA, PFOAand3.75yghg EsftoirmPaFtHeSd value Differences in liver fluorocarbons concentrations were also observed between fish species collected at the site. Liver concentrations for the selected fluorocarbons increased in the following manner: PFOS: FOSA: Catfish < Gar <Largemouth ba<Sstrisped bass (Largemouth bass)< Catfish < Gar < Striped bass 000441 2 PFOA: PFHS: (Catfis=h Largemouth bass<) Gar < Striped bass (Striped bass = Catfis<h Largemouth bass) < Gar The fish in parentheses indicate liver fluorochemical concentration below the LOQ. `Except for PFOS, there were no statistically significant differences in fluorochemical liver concentrations between fish species collected at Guntersville. For PFOS, there was 2 160-fold difference between catfish that had the least concentration and striped bass with the greatest liver concentration. FOSA, PFOA, and PHS liver concentrations in fish from Guntersville were all less than their respective LOQs. The significanceofthese results and a true understandingofthe magnitudeof the observed differences at this site areunknown at this timedue tothevariability in thedataand small sample size. Average liver concentrations for PFOS, FOSA, PFOA, and PEHS for all fish collected from the Outfall location were 15,692, 7,195, 581, and 384 pg/kg wet weight, respectively. Aswas observedatthe Guntersville site, differences in liver fluorochemical concentrations were also observed between fish species collected at the site. Liver `concentrationsofthe selected fluorochemicalsatOutfall site increasedasfollows: PFOS: FOSA: PFOA: PFHS: `Shad < Catfish <Gar <Largemouth Bass <White Perch Largemouth Bass <Shad< Gar < Catfish < White Perch LargemouthBass <Shad <Catfish <WhitePerch <Gar Largemouth Bass <Catfish < Shad <Gar <WhitePerch Except for PFOA, there were no statistically significant differences in species specific liver concentrationsofthe selected fluorocarbons for fish from the Outfall. For PFOS, FOSA, and PFHS there were 5.4, 7.1 and 178-fold differences between the least and greatest liver concentrations. However,dueto the small sample size and large amount of vaiability observed in the data, these differences were not statistically significant. For PFOA liver concentrations, there was a 516-fold difference between the least and greatest concentration. However, only shad and gar liver concentrations were significantly different. Largemouth bass was not included in the analysis dueto the fact that there was 21 000442 only a single valueforthis species. The magnitude and significanceofthese differences is unknown at this time due to the variability in the data and small sample size. 7.4.2 Wholefish concentrationsofPFOS, FOSA, PFOA,andPFHS Fluorochemicals were detected in all fish collected from both the Guntersville and Outfall locations (Table 10, Appendix I). `Table 10. Whole body concentrations (wet weight) ofselected fluorochemicals in fish collected from the Tennessee River in the Decatur Alabama area. * Species PFOS FOSA PFOA PRES or) Ggke) Ggke) (uke) Guntersville Catfish 75 75 201 7.58" Gar 15.1 75 201 75" (52) Striped Bass. 65.6 104 8.03" 7.5" @32) 0.96) Largemouth Bass 230 8.76 8.03 7.5* Outtall Catfish Gar Shad : 1190 ND a7) 1863 ND 1679) ND ND 1196 1.4 (1406) 5.52) 1545 355 (403) 250) 540 82) (368029) `White perch ND ND 278 405.5 3) 299) Largemouth bass ND 557 201 75 *RCeosnucletnstwraatsiroenpsorateedresptohretleisdmimtoefanqsuaanntdisftiacnadtaiornd:d5evkiga/tkigofnos.rPFOS,FOSA,PFHS,8.03 g/kgfor NDPsiFgOniAfies thatthecompoundispresentbutnotquantifiedduefo th dat notmeeting quality `control criteria 000443 = The least fluorocarbon concentrations were observed in fish collected from the Guntersville location while the greatest concentrations were observed in fish from near the Outfall. Mean PFOS, FOSA, PFOA and PFHS concentration for all fish collected from the Outfall were approximately 23-fold, 2-{old, 9-fold and 12-fold greater than those measured in Guntersville fish, respectively. Mean whole body concentrations for PFOS, FOSA, PFOA and PEHS for all fish collected from the Guntersville site were 59.1, 9.43, 11.7 and 7.50 pg/kg wet weight, respectively. Species differences in whole body concentration at the site were also observed with concentrations increasing as follows: PFOS: FOSAA: PFOA: PFHS: Catfish <Ga<r Striped bas<s Largemouth bass Catfish = Gar < Largemouth bass < Striped bass Largemouth bas=s Striped bass <Catfish < Gar All species equal duetobeing at LOQ Due to the small sample size, there were no statistically significant differences between `whole body concentrations for the species collected at this site. Furthermore, except for PFOS, there was less than a 3-fold difference between the least and greatest fluorochemical concentration in the species being evaluated in this study. For PFOS, there was a 30-fold difference between the least (catfish) and the greatest (largemouth bass) concentrations indicating that there is a potential for differences in the bioaccumulation ofPFOS by fish species at this ite. Mean whole body concentration for PFOS, FOSA, PFOAand PFHSforfish caughtat the Outfall were 1332.0, 20.1, 106.4, and 86. 9 pg/kg wet weight, respectively. As observed at the Guntersville location, differences in whole body fluorochemical concentrations were also observed between species caught on site. Whole body concentrations of fluorochemicals in Outfall site increased as follows: 000444 zB 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 bass < Catfish = Shad < White perch `The species listed in the parentheses were not quantified during the analyses and could not be evaluated in this report. Aswith the Guntersville fish, small sample size precluded any statistical analysisofthe data to evaluate differences between species at the Outfall location. Thus, while these data show that there are differences between locations and between fish and locations, the small sample size precludes an evaluation of the significance and magnitudeofthesedifferences. 75 Fluorochemicals in Clam Tissues Fluorochemical concentrations were also measured in clam tissues collected at both sites (Table 11, Appendix H). PFOS concentrations did not differ between the sites and rangedfrom15.6 ug/gto 14.1 ug/gwetweightat GuntersvilleandtheOutfall, respectively. Tn contrast, there was a 42.8-fold difference in FOSA clam tissue concentrations with 25.1 pg/kg and 1074 pg/kg, wet weight, being measured at Guntersville and Outfall locations, respectively.Therewere no significant differences in the concentration of PFOA and PEHS in clam tissue collected at eachofthe two sites. Theresultsofthe clam analysesreflectthe areas from which the samples were collected. Due to substrate problems, Outfall clams were collectedatthe 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 downstrofeathme 3M Outfall have retumedto backgroundlevelswithin in the Tennessee River. 000445 24 Table 11. Tissue concentrations of selected fluorochemicals in clams collected from the Tennessee River in the Decatur Alabama area. ' PFOS TFOSA PFOA PRES Location (ug/ke) (g/kg) Ggkg) (vg/ke) Guntersville, 156 251 43 0.946 Outfall 14.1% 1074 8.42" 037 37) (358) [AD 53) *L"iComofqinuanpictraotsciesnoino:dn21s8.tm8eagrnisaganfdostraPndFiaOrSd,odeFvOinaStAi,sonPs.FOA,3.75 ggforPFS. `Concentrationsreportedbelow LOQsareestimatedvalues 8 REFERENCES Hansen, KJ. and HO. Johnson. 2000. Determination of perfluorooctanoate sulfonate (PFOS), perfluorooctane sulfonylamide (FOSA), and perfluorooctanoate (PFOA) in waterby liquid-solid extraction and high-performance liquid chromatography/tandem mass spectrometery (HPLC/MS/MS). 3M Environmental Laboratory method. Number ETS-8-154.0. 3M Environmental Laboratory, St. Paul, MN. LIMs Report numbers: E00-2361, E001958, E01-0520. 000446 25 9 APPENDICES Appendix A. Structure and chemical characteristics of selected fluorochemicals `monitored in water, sediment and biota ofthe Tennessee River in the Decatur Alabama area. Appendix B. Water and Sediment locations within the Tennessee River study areas Appendix C. Water, sediment, clams,andfish sampling protocols Appendix D. Centre Analytical Laboratories analytical reportforthe characterization of fluorochemicals in water and sediment. Appendix E. Water quality data collected at sample locations. Appendix F. Topographic maps of sample locations in the Tennessee River study area. Maps include water quality data, water or sediment fluorochemical concentrations for sample locations. Figur1e. Water quality parameters. FFiigguurree 23.. FFlluuoorroocchheemmiiccaallss iinn ssuerdfiamceentwsa,tewrest weight Figure 4. Fluorochemicals in sediments, dry weight Appendix G. Physiological data for fish collected from the Tennessee River. AppendixB. Fluorochemicals concentrations in fish livers and clam tissues collected fromthe Tennessee River in the Decatur Alabama area AppendiIx. Whole body fluorochemical concentrations in fish collected from the Tennessee River in the Decatur Alabama area. 0004477 26 CeSonstRerseearAchnalyticfiaClolLlaPobAgToBaRr0,Tator--iWeinsic,aniIanabco.on Phone:(814) 231-8032 Fax: (814) 231-1253or(814)231-1580 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 Testing Laboratory Centre Analytical Laboratory, Inc. 3048 Research Drive State College, PA 16801 3M Environmental Laboratory Contact KeBnltdRg. 2Li3n-ds0t0rom 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 P.O. Box 33331 St. Paul, MN 55133-3331 pac rors 000248 ---------- ee---- ---- -- 1 Introduction GSRaaomnpultessaAwoyrreeapcoolrltoLecdafboodorttroharmiasnha,olIyThsio.sno(nCfsosanatseeer)Rifievsemorfawtnhdae arIr aMpnEadrnstvoeifcorm3meePnnrtotsjaaolmLpalEbeo0r0ar-t1eo9rc5ye8., Tbhya The Garr sy numberassignedothaproject 023.014. Th sampioswerapropered ar analyz byLCMSMS for tho folowing st of fuorochomicals: `Specificfluorochemicalcharacterizationbyliquidchromatography /tandemmassspectrometry (LCwaM s reqS uest/ edfoM rallS samp) les.Atotalof68samples werereceivedforanalysis. + Tabi :TargetAries "RaTonhwdeearvnoaelurytttinscaarplmsraooicnhuoHrdlessuwhsiaehvefGnoarowntatbiee.rensTafhmlpalymevesatwkheaortdeasvdwafeocraothemisdmabaydlGesa.fnDioot.atThhroesvosadecmnaetdnihtoesnrapemrpclttoehcseo,l highestquality dataavallableatthistime. 2 Sample Receipt "ThaarssaSmpolSleoasemdpocbreotswoeuebnrat1d9rn00casenhdcieol2.p3l0sS0.Ccoahntaakiwnemaerr<esuaspclnooddwynlieenrefooneom7ta2ptsr5ne0se.frpTvreheds.esnStiaeydmaisixn AttachmenC.t. 3 HoldingTimes TwIrehwreaotarlnoraacytnacdeadtlamhooatmhahtai.sc1oo4sd-whdaaayvshovisanhdogawtntoaidm0aegc.aoHiopnvsaatevemrerc,oivseruhioesuhalotlbd1ion0rg0aemnddotho1af00tf104eoddhay.fsfo.orStapiemcrpailtoeodssns ongert14hcaayns. raceacrs 000449 _------ 1 1 ' ; 4 Methods -AnalayndtPriepcaraatolry ) 4411.1 SLamOpMleSPMrS epfeorLrCaMStMSiAnaolysnis rWeamtoevresraemspidluoeslwcehrioinne.lSyoriaptheadseweixhtr2a0ct0iounl.(oSfP2E5)w0aMsGuAs.eSdo1c0kpretphairoestuhleosaSmoplloesnftoor ! "LThOoMcSarMtScgonwaassif.stAofkort-omdiwliitther5pmoit.ioonf4o0f%sammeptlheaWneoslinrawnasteerrosdoli0toan.GrTyhSoPEaclaartteivcages. i mdeitshcaanrdoeldwaansdtcohleeSctPeEfcoorlanuamlnywsiassbyeLnOaMiSiMedSw.itThh1i0s0t% meethasnroesltu.ltAemd5imniae.npoanigrhtttioonfd concoef thnostamprosapritor10inoalns. Fo5rmtihoefsmeedthiamneonlt.sTahmopiexet,raactrsepwroesreonttateirveedpaotnidondiotfseadm1p0lef(a5 lrvaomusm)ewoafs4fr0smtLexwtriahctTeydpnofo| bVeagteirn.iTnghweidhituhteesdoeixtrpahcatssweeexrioatchieonn.treaedIn thesamemannarasthewatersamples, 412 SampleAnalysisbyLOMSMS IcnoHluPmLnC.,Baansealdioqunottohefeaxftfriantcyt osfitnhjeecatneadaltnodfpratshseesdttahtrioounagrhyaphuasce pnhtahseeccohkraonmnatroelgartiavpeh1i0c hHoPLiCusiadpmaroabtiiloenp,hEaSsIeM,Stphreaovniadtesa irraapinaenddfaocrcuarcahlaoramcetearnisstfiocraamnoaluynztiongmawei.deFroalnogweionfg moirgdatneimcpcoormaptouurnosd;sm,ailneccluuidaisngfauroorloocnhizaerdi,cfarla.gEmleencttrao,sparnaydidsegteonceireadll.y oopnesrcaiheadratarcetlaetrivoielsfy Knownfurochemicalsaraobservedand quantitatedagains standards. `AanHaolywziettthePascakmaprdlHeePx1t1r0ac0tHsP.ALnGaalyyssitsowmacosuppelrdotomeaMdiucsrionmgasssslUetcitmedaMreSaMciSonwmeosniutsoeridngo (S3F1M0)0.aWnadlo1r7s/a0m0p.lSoescwiemreontasxatmapclteosdowner8o2e0xt0raanctde8d/83/40100a0nadnadn8a/l1y0z/a0d0bayndMwSerSeabneatlwyezeedn ``abnydMiSnIstMrSubmeenttwpeareanm8el/o0rs0caanndbef17o/u0n0d.iTnAhtoiaHcPhLmCenatnsdaMnSdIME.Smethodsusedforanalysis 5 Analysis 51 foCAar7l-tplhobaicrnotacmtapiloobunrantdosncufvInetrwosats.aTnhaelyczaeldoraattohnopboeignitsnWinograenprdoepnadroefdathe0a,n2al5y,t5i0c,al1s0eq0u,e2n5c0, 50c0,hapnodi1.0U0s0inngLi(noaptr.Tghroeinssntrwumiehntr1exswpionnsegv,ersus ohepeco.ncentrreatpiotnwaaspolroddfor caocecfefipctiaebnlte(11)a2n0d9c8o5ef(i2ce0n9t7o0f)d.etenminato(n1) wero determined. Acalbration uveis Calbrationstandardserepreparedusingthesame SPEprocedurousedforsamples. racesors 000450 , \ \ CFCarlobuorgahtoonunchcheecrksaasWniaahnnedesar.+tds/se2wq0euar%eoonafctnera.elyoCczahendapnplolvracnseicec,.a1lsy (asboaryineodoAtothfev.saanmdpar jaecniaorhs)a , Forth resusreports her,clbrationcreaveromat. ) 52 EeBxxrlatacnoikonsn bhaarrkksswsohrouedrnookphaevdoaanndy arnoaoltyaznevaeashparvosyeaxaatcoosnbobvaecihocfosanmcpelret.Tohofe ow evel calbraion inca.For seSamos, hosachinberkswerd compan. , lIaonvsvluoacmnaetynatbtaloranntskaasnnndataherds,foapnmrosofofncotoakinnoamewatnbhohanvioehlso1ovvslesorawtmlwpeelreeelsc.lsAbograaainina,olnyizsebdaafcrakarssa.vehrFyooirun1hdot } Sampesprosaiodne th ns parksare compan 53 `SSuuomgoagtoastpeisesaronot component ofthe LGMSMSanalyticalmethod. ! 54 Maatlrrix5pSpikveersopreparo forevery eldsamp using llcompoundsof lcs. Matix 5pkorecoveries aro gen In Azchmon8t. roFcdvsepfiskeasrwserioosucblrutdeedd wiiAtthsncohsmeednitmBenTtahnedseodniemeunstfascaolaetesrhsoawmepdleno.Ffockovesrpyiokfe 10 kd3pko,Ncaing that herews aproiem wi hesedimentSeid King rococre. FSiamplcesosnhtoswaemdprleecsosvperdsbaet2w0e0epnp7t0aanndd1010300p%t. vTehreesruebsmuitseadr.oTahlsofinsckcdeodnt Aacments. " 55 ADAupmlkidcsaaatmepnisosweroanalyzei cpiate Reusaro hen alongwihthesamp resus 56 LaFobroLrGaMtSoIrVySaCnoalnytsreso,lMSaimpwlaieosrw. sspa withalcompound ofilerestat25an 250 n65gchLtCnSg.Raecshsaaar cgiiveosnstno.nAglwiehctohvoereaswfaotaalIncAoimcphomuonnd'swsorabndaE.w 70-10% in 57 STahemrpealreo1R0eoltahtresdaCmopmrmeetnetcsometsfor isca st 6 Data Summary aPlrarceepsorctoedtapcahrmsepnetrAlfoo n(c5%a)l(1)Is.iSngemofehnoasanmaptraeosuusla.rSurpfoacree toparresspurs Sion 5p) (09KG)onboth an 8ocoodand rywohbasi. Pacescre 000451 - \ | ) 7 Data/SampleRetention , {Soaormcshpomarao aropbiobsaayodGtnefenasan.onmornotthoafbrlehmeordoaaarnsdshauredGdorp sospotrshraereeSopodsedd. Aal ; 8 Attachments a1 Amon ess [PRT -------- 83 AtachGamineofnCutst: 4 AtachmontD:LOMSISRawAnica Di(SucoWal Sampies) 85 AtachmontE:LGMSMSRaAnsysDea(ScimentSamp) 9 Signatures Tom Fan, = i Kedova,iVno Hes Ore Lab MembersCantii0Dnatga KarenStn Bue/0/ bfpg)e, [ Puassors 000452 SECTION A ANALYTICAL REPORT \ 30a18ReA searchDivs,Sat CoLlleage bPAo66r01aStTHo2r19i05e2 sFA,X STIAnTcR.es | | em ver t ae toutes Doncotoces | POSG) POMGOD FOGG Pon) , SBFseuwyosen Siow Fo orwo w8wm a- =52 =-=) i a 8 Ey | SSoSihiseikzeons Utoee thw O&2N =8ea 2=25 =2 BSSeuehtnkooen ER " to mh2 ea un FT] ae8a o za ==u-= Fiayo.n he -- ooowem = a ==E=N Fr. = Row == a=im =, a= SEeotoone iaoe toGaoeen om oe =a=F = oToo. ao==e ge = == Seoeatanooew F vmeee r.m ew w,i=-cs -- o= =n ===J: SBFneoi=eon ene Bt oe = ew e P= mm = h-TbEso = =fooaen ==== = E TBneneyne SFrnsens o - - "om= =ify Ei==S 2=Exn oom z 2= fBaHerodrtn-a-- oo=ne =oo=am =-= =Eu=mS =&== Lif etc 00 cc py5107 EGR,PHS, ndPFOSA 75OPO ifoeaton 10ro3e .bhrl eds 10-Compomdessenint Compehc ad ten LD 00,ekrkcE. -- s@e y en F er oa r AE i p meee 000454 ANALYTICAL REPORT : S01A 5 FesQsaN rchDrive,Sats CoLlleaSgebPhAoe16r901a_t814o-23rr7-i0i03e2esFA,X14-I29n1-c12.53 \ | erce tscmsrs Msemaiietioion Osnconcus POSGOR) E Si- inro Faa= aAnnen Jo"a SShSEhohysiioons =oooe=nn ia4tne SSShhhaine Sion Foi on i8o a8 SSiieidtEion aa oSiioen ii2ee3 SRSiaahEioonn FGFadrH --o Bia == = PROMGS) POG) Piso) 8awi a===0 =a2& B&=FoA =@== =8=te %8 a = Ii aaaa e IIH 8aaa iJio 0 x 2 Un Doct 00bra sce pin2.3 fo PES,PV,rd OSA rd751.POM Unkct ttn.) orbcd 25 br compris 10-Compnirtdtd 10:Copoinddense ener2 0410 ost urn otc eerion I 000455 ANALYTICAL REPORT AN Centre Analytical . 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[---- PTeBe) =a%FsA u5an Ea4A] 2=-%2=2 2s EE -- 000457 LING (TN So) ig eA Centre Analytical | S348Fear Divs, tts CLoreag bPAoUrTatSTEoE3rI AiOEesFA,R STIEncE.R , | nos coarse rotten Dunotoses | FTOoSu) PTRoOwBnAe) PpOMeGOuK) aTeKu)n } ESE=2edr2y00.. fr eogoa=%hau. 0=22217 n2=2o a2 2 2>N22O 2 252N22O v. EEBSeiEteon Bii2a= 22 2 =22% 2%2 2222 | ntoDan001brenden pm 0 Kt A nn AY -- o-oo aen50 05. Pentt, ot00<va<tan @EC e--p ----i----mm rm e iSs A mabrom 000458 ANALYTICAL REPORT ` 504A 8Rese.aN rchDivs,SataCoLloagbsbPAeoT0r907atSTEo23r73i052esFA,XoSTEI2e3n7-c.12.83 [---- Mo------ Donatos DTOyS) PreOnO?N) F--A--N"G aByry) ! 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