Document O1Oj14jzL4MMmboL5kq8Q4mzK

SELECTED FLUOROCHEMICALS IN THE DECATUR, ALABAMA AREA Prepared for: 3M St. Paul, Minnesota Prepared by: EntriL, Inc. John P. Giesy, Ph.D. John L. Newsted, Ph.D. East Lansing, Michigan Project No. 178401 June, 2001 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 objectives of the study were to determine the concentrations of selected fluorochemicals in biotic and abiotic phases within the Tennessee River in the vicinity of the 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 (PFHS). Surface waters and sediments were collected from five primary locations. These areas consisted of a location near the 3M point of discharge (Outfall), a stream the receives the 3M Facility effluent (Bakers Creek), a downstream location (Fox Creek), a location upstream of 3M Facility but below the City of Decatur (DWTP), and a reference location upstream of Guntersville Dam. Clams were collected from the CJuntersville 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 according to 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 ciownstream location, Fox Creek. Average surface water PFOS concentrations ranged from 0.009 to 151 _tg/L for Guntersville and Outfall, respectively. Average PFOS sediment concentrations ranged from 0.180 to 5930 lxg/kg (wet weight) for Guntersville and the 3M Outfall, respectively. However, while fluorochemical concentrations in sediments and surface waters were greater in locations downstream of the 3M Outfall, the downstream sample locations within the main stem of the 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, locations that are in the immediate vicinity the 3M Outfall, were significantly greater than those in the 2 reference location. From these results, it can be concluded that the effluent from the 3M Ouffall does not significantly affect fluorochemical concentrations in sediments or surface waters in the main stem of the Tennessee River. Fluorochemicals were detected in all fish collected from both the Guntersville reference area and 3M Outfall. The least fluorochemical concentrations were observed in fish collected from Guntersville while the greatest concentrations were observed in fish from the Out-fall. For instance, at Guntersville, average whole body concentrations for PFOS, FOSA, PFOA, and PFI-IS were 59.1, 9.43, 11.7 and 7.50 lxg/k_ (wet weight) respectively. For fish from the outfall, average whole body concentrations for PFOS, FOSA, PFOA and PFI-IS were 1332.0, 20.1, 106.4, and 86.9 llg]kg, (wet weight) respectively. While there were species specific differences in the accumulation of the selected fluorocarbons into fish collected from either Guntersville or 3M Ot_all 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 from the Outfall were greater than concentrations observed in clams collected from the Guntersville reference site. However, PFOS and PFHS tissue concentrations in Outfall clams were not greater than concentrations in clams collected from Guntersville. 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 due to the small sample size and variability. 2 INTRODUCTION Entrix, Inc (ENTRIX) is providing a report on activities to assess the impact of effluents containing fluorochemicals from the 3M Facility in Decatur, Alabama to the Tennessee River. Water, sediment, clams and fish were collected from upstream and downstream locations of the 3M Facility and were used to evaluate the magnitude of releases of target compounds from the Facility to the Tennessee River. The objectives of the research are to determine concentrations of selected fluorochemicals in abiotic and biotic phases of the Tennessee River system in the vicinity of the 3M Facility at Decatur, Alabama. Fluorochemicals selected for evaluation in this study included: perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (FOSA), pertluorooctanoate (PFOA) and perfluorohexane sulfonate (PFHS) (Appendix A). In addition, trifluoroacetic acid was also evaluated in water and sediment samples taken from the Tennessee River. 3 FIELD SAMPLING 3.1 Site Description Four primary locations were selected for the field investigation (Figure 1, Appendix B). These areas consisted of a location near the 3M point of discharge (Ouffall), a downstream location, a location upstream of 3M but below the City of Decatur, and a reference location upstream of G-untersviUe Dam. Specifically, samples were collected adjacent to the 3M Facility Outfall (includes Outfall and Bakers Creek) that corresponds River miles 301-302. Samples were also collected downstream of the 3M Facility near the mouth of 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). To better evaluate the impact of the effluent from the 3M Ouffall, the Bakers Creek location was divided into two sub-locations, Bakers Creek-1 included Stations 1, 2 and 3 that were collected near the ouffall and within Bakers Creek. Stations 4, 5 and 6 and were collected near the interface of the mouth of Bakers Creek and the Tennessee River and are identified as Bakers Creek-2. 4 Bakers Creek .._.." Fox Creek Decatur Decatur Wastewater Treatment Plant Decatur Drinking Water Plant N Guntersville Reference Site T Chattanooga Tennessee River Dam Flow Direction /F low J_ Direction Figure 1. Tennessee River and sampling locations evaluated during study. Guntersviile Reservoir 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 on the northern side of the Tennessee River across from the mouth of Fox Creek. Locations and sample codes for samples collected from the Tennessee River are given (Table 1). 3.2 Field Sampling Logistics Sampling at selected sites on the Tennessee River was initiated on June 19, 2000 by ENTRIX. Collection of water and sediment samples continued until June 21, 2000. During the collection of sediments, clams were also collected. Fish collection was initiated on June 21 and continued through June 22, 2000. Water, sediment, clams and fish were collected as outlined in Entrix sampling protocols (Appendix C). 3.3 SAMPLE COLLECTION 3.3.1 Water Collection Water samples were collected using ENTRIX sampling protocols from a total of 26 locations (Table 1, Appendix B). At each location, water quality parameters were measured using YSI Model 63 and 95 meters. Six samples were collected from the areas surrounding the 3M Outfall, the City of Decatur wastewater treatment facility and the upstream reference location. Seven water samples were collected from the area downstream of the 3M Facility near Fox Creek. In addition to these 25 samples of surface 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 ice at 4C, and delivered to the 3M Environmental Laboratory, St. Paul, MN. 3.3.2 Sediment Collection Sediment samples were collected from the same location, as were the water samples (Table 1, Appendix B). A total of 25 grab samples were collected from the Tennessee River. Six samples were collected from areas surrounding the 3M Outfall, 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 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 of a PONAR dredge following standard protocols. Sediments were placed into labeled 250 ml widemouth LDPE containers, stored on ice at 4(2, and shipped to the 3M Environmental Laboratory, St. Paul,MN. Table 1. Location and identification of sediment and water samples collected from the Tennessee River in Alabama Water Sample SW-01 SW-02 SW-03 SW-04 SW-05 SW-06 SW-07 SW-08 SW-09 SW-10 SW-11 SW-12 SW- 13 SW- 14 SW- 15 SW- 16 SW-17 SW- 18 SW- 19 SW-20 SW-21 SW-22 SW-23 SW-24 SW-25 SW-26 SW-27 Sediment SED-01 SED-02 SED-03 SED-04 SED-05 SED-06 SED-07 SED-08 SED-09 SED-10 SED-11 SED-12 SED- 13 SED- 14 SED- 15 SED- 16 SED- 17 SED- 18 SED- 19 SED-20 SED-21 SED-22 SED-23 SED-24 SED-25 Sample SED-27 Location Bakers Creek Bakers Creek Bakers Creek Bakers Creek Bakers Creek Bakers Creek Fox Creek Fox Creek Fox Creek Fox Creek Fox Creek Fox Creek Decatur WWTP Decatur WWTP Decatur WWTP Decatur WWTP Decatur WWTP Decatur WWTP Guntersville Guntersville Guntersville Guntersville Guntersville Gunters_lle 3M Outfall Fox Creek Fox Creek i Sublocation/Code BCR1 BCR1 BCR1 BCR2 BCR2 BCR2 FCR1 FCR2 FCR2 FCR2 FCR1 FCR1 WWTP WWTP WWTP WWTP WWTP WWTP GTVL GTVL GTVL GTVL GTVL GTVL OUTF FCR1 FCR1 3.3.3 Clam Collection Samples of the Asian clam (Corbicula fluminea) were targeted for collection from a location downstream of the 3M Facility and from a location upstream of Guntersville 7 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 accumulation of fluorochemicals into aquatic biota. Due to the habitat requirements of C. fluminea, dam samples were not co-located with water or sediment samples. Clams were collected using a Petit PONAR dredge. However, due to difficulties in locating clam beds as well as interference of substratum with the PONAR dredge, the collection of clams was limited to two composite samples from locations in the vicinity of sediment samples. One sample (approximately 25 clams/sample) was taken from a location downstream of the 3M Facility (SED-08, -09, -10) and one upstream sample was collected from the Guntersville location (SED-20, - 21, - 22, -23, 24). Clams from each location were placed into labeled plastic bags and shipped on ice to the MSU-ATL (Michigan State University-Aquatic Toxicology Laboratory), East Lansing, MI. 3.3. 4 Fish Collection Fish were collected from two locations (Table 2). One location was in the vicinity of the 3M Outfall and the other was located within the reference area upstream of Guntersville Dam. The fish samples were collected using both hook and line as well as gill net. Gill nets (passive gear) were placed in the lower energy environments where concentrations of fish were generally greater. Due to the techniques employed for collection of fish, all fish caught in each of 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). Centre. The analytical methods used for the water samples were validated by 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. Summaries of each protocol are given: Table 2. Sample identification Tennessee River. Sample ID LM1 LM2 SHAD 1 SHAD2 SHAD3 SHAD4 SHAD5 SHAD6 SHAD7 SHADS 1 WP2 CAT1 CAT2 CAT3 CAT4 GAR1 GAR2 GAR3 GAR4 GAR5 GAR6 SB 1 SB2 SB3 SB4 SB5 SB6 SB7 SB8 SB9 SB l 0 SB 11 SB 12 SB 13 SB 14 Location Guntersville 3M OutfaU 3M OutfaU 3M Ouffall 3M Outfall 3M Outfall 3M OutfaU 3M Outfall 3M Outfall 3M Outfall 3M Ouffall 3M Outthll Gtmtersville Guntersville 3M Outfnll 3M Outfall GuntersviUe Guntersville Gtmtersville Guntersville 3M Outfall 3M Outfnll Guntersville Guntersville Guntersville Guntersville Guntersville CmntersviUe Guntersville GuntersviUe Guntersville Guntersville Guntersville Guntersville Guntersville Gtmtersville and location of individual fish collected from the Largemouth bass Largemouth bass Skipjack Herring Skipjack Herring Skipjack Herring Skipjack Herring Skipjack Herring Skipjack Herring Skipjack Herring Skipjack Herring White Perch White Perch Catfish Catfish Catfish Catfish Gar Gar Gar Gar G-at Gar Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Striped Bass Species Micropterus salmoides Mieropterus salmoides Alosa chrysochloris Alosa chrysochloris Alosa chrysochloris Alosa chrysochloris Alosa chrysochloris Alosa chrysoehloris Alosa chrysoehloris Alosa chrysochloris Morone americana Morone americana Ictalurus punetatus Ictalurus punetatus Ictalurus punctatus Ietalurus punctatus Lepisosteus sp. Lepisosteus sp. Lepisosteus sp. Lepisosteus sp. Lepisosteus sp. Lepisosteus sp. Morone saxatilis Morono saxatilis Morone saxatilis Morone saxatilis Morone saxatilis Morone saxatilis Morone saxatilis Morone saxatilis Morone saxatilis Morone saxafilis Morone saxatilis Morone saxatilis Morone saxatilis Morone saxatili.q 9 4.1 Water Analysis Water samples were initially treated with 200 _tl 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-milliliter portion of sample was transferred to a Cls SPE cartridge and the cartridge was eluted with 5 ml of 40% methanol in water. The eluate was discarded and the SPE column was eluted with 5 ml of 100% methanol. The eluate was collected for analysis by LC/MS/MS. This treatment resulted in an eight-fold concentration of the samples. 4.2 Sediment Analysis For sediment samples, a 5 g portion was extracted into 5 ml methanol. The extracts were filtered and diluted to final volume of 40 ml with ASTM Type I water. The diluted extracts were then treated in the same manner as the water samples, beginning with the solid phase extraction. Sediment and water extracts were analyzed by use ofa Hewlett-Packard HP1100 HPLC system coupled to a MicroMass Ultima MS/MS. Analysis was performed using selected reaction monitoring (SRM). HPLC conditions and MS/MS methods used for analysis and instrument parameters are given in the procedure described below. 4.3 Fish Liver Analysis 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, "'Extractionof Potassium Perfluorooctanesulfonate or other Fluorochemical Compounds from Liver for Analysis using HPLC-Electrospray/Mass Spectrometry". Briefly, fish were thawed and livers were removed, weighed and then homogenized in HPLC grade water. An aliquot of liver homogenates were spiked with a surrogate standard and then 0.5 M tetrabutyl ammonium hydrogen sulfate (TBA) and 0.25 M sodium carbonate/sodium bicarbonate was added to each sample. Five ml methyl-tert-butyl ether was added to each tube and the sample was capped and shaken for 20 min. The samples were then centrifuged for 25 rain at 3500 rpm and 4.0 ml of the organic layer was 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 l_m nylon filters into glass autovials for chromatographic analyses. 4.4 Clam Tissue Analysis Clam tissues were extracted with acetonitfile followed by a solid phase column cleanup of the 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 and then centrifuged for 30 min at 3500xg. The supematant was passed through a column of Florisil and activated charcoal and the eluate was collected in 50 ml polypropylene tube. The column was eluted with 15 ml methanol and both eluates were combined. Two drops of octanol were added to the eluate and then the sample was reduced to near dryness under a flow of nitrogen gas. The sample was resuspended in 1 ml methanol and passed through a 0.2 ttm nylon filter into autovials for chromatographic analysis. 5 QAJQC Standard operating procedures for sample collection and preparation were maintained during the entire project. Proper QA/QC samples, as required by 31_ 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 _d of a 10 ppm stock solution containing PFOS, FOSA, PFOA, and PFHS 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 record of the conditions of the 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 limit of quantification (LOQ) are analyte and matrix specific, method and matrix blanks along with matrix 11 spikes were used to determine accuracy and precision of the extractions and final chemical determination. Water and sediment concentrations were not corrected for either matrix spike recoveries or corrected for purity of the fluorochemical standards. Fish tissue fluorocarbon concentrations were reported as wet weight and were not converted to a dry weight basis. 6 STATISTICAL ANALYSES Statistical analyses were preformed with SAS (Version 8, SAS Institute, 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 means of the 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, lb, lc, and ld). Dissolved oxygen and pH were variable within the study there were no significant differences observed between values measured in waters collected from the 3M Outfall or Bakers Creeks and those from upstream or downstream locations. Conductivity and temperature measured at the 3M Outfall and within Bakers Creek (BCR1) were significantly different from the upstream and downstream sample locations. However, there was no significant difference between that from Bakers Creek 2 samples and those collected from either the upstream and downstream sampling locations. This result indicates that the effect of the effluent from the 3M Facility on water quality parameters was limited to a small area near the 3M Outfall. 12 Table 3. Water quality parameters for samples collected from the Tennessee River, in the Decatur Alabama area. Values are reported as means and standard deviations i DO Conductivity Temperature pH Location Guntersvi'lle (rag/L) 7.6 (_os/cm) 192.8 (C) (s.u) 29.0 8.2 (0.8) (5.4) (0.3) (0.4) DWTP 10.0 * (1.3) 184.7 (3.4) 29.3 8.8 (0.3) (0.2) Outfall 6.5 4650 * 33.2 * 7.2 Bakers Creek-1 7.75 (1.4) 1843.3 * (1749.0) Bakers Creek-2 9.0 (0.6) 463.0 (108.9) Fox Creek- 1 8.1 (0.4) 179.0 (2.9) Fox Creek-2 8.8 (1.3) 162.7 (8.1) Significantly differentfromGumersvilleReservoirat a = 0.05 30.7 * (1.4) 29.6 (0.6) 27.8 (0.2) 27.8 (0.5) 7.7 (0.5) 8.0 (0.1) 8.2 (0.3) 8.2 (0.5) 7.2 Fluorochemicals in Surface waters Fluorochemicals were detected in all surface waters collected fi'om 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 concentrations of PFOS, FOSA, PFOA and PFHS in surface water was as follows: GTVL < DWTP < FCR1 < FCR2 < BCR2 < BCR1 < Outfall. Concentrations of surface water fluorochemicals at only the 3M Outfall and Bakers Creek 1 locations were significantly greater than those measured at Guntersville Reservoir. Trifluoroacetic acid (TFA) concentrations were elevated in 3M Outfall (mean =1420 lag/L), Bakers Creek 1(mean = 680 lag/L) and Bakers Creek 2 (143 lag/L) samples but were less than the reporting limit of 100 lag/L in water samples collected from the other 13 sampling locations. This result indicates that the effect of the effluent from the 3M Facility on TFA water concentration was limited to a small area near the 3M Ouffall. Table 4. Mean concentration of fluorocarbons in surface waters of the Tennessee River in the Decatur, Alabama area. deviations Concentrations in means and standard PFOS FOSA ' PFOA PFHS Location Guntersville (pg/L) 0.009 (_tg/L) 0.004 (_tg/L) 0.008_ (pg/L) 0.003 (0.002) (0.002) DWTP 0.053 (0.013) 0.016 (0.025) 0.028 (0.006) 0.006 (0.006) Outfall 150.50" (7.778) 7.985* (0.148) 1900.00" (0.00) 42.70* (1.697) Bakers Creek-1 82.260* (56.672) 5.424* (3.074) 1023.60" (712.64) 22.374* (14.665) Bakers Creek-2 13.838 (2.351) 1.191 (0.244) 129.375 (31.892) 4.034 (0.575) Fox Creek- 1 0.54 (0.05) 0.169 (0.022) 2.647 (0.614) 0.566 (0.102) Fox Creek-2 0.179 0.055 1.001 0.168 (0.110) (0.033) (0.441) (0.114) * Significantly different from Gtmtersville Reservoir at a = 0.05 l Limit of quantitalion for all fluorochemicals water is 0.025 Itg/L. All fluorochemical concentrations reported below the LOQ are estimates. Additional statistical analyses were conducted on fluorochemicals in surface waters to further examine the difference between sample locations (GTVL, DWTP, BCR2, FCR1, and FCR2) located within the Tennessee River. Results from the first analysis showed that both the 3M Outfall and BCR1 could be influencing the results of the statistical analyses by acting in a manner similar to that of an outlier. For instance, the concentration of PFOS at the 3M outfall and BCR1 were approximately 17,000-fold and 9,700-fold, greater, respectively, than the concentration observed at the GuntersviUe location. Removal of the 3M Outfall and BCR1 samples from the analysis allowed for the evaluation of the hypothesis that there were no statistically significant differences in 14 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 FCR1 were significantly greater than Guntersville, they were not significantly different from the furthest downstream location. Thus, at FCR2, the furthest downstream location, the concentration of targeted 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 from within or near the main channel of the Tennessee River _ Site PFOS FoSA PFOA PFHS BCR2 A A A A FCR1 B B B B FCR2 WWTP GTVL B B,C B C B C B C B C B C a Siteswiththe sameletterarenotsignificantlydifferentata = 0.05 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 channel of the river immediately below Bakers Creek as compared to those measured at the reference location. Z3 Sediment concentrations of fluorocarbons Fluorocarbons were detected in all sediments collected from the study sites (wet weight: Appendix F-figures 3a, b, c, d and dry weight: Appendix F-figures 4a, b, c, d). 15 Table 6. Mean concentration of fluorochemicals in sediments taken from the Tennessee River in the Decatur Alabama areaa ii Location Wet weight sediment concentrations PFOS FOSA PFOA PFHS Dry weight sediment concentrations PFOS FOSA PFOA PFHS Guntersville O.18 (0.07) 0.08 (0.01) 0.08 (0.01) 0.08 b 0.43 (0,20) O.19 (0,04) O.19 (0.04) DWTP 0.98 (0.42) 0.15 (0.06) 0.09 (0.02) 0.08 (0.01) 1.72 (0.83) 0,26 (0,11) 0.16 (0.04) OutfaU 5930.00* (254.56) 1200.00" (42.43) 1855.00" (106.07) 135.00" (4.24) 12600.00* (565.69) 2555.00* (91.92) 3950.00* (226.27) Bakers Creek 1 1298.67' (751.89) 283.30* (176.21) 892.00* (345.80) 42.10' (22.05) 2275.67* (142.76) 503.17' (364.31) 1548.17" (774.63) Bakers Creek 2 192.00 (191.27) 54.09 (36.33) 237.61 * (283.01) 11.46" (8.08) 272.64 (279.05) 75.91 (53.03) 338.43* (410.79) Fox Creek 1 2.58 (1.37) 1.70 (1.09) 1,81 (0.77) 0.22 (0.11) 4.51 (2.88) 2.99 (2.21) 3.11 (1.68) Fox Creek 2 0.93 0.44 0.80 0.08 b 2.02 0.95 1.73 (0.10) (0.05) (0.22) Significantly different form Guntersville Reservoir at _ = 0.05 a Concentrationgsivenas meanswithstandardeviationsinparenthesis b Limit of quantification of all fluorocarbons in sediment is 0.20 llg/kg wet weight. (0.22) 40.10) (0.46) All values reported below the LOQ are estimates. O.19 (0,04) 0.14 (0.04) 287.50* (9.19) 74.6* (48.57) 16.18 (11.91) 0.38 (0.23) 0.17 b 16 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 Otafall (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, concentrations of 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 fluoroehemicals 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, FCR1, and FCR2). Results from the second set of analyses showed that only the BCR2 concentrations of targeted fluorochemieals were greater than those observed at Guntersville Reservoir reference location on both a wet and dry weight basis. Thus, while concentrations at the Out-fall and within Bakers Creek were statistically greater than the reference location, concentrations in sediments downstream of the 3M Facility were not statistically greater than those measured at the upstream reference location. The results of both of these analyses indicated that that there is little accumulation of the target fluorochemicals in sediments downstream of the 3M Outfall. Sediment trifluoroaeetic acid (TFA) concentrations were not significantly different between the sampling locations within the main channel of the Tennessee River. TFA concentrations for all sample locations except the 3M Outfall were less than the reporting limit of 500 _tg/kg, wet weight. The 3M Outfall sediment TFA concentration averaged 17 510 tag/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. Z4 Fish Mean length, whole body weight and liver weight data for all fish species collected from the Tennessee River in the Decatur Alabama area are given (Table 7, Appendix G). Table 7. Mean length, weight, and liver weight for fish collected from the Tennessee River (Collected on 06/21/00-06/22/00)k Sample ID Length Weight Liver wt LM l Location (cm) , (g) (g) Gunters_lle 26.5 195 1.32 3M Out'Fall 32 454 2.92 SHAD WP1 CAT GAR SB 3M Ouffa1_1 3M Ouffzll GuntersviUe 3M OutfaU Guntersville 3M outfall Guntersville 34 (7.6) 16.8 (0.36) 32.5 (2.12) 40.5 (12.0) 58.4 (5.25) 48.3 (5.3) 23.3 (2.17) 352 (160) 76 (7.1) 376 (112) 659.2 (531.2) 765 (170) 460.7 (170.4) 168 (55.6) i valuesare meanswith standarddeviations(in parentheses) 1.95 (0.985) 0.42 (0.04) 5.6 (0.18) 6.8 (3.8) 6.4 (4.3) 3.6 (1.9) 1.01 (0.34) Due to the small sample size and large amount of variability in the endpoints, there were 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 analysis of both condition factor and LSI showed no significant differences between sites for the species collected from both locations. The lack of any statistical significance was influenced by large amount variability in the data and by the 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. Table 8. Species and location specific condition factor (K) and liver somatic index (LSI) for fish collected from the Tennessee River in the Decatur Alabama area. Species Largemouth Bass Location 3M Ouffall K2 i 1.3855 LSI 3 2.92 Shad White perch Catfish Largemouth Bass 3M Ouffall 3M Ouffall 3M Ouffall Guntersville 0.8207 (0.1224) 1.6146 (0.0481) 0.8724 (0.0102) 1.0478 0.4772 (0.2877) 0.5463 (0.0043) 1.1935 (0.3923) 0.6769 Catfish Gar Guntersville Guntersville 1.0743 (0.1142) 0.3 815 (0.0180) Striped Bass Guntersville 1.2094 (0.1207) 2 Datapresentedas meanandstandarddeviation 3 Condition factor (K) was calculated as K= 0Vt x 100)/L 3 Liver somatic index (LSI) was calculated as LSI= (Liver wt/total wt) xl00 1.5826 (0.5186) 0.8649 (0.6137) 0.6241 (0.1902) 7.4.1 Concentrations of PFOS, FOSA, PFOA, AND PFHS in fish livers. Fluorocarbons were detected in all livers removed from fish collected at both the Guntersville and Ouffall 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 Ouffall were approximately 19-fold, 340-fold, 109-fold and 710-fold greater than those observed in Guntersville fish, respectively. 19 Average liver concentrations for PFOS, FOSA, PFOA, and PFHS for all fish collected at the Guntersville site were 1036, 22.0, 22.1 and 3.79 lxg/kg wet weight, respectively. Table 9. Liver concentrations of selected fluorocarbons Tennessee River in the Decatur, Alabama area. a PFOS FOSA Species Guntersviile Catfish (_tg/kg) 87.3 (_tg/kg) 20.3 (22.2) (5.0) Gar 249.3 20.95 (185.9) (16.4) Striped Bass 1330.0 (763) 23.19 (10.0) Largemouth Bass 643 18.8b in fish collectferdom the PFOA (pg/kg) 18.8b PFHS (_ter/kg) 3.75 b 18.8 b 24.7 (17.6) 18.8b 4.58 (1.65) 3.75 b 3.75 b Outfali Catfish 10093.5 14521.5 252.9 30.2 (5,777.8) (2090.9) (277.3) (28.6) Gar 13892.0 5,089.0 1,934.5 256.5 (3073.1) (3,739.2) (652.7) (89.9) Shad 9195.2 4,420.0 96.9 129.1 (13252.2) (4047.3) (49.0) (145.3) White perch 49285.0 (37657.7) 17403.0 (14679.5) 1628.5 (1228.2) 2069.5 (1941.0) Largemouth bass 27143.0 2456.0 3.75 c 11.6 II i i a Concentrationsare repottedasmeansand _andarddeviations. b Resultswasreportedas the limitof qtmntitation:18.8lxg/kgfor PFOS,FOSA,PFOA and 3.75lxg/kg for PFHS cEstimatedvalue. 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 bass < Striped bass (Largemouth bass)< Catfish < Gar < Striped bass 20 PFOA: PFHS: (Catfish = Largemouth bass) < Gar < Striped bass (Striped bass = Catfish < 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 a 160-fold difference between catfish that had the least concentration and striped bass with the greatest liver concentration. FOSA, PFOA, and PFHS liver concentrations in fish from Guntersville were all less than their respective LOQs. The significance of these results and a true understanding of the magnitude of the observed differences at this site are unknown at this time due to the variability in the data and small sample size. Average liver concentrations for PFOS, FOSA, PFOA, and PFHS for all fish collected from the Outfall location were 15,692, 7,195, 581, and 384 _tg/kg wet weight, respectively. As was observed at the Guntersville site, differences in liver fluorochemical concentrations were also observed between fish species collected at the site. concentrations of the selected fluorochemicals at Ouffall site increased as follows: Liver PFOS: FOSA: PFOA: PFHS: Shad < Catfish < Gar < Largemouth Bass < White Perch Largemouth Bass <Shad< Gar < Catfish < White Perch Largemouth Bass < Shad < Catfish < White Perch < Gar Largemouth Bass < Catfish < Shad < Gar < White Perch Except for PFOA, there were no statistically significant differences in species specific liver concentrations of the selected 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, due to the small sample size and large amount of variability 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 due to the fact that there was 21 only a single value for this species. The magnitude and significance of these differences is unknown at this time due to the variability in the data and small sample size. 7.4.2 Wholefish concentrations of PFOS, FOSA, PFOA, and PFHS 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) of selected fluorochemicals in fish collected from the Tennessee River in the Decatur Alabama area. a PFOS FOSA PFOA PFHS Species Gunterswille Catfish (lag;/k_) 7.5b (_tg/kg) 7.5b (lag&g) 20. lb (_tg]kg) 7.5 b Gar Striped Bass Largemouth Bass 15.1 (15.2) 65.6 (23.2) 230 7.5 b 10.4 (0.96) 8.76 20.1b 7.5b 8.03b 7.5b 8.03b 7.5 b Outfali Catfish Gar Shad 1190 (170) 1863 (1679) ND ND 119.6 11.4 (140.6) (5.52) ND 154.5 35.5 (40.3) (25.0) ND 54.0 38.9 (48.2) (60.2) White perch ND ND 278 405.5 (69.3) (129.4) Largemouth bass ND 557 20.1 b 7.5 b i i i a Concentrations are reported as means and st_mdord deviation_ b Results was reported as the limit of quamJficalio_7.5 lxg/kg for PFOS, FOSA, PFHS, 8.03 lag/kg for PFOA ND signifies that the compound is present but not quantified due to the data not meeting quality control criteria. 22 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-fold, 9-fold and 12-fold greater than those measured in Guntersville fish, respectively. Mean whole body concentrations for PFOS, FOSA, PFOA and PFHS for all fish collected from the Guntersville site were 59.1, 9.43, 11.7 and 7.50 lxg/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 < Gar < Striped bass < Largemouth bass Catfish = Gar < Largemouth bass < Striped bass Largemouth bass = Striped bass < Catfish < Gar All species equal due to being 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 of PFOS by fish species at this site. Mean whole body concentration for PFOS, FOSA, PFOA and PFHS for fish caught at the Ouffall were 1332.0, 20.1, 106.4, and 86. 9 lxg/kg wet weight, respectively. As observed at the Guntersville location, differences in whole body fluorochemieal concentrations were also observed between species caught on site. Whole body concentrations of fluorochemicals in Outfall site increased as follows: 23 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. As with the Guntersville fish, small sample size precluded any statistical analysis of the data to evaluate differences between species at the Ot_all 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 magnitude of these differences. Z 5 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 ranged from 15.6 _tg/kg to 14.1 pg/kg wet weight at Guntersville and the Outfall, respectively. In contrast, there was a 42.8-fold difference in FOSA clam tissue concentrations with 25.1 Ixg/kg and 1074 ttg/kg, wet weight, being measured at Guntersville and Outfall locations, respectively. There were no significant differences in the concentration of PFOA and PFHS in clam tissue collected at each of the two sites. The results of the clam analyses reflect the areas from which the samples were collected. Due to substrate problems, Outfall clams were collected at the Fox Creek location. This location had surface water and sediment fluorochemical concentrations that were statistically similar to those observed at the Guntersville location. Thus, these results indicate that for at least clams, the environmental concentrations of fluorochemicals downstream of the 3M Outfall have returned to background levels within in the Tennessee River. 24 Table 11. Tissue concentrations of selected fluorochemicals collected from the Tennessee River in ithe Decatur Alabama area. pros rosa Proa Location (_tg/kg) (_tg/kg) (pg/kg) Guntersville 15.6_ 25.1 4.382 in clams PFrIs (_tg/kg) 0.9462 OutfaU 14.12 1074 8.422 0.37: (13.7) (1358) (7.18) Concentrations presented as means and standard deviations. 2 Limits of q_mntitation: 18.8 lig/kg for PFOS, FOSA, PFOA, 3.75 Concentrations reported below LOQs are estimated values (0.53) l_g/kg for PFHS. 8 REFERENCES Hansen, K.J. and H.O. Johnson. 2000. Determination of perfluorooctanoate sulfonate (PFOS), perfluorooctane sulfonylamide (FOSA), and perfluorooctanoate (PFOA) in water by 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. 25 9 APPENDICES Appendix A. Structure and chemical characteristics of selected fluorochemicals monitored in water, sediment and biota of the Tennessee River in the Decatur Alabama area. Appendix B. Water and Sediment locations within the Tennessee River study areas Appendix C. Water, sediment, dams, and fish sampling protocols Appendix D. Centre Analytical Laboratories analytical report for the 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. Figure 1. Water quality parameters Figure 2. Fluorochernicals in surface waters Figure 3. Fluorochemicals in sediments, wet weight Figure 4. Fluorochemicals in sediments, dry weight Appendix G. Physiological data for fish collected from the Tennessee River. Appendix H. Fluorochemicals concentrations in fish livers and clam tissues collected from the Tennessee River in the Decatur Alabama area. Appendix I. Whole body fluorochemical concentrations in fish collected from the Tennessee River in the Decatur Alabama area. 26 'qCGnts Anakical LaboPatoris, Inc. 3048 Research Drive State College, P_,16801 www.centrelab.com he: (814) 231-8032 Fax:(814) 231-1253 or (814) 231-1580 Analy,cReport Fluorochemlcal Characterization of Water and Sediment Samples MSU-Entrix (Tennessee River) FACT-GEN-037 (E00-1958) Centre Analytlcal Laboratory Report No. 023-0140 (Revlslon 2) Revision Date 6/28/01 Testing Laboratory Centre AnalyticalLaboratory,Inc. 3048 ResearchDrive State College, PA 16801 3M Environmental Laboratory Contact KentR. Linclstrom Bldg. 2-3E-09 P.O. Box 33331 SL Paul, MN 55133-3331 Phone: (651) 778-5352 Requester Dale BaconPh.D. 3M EnvironmentaTl echnology& SafetyServices Bldg.2-3E-09 P.O. Box 33331 St. Paul,MN 55133-3331 PAGE10F$ 1 Introduction Results are reportedfor the analysisof a sedes of water and sed_ent samples received by Centre Analytical Laboratories,Inc. (Centre) from the 3M Environmentalt_horatory. The samples were collectedfrom the Tennessee River and ere part of 3M Project E00-1958. The Centrestudynumberassignedto the projectis 023-014. Specificfluorochemicacl haracterizationby liquidchromatography/ tandem mass spectrometry (LC/MS/MS) was requestedfor all samples. A total of66 sampleswere receivedfor analysLs. The samples were preparedand analyzed by LC/MS/MS forthe followinglistoffluorochemicals: Table 1: Target Analysis Compound Name PerfluorooctaneSulfonate PerfluorooctaneSulfonylamide Perfluorooctanoate PerfluomhexanoSulfonate Acronym PFOS PFOSA POAA PFHS The analyticalmethodsused for water sampleswere validated by Centre. The validationprotocol and results are on file _ Centre. The methods were modified for the sediment samples, however the procedureshave not been fullyvalidatedfor this matrix.Data presentedhere is the highestqualitydata availableat this time. 2 Sample Receipt The samples were submittedin individualplasticcontainersand were not preserved. Sixty-six inclividuasl ample containerswere received. Samples were receivedon 7/26/00. The samples were collected between 6/19/00 and 6/22/00. Chain-of-custodyinformationis presented in AttachmentC. 3 Holding Times The analyticalmethod used was validatedagainsta maximumholdingtime of 14 days. Samples were received afterthe 14-day holdingtime. However, it shouldbe noted that fieldfortifications in water and othermatriceshave shownacceptablerecoveriesat 100 and 1000 ng/Lfor periods longerthan 14 days. PAiC2_(_ 6 4 Methods - Analytical and Preparatory 4.1 LC/MS/MS 4.1.1 SamplePreparationfor LC/MS/MSAnalysis Watersampleswere initiallytreatedwith200 uL of250 mg/Lsodiumthiosulfatesolutionto removeresiduacl hlorineS. olidphaseextraction(SPE)was usedto preparethesamplesfor LC/MS/MSanalysisA. forty-millUipteorrtionof samplewastransferretdoa C_0SPEcartridge. The cartridgewasfirstelutedwith5 mLof 40%methanoiln watersolution.The eluatewas discardedandthe SPE columnwas thenelutedwith100/0methanol.A 5 mLportionof methanolwas collectedforanalysisby LC/MS/MS. Thistreutmenrtesultedin an eight-fold concentratioonfthesamplespriorto a,'_ysis. Forthe sedimenstamplesa, representativpeortionofsample(5 grams)wasf,'stextractedinto 5 mlofmethanol.The extractswerefilteredanddilutedto a finalvolumeof 40 mLwithTypeI water. The dilutedextractsware thentreatedin thesamemanneras the watersamples, beginninwgiththe solUphaseextract_n. 4.1.2 SampleAnalysisby LC/MS/MS In HPLC,analiquotof extractisinjectedandpassedthrougha rcluid-phascehromatographic column.Basedontheaffinityof theanalyteforthestationarpyhaseinthecolumnrelativeto theliquidmobilephase,the analyteis retainedfor a characteristaicmountof time. Following HPLCseparationE, S/MSprovideas rapidandaccuratemeansforanalyzinga widerangeof organiccompoundsin, cludinfgluorochemicaElsl.ectrospraiysgenerallyoperatedat rela_ely mildtemperaturesm;oleculesare ionized,fragmenteda,nd detected. Ionscharacteristoicf knownfluorochemicaalrseobservedandquantitateadgainsst tandards. A Hewlett-PackaHrdP1100HPLCsystemcoupledtoa MicromasUsltimeM. S/MSwasusedto analyzethe sampleextracts.Analysiswas performedusingselectedreactionmonitoring (SRM).Watersampleswereextracteodn 8/2/00and8/3/00andanalyzedbyMS/MSbetween 8/3/00and8/17J00S. edimenst ampleswereextracted8/4/00and8/10/(Xa) ndwereanalyzed by MS/MSbetween8/8/00 and8/17/00.The HPLCand MS/MSmethodsusedfor analysis andinstrumenptarametercsanbefoundinAttachmentDsandE. 5 Analysis 5.1 Calibration A 7-pointcalibratiocnurvewasanalyzedat the beginningandendoftheanalyt_aisequence forthecompoundosf interestT. he calibrationpointswerepreparedat 0, 25, 50, 100,250, 500, and1000ng/L(,opt)T. he instrumenrtesponseversusthe concentratiownas plottedfor eachpoinL Usinglinearregressiown ith1/x weightingth, e slope,y-intercepatndcorrelation coefficien(tr) andcoe_ientof determinatio(nr') weredetermined.A calibrationcurveis acceptablief r >__0.98(r5=_>0.970). CalibratiosntandardsarepreparedusingthesameSPEproceduruesedforsamples. _tlon checkstandardws ereanalyzedperiodicall(yeverythreetofivesampleInjections) throughoutthe analysissequence.Complianceis obtained if the standardanalyte concenb'ationarsewithin+/-20%oftheactuavl alue. Fortheresultsre_ here,calibratiocnriteriaweremet. 5.2 Blanks Extractionblankswerepreparedandanalyzedwitheveryextractionbatchof samplesT. he extractiobnlanksshouldnothaveanytargetanalytespresenat t orabovetheconcentratieonf the low-leveclalibratiosntandardF. orthesesamplest,heextractiobnlankswerecompliant. Instrumenbtlanksin theformof cleanmethanosl olvenwt ereaLsoanalyzedaftereveryhighlevelcaJibratiosntandarda,ndafterknownhigh-levesl amples.Again,theblanksshouldnot have any targetanaJytapsresentat or abovethe low-levecl alibrationstandard.For the samplespresentedheretheinstrumenbtlanksarecornprmnL 5.3 Surrogates Surrogatespikesarenota componenotf theLC/MS/MSanalyticaml ethod. 5.4 Matrix Spikes Matrixspies werepreparedfor everyfieldsampleusingallcompoundosf Interest.Matrix spikerecoverieasregiveninAttachmenBt. Fieldspikesweresubmittedwithone sedimenat ndone surfacewatersample. FieldSl]](e recoverieasre alsoincludedin AttachmenBt . The sedimenst ampleshowedno recoveryof thefieldspike,indicatintghattherewasa problemwiththesedimenftieldsp_Jngprocedure. Field controsl amplessp_ed at 200 pptand 1000 pl0twere submitted.The fieldcontrol samplesshowedrecoveriesbetween70 and 130%. The resultsare also includedin AttachmenBt . 5.5 Duplicates All(midsampleswereanalyzedin duplicate.Resultsaregivenalongwiththesampleresults in Att_u_-hmentA. 5.6 Laboratory Control Samples ForLC/MS/MSanalysesM, illiqwaterwasspikedwithallcompoundosfinteresat t 25and250 ng/Lduringeachextractiosnet. Allrecoveriesforallcompoundws erebetween70-130%in eachLCS. Resultsaregivenalongwiththe rawdatainAttachmentDs andE. 5.7 Sample Related Comments Therearenoothersamplerelatedcommentsforthisdataset. 6 Data Summary PleaseseeAttachmenAt fora detailedlistingoftheanalyticarlesultsS. urfacewaterresults are repodedin partspertn'llio(nppt)(ng/L).Sedimenst ampleresultsarereportedin partsper billion(ppb)(ug/Kgo) nbothanas-receivedanddry-weighbtasis. PA_ 4 OF6 7 Data/Sample Retention ) Samplesaredisposedofonemonthafterthereportisissuedunlessotherwissepecit'_:LAll electronicdata is archivedon retrievablme ediaand hardcopyreportsare storedin data I foldemrsa'rltainedbyCentre. i 8 Attachments &l AUachrnerdRkesurm 82 AttachmenBt:_ SI]keRecoveries i 8.3 AttachmenCt :ChainofCustody 8.4 AttachmentD: LC#MS/MSRawAnalyticaDlata(SurfaceWaterSamples) 8.5 AttachmenEt: LCtMS/MSRawAnalyticaDlata(SedimenSt amples) 9 Signatures j_ohn M.._..r!y., l___anager .. Dale OtherLab MembersConldbutintgo Data KarenSmith PAGEOSF6 SECTION A ANALYTICAL REPORT 3048 Research CLaebnotrreatorAiEnsa,lyticaIlnc. Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 I Analytical Results GEN-037 Surface Waters I 3M Staple Identification Date Collected PFOS (ng/L) PFOSA (ng/L) POAA (ng/L) PFItS (ng/L) I SW-FB01 SW-13 SW-13 Dup 8W-14 I 8W-14 Dup SW-15 SW-15 I::)up _N-16 SW-16 Dup I SW-17 8W-17 Dup 8W-18 SWo18 Dup SW-18 Field Duplicate SW-25 $W-25 Dup $Wo26 SWo26 Dup $W-01 SW-01 Dup SW-02 SW-02 Dup SW-03 SW-03 Dup SW-04 SW-04 Dup SW405 $W-05 Dup SW-06 SW-06 Dup SW-06 Fiald Dupl'ste $W-11 6W-11 Dup SW-11 FMS1 SW-11 FMS2 8W-FSCS1 SW-FSCS2 SW-12 SW-12 Dup SW-12 l:mid Duplicate SW-27 SW-27 Oup 6/20/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/I 6/00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/20/00 6/20/00 6/20/00 6/20/00 6/20/00 6/20/00 6/20/00 6/20/00 6/20/00 6/20/00 6/20/00 NQ 60.2 65.2 67.0 64.0 49.7 59.7 53-5 52.9 41.2 68.4 32.9 33.2 40.6 156000 145000 77300 78300 131000 154000 68700 67700 11900 13300 14500 10900 14800 18200 11900 11900 15200 565 497 687 1350 223 993 565 574 588 592 579 ND NQ NQ NQ NO NQ NQ NQ NO NQ NQ NQ NQ NQ 7880 8080 6960 6700 7900 8830 4400 4940 1120 1160 1300 878 1430 1610 1020 988 1140 151 141 316 1050 219 717 164 188 190 181 188 ND 30.7 32.0 30.1 32.1 25.6 30.3 26 29.2 NQ 42.0 NQ NQ NQ 1900000 1900(X)0 58200 57200 1700000 1800000 748000 753000 117000 12800O 107000 102000 16_000 187000 104000 104000 143000 2050 1920 2040 2470 192 903 2648 3030 2990 3410 3510 ND NQ NQ 26.4 NQ NQ NQ NQ NO NQ NQ < 25 < 25 NQ 43900 41500 12100 11500 35300 38800 17000 17700 3070 346O 4259 3210 4130 5030 3920 3800 4470 446 410 584 1090 194 889 637 654 635 658 Limitof Detection(LOD) for the procedureis appo:dmately2.5 ng/I. for PFOS, PFH$, and PFOSA and 7.5 ng/I. for POAA Limitof QuanUtation(LOQ) for the procedureis 25 ng/l. forall compounds ND - Compoundnot detected NQ - Compounddetectedst a level betweenthe LOD and lOCI. Result is not quantifiable. ND < LOD < NQ < LOQ Piemm refer to the reverse side for our st_Klard terms and conditions. ANALYTICAL REPORT 3048 Research CLaGbnotrsatorAiEns.a, lgticIanlc. Drive, State College PA 16801 814-231.8032 FAX 814-231-1253 I AnalyticM Results GEN-037 Surface WINs I 3M Sample IdenUllcation Date Collected Pros (ng/L) PFOSA (rigA.) POAA (n0/I) PFHS (ng/L) I SW-07 SW<)7 Dup _N-08 SW-08 Oup SW<)9 SW-09 Dup SW-IO SW- 10 Dup SW-19 SW-19 Dup SW-20 SW-20 Dup SW-21 SW-21 Dup SW-22 SW-2,?.Dup SW-23 SW-23 Dup SW-24 SW-24 Dup SW-FB02 6/2O/O0 5O9 149 2220 52O 6/20/00 464 143 2050 474 6/20/00 319 6/20/00 315 99.4 1630 324 96.3 1430 805 6/20/00 97.6 36.1 582 86.3 6/20/00 98.8 35.4 559 83.3 6/20/00 116 34.4 g25 110 6/20/00 109 312 882 96.9 6/21/00 NQ ND ND ND 6/21/00 NQ ND ND ND 6/21/00 NQ NQ ND ND 6/21/00 NQ NQ ND ND 6/21/00 NQ NQ ND ND 6/21/00 NQ NQ ND NO 6/21/00 NQ NQ ND ND 6/21/00 NQ NQ NO ND 6/21/00 NQ NQ NO NO 6/21/00 NQ NQ ND NO 6/21/00 NQ NQ ND NO 6/21/00 NQ NQ ND NO 6/,22/00 NO ND ND NO Limitof Deteclion (LOD) forthe procedure Is appoximately2.5 ng/Lfor PFOS, PFHS, and PFOSA and 7.5 ng/Lfor POAA Limitof Quantltation(IOCi) for the procedure1825 ng/L forall compounds ND - Compoundnot detected NQ - Compound det_ted at a level between the LOD and LOQ. Result is not quan_lable. ND < LOD < NQ < LOQ (_ P/ease refer to _herevenm s/de for our mndard lWms and cond/t/on ANALYTICAL REPORT , CLasbnotrratoriGAnsla,lgticalInc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 I Analytical Results GEN-037 Sedl_tl I 3M Sample Identification Dale Cohctecl PF06 (ug/Kg) (is receivecs) PFOSA (ug/K9) (is receiv,.:l) POAA (ug/Ko) (as received) I $od-ll 6/20/00 1.56 0.818 1.17 Sed-11 Oup 6/20/00 1.62 0.848 1.t8 Sed-12 6/26/00 3.47 2.48 2.34 8od-12 Dup 6_20J00 2.85 2.09 2.31 Sed- 12 Field Dup Sed-13 6/20/00 4.80 3.50 2.32 6/19/00 1.82 0.255 HQ Sed-13 Oup Sod-14 6/19/00 1.38 0.225 NQ 6/1WOO 0.43 NQ ND Sed-14 Dup Sod-15 6/1911)0 0.506 NQ ND 6/19100 1.53 0.248 NQ 88d-15 Dup 6/19/00 1.30 NQ ND Sod-16 6/19/00 0.452 ND ND SOd-16 Dup SOd-17 6/19/00 0.574 ND ND 6/I 9/00 1.03 NQ ND Sed-17 Dup Sod-18 6/16/00 0.896 NQ ND 6119/00 0.824 NQ NQ Sed-18 Dup 6/19/00 0.816 NQ NQ Sod-18 ReU Dup Sed-25 6/19/00 6/19/00 1.38 5750 NQ 1170 NQ 1930 Se_25 Dup Sed-27 6/19/00 6/20/00 6110 3,63 1230 1.55 1780 2,49 Sod-27 Dup 6/20/00 3.54 2.90 2.76 Limitof Detection(LOD) forthe procedureIs appo_nataly 0.08 ug/Kgforall compounds Umit of Quantltatlon(LOQ) for the pmcodum is 0.20 ug/Kg ford compounds ND - Compounclnot cletected NQ - Compounddetected at a levelbetween the LOD and LOQ. Resultis not quan_able. ND < LOD < NQ < LOQ PFHS (ug/Kg) (as receh,_) NQ NQ 0.278 0.295 0.310 ND ND ND ND NO ND ND ND ND ND ND ND 132 138 0.330 0.320 _ refer m i_ mver_ mTdofor our _mdard mmw w_ _.s " ANALYTICALREPORT , CI.aGbnotraGtorAi sn.algticaIlnc. 3048 Research Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 I I Analytical Results GEN-037 Sediments 3M Sample Identlfir.ation Date Collecled PFO$ (ug/Kg) PFOSA (ug/Kg) POAA (ug/Kg) PFH8 (ug/l(g) (asrecek_ (n receMx_ (asre_ved) (is re_ved) I Sed-01 6/19/00 1400 270 1010 56.5 Sed-01 Dup Sed.02 6/19/00 1720 317 862 39.6 6/19/00 1860 431 1270 67.4 I Sed-02 Dup Sed-03 6/19/00 2070 513 1230 69.4 6/19J00 309 73.6 453 16.9 Sed-0_ Dup Sed-04 _HJ-04 Dull I Sed-05 6/19100 433 95.2 527 22.8 6/19/00 465 107 654 24,5 (]/19/00 478 96.9 643 21.9 6/19/00 69.9 54.6 105 7.22 Sed-06 Oup Sed-06 6/19/00 85.5 56.9 135 7.79 6/19/00 64.7 19.3 36.7 5.99 Sed-06 Dup I Sed-06 FieldDup Sed-07 Sed-07 DUp Sed-08 6/19/00 83.6 23.1 47.7 6.56 6/19/00 97.3 20.8 41.9 6.24 6/20/00 1.01 0.596 0.880 ND 0/20/00 0.872 0.553 0.848 NQ 6/20/00 0.936 0.491 0.710 ND Sed-08 Dup Sed-09 Sed-09 Dup Sed-10 6/'20/00 1.12 0.471 0.740 ND 6/20/00 0.92 0.468 1.08 ND 6QOKX) 0.912 0.447 1.07 NO 6/20/00 0.864 0.373 0.582 ND Sed-10 Dup Sed-lg Sed-19 Dup 6/20/00 0.832 0.393 0.612 ND 6/21/00 NQ ND ND ND 6/21/00 NO ND ND ND Umlt 04DetecUon(LOD) forthe pmcedlureis appoxinmtely0.08 ug_g forall compounds Limitof Quantitation(LOQ) forthe procedureis0.20 ug/Kgfor allcompounds ND - Compound not detected NQ - Compound detectedat a level betweenthe LOD and LOCi. Resultis not quantifiable. NO < LOD < NQ < LOQ (_ P/eue refer to the m_erae s/de for our mnckwd lerms and ond/Uons. ANALYTICALREPORT 3048 Research CLaEbnotrreatorAiEnsa,lgticaInl c. Drive, State College PA 16801 814-231-8032 FAX814-231-1253 I Analytical Results GEN-037 Sediments I 3M Sample Identification Date Collected Pros (uo/Ko) PFOSA (ug/Kg) POAA (uo/Kg) PFH$ (ug/Kg) (as recalvad) (as received) (sis received) (all received) I Sed-20 6/21/00 0.217 ND ND ND Seal-20Dup 6/21/00 0.318 NQ ND ND Secl-21 6/21/00 NQ ND ND ND I Seal-21 Dup 8ecl-22 Sed-22 Dup Seal-23 0/21/00 NQ ND NO ND 6/21/00 NQ ND ND ND 6/21/00 NQ ND ND ND 6/21/00 NQ ND ND ND Sed-23 Dup Sed-24 6/21/00 NQ ND ND ND 6/21/00 0.266 NQ NQ ND Seal-24Dup 6/21/00 0.257 NQ NQ ND I limit of Detection(LOD) for the procedureis appodmately 0.08 ug/Kg forall compounds Umit of Quan_tation(LOCI)forthe procedureis 0.20 ug/K0 for d compounda , ND - Compoundnot detected NQ - Compound detected at a level between the LOD and LOQ. Result is not quantifiable. ND < LOD < NQ < LOQ Please refer to rlm reverse slde for our smndNd terms and condltlOmL 3048 Research CLaGbnotrraEtoriAGnsa,lgticalInc. Drive, State College PA 16801 814-231-8032 FAX 814-231-1253 J Analytical Results GEN-037 Sediments I 3M Sample Identification Date Collected PFOS (ug/Kg) PFOSA (ug/Kg) POAA (ug/Kg) PFH$ (ug/Kg) (dry weight) (dry weight) (dry weight) (dry vndght) I Sed-11 6/20/00 2.03 1.07 1.54 NQ 8ed-11 Dup 8ed-12 6/20/00 2.13 1.12 1,55 NQ 6/20/00 6.46 4.62 4.36 0.518 Sed-12 0up 6/20/00 5.31 3.89 4.30 0.549 Seal-12 FieldDup Sod-18 6t20/00 9.14 6.67 4.42 0.690 6/19/00 2.72 0.429 NQ NQ Sed-13 Dup Seal-14 6/19/00 2.32 0.378 NQ ND 6/19/00 0.572 NQ ND ND Sed-14 Dup 6/19/00 0.673 NQ ND NO 8ed- 15 6/19/00 2.35 0.382 NQ ND Sed-15 Dup Seal-! 8 6/19/00 2.00 0.235 ND ND 6/19/00 0.657 ND NO ND Seal-16Dup Sed-17 6/19/00 0.834 ND ND ND 6/19/00 2.73 NQ ND ND Sed-17 Dup Seal-13 6/19/00 2.42 NO ND ND 6/19/00 1.38 NQ NQ ND Seal-18 Dup 6/19/00 1.34 NO NQ ND Sed-19 FieldDup Sed-25 6/19/00 2.28 NQ NQ ND 6/19/00 12200 2490 4110 281 Sed-25 Dup 6/19/00 13000 2620 37g0 294 Sed-27 6/20/00 6.54 2.79 4.49 0.595 Sed-27 Dup 6/20/00 6.38 5.23 4.97 0.577 Umit of Detection (LOD) for the procedureis appoximstely0.08 ug/Kg for =11compounds(as received) Umit of Ouantilation (LOQ) for the procedureis 0.20 ug/Kgfor allcompounds(as received) ND - Compound not detected NQ - Compound detected at a level betweenthe LOD and LOQ. Result is notquantifiable. ND < LOD < NQ < LOQ LYTICALREPORT 3048 Research CLaEbnotrrEatorAiGnsa,l,gticaIlnc. Drive, State College PA 16801 814-231-8032 " FAX 814-231-1253 Analytical Results GEN-037 Sediments 3M Sample Identification Date Collected PFOS (ug/K9) (dry weight) PFOSA (ug/Kg) (dry weight) POAA (ug/Kg) (dry weight) Sed_l Sed-01 Dup Sed_2 Sed-02 Dup Sed-03 Sed-03 Dup Sod-04 8ed_4 Dup Sed-05 Sod-05 Dup ,,,_d-06 8ed-08 Dup Sed-08 Field Dup Sed-07 Sed-07 Dup Sed-08 Sed-08 Dup Sed-09 Sed-09 Dup Sed-10 Sed-10 Dup Sed-19 Sed-19 Dup 6/1_0 6/19/00 6/ISV00 6/19/00 6/19/00 6/19/00 6/19/00 6/19/OO 6/19/00 6/19/00 6/19/00 6/19/00 6/19/00 6/20/00 6Q0/00 6/20/00 6/20/00 6/20A00 6/20/00 6/20/00 6/20/00 6/21/00 6/21/00 2150 2640 3eeo 4070 472 682 671 090 94.8 118 88.9 115 133 1.36 1.15 2.04 2.44 1.96 1.94 1.89 1.82 NQ NO 418 487 54a 1010 113,0 146 154 140 73.9 77.0 26.5 31.7 28.3 0.806 0.745 1.07 1.03 0.998 0.953 0.816 0.860 ND NO 185O 1320 25oo 2420 893 806 944 927 142 183 50.4 65.5 57.1 1.19 1.14 1.55 1.81 2.30 2,28 1.27 1.34 ND ND Umlt of Detection(LOD) for ll'mprocedureis appoximatety0.08 ug/Kg forall compounds(as received) Umit of Quantitallon (LOCi)for the procedureis 0.20 ug/Kg for allcompounds(as received) NO - Compound not detected NO - Compound detectedat a levelbebNeeflthe LOD and LOCI. Result is not quantifiable. NO < LOD < NQ < LOQ PFHS (ug/K9) (dry weight) SS.1 60.8 133 137 25.8 34.9 35.4 31.8 9.77 10.5 8,23 9.01 8.72 ND NQ NO ND ND NO ND ND ND ND PMase refer to ttm remrse #de for our standard _ and concr4fon_ 3048 Research CLanbtroeratorA,sn,.algticaInlc. Drive, State College PA 16801 814-231.8032 FAX 814-231-1253 Analylllcal Results GEN-037 Sediments 3M Sample IdontH1cation Sed-20 Sed-20 Dup Seal-21 Seal-21 Dup Sed-22 8ed-22 Dup Sed-23 Sed-23 Dup Sed-24 Sed-24 Dup Date Collected 6/21/00 6/21/00 6/21/00 6/21/00 6/21/00 6/21/00 6/21/00 6/21/00 6/21/00 6/21/00 PFOS (ug/Kg) (dry weight) 0.558 0.817 NQ NQ NQ NQ NQ NQ 0.600 0.580 PFO_ (ug/Kg) (dry weight) hid NQ ND ND ND NO NO ND NQ NQ POAA (ug/Kg) (dry weight) ND ND NO ND ND ND ND ND NQ NQ Limitof Detection(LOD) forthe procedureis appoximately0.08 ug/Kgfor all compounds(as received) Limitof Quantltatio_(LOQ) for the procedure is0.20 ug/Kg for allcompounds(as received) ND - Compound not detected NQ - Compounddetected at 8 level be(we_ the LOD and LOQ. ResuRis not quantifiable. ND < LOD < NQ < LOQ PFItS (ug,_o) (dry weight) NO ND ND ND ND ND ND ND NO ND "PleaNreferWfhereversesideforouretandKdtenns_md_s.