Document v61Bqbx8kK4JZzxmRkJpwz4Y

BACK TO MAIN - 1 - PERFLUOROOCTANESULFONATE AND RELATED FLUOROCHEMICALS IN OYSTER, CRASSOSTREA VIRGINICA, FROM THE GULF OF MEXICO AND CHESAPEAKE BAY John P. Giesy* Kurunthachalam Kannan Department of Zoology, National Food Safety and Toxicology Center, Institute for Environmental Toxicology, Michigan State University, East Lansing, MI 48824, USA *To whom correspondence should be addressed: Prof. J.P. Giesy 218C National Food Safety and Toxicology Ctr Michigan State University East Lansing, MI 48824 USA Tel: (517)-353-2000; Fax: 517-432-2310; E- mail: jgiesy@aol.com Prepared for: 3M St. Paul, MN June 20, 2001 BACK TO MAIN - 2 - SUMMARY Concentrations of perfluorooctanesulfonate (PFOS), a metabolite of several sulfonated perfluoroorganic compounds, were measured in oysters collected from 77 locations in the Gulf of Mexico and Chesapeake Bay of the US coast. Similarly, perfluorooctanesulfonamide (FOSA), perfluorooctanoic acid (PFOA) and perfluorohexanesulfonate (PFHS) were also measured in oysters. PFOS was detected in oysters collected from 51 of the 77 locations at concentrations ranging from <42 to 1225 ng/g, on a dry weight basis. FOSA was detected in three of the 77 samples. PFOA and PFHS were not found in oysters at qua ntifiable concentrations. This study provides baseline data for future monitoring programs to examine long-term trends in concentrations of PFOS. INTRODUCTION Bivalves (oysters and mussels) have been widely used as sentinel organisms for monitoring spatial and temporal distribution of trace metals and organic residues in marine coastal and estuarine ecosystems. In this study, American oysters Crassostrea virginica collected in the Gulf of Mexico and the Chesapeake Bay during December 1996 - February 1998 were analyzed for the presence of PFOS, FOSA, PFOA and PFHS in order to establish baseline concentrations of this organic fluorochemical. C. virginica was chosen because this species is used as one of the sentinels in mussel watch program. MATERIALS AND METHODS Samples. Sampling of oysters and mussels have been described elsewhere (1,2). Briefly, sampling locations have been selected with the intention of collecting samples that are `representative' of the surroundings. Areas of point source inputs (e.g., waste discharge) have been avoided. Sampling locations for oysters are shown (Figs. 1 and 2; Table 1). Samples were collected from December to February of 1996-1998. Depending upon the depth of the water column, which ranged from 0.5 to 3.5 m, oysters were collected by hand, tongs or dredge. Composite samples of 20 oysters from each location were prepared by homogenizing the soft parts. For each composite sample, an aliquot of oyster tissue was dried in an oven at 60C for determination of dry weight. Analysis. Details of the analytical procedure have been outlined in 3M Environmental Laboratory, St. Paul, MN standard operating procedures for the analysis of fluorochemicals in tissues. The analytical work was generated by the 3M Environmental Laboratory. (Refer to Reference (3) for the specific reports.) Concentrations of PFOS in oyster tissues were determined by use of high performance liquid chromatography (HPLC) coupled with electrospray tandem mass spectrometry (4). Briefly, 1 g of oyster tissues was homogenized with BACK TO MAIN - 3 - MilliporeTM water and combined with an ion-pairing reagent. After thorough mixing, the fluorochemical ion pair was partitioned into organic solvent and concentrated prior to analysis. Analyte separation and detection was performed as described earlier (5) with the following exceptions. Ten L of extract was injected onto the column with a 2 mM ammonium acetate/methanol mobile phase starting at 10% methanol. At a flow rate of 300 L/minute, the gradient increased to 100% methanol at 11.5 minutes before reverting to original conditions at 13 min. For quantitative determination, the HPLC system was interfaced to a Micromass (Beverly, MA) Quattro II atmospheric pressure ionization tandem mass spectrometer operated in the electrospray negative mode. Instrumental parameters were optimized to transmit the [M-K]ion. When possible, multiple daughter ions were monitored, but quantitation was based on a single product ion, evaluated versus an unextracted standard curve. The presence of PFOS was verified by quantitative agreement (+/-30%) between 2 or more product ions. The limit of quantitation (LOQ) for PFOS was 10 ng/g, wet wt. Data quality assurance and quality control protocols included surrogate matrix blanks, matrix spikes, surrogate spikes, laboratory blanks and continuing calibration verification. Recoveries of PFOS spiked into oyster tissues and passed through the analytical procedure varied from 64 to 83% (n=6), with a mean recovery of 748%. Concentrations of PFOS were not corrected for the recoveries of the surrogate standard or matrix spike recoveries. The PFOS standard was 86.9% pure. Concentrations were not corrected for purity of the PFOS standard. Radiolabled material was not available to verify the accuracy of matrix spikes studies. However, assuming that matrix spike studies are a suitable indication of endogenous analyte levels, and taking into account the analytical quality control, this data is estimated to be accurate to +/-40%. Matrix spike recoveries are given in Appendix II. RESULTS AND DISCUSSION Perfluorooctanesulfonate was found in 66% of the oyster samples analyzed. PFOA and PFHS were not found in oysters at quantifiable concentrations. FOSA was detected in three of the 77 samples and the maximum concentration observed was 2350 ng/g, dry wt, in Dog River, Mobile Bay, Alabama (Appendix I). Concentrations of PFOS in oysters ranged from <42 to 1225 ng/g on a dry weight (dw) basis (Table 1). The highest concentrations were found at Lavaca River Mouth in Matagorda Bay, Texas. Median concentration of PFOS in oysters from the Gulf of Mexico was 387 ng/g, dw. Except for oysters from Hog Point in Chesapeake Bay, none of the oysters collected from Chesapeake Bay contained quantifiable concentrations of PFOS. Concentrations of PFOS varied widely within a given waterbody. For instance, oysters collected from Joe's Bayou in Choctawhatchee Bay, Florida, were determined to contain 608 ng PFOS/g, dw, whereas those collected at Santa Rosa in Choctawhatchee Bay did not contain quantifiable concentrations. Similarly, while oysters from Hanna Reef in Galveston Bay were determined to contain 74 ng PFOS/g, dw, samples from Confederate Reef, located within a distance of 50 km, contained 883 ng/g, dw. The mean concentrations of PFOS in oysters from Texas, Mississippi, Alabama and Florida were similar (p>0.05; Student's t-test) and significantly greater than those found in Virginia (Fig. 3). In other words, within a 95% probability, concentrations of PFOS in oysters BACK TO MAIN - 4 - from TX, MS, AL and FL were similar with the exception of VA. In general, concentrations of PFOS in oysters from the Chesapeake Bay were low. A notable exception to this observation was Hog Point, MD, in the central part of Chesapeake Bay where one sample was determined to contain 1100 ng PFOS/g dw; this was the second highest level measured in this study. This study provides baseline concentrations of PFOS in oysters collected from the Gulf of Mexico. These baseline measurements in oysters will be useful for evaluating the temporal trends in PFOS concentrations in the future. REFERENCES 1. Lauenstein GG, Harmon MF, Gottholm BW. 1993. National status and trends program: Monitoring site description (1984-1990) for the national mussel watch and benthic surveillance projects. NOAA Technical Memorandum NOS ORCA 70 Silver Spring, MD. 2. O'Connor TP, Beliaeff B. 1995. Recent Trends in Coastal Environmental Quality: Results from the Mussel Watch Project. U.S. Department of Commerce, National Oceanic and Atmospheric Administration, Silver Spring, Maryland 20910-3281. 3. 3M Environmental Laboratory, St. Paul, MN LIMs Report number E00-2329, E00-2361. 4. Hansen, K.J.; Clemen, L.A.; Ellefson, M.E.; Johnson, H.O. Environ. Sci. Technol.2001, 35, 766-77. BACK TO MAIN - 5 - Table 1. Concentrations of PFOS in oyster, Crassostrea virginica, collected from the Gulf of Mexico and Chesapeake Bay during 1996-1998. Location Number 1 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 Site name Location Navarez Park Faka Union Bay Sabine Point Henderson Creek Mullet Key Old Tampa Bay Postil Point Joe's Bayou Hillsborough Bay Flamingo Joe Bay Off Santa Rosa Apalachee Bay St. Andrew Bay Panama City Florida Bay Choctawhatchee Bay Apalachicola Bay Florida Bay Charlotte Harbor Apalachicola Bay Cedar Key Tampa Bay Everglades Pensacola Bay Rookery Bay Tampa Bay Tampa Bay Choctawhatchee Bay Choctawhatchee Bay Tampa Bay Florida Bay Florida Bay Choctawhatchee Bay Spring Creek Watson Bayou Municipal Pier Flamingo Joe's Bayou Dry Bar Joe Bay Fort Myers Cat Point Bar Black Point State Latitude Longitude FL 2747.32' 8245.26' FL 2554.13' 8130.85' FL 3020.98' 8709.29' FL 2601.55' 8144.21' FL 2737.28' 8243.60' FL 2801.42' 8238.00' FL 3028.72' 8628.72' FL 3024.63' 8629.45' FL 2751.27' 8223.39' FL 2508.45' 8055.41' FL 2512.91' 8032.04' FL 3024.70' 8612.27' FL 303.8' 8419.32' FL 308.55' 8537.93' FL 309.07' 8539.78' FL 258.47' 8055.42' FL 3024.65' 8629.45' FL 2940.35' 853.94' FL 2512.73' 8032.04' FL 2633.5' 8155.37' FL 2943.45' 8453.05' FL 2912.4' 834.17' Collection Date 01/26/98 02/01/98 01/07/98 01/27/98 02/03/98 01/25/98 01/22/98 01/22/98 02/02/98 01/28/98 01/29/98 01/23/98 01/24/97 01/23/97 01/23/97 01/26/97 01/21/97 01/30/97 01/26/97 01/27/97 01/24/97 01/29/97 dry wt mass % 21 9 11 11 15 14 18 13 12 15 15 8.7 14 20 20 18 19 17 15 21 20 18 PFOS ng/g, dry wt 339 733 564 630 387 429 494 608 131 100 98 153 639 330 330 513 494 544 636 391 82 76 5 BACK TO MAIN - 6 - 62 Choctawhatchee Bay Off Santa Rosa FL 3024.72' 8612.22' 01/22/97 20 <50 63 Panama City Little Oyster Bar FL 3015.08' 8540.86' 01/22/97 20 <50 MeanSD 16 367219 37 Cedar Point Reef Mobile Bay AL 3018.91' 8808.06' 01/08/98 14 379 38 Dog River Mobile Bay AL 3035.50' 8802.40' 01/09/98 11 545 39 Hollingers Island Mobile Bay AL 3033.81' 8804.51' 01/09/98 20 <50 Channel MeanSD 15 325206 21 Terrebonne Bay Lake Felicity LA 2915.83' 9023.88' 01/05/98 20 292 22 Calcasieu Lake Lake Charles LA 3003.51' 9318.45' 12/04/97 12 703 23 Bay Gardene Breton Sound LA 2935.93' 8937.29' 01/21/98 8.3 997 24 Terrebonne Bay Lake Barre LA 2915.57' 9035.66' 01/05/98 12 717 25 Calcasieu Lake St. Johns Island LA 2949.82' 9323.22' 12/03/97 15 93 26 Malheureux Point Lake Borgne LA 2952.01' 8940.71' 01/14/98 13 118 27 Gulf Outlet Lake Borgne LA 2956.69' 8950.14' 01/21/98 9.4 <106 28 Joseph Harbor Joseph Harbor LA 2938.21' 9246.01' 01/12/97 18 485 Bayou Bayou 29 Barataria Bay Bayou Saint LA 2924.29' 8959.93' 01/08/97 22 <45 Denis 30 Sabine Lake Blue Buck Point LA 2947.45' 9354.38' 01/13/97 16 <63 31 Caillou Lake Caillou Lake LA 2915.19' 9055.6' 01/09/97 15 <67 32 Vermilion Bay Southwest Pass LA 2934.77' 923.06' 01/10/97 20 <50 33 Atchafalaya Bay Oyster Bayou LA 2915.33' 918.17' 01/11/97 20 <50 MeanSD 15 291312 34 Biloxi Bay Mississippi MS 3023.56' 8851.47' 01/13/98 13 661 Sound 35 Pass Christian Mississippi MS 3018.14' 8919.66' 01/13/98 17 538 Sound 36 Pascagoula Bay Mississippi MS 3020.17' 8835.35' 01/05/98 19 <53 Sound 6 BACK TO MAIN - 7 - MeanSD 16 417263 1 South Bay Lower Madre TX 2602.49' 9710.68' 12/08/97 13 674 2 Port Isabel Lower Laguna TX 2604.65' 9712.26' 12/08/97 16 540 Madre 2 Bill Days Reef Espiritu Santo TX 2824.22' 9628.85' 12/10/97 13 101 4 Corpus Christi Boat Harbor TX 2750.17' 9722.81' 12/16/96 12 685 5 Matagorda Bay Lavaca River TX 2839.62' 9635.07' 12/18/96 7.5 1225 Mouth 6 Aransas Bay Long Reef TX 283.29' 9657.07' 12/17/96 18 508 7 Brazos River Freeport Surfside TX 2855.27' 9520.37' 12/03/96 17 480 8 Galveston Bay Confederate Reef TX 2915.8' 9454.98' 12/05/96 10 883 9 Mesquite Bay Ayres Reef TX 2810.38' 9650.1' 12/17/96 13 625 10 Galveston Bay Offatts Bayou TX 2917.04' 9450.18' 12/05/96 18 430 11 Galveston Bay Yacht Club TX 2937.32' 9459.75' 12/06/96 13 508 12 Corpus Christi Nueces Bay TX 2751.13' 9721.59' 12/16/96 14 407 13 Galveston Bay Todd's Dump TX 2930.18' 9453.76' 12/04/96 15 549 14 Brazos River Cedar Lakes TX 2851.48' 9527.88' 12/03/96 14 106 15 Galveston Bay Hanna Reef TX 2928.82' 9444.51' 12/04/96 20 74 16 Matagorda Bay Gallinipper Point TX 2834.73' 9633.78' 12/19/96 12 <83 17 Copano Bay Copano Reef TX 288.52' 977.68' 12/19/96 23 <43 18 Matagorda Bay Tres Palacios TX 2839.98' 9614.01' 12/20/96 14 <71 Bay 19 Matagorda Bay Carancahua Bay TX 2839.9' 9622.98' 12/18/96 14 <71 20 Matagorda Bay East Matagorda TX 2842.67' 9553' 12/20/96 21 <48 Chesapeake Bay MeanSD 15 Dandy Point VA 375.9' 7617.69' 01/12/97 15 406 320 <67 Chesapeake Bay James River VA 373.92' 7637.93' 01/14/97 24 <42 Potomac River Mattox Creek VA 3813.4' 7657.69' 01/09/97 21 <48 Potomac River Ragged Point VA 389.3' 7635.05' 01/09/97 19 <53 7 BACK TO MAIN - 8 - Chesapeake Bay Cape Charles VA 3717.07' 760.92' 01/14/97 21 Rappahannock River Ross Rock VA 3754.12' 7647.27' 01/11/97 22 Chesapeake Bay Hog Point MeanSD 20 MD 3818.74' 7623.87' 01/08/97 9 Potomac River Swan Point MD 3816.9' 7656.02' 01/09/97 17 Chesapeake Bay Choptank River MD 3836.44' 767.2' 01/07/97 17 Chesapeake Bay Mountain Point MD 394.32' 7624.76' 01/06/97 20 Bar Chesapeake Bay Bodkin Point MD 399.44' 7624.29' 01/06/97 23 Chesapeake Bay Hackett Point Bar MD 3858.17' 7624.88' 01/07/97 18 MeanSD 17 Bahia de Boqueron Puerto Rico PR 1800.48' 6710.69' 02/17/98 13 Bahia de Jobos Puerto Rico PR 1756.37' 6610.89' 02/18/98 16 Mean 15 1 Location numbers correspond to those presented in Figure 1. Values below the LOQ were assigned at that concentration of 10 ng/g, ww for the calculation mean and SD. <48 <45 <50 8 1106 <59 <59 <50 <43 <56 229 392 543 331 437 8 BACK TO MAIN - 9 - Gulf of Mexico Mi0 100 200 Louisiana Mississippi Alabama Georgia Km 100 300 363839 56 Texas Houston 22 27 35 42 46 51 63 15 1311 New Orleans 26 34 37 54 52 161814 8 10 3025 2832 3121 23 47 53 62 57 60 61 Florida 5 17 3 7 20 33 24 29 4? 69 19 45 12 40 48 U.S.A 44 2 1 59 Mexico 43 41 55 50 49 58 Fig. 1. Map of Gulf of Mexico showing sampling locations of oysters. Details of the locations for the corresponding numbers are presented in Table 1. 9 BACK TO MAIN - 10 - Bodkin Point Mountain Point BHaarckett Point Bay Potomac River Swan Point Hog Choptank River Mattox Creek Point Ragged Point Ross Rock Atlantic Ocean James River CChapareles Dandy Point VIRGINIA N Fig. 2. Map of Chesapeake Bay showing sampling locations of oyster 10 - 11 - 800 700 600 500 400 300 200 100 0 BACK TO MAIN Conc (ng/g, dry wt) (n Florid =24) a (n=Alabam 3) a (n=Louisia 13) na (n=Mississ 3) ippi (n Texas =20) (n=Virgini 6) a (n=Maryla 6) nd (n=Puerto 2) Rico Fig. 3. Concentrations (mean SD) of PFOS (ng/g, dw) in oyster, Crassostrea virginica, from various coastal locations in the Gulf of Mexico and Chesapeake Bay. Concentrations are presented state-wise. . 11 BACK TO MAIN - 12 - APPENDIX I Concentrations of (ug/g, wet for solid tissues) fluorochemicals in biota Species American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster Lab ID (1) K10201 (2) K10129 (3) K10137 (4) K10250 (5) K10135 (6) K10070 (7) K10078 (8) K10133 (9) K10244 (10) K10080 (11) K10581 (12) K10539 (13) K10082 (14) K10629 (15) K10515 (16) K10246 (17) K10131 (18) K10601 (19) K10535 (20) K10585 (21) K10631 (22) K10559 (23) K10609 (24) K10541 (25) K10577 (26) K10473 (27) K10561 (28) K10465 (29) K10569 (30) K10517 Tissue Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Location Chesapeake Bay Corpus Christi Matagorda Bay Apalachee Bay Aransas Bay Brazos River Galveston Bay Mesquite Bay St. Andrew Bay Galveston Bay Navarez Park Cedar Pt. Reef Galveston Bay Bahia de Boqueron Terrebonne Bay Panama City Corpus Christi Faka Union Bay Sabine Pt. Henderson Creek Bahia de Jobos Biloxi Bay Mullet Key Dog River Old Tampa Bay South Bay Pass Christian Calcasieu Lake Bay Gardene Terrebonne Bay PFOS 0.100 0.082 0.092 0.089 0.091 0.082 0.088 0.081 <LOQ (0.0750 ug/g) 0.077 0.071 <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 0.071 <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 0.069 <LOQ (0.0750 ug/g) 0.086 <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 0.088 0.092 0.084 0.083 0.086 PFHS <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) PFOA <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) FOSA <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 0.074 <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 0.258 <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 12 BACK TO MAIN - 13 - American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster (31) K10263 (32) K10227 (33) K10275 (34) K10265 (35) K10573 (36) K10076 (37) K10475 (38) K10575 (39) K10192 (40) K10267 (41) K10467 (42) K10563 (43) K10252 (44) K10072 (45) K10603 (46) K10593 (47) K10565 (48) K10597 (49) K10074 (50) K10272 (51) K10571 (52) K10205 (53) K10167 (54) K10194 (55) K10215 (56) K10219 (57) K10207 (58) K10223 (59) K10199 (60) K10157 (61) K10143 (62) K10185 (63) K10217 (64) K10519 (65) K10178 (66) K10141 (67) K10145 Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Florida Bay Choctawhatchee Bay Apalachicola Bay Florida Bay Postil Pt. Galveston Bay Port Isabel Joe's Bayou Joseph Harbor Bayou Charlotte Harbor Calcasieu Lake Malheureux Pt. Apalachicola Bay Brazos River Hillsborough Bay Flamingo Bill Days Reef Joe Bay Galveston Bay Cedar Key Off Santa Rosa Potomac River Barataria Bay Sabine Lake Chesapeake Bay Chesapeake Bay Potomac River Choctawhatchee Bay Potomac River Chesapeake Bay Matagorda Bay Caillou Lake Chesapeake Bay Pascagoula Bay Vermilion Bay Copano Bay Matagorda Bay 0.092 0.094 0.092 0.095 0.089 0.082 0.086 0.079 0.087 0.082 0.014 0.015 0.016 0.015 0.016 0.015 0.013 0.015 0.015 0.014 0.013 <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 13 BACK TO MAIN - 14 - American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster American Oyster (68) K10139 (69) K10147 (70) K10567 (71) K10153 (72) K10203 (73) K10225 (74) K10155 (75) K10190 (76) K10159 (77) K10543 Whole Whole Whole Whole Whole Whole Whole Whole Whole Whole Matagorda Bay Matagorda Bay Gulf Outlet Chesapeake Bay Rappahannock River Panama City Chesapeake Bay Atchafalaya Bay Chesapeake Bay Hollingers Is. Channel <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.0376 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.00750 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0187 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) <LOQ (0.0750 ug/g) 0.087 PFOS = Perfluorooctanesulfonate FOSA = Perfluorooctanesulfonamide PFHS = Perfluorohexanesulfonate PFOA = Perfluorooctanoate I = May need to rerun all samples for FOSA, interferent present in both analyses. LOQ = Limit of quantitation - Values in parenthesis 14 BACK TO MAIN - 15 - APPENDIX II Matrix spike and matrix spike duplicate recoveries (%) of fluorochemicals spiked oyster tissues Group Sample # PFOS RPD PFHS RPD QC (35) K10573-MS ext. 09/07/00 (35) K10573-MSD 77% 3% 36% 23% (37) K10475-MS (37) K10475-MSD 80% 7% 41% 1% (63) K10217-MS (63) K10217-MSD 64% 16% 24% 12% RPD = Relative percent deviation ; Mean values are reported PFOA = Perfluorooctanoate PFOS = Perfluorooctanesulfonate FOSA = Perfluorooctanesulfonamide PFOA RPD FOSA RPD 66% 30% 45% 35% 74% 3% 69% 5% 76% 8% 43% 12% PFHS = Perfluorohexanesulfonate 15 BACK TO MAIN BACK TO MAIN - 17 - 17