East Lansing, Michigan 48824, USA ... lected in the Gulf of Mexico and the Chesapeake Bay during. December 1996 âFebruary .... Charlotte Harbor. Fort Myers.
Arch. Environ. Contam. Toxicol. 42, 313–318 (2002) DOI: 10.1007/s00244-001-0003-8
A R C H I V E S O F
Environmental Contamination a n d Toxicology © 2002 Springer-Verlag New York Inc.
Perfluorooctane Sulfonate in Oysters, Crassostrea virginica, from the Gulf of Mexico and the Chesapeake Bay, USA K. Kannan,1 K. J. Hansen,2 T. L. Wade,3 J. P. Giesy1 1
National Food Safety and Toxicology Center, Department of Zoology, Institute for Environmental Toxicology, Michigan State University, East Lansing, Michigan 48824, USA 2 3M Environmental Laboratory, 935 Bush Avenue, St. Paul, Minnesota 55133, USA 3 Geochemical and Environmental Research Group, Texas A&M University, 833 Graham Road, College Station, Texas 77845, USA
Received: 4 June 2001 /Accepted: 21 September 2001
Abstract. Concentrations of perfluorooctane sulfonate (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 United States. PFOS was detected in oysters collected from 51 of the 77 locations at concentrations ranging from ⬍ 42 to 1,225 ng/g on a dry weight basis. This study provides baseline data for future monitoring programs to examine long-term trends in concentrations of PFOS.
Since the 1970s, there has been a steady increase in the use of fluorinated organic compounds for a variety of industrial applications (Kissa 2001). Fluorinated surfactants are an important class of organic chemicals that have been used in soil- and stain-resistant coatings for fabrics, carpets, and leather and in grease- and oil-resistant coatings for paper products and food containers (Key et al. 1997; US EPA 2000; Kissa 2001). The use of sulfonyl-based fluorochemicals can be divided into three main categories: (1) surface treatments, (2) paper protectors, and (3) performance chemicals. Surface treatment applications provide soil, oil, and water resistance to personal apparel and home furnishings. Specific applications in the surface treatment category include protection of apparel, leather, fabric, upholstery, and carpet. According to the U.S. Environmental Protection Agency, 37% of the production of fluorinated surfactants is used for surface treatment applications (US EPA 2000). Surface treatments are applied in industrial settings, such as textile mills, leather tanneries, finishers, fabric producers, and carpet manufacturers (US EPA 2000). Sulfonyl-based fluorochemicals have also been used by consumers to treat apparel, leather, upholstery, carpet, and automobile interiors. Historically, sulfonated fluorochemicals were also applied to paper products, such as plates, food containers, bags, and wraps, to provide grease, water, and oil resistance. In 2000, coatings on paper products accounted for 42% of 3M’s total sulfonyl-based fluorochemical production (US EPA
Correspondence to: K. Kannan
2000). Fluorochemicals in the performance chemicals category are used in a wide variety of industrial, commercial, and consumer applications, such as fire-fighting foams, mining and oil well surfactants, acid mist suppressants for metal plating and electronic etching baths, alkaline cleaners, floor polishes, photographic film, denture cleaners, shampoo, and an ant insecticide (US EPA 2000; Moody and Field 2000). Salts of perfluorocarboxylic acids and perfluoroalkane sulfonic acids are considered to be thermally stable and resistant to the effects of acids, bases, oxidants, and reductants (Kissa 2001). The wide use of these relatively stable compounds has raised concerns about the fate of fluorochemicals in the environment and, ultimately, the potential for inadvertent exposure to humans and wildlife. Perfluorooctane sulfonate (PFOS) has been identified in sera samples of nonoccupationally exposed humans (Hansen et al. 2001). Recent studies have documented the occurrence of PFOS in fish, mammals, and birds from various parts of the world, including the Arctic Ocean (Giesy and Kannan 2001; Kannan et al. 2001a, 2001b). 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 (O’Connor 1996). The Mussel Watch project within the National Status and Trends program of the National Oceanic and Atmospheric Administration annually monitors residues in bivalves collected from US coastal waters. 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 to establish baseline concentrations of this organic fluorochemical. Archived samples, which were collected as a part of National Status and Trends program, were analyzed.
Materials and Methods Samples Sampling of oysters and the selection of sites have been described elsewhere (Sericano et al. 1990; Lauenstein et al. 1993; O’Connor and
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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
Beliaeff 1995; O’Connor 1996). Briefly, sampling locations have been selected with the intention of collecting samples that are representative of the surroundings. Small patches of contamination and known points of waste discharge have been avoided (this is how sampling was performed for the Mussel Watch program). Sampling locations for oysters are shown in Figures 1 and 2, and sampling quadrants are given in Table 1. Samples were collected from December to February of 1996 –1998. Depending on 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 collected and prepared by homogenizing the soft parts. For each composite sample, an aliquot (⬃ 2 g) of oyster tissue was dried in an oven at 60°C for determination of dry weight.
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 74 ⫾ 8%. Concentrations of PFOS were not corrected for the recoveries of the surrogate standard or matrix spike recoveries. The PFOS standard was 86.4% pure. Concentrations were not corrected for purity of the PFOS standard. Radiolabeled 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%.
Results and Discussion Analysis Concentrations of PFOS in oyster tissues were determined by use of high-performance liquid chromatography (HPLC) coupled with electrospray tandem mass spectrometry (Hansen et al. 2001). Briefly, 1 g of oyster tissues was homogenized with Milli-Q 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 (Hansen et al. 2001) with the following exceptions. Ten microliters 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/min, the gradient increased to 100% methanol at 11.5 min before reverting to original conditions at 13 min. For quantitative determination, the HPLC system was interfaced to a Micromass威 (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 two or more product ions. The limit of quantitation (LOQ) for PFOS was 10 ng/g, wet weight. Data quality assurance and quality control protocols included surrogate matrix blanks, matrix spikes, surrogate spikes, laboratory
PFOS was found (at concentrations above the LOQ) in 64% of the oyster samples analyzed. Concentrations of PFOS in oysters ranged from ⬍ 42 to 1,225 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 among all 77 sites was 387 ng/g DW. Except for one oyster sample from Hog Point in the central part of the Chesapeake Bay, none of the oysters collected from Chesapeake Bay contained detectable concentrations of PFOS. Concentrations of PFOS varied widely within a given water body. 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, though 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 t-test) and significantly greater than those found in Virginia (Figure 3). In other words, within a 95% probability,
PFOS in Oysters
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Fig. 2. Map of Chesapeake Bay showing sampling locations of oysters
concentrations of PFOS in oysters 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 1,100 ng PFOS/g DW; this was the second highest level measured in this study. The range of PFOS concentrations measured in oyster tissues was slightly less than that of PCBs (3.6 –1740 ng/g DW) or DDTs (3–3570 ng/g DW) in oysters collected from the Gulf of Mexico in 1987 (Sericano et al. 1990).
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.
Acknowledgement. This study was supported by 3M, St. Paul, MN. Technical assistance of Lisa Clemen and Harold Johnson, 3M Environmental Laboratory, Minnesota, is gratefully acknowledged. We thank Stephen Sweet, Texas A&M University, Texas, for his assistance with samples.
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
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Table 1. Concentrations of PFOS in oyster, Crassostrea virginica, collected from the Gulf of Mexico and the Chesapeake Bay during 1996 – 1998 Latitude
Longitude
Collection Date
FL FL FL FL FL FL
27°47.32⬘ 25°54.13⬘ 30°20.98⬘ 26°01.55⬘ 27°37.28⬘ 28°01.42⬘
82°45.26⬘ 81°30.85⬘ 87°09.29⬘ 81°44.21⬘ 82°43.60⬘ 82°38.00⬘
01/26/98 02/01/98 01/07/98 01/27/98 02/03/98 01/25/98
21 9 11 11 15 14
339 733 564 630 387 429
FL
30°28.72⬘
86°28.72⬘
01/22/98
18
494
FL FL FL FL
30°24.63⬘ 27°51.27⬘ 25°08.45⬘ 25°12.91⬘
86°29.45⬘ 82°23.39⬘ 80°55.41⬘ 80°32.04⬘
01/22/98 02/02/98 01/28/98 01/29/98
13 12 15 15
608 131 100 98
FL FL FL FL FL FL FL FL FL FL FL FL FL
30°24.70⬘ 30°3.8⬘ 30°8.55⬘ 30°9.07⬘ 25°8.47⬘ 30°24.65⬘ 29°40.35⬘ 25°12.73⬘ 26°33.5⬘ 29°43.45⬘ 29°12.4⬘ 30°24.72⬘ 30°15.08⬘
86°12.27⬘ 84°19.32⬘ 85°37.93⬘ 85°39.78⬘ 80°55.42⬘ 86°29.45⬘ 85°3.94⬘ 80°32.04⬘ 81°55.37⬘ 84°53.05⬘ 83°4.17⬘ 86°12.22⬘ 85°40.86⬘
Mobile Bay Mobile Bay
AL AL
30°18.91⬘ 30°35.50⬘
88°08.06⬘ 88°02.40⬘
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 01/22/97 01/22/97 Mean ⫾ SD 01/08/98 01/09/98
8.7 14 20 20 18 19 17 15 21 20 18 20 20 16 14 11
153 639 330 330 513 494 544 636 391 82 76 ⬍50 ⬍50 367 ⫾ 219 379 545
Mobile Bay
AL
30°33.81⬘
88°04.51⬘
LA LA LA LA LA LA LA
29°15.83⬘ 30°03.51⬘ 29°35.93⬘ 29°15.57⬘ 29°49.82⬘ 29°52.01⬘ 29°56.69⬘
90°23.88⬘ 93°18.45⬘ 89°37.29⬘ 90°35.66⬘ 93°23.22⬘ 89°40.71⬘ 89°50.14⬘
01/09/98 Mean ⫾ SD 01/05/98 12/04/97 01/21/98 01/05/98 12/03/97 01/14/98 01/21/98
20 15 20 12 8.3 12 15 13 9.4
⬍50 325 ⫾ 206 292 703 997 717 93 118 ⬍106
LA
29°38.21⬘
92°46.01⬘
01/12/97
18
485
LA LA LA LA LA
29°24.29⬘ 29°47.45⬘ 29°15.19⬘ 29°34.77⬘ 29°15.33⬘
89°59.93⬘ 93°54.38⬘ 90°55.6⬘ 92°3.06⬘ 91°8.17⬘
22 16 15 20 20 15 13 17 19 16 13
⬍45 ⬍63 ⬍67 ⬍50 ⬍50 291 ⫾ 312 661 538 ⬍53 417 ⫾ 263 674
16 13
540 101
Location Numbera
Site Name
Location
40 41 42 43 44 45
Navarez Park Faka Union Bay Sabine Point Henderson Creek Mullet Key Old Tampa Bay
46
Postil Point
47 48 49 50
Joe’s Bayou Hillsborough Bay Flamingo Joe Bay
51 52 53 54 55 56 57 58 59 60 61 62 63
Off Santa Rosa Apalachee Bay St. Andrew Bay Panama City Florida Bay Choctawhatchee Bay Apalachicola Bay Florida Bay Charlotte Harbor Apalachicola Bay Cedar Key Choctawhatchee Bay Panama City
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 Off Santa Rosa Little Oyster Bar
37 38
Cedar Point Reef Dog River Hollingers Island Channel
39 21 22 23 24 25 26 27
State
28
Terrebonne Bay Calcasieu Lake Bay Gardene Terrebonne Bay Calcasieu Lake Malheureux Point Gulf Outlet Joseph Harbor Bayou
29 30 31 32 33
Barataria Bay Sabine Lake Caillou Lake Vermilion Bay Atchafalaya Bay
Lake Felicity Lake Charles Breton Sound Lake Barre St. Johns Island Lake Borgne Lake Borgne Joseph Harbor Bayou Bayou Saint Denis Blue Buck Point Caillou Lake Southwest Pass Oyster Bayou
34 35 36
Biloxi Bay Pass Christian Pascagoula Bay
Mississippi Sound Mississippi Sound Mississippi Sound
MS MS MS
30°23.56⬘ 30°18.14⬘ 30°20.17⬘
88°51.47⬘ 89°19.66⬘ 88°35.35⬘
1
South Bay
TX
26°02.49⬘
97°10.68⬘
2 3
Port Isabel Bill Days Reef
Lower Madre Lower Laguna Madre Espiritu Santo
01/08/97 01/13/97 01/09/97 01/10/97 01/11/97 Mean ⫾ SD 01/13/98 01/13/98 01/05/98 Mean ⫾ SD 12/08/97
TX TX
26°04.65⬘ 28°24.22⬘
97°12.26⬘ 96°28.85⬘
12/08/97 12/10/97
Dry Weight Mass %
PFOS ng/g, DW
PFOS in Oysters
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Table 1. Concentrations of PFOS in oyster, Crassostrea virginica, collected from the Gulf of Mexico and the Chesapeake Bay during 1996 – 1998 Location Numbera
Latitude
Longitude
Collection Date
Dry Weight Mass %
PFOS ng/g, DW
TX
27°50.17⬘
97°22.81⬘
12/16/96
12
685
TX TX TX TX TX TX TX TX TX TX TX TX TX TX TX TX
28°39.62⬘ 28°3.29⬘ 28°55.27⬘ 29°15.8⬘ 28°10.38⬘ 29°17.04⬘ 29°37.32⬘ 27°51.13⬘ 29°30.18⬘ 28°51.48⬘ 29°28.82⬘ 28°34.73⬘ 28°8.52⬘ 28°39.98⬘ 28°39.9⬘ 28°42.67⬘
96°35.07⬘ 96°57.07⬘ 95°20.37⬘ 94°54.98⬘ 96°50.1⬘ 94°50.18⬘ 94°59.75⬘ 97°21.59⬘ 94°53.76⬘ 95°27.88⬘ 94°44.51⬘ 96°33.78⬘ 97°7.68⬘ 96°14.01⬘ 96°22.98⬘ 95°53⬘
Dandy Point James River Mattox Creek Ragged Point Cape Charles Ross Rock
VA VA VA VA VA VA
37°5.9⬘ 37°3.92⬘ 38°13.4⬘ 38°9.3⬘ 37°17.07⬘ 37°54.12⬘
76°17.69⬘ 76°37.93⬘ 76°57.69⬘ 76°35.05⬘ 76°0.92⬘ 76°47.27⬘
MD MD MD
38°18.74⬘ 38°16.9⬘ 38°36.44⬘
76°23.87⬘ 76°56.02⬘ 76°7.2⬘
7.5 18 17 10 13 18 13 14 15 14 20 12 23 14 14 21 15 15 24 21 19 21 22 20 9 17 17
1,225 508 480 883 625 430 508 407 549 106 74 ⬍ 83 ⬍ 43 ⬍ 71 ⬍ 71 ⬍ 48 406 ⫾ 320 ⬍ 67 ⬍ 42 ⬍ 48 ⬍ 53 ⬍ 48 ⬍ 45 ⬍ 50 ⫾ 8 1,106 ⬍ 59 ⬍ 59
Chesapeake Bay Chesapeake Bay Chesapeake Bay
Hog Point Swan Point Choptank River Mountain Point Bar Bodkin Point Hackett Point Bar
12/18/96 12/17/96 12/03/96 12/05/96 12/17/96 12/05/96 12/06/96 12/16/96 12/04/96 12/03/96 12/04/96 12/19/96 12/19/96 12/20/96 12/18/96 12/20/96 Mean ⫾ SD 01/12/97 01/14/97 01/09/97 01/09/97 01/14/97 01/11/97 Mean ⫾ SD 01/08/97 01/09/97 01/07/97
MD MD MD
39°4.32⬘ 39°9.44⬘ 38°58.17⬘
76°24.76⬘ 76°24.29⬘ 76°24.88⬘
Bahia de Boqueron Bahia de Jobos
Puerto Rico Puerto Rico
PR PR
18°00.48⬘ 17°56.37⬘
67°10.69⬘ 66°10.89⬘
01/06/97 01/06/97 01/07/97 Mean ⫾ SD 02/17/98 02/18/98 Mean
20 23 18 17 13 16 15
⬍ 50 ⬍ 43 ⬍ 56 229 ⫾ 392 543 331 437
Site Name
Location
4
Corpus Christi
5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Matagorda Bay Aransas Bay Brazos River Galveston Bay Mesquite Bay Galveston Bay Galveston Bay Corpus Christi Galveston Bay Brazos River Galveston Bay Matagorda Bay Copano Bay Matagorda Bay Matagorda Bay Matagorda Bay
Boat Harbor Lavaca River Mouth Long Reef Freeport Surfside Confederate Reef Ayres Reef Offatts Bayou Yacht Club Nueces Bay Todd’s Dump Cedar Lakes Hanna Reef Gallinipper Point Copano Reef Tres Palacios Bay Carancahua Bay East Matagorda
Chesapeake Bay Chesapeake Bay Potomac River Potomac River Chesapeake Bay Rappahannock River Chesapeake Bay Potomac River Chesapeake Bay
State
a
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 of mean and SD.
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