Environ. Sci. Technol. 2006, 40, 7642-7648
Perfluorooctanesulfonate and Related Fluorochemicals in Albatrosses, Elephant Seals, Penguins, and Polar Skuas from the Southern Ocean LIN TAO,† K U R U N T H A C H A L A M K A N N A N , * ,† NATSUKO KAJIWARA,‡ MO ˆ NICA M. COSTA,§ GILBERTO FILLMANN,§ SHIN TAKAHASHI,‡ AND SHINSUKE TANABE‡ Wadsworth Center, New York State Department of Health, Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Empire State Plaza, P.O. Box 509, Albany, New York 12201-0509, Center for Marine Environmental Studies, Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577, Japan, and Departamento de Oceanografia, Fundac¸ a˜o Universidade Federal do Rio Grande, C.P. 474, 96201-900, Rio Grande, RS, Brazil
Perfluorinated chemicals (PFCs) have been used as surfactants in industrial and commercial products for over 50 years. Earlier studies of the geographical distribution of PFCs focused primarily on the Northern Hemisphere, while little attention was paid to the Southern Hemisphere. In this study, livers from eight species of albatrosses, blood from elephant seal, and blood and eggs from penguins and polar skua collected from the Southern Ocean and the Antarctic during 1995-2005 were analyzed for 10 PFCs. In addition, for comparison with the Southern Ocean samples, we analyzed liver, sera, and eggs from two species of albatrosses from Midway Atoll in the North Pacific Ocean. Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) were found in livers of albatrosses from the Southern Ocean. PFOS was the major contaminant, although the concentrations were 98%, Guelph, ON, Canada). All solvents were HPLC grade, and all reagents were ACS grade (J. T. Baker, Phillipsburg, NJ). Samples. A total of 102 albatross livers, 59 elephant seal blood samples, eight penguin blood samples, six penguin eggs, three skua blood samples, and three skua eggs were collected from Southern Ocean locations and the Antarctic (Figure 1 and Table 1). Albatross liver samples came from eight species, namely, Black-browed albatross (Thalassarche melanophrys), Gray-headed albatross (Thalassarche chrysostoma), Laysan albatross (Diomedea immutabilis), Lightmantled Sooty albatross (Phoebetria palpebrata), Royal albatross (Diomedea epomophora), Shy albatross (Thalassarche cauta), Wandering albatross (Diomedea exulans), and Yellow-nosed albatross (Thalassarche chlororhynchos), collected from the Indian Ocean (39-40°S, 90-103°E), the South Atlantic Ocean (40-43°S, 2-11°E), and the South Pacific Ocean (38°S, 155°E) during 1992-1996. Albatrosses were
individuals that had been caught accidentally in fishing gear. Species name, sampling location, liver weight, gender, body weight, and body length were recorded. Blood samples from Elephant seals (Mirounga leonine) were collected from Elephant Island, South Shetlands (61°S, 55°W) during 2003/ 2004 and 2004/2005. Whole blood was collected from the extradural vein; the gender and age class of the elephant seals were recorded. Elephant seal blood samples were collected according to the Scientific Committee on Antarctic Research (SCAR) and Convention on the Conservation of Living Marine Resources (CCLMAR) protocols with appropriate permits and licenses. Adelie penguin (Pygoscelis adeliae) blood samples were collected at Admiral Bay, South Shetlands (62.1°S, 58.5°W) during January and February 2001. Unhatched Adelie penguin eggs and eggs and whole blood of South polar skua (Stercorarius maccormicki) were collected from Edmonson Point, Antarctica (74°S, 165°E) in 1995/1996 and 1998/1999. For comparison, serum and livers from 10 Laysan albatross (D. immutabilis) and pooled eggs of Laysan and Black-footed (D. nigripes) albatrosses collected on Midway Atoll in the North Pacific Ocean (28°N, 177°W) in 1994 were analyzed. All samples were kept frozen at -20 °C until analysis. Analysis. PFCs in liver, blood, and eggs were analyzed following the method described elsewhere (14). For blood samples, 1 mL of whole blood, 5 ng of internal standards (PFBS, 13C4-PFOS, and 13C4-PFOA), 2 mL of 0.25 M sodium carbonate buffer, and 1 mL of 0.5 M tetrabutylammonium hydrogensulfate solution (adjusted to pH 10) were mixed in a 15 mL polypropylene (PP) tube. The sample was then extracted with 5 mL of methyl-tert-butyl ether (MTBE) by shaking vigorously for 45 min. The MTBE layer was separated by centrifugation at 3500 rpm for 5 min and then transferred into another PP tube. The MTBE extract was evaporated to near-dryness under a gentle stream of nitrogen and then reconstituted with 1 mL of methanol. The sample was vortexed for 30 s and filtered through a 0.2 µm nylon filter into an autosampler vial. For the extraction of liver samples, a small amount of liver tissue (about 1 g) was homogenized with 5 g of Milli-Q water, and then 1 g of the homogenate was transferred into a PP tube and extracted following the procedure described previously. For egg samples, 0.5 g of whole egg homogenate was transferred into a PP tube and extracted in a procedure similar to that for blood as described previously. Matrix matched calibration standards (seven points ranging from 0.5 to 75 ng/mL) were prepared by spiking different amounts of calibration standards into a sample that contained no quantifiable amount of the target VOL. 40, NO. 24, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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TABLE 1. Concentrations of PFOS and PFOA (ng/g, Wet Wt) in Albatrosses from the Southern Ocean and North Pacific Oceana PFOS sample type
DRb
range
PFOA mean/medianc
DRb
range
mean/medianc
Black-browed Gray-headed Laysan Light-mantled Sooty Royal Shy Wandering Yellow-nosed
17:18 25:26 1:1 7:8 2:4 7:7 1:1 6:8
Indian Ocean (Liver)
