A Survey of Perfluorooctane Sulfonate and Related Perfluorinated Organic Compounds in Water, Fish, Birds, and Humans from Japan SACHI TANIYASU, † KURUNTHACHALAM KANNAN,* ,‡ YUICHI HORII, † NOBUYASU HANARI, † AND NOBUYOSHI YAMASHITA † National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan, Wadsworth Center, Empire State Plaza, New York State Department of Health, P.O. Box 509, Albany, New York 12201-0509, and Department of Environmental Toxicology and Health, State University of New York, Albany, New York 12202-0509 Occurrence of perfluorooctane sulfonate (PFOS) in the tissues of humans and wildlife is well documented. In this study, concentrations and distribution of PFOS, perfluo- rohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) were determined in samples of surface water, fish and bird blood and livers, and human blood collected in Japan. Notable concentrations of PFOS were found in surface water and fish from Tokyo Bay. PFOS was found in all of the 78 samples of fish blood and liver analyzed. Based on the concentrations of PFOS in water and in fish livers, bioconcentration factors were calculated to range from 274 to 41600. Concentrations of PFOS in the blood of Japanese human volunteers ranged from 2.4 to 14 ng/mL. PFHS was detected in 33% of the fishes analyzed, at concentrations severalfold less than those of PFOS. Introduction Perfluorooctane sulfonate (PFOS) and its salts are fully fluorinated organic compounds that can be produced synthetically or through the degradation of other perfluo- rochemical products. Recent studies have shown that PFOS is a persistent and bioaccumulative globalcontaminant (1- 6).Sulfonyl-based perfluoroalkylated compoundshave been produced and used for over 40 years (1) for soil/stain resistance and surfactant applications and are used in various textiles,upholstery,carpeting,and specialtypapers,including food-contact materials and fire-fighting foams. Perfluoro- hexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS)are impurities in certain fluorochemicalformulations, including aqueous film-forming foams (AFFF). Occurrence ofperfluorocarboxylates in groundwater and AFFFproducts has been shown (7, 8). The 3M Company, a major manu- facturer of sulfonyl-based perfluorochemicals, announced the phase-out ofproduction ofPOSF-based chemicals from December 2000, because of concerns about the persistence of PFOS in the environment and the potential for long-term environmentaleffects(9).The discoveryoffluorinated organic compounds in human serum and in the environment has led to the initiation ofstudies to characterize the distribution, dynamics, and fate of such chemicals in the environment. PFOSand related perfluorinated chemicals are also thought to be produced by other manufacturers in other countries. Since July 2000, the Organization of Economic Cooperation and Development (OECD)led an internationalcollaboration on the scientific assessment ofPFOS. Therefore, data on the occurrence and distribution of perfluorochemicals in the environment are needed for accurate risk assessment in all countries. Studies on the occurrence of perfluorinated compounds in wildlife have focused on samples collected from North America and Europe (3-6).Studiesdescribingthe occurrence of perfluorinated compounds in coastal surface waters and fishes have not been previouslyreported.Japan is one ofthe most highly industrialized nations in the world, and the use of perfluorinated compounds is expected to have occurred there in variousapplications.In 2000,the first nationalproject on PFOS in Japan was started at the National Institute for Advanced Industrial Science and Technology, with the support of New Energy and Industrial Technology Develop- ment Organization (NEDO). A preliminary survey was conducted in 2001 to estimate PFOS in Japanese humans; this survey showed measurable concentrations (a few tens of parts-per-billion) in blood (10-12). In the present study, we report results of a survey of PFOS, PFHS, and PFBS in samplesofwater,fish,birds,and humans,collected in Japan. Additionally,thisstudyprovidesevidence forthe field-based bioconcentration factors of PFOS in fish. Materials and Methods Sample Collection. Twenty-two surface seawater samples were collected from Ishikari Bay and Lake Shikotsu in Hokkaido, Tokyo Bay, Osaka Bay, Hiroshima Bay, Ariake Bay, and Kin Bayin Okinawa (Figure 1).Three freshwater samples were collected from Lake Biwa, the largest lake in Japan, located in central Shiga Prefecture. Samples were collected using a clean stainless steel grab sampler and stored in new 1Lpolypropylene containerswith narrowmouthsand screw tops. The containers were rinsed with methanol, deionized water,and water from the particular samplinglocation prior to use. Teflon bottles and Teflon-lined caps were avoided throughout the analysis, as interference might have been introduced into the sample extracts. The amount of sus- pended matter was kept to a minimum. To reduce residual chlorine, we added 200 μLof250mg/mLsolution ofsodium thiosulfate to each bottle. In most cases, samples were extracted within 24 h after collection; otherwise, samples were kept at 4 °Cuntilanalysis.Allofthe water samples were collected during March to September, 2002. Forty-eight blood samples and 30 liver samples were collected from 23 species offish during March-August, 2002, from Tokyo Bay, Osaka Bay, Hiroshima Bay, Ariake Bay, Kin Bay (Okinawa), and Lake Biwa (Figure 1). Fish were caught byhookand line orobtained from localfisherman.Allspecies were coastal fishes except those from Lake Biwa. Fish were captured alive for the collection of blood and liver samples. Blood samples were drawn from the caudal artery of fish that were still alive, and liver samples were obtained after dissection.Samples from biota and seawater were placed on dry ice and kept in the dark from the time of collection until *Correspondingauthor phone: (518)474-0015;fax: (518)473-2895; e-mail: kkannan@wadsworth.org. Corresponding author address: Wadsworth Center, New York State Department of Health, Empire State Plaza, P.O. Box 509, Albany, NY 12201-0509. † National Institute of Advanced Industrial Science and Technol- ogy. ‡ Wadsworth Center and State University of New York. Environ. Sci. Technol. 2003, 37, 2634-2639 2634 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 12, 2003 10.1021/es0303440 CCC: $25.00  2003 American Chemical Society Published on Web 05/14/2003