REPORT OF HYDROGRAPHIC AND OCEANOGRAPHIC RESEARCHES No.46 March, 2010 PFCs Distribution and Origin estimate of Perfluoro compounds PFCs in

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46 22 3 23 REPORT OF HYDROGRAPHIC AND OCEANOGRAPHIC RESEARCHES No.46 March, 2010 PFCs Distribution and Origin estimate of Perfluoro compounds PFCs in East China Sea Satoshi YAMAO, Junko SHIMIZU, Xinyu GUO, Shuhei TANAKA, Kunacheva Chinagarn, Shigeo FUJII Abstract PFCs distribution in water and sediment as well as water mass structures were observed at the stations in the East China Sea and its adjacent continental shelf edge in December In surface water, the concentration of PFHxA, PFHpA, PFOA and PFOS were relatively higher in the southern area, while PFNA concentration was higher in the northern area. In sediment samples, three types of PFCs distribution were obtained : PFOS and PFHpA showed higher concentration in Kuroshio upstream area ; peak concentration of PFNA and PFUnA were observed in Okinawa Trough ; PFHxA and PFOA showed relatively high concentration in shallower side of the continental shelf edge. Based on the distributions of PFCs, sources of particulate PFCs inside the Kuroshio water were estimated. Particulate PFHpA and PFOS were loaded to the Kuroshio water mass from more upstream of Kuroshio Current than the study area suspended PFNA was from the East China Sea continental shelf, according to the particle transportation excess the continental shelf edge particulate PFHxA and PFOA were from both the upstream of Kuroshio Current and the continental shelf. Using PFHxA, PFHpA, PFOA and PFOS as tracers, the origin of suspended solid contained inside the Kuroshio water was examined with a mixing model. The result suggested that almost all of suspended solid loaded from upstream of the Kuroshio Current disappeared from the water column in the middle reach of the Kuroshio in the East China Sea while all of suspended solid found in the Tokara Strait were originated from the East China Sea continental shelf. Key words : PFCs distribution, East China Sea, Kuroshio, origin of PFCs, origin of suspended solid Ocean Research Laboratory Marine Pollution Research Laboratory Ehime University CMES Graduate School of Global Environmental Studies Kyoto University 13

Satoshi YAMAO, Junko SHIMIZU, Xinyu GUO, Shuhei TANAKA, Kunacheva Chinagarn, Shigeo FUJII HP Kawahara et al., POPs POPs POPs POPs POPs POPs L Shimizu et al., POPs PFCs POPs L PFCs PFOS POPs COP B PFCs PFCs POPs PFOS PFOA Yamashita et al., POPs PFCs PFCs PFCs PFCs Fig Fig m mm m X PET GF/B ADVANTEC µm Waters L Presep C Agri mg Oasis HLB Waters CTD SBE SEACAT Profiler SBE 14

Distribution and Origin estimate of Perfluoro compounds (PFCs) in East China Sea PFOA PFOS PFCs GF/B SS PFCs L ml PFCs L HPLC ESI MS/MS SL Agilent technologies GATripleQuad Agilent technologies PFCs Table Figure Location of the observational station and bottom topography. Red circle shows the water sampling station and filled circle means the sediment sampling station. Fig cm Table Blank, LOD and LOQ of PFCs detected in this study. 15

Satoshi YAMAO, Junko SHIMIZU, Xinyu GUO, Shuhei TANAKA, Kunacheva Chinagarn, Shigeo FUJII Table Distance to each observational station from Kuroshio axis. Shaded cells shows the stations on Kuroshio current. Figure Observational station and satellite image of SST observed onth December. Figure TS diagram of whole data derived from this study. m HP Table km EP EP EP EP Terra MODIS SST Fig EP EP EP EP Fig EP EP PFCs PFOS, PFOAPFNA FigPFOS PFOA EP PFOS PFNA 16

Distribution and Origin estimate of Perfluoro compounds (PFCs) in East China Sea EP PFCs PFHxA PFHpA PFOS,PFOA PFBA,PFPAPFDA PFUnA PFCs Fig PFOS PFHpA PFNA PFUnA EP PFOA ng g PFOS ng g PFNA,PFUnA ng g ng g PFHxA,PFOA EP EP PFHxA ng g PFOA ng g EP PE PFHxA ng g PFOA ng g Figure Horizontal distribution of PFCs in the surface layer of water column. a PFOA, b PFNA, c PFOS PFCs FigPFOA PFOS EP EP PFOA,PFOS PFOA PFOS EP PFNA PFNA EP EP PFNA PFNA 17

Satoshi YAMAO, Junko SHIMIZU, Xinyu GUO, Shuhei TANAKA, Kunacheva Chinagarn, Shigeo FUJII Figure Horizontal distribution of PFCs in the surface layer of sediment. a PFHxA, b PFHpA, c PFOA, d PFNA, e PFUnA, f PFOS 18

Distribution and Origin estimate of Perfluoro compounds (PFCs) in East China Sea Figure PFCs concentration in the water column at the station on Kuroshio. Blue column shows dissolved PFCs and red column shows particlate one. a PFHxA, b PFHpA, c PFOA, d PFNA, f PFOS 19

Satoshi YAMAO, Junko SHIMIZU, Xinyu GUO, Shuhei TANAKA, Kunacheva Chinagarn, Shigeo FUJII SS PFCs Fig m SS PFCs PFHpA PFOS EP EPEP EPEP PFHpA PFOS PFHxA PFOA EP PFHpA PFOS EP PFHxA PFOA EP EP EP EP PFHpA PFOS EP PFHxA PFOA PFHxA PFOA EP EPEPEP Fig a c PFHpA PFOS PFHxA,PFHpA,PFOA PFOS Figure Vertically averaged PFCs at each stations. a PFHxA, b PFHpA, c PFOA, d PFNA, e PFOS 20

Distribution and Origin estimate of Perfluoro compounds (PFCs) in East China Sea PFHxA PFOA PFHpA PFOS PFNA EP EP EP pg L pg L PFNA PFNA PFNA PFNA EP EPEP PFNA PFNA PFUnA EP PFUnA PFCs PFCs PFCs a a SS Fig Figure Scattering plot of SS and chlorophyll a derived from the station on Kuroshio EPEP EP and EP. PFCs SS Fig a SS Fig b PFCs SS PFCs PFHpA PFOS EP EP PFCs 21

Satoshi YAMAO, Junko SHIMIZU, Xinyu GUO, Shuhei TANAKA, Kunacheva Chinagarn, Shigeo FUJII Figure Contribution of the SS originated from the upper stream of Kuroshio. Figure Vertical distribution of SS mg l in the section a along and b across the Kuroshio. SS SS PFNA PFCs SS SS Fig SS EP EP SS EP SS SS SS EP SS Isobe et al EP Fig Fig Yanagi et al PN 22

Distribution and Origin estimate of Perfluoro compounds (PFCs) in East China Sea Figure Vertical distribution of salinity in the section across the Kuroshio. PFCs PFCs PFCs PFHpA PFOS PFHxA PFOA PFNA PFNA PFUnA PFHpA PFOS EP PFCs PFCs PFCs PFCs PFCs PFCs PFCs GCOE POPs HP : http : //www kaiho.mlit.go.jp/ KANKYO/KAIYO/qboc/index.html 23

Satoshi YAMAO, Junko SHIMIZU, Xinyu GUO, Shuhei TANAKA, Kunacheva Chinagarn, Shigeo FUJII HP : http : //www. umigomi.com/outline/ References Isobe A., Fujiwara E., Pil Hun Chang, Sugimatsu K., Shimizu M., Matsuno T. and Manda A., Intrusion of Less Saline Shelf Water into the Kuroshio Subsurface Layer in the East China Sea, Journal of Oceanography Kawahara M., Uye S., Ohtsu K., Iizumi H., Unusual population explosion of the giant jellyfish Nemopilema nomurai Scyphozoa : Rhizostomeae in East Asian waters, Mar. Ecol. Prog. Ser., Shimizu J., Takahashi S., Isobe T., S. Annamalai, K. Chinagarn, Hukaumi M., Uchida K., Matsumura T., Toju H., Tanaka S., Fujii S., Tanabe S., Development of Monitoring System for Persistent Organic Pollutants in Offshore Waters around Japan : Results from the First Investigation in the East China Sea, Organohalogen Compounds Yanagi T., Takahashi S., Hoshika A. and Tanimoto T., Seasonal Variation in the Transport of Suspended Matter in the East China Sea, Journal of Oceanography Yamashita N., K. Kannan, Taniyasu S., Horii Y., G. Petrick and Gamo T., A global survey of perfluorinated acids in oceans, Marine Pollution Bulletin PFCs PFHxA PFHpA PFOA PFOS PFNA PFOS PFHpA PFNA PFUnA PFHxA PFOA PFCs PFCs PFCs PFHpA PFOS PFNA PFHxA PFOA PFHxA,PFHpA,PFOA PFOS EP 24