残留性有機フッ素化合物PFOS・PFOAおよびその ... - 河川環境管理財団

24 4 75 km 8,240 km 2 10 1 1,196 19 12 4 5 32 km 163 km 2 21 km 627 km 2 2 2007 11 23 1 022 19 mm 4 mm 1 115 3 km 2 67 10 km 2 300 km 2 3 18 28 14 14 28 95% 3,174 km 2 63% 14 PFCs PP 2

3 3 1 2 9 L19 2007 11 14 0 13 1 mm4 mm 1 mm 1 NEw7w5w69 10Kyoto City(km)10 13301112 415 14w1w2w816 217 5 187 619 8w31w420240 10 (km) 27 2122 w928 23w1029 3033 2526 32 31 Osaka City Osaka Bay PFCs 7 w6,w7 2

8 33 4 10w110 2004 11 25 2005 3 16 2005 11 1 2006 9 6 2L PFOS PFOA PFOS PFOA PFOS 3001,000 ng/L PFOA 40600 ng/L PFOA 40 ng/L PFCs

PFCs -LC-MS/MS LC-MS/MS PFCs LC-MS/MS PFCsPFCs PFAS4, 6, 8 3 PFCA 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 16, 18 12 1 8:2 FTOH 2 18 95% 8:2 FTOH 15 100 mgLC-MSPFOcDA 100 mL

PFOcDA 2 LPFAS 3 PFCA 11 14 14 PFCsQiu 6 14 Lien 7 PFOSPFOAPresep-C AgriShortPresep-C Agri-Presep-C Agri 8 PFOSPFOA14 PFCs Milli-Q Milli-Q Milli-Q 1 L Presep-C Agri LC-MS PFOA Milli-Q Milli-Q 1 L 14 PFCs 1 ng/L, 10 ng/L, 100 ng/L PFBSPFBAPFPeA PFHxAPFTeDAPFHxDA PFCs

8 PFCs PFHpA PFDoDA 80%PFHpA PFDoDA 1ng/L PFOA 1 ng/L PFHpA PFDoDA % 8 PFOSPFOA GF/BPrecep-CAgri, Wako Waters 10 mL/min3 mL 25 %Sample 1000 mLGF/B)(1 µm)(10 mL/min)PET ()1 mLWaters m/zPFOS C8-S-CF 3 (CF 2 ) 7 SO 3 Perfluorooctane sulfonate 499PFOA C8-A-CF 3 (CF 2 ) 6 CO 2 Perfluorooctanoate 413PFHxS C6-S-CF 3 (CF 2 ) 5 SO 3 Perfluorohexane sulfonate 399PFHpA C7-A-CF 3 (CF 2 ) 5 CO 2 Perfluoroheptanoate 363PFNA C9-A-CF 3 (CF 2 ) 7 CO 2 Perfluorononanoate 463PFDA-C10-A CF 3 (CF 2 ) 8 CO 2 Perfluorodecanoate 513PFUnA-C11-A CF 3 (CF 2 ) 9 CO 2 Perfluoroundecanoate 563PFDoA-C12-A CF 3 (CF 2 ) 10 CO 2 Perfluorododecanoate 613AgilentZorbax XDBC-18(mm) 2.1(mm) 150V)TSQ7000ESI175Negative1500

PFOSCF 3 (CF 2 ) 7 SO - 3 , Wako 508-53921PFOACF 3 (CF 2 ) 6 COO - , Wako 163-09542PFAS(Perfluoroalkyl sulfonate)1 PFCA (Perfluoroalkyl carboxylate)5 8 LC/MS/MSTSQ7000LC/MS LC/MSESI Negative IonLC10 mMPFOS[M-H] - = 499 PFOA[M-H] - = 413PFHxS[M-H] - = 399PFHpA[M-H] - = 363PFNA[M-H] - = 463PFDA[M-H] - = 513PFUnA[M-H] - = 563PFDoDA[M-H] - = 613

100µg/LPFOSPFOAPFCs Parent IonProduct Ionm/z (IDL: Instrument Detection Limit) (IQL: Instrument Quantification Limit) IDLIQLS/NSignal to Noisefactor 515 7 (s) 9 IDL = t(6, 0.01)×s = 3.143×s ( 3-1)IQL = 3×IDL ( 3-2)t(6, 0.01) 1% 6 t ()PFCAsIQL 1 µg/LPFHxSPFOS 6 µg/L,3 µg/LPFHxSPFOSMSMS/MSSO 3 2- IQLPFCAsPFCAsIQLPFCAsPFCAs ASE: Accelerated Solvent Extraction Dionex ASE200 5 mm 2 mm 2.000 psi 100 5 , 10 , 3 50 mL Milli-Q 1 L 5%

PFCs 14 R6 13 PFCs PFHpAPFOA PFNA PFHxSPFUnDA PFDoDA PFCs PFCs LOQ40 ng/L 9 R19 5 R1014R19 ng/L R1014 30 ng/L PFCs R1013 PFCs PFOA PFOA 12 ng/L PFCs 3 ng/L PFCs 2 R6R1R13R10R12PFCs

PFCs PFCsM r (kg/year)= PFCs (ng/L)× (m 3 /s)×60 2 ×24×365 ( 4-1) (%) = M r /ΣM r ×100 ( 4-2): 12 (m 3 /s) 4-1 4-2 14 PFCs 4 NDLOQ 0 ND

PFOS 3 90PFHpA 2 50PFOA 30, PFNA 60 1/3 PFCs 4 PFHpA 4 2007 12 1112 5 PFCsM e (kg/year)= PFCs (ng/L)× (m 3 /d)×365 ( 4-3): 24 (m 3 /d) 4-3 PFCs PFNA 8.7 kg/year PFOA PFOS 1.0 kg/year PFDAPFUnDA PFDoDA 1 kg/year PFHxS PFHpA 0 14 PFDoDA PFCs

PFCs PFCs PFCs PFOSPFOAPFNA PFDA PFCs 5.333 ng/L 17 ng/LPFCs 33 ng/LL65.3 ng/L PFOA8.8 ng/L PFNA3.4 ng/LPFOS 1.4 ng/L PFCs PFCs PFCs 1 PFOA 2 PFCs PFCs 3

PFCs PFCs PFOA PFNA PFOA PFNA L2 PFOA PFNA PFCs 2 PFCs ng/L PFOA PFOSPFOA 2005 11 1 PFOS

1.7 ng/L 54.1 ng/L 2005 11 1 1.43.4 ng/L PFOA 6.5 ng/L 13,821 ng/L200511 1 517 ng/L 0. 1. 2.3.4. 5.6.7.8.9.10.11.12.13.14.15.16.17.18.19.20.21.22.23.24.25.26.27.28.29.30.31.32.33.Khon KaenHanoiKota KinabaluOrebro0.1 1 10 100 1,000 1 10 100 1,000 10,000 100,000PFOS(ng/L)PFOA(ng/L)Nov.07, 2007Nov.01, 2005 PFHxSPFHpAPFNAPFDAPFUnAPFDoA PFOA PFNA 11.5 ng/LPFOS 9.1 ng/LPFHxS 2.8 ng/L 0.3 ng/L 9.3 ng/L PFHpA 9.1 ng/L 0.9ng/L 112 ng/L PFNA 11.5 ng/L 0.6 ng/L 50.7 ng/L PFDA 2.6 ng/L 0.6 ng/L 13.9 ng/L PFUnA 2.7 ng/L

0.4 ng/L 20.4 ng/L PFDoA 2.0 ng/L 9.7 ng/L PFOSPFOA PFNAPFHpA PFOS PFNA 0.1.2.3.4.5.6.7.8.9.10.11.12.13.14.15.16.17.18.19.20.21.22.23.24.25.26.27. 28.29.30.31. 32.33.PFHxSPFHpAPFNAPFDAPFUnAPFDoA0.1 1 10 100 1,000 0.1 1 10 100 1,000PFCs(ng/L)PFCs(ng/L) 10 PFOSPFOAPFHxSPFHpAPFNAPFDAPFUnAPFDoA PFOA 186 ng/L PFNA 47 ng/LPFOS 22 ng/LPFHxS 9 ng/LPFHpA 9 ng/LPFUnA 8 ng/LPFDA 7 ng/LPFDoAPFOA W10 797 ng/LW5W9 200 ng/L PFNA PFOS W5 W8 100 ng/L PFDoA 1 10 PFOA 258 g/dayPFNA 50 g/dayPFOS 18 g/day PFCs 357 g/day 39 W10 PFOA

Sites* Flow rateConcentrationPFOS PFOA PFHxS PFHpA PFNA PFDA PFUnA PFDoA(10 3 m 3 /day)(ng/L)W1 90 ND 73 ND 4 18 4 2 NDW2 15 ND 70 ND 5 28 3 1 NDW3 83 15 91 ND 6 18 5 5

1 (-) = (mg/d) (mg/d) ( 4-4) PFCs PFCs 0.8 PFDoDA 7 PFDoDA 0.76 0.8 PFCs PFOS 1 1.80 1/2 1 PFCs PFOA 40 ng/L PFOA 40 ng/L 40 ng/L 30 ng/L 40 ng/L PFOA 80 ng/L 40 ng/L PFOA PFOA PFOA 40 ng/L

8 PFCs 1 PFCs PFOSPFHpAPFOA PFNA 30%2 PFC PFOA 4.2 ng/L PFCs ng/L PFOA 3 PFCsPFCs 4 PFOA PFNA PFOA PFNA PFCs PFHxSPFHpAPFOA PFDoDA 50%41%44% 39%PFOSPFNAPFDA PFUnDA 71%, 49%, 56%

62%5 PFOA PFOA 25% 1.6% 3 6 PFCs 60 ng/L PFCs PFCs PFOSPFNAPFDAPFUnDA 7 PFOA PFOA PFOA 2010/1015 PFOA PFOS PFOS PFOA PFCsPFBS PFBA---PFOA PFCs () 19 1 PFCs 2 1 10)

1USEPA, Hazard assessment, 20032(Binding of perfluorinated fatty acids to serum proteins, Jones P.D., Environmental Toxicologyand Chemistry, (2003))3 Gene Expression Profiles in Rat Liver Treated with Perfluorooctanoic Acid (PFOA), KeerthiS.Guruge et al., Toxicological Sciences, (2006)4, , , : GIS , , vol.12, No.3, pp.85-90, 19985: 18 6Yong Qiu: Study on Treatment Technologies for Perfluorochemicals in Wastewater, , 20077Lien, N. P. H.: Study on Distribution and Behavior of PFOS (Perflurooctane Sulfonate) andPFOA (Perfluorooctanoate) in Water Environment, , 20078, , : LC/MS ,, vol.8, pp.126-127, 20059) : ; 2 ; 10, , 2007

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