1. Trends of PCB isomeric patterns in Japanese environmental media, food, breast milk and blood in view of risk assessment Takeshi Nakano 1, Yoshimasa Konishi 2, Rie Masho 3 and Chiharu Tohyama 4

2. ２, ３, ４, ７, ８－ PeCDF ３, ４, ５, ３ ’, ４ ’ － Co- PCB ２, ３, ７, ８－ TCDD １, ２, ３, ５, ６, ７－ HxCN ７５ congeners １３５ congeners ２０９ congeners

3. Trend of PCB Use in Japan Total 58,000t Amount of PCB use (t)

4. PCB product use in Japan Ar-1242 1248 1254 1260 1969-1971 KC-300 400 500 600

5. KC300 KC400 KC500 KC600 Japan Homologue pattern reflects product use

6. PCB Homologue Distribution and Source Estimation

7. Source estimation KC ３０ ０ KC ４０ ０ KC ５０ ０ KC ６０ ０ Sediment A Sediment B Ship paint N.C.P. Insulator capacitor

8. To evaluate environmental risk

9. Daily variation of PCDD/Fs and PCBs in ambient air

13. Daily variation of Dioxin Concentration

14. Time trend of PCDD/F levels in ambient air

15. Time trend of PCDDs/PCDFs （ TEQ ） Matsumura et al, symposium of J.Env.Chem, 2003.6 Dioxin Emission Reduction Plan

16. 0.00 0.10 0.20 0.30 0.40 0.50 0 10002000300040005000600070008000 Emission inventry (g-TEQ/year ） PCDDs/PCDFs （ pg-TEQ/m3) 1997 1998 1999 2000 2001 Emission inventry vs Level in air Matsumura et al, symposium of J.Env.Chem, 2003.6

17. Time trend of Co-PCBs （ TEQ ）

19. Time trend of PCB levels in ambient air (log scale)

20. 0.01 0.1 1 10 100 1000 19701975198019851990199520002005 Time trend of PCBs concentration in ambient air (pg/m 3 ) Time trend of PCBs concentration in ambient air (ng/m 3 ) (pg/m 3 ) (ng/m 3 ) Ambient air

21. Low volume air sampler

22. Time trend of PCB levels in breast milk

23. Time trend of breast milk levels Dioxins PCB pg TEQ / g-fat µg g-fat 60 40 20 0 Year (1973-2000) Konishi et al. (2003) Konishi et al (2003) Organohalogen compds pg TEQ/g-fat µg / g-fat Year (1973-2000) 60 40 20 0 0.3 0.2 0.1 0

24. Development of congener specific analysis for PCBs using HT8-PCB

25. Congener number number of isomerof peak mono 3 3 di 12 10 tri 24 23 tetra 42 39 penta 46 38 hexa 42 40 hepta 24 23 octa 12 12 nona 3 3 deca 1 1 total 209 192

26. Matsumura et al, J. Env. Chem. (2002) GC/MS-SIM chromatogram of TrCB (HT8-PCB) PCB product 13 C-TrCB

27. Matsumura et al, J. Env. Chem. (2002) GC/MS-SIM chromatogram of PeCB (HT8-PCB) 13 C-PeCB PCB product

28. Congener profiles of PCBs in environmental samples

29. Congener profiles of PCBs(Di-, Tri-) in environmental samples

30. Congener profiles of PCBs in environmental and human samples

31. Congener profiles of PCBs(Hexa-) in environmental and human samples

32. Congener profiles of PCBs(Hepta-) in environmental and human samples

33. Congener profiles of PCBs in human samples (breast milk)

34. Isomer profiles of TeCB PCB product mother milk #74 #66 #74 #66 #70 #52 #44 #60 #56 25-25 25-23 25-34 245-4 24-34 234-4 23-34 245-4

35. Isomer profiles of PeCB PCB product mother milk #118 #105 #99 #110 #101 245-24 245-34 234-34 245-25 245-24 236-34 236-25 #95

36. Isomer profiles of HxCB PCB product mother milk #153 #138 #149 #138 236-245 234-245 245-245

37. Isomer profiles of HpCB PCB product breast milk #180 #170 #187 234-2345 245-2345 245-2356

38. Congener profiles of PCBs in human samples (pooled blood)

39. ＃ 28 ＃ 31 ＃ 74 ＃ 80 ＃ 99 ＃ 118 ＃ 153 ＃ 138 ＃ 163/ ＃ 164 ＃ 187 ＃ 180 ＃ 170 Tri-CBs Tetra-CBs Penta-CBs Hexa-CBs Hepta-CBs Chromatogram of PCB in human blood （ 3~7Cl ） Hirai et al, (2003) Organohalogen compounds #187 #180 #153 #138 #74 #99 #118 #28 245-2345 245-245 245-234 245-34 245-2356 245-4 245-24 24-4

40. (n=24) CongenersMean ± 2S.D. Existence Ratio* (BZ#)(ng /g-lipid)(%) #153 28.0 ± 22.3 #18014.9 ± 16.611.8 #13810.4 ± 9.28.3 #1878.3 ± 8.56.6 #1186.9 ± 5.95.5 #163,1646.4 ± 6.25.1 #994.7 ± 4.23.8 #744.6 ± 2.63.6 #1464.1 ± 3.73.3 #1703.8 ± 4.13.0 #1562.8 ± 3.02.3 Sum75.6 * Mean is compare to total PCBs level Levels of the predominant PCB congeners in human blood Hirai et al, (2003) Organohalogen compounds 245-2345 2345-234 245-245 245-234 245-4 245-24 245-34 245-2356 245-235 2345-34 22.3 34.1 42.4 49.0 54.5 59.6 63.4 67.0 70.3 73.3 75.6 cumulative (%)

41. human milk/adipose tissue #74 (2,4,4',5-) #99 (2,2’,4,4',5-) #118 (2,3’,4,4',5-) #153 (2,2',4,4',5,5'-) #138 (2,2',3,4,4',5'-) #187 (2,2',3,4’,5,5’,6-) PCB congeners predominant in human samples

42. PCB levels and Homologue profiles in Environmental samples

43. PCB levels in air, water, sediment and biota (2002, MOE Japan) Air Sediment Water Biota 0.1-10ng/m 3 0.1-10ng/L 0.05-800ng/g-dry 0.1-800ng/g-wet

44. Homologue profiles of PCBs in human samples

45. Air Water Bird 0 5 10 15 20 25 30 35 40 45 50 abundance(%) Human blood Breast milk

46. Congener profiles of TrCB,TeCB in human and combustion sample (A)

47. PCB congeners predominant in human samples (TrCB, TeCB) PCB product Combustion Breast milk Combustion PCB product Breast milk

48. Congener profiles of TrCB,TeCB in combustion sample (B)

49. (stack gas) TrCB TeCB #68 #51 #47 24-26 24-24 24-35

50. Congener profiles of PCB in human sample

51. 12 DL-PCB(TEF)+di-ortho-PCB Predominant PCB in product Contribution of DL-PCBs in breast milk

52. Congener profiles of PCB in food sample

53. PCB congener profiles in food sample (Konishi et al ) 2001 1982 ng/day

54. Congener profiles of PCB in human sample

55. 1973 2000 PCB congener composition in human breast milk #187 #180 #153 #138 #74 #99 #118 #187 #180 #153 #138 #74 #99 #118

56. Salmon Breast milk PCB congener composition in human breast milk PCB congener composition in salmon #187 #180 #153#138 #66 #101 #118 #187 #180 #153 #138 #74 #99 #118

57. PCB product human #74 #66 245-4 24-34 #99 #101 245-24 245-25 #146 #149 245-235 245-236

58. PCB metabolite OH-PCB, (OH) 2 -PCB

59. Thyroxine 4-OH-3,3’,4’,5-tetrachlorobiphenyl Thyroxine & TTR binding OH-PCB 4-OH-CB-79

60. Thyroxine 4-OH-2,3,3’,4’,5-pentachlorobiphenyl Thyroxine & TTR binding OH-PCB 4-OH-CB-107

61. CB-118 CB-105

62. 4-OH-CB-146 CB-138 CB-153

63. 4-OH-CB-187 CB-187 CB-183

64. Sediment OH-TrCB OH-TeCB OH-PeCB Chromatogram of PCB-OH by methylation (Sakiyama et al. J.Env.Chem.) OH-TrCB OH-TeCB OH-PeCB Fish (Sea Bass) 4-OH-CB-107 ?

65. PCB metabolite MeSO 2 -PCB

66. CB- 4-MeSO 2 -CB-87 CB-

67. 4-MeSO 2 -CB-101

68. 4-MeSO 2 -CB-149 CB- Chiral metabolite

69. 4-MeSO 2 -CB-149 Chiral metabolite

70. Proposal of index PCB congeners to analyse

71. Proposal of index PCB - Toxicity: DL-/non-DL-PCB, endocrin disrupt potent - Isotope labled congener : available or not - Source estimation : homologue & congener profiles - QA/QC : toxic congener level as impurity is very important think about the list from a different perspective

72. Proposal of index PCB - Formation/degradation mechanism : think about the list from a different perspective - Complete assignment : to avoid miss assign - Retention Time : to avoid co-elution - Predominant congener : - Window congener for analysis :

73. Index PCB congeners should be updated, if there’s any new information. Present list #1, #3, #4, #8, #9, #10, #11, #12, #15, #18, #19, #28, #31, #33, #35, #37, #38, #44, #49, #52, #54, #57, #66, #70, #74, #77, #78, #79, #81, #87, #95, #99, #101, #104, #105, #110, #111, #114, #118, #123, #126, #138, #149, #153, #155, #156, #157, #162, #167, #169, #170, #174, #178, #180, #187, #188, #189, #194, #195, #199, #202, #203, #205, #206, #208, #209.

74. Sharing information - What kind of infomation - How to share - When will we start - Why does we share/exchange - Who will participate - Where can we do

75. Lunch session in Berlin, dioxin 2004 will be planned for similar purpose. - discuss using mailing list - Let’s start to discuss - How to share

76. Acknowledgements Matsumura for work with PCB congener profiles. Okuno, Tanno, Majima, Kitamoto, Gotoh, Kurata for breast milk work. Fujiwara, Tsurukawa for sealant work. Fujimori for PCB destruction work. Nakano Isamu for my life.

77. Thank you for your attention! Special Thanks to Zhonie, Copper, beautiful sky, flat corn fields in Urbana-Champaign. and All participants from Funky Japanese guy with camera.

78. To All participants from Funky Japanese guy with camera. You can see your pictures soon. http://ee-net.ne.jp/illinois/

79. -PCB metabolite OH-PCB, (OH) 2 -PCB, MeSO 2 -PCB - Chiral PCBs atropisomer; enantiomer - Nomenclature PCB No. [IUPAC & BZ]&Cl position : write down both e.g. CB-94(26-235)

80. various PCB waste capacitorreactor waste sludge waste sludge (solid)activated carbonwaste cloth PCT transformer stabilizer PCB waste sludge （ outdoor ） solidified concrete ＋ asphalt pavement soil adsorbent

81. Sealant containing PCB - material that is used for sealing of building - sealant of polysulfide polymer made during 1968-1972 contains PCB glass window sealant of building joint department in building joint department in floor

82. Homologue profiles of PCB in sealant and air Sealant （ Low-Cl) Sealant （ High-Cl) Room air

83. transformer and capacitor : 370,000 stabilizer for Flu. lamp : 2,400,000 non carbon paper : 644,000 kg waste sludge : 117,000 kg waste : 105,000,000 kg other equipments : 33,000 waste PCB etc : PCB waste stock

84. transformer and capacitor : 370,000 stabilizer for Flu. lamp : 2,400,000 non carbon paper : 644,000 kg waste sludge : 117,000 kg waste : 105,000,000 kg other equipments : 33,000 waste PCB etc :

85. PCB waste stock transformer and capacitor : 370,000 stabilizer for Flu. lamp : 2,400,000 non carbon paper : 644,000 kg waste sludge : 117,000 kg waste : 105,000,000 kg other equipments : 33,000 waste PCB etc :

86. Isomer distribution (P 7 CB, Port Island in June,2001) KC300-600 Sea Water Mussel Intensity #174 #180 #170

87. Isomer distribution (O 8 CB, Port Island in June, 2001) KC300-600 Sea Water Mussel Intensity #202#201 #196 #203#194#195 #199