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Analysis of Low Brominated DD/F

Analysis of Low Brominated DD/F. Takeshi Nakano (Hyogo Pref. Inst. of Pub. Health and Env.Sci.). PCDD/DF/PCB in environment. ２ , ３ , ４ , ７ , ８－ PeCDF. ２ , ３ , ７ , ８－ TCDD. ７５ congeners. １３５ congeners. ７５ congeners. ２０９ congeners. １ , ２ , ３ , ５ , ６ , ７－ HxCN.

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Analysis of Low Brominated DD/F

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  1. Analysis of Low Brominated DD/F Takeshi Nakano (Hyogo Pref. Inst. of Pub. Health and Env.Sci.) PCDD/DF/PCB in environment

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

  3. Trend of PCB Use in Japan Total58,000t Amount of PCB use (t)

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

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

  6. PCB Homologue Distribution and Source Estimation

  7. Source estimation KC３００ KC５００ Insulator N.C.P. capacitor Sediment A Sediment B KC４００ KC６００ Ship paint Insulator capacitor

  8. To evaluate environmental risk

  9. Daily variation of PCDD/Fsand PCBs in ambient air

  10. Daily variation of Dioxin Concentration

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

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

  13. Emission inventry vs Level in air 0.50 1997 0.40 1998 0.30 1999 PCDDs/PCDFs（pg-TEQ/m3) 0.20 2000 0.10 2001 0.00 0 8000 7000 6000 5000 4000 3000 2000 1000 Emission inventry (g-TEQ/year） Matsumura et al, symposium of J.Env.Chem, 2003.6

  14. Time trend of Co-PCBs（TEQ） Matsumura et al, symposium of J.Env.Chem, 2003.6

  15. Time trend of Co-PCBs（TEQ）

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

  17. 3 ( ng/m ) 3 ( pg/m ) 1000 100 10 1 0.1 0.01 1970 1975 1980 1985 1990 1995 2000 2005 3 Time trend of PCBs concentration in ambient air (ng/m ) 3 Time trend of PCBs concentration in ambient air (pg/m ) Ambient air

  18. Time trend of PCBlevelsin breast milk

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

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

  21. Congener number number of isomer of peakmono 3 3di 12 10tri 24 23tetra 42 39penta 46 38hexa 42 40hepta 24 23octa 12 12nona 3 3deca 1 1 total 209 192

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

  23. P5CB 800000 Intensity 400000 0 20 22 24 26 28 30 32 34 36 38 Retention Time (min) Calculated Retention Time #104 #103 #100 #102 #121 #101 #113 #112 #119 #117 #125 #116 #111 #120 #110 #124 #109 #107 #123 #106 #118 #114 #122 #105 #127 #126 #96 #94 #93 #98 #95 #88 #91 #92 #84 #89 #90 #99 #83 #86 #97 #87 #85 #82 #108 #115 13C-P5CB 50000 Intensity 0 20 22 24 26 28 30 32 34 36 38 Retention Time (min) GC/MS-SIM chromatogram of PeCB (HT8-PCB) PCB product 13C-PeCB Matsumura et al, J. Env. Chem. (2002)

  24. Congener profiles of PCBsin environmental and human samples

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

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

  27. Congener profiles of PCBsin human samples(pooled blood)

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

  29. (n=24) Congeners Mean 2S.D. ± Existence Ratio* (BZ#) (ng /g-lipid) (%) #153 28.0 28.0 22.3 ± #180 14.9 16.6 11.8 ± #138 10.4 9.2 8.3 ± #187 8.3 8.5 6.6 ± #118 6.9 5.9 5.5 ± #163,164 6.4 6.2 5.1 ± #99 4.7 4.2 3.8 ± #74 4.6 2.6 3.6 ± #146 4.1 3.7 3.3 ± #170 3.8 4.1 3.0 ± #156 2.8 3.0 2.3 ± Sum 75.6 * Mean is compare to total PCBs level Levels of the predominant PCB congeners in human blood cumulative (%) 22.3 34.1 42.4 49.0 54.5 59.6 63.4 67.0 70.3 73.3 75.6 245-245 245-2345 245-234 245-2356 245-34 245-24 245-4 245-235 2345-234 2345-34 Hirai et al, (2003) Organohalogen compounds

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

  31. Analysis of Low Brominated DD/F ANALYSIS of MBDD/MBDF to T3BDD/T3BDF on a SP2331 - COLUMN

  32. Introduction In the last two decades the increased use of brominated organic compounds especially brominated flame retardants (BFR) resulted in the presence of brominated compounds indoor, in the waste stream and in the environment.

  33. Introduction Some of the BFR, in particular the PeBDE, are associated with the presence and the formation potential of brominated dibenzo-p-dioxins and furans (PBDD/PBDF). Therefore the congener specific analysis of PBDD/PBDF received more attention in recent time.

  34. Introduction In this respect also the analysis of low brominated DD/F homologues might be interesting in some processes and samples: Brominated aromatic compounds are subjected to debromination reaction under various conditions are dehalogenated more rapidly compared with chlorinated aromatic compounds.

  35. Introduction Under UV or exposure to sunlight, brominated aromatic compounds can undergorapid debromination .photo degradation Debromination reactions are also observedduring thermaldegradation of polybrominatedaromatics . thermal degradation

  36. Introduction Therefore it might be interesting to have selected samples analysed for low brominated DD/DF. For this study we synthesised a low brominated DD and DF mixture and optimised a temperature program on a SP2331 column.

  37. Introduction We have been reported complete assignment of M1CDD/F to T3CDD/F on SP-2331 (Dioxin 2000) DB5MS (Dioxin 2001) DB-Dioxin (Dioxin 2002) In this study, as the first step of complete assignment of M1BDD/F-T3BDD/F (74congeners)

  38. Materials and Methods Standards.(synthesised) The PBDD standards were synthesized by pyrolysis of bromophenols in Pyrex ampoules. The PBDD was synthesized by condensation of 2-monobromophenol, 2,4- and 2,6- dibromophenol(DBP) 2,4,6-tribromophenol (TBP) at 350ºC (30 min).

  39. StandardsPBDD by condensation 2-BP + 2,4- DBP 2-M1BDD 2-BP + 2,6- DBP 1-M1BDD 2,4-DBP + 2,4- DBP 2,7/2,8-D2BDD 2,4-DBP + 2,6- DBP 1,7/1,8-D2BDD 2,6-DBP + 2,6- DBP 1,6/1,9-D2BDD 2-BP + 2,4,6-TBP 1,3-D2BDD 2,4- DBP + 2,4,6-TBP 1,3,7/1,3,8-T3BDD 2,6- DBP + 2,4,6-TBP 1,3,6/1,3,9-T3BDD 2,4,6- TBP + 2,4,6-TBP 1,3,6,8/1,3,7,9-T4BDD

  40. Materials and Methods Standards.(synthesised) For the PBDF mixture all three 2-/3-/4- bromophenol isomers, phenol, 2,4-DBP were pyrolysed at 370ºC (15 minutes) in the presence of trace amounts of CuBr2

  41. StandardsPBDF 4-BP + phenol 2-M1BDF 3-BP + phenol 1-/3-M1BDF 2-BP + phenol 4-M1BDF 2,4-DBP + phenol 2,4-D2BDF 4-BP + 4-BP 2,8-D2BDF 3-BP + 3-BP 1,7-/3,7-/1,9-D2BDF 2-BP + 2-BP 4,6-D2BDF ------------------------------------------------------- 2,4-DBP + 4-BP 2,4,8-T3BDF ------------------------------------------------------- 2,4-DBP + 2,4-DBP 2,4,6,8-T4BDF

  42. Materials and Methods Standards.(commercially available ) We obtained commercially available standards 2,7/2,8-D2BDD, 2,3,7-T3BDD 1,2,3,4-, 1,3,6,8-, 1,3,7,9-, 1,3,7,8-, 2,3,7,8-T4BDD 2,7-D2BDF, 2,8-D2BDF, 2,3,8-T3BDF EBC-2500 8-Br-2,3-CDF, 8-Br-2,3,4-CDF, 7-Br-2,3-CDD, 2-Br-3,7,8-CDD, EDF-2046: 13C-2,3,7,8-TeBrDF, 13C-2,3,7,8-TeBrDD (Te～HxBrDD/DF)

  43. GC/MS Analysis The analysis was carried out using HP 5890 II gas chromatograph connected to JMS-700 mass spectrometer (JEOL Ltd. Japan) operating at a resolution >10,000.

  44. Temperature program Temperature program used for congener specific separation of the MBDD/F-T3BDD/F on SP2331 column (60m, 0.32mm i.d., 0.20um,): 120°C, 1 min. isothermal; 20°C/min. to 200°C, 2°C /min. to 260°C, 30min. isothermal. Carrier gas flow rate: He 1.2mL/min.

  45. Table.1　Monitoring ion M1BrDD 261.9629 263.9610 D2BrDD 339.8735 341.8715 T3BrDD 419.7820 421.7800 T4BrDD 497.6925 499.6904 M1BrDF 245.9680 247.9661 D2BrDF 323.8785 325.8765 T3BrDF 403.7870 405.7850 T4BrDF 481.6975 483.6955

  46. Results and Discussion The use of the 2,4-DBP (resulting in 2- and 3- (7- and 8-) PBDD substitution) and 2,6-DBP (resulting in 1- and 4- (6- and 9-) PBDD substitution) produced a wide range of congeners within the D2BDD.

  47. 1 M1BrDD 2 D2BrDD 13 27/28 19 T3BrDD 136 138 139 137 129 237 GC/MS-SIM chromatogram of M1BrDD～T3BrDD SP2331 ; 60m x 0.32mmid. 0.20um; 120°C (1 min.), 20°C/min. to 200°C, 2°C /min. to 260°C (30min).; He 1.2mL/min.

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