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Analysis and congener patterns of PCDD/Fs, PCBs and PCNs in ambient air

Explore mechanisms of PCDD/F formation/degradation & develop correlation between low chlorinated compounds & TEQ values for waste incineration. Analyze low chlorinated DD/F in environmental samples to estimate dioxin sources and related compounds.

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Analysis and congener patterns of PCDD/Fs, PCBs and PCNs in ambient air

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  1. Analysis and congener patterns of PCDD/Fs, PCBs and PCNs in ambient air Takeshi NAKANO Hyogo prefectural Institute of Public Health & Environmental Sciences

  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. Congener specific analysis of PCDD/Fs

  4. IntroductionIsomer specific analysis of low chlorinated DD/DF  The analysis of low chlorinated isomers seems interesting from several points of view: For the investigation of the mechanisms of PCDD/F formation/degradation, the low chlorinated compounds offer valuable additional information.

  5. For on-line measurement of PCDD/F in waste incineration, some recent research projects focused on estimating TEQ values by measurement of low chlorinated PCDD/F as indicator compound. To establish this correlation, it seems important to measure not only the total amount of the low chlorinated homologues but to calculate and correlate specific isomers.

  6. Furthermore, the low chlorinated DD/F may give valuable information for environmental samples. The analysis of isomer distributions in environmental samples is the key to estimating the source of dioxins and related compounds. (Also in this field, many data are published for T4CDD/F-OCDD/F, however, insufficient data are available for mono- to tri-chlorinated dioxin/furan.)

  7. Standard: a) Authentic standards: commercially available13, 27, 28, 23, 36, 26, 34, 46-DiCDFs (8 isomers / 16 isomers)Authentic standards of 136,138,146,147,149,234,236,238,246,247,267,346 -TrCDFs(12 isomers / 28 isomers)

  8. b) Synthesis of PCDD by pyrolysis of chlorophenols in presence of KOH (250C-300C, 60min) c) Synthesis of PCDF by pyrolysis of chlorophenols (370-400C, 15-30min) d) Synthesis of PCDF by pyrolysis of PCB (400-450C, 15min)

  9. Synthesis PCDFSynthesis of single isomers (in one homolog): 2-chloroPhenol : 4,6-DiCDFSynthesis of mixtures 3,4-dichloroPhenol (result in 1,2- and 2,3-fragment) 3-chloroPhenol (result in 1- and 3-fragment)

  10. 2-MCP 3-MCP 1,4,9-TrCDF 1,4,6-TrCDF 2,5-DCP 1,4,7-TrCDF 4-MCP 1,4,8-TrCDF Authentic standard (1,4,7- : NMR) Synthesis of 1,4,X-T3CDF isomers from chlorophenol

  11. Synthesis PCDDSynthesis of single isomers 1-MCDD, 2-MCDD, 12-DCDD, 13-DCDD, 23-DCDD, 123-TCDD, 124-TCDD, 236-TCDD, 237-T3CDD

  12. Synthesis PCDD Most cases simple PCDD mixtures with two isomers (smiles rearangement): 2,3+2,3,4 result in 1,2,6- and 1,2,9-T3CDD 1,2,6-D 1,2,9-D 2,3-CP+2,3,4-DCP Assignment in mixture of two isomers: With the same ring fragment substitutionthe more polar compound elutes later.

  13. DB-DIOXIN SP-2331 D2CDD 19 13 13 D2CDD 19 T3CDD 137 129 T3CDD 129 137 GC/MS-SIM chromatogram of PCDD

  14. DB-DIOXIN SP-2331 D2CDF 19 13 D2CDF 13 46 T3CDF T3CDF 346 137 129 137 GC/MS-SIM chromatogram of PCDF

  15. Separation of low chlorinated DD The No. of separation peaks isomer ULTRA-2 DB-5MS SP-2331 DB-DIOXIN MCDD 2 2 2 2 2 D2CDD 10 5 4 8 9 T3CDD 14 6 5 12 12

  16. Separation of low chlorinated DF The No. of separation peaks isomer ULTRA-2 DB-5MS SP-2331 DB-DIOXIN MCDF 4 4 4 4 4 D2CDF 16 8 10 14 15 T3CDF 28 8 10 23 21

  17. Conclusions a) The isomer specific analysis of MCDD/MCDF to T3CDD/T3CDF was established on three standard columns·SP-2331 ·DB Dioxin·DB 5MS

  18. Conclusionsb) The low chlorinated PCDD/DF can be analysed together with T4CDD/F to OCDD/F ( one GC/MS injection).c) The DB-Dioxin and the SP-2331 column is effective for an isomer specific analysis of low chlorinated PCDF as it is requested for detailed mechanistic studies.

  19. Homologue profiles of PCDD/Fs in ambient air

  20. Homologue profiles of PCDD/Fs in ambient air

  21. Homologue profiles of PCDD/Fs in river water

  22. Kako river Kako river =200pg/L Σ =20pg/L Σ =100pg/L Σ =20pg/L Σ 80 80 PCDF PCDD PCDF PCDD 60 60 40 pg/L) pg/L) 40 ( ( 20 20 0 0 D2Cl P5Cl D2Cl P5Cl M1Cl O8Cl M1Cl O8Cl Hp7Cl Hx6Cl Hx6Cl Hp7Cl Tr3Cl Te4Cl Tr3Cl Te4Cl Homologue profiles of PCDD/Fs in river water Homologue profiles of PCDD/Fs in river water 2,4-D CNP PCP

  23. Homologue profiles of PCDD/Fs in river water(SPM)

  24. TeCDD Japan USA CNP No CNP PCDD PCDD PCDD PCDD PCDD

  25. Congener profiles of PCDD/Fs in ambient air

  26. 2,4-DCP related PCDD 2,4-D, NIP

  27. Daily variation of PCBsin ambient air

  28. PCB濃度と気温 降雨量 PCB濃度と気圧 大気中PCB濃度変動と気温・降雨・気圧

  29. ローボリウムサンプラー

  30. Congener profiles of Co-PCBsin ambient air

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

  32. 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

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

  34. 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) Matsumura et al, J. Env. Chem. (2002)

  35. T4CB / Average 1511918 Intensity 0 18.8 19.2 19.6 20.0 20.4 20.8 21.2 21.6 22.0 22.4 Retention Time (min) GC/MS-SIM chromatogram of TeCB (HT8-PCB) #48/47 #52 #69 #65 #75 (#103) #64 #73 #72 #71 #49 #62 #68 #44 #59 #42 #43 46 # #41 (#104) (#100) (#96) Fig. 2 - 1 Average Mass Chromatogram of T4CB in all 209 PCB standard mixture solution (1) Matsumura et al, J. Env. Chem. (2002)

  36. Congener profiles of PCBsin environmental samples

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

  38. Congener profiles of PCBsin environmental and human samples

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

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

  41. Congener profiles of PCBsin human samples

  42. #70 PCB product #66 25-25 25-34 25-23 #52 245-4 #44 23-34 #74 #56 #60 245-4 mother milk #74 24-34 #66 234-4 #60 Isomer profiles of TeCB

  43. 245-25 236-34 #101 PCB product 236-25 #110 #118 #95 245-24 #105 #99 245-34 mother milk #118 245-24 #99 234-34 #105 Isomer profiles of PeCB

  44. #153 236-245 PCB product 245-245 #149 234-245 #138 #153 mother milk 245-245 234-245 #138 Isomer profiles of HxCB

  45. #180 PCB product 245-2345 245-2356 #187 234-2345 #170 #180 mother milk 245-2345 245-2356 #187 234-2345 #170 Isomer profiles of HpCB

  46. 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

  47. PCB congeners predominantly found in humans are shown to be #138, #153 and #180.245-234, 245-245, 245-2345 Through identification of all isomers is money and time consuming and thus impractical in regular monitoring processes.

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