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兵庫県立健康環境科学研究センター 中野　武

低臭素化ダイオキシン類の 異性体分析. 兵庫県立健康環境科学研究センター 中野　武. 現状. PCDD/DF 分析法は、毒性係数の示されている 17 異性体、 4 ～ 8 塩素化 DD/DF のみを対象. 低塩素化 DD/DF の異性体分布は、生成機構や分解過程の解明、毒性評価、起源推定などに非常に重要な情報を提供する. 低塩素化ダイオキシン類 の異性体分析. ● SP-2331 ● DB-DIOXIN ● DB5-MS. Column;. SP-2331 and DB-DIOXIN. Polarity: 　DB-DIOXIN　< 　SP-2331　

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兵庫県立健康環境科学研究センター 中野　武

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  1. 低臭素化ダイオキシン類の 異性体分析 兵庫県立健康環境科学研究センター 中野　武

  2. 現状 PCDD/DF分析法は、毒性係数の示されている17異性体、4～8塩素化DD/DFのみを対象 低塩素化DD/DFの異性体分布は、生成機構や分解過程の解明、毒性評価、起源推定などに非常に重要な情報を提供する

  3. 低塩素化ダイオキシン類の異性体分析 ●SP-2331 ●DB-DIOXIN ●DB5-MS

  4. Column; SP-2331 and DB-DIOXIN Polarity: 　DB-DIOXIN　< 　SP-2331　 DB-Dioxin 　44% methyl, 28% phenyl, 　20% cyanopropyl 　8% polyoxyethylene SP-2331 90%　biscyanopropyl 10%　phenylcyanopropyl

  5. Standard: a) Authentic standards: 13, 27, 23, 36, 28, 26, 34, 46-DiCDFs Authentic standards of 136,138,146,147,149,236,238,246,267,346 -TrCDFs

  6. b) Synthesis of PCDD by pyrolysis phenols in presence of KOH at temperature between 250C-300Cc) Synthesis of PCDF by pyrolysis of respective Phenols in pyrex ampoule (370-400C, 15-30min)d) Synthesis of PCDF by pyrolysis of PCB in pyrex ampoule (400-450C, 15min)

  7. PCDF formation from chlorophenols

  8. 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)

  9. 4-MCP 1,2,8-TrCDF 2,3,8-TrCDF 3,4-DCP

  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. Authentic standard Cl1 H9 H8 H2 Cl7 H3 H6 Cl4 H2 ;H3 H6 H9 H8 NMR 1,4,7-TrCDF

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

  13. 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 Assignment in mixture of two isomers: With the same ring fragment substitution　the more polar compound elutes later.

  14. Chromatogram on Columns; Comparison Retention Behavior Chromatograms - DB-Dioxin   - SP2331 column

  15. Ambient air SP-2331

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

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

  18. Assignment for MCDD/F to T3CDD/F

  19. 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

  20. 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 15 16 T3CDF 28 8 10 23 21

  21. R.T. Behavior : Substitution Fragments SP-2331 and DB-DIOXIN Elution order on DB-DIOXIN 2,4-, 3,7- isomers : earlier 1,2-, 1,6-, 1,9- isomers : later compare with SP-2331 PCDF

  22. GC/MS-Chromatogram of D2CDF DB-Dioxin SP-2331 24 12 SP-2331 37 19 16

  23. GC/MS-Chromatogram of T3CDF DB-Dioxin SP-2331 SP-2331 149 129 139

  24. R.T. Behavior : Substitution Fragments SP-2331 and DB-DIOXIN Elution order on DB-DIOXIN 1,4- isomers : earlier compare with SP-2331 PCDD

  25. GC/MS-Chromatogram of D2CDD DB-Dioxin 16 14 D CDD 2 SP-2331 DB-Dioxin 19 13 18 27/28 12 17 23 14 28.0 28.4 28.8 29.2 29.6 30.0 30.4 30.8 31.2 31.6 32.0

  26. GC/MS-Chromatogram of T3CDD DB-Dioxin 147 146

  27. CN CN C C C H H H 3 3 3 6 6 6 O Si O Si CN 低臭素化ダイオキシン類の異性体分析 x y ●SP-2331 (95%cyanopropyl 5%phenyl-siloxane) ●BPX-35 (35%phenylpolysilphenylene-siloxane)

  28. Standards. For the PBDF mixture all three monobromophenol isomers, Phenol and 2, 4-DBP were pyrolysed at 370ºC (15 minutes) in the presence of trace amounts of CuBr2. Authentic standards 2,7-D2BDF, 2,8-D2BDF, 2,3,8-T3BDF,

  29. 合成した臭素化DF標品混合物は、 使用した2-/3-/4-ブロモフェノールの量を反映し、2->1-,3->4-(4:2:2:1)であった。 DiBrDFの場合、24- 以外に28-, 18-, 27- , 17-, 19-, 26-, 37- , 16-, 36- , 46-が含まれ、 TrBrDFは、248- , 168- , 247- , 246- 、 TeBrDFの場合、2468-が主要な異性体である。 低臭素化DD/DF異性体について、市販標品のRT、標品混合物中の異性体予測生成比、異性体の溶出順序の規則性から、推定した。

  30. 2 M1BrDF 1 3 4 D2BrDF 28 27 18 17 24 26 36 37 46 13 16 T3BrDF 237/149 248 238 246 347/236 247 138/136 346 137 168 M1BrDF～T3BrDFのGC/MS-SIMクロマトグラム　 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.

  31. M1BDF / Average 2726152 Intensity 2 1 3 0 4 10 11 Retention Time (min) BrClDF / Average 14887 Intensity 503 28 27 13 14 15 18 Retention Time (min) 24 17 26 13 46 D2BDF / Average 792528 Intensity 0 16 17 18 19 Retention Time (min) BPX-35 ; 30m x 0.32mm id. 0.25um; 120°C (2 min.), 20°C/min. to 180°C, 2°C /min. to 220°C, 10°C /min. to 300°C (10min).; He 1.0mL/min.

  32. T3BDF / Average 312320 Intensity 0 26 27 28 29 Retention Time (min) T4BDF / Average 87023 Intensity 0 31 32 33 Retention Time (min) BPX-35 ; 30m x 0.32mm id. 0.25um; 120°C (2 min.), 20°C/min. to 180°C, 2°C /min. to 220°C, 10°C /min. to 300°C (10min).; He 1.0mL/min.

  33. Standards. The PBDD standards were synthesized by pyrolysis of bromophenols in Pyrex ampoules. The PBDD was synthesized by condensation of 2-monobromo phenol, 2, 4- and 2, 6- dibromophenol (DBP) and 2, 4, 6-tribromophenol (TBP) at 350ºC (30 min). Authentic standards: 2,7/2,8-D2BDD, 2,3,7-T3BDD.

  34. 合成した臭素化DD標品混合物は、 DiBrDDは、13-、27/28- 、 TrBrDDは、137-, 138- 、 136-, 139- TeBrDDは、1368-, 1379- が含まれていた。

  35. 1 M1BrDD 2 D2BrDD 18 13 14/17 27/28/23 16 19 12 T3BrDD 136 138 124 137 129 237 M1BrDD～T3BrDDのGC/MS-SIMクロマトグラム 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.

  36. 1 2 M1BDD / Average 4457267 Intensity 0 10.4 10.8 Retention Time (min) BrClDD / Average 9893 Intensity 524 14 15 16 27/28 Retention Time (min) D2BDD / Average 13 2389477 Intensity 0 17 18 19 Retention Time (min) BPX-35 ; 30m x 0.32mm id. 0.25um; 120°C (2 min.), 20°C/min. to 180°C, 2°C /min. to 220°C, 10°C /min. to 300°C (10min).; He 1.0mL/min.

  37. T3BDD / Average 1307231 Intensity 0 27 28 29 Retention Time (min) T4BDD / Average 191064 Intensity 0 31.0 31.5 32.0 32.5 Retention Time (min) 1368 1379 BPX-35 ; 30m x 0.32mm id. 0.25um; 120°C (2 min.), 20°C/min. to 180°C, 2°C /min. to 220°C, 10°C /min. to 300°C (10min).; He 1.0mL/min.

  38. 排ガス試料 PCB濃度が高い場合、 DiBrDF(323.8785, 325.8765) は PeCB(323.8834,325.8805)の妨害を受ける。 臭素系DD/DF は BrDF>>BrClDF＞BrCl2DF、 BrDD>>BrClDD＞BrCl2DD

  39. 28 STD mix 27 649323 D2BrDF 0 16 20 24 Retention Time (min) #118 Sample 568627 #105 #114 D2BrDF 28 27 0 16 20 24 Retention Time (min) PCB濃度が高い場合、DiBrDF(323.8785, 325.8765) はPeCB(323.8834,325.8805)の妨害を受ける。 GC/MS-SIMクロマトグラム(D2BrDF) 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.

  40. Sample-A 171522 BrClDF 0 14 16 18 20 Retention Time (min) Sample-B 86858 BrClDF 0 14 16 18 20 Retention Time (min) 臭素系DD/DF はBrDF>>BrClDF＞BrCl2DF、BrDD>>BrClDD＞BrCl2DD GC/MS-SIMクロマトグラム(BrClDF) 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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