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ANALYSIS OF LOW BROMINATED DD/F ANALYSIS OF MBDD/MBDF TO T 3 BDD/T 3 BDF ON A SP2331 - COLUMN

ANALYSIS OF LOW BROMINATED DD/F ANALYSIS OF MBDD/MBDF TO T 3 BDD/T 3 BDF ON A SP2331 - COLUMN. Takeshi Nakano , Chisato Matsumura, Roland Weber 1 Hyogo Prefectural Inst. of Pub. Health and Env. Sci. 1 Ulmenstrasse 3, 73035 Goeppingen, Germany. Introduction.

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ANALYSIS OF LOW BROMINATED DD/F ANALYSIS OF MBDD/MBDF TO T 3 BDD/T 3 BDF ON A SP2331 - COLUMN

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  1. ANALYSIS OF LOW BROMINATED DD/F ANALYSIS OF MBDD/MBDF TO T3BDD/T3BDF ON A SP2331 - COLUMN Takeshi Nakano, Chisato Matsumura, Roland Weber1 Hyogo Prefectural Inst. of Pub. Health and Env. Sci. 1Ulmenstrasse 3, 73035 Goeppingen, Germany.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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)

  8. 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).

  9. 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

  10. 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

  11. 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

  12. 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)

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 1 M1BrDD 2 D2BrDD 13 27/28 19 T3BrDD 136 138 139 137 129 237 GC/MS-SIMchromatogram 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.

  18. Reliable assignment (blue color) Confirmation by authentic standards Progressing assignment （red color） Estimation from -formation ratio (major/minor) -regularity of elution order -comparison of RRTfor PXDD/F (Cl and Br)

  19. Brominated DD Mixture (Symthesised ) Major component DiBrDD 13-, 27/28- , 16-/19-, 17/18- TrBrDD 137-, 138-, 136-, 139- TeBrDD 1368-, 1379-

  20. 2-MBP 1,3,6-D 1,3-DBDD 2,4-DBP 1,3,7-D 2,6-DBP 1,3,8-D 2,8-DBDD 1,3,9-D 2,4,6-TBP 2,7-DBDD

  21. 1 M1BrDD 2 D2BrDD 18 13 14/17 27/28/23 16 19 12 T3BrDD 136 138 139 137 129 237 GC/MS-SIMchromatogram 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.

  22. Results and Discussion The use of all three monobromophenols produced a wide range of congeners within the D2BDF. Due to the higher pyrolysis temperatureand the addition of CuBr2 the isomerisation/bromination reactions had a significant impact and hence a broad range of T3BDF were formed .

  23. 2 M1BrDF 1 3 4 D2BrDF 28 27 46 13 T3BrDF 238 346 137 GC/MS-SIM chromatogram of M1BrDF～T3BrDF　 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.

  24. Reliable assignment (blue color) Confirmation by authentic standards Progressing assignment （red color） Estimation from -formation ratio (major/minor) -regularity of elution order -comparison of RRTfor PXDD/F (Cl and Br)

  25. Brominated DF Mixture (Symthesised ) Major component M1BDF 2-, 1-, 3- , 4- (4:2:2:1) D2BDF 24-, 28- , 18-, 27-, 17-, 19-, 26-, 37- 16-, 26-, 46- T3BDF 248-, 247-, 246-, 249-(168-) T4BDF 2468-

  26. 4-MBP 2,8-DBDF 2-MBDF 3-MBP 1-MBDF 3-MBDF 2-MBP 4-MBDF 2,4-DBP 2,4-DBDF

  27. 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 GC/MS-SIM chromatogram of M1BrDF～T3BrDF　 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.

  28. MBDF MCDF DBDF DCDF TBDF TCDF PCDF　　　　　　　　　　　　　　　PBDF

  29. On the high polar SP2331-column, all 4 M1BDF were separated and also for D2BDF and T3BDF a reasonable selectivity was achieved. However on the less polar DB5 column even the 4 brominated M1BDF were not completely separated while the 4 chlorinated M1CDF isomers could be separated also on this low polar column. This demonstrates that the selectivity for brominated congeners is smaller compared with the chlorinated congeners.

  30. Separation of low chlorinated DD/F (Dioxin 2000, 2001, 2002) congenerULTRA-2 DB-5MS SP-2331 DB-DIOXIN MCDF4 4 4 4 4 D2CDF 16 8 10 15 16 T3CDF 28 8 10 23 21 congenerULTRA-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

  31. Comparison of Separation for PXDD/F on SP-2331(Cl/Br) congener Cl Br MXDF 4 4 4 D2XDF 16 15 13 T3XDF 28 23 15 congener Cl Br MXDD 2 2 2 D2XDD 10 8 7 T3XDD 14 12 9 the selectivity for brominated congeners is smaller compared with the chlorinated congeners.

  32. Comparison of Separation D2CDF and D2BDF 1,9-D2CDF 1,9-D2BDF

  33. Low Brominated DD/F in Stack Gas Samples

  34. 28 STD mix 27 649323 D2BrDF 0 16 20 24 Retention Time (min) #118 Stack Gas 568627 #105 #114 D2BrDF 28 27 0 16 20 24 Retention Time (min) PeCB(323.8834,325.8805) DiBrDF(323.8785, 325.8765) #126 GC/MS-SIMchromatogram(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.

  35. Sample-A 171522 BrClDF 0 14 16 18 20 Retention Time (min) Sample-B 86858 BrClDF 0 14 16 18 20 Retention Time (min) BrClDF＞BrCl2DF, BrClDD＞BrCl2DD GC/MS-SIM chromatogram(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.

  36. Thank you for your attention

  37. Low Chlorinated DD/F in Environmental Samples

  38. 環境大気 Ambient air

  39. Ambient air Incineration (flyash) 環境大気の異性体分布(MCDF～TrCDF) Isomer distribution of ambient air(MCDF-TrCDF)

  40. Ambient air Incineration (flyash) 環境大気の異性体分布(MCDD～TrCDD) Isomer distribution of ambient air(MCDD-TrCDD)

  41. 28- 2- 37-DiCDF 23- 27-DiCDF 27- 23-DiCDF 37- 28-DiCDF 128-TrCDF 238- 237-TrCDF 128- 238-TrCDF 237- 1278-TCDF 2378-TCDF 塩素漂白パターンの異性体分布(MCDF～TrCDF) Isomer distribution of bleaching process(MCDF-TrCDF)

  42. 238- 128- 2- 28- 237- 27- 塩素漂白パターンの異性体分布(MCDF～TrCDF) Isomer distribution of bleaching process(MCDF-TrCDF) Ambient air 24- 124- Isomer distribution of ambient air(MCDF-TrCDF) 環境大気の異性体分布(MCDF～TrCDF)

  43. 4-MCP 1,2,8-TrCDF 3,4-DCP 2,3,8-TrCDF

  44. O- m- 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) p- Synthesis of 1,4,X-T3CDF isomers from chlorophenol

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

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