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T.NAKANO and R.WEBER*

Analysis of Low Chlorinated PCDD/F Isomer Specific Analysis of MCDD/MCDF to T 3 CDD/T 3 CDF on DB-Dioxin-Column. T.NAKANO and R.WEBER*. Hyogo Pref. Inst. of Public Health & Environ. Sci. *Inst. of Organic Chem., Univ. of Tuebingen. Errata. I found my fixed abstract was not received.

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T.NAKANO and R.WEBER*

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  1. Analysis of Low Chlorinated PCDD/F • Isomer Specific Analysis of • MCDD/MCDF to T3CDD/T3CDF • on DB-Dioxin-Column T.NAKANO and R.WEBER* Hyogo Pref. Inst. of Public Health & Environ. Sci. *Inst. of Organic Chem., Univ. of Tuebingen

  2. Errata I found my fixed abstract was not received. Vol.55, p.123-126 Table 1 and Figure 2 ( 2,3-D 2,8-D ) DCDD 13 28.51 27 29.57 23 29.57 28 29.73 DCDD 13 28.51 27 29.57 28 29.57 23 29.73 Roland Weber pointed out before, that the 2,7-D is not single authentic standard. (2,7-D contains 2,8-D as impurity, and can not separate) I am hating computer virus (Klez etc)

  3. IntroductionRelevance of isomer specific analysis of T4CDD/F-OCDD/F Due to the high toxicity of PCDD/F substituted in 2,3,7,8-position, a lot of attention was paid to the isomer specific analysis of tetra- to octachlorinated DD/DF in the last two decades. Since, exclusively, the congeners substituted in all four 2,3,7,8-position exhibit the dioxin related toxicity, lower chlorinated congeners were not assigned with TEQ values and, therefore, not a lot of attention was paid to them.

  4. IntroductionIsomer specific analysis of low chlorinated DD/F 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 origin 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. GC/MS Analysis.The analysis was carried out using an HP 5890 II gas chromatograph connected to a JMS-700 mass spectrometer (JEOL Ltd. Japan) (operating at a resolution >10 000).

  8. 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

  9. Temperature program DB-Dioxin (60m, 0.25mm i.d., 0.15um, J&W): Temperature program used for isomer specific separation of the MCDD/F-T3CDD/F on DB-Dioxin column: 50C, 1 min. isothermal; 20C/min. to 150C, 3C /min. to 270C, 14min. isothermal. Carrier gas flow rate : He 1.0mL/min.

  10. Temperature program SP-2331: (60m, 0.25mm i.d., 0.25um, SUPELCO): Temperature program used for isomer specific separation of the MCDD/F-T3CDD/F on SP-2331 column:120C, 2 min. isothermal; 30C/min. to 200C, 2C/min. to 260C, 6 min. isothermal.Carrier gas flow rate : He 1.0mL/min.

  11. 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)

  12. 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)

  13. 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)

  14. 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

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

  16. 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.

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

  18. 1,4,6-D 1,4-D 1,4,7-D 2,3-D 2,3,7-D Elution order for D2CDD to T3CDD elutes earlier elutes later

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

  20. 2,4,7-F 2,4,8-F 3,4,7-F 3,7-F 4,6-F 3,4,6-F 2,4-F 1,2,9-F 1,3,9-F 1,6-F 1,2-F 1,4,9-F 1,9-F Elution order for D2CDF to T3CDF elutes earlier elutes later

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

  22. 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

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

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

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

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

  27. 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

  28. 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

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

  30. 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.

  31. Acknowledgement The authors would like to express their thanks to Dr. Brian Gullett and Dr. Dennis Tabor(US-EPA) , Dr. Junji Ogakifor donating some standards,to Terry Humphries for critical reading of the manuscript.

  32. See you next!Thank you for your attention.

  33. Homologue distribution of PCDF in Ambient air

  34. 4-MCP 1,2,8-TrCDF 2,3,8-TrCDF 3,4-DCP

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

  36. PCDF formation from chlorophenols We can control the ratio of isomers by changing the ratio of chlorophenol. Case of 3-MCP + 2-MCP if 2-MCP > > 3-MCP 46- > 16- > 36- > 17- > 37- > 19-F if 3-MCP >> 2-MCP 17- > 37- > 19- > 16- > 36- > 46-F

  37. Ambient air SP-2331

  38. 2,5-dichloroPhenol + 3-chloroPhenol 1,4,9- and 1,4,7- (1,4,9- , 1,4,7- : authentic standard)3-chloroPhenol and 3,4-dichlorophenol 1,2,7-, 1,2,9-, 1,7,8-, 2,3,7- Assignment additional synthesis via PCB. 2,3,4' T3CB result in 1,2,7-T3CDF

  39. Roland Weber pointed out before, that the 2,7-D is not single authentic standard. (2,7-D contains 2,8-D as impurity, and can not separate) As for 2,7-D2CDD, Basically the position is 2,7-D should be presented as an unknown ratio mixture of the two compounds 2,7-/2,8-D .

  40. D2CDD 2,7-/2,8-D 13C-D2CDD 2,7-/2,8D 2,3-D Dennis Tabor (EPA)

  41. But, I believe the poor peak shape of my standard for 2,3-DCDD has lead to an poor assignment. I have 2,7 and 2,3 in my 13C standards and have not gotten the poor peak shape from them. I believe that the toluene or other solvent must be causing you a problem. In my standard which do not have toluene 2,7 comes out before 2,3. The first two traces are the 252/254 of the native DCDD. The second two traces are the 264/266 of the 13C DCDD. The current GC/MS that I am using is Low Res. Therefore the 13C 2,8-DCDF causes me not to be able to see 1,4-DCDD.

  42. Basically the low chlorinated PCDD/PCDF can be analysed together with T4CDDF-OCDD/F. Behavior on Alumina column. Low chlorinated isomers may be oxidized during extensive Sulfuric acid treatment.

  43. Assignment for MCDD/F to T3CDD/F

  44. Elution order for D2CDD to T3CDD

  45. Elution order for D2CDD to T3CDD

  46. Elution order for D2CDF to T3CDF

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