Page 1 Analysis of Low Chlorinated PCDD/F - Isomer Specific by x5S1Ng60

VIEWS: 11 PAGES: 40

									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
  DB-Dioxin
    44% methyl, 28% phenyl,
    20% cyanopropyl
    8% polyoxyethylene
  SP-2331
    90% biscyanopropyl
    10% phenylcyanopropyl
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
b) Synthesis of PCDD by pyrolysis phenols
in presence of KOH at temperature between
250C-300C

c) 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)
PCDF formation from chlorophenols
Synthesis PCDF

Synthesis of single isomers (in one
homolog):
 2-chloroPhenol : 4,6-DiCDF

Synthesis of mixtures
3,4-dichloroPhenol
 (result in 1,2- and 2,3-fragment)
3-chloroPhenol
  (result in 1- and 3-fragment)
 4-MCP



          1,2,8-TrCDF




          2,3,8-TrCDF
3,4-DCP
              2-MCP
                             3-MCP



                                             1,4,9-TrCDF
1,4,6-TrCDF


                       2,5-DCP



                                          1,4,7-TrCDF
1,4,8-TrCDF    4-MCP
                                     Authentic standard
                                       (1,4,7- : NMR)

 Synthesis of 1,4,X-T3CDF isomers from chlorophenol
Authentic standard


                H9   Cl1
        H8                      H2

        Cl7                     H3
               H6    Cl4
                                          H 2 ; H3

                           H6

   H9
                                     H8




              NMR 1,4,7-TrCDF
Synthesis PCDD

Synthesis of single isomers
1-MCDD, 2-MCDD,
12-DCDD, 13-DCDD, 23-DCDD,
123-TCDD, 124-TCDD, 236-TCDD, 237-T3CDD
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.
Chromatogram on Columns;
Comparison Retention Behavior

Chromatograms
- DB-Dioxin
- SP2331 column
Ambient air   SP-2331
      DB-DIOXIN                       SP-2331


 D2CDF

13                   19


                           13              D2CDF
                                           46
  T3CDF

                          T3CDF                    346
137                129
                                137


             GC/MS-SIM chromatogram of PCDF
      DB-DIOXIN                      SP-2331

  D2CDD           19
 13



                          13                   D2CDD
                                     19
  T3CDD
137
                  129
                         T3CDD
                                                 129
                               137


           GC/MS-SIM chromatogram of PCDD
Assignment for MCDD/F to T3CDD/F
  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
  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
R.T. Behavior : Substitution Fragments
     SP-2331 and DB-DIOXIN
  PCDF
  Elution order on DB-DIOXIN
   2,4-, 3,7- isomers : earlier
   1,2-, 1,6-, 1,9- isomers : later
  compare with SP-2331
GC/MS-Chromatogram of D2CDF




                  SP-2331
 DB-Dioxin


             24




                                 SP-2331
                            12

             37
                                           19

                   16
GC/MS-Chromatogram of T3CDF
             DB-Dioxin




                    SP-2331




                                SP-2331
                          149
                                          129




              139
R.T. Behavior : Substitution Fragments

   SP-2331 and DB-DIOXIN
PCDD
 Elution order on DB-DIOXIN
  1,4- isomers : earlier
 compare with SP-2331
GC/MS-Chromatogram of D2CDD
                         DB-Dioxin




                                                                     16
                                               14
                 D2 CDD




                                            DB-Dioxin
                                                        SP-2331




                                                                                     19
                               27/28
            13




                                                             18




                                                                            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
GC/MS-Chromatogram of T3CDD
                DB-Dioxin




          147
                      146
    低臭素化ダイオキシン類
       の異性体分析
                          CN             CN
                          C3 H           C3 H
                               6              6
                        O Si           O Si

                          C3 H
                               6
                          CN
                                   x              y




●   SP-2331 (95%cyanopropyl 5%phenyl-siloxane)
●   BPX-35 (35%phenylpolysilphenylene-siloxane)
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,
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。
                                                                            2

                                      M1BrDF


                                                        1             3

                                                                                               4




                                        D2BrDF                                                 28
                                                                                     27
                                                                 18

                                                            17                  24
                                                                                                    26
                                                                                          36
                                                                           37                                 46
                                             13                       16




                                        T3BrDF                             248




                                                                                                    237/149
                                                                                                    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.
                 M1BDF / Average                2
                    2726152




                   Intensity
                                          1 3
                                                      4

                                0
                                               10        11
                                          Retention Time (min)
                 BrClDF / Average
                      14887


                   Intensity
                               503
                                            13      14      15
                                          Retention Time (min)
                                                                    28
                 D2BDF / Average                               27
                    792528                           18
                   Intensity




                                                17        24
                                     13                                  26
                                                                              46

                                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.
                         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.
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.
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。
                                                                        1
                                                                                   M1BrDD
                                                         2




                                                                                       D2BrDD
                                                                      18
                                                  13          14/17

                                                       27/28/23
                                                                            16          19

                                                                                  12




                                                                                       T3BrDD
                                            138         136
                                                                  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.
                           M1BDD / Average                                1
                           4457267
                                                                  2




               Intensity
                                       0

                                                         10.4                        10.8

                                                         Retention Time (min)


                           BrClDD / Average
                                9893
               Intensity




                                 524

                                                    14           15                  16

                                                         Retention Time (min)


                           D2BDD / Average
                                                                        27/28
                           2389477
               Intensity




                                                   13

                                       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.
             T3BDD / Average
                1307231



        Intensity

                      0
                                 27                 28                29
                                        Retention Time (min)

             T4BDD / Average     1368
                191064
                                      1379
        Intensity




                      0
                               31.0          31.5   32.0       32.5
                                        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.
 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
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。
                                                                                28
                                          STD mix
                        649323                                             27



                   D2BrDF




                                  0


                                             16                    20                 24

                                                    Retention Time (min)



                                                            #118

                        568627            Sample                   #114     #105


                   D2BrDF
                                                                                 28


                                                                           27

                                  0


                                             16                    20                 24

                                                    Retention Time (min)


                                      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.
    臭素系DD/DF はBrDF>>BrClDF>BrCl2DF、BrDD>>BrClDD>BrCl2DD
                                             Sample-A
                       171522


                     BrClDF




                                 0

                                               14              16          18        20

                                                    Retention Time (min)




                         86858             Sample-B

                     BrClDF




                                 0


                                               14              16          18        20

                                                    Retention Time (min)


                                 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.

								
To top