ANALYSIS OF LOW ANALYSIS OF LOW BROMINATED DD/F BROMINATED DD/F

ANALYSIS OF MBDD/MBDF TO TANALYSIS OF MBDD/MBDF TO T33BDD/TBDD/T33BDF BDF

ON A SP2331 - COLUMNON A SP2331 - COLUMN

Takeshi Nakano, Chisato Matsumura, Roland Weber1

Hyogo Prefectural Inst. of Pub. Health and Env. Sci.1Ulmenstrasse 3, 73035 Goeppingen, Germany.

IntroductionIntroduction In the last two decades the increased use of In the last two decades the increased use of

brominated organic compounds especially brominated organic compounds especially brominated flame retardantsbrominated flame retardants (BFR) (BFR) resulted in the presence of brominated resulted in the presence of brominated compounds indoor, in the waste stream and compounds indoor, in the waste stream and in the environment.in the environment.

IntroductionIntroductionSome of the BFR, Some of the BFR,

in particular the in particular the PeBDEPeBDE, are associated with , are associated with the presence and the formation potential of the presence and the formation potential of brominated dibenzo-p-dioxins and furans brominated dibenzo-p-dioxins and furans (PBDD/PBDF). (PBDD/PBDF).

Therefore the congener specific analysis of Therefore the congener specific analysis of PBDD/PBDF received more attention in PBDD/PBDF received more attention in recent time. recent time.

IntroductionIntroductionIn this respect also the analysis of low In this respect also the analysis of low

brominated DD/F homologues might be brominated DD/F homologues might be interesting in some processes and samples: interesting in some processes and samples:

Brominated aromatic compounds Brominated aromatic compounds

are subjected to debromination reaction are subjected to debromination reaction under various conditionsunder various conditions

are dehalogenated more rapidly compared are dehalogenated more rapidly compared with chlorinated aromatic compounds.with chlorinated aromatic compounds.

IntroductionIntroductionUnder UV or exposure to sunlight,Under UV or exposure to sunlight,

brominated aromatic compounds can undergobrominated aromatic compounds can undergo rapid debrominationrapid debromination . . photo degradationphoto degradation

DebrominationDebromination reactions are also observed reactions are also observed during during thermalthermal degradationdegradation of polybrominated of polybrominated aromatics . aromatics . thermal degradationthermal degradation

IntroductionIntroductionTherefore it might be interesting to have selected Therefore it might be interesting to have selected

samples analysed for low brominated DD/DF. samples analysed for low brominated DD/DF.

For this study we synthesised a low brominated For this study we synthesised a low brominated DD and DF mixture and optimised a DD and DF mixture and optimised a temperature program on a SP2331 column. temperature program on a SP2331 column.

IntroductionIntroductionWe have been reported complete assignmentWe have been reported complete assignment

of Mof M11CDD/F to TCDD/F to T33CDD/F on CDD/F on

SP-2331 (Dioxin 2000)SP-2331 (Dioxin 2000)

DB5MS (Dioxin 2001)DB5MS (Dioxin 2001)

DB-Dioxin (Dioxin 2002)DB-Dioxin (Dioxin 2002)

In this study, as the first step of complete In this study, as the first step of complete assignment assignment of Mof M11BDD/F-TBDD/F-T33BDD/F (74congeners)BDD/F (74congeners)

Standards.Standards. (synthesised)(synthesised)

The The PBDDPBDD standards were synthesized standards were synthesized

by pyrolysis of by pyrolysis of bromophenolsbromophenols

in Pyrex ampoules.in Pyrex ampoules.

The The PBDDPBDD was synthesized by condensation of was synthesized by condensation of 2-monobromophenol, 2-monobromophenol,

2,4- and 2,6- dibromophenol(DBP) 2,4- and 2,6- dibromophenol(DBP)

2,4,6-tribromophenol (TBP) 2,4,6-tribromophenol (TBP)

at 350ºC (30 min). at 350ºC (30 min).

Materials and MethodsMaterials and Methods

StandardsStandards PBDDPBDD by condensation by condensation

2-2-BP + BP + 2,4- DBP 2-M2,4- DBP 2-M11BDDBDD

2-2-BP + BP + 2,6- DBP 1-M2,6- DBP 1-M11BDDBDD

2,4-D2,4-DBP + BP + 2,4- DBP 2,7/2,8-D2,4- DBP 2,7/2,8-D22BDDBDD

2,4-D2,4-DBP + BP + 2,6- DBP 1,7/1,8-D2,6- DBP 1,7/1,8-D22BDDBDD

2,6-D2,6-DBP + BP + 2,6- DBP 1,6/1,9-D2,6- DBP 1,6/1,9-D22BDDBDD

2-2-BP + BP + 2,4,6-TBP 1,3-D2,4,6-TBP 1,3-D22BDDBDD

2,4- DBP 2,4- DBP + + 2,4,6-TBP 1,3,7/1,3,8-T2,4,6-TBP 1,3,7/1,3,8-T33BDD BDD

2,6- DBP2,6- DBP + + 2,4,6-TBP 1,3,6/1,3,9-T2,4,6-TBP 1,3,6/1,3,9-T33BDD BDD

2,4,6- TBP2,4,6- TBP + + 2,4,6-TBP 1,3,6,8/1,3,7,9-T2,4,6-TBP 1,3,6,8/1,3,7,9-T44BDD BDD

Standards.Standards. (synthesised)(synthesised)

For the For the PBDFPBDF mixture mixture

all three 2-/3-/4- bromophenol isomers, all three 2-/3-/4- bromophenol isomers,

phenol, phenol,

2,4-DBP 2,4-DBP

were pyrolysed at 370ºC (15 minutes) were pyrolysed at 370ºC (15 minutes)

in the presence of trace amounts of in the presence of trace amounts of CuBrCuBr22

Materials and MethodsMaterials and Methods

StandardsStandards PBDFPBDF

4-4-BP + BP + phenol 2-Mphenol 2-M11BDFBDF

3-3-BP + BP + phenol 1-/3-Mphenol 1-/3-M11BDFBDF

2-2-BP + BP + phenol 4-Mphenol 4-M11BDFBDF

2,4-D2,4-DBP + BP + phenol 2,4-Dphenol 2,4-D22BDFBDF

4-4-BP + BP + 4-BP 2,8-D4-BP 2,8-D22BDFBDF

3-3-BP + BP + 3-BP 1,7-/3,7-/1,9-D3-BP 1,7-/3,7-/1,9-D22BDFBDF

2-2-BP + BP + 2-BP 4,6-D2-BP 4,6-D22BDFBDF------------------------------------------------------- ------------------------------------------------------- 2,4-D2,4-DBP + BP + 4-4-BP BP 2,4,8-T 2,4,8-T33BDFBDF--------------------------------------------------------------------------------------------------------------2,4-D2,4-DBP + 2,BP + 2,4-DBP 2,4,6,8-T4-DBP 2,4,6,8-T44BDF BDF

Standards.Standards. (commercially(commercially available available ) )

We obtained commerciallyWe obtained commercially available available standards standards

2,7/2,8-D2,7/2,8-D22BBDDDD, ,

2,3,7-T2,3,7-T33BBDDDD

1,2,3,4-, 1,3,6,8-, 1,2,3,4-, 1,3,6,8-, 1,3,7,9-, 1,3,7,8-, 1,3,7,9-, 1,3,7,8-, 2,3,7,8-T 2,3,7,8-T44BBDDDD

2,7-D2,7-D22BBDFDF, ,

2,8-D2,8-D22BBDFDF, ,

2,3,8-T2,3,8-T33BBDFDF

Materials and MethodsMaterials and Methods

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)

GC/MS AnalysisGC/MS Analysis

The analysis was carried out The analysis was carried out

using HP 5890 II gas chromatograph using HP 5890 II gas chromatograph connected to JMS-700 mass spectrometer connected to JMS-700 mass spectrometer (JEOL Ltd. Japan)(JEOL Ltd. Japan)

operating at a resolution >10,000. operating at a resolution >10,000.

Temperature programTemperature programTemperature program used for congener specific Temperature program used for congener specific

separation of the MBDD/F-Tseparation of the MBDD/F-T33BDD/F BDD/F

on on SP2331SP2331 column (60m, 0.32mm i.d., 0.20um,): column (60m, 0.32mm i.d., 0.20um,):

120°C, 1 min. isothermal; 120°C, 1 min. isothermal;

20°C/min. to 200°C, 20°C/min. to 200°C,

2°C /min. to 260°C, 30min. isothermal. 2°C /min. to 260°C, 30min. isothermal.

Carrier gas flow rate: He 1.2mL/min. Carrier gas flow rate: He 1.2mL/min.

Table.1Table.1 　　 Monitoring ionMonitoring ion

MM11BrDD 261.9629BrDD 261.9629 263.9610263.9610

DD22BrDD 339.8735BrDD 339.8735 341.8715341.8715

TT33BrDD 419.7820BrDD 419.7820 421.7800421.7800

TT44BrDD 497.6925BrDD 497.6925 499.6904499.6904

MM11BrDF 245.9680BrDF 245.9680 247.9661247.9661

DD22BrDF 323.8785BrDF 323.8785 325.8765325.8765

TT33BrDF 403.7870BrDF 403.7870 405.7850405.7850

TT44BrDF 481.6975BrDF 481.6975 483.6955483.6955

Results and DiscussionResults and Discussion

The use of the 2,4-DBP (resulting in 2- and 3- The use of the 2,4-DBP (resulting in 2- and 3- (7- and 8-) PBDD substitution) and (7- and 8-) PBDD substitution) and

2,6-DBP (resulting in 1- and 4- (6- and 9-) 2,6-DBP (resulting in 1- and 4- (6- and 9-) PBDD substitution) produced a wide range PBDD substitution) produced a wide range of congeners within the Dof congeners within the D22BDD.BDD.

11 12 13 14 15 16 Retention Time

0

3095833

M1BDD

16 17 18 19 20 21 22 23 24 Retention Time

0

760425

D2BDD

25 26 27 28 29 30 31 32 Retention Time

0

398216

T3BDD

138139

237129

136

137

2

1

13

1927/28

M1BrDD

D2BrDD

T3BrDD

GC/MS-SIM chromatogram 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.

Reliable assignment (blue color)

Confirmation by authentic standards

Progressing assignment （ red color ）

Estimation from

-formation ratio (major/minor)

-regularity of elution order

-comparison of RRT for PXDD/F (Cl and Br)

Brominated DD Mixture (Symthesised )

Major component

DiBrDD 13-, 27/28- , 16-/19-, 17/18-

TrBrDD 137-, 138-, 136-, 139-

TeBrDD 1368-, 1379-

2-MBP

2,6-DBP

2,4-DBP

2,4,6-TBP

1,3-DBDD

2,8-DBDD

2,7-DBDD

1,3,6-D

1,3,7-D

1,3,8-D

1,3,9-D

11 12 13 14 15 16 Retention Time

0

3095833

M1BDD

16 17 18 19 20 21 22 23 24 Retention Time

0

760425

D2BDD

25 26 27 28 29 30 31 32 Retention Time

0

398216

T3BDD

138139

237129

136

137

2

1

13

19

12

27/28/23

18

16

14/17

M1BrDD

D2BrDD

T3BrDD

GC/MS-SIM chromatogram 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.

Results and DiscussionResults and Discussion

The use of all three monobromophenols produced a The use of all three monobromophenols produced a wide range of congeners within the Dwide range of congeners within the D

22BDF.BDF.

Due to the Due to the higher pyrolysis temperaturehigher pyrolysis temperature and the addition of and the addition of CuBrCuBr

22

the the isomerisation/brominationisomerisation/bromination reactions had a reactions had a significant impact and hence a broad range of significant impact and hence a broad range of TT33BDF were formed . BDF were formed .

11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 Retention Time

0

1587256

M1BDF

16 17 18 19 20 21 22 23 24 25 Retention Time

0

497896

D2BDF

24 26 28 30 32 34 Retention Time

0

102569

T3BDF

4613

2728

346

238

137

1 3

2

4

M1BrDF

D2BrDF

T3BrDF

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.

Reliable assignment (blue color)

Confirmation by authentic standards

Progressing assignment （ red color ）

Estimation from

-formation ratio (major/minor)

-regularity of elution order

-comparison of RRT for PXDD/F (Cl and Br)

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-

2,8-DBDF2-MBDF

1-MBDF 3-MBDF

4-MBDF

2,4-DBDF

2,4-DBP

2-MBP

3-MBP

4-MBP

11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 Retention Time

0

1587256

M1BDF

16 17 18 19 20 21 22 23 24 25 Retention Time

0

497896

D2BDF

24 26 28 30 32 34 Retention Time

0

102569

T3BDF

46

17

13

18

1637

24

27

36

28

26

247

248

246

346

238

138/136

137 168

1 3

2

4

M1BrDF

D2BrDF

T3BrDF

347/236

237/149

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.

9 10 11 12 13 14 15 16 17 18 19 20 21 22

9 10 11 12 13 14 15 16 17 18 19 20 21 22

9 10 11 12 13 14 15 16 17 18 19 20 21 22

1

4

2

3

MCDF

13 17

1418

1612

3727

36

46

3426

28

24

19

23

137

DiCDF

TrCDF

138

346

129

267

347/

236

137

237/

149

246

248

136 16

813

412

4/14

7

178

148

126

128

247

167

139/

127

146

123

11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 Retention Time

0

1587256

M1BDF

16 17 18 19 20 21 22 23 24 25 Retention Time

0

497896

D2BDF

24 26 28 30 32 34 Retention Time

0

102569

T3BDF

PCDF 　 　 　 　 　 　 　 　 　 　 　 　 　 　 　 PBDF

MCDF

DCDF

TCDF

MBDF

DBDF

TBDF

On the high polar On the high polar SP2331SP2331-column, all 4 M-column, all 4 M11BDF BDF

were separated and also for Dwere separated and also for D22BDF and TBDF and T33BDF BDF

a reasonable selectivity was achieved. a reasonable selectivity was achieved.

However on the less polar However on the less polar DB5DB5 column even the 4 column even the 4 brominatedbrominated M M

11BDF were not completely BDF were not completely

separated while the 4 separated while the 4 chlorinatedchlorinated M M11CDF CDF

isomers could be separated also on this low isomers could be separated also on this low polar column. polar column.

This demonstrates that the selectivity for This demonstrates that the selectivity for brominatedbrominated congeners is smaller compared congeners is smaller compared with the with the chlorinatedchlorinated congeners. congeners.

Separation of low Separation of low chlorinatedchlorinated DD/F DD/F

　　 (Dioxin 2000, 2001, 2002) congener　　ULTRA-2 DB-5MS SP-2331 DB-DIOXIN

MCDF 4 4 4 4 4D2CDF 16 8 10 15 16T3CDF 28 8 10 23 21 congener　　ULTRA-2 DB-5MS SP-2331 DB-DIOXIN

MCDD 2 2 2 2 2D2CDD 10 5 4 8 9

T3CDD 14 6 5 12 12

Comparison of Comparison of Separation for Separation for PXDD/FPXDD/F

on SP-2331on SP-2331 (Cl/(Cl/Br)Br)congenercongener ClCl BrBr

MXDFMXDF 4 4 4 4 4 4D2XDFD2XDF 1616 1515 1313T3XDFT3XDF 2828 2323 1515

congenercongener ClCl BrBrMXDDMXDD 2 2 2 2 2 2D2XDDD2XDD 1010 8 8 7 7T3XDDT3XDD 1414 1212 9 9

the selectivity for the selectivity for brominatedbrominated congeners is smaller compared with the congeners is smaller compared with the chlorinatedchlorinated congeners. congeners.

Comparison of Comparison of Separation Separation

DD22CDF and DCDF and D22BDFBDF

1,9-D1,9-D22CDF 1,9-DCDF 1,9-D22BDFBDF

Low Low BrominatedBrominated DD/F DD/F in Stack Gas Samplesin Stack Gas Samples

16 20 24

Retention Time (min)

0

649323

16 20 24

Retention Time (min)

0

568627

D2BrDF

D2BrDF

STD mix

Stack Gas

2728

#118#105#114

28

27

GC/MS-SIM chromatogram(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.

PeCB(323.8834,325.8805)DiBrDF(323.8785, 325.8765)

#126

14 16 18 20

Retention Time (min)

0

171522

14 16 18 20

Retention Time (min)

0

86858

BrClDF

BrClDF

Sample-B

Sample-A

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.

BrClDF ＞ BrCl2DF, BrClDD ＞ BrCl2DD

Thank you for your Thank you for your attentionattention

Low Low ChlorinatedChlorinated DD/F DD/F in Environmental in Environmental

SamplesSamples

9 10 11 12 13 14 15 16 17 18 19 20 21 22

9 10 11 12 13 14 15 16 17 18 19 20 21 22

9 10 11 12 13 14 15 16 17 18 19 20 21 22

1

4

2

3

MCDF

13 17

1418

1612

3727

36

46

3426

28

24

19

23

137

DiCDF

TrCDF

138

346

129

267

347/

236

137

237/

149

246

248

136 16

813

412

4/14

7

178

148

126

128

247

167

139/

127

146

123

環境大気環境大気Ambient air

環境大気

0

0.05

0.1

0.15

0.2

0.25

0.3

1 3 2 4 13 17 14 18 16

12, 24 37 27 23

36, 28 26

19, 34 46 137

138

136

168

134

124,

147

178

148

123

139,

127

146

167

247

128

126

248

246

237,

149

234,

238

347,

236

267

129

346

燃焼起源

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

1 3 2 4 13 17 14 18 16

12, 24 37 27 23

36, 28 26

19, 34 46 137

138

136

168

134

124,

147

178

148

123

139,

127

146

167

247

128

126

248

246

237,

149

234,

238

347,

236

267

129

346

環境大気の異性体分布 (MCDF ～ TrCDF)環境大気の異性体分布 (MCDF ～ TrCDF)

Ambient air

Incineration (flyash)

Isomer distribution of ambient air(MCDF-TrCDF)

環境大気

00.10.20.30.40.50.60.70.8

2 1 13

27, 2

3, 2

8

14, 1

7 18 16 12 19 137

138

136

124

139,

237 147

123

178

127

128

146

126

129

燃焼起源

0

0.1

0.2

0.3

0.4

0.5

0.6

2 1 13

27, 2

3, 2

8

14, 1

7 18 16 12 19 137

138

136

124

139,

237 147

123

178

127

128

146

126

129

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

Incineration (flyash)

Ambient air

塩素漂白パターンの異性体分布 (MCDF ～TrCDF)

塩素漂白パターンの異性体分布 (MCDF ～TrCDF)

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

1 3 2 4 13 17 14 18 16 12 24 37 27 23 28 26 34

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

137

138

136

168

134

124

147

178

148

123

139

127

146

167

247

128

126

248

246

237/

149

234/

238

347/

236

267

346

28-28-

23-23-

27-27-37-37-

2-2-

238-238-

128-128-

237-237-

1278-TCDF1278-TCDF

2378-TCDF2378-TCDF

238-TrCDF238-TrCDF

237-TrCDF237-TrCDF

128-TrCDF128-TrCDF

37-DiCDF37-DiCDF

27-DiCDF27-DiCDF

23-DiCDF23-DiCDF

28-DiCDF28-DiCDF

Isomer distribution of bleaching process(MCDF-TrCDF)

塩素漂白パターンの異性体分布 (MCDF ～TrCDF)

塩素漂白パターンの異性体分布 (MCDF ～TrCDF)

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.701 3 2 4 13 17 14 18 16 12 24 37 27 23 28 26 34

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

137

138

136

168

134

124

147

178

148

123

139

127

146

167

247

128

126

248

246

237/

149

234/

238

347/

236

267

346

環境大気

0

0.05

0.1

0.15

0.2

0.25

0.3

1 3 2 4 13

17

14

18

16

12,

24

37

27

23

36,

28

26

19,

34

46

137

138

136

168

134

124, 1

47

178

148

123

139, 1

27

146

167

247

128

126

248

246

237, 1

49

234, 2

38

347, 2

36

267

129

346

環境大気の異性体分布 (MCDF ～ TrCDF)環境大気の異性体分布 (MCDF ～ TrCDF)

28-28-

27-27-

238-238-128-128-

237-237-2-2-

124-124-

24-24-

Isomer distribution of ambient air(MCDF-TrCDF)

Isomer distribution of bleaching process(MCDF-TrCDF)

Ambient air

O

Cl

ClCl

O

ClCl

Cl

OH

Cl

OH

Cl

Cl

2,3,8-

1,2,8-+

4-MCP

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

1,2,8-TrCDF

O

Cl

O

OH

OH

Cl

1,4,7-

1,4,9- Cl

Cl

Cl

Cl

Cl

Cl

Cl

OH

OH

O

Cl

1,4,6- Cl

O

Cl

1,4,8- Cl

Cl

Cl

Cl

Cl

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

Authentic standard (1,4,7- : NMR)

2,5-DCP

4-MCP

3-MCP

2-MCP

O-m-

p-

1,4,6-TrCDF

1,4,8-TrCDF

1,4,9-TrCDF

1,4,7-TrCDF

NMR 1,4,7-TrCDF

Authentic standard

H9

H6H8

H2 ; H3