1. Takeshi Nakano1 and Katsunori Anezaki2 2Hokkaido Research Organization
PCB CONGENER PROFILE OF UNINTENTIONAL FORMATION FROM PIGMENT MANUFACTURING PROCESS
Takeshi Nakano1 and Katsunori Anezaki2
1Osaka University
2Hokkaido Research Organization
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

2. Chlorinated Paraffins
PCB CONGENER PROFILE OF UNINTENTIONAL FORMATION FROM PIGMENT MANUFACTURING PROCESS
FeCl3
3,3’-dichlorobenzidine
Chlorinated Paraffins
Diphenyl Silane diol
Organic pigment
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

3. PCB product ND CB-127 CB-126 PCB product CB- 78 ND CB- 79 CB- 11 ND
Strong acid & heat ND
CB-127
CB-126
PCB
product
CB- 78 ND
CB- 79
CB- 11 ND
CB- 77
CB- 35
Unique distributions of major PCB congeners
from 3,3’-dichloro benzidine manufacturing sites.

4. Chlorinated Paraffins
PCB CONGENER PROFILE OF UNINTENTIONAL FORMATION FROM PIGMENT MANUFACTURING PROCESS
FeCl3
3,3’-dichlorobenzidine
Chlorinated Paraffins
Diphenyl Silane diol
Organic pigment
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

5. High Volume Air Sampler
Noise/Vibration absorption rubber
Using chlorinated paraffins containing PCB

6. Chlorinated Paraffins
PCB CONGENER PROFILE OF UNINTENTIONAL FORMATION FROM PIGMENT MANUFACTURING PROCESS
FeCl3
Chlorinated Paraffins
3,3’-dichlorobenzidine
Diphenyl Silane diol
Organic pigment
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

7. dichlorodiphenylsilane
TCPS
DCDPS
CTPS
PCB-6
PCB-3 + D
Cu,Ag
PCB-13
PCB-15
PCB-4
PCB-11
PCB-8 Si
Trichlorophenylsilane
Dichlorodiphenylsilane
Chlorotriphenylsilane
PCB-1
PCB-2
MoCBs
DiCBs
Chlorobenzene
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.
dichlorodiphenylsilane

8. PCB congeners in silicone-based glue (mg/kg)
PCBs
Sample
glue_W Lot.2012
glue_C Lot.2012
glue_C Lot.2013a
glue_W Lot.2013
glue_C Lot.2013b
Congener IUPAC #
Chlorine positions
Manuf. Z #1
2-MoCB
6.0
9.8
1.6
0.82 #2
3-MoCB
9.1 16
7.6
1.7 #3
4-MoCB
8.1 12
6.8
1.4 #4
2,2¢-DiCB
0.064
0.11
0.059
0.024 #6
2,3¢-DiCB
1.0
0.60
0.15 #8
2,4¢-DiCB
0.13
0.28
0.25
0.078
#11
3,3¢-DiCB
0.40
0.59
0.50
0.12
#13
3,4¢-DiCB
0.54
0.68
0.76
#15
4,4¢-DiCB
0.082
0.17
0.035
MoCBs 23 37
4.0
DiCBs
2.0
2.8
2.3
0.55
S PCBs 25 40 18
4.5
(ND)
Blank spaces indicate that none of that component was detected.
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.
PCB congeners in silicone-based glue (mg/kg)

9. PCB congeners in trichlorophenylsilane(mg/kg)
PCBs
Sample
Trichlorophenylsilane (TCPS)
Congener IUPAC #
Chlorine positions
Manuf. A B C D F H #1
2-MoCB
1.7
0.0011
0.023
0.057
0.0083 #2
3-MoCB
0.62
0.0035
0.013
0.020
0.0028 #3
4-MoCB
0.30
0.0098
MoCBs
2.7
0.0081
0.049
0.097
0.021
S PCBs
Blank spaces indicate that none of that component was detected.
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.
PCB congeners in trichlorophenylsilane(mg/kg)

10. PCB congeners in dichlorodiphenylsilane(mg/kg)
Table 3 Concentrations of PCB congeners in dichlorodiphenylsilane(mg/kg)
PCBs
Sample
Dichlorodiphenylsilane (DCDPS)
Congener IUPAC #
Chlorine positions
Manuf. A B D E F G H #1
2-MoCB
0.46 88
1.0 92 10
1.3 #2
3-MoCB
6.5
530
4.9
0.32
410 11
0.65 #3
4-MoCB
5.2
540
4.1
0.16
340
5.9
0.40 #4
2,2¢-DiCB
4.3
5.1
0.047
4.7
7.7
5.3
2.8 #6
2,3¢-DiCB
1.8 58
0.30
2.6 65
5.7
0.88 #8
2,4¢-DiCB
0.55 36
0.20
0.77 28
1.9
0.35 #9
2,5-DiCB
0.013
0.062
#11
3,3¢-DiCB
0.25 61
0.38
0.040 29
0.055
#13
3,4¢-DiCB
0.13 77
0.39
0.19 26
0.21
#15
4,4¢-DiCB
0.011 62
0.28
0.037
#16
0.014
#17
2,2',4-TrCB
0.0046
0.12
0.043
#18
2,2',5-TrCB
0.016
0.10
0.041
0.084
#20/33
2,3,3'-TrCB
0.078
2',3,4-TrCB
#25
2,3',4-TrCB
0.032
0.0082
#26
2,3',5-TrCB
0.030
0.0076
#28
2,4,4'-TrCB
3.7
0.52
0.042
#31
2,4',5-TrCB
0.33
0.066
#32
0.080
0.021
#37
3,4,4'-TrCB
0.071
0.019
#41
0.0061
#44
0.0034
#47/48
0.052
2,2',4,5-TeCB
#49
#52
2,2',5,5'-TeCB
#53
0.0019
#64
2,3,4',6-TeCB
0.0027
#65/75
0.0044
#66
0.0071
#74
2,4,4',5-TeCB
0.010
MoCBs 12
1200
9.4
1.5
840 27
2.4
DiCBs
7.0
300
1.6
8.1
160 13
TrCBs
4.5
0.73
TeCBs
0.11
S PCBs 19
1500
9.6
1000 41
Blank spaces indicate that none of that component was detected.
Cluster congeners that co-elute on HT8-PCB column is expressed by "/".
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.
PCB congeners in dichlorodiphenylsilane(mg/kg)

11. Chlorotriphenylsilane (CTPS) PCB congeners in chlorotriphenylsilane
PCBs
Sample
Chlorotriphenylsilane (CTPS)
Congener IUPAC #
Chlorine positions
Manuf. A B C F G H #1
2-MoCB
0.0072
0.060
0.0068
0.17
0.065
0.075 #2
3-MoCB
0.0055
0.010
0.11
0.036
0.077 #3
4-MoCB
0.018
0.12
0.0022
0.47
0.24
0.19 #8
2,4¢-DiCB
0.0088
0.021
0.0070
#11
3,3¢-DiCB
0.0012
#13
3,4¢-DiCB
0.0080
0.0085
0.0035
#15
4,4¢-DiCB
0.023
0.040
0.28
0.50
0.15
#28
2,4,4'-TrCB
#37
3,4,4'-TrCB
#66
0.016
MoCBs
0.031
0.25
0.019
0.75
0.34
DiCBs
0.30
0.53
0.16
TrCBs
0.0038
0.10
TeCBs
S PCBs
0.054
1.1
0.98
0.51
Blank spaces indicate that none of that component was detected.
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.
PCB congeners in chlorotriphenylsilane

12. Diphenylsilanediol (DPSDO) PCB congeners in diphenylsilanediol (mg/kg)
PCBs
Sample
Diphenylsilanediol (DPSDO)
Congener IUPAC #
Chlorine positions
Manuf. A G H #1
2-MoCB
0.036
1.1
0.89 #2
3-MoCB
0.049 11 38 #3
4-MoCB
8.7 33 #4
2,2¢-DiCB
0.16
2.0 #6
2,3¢-DiCB
1.6 13 #7
2,4-DiCB #8
2,4¢-DiCB
0.79
4.7 #9
2,5-DiCB
0.0071
#11
3,3¢-DiCB
2.1
#13
3,4¢-DiCB
2.8
#15
4,4¢-DiCB
0.98
2.3
#28
2,4,4'-TrCB
0.016
MoCBs
0.12 21 71
DiCBs
8.4 44
TrCBs
S PCBs 30
120
Blank spaces indicate that none of that component was detected.
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.
PCB congeners in diphenylsilanediol (mg/kg)

13. Boiling point of PCB homologues and chlorophenylsilanes
Table 6 Boiling point of PCB homologues and chlorophenylsilanes
boiling point (°C)
ref.
chlorophenylsilanes
Trichlorophenylsilane(TCPS)
201
[19]
Dichlorodiphenylsilane(DCDPS)
305
[20]
Chlorotriphenylsilane(CTPS)
378
[21]
PCB homologuesa
mono-CBs
285
[22]
di-CBs
312
Tri-CBs
337
Tetra-CBs
360
a Average properties of all isomers in group.
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.
Boiling point of PCB homologues and chlorophenylsilanes

14. UNINTENTIONAL FORMATION OF PCB FROM CHEMICAL MANUFACTURING PROCESS
FeCl3
3,3’-dichlorobenzidine
Chlorinated Paraffins
Diphenyl Silane diol
Organic pigment
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

15. in Commercial Pigments
Concentrations and Congener Profiles of Polychlorinated Biphenyls, Pentachlorobenzene, and Hexachlorobenzene
in Commercial Pigments
Pigment: Generic term for water-insoluble or oil-insoluble powder used for coloring. Organic pigments are those comprising organic compounds.

16. A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process.
In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard (50ppm).
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

18. PCB congener profiles of
Results
PCB congener profiles of
azo pigment
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

19. Ｎ－acetoacetyl aniline
NaNO2, HCl
3,3’-dichloro benzidine
diazonium
Ｎ－acetoacetyl aniline
diazonium
pigment production
disazo

20. 2,2’,5,5’- tetrachloro benzidine
CB-52(25-25)
(CuCl2)
NaNO2, HCl
ザンドマイヤー反応
芳香族ジアゾニウム塩をフッ素を除くハロゲン化銅(I)あるいはシアン化銅(I)、チオシアン化銅(I)の存在下に生成させ、加温分解すると、元のアミノ基の位置が対応するハロゲンあるいはシアノ基・チオシアノ基で置き換えられた置換アリール体が得られる。この反応は1884年に発見した T. Sandmeyer に因んでザンドマイヤー反応と呼ばれる。この反応は一電子移動を含むラジカル的な機構を経て進行し、中間体としてアリール銅化合物を経由すると考えられている。
Ar-N+≡N + CuX → Ar-X + Cu+ + N2↑ (X = Cl, Br, CN, SCN) ハロゲンがフッ素の場合はフッ化銅(II)がフッ化銅(I)に比べて安定なため反応が進行しない（フッ化銅(I) は放置すると不均化を起こしてフッ化銅(II)と金属銅となる）。
CB-101(245-25)
2,2’,5,5’- tetrachloro benzidine
Sandmeyer reaction
Ar-N+≡N + CuX → Ar-X + Cu+ + N2↑
CB-153( )

21. PCB congeners in pigment (disazo) permanent yellow lemon; PY81;
2,2’,5,5 ’- tetrachloro benzidine
　PCB congeners in pigment (disazo)
permanent yellow lemon; PY81;

22. - Organic Pigment Pigment-A Pigment-B D2CB T3CB T4CB #11(3-3)
#35(34-3)
#77
Pigment-A
M1CB
P5CB
(N.D.)
(34-34)
#101
(ﾌﾗｸﾞﾒﾝﾄｲｵﾝ)
#52
Pigment-B
(25-25)
(245-25)

23. analysis of pigment(1) : Pigment Orange 13
azo-type pigment
Company B 　 pyrazolone ogange(C.I. PO13)
Total PCBs mg/kg(ppm) Cl
Only #11, #35, and #77 were found.
# mg/kg
#11 accounting for over 80% of the total PCBs. Cl
# mg/kg Cl Cl
NH2
H2N
# mg/kg
3,3’-dichlorobenzidine
#77 is a dioxin-like PCB(DL-PCB).
The dioxin concentration calculated using the TEF for this congener was 49pg-TEQ/g

24. analysis of pigment(2) : Pigment Yellow 81
azo-type pigment
Company B 　 benzidine yellow (C.I. PY81)
Total PCBs mg/kg(ppm) Cl
# mg/kg
#52 : >99% of total PCBs. Cl
# mg/kg Cl
NH2
H2N Cl
# Tr (major)
2,2’,5,5’-tetrachlorobenzidine Cl
# Tr (major)

25. azo-type pigment Pigment yellow12 （benzidine yellow） raw material CH3CO CO
CH3
CH3 Cl
H3C
HNOC CH
N=N
N=N CH
CONH
CH3 Cl
Pigment yellow12
（benzidine yellow）
raw material Cl Cl
NH2
H2N
#11
3,3’-dichlorobenzidine Cl
#35
#77 Cl

26. azo-type pigment Pigment yellow81 （benzidine yellow） raw material Cl
N=N CH CO
CH3
CONH
HNOC
H3C
Pigment yellow81
（benzidine yellow）
raw material Cl Cl
NH2
H2N
#52
2,2’,5,5’-tetrachlorobenzidine Cl Cl
#101
#153

27. PCB congener profiles of azo pigment
azo-type pigment
PCB congener profiles of azo pigment

28. PCB congener profiles of phthalocyanine pigment
Results
PCB congener profiles of phthalocyanine pigment
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

29. phthalocyanine-type pigment
By-product
raw material Cl
phthalic anhydride
urea
copper chloride
PeCBz
pigment blue 15
(phthalocyanine blue) Cl
chlorination D
HCB
pigment green 7
(phthalocyanine green)
pigment green 7 Cl
#209 Cl
#208
highly chlorinated PCBs

30. Example of analysis of pigment(3)
phthalocyanine-type pigment
Company B 　 phthalocyanine green (C.I. PG7)
Total PCBs mg/kg(ppm) Cl
# mg/kg
#209 accounting for over 99% of the total PCBs. Cl
# mg/kg Cl Cl
#202,#206,#208 Tr
Pentachlorobenzene
Hexachlorobenzene

31. PCB congener profiles of phthalocyanine pigment
pigment green 7
phthalocyanine-type pigment
pigment blue 15
PCB congener profiles of phthalocyanine pigment

32. Congener pattern Pigment yellow81 pyrazolone ogange
#52
#101
#153
#35
#77
#11
pyrazolone ogange
#209
phthalocyanine green
KC400
Congener pattern

33. PCB congener profiles of diketo-pyrrolo-pyrrole pigments
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

34. PCB congener profiles of dioxazine violet pigments
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

35. unintentional formation
pigment
solvent
PV23 Δ
unintentional formation

36. CHL: Chloranil / AEC : 3-amino N-ethyl-carbazole
m-DCB
0.25
o-DCB
<0.1
o-DCB + CHL + AEC 30
o-DCB + AEC 1
PV-23
O-DCB +CHL 0
O-DCB +AEC 1
O-DCB + CHL+AEC 30
V-70L
o-DCB + CHL
<0.1
p-DCB
CHL: Chloranil / AEC : 3-amino N-ethyl-carbazole

37. + 3-amino N-ethylcarbazole
PV23
o-DCB + Chloranil
trace
PCB- 56
PCB- 77
o-DCB + 3-amino
N-ethyl-carbazole
PCB- 40
23- 34
34- 34
23- 23
o-DCB only
trace
PV23-DCB
PCB- 40
PCB- 56
PCB- 77
o-DCB + Chloranil
+ 3-amino N-ethylcarbazole
23- 23
23- 34
34- 34

38. V-70L : rac-2,2'-Azobis[(2R*)-2,4-dimethyl-4-methoxypentanenitrile]
40min
o-DCB + V-70L
Radical initiator
20min
o-DCB + V-70L
VP-70L
Radical initiator
V-70L : rac-2,2'-Azobis[(2R*)-2,4-dimethyl-4-methoxypentanenitrile]

39. m-DCB + V-70L
o-DCB + V-70L
PV23

40. PCB FORMATION FROM PCBz via different PCBz radicals
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

41. Only one PCB isomer Formation
from one PCBz radical
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

42. one PCB isomer formation
V-70L Δ
CB-52 (25-25)
p-dichlorobenzene
V-70L Δ
CB155 ( )
1,3,5-trichlorobenzene

43. 3 PCB isomers Formation from 2 PCBz radicals
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

44. CB-56 > CB-77 > CB-40 o-dichlorobenzene3 11 2
V-70L Δ
CB-56 (23-34)
CB-77 (34-34)
CB-40 (23-23)
CB-5 (23-)
CB-12 (34-)
o-dichlorobenzene

45. CB-157 > CB-128 > CB-169 1,2,3-trichlorobenzene
V-70L Δ
1,2,3-trichlorobenzene

46. trichlorobenzene  HxCB
CB-157 > CB-128 > CB-169
124-TCBz ->HxCB
135-TCBz ->HxCB
#155 ( )
CB-157
( )
123-TCBz ->HxCB
CB128
( )
CB-169 ( )
CB-169 ( )
CB155 ( )
Window-PCB
trichlorobenzene  HxCB

47. 6 PCB isomers Formation from 3 PCBz radicals
A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard.

48. CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15
V-70L Δ
CB-4 (2-2)
CB-6 (2-3)
CB-11 (3-3)
CB-8 (2-4)
CB-13 (3-4)
CB-15 (4-4)
chlorobenzene  DiCB

49. CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15
#6 (2-3)
#13 (3-4)
#8 (2-4)
#11 (3-3)
#4 (2-2)
#15 (4-4)
#12
(34-) #9
(25-) #8
(2-4)
#11
(3-3)
#10
(26-) #4
(2-2)
#15
(4-4)
chlorobenzene  DiCB

50. CB-68 > CB-47 > CB-73, CB-51 > CB-80 > CB-54
V-70L Δ
m-dichlorobenzene

51. m-DCBz  TeCB #68 #47 #73 #51 #80 #54 #54 #49 #57 #52 #44 #70 #74 #66
#78
#81
#79
#77
m-DCBz  TeCB

52. CB-157 > CB-128 > CB-169 1,2,3-trichlorobenzene
V-70L Δ
1,2,3-trichlorobenzene

53. trichlorobenzene  HxCB
CB-157 > CB-128 > CB-169
124-TCBz ->HxCB
135-TCBz ->HxCB
#155 ( )
CB-157
( )
123-TCBz ->HxCB
CB128
( )
CB-169 ( )
CB-169 ( )
CB155 ( )
Window-PCB
trichlorobenzene  HxCB

54. CB-146, CB-149, CB-135 > CB-153, CB-136, CB-133
V-70L Δ
1,2,4-trichlorobenzene

55. 1,2,4-TrCBz  HxCB CB-149 CB146 (236-245) (235-245) CB-135 (235-236)
( )
CB-136
( )
CB-153
( )
1,2,4-TrCBz  HxCB

56. from 3,3’-dichlorobenzidine contain #11, #35, #77
- Results
pigment
from 3,3’-dichlorobenzidine
contain #11, #35, #77
[ such as PO-13,14 PY-12,13,14,17,55,83 ]
from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
[ such as PY-81 ]
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

57. (before chlorination) phthalocyanine-type pigment contain HCBz, PeCBz
- Results
(before chlorination)
phthalocyanine-type pigment
contain HCBz, PeCBz
[ such as PB-15 ]
(after chlorination)
contain #209, HCBz, PeCBz
[ such as PG-7 ]
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

58. from p-chlorobenzonitrile contain #8, #13, #15, #4, #6, #11
- Results
pigment
from p-chlorobenzonitrile
contain #8, #13, #15, #4, #6, #11
[ such as PR-254, 255 ]
from o-dichlorobenzene as solvent
contain #56, #77, #40
[ such as PV-23 ]
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

59. - pigment from 3,3’-dichlorobenzidine contain #11, #35, #77
- Results
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- pigment from o-chlorobenzene as solvent
contain #40, #56, #77
- phthalocyanine-type pigment
contain #209, PeCBz, HCBz
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

60. However, the New Jersey effluent was more purely 3,3’-DiCB.
3,3’-DiCB has been associated with 3,3’-dichlorobenzidine salts which are intermediates in the manufacture of yellow pigments.
The pigment factory also discharged two other congeners at high concentrations, 3,3’,4-TriCB and the coplanar 3,3’,4,4’-TeCB. Coplanar 3,3’,4,4’,5- PeCB was also seen in the discharge at higher than usual proportions.
However, the New Jersey effluent was more purely 3,3’-DiCB.
Identification of a novel PCB source through analysis
of 209 PCB congeners by US EPA modified method 1668
Simon Litten et al, Chemosphere, 46, (2002)
The highest PCB concentration (110 ng/l) seen in a
survey of final effluents from all 14 New York City
wastewater treatment plants (WPCFs) as well as four
other upstate WPCFs discharging to the Hudson River
consisted of 85% 3,30-DiCB. Furthermore, 3,30-DCB
was found to constitute more than 90% of 250 ng/l PCB
in effluent from a WPCF in New Jersey. Identification of
this non-Aroclor congener was confirmed for three
samples using full scan GC/MS. The mass spectrum
observed exactly matched those of a dichlorobiphenyl
and the retention time matched that of the 3,30-isomer.
This congener has not been previously sought in New
York State’s environmental monitoring because it was
believed to be absent from commercial PCB mixtures
(Shultz et al., 1979), not a coplanar congener, and unlikely
to be a dechlorination product (Ye et al., 1992,
Rhee, 1993). 3,30-DiCB has been associated with 3,30-
dichlorobenzidine salts which are intermediates in the
manufacture of diarylide yellow pigments (Erickson,
1977).
3,30-DiCB contributed 32% and 80% of total PCB at
two other New York treatment plants, one that dewatered
the sludge from the primary site, and from
another plant also treating pigment wastes. While 3,30-
DiCB is present at less than 0.05% in Aroclors (Shultz et
al., 1979), the median ambient dissolved phase relative
abundance was 2.4% and its median solid phase relative
abundance was 0.58%. Bottom sediments throughout
the harbor contain 3,30-DiCB at abundances similar to
those seen in suspended sediments.
PISCES deployed at the pigment plant’s discharge to
the sewer system, at five main trunks in the collection
system and in the influent to the WPCF (Table 1) confirmed
the pigment factory as the principal source of
3,30-DiCB. The pigment factory also discharged two
other congeners at high concentrations, 3,30,4-TriCB
and the coplanar 3,30,4,40-TeCB. Coplanar 3,30,4,40,5-
PeCB was also seen in the discharge at higher than usual
proportions. However, the New Jersey effluent was more
purely 3,30-DiCB.
Fig. 1shows the percent contribution of all 12 coplanar
PCBs and just 3,30,4,40,5-PeCB to total dioxin/
furan/PCB TEQ at the New York WPCFs. The sample
with a total highest TEQ (2030 fg/l) where PCBs and
3,30,4,40,5-PeCB contributed 88% and 71% respectively
of the TEQ was the one receiving the pigment waste.
Some pigment manufacture contributes significant
concentrations of non-Aroclor PCB and dioxin toxicity.
As the relative impact of currently produced non-
Aroclor PCB will increase with time, investigators may
wish to broaden their congener lists to include substances
that were very minor constituents of commercial
PCB mixtures.

61. Simon Litten et al, Organohalogen compounds, 46, 369-372(2000)
A working hypothesis is that lUPAC 11 originates from a commonly used item, perhaps printing ink, and is seen in greater abundances from sites where the base material is manufactured, handled, or spilled.
One other observation is that the site showing the maximum concentration of lUPAC 11 was also the site showing the maximum concentration of lUPAC 126. Whether these results are related or are merely a coincidence of separate events in the same service area is as yet unknown.
DETERMINATION OF PCDD/PCDF AND 209 PCB CONGENERS IN NEW YORK HARBOR AND HUDSON BASIN USING FILTRATION/XAD INTEGRATING SAMPLERS AND US EPA METHODS 1668 AND 1613B
Simon Litten et al, Organohalogen compounds, 46, (2000)
PCB　Simon Litten
Among the individual PCB congeners resolved by the modified Method 1668 is lUPAC 11
(3,3'-DiCB). Identification of RJPAC 11 was confirmed by examining three samples using low
resolution open-scan GC/MS. The fragmentation pattems observed exactly matched those of
dichlorobiphenyl and the elution time matched that ofthe 3,3'- isomer. While the literature
indicates that lUPAC 11 is present at less than 0.05% in Aroclors'', the median ambient dissolved
phase ratio (from XAD) was 2.4% and its median solid phase (from filters) was 0.58%. Ratios
from final freated wastewater were similar- 1.8% from XAD and 0.99% from filters. However,
three wastewater sites show lUPAC 11 to constitiite from SO to 92% ofthe total dissolved (XAD)
PCBs. The sample with 92% lUPAC 11 had a total of 32 ng/L dissolved (XAD) PCB. The NYS
Water Qualily Slandard (WQS) for PCB (for human consumption offish) is O.OOI ng/L.
lUPAC 11 has been associated with 3,3'-dichlorobenzidine salts which are intermediates in tiie
manufacture of dry phthalocyanine blue, phthalocyanine green, and diarylide yellow pigments'.
Phthalocyanine blue and green are used for mbber, plastics, inks, paints, coatings, and floor
coverings. Phthalocyanine blue (called "phthalo blue") is commonly used for cyan and diarylide
yellow is used for yellow in newspaper printing''.
A working hypothesis is that lUPAC 11 originates from a commonly used item, perhaps printing
ink, and is seen in greater abundances from sites where the base material is manufactured,
handled, or spilled.
One other observation is that the site showing the maximum concenfration of lUPAC 11 was also
the site showing the maxunum concentration of lUPAC 126. Whether these results are related or
are merely a couicidence of separate events in the same service area is as yet unknown.

62. Seasonal variations of PCBs, DiCBs, and #11 in ambient air
- Results
Seasonal variations of PCBs, DiCBs, and #11 in ambient air
( Sapporo city, Japan)
April 2005 ~ March 2011
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

63. Seasonal variations of PCBs, DiCBs, and #11 in ambient air
PCBs Conc. (pg/m3)
Temperature(oC), DiCBs、#11Conc. (pg/m3)
Seasonal variations of PCBs, DiCBs, and #11 in ambient air
( Sapporo city : April 2005 ~ March 2011)
PCBs: pg/m3, ave:361 pg/m3
#11: pg/m3, ave:11.4 pg/m3

64. Anezaki, Nakano :ESPR (2013)
Sapporo
#11 / ΣPCBs
Ratio (%)
#52 / ΣPCBs
Muroran
#11 / ΣPCBs
Ratio (%)
#52 / ΣPCBs
Anezaki, Nakano :ESPR (2013)

65. Anezaki, Nakano :ESPR (2013)
Sapporo
#11 / DiCBs
Ratio (%)
#52 / TeCBs
Muroran
#11 / DiCBs
Ratio (%)
#52 / TeCBs
Anezaki, Nakano :ESPR (2013)

66. BAT (Best Available Techniques) BEP (Best Environmental Practices)
- Conclusion
use
BAT (Best Available Techniques)
BEP (Best Environmental Practices)
to reduce emissions and human risk.
organic pigment product 22,510t (2010)
cosmetics
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

67. organic pigment product 22,510t (2010) use
- Conclusion
organic pigment product 22,510t (2010)
use
BAT (Best Available Techniques)
BEP (Best Environmental Practices)
to reduce emissions and human risk.
paint ink plastic
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

68. ICAEC2014 Nov. 24-26, 2014 Chulabhorn Institute Bangkok
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

69. - 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

70. Thank you for your attention
感谢您的关注
Thank you for your attention

73. PCBs in commercial pigment for oil painting

74. - pigment from 3,3’-dichlorobenzidine contain #11, #35, #77
- Results
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- pigment from o-chlorobenzene as solvent
contain #40, #56, #77
- phthalocyanine-type pigment
contain #209, PeCBz, HCBz
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

75. 3,3’-ジクロロベンジジン
（ジアゾニウム塩）
3,3’-ジクロロビフェニル（PCB-11)

76. 3,3’,4,4’-テトラクロロビフェニル（PCB-77)

77. BAT (Best Available Techniques) BEP (Best Environmental Practices)
- Conclusion
use
BAT (Best Available Techniques)
BEP (Best Environmental Practices)
to reduce POPs emissions.
- 有機顔料中の副生PCB異性体を分析し,
- pigment from 3,3’-dichlorobenzidine
contain #11, #35, #77
- pigment from 2,2’,5,5’-tetrachlorobenzidine
contain #52, #101, #153
- phthalocyanine-type pigment
#209
顔料製造の過程と密接な関連が推定された。
- 顔料中のPCBは、精製過程で残ったものと推測され、これら、副反応で生成する異性体は、排水や、廃棄物として、環境への負荷が起こる例も報告されており、負荷低減への対策も必要である。

78. 顔料由来の異性体と
環境試料中のPCB

79. PCB製品 底質 PCB-11 水質 雨水 大気 中野ら, 環境化学討論会要旨集 P-281 (2001)
一般に、大気中PCNは燃焼起源の異性体の存在が特徴的であり、PCN製品の異性体組成と燃焼起源の異性体の混合した様相を示すのに対して、PCBでは大気中の異性体組成がPCB製品と酷似している。しかし、PCBの低塩素成分に注目すると、PCB製品と比較して2,2'-(#4)/2,6-(#10)の相対的減少と3,3'-(#11)の相対的増加が見られた。
雨水、降下物、底質中でも２塩素、３塩素化PCBの異性体分布では、PCB製品と比較してオルト位に塩素のない異性体3,3'-(#11)、3,4-(#12)、3,4'-(#13)、 3,3’,4-(#35)、 3,4,4'-(#37)が相対的に増加していた。
河口域、海域では、底質、生物中の#180/#118の存在比、#189/#118の存在比が、河川底質と比較して相対的に高くなる傾向があった。モニタリング時に測定されるコプラナPCBの14異性体の中で、#180、#170はKC600の起源推定に利用しうる。
海域と河川の底質を比較すると、１塩素～３塩素のPCBは類似の異性体分布を示すが、海域底質の#11や#37の含有率は河川よりかなり大きくなる傾向が見られた。雨や大気といった大気系の試料で見られる#11の含有率の高さが、何に由来するのかは、さらなる研究が必要である。環境大気中での光分解によるオルト位の脱塩素(#26/#20->#11)が、ひとつのプロセスとして推定される。底質中でも、4塩素以上のPCB異性体のパターンは、PCB製品の異性体組成に類似している。低塩素成分での異性体分布の変化が、底質中の嫌気的微生物分解によるのか、燃焼過程や化学プロセスなど、全く別の発生源からの負荷であるのか、不明である。EPAの水質モニタリング調査で、#11の存在割合の高い試料が、印刷インクに原料に使用される、3,3'-ジクロロベンジジン由来であることを報告している [1]。1980年当時の海域底質では、#11の含有率はPCB製品と同様の割合を示し、決して高くないので、#11がPCB起源推定の、新たな指標となりうると思われる。 大気
図　PCB製品および環境試料中のDi-TrCB異性体分布 #10/(2,6-)#4(2,2'-), #8(2,4-)/#5(2,3-), #11(3,3'-), #12(3,4-)/#13(3,4'), #15(4,4'-),
#18(2,2',5-)/#17(2,2',4-), #16(2,2',3-)/#32(2,4',6-), #26(2,3',5-), #25(2,3',4-),#31(2,4',5-)/#28(2,4,4'-),#33(2',3,4-)/#20(2,3,3'-),#35(3,3',4-), #37(3,4,4'-)
中野ら, 環境化学討論会要旨集 P-281 (2001)

80. 中野武　 50才
Simon Litten

81. PCB製品 底質 PCB-11 水質 雨水 大気 中野ら, 環境化学討論会要旨集 P-281 (2001)
一般に、大気中PCNは燃焼起源の異性体の存在が特徴的であり、PCN製品の異性体組成と燃焼起源の異性体の混合した様相を示すのに対して、PCBでは大気中の異性体組成がPCB製品と酷似している。しかし、PCBの低塩素成分に注目すると、PCB製品と比較して2,2'-(#4)/2,6-(#10)の相対的減少と3,3'-(#11)の相対的増加が見られた。
雨水、降下物、底質中でも２塩素、３塩素化PCBの異性体分布では、PCB製品と比較してオルト位に塩素のない異性体3,3'-(#11)、3,4-(#12)、3,4'-(#13)、 3,3’,4-(#35)、 3,4,4'-(#37)が相対的に増加していた。
河口域、海域では、底質、生物中の#180/#118の存在比、#189/#118の存在比が、河川底質と比較して相対的に高くなる傾向があった。モニタリング時に測定されるコプラナPCBの14異性体の中で、#180、#170はKC600の起源推定に利用しうる。
海域と河川の底質を比較すると、１塩素～３塩素のPCBは類似の異性体分布を示すが、海域底質の#11や#37の含有率は河川よりかなり大きくなる傾向が見られた。雨や大気といった大気系の試料で見られる#11の含有率の高さが、何に由来するのかは、さらなる研究が必要である。環境大気中での光分解によるオルト位の脱塩素(#26/#20->#11)が、ひとつのプロセスとして推定される。底質中でも、4塩素以上のPCB異性体のパターンは、PCB製品の異性体組成に類似している。低塩素成分での異性体分布の変化が、底質中の嫌気的微生物分解によるのか、燃焼過程や化学プロセスなど、全く別の発生源からの負荷であるのか、不明である。EPAの水質モニタリング調査で、#11の存在割合の高い試料が、印刷インクに原料に使用される、3,3'-ジクロロベンジジン由来であることを報告している [1]。1980年当時の海域底質では、#11の含有率はPCB製品と同様の割合を示し、決して高くないので、#11がPCB起源推定の、新たな指標となりうると思われる。 大気
図　PCB製品および環境試料中のDi-TrCB異性体分布 #10/(2,6-)#4(2,2'-), #8(2,4-)/#5(2,3-), #11(3,3'-), #12(3,4-)/#13(3,4'), #15(4,4'-),
#18(2,2',5-)/#17(2,2',4-), #16(2,2',3-)/#32(2,4',6-), #26(2,3',5-), #25(2,3',4-),#31(2,4',5-)/#28(2,4,4'-),#33(2',3,4-)/#20(2,3,3'-),#35(3,3',4-), #37(3,4,4'-)
中野ら, 環境化学討論会要旨集 P-281 (2001)

82. 図 底質、表層水中の2塩素化ﾋﾞﾌｪﾆｰﾙのSIMｸﾛﾏﾄｸﾞﾗﾑ
河川水
【結果および考察】
底質、表層水中の2塩素化ﾋﾞﾌｪﾆｰﾙのﾏｽｸﾛﾏﾄｸﾞﾗﾑを一例を図1に示した。
表層水で、2塩素化ﾋﾞﾌｪﾆｰﾙに占める#11の割合は1.9−22%の範囲で、平均は8.5％であった。また全PCB濃度に対する#11の比率は0.4－3.5（平均1.2%）の範囲にあった。また、#37および#77は3塩素化および4塩素化ﾋﾞﾌｪﾆｰﾙ中でそれぞれ、1.4−5.9%（平均3.0%）、0.7−1.2%（0.9%）の割合で検出された。
底質では#11/2塩素化ﾋﾞﾌｪﾆｰﾙは、2.7−94%（平均41%）であった。また、全PCBに占める#11の割合は0.18〜33%（平均4.6%）で、全PCB濃度に対して無視できないﾚﾍﾞﾙの地点があった。
表層水、底質中の#11の影響を評価するため、#37が3塩素化ﾋﾞﾌｪﾆｰﾙに占める割合、および#77が4塩素化ﾋﾞﾌｪﾆｰﾙに占める割合について考察した。表層水あるいは底質で、#11/2塩素化ﾋﾞﾌｪﾆｰﾙが高い方から3地点と低い方から3地点のﾃﾞｰﾀを抽出した。表層水で#11/2塩素化ﾋﾞﾌｪﾆｰﾙが高い3地点と低い3地点における#37/3塩素化ﾋﾞﾌｪﾆｰﾙの値は、4.7および2.5%で、#11/2塩素化ﾋﾞﾌｪﾆｰﾙが高いと、#37が3塩素化ﾋﾞﾌｪﾆｰﾙに占める割合は明らかに高くなっていた。#77/4塩素化ﾋﾞﾌｪﾆｰﾙの値はそれぞれ1.2、1.0%で#37ほど顕著ではないが若干の増加がみられた。
底質で、#11/2塩素化ﾋﾞﾌｪﾆｰﾙが高い3地点と低い3地点の#37/3塩素化ﾋﾞﾌｪﾆｰﾙはそれぞれ8.6、4.9%、低い3地点での#77/4塩素化ﾋﾞﾌｪﾆｰﾙの値は2.0、1.3で#11/2塩素化ﾋﾞﾌｪﾆｰﾙが高いとやはり#77が4塩素化ﾋﾞﾌｪﾆｰﾙに占める割合も増加していた。
PCB製品に極微量しか存在しない#11が環境中からかなりの頻度で検出され、#11は構造的に類似する#37および#77と何らかの関係があることが示唆された
河川水
図　底質、表層水中の2塩素化ﾋﾞﾌｪﾆｰﾙのSIMｸﾛﾏﾄｸﾞﾗﾑ
#10/(2,6-)#4(2,2'-), #8(2,4-)/#5(2,3-), #11(3,3'-), #12(3,4-)/#13(3,4'), #15(4,4'-)
角谷ら, 環境化学討論会要旨集 P-281 (2001)

83. Simon Litten et al, Chemosphere, 46, 1457-1459(2002)
Identification of a novel PCB source through analysis
of 209 PCB congeners by US EPA modified method 1668
Simon Litten et al, Chemosphere, 46, (2002)
PISCES survey, 7/27/00–8/2/00 to locate sources of PCB congeners (ng/l)
Total PCB
PCB-11
PCB-35
PCB-77
PCB-126
TEQ(fg/L)
Pigment discharge
4200
3600
380
190
1.6
18000
WPCF influent
520
490
2.3
2.5
0.01
150
Trunk1 18
0.07
<0.001 15
Trunk2 12
0.4
0.02
<0.0004 13
Trunk3
0.6
0.03 8
Trunk4 3
0.08
0.04
0.05 2
Trunk5 1
0.2
0.001
The highest PCB concentration (110 ng/l) seen in a
survey of final effluents from all 14 New York City
wastewater treatment plants (WPCFs) as well as four
other upstate WPCFs discharging to the Hudson River
consisted of 85% 3,30-DiCB. Furthermore, 3,30-DCB
was found to constitute more than 90% of 250 ng/l PCB
in effluent from a WPCF in New Jersey. Identification of
this non-Aroclor congener was confirmed for three
samples using full scan GC/MS. The mass spectrum
observed exactly matched those of a dichlorobiphenyl
and the retention time matched that of the 3,30-isomer.
This congener has not been previously sought in New
York State’s environmental monitoring because it was
believed to be absent from commercial PCB mixtures
(Shultz et al., 1979), not a coplanar congener, and unlikely
to be a dechlorination product (Ye et al., 1992,
Rhee, 1993). 3,30-DiCB has been associated with 3,30-
dichlorobenzidine salts which are intermediates in the
manufacture of diarylide yellow pigments (Erickson,
1977).
3,30-DiCB contributed 32% and 80% of total PCB at
two other New York treatment plants, one that dewatered
the sludge from the primary site, and from
another plant also treating pigment wastes. While 3,30-
DiCB is present at less than 0.05% in Aroclors (Shultz et
al., 1979), the median ambient dissolved phase relative
abundance was 2.4% and its median solid phase relative
abundance was 0.58%. Bottom sediments throughout
the harbor contain 3,30-DiCB at abundances similar to
those seen in suspended sediments.
PISCES deployed at the pigment plant’s discharge to
the sewer system, at five main trunks in the collection
system and in the influent to the WPCF (Table 1) confirmed
the pigment factory as the principal source of
3,30-DiCB. The pigment factory also discharged two
other congeners at high concentrations, 3,30,4-TriCB
and the coplanar 3,30,4,40-TeCB. Coplanar 3,30,4,40,5-
PeCB was also seen in the discharge at higher than usual
proportions. However, the New Jersey effluent was more
purely 3,30-DiCB.
Fig. 1shows the percent contribution of all 12 coplanar
PCBs and just 3,30,4,40,5-PeCB to total dioxin/
furan/PCB TEQ at the New York WPCFs. The sample
with a total highest TEQ (2030 fg/l) where PCBs and
3,30,4,40,5-PeCB contributed 88% and 71% respectively
of the TEQ was the one receiving the pigment waste.
Some pigment manufacture contributes significant
concentrations of non-Aroclor PCB and dioxin toxicity.
As the relative impact of currently produced non-
Aroclor PCB will increase with time, investigators may
wish to broaden their congener lists to include substances
that were very minor constituents of commercial
PCB mixtures.

84. Simon Litten et al, Chemosphere, 46, 1457-1459(2002)
人口水路１　18ng/L
Simon Litten et al, Chemosphere, 46, (2002)

85. 安藤良ら, 名古屋市環境科学研究所所報第38号 31-40(2008)
　GC/MS/MS法による底質及び魚類のポリ塩化ビフェニル類(PCBs)の全異性体分析方法の検討を行うとともに,底質および魚類中のPCBs 異性体の汚染状況についても調査した.GC/MS/MS法によるPCBs測定は選択的に塩素化数別の定量に優れ,また,各異性体成分のIDL(装置検出限 界)値が1から2ug/Lの感度であることから,底質及び魚類におけるPCBs異性体分析の測定に適用が可能であった.
　底質の汚染状況は TeCBs(四塩化ビフェニル類)が主成分であった.PCBs異性体はPCB製品の構成成分と類似していたが,DiCBsの分布率が高い水域があ り,PCBs製品に含まれていない#11の割合が高かった.魚類の汚染状況はTeCBsとPeCBsが主成分で,PCB製品の構成成分と類似していなかっ た.PCBs異性体により魚類への蓄積が異なるためで,#28,#31,#66,#118,#99,#153,#138等の分布率が著しく高かった
安藤良ら,　名古屋市環境科学研究所所報第38号 31-40(2008)

86. 底質中のPCB分析

87. 表 #11の測定値比較 分析方法 #11(μg/kg) 加圧流体抽出法 0.13 ソックスレー抽出法 0.1 加熱アルカリ分解法(乾泥)
表　#11の測定値比較
分析方法
#11(μg/kg)
加圧流体抽出法
0.13
ソックスレー抽出法
0.1
加熱アルカリ分解法(乾泥)
0.3
加熱アルカリ分解法(湿泥) 16
松木司ら,　広島市衛生研究所年報第24号 (2005)

88. PCB-11 加圧流体抽出法 ソックスレー抽出法 加熱アルカリ分解法(乾泥) 加熱アルカリ分解法(湿泥) PCB STD
#11 は の
染料製造等 ,
である
中間産物 ジク -
3,3' に
ロロベンジジン 報告
することが 由来 。
されている 5
そこで ） 分解
アルカリ 加熱 で 過程 から 生成 が かを 否
するか した 検証 1 表 す 示 を 試料
,#11 し 測 定 った 行 と ① ②
ンジジン
ジクロロベ 直接 ④ ⑤ での
底質雰囲気中
ジクロロベンジジン ③
比較試料 々 各 (
分解法 乾泥 ) 様 同 処理
ただし 理
精製処
,DMSO/
硫酸処理
ヘキサン
分配及
シリカ 多層 び ゲル ｡
わなかった
PCB　STD
松木司ら,　広島市衛生研究所年報第24号 (2005)

89. Lisa A.Rodenburg, Jia Guo, Songyan Du, and Gregory J.Cavallo
Evidence for Unique and Ubiquitous Environmental Sources of 3,3′-Dichlorobiphenyl (PCB 11)
Lisa A.Rodenburg, Jia Guo, Songyan Du, and Gregory J.Cavallo
Environ. Sci. Technol. 2010, 44, 2816–2821
The non-Aroclor congener 3,3′-dichlorobiphenyl (PCB 11) has
been recently detected in air, water, biota, sediment, and
suspended sediment. Although it has been known since at
least the 1970s that this congener is produced inadvertently
during the production of diarylide yellow pigments, this work
presents the first evidence that the use of these pigments in
consumer goods results in the dispersion of PCB 11 throughout
the environment at levels that are problematic in terms of
achieving water quality standards for the sum of polychlorinated
biphenyls (PCBs). In this work, PCB 11 is measured at ppb
levels in consumer goods that are likely to be discarded in ways
that allow them to enter wastewater treatment plants and
combined sewer overflows, including newspapers, magazines,
cardboard boxes used for food packaging, and plastic bags.
Also, using data sets acquired for the purpose of calculating total
maximum daily loads (TMDLs) for PCBs, PCB 11 loads to the
NewYork/NewJersey HarborandDelaware River are calculated.
Despite the fact that there are no known manufacturers of
diarylide yellow pigments in the Delaware River watershed, the
loads of PCB 11 to the Delaware River exceed the TMDL for
the sum of PCBs by nearly a factor of 2. The ratio of PCB 11 to
a characteristic dechlorination end product, PCB 4 (2,2′-
dichlorobiphenyl), in these data sets indicates that dechlorination
is not a significant source of PCB 11 in these systems. In the
upper Hudson River, where extensive dechlorination of heavy
PCB congeners occurs, the ratio is just In contrast,
downstream in the NY/NJ Harbor as well as in the Delaware
River the ratio is much higher and more variable. Pigment
use therefore appears to be the main source of PCB 11 in these
systems, and this congener is likely to present a significant
obstacle to achieving PCB water quality standards throughout
the United States.

90. Inadvertent Polychlorinated Biphenyls in Commercial Paint Pigments
Dingfei Hu and Keri C. Hornbuckle
Environ. Sci. Technol. 2010, 44, 2822–2827
A polychlorinated biphenyl (PCB) that was not produced as
part of the Aroclor mixtures banned in the 1980s was recently
reported in air samples collected in Chicago, Philadelphia,
the Arctic, and several sites around the Great Lakes. In Chicago,
the congener 3,3′-dichlorobiphenyl or PCB11 was found to
bethefifthmostconcentratedcongenerandubiquitousthroughout
the city. The congener exhibited strong seasonal concentration
trends that suggest volatilization of this compound from
common outdoor surfaces. Due to these findings and also the
compound’s presence in waters that received waste from
paint manufacturing facilities, we hypothesized that PCB11 may
be present in current commercial paint. In this study we
measured PCBs in paint sold on the current retail market. We
tested 33 commercial paint pigments purchased from three
local paint stores. The pigment samples were analyzed for all
209 PCB congeners using gas chromatography with tandem
mass spectrometry (GC-MS/MS). More than 50 PCB congeners
including several dioxin-like PCBs were detected, and the
PCB profiles varied due to different types of pigments and
different manufacturing processes.PCBcongenersweredetected
in azo and phthalocyanine pigments which are commonly
used in paint but also in inks, textiles, paper, cosmetics, leather,
plastics, food and other materials. Our findings suggest
several possible mechanisms for the inadvertent production of
specific PCB congeners during the manufacturing of paint
pigments.

91. 顔料由来の異性体と
環境大気中のPCB

92. Discovery of non-aroclor PCB (3,3'-dichlorobiphenyl) in Chicago air.
Hu D, Martinez A, Hornbuckle KC
Environ Sci Technol Nov 1; 42(21):
Discovery of non-aroclor PCB (3,3'-dichlorobiphenyl) in Chicago air.Hu D, Martinez A, Hornbuckle KC
Environ Sci Technol Nov 1; 42(21):
Atmos Environ April; 44(12): 1550–1557.
doi:  /j.atmosenv

93. Anezaki et al, organohalogen compounds 74,1433-1436 (2012)
Fig. 3 Seasonal variations of PCBs, DiCBs and #11 congener in Sapporo city
Anezaki et al, organohalogen compounds 74, (2012)