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.

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.

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.

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.

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

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.

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

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)

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 0.00072 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)

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)

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

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)

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

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.

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.

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.

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。

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

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(245-245)

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

- 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)

analysis of pigment(1) : Pigment Orange 13 azo-type pigment Company B 　 pyrazolone ogange(C.I. PO13) Total PCBs 17 mg/kg(ppm) Cl Only #11, #35, and #77 were found. #11 14mg/kg #11 accounting for over 80% of the total PCBs. Cl #35 2.2mg/kg Cl Cl NH2 H2N #77 0.49mg/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

analysis of pigment(2) : Pigment Yellow 81 azo-type pigment Company B 　 benzidine yellow (C.I. PY81) Total PCBs 740mg/kg(ppm) Cl #11 0.53mg/kg #52 : >99% of total PCBs. Cl #52 730mg/kg Cl NH2 H2N Cl #101 Tr (major) 2,2’,5,5’-tetrachlorobenzidine Cl #153 Tr (major)

azo-type pigment Pigment yellow12 （benzidine yellow） raw material CH3 CO 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

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

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

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。

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

Example of analysis of pigment(3) phthalocyanine-type pigment Company B 　 phthalocyanine green (C.I. PG7) Total PCBs 0.43mg/kg(ppm) Cl #209 0.42mg/kg #209 accounting for over 99% of the total PCBs. Cl #208 0.0048mg/kg Cl Cl #202,#206,#208 Tr Pentachlorobenzene Hexachlorobenzene

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

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

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。

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。

unintentional formation pigment solvent PV23 Δ unintentional formation

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

+ 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-20130517 PCB- 40 PCB- 56 PCB- 77 o-DCB + Chloranil + 3-amino N-ethylcarbazole 23- 23 23- 34 34- 34

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 20130531 Radical initiator V-70L : rac-2,2'-Azobis[(2R*)-2,4-dimethyl-4-methoxypentanenitrile]

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

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.

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.

one PCB isomer formation V-70L Δ CB-52 (25-25) p-dichlorobenzene V-70L Δ CB155 (246-246) 1,3,5-trichlorobenzene

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.

CB-56 > CB-77 > CB-40 o-dichlorobenzene 3 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

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

trichlorobenzene  HxCB CB-157 > CB-128 > CB-169 124-TCBz ->HxCB 135-TCBz ->HxCB #155 (246-246) CB-157 (234-345) 123-TCBz ->HxCB CB128 (234-234) CB-169 (345-345) CB-169 (345-345) CB155 (246-246) Window-PCB trichlorobenzene  HxCB

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.

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

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

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

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

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

trichlorobenzene  HxCB CB-157 > CB-128 > CB-169 124-TCBz ->HxCB 135-TCBz ->HxCB #155 (246-246) CB-157 (234-345) 123-TCBz ->HxCB CB128 (234-234) CB-169 (345-345) CB-169 (345-345) CB155 (246-246) Window-PCB trichlorobenzene  HxCB

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

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

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。

(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。

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。

- 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。

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, 1457-1459(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.

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, 369-372(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.

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。

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: 69-1200 pg/m3, ave:361 pg/m3 #11: 2.4-37 pg/m3, ave:11.4 pg/m3

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

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

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。

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。

ICAEC2014 Nov. 24-26, 2014 Chulabhorn Institute Bangkok http://www.j-ec.or.jp/icaec/ http://ee-net.ne.jp/dioxin/ - 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。

- 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。

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

PCBs in commercial pigment for oil painting

- 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。

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)

3,3’,4,4’-テトラクロロビフェニル（PCB-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。

顔料由来の異性体と 環境試料中のPCB

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)

中野武　 50才 Simon Litten

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)

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)

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, 1457-1459(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.

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

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)

底質中のPCB分析

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)

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)

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 0.012. 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.

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.

顔料由来の異性体と 環境大気中のPCB

Discovery of non-aroclor PCB (3,3'-dichlorobiphenyl) in Chicago air. Hu D, Martinez A, Hornbuckle KC Environ Sci Technol. 2008 Nov 1; 42(21):7873-7. Discovery of non-aroclor PCB (3,3'-dichlorobiphenyl) in Chicago air.Hu D, Martinez A, Hornbuckle KC Environ Sci Technol. 2008 Nov 1; 42(21):7873-7. Atmos Environ. 2010 April; 44(12): 1550–1557. doi: 10.1016/j.atmosenv.2010.01.006

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 74,1433-1436 (2012)