Anezaki K 1 , Takahashi G 2 , Tawara K 2 , Nakano T * 3

Concentrations and Congener Profiles of Polychlorinated Biphenyls,

Pentachlorobenzene, and Hexachlorobenzene

in Commercial PigmentsAnezaki K1, Takahashi G2, Tawara K2, Nakano T*3

1 Hokkaido Research Organization, Institute of Environ Sci, Japan2 Hyogo Environmental Advancement Association3 Center for Advanced Science and Innovation, Osaka Univ , Japan

-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).

Analytical Procedure

pigment

sulfuric acid, hexane separatory funnel (Glass tube)

sodium sulfate(dehydration)

H2SO4

surrogates(13C-PCBs, 13C-PeCBz, 13C-HCBz)

Multilayer silica-gel column with hexane

extract

Supelclean sulfoxide SPE + Ag-ION SPE with 5%DCM/hexaneRecovery standards(13C-PCBs)

HRGC-HRMS HRGC: HP6890, Agilent Technologies, USAHRMS: JMS-700D, JEOL, Japancapillary column: HT8-PCB, 0.25mm i.d., Kanto Kagaku, Japan

Surrogate1) Recoverystandards1)

PCBsMoCBs #3DiCBs #15 #8TrCBs #28 #32TeCBs #60 #70PeCBs #101 #97HxCBs #141 #153HpCBs #178 #180OcCBs #194 #205NoCBs #208 #206DeCB #209Chlorobenzenes

PeCBz #32HxCBz #32

1) denote 13C12 labeled standards

HomologueCongener IUPAC #

Table 1 List of PCBs, PeCBz and HxCBzstandards

The pigments 15 azo-type 5 phthalocyanine-type pigments.

Type Concentration levels(ppm=mg/kg) PCB congener patterns

azo-typePCBs: 0.16~ 740 ppmPeCBz: N.D.~ 0.018 ppmHCBz: N.D.~ 0.019 ppm

DL-PCBs(#77): 0~49 pg-TEQ/g

#11, #35, and #77, or

#52, #101, and #153 were found.#11 or #52 was dominant

phthalocyanine-type

PCBs: N.D.~ 0.43ppmPeCBz: 0.0057~ 8.5 ppmHCBz: 0.020~ 19 ppm

Nona-Deca chlorinated PCBs(#206, #207, #208, #209) were found.#209 was dominant.

Cl

Cl

N=N N=N RR

Results

PCB congener profiles of azo pigment

A A A A A A A A A A A A A B B

a1 a2 a3 a4 a5 a6 a7 a8 a9 a10 a11 a12 a13 a14 a15

0

20

40

60

80

100

#99#52

#11

ratio

(%)

#11

#35#77

#52

azo-type pigment

PCB congener profiles of azo pigment

NaNO2, HCl3,3’-dichloro

benzidine

disazopigment production

diazonium

diazonium

Ｎ－acetoacetyl

aniline

Cl

ClCl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

NH2H2N

Cl

Cl

(CuCl2)NaNO2, HCl

Cl

Cl

NN

Cl

Cl

NN

Cl Cl

Sandmeyer reactionAr-N+≡N + CuX → Ar-X + Cu+ + N2↑

CB-52(25-25)

CB-101(245-25)

CB-153(245-245)

2,2’,5,5’- tetrachloro benzidine

Compound View J EOL DioK V4.02 2011/ 05/ 31 15:04:30 Page 1DqData: rh (), Injection= P115 (UNK)Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date>

12 14 16 18 20 22 24 26 28 30Retention Time (min)

(341082)

0

20

40

60

80

100

Inten

sity

D2CB / Average


(16777200)

0

20

40

60

80

100

Inten

sity

T4CB / Average


(225850)

0

20

40

60

80

100

Inten

sity

P5CB / Average


(180016)

0

20

40

60

80

100

Inten

sity

H6CB / Average

#11 (3-3)

#52(25-25)

#101(245-25)

#153(245-245)

　 PCB congeners in pigment (disazo)permanent yellow lemon; PY81;

Cl

ClCl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

NH2H2N

Cl

Cl

2,2’,5,5 ’- tetrachloro benzidine

- Organic Pigment 㩷

Compound View

㩷

J EOL DioK V4.01 2012/ 04/10 14:38:21 Page 1

㩷

DqData: rh (), Injection= pigment_sample (UNK)

㩷

Original: rh_T-PCB-110420.mfl, InjectionNo= 18, Sample= PG032, Date= <Date>

12 14 16 18 20 22 24 26 28Retention Time (min)

(1606)(5038)

0255075100

Inten

sity

M1CB / Average


(3394356)

0

25

50

75

100

Inten

sity

D2CB / Average


(927733)

0

25

50

75

100

Inten

sity

T3CB / Average


(1169387)

0

25

50

75

100

Inten

sity

T4CB / Average


(911)(3926)

0255075100

Inten

sity

P5CB / Average

D2CB

T3CB

T4CB

#11(3-3)

#35(34-3)

#77

Pigment-A

M1CB

P5CB

(N.D.)

(N.D.)

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

(34-34)

㩷

Compound View

㩷

J EOL DioK V4.01 2012/ 04/ 10 14:48:42 Page 1

㩷

DqData: rh (), Injection= P115 (UNK)

㩷

Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date>


(4846)

0255075100

Inten

sity

M1CB / Average


(341082)

0

25

50

75

100

Inten

sity

D2CB / Average


(5258927)

0

25

50

75

100

Inten

sity

T3CB / Average


(16777200)

0

25

50

75

100

Inten

sity

T4CB / Average


(225850)

0

25

50

75

100Int

ensit

yP5CB / Average

D2CB

T3CB

T4CB

P5CB

#11(3-3)

#101

( ﾌﾗｸﾞﾒﾝﾄｲｵﾝ )

#52

Pigment-B

M1CB(N.D.)

Cl

Cl

Cl

ClCl

Cl

Cl

ClCl

Cl

Cl

(25-25)

(245-25)

Cl

Cl

NH2H2N

Cl

Cl

analysis of pigment(1) : Pigment Orange 13

azo-type pigment Company B 　 pyrazolone ogange(C.I. PO13)

Total PCBs 17 mg/kg(ppm)

Cl

Cl

#11 14mg/kg

Cl

Cl

Cl #35 2.2mg/kg

Cl

Cl

Cl Cl #77 0.49mg/kg

Only #11, #35, and #77 were found.

#11 accounting for over 80% of the total PCBs.

Cl

Cl

NH2H2N

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

azo-type pigment

Cl

Cl

N=N N=NCH CH

CO

CH3

CONH

CH3

CH3

CO

CH3

HNOC

CH3

H3C

Pigment yellow12（ benzidine yellow ）

Cl

Cl

NH2H2N

3,3’-dichlorobenzidine

raw material Cl

Cl#11

#77

Cl

Cl

Cl Cl

Cl

Cl

Cl

#35

analysis of pigment(2) : Pigment Yellow 81azo-type pigment Company B 　 benzidine yellow (C.I. PY81)

Total PCBs 740mg/kg(ppm)Cl

Cl

#11 0.53mg/kg

#52 730mg/kg

#101 Tr (major)

#52 : >99% of total PCBs.Cl

ClCl

Cl

Cl

Cl

NH2H2N

Cl

Cl

2,2’,5,5’-tetrachlorobenzidine

Cl

ClCl

Cl

Cl

Cl

ClCl

Cl

Cl Cl #153 Tr (major)

azo-type pigment

raw material

Cl

Cl

NH2H2N

Cl

Cl

2,2’,5,5’-tetrachlorobenzidine

Cl

ClCl

Cl

#52

Cl

Cl

N=N N=NCH CH

CO

CH3

CONH

CH3

CH3

CO

CH3

HNOC

CH3

H3C

Pigment yellow81（ benzidine yellow ）

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

ClCl

Cl

Cl Cl

#153#101

Results

PCB congener profiles of phthalocyanine pigment

A A A A Bp1 p2 p3 p4 p5

0102030405060708090

100

#11

#206

#208

ratio

(%)

PCB congener profiles of phthalocyanine pigment

phthalocyanine-type pigment pigment green 7

pigment blue 15

Example of analysis of pigment(3)Company B 　 phthalocyanine green (C.I. PG7)

Total PCBs 0.43mg/kg(ppm)

#209 0.42mg/kg

#208 0.0048mg/kg

#202,#206,#208 Tr

#209 accounting for over 99% of the total PCBs.

Pentachlorobenzene

phthalocyanine-type pigment

Cl

Cl

Cl Cl

Cl Cl

ClCl Cl

Cl

Cl

Cl

Cl Cl

Cl Cl

ClCl Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Hexachlorobenzene

phthalocyanine-type pigment

phthalic anhydrideurea

copper chloride

raw material

pigment green 7(phthalocyanine green)

pigment blue 15(phthalocyanine blue)

chlorination

pigment green 7

By-product

Cl

Cl

Cl Cl

Cl Cl

ClCl Cl#209

Cl Cl

Cl

Cl Cl

Cl Cl

ClCl Cl#208

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

PeCBz

highly chlorinated PCBs

D HCB

Congener pattern

0

20

40

60

80

100

0

20

40

60

80

100

0

20

40

60

80

100

#5,#8

#11 #12,#13

#18 #28 #35 #44 #52,#69

#66 #77 #87,#115

#101 #105 #110 #118 #128 #138 #153 #170 #180 #202 #206 #207 #208 #2090

2

4

6

8

10

Pigment yellow81

pyrazolone ogange

phthalocyanine green

KC400

Cl

ClCl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

#11 #35 #77

#52

#209

#101 #153

Table 2 Concentaration of PCBs, PCBz and HCBz in commercial pigmentTotal PCBs Total TEQ* PeCBz HCBz

Sample # C.I. name maker mg/kg pg-TEQ/g mg/kg mg/kg Chemical classa1 PO13 A 9.6 3.6 ND ND #11, #35, #77 pyrazolonea2 PO16 A 0.34 3.0 #11, #35, #77 disazoorangea3 PY12 A 0.69 0.9 0.0016 0.0021 #11, #35, #77 disazoyellowa4 PY13_1 A 0.87 3.0 0.0024 0.0030 #11, #35, #77 disazoyellowa5 PY13_2 A 1.2 1.6 ND ND #11, #35, #77 disazoyellowa6 PY14 A 1.4 1.9 0.0016 0.0038 #11, #35, #77 disazoyellowa7 PY17_1 A 0.34 2.4 0.0024 0.0039 #11, #35, #77 disazoyellowa8 PY17_2 A 0.83 0.84 0.0027 0.0060 #11, #35, #77 disazoyellowa9 PY55 A 0.73 0.41 0.0014 0.0032 #11, #35, #77 disazoyellowa10 PY83_1 A 1.5 0.21 0.0010 0.0026 #11, #35, #77 disazoyellowa11 PY83_2 A 3.0 2.4 0.0016 0.0028 #11, #35, #77 disazoyellowa12 PY83_3 A 4.1 1.8 ND ND #11, #35, #77 disazoyellowa13 PY83_4 A 0.33 0 0.0013 0.0063 #11, #35, #77 disazoyellowp1 PG7_1 A 0.43 0 8.5 19 #209 phthalocyaninep2 PG7_2 A 0.16 0 3.8 9.6 #209 phthalocyaninep3 PG7_3 A 0.20 0 4.0 7.9 #209 phthalocyaninep4 PG7_4 A 0.27 0 3.2 10 #209 phthalocyaninea14 PY14(PY81?) B 740 0 0.018 0.019 #52 disazoyellowa15 PO13 B 17 49 0.0098 0.0031 #11, #35, #77 pyrazolonep5 PB15 B ND 0 0.0057 0.020 - phthalocyanine

* DLPCBs- based TEQ** ND: Not detected (<LOD)

PCBs>50mg/kgPCBs>0.5mg/kg

dominant PCBcongeners

PCBs in commercial pigment for oil painting

Table 3 Dominant PCB congeners in commercial oil-based paintbrand name maker C.I. name PCBs conc.(mg/kg) dominant congenerPermanent Yellow light X PY14 1.8 #11, #35, #77Permanent Yellow deep X PY152 1.2 #11, #35, #77Permanent Yellow lemon X PY81 120 #11, #52, #101, #153Permanent Yellow Orange X PO14 6.1 #11, #35, #77Permanent Yellow deep Y PY83 6.3 #11, #35, #77Permanent Yellow lemon Y PY81 170 #52Permanent Yellow deep Z - 1.4 #11, #35Permanent Yellow light Z - 0.046 -

- Results

- pigment from 3,3’-dichlorobenzidine contain #11, #35, #77

- pigment from 2,2’,5,5’-tetrachlorobenzidine contain #52, #101, #153

- phthalocyanine-type pigment contain #209, PeCBz, HCBz

- Results

Seasonal variations of PCBs, DiCBs, and #11 in ambient air

( Sapporo city, Japan)April 2005 ~ March 2011

Apr-05Jun-05

Aug-05Oct-

05Dec-

05Feb

-06

Apr-06Jun-06

Aug-06Oct-

06Dec-

06Feb

-07

Apr-07Jun-07

Aug-07Oct-

07Dec-

07Feb

-08

Apr-08Jun-08

Aug-08Oct-

08Dec-

08Feb

-09

Apr-09Jun-09

Aug-09Oct-

09Dec-

09Feb

-10

Apr-10Jun-10

Aug-10Oct-

10Dec-

10Feb

-11-10

0

10

20

30

40

50

60

-200

0

200

400

600

800

1000

1200

1400Temp.#11DiCBsPCBs

Seasonal variations of PCBs, DiCBs, and #11 in ambient air ( Sapporo city : April 2005 ~ March 2011)

Tem

pera

ture

(o C),

DiCB

s、#1

1Con

c. (p

g/m

3 )PCBs Conc. (pg/m

3)

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

- Conclusionuse BAT (Best Available Techniques) BEP (Best Environmental Practices)

to reduce emissions and human risk.organic pigment product 22,510t (2010)

paint ink plastic

Thank you for your kind attentions

See you in Korea, dioxin2013

You can see your photos at

http://www.dioxin20xx.org/

http://ee-net.ne.jp/dioxin/

PCB congener profile from pigment factory (Litten S. 2002)

0500

1000150020002500300035004000

PCB-11 PCB-35 PCB-77 PCB-126

ng/ L pigment factory (Litten S. 2002)

0

20

40

60

80

#11/DiCBs

DiCBs/PCBs

Ratio

(%)

Seasonal variations of #11/DiCBs and DiCBs/total PCBs ratios in ambient air(Sapporo city, 2005-2011)

Sum

mer

Win

ter

Apr-05Jun-05

Aug-05Oct-

05Dec-

05Feb

-06

Apr-06Jun-06

Aug-06Oct-

06Dec-

06Feb

-07

Apr-07Jun-07

Aug-07Oct-

07Dec-

07Feb

-08

Apr-08Jun-08

Aug-08Oct-

08Dec-

08Feb

-09

Apr-09Jun-09

Aug-09Oct-

09Dec-

09Feb

-10

Apr-10Jun-10

Aug-10Oct-

10Dec-

10Feb

-110

100

200

300

400

#11/#101

Seasonal variations of #11/#101 ratio in ambient air ( Sapporo city : 2005-2011 )

#11: pigment related #101: PCB product

Ratio

(%)

Cl

Cl

NH2

O

HNHO

O

HNHO

NN

Cl

Cl

Pigment Red 2

2,5-dichloroaniline

monoazo

diazonium

有機顔料製造過程での PCB 生成

○中野　武 1，姉崎克典 2，高橋玄太 3，俵健二 3

（ 1 大阪大学工学研究科， 2 北海道環境科学研究センター，

3 ひょうご環境創造協会）

はじめに

　一部の有機顔料製造工程で非意図的

生成 PCB 含有

化成品工業協会自主測定

経済産業省　事業者に指導

国際的な基準を超える有機顔料

製造、輸入及び出荷を停止

はじめに

顔料着色に用いる粉末

水や油に不溶なものの総称

有機顔料有機化合物を成分とする顔料

アゾ顔料（モノアゾ , ジスアゾ , ピラゾロン） PY, PO, PRフタロシアニン顔料（ PG ）多環式顔料（ PV, PR ）

PCB 測定・異性体組成の特徴

方法

前処理は、試料を濃硫酸に入れ溶解させ、ヘキサンで抽出後、硫酸シリカゲルカラム（ 12mL Tube / SUPELCO ）でクリーンアップを行い、濃縮後、最終検液とした。

測定は、 GC/HRMS （ JMS-700 / JEOL ）、 GC カラムには RH-12ms （ INVENTX ）を用いた。

異性体同定には、 GC-TQMS( 450-GC/320-MS, Bruker)GC カラム HT8-PCB でも確認した。

顔料中の PCB 異性体

方法

図１に代表的な、顔料中の PCB の GC/MS クロマトグラムを示す。原料の 3,3’- ジクロルベンジジンや2,2’,5,5’- テトラクロロベンジジンに対応し、特徴的な単純な組成を示す。すなわち、顔料由来の特定の PCB異性体が、ジクロルベンジジンやテトラクロロベンジジンのジアゾニウム塩を経て、副生成する。これらの顔料合成過程で、 PCB の副生する反応は、よく知られている。テトラクロロベンジジン及びＮ－アセトアセチル－ 2,4- ジメチルアニリンを原料とする黄色顔料PY81 の製造過程で、アゾカップリングの際に、テトラゾ化液とアルカリ水溶液の添加速度のバランスにより、pH を一定に制御し、顔料合成中の PCB 副生を抑制する特許が提案されている。

方法

フタロシアニン系の顔料、フタロシアニングリーンはpigment blue 15 を塩素化し製造される。 #209 、 PeCBz 、 HCB 濃度が高い特徴があり、不純物の量や種類、塩素化工程における温度の違いなどが影響しているものと推測される。

Documents

Anezaki K 1 , Takahashi G 2 , Tawara K 2 , Nakano T * 3