Transcript PowerPoint

Concentrations and Congener Profiles
of Polychlorinated Biphenyls,
Pentachlorobenzene, and
Hexachlorobenzene
in Commercial Pigments
Anezaki K1, Takahashi G2, Tawara K2, Nakano T*3
1 Hokkaido Research Organization, Institute of Environ Sci, Japan
2 Hyogo Environmental Advancement Association
3 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
separatory funnel
(Glass tube)
sulfuric acid, hexane
H2SO4
sodium sulfate(dehydration)
extract
surrogates(13C-PCBs, 13C-PeCBz, 13C-HCBz)
Multilayer silica-gel column with hexane
Supelclean sulfoxide SPE + Ag-ION SPE with 5%DCM/hexane
Recovery standards(13C-PCBs)
HRGC-HRMS
HRGC: HP6890, Agilent Technologies, USA
HRMS: JMS-700D, JEOL, Japan
capillary column: HT8-PCB, 0.25mm i.d., Kanto
Kagaku, Japan
Table 1 List of PCBs, PeCBz and HxCBz
standards
Congener IUPAC #
Recovery
Homologue
1)
Surrogate
standards1)
PCBs
MoCBs
DiCBs
TrCBs
TeCBs
PeCBs
HxCBs
HpCBs
OcCBs
NoCBs
DeCB
#3
#15
#28
#60
#101
#141
#178
#194
#208
#209
#8
#32
#70
#97
#153
#180
#205
#206
Chlorobenzenes
PeCBz
HxCBz
1) denote
13
#32
#32
C12 labeled standards
The pigments
15 azo-type
5 phthalocyanine-type pigments.
Concentration levels
(ppm=mg/kg)
Type
azo-type
Cl
R
N=N
N=N
Cl
phthalocyanine-type
R
PCB congener patterns
#11, #35, and #77, or
PCBs: 0.16~ 740 ppm
PeCBz: N.D.~ 0.018 ppm
HCBz: N.D.~ 0.019 ppm #52, #101, and #153
were found.
#11 or #52 was
DL-PCBs(#77):
0~49 pg-TEQ/g dominant
Nona-Deca chlorinated
PCBs(#206, #207, #208,
PCBs: N.D.~ 0.43ppm
#209) were found.
PeCBz: 0.0057~ 8.5 ppm #209 was dominant.
HCBz: 0.020~ 19 ppm
Results
PCB congener profiles of
azo pigment
azo-type pigment
#11
#52
100
ratio(%)
80
60
40
#35
#77
20
0
A
A
A
A
A
A A
a1 a2 a3
a4 a5 a6
a7
A
a8
A
A
A
A
A
#11
#35
#52
#77
#99
B
B
a9 a10
a11 a12
a13 a14
a15
PCB congener profiles of azo pigment
NaNO2, HCl
3,3’-dichloro
benzidine
diazonium
Ｎ－acetoacetyl
aniline
diazonium
pigment production
disazo
NaNO2, HCl
(CuCl2)
CB-52(25-25)
CB-101(245-25)
2,2’,5,5’- tetrachloro benzidine
Sandmeyer reaction
Ar-N+≡N + CuX → Ar-X + Cu+ + N2↑
CB-153(245-245)
Compound View
JEOL DioK V4.02 2011/05/31 15:04:30 Page 1
DqData: rh (), Injection= P115 (UNK)
Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date>
(341082) D2CB / Average
100
#11 (3-3)
Intensity
80
60
40
20
0
12
14
16
18
20
22
Retention Time (min)
24
26
28
30
24
26
28
30
(16777200) T4CB / Average
100
#52(25-25)
Intensity
80
60
40
20
0
2,2’,5,5 ’- tetrachloro
benzidine
12
14
16
18
(225850) P5CB / Average
100
#101(245-25)
80
Intensity
20
22
Retention Time (min)
60
40
20
0
12
14
16
18
20
22
Retention Time (min)
24
(180016) H6CB / Average
100
28
30
#153(245-245)
80
Intensity
26
60
40
20
0
12
14
16
18
20
22
Retention Time (min)
24
26
28
30
PCB congeners in pigment (disazo)
permanent yellow lemon; PY81;
- Organic Pigment
Pigment-A
Compound View
JEOL DioK V4.01 2012/04/10 14:38:21 Page 1
DqData: rh (), Injection= pigment_sample (UNK)
Original: rh_T-PCB-110420.mfl, InjectionNo= 18, Sample= PG032, Date= <Date>
JEOL DioK V4.01 2012/04/10 14:48:42 Page 1
DqData: rh (), Injection= P115 (UNK)
Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date>
M1CB / Average
M1CB
(5038)
100
(1606)
75
50
250
14
16
18
20
22
Retention Time (min)
(3394356) D2CB / Average
100
24
26
50
12
14
16
18
20
22
Retention Time (min)
24
26
18
20
22
Retention Time (min)
24
26
#11(3-3)
28
D2CB
50
25
12
28
14
16
18
20
22
Retention Time (min)
24
26
(5258927) T3CB / Average
100
(927733) T3CB / Average
100
T3CB
50
25
28
T3CB
(ﾌﾗｸﾞﾒﾝﾄｲｵﾝ)
75
Intensity
#35(34-3)
75
Intensity
16
0
12
50
25
0
0
14
16
18
20
22
Retention Time (min)
24
26
12
28
14
16
18
(16777200) T4CB / Average
100
(1169387) T4CB / Average
100
#77
T4CB
(34-34)
25
20
22
Retention Time (min)
24
26
#52
(25-25)
50
28
T4CB
75
Intensity
12
Intensity
14
75
0
50
M1CB
(341082) D2CB / Average
100
25
75
(N.D.)
(4846)
100
75
50
250
28
D2CB
#11(3-3)
75
Intensity
Intensity
(N.D.)
Intensity
Intensity
M1CB / Average
12
Pigment-B
Compound View
25
0
0
12
14
16
18
20
22
Retention Time (min)
24
26
12
28
14
16
18
20
22
Retention Time (min)
(225850) P5CB / Average
100
P5CB / Average
P5CB
(3926)
(911)
100
75
50
250
26
28
#101
P5CB
75
Intensity
Intensity
(N.D.)
24
(245-25)
50
25
0
12
14
16
18
20
22
Retention Time (min)
24
26
28
12
14
16
18
20
22
Retention Time (min)
24
26
28
analysis of pigment(1) : Pigment Orange 13
azo-type pigment
Company B
pyrazolone ogange(C.I. PO13)
Total PCBs 17 mg/kg(ppm)
Cl
#11 14mg/kg
Cl
Only #11, #35, and #77 were found.
#11 accounting for over 80% of
the total PCBs.
Cl
#35 2.2mg/kg
Cl
Cl
Cl
Cl
Cl
Cl
#77 0.49mg/kg
Cl
#77 is a dioxin-like PCB(DL-PCB).
The dioxin concentration calculated using the
TEF for this congener was 49pg-TEQ/g
H2 N
NH2
Cl
3,3’-dichlorobenzidine
azo-type pigment
CH3
CO
CH3
H 3C
CH3
CH
HNOC
CO
Cl
N=N
N=N
CH3
Cl
CH3
CONH
CH
Pigment yellow12
（benzidine yellow）
Cl
raw material
Cl
H2 N
NH2
#11
Cl
Cl
3,3’-dichlorobenzidine
Cl
Cl
Cl
Cl
Cl
Cl
#35
Cl
#77
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
Cl
Cl
#52 : >99% of total PCBs.
Cl
#52 730mg/kg
Cl
Cl
Cl
Cl
Cl
#101 Tr (major)
Cl
Cl
Cl
H2 N
NH2
Cl
Cl
Cl
2,2’,5,5’-tetrachlorobenzidine
Cl
Cl
Cl
Cl
Cl
Cl
#153 Tr (major)
azo-type pigment
CH3
CH3
H 3C
HNOC
CH3
CO
CH
Cl
CO
Cl
N=N
N=N
Pigment yellow81
（benzidine yellow）
raw material
Cl
H2 N
CH3
CONH
CH
Cl
Cl
CH3
Cl
Cl
Cl
NH2
Cl
Cl
#52
Cl
Cl
2,2’,5,5’-tetrachlorobenzidine
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
#101
Cl
Cl
#153
Cl
Results
PCB congener profiles of
phthalocyanine pigment
phthalocyanine-type pigment
pigment green 7
100
ratio(%)
80
pigment blue 15
60
40
#209
#208
#207
#206
#202
#11
20
0
A
p1
A
p2
A
A
p3
B
p4
p5
PCB congener profiles of phthalocyanine pigment
Example of analysis of pigment(3)
phthalocyanine-type pigment
Company B
phthalocyanine green (C.I. PG7)
Total PCBs 0.43mg/kg(ppm)
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl Cl
#209 0.42mg/kg
Cl
#208 0.0048mg/kg
Cl
Cl
Cl
Cl
Cl
#209 accounting for over 99% of
the total PCBs.
Cl
Cl
Cl
Cl
#202,#206,#208 Tr
Cl
Cl
Cl
Pentachlorobenzene
Cl
Cl
Cl
Cl
Cl
Hexachlorobenzene
phthalocyanine-type pigment
By-product
raw material
Cl
phthalic anhydride
urea
copper chloride
Cl
Cl
Cl Cl
Cl
Cl
HCB
Cl
Cl
Cl
Cl Cl
#209
Cl
Cl
Cl
Cl
Cl
Cl
chlorination
D
pigment green 7
Cl
Cl
PeCBz
pigment blue 15
(phthalocyanine blue)
pigment green 7
(phthalocyanine green)
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
#208
Cl
highly chlorinated PCBs
100
80
60
Pigment yellow81
#52
40
20
#101
0
#153
100
80
60
40
#11
#35
#77
pyrazolone ogange
20
0
#209
100
80
60
40
phthalocyanine green
20
0
10
8
6
4
KC400
2
0
Congener pattern
Table 2 Concentaration of PCBs, PCBz and HCBz in commercial pigment
Total PCBs Total TEQ*
PeCBz
Sample # C.I. name
maker
mg/kg
pg-TEQ/g
mg/kg
a1
PO13
A
9.6
3.6
ND
a2
PO16
A
0.34
3.0
a3
PY12
A
0.69
0.9
0.0016
a4
PY13_1
A
0.87
3.0
0.0024
a5
PY13_2
A
1.2
1.6
ND
a6
PY14
A
1.4
1.9
0.0016
a7
PY17_1
A
0.34
2.4
0.0024
a8
PY17_2
A
0.83
0.84
0.0027
a9
PY55
A
0.73
0.41
0.0014
a10
PY83_1
A
1.5
0.21
0.0010
a11
PY83_2
A
3.0
2.4
0.0016
a12
PY83_3
A
4.1
1.8
ND
a13
PY83_4
A
0.33
0
0.0013
p1
PG7_1
A
0.43
0
8.5
p2
PG7_2
A
0.16
0
3.8
p3
PG7_3
A
0.20
0
4.0
p4
PG7_4
A
0.27
0
3.2
a14
PY14(PY81?)
B
740
0
0.018
a15
PO13
B
17
49
0.0098
p5
PB15
B
ND
0
0.0057
* DLPCBs- based TEQ
** ND: Not detected (<LOD)
PCBs>50mg/kg
PCBs>0.5mg/kg
HCBz
mg/kg
ND
0.0021
0.0030
ND
0.0038
0.0039
0.0060
0.0032
0.0026
0.0028
ND
0.0063
19
9.6
7.9
10
0.019
0.0031
0.020
dominant PCB
congeners
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#11, #35, #77
#209
#209
#209
#209
#52
#11, #35, #77
-
Chemical class
pyrazolone
disazoorange
disazoyellow
disazoyellow
disazoyellow
disazoyellow
disazoyellow
disazoyellow
disazoyellow
disazoyellow
disazoyellow
disazoyellow
disazoyellow
phthalocyanine
phthalocyanine
phthalocyanine
phthalocyanine
disazoyellow
pyrazolone
phthalocyanine
PCBs in commercial pigment for oil painting
Table 3 Dominant PCB congeners in commercial oil-based paint
brand name
maker C.I. name PCBs conc.(mg/kg)
Permanent Yellow light
X
PY14
1.8
Permanent Yellow deep
X
PY152
1.2
Permanent Yellow lemon
X
PY81
120
Permanent Yellow Orange
X
PO14
6.1
Permanent Yellow deep
Y
PY83
6.3
Permanent Yellow lemon
Y
PY81
170
Permanent Yellow deep
Z
1.4
Permanent Yellow light
Z
0.046
dominant congener
#11, #35, #77
#11, #35, #77
#11, #52, #101, #153
#11, #35, #77
#11, #35, #77
#52
#11, #35
-
- 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
50
40
Temp.
#11
DiCBs
PCBs
1400
1200
1000
800
30
600
20
400
PCBs Conc. (pg/m3)
Temperature(oC), DiCBs、#11Conc. (pg/m3)
60
10
200
0
-10
0
-200
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
- Conclusion
use
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/
ng/L
4000
3500
3000
2500
2000
1500
1000
500
0
pigment factory (Litten S. 2002)
PCB-11
PCB-35
PCB-77
PCB-126
PCB congener profile from
pigment factory (Litten S. 2002)
Jan-11
Oct-10
Jul-10
Apr-10
Jan-10
Oct-09
Jul-09
20
Apr-09
Jan-09
Oct-08
Jul-08
Apr-08
Jan-08
Oct-07
Jul-07
Apr-07
Jan-07
Oct-06
Jul-06
Apr-06
Jan-06
Oct-05
Jul-05
Apr-05
Ratio(%)
80
60
40
#11/DiCBs
DiCBs/PCBs
0
Seasonal variations of #11/DiCBs and DiCBs/total PCBs
ratios in ambient air(Sapporo city, 2005-2011)
Winter
Summer
#11: pigment related
Seasonal variations of #11/#101 ratio
in ambient air ( Sapporo city : 2005-2011 )
#101: PCB product
Feb-11
Dec-10
Oct-10
Aug-10
Jun-10
Apr-10
Feb-10
Dec-09
Oct-09
Aug-09
Jun-09
Apr-09
Feb-09
Dec-08
Oct-08
Aug-08
Jun-08
Apr-08
Feb-08
Dec-07
Oct-07
Aug-07
Jun-07
Apr-07
Feb-07
Dec-06
300
Oct-06
Aug-06
Jun-06
Apr-06
Feb-06
Dec-05
Oct-05
Aug-05
Jun-05
Apr-05
Ratio(%)
400
#11/#101
200
100
0
monoazo
diazonium
2,5-dichloroaniline
Pigment Red 2
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
化成品工業協会 自主測定
一部の有機顔料
経済産業省
国際的な基準を超え
る有機顔料
製造工程で非意図的
生成PCB含有
事業者に指導
製造、輸入及び出荷を
停止
はじめに
着色に用いる粉末
水や油に不溶なものの総称
顔料
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。