PCB and PCN in Environment

1
PCB and PCNin Environment
-Fate and Source-
Takeshi Nakano
(Hyogo Pref. Inst. of Env. Sci.)
ntakeshi_at_pref.hyogo.jp
2
Sudden Death of Dr. Imagawa on 19th Feb.
2001 It is truly a shame to lose him at such a
young age, and I thank for his help to my study
Dr. Imagawa / Dioxin symposium in Kyoto (1994)
3
23478-PeCDF
2378-TCDD
75
135
75
209
123567-HxCN
34534-Co-PCB
4
PCB issue in Japan
5
PCB in Japan ca 60,000t
National Project in 1985-1989 Decomposition in
Takasago, Hyogo pref. Liquid-PCB 5,500t
90 of PCB still remain in Environment
6
DD/DF/PCB Levels in Air Chemosphere (1986)
Daily Variation of DD/DF/PCB Atmospheric
Environment(1990)
PCB in Water Environment IWPRC(1990)
PCN in Combustion Process Organohalogen compounds
(1994)
7
1995.1.17 546am Great Earthquake
8
PCN in rain water after great fire
ng/L
PCN
PCN concentration in rain water
(day)
The progress number of days after the earthquake
disaster
9
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10
TEQ Level of technical PCB
11
PCB concentration and TEQ value
KC300
KC400
KC500
KC600
2x10-5
0.7x10-5
6x10-5
3x10-5
pg-TEQ/g
0.7x107
2 x107
6 x107
3 x107
12
90 of PCB still remain in Environment
PCB

• Transformer (Japan Railway, Power company )
• Carbon free Paper(Non Carbon Paper)
• Sealant PCB (old building before 1972)
• Fluorescent

13
PCB
Homologue Distribution and Source Estimation
14
Source estimation
KC300
KC500
Insulator
N.C.P.
capacitor
Sediment A
Sediment B
KC400
KC600
Ship paint
Insulator
capacitor
15
Isomer distribution and Source estimation
Sediment A
Water A
KC300
16
Isomer distribution and Source estimation
KC400
KC500
KC600
17
PCN TEQ Level in Ambient Air
18
Atmospheric PCN (pg-TEQ/m3) in Japan (JEPA)
1
0.1
0.01
0.001
0.0001
0.00001
0
1
2
3
4
5
6
7
8
9
10
19
PCN Profiles in Ambient air
20
0.600
0.500
0.400
0.300
0.200
0.100
0.000
Cl1
Cl2
Cl3
Cl8
Cl4
Cl5
Cl6
Cl7
Homologue distribution of PCN in Ambient air
21
Kobe
On the mountain
Industrial site
Homologue distribution of PCN in Ambient air
22
PCN (vaporparticle)
PCB(gas phase)
Homologue distribution in Ambient air
23
Ambient air (pg-TEQ/m3)
Ambient air (pg/m3)
Total concentration
TEQ concentration
Atmospheric level of PCB/PCN/PCDD/PCDF
24
PCN Profiles in Ambient Air. (Kobe)
25
PCN MCN 1,2 PeCN 49-62
DiCN 3-12 HxCN 63-72 TrCN
13-26 HpCN 73,74 TeCN 27-48
OCN 75
HxCN
PeCN
TeCN
TrCN
DiCN
PCN congener distribution in ambient air.
26
Air
Air
Depo
Rain
Technical
Sediment
Water
Landfill
PCN isomer distribution
27
23-
1237-
Air Rain
Water sediment
236-
1234-
ß
167-
137-
146-
Air
1267-
12367-
12346-
Selected PCN isomers from result of PCA
28
TEQ contribution of PCDD/PCDFPCB/PCN in
Ambient Air
29
Ambient air
Contribution in TEQ value
TEQ value
Total conc.
30
Annual inventory of Dioxin from Municipal
Incinerator
31
Hyogo pref
Emission (g-TEQ/year)
Japan
Emision (g-TEQ/year)
32
TEQ contribution of PCDD/PCDFPCB/PCN in
environmental samples
33
Contribution in TEQ value
water
soil
Air
sediment
depo
34
Daily variation of PCB in ambient air
35
Air Sampling 1000m3

• High volume air sampler
• Quartz Micro Fiber for particulate
• Poly Urethane Foam for gas phase

36
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37
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38
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39
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40
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41
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42
Relation between distribution of gas and
particulate-PCB with temperature (?C) and
atmospheric pressure (hPa).
43
Co-PCB in air and technical PCB
Hepta
Hexa
Penta
Tetra
Tri
Di
30
KC 300-600
3,3-
4,4-
20
3,4,3-
3,4,4-
3,4-/ 3,4-
3,4,3,4-
10
0
Gas phase
30
PUF
20
10
0
particulate
30
QMF
20
10
0
11
15
35
37
74
70
66
56
77
107
123
118
114
105
126
156
157
169
180
193
191
170
190
189
12/13
80/55
44
Importance of Low chlorinated DD/DF
Isomer distribution
formation mechanism
Biodegradation pathway
degradation mechanism
Important information
Source estimation
on site analysis
Monitoring of stack gas
MCDF gtgt TCDF
PCB PCN PCDD PCDF
Monitoring of Environment
Air, Water
45
13C12-MCDD
13C12-MCDF
13C12-DiCDD
13C12-DiCDF
13C12-TrCDD
13C12-TrCDF
13C12-TeCDD
13C12-TeCDF
13C12-PeCDD
13C12-PeCDF
13C12-HxCDD
13C12-HxCDF
13C12-HpCDD
13C12-HpCDF
13C12-OCDD
13C12-OCDF
Breakthrough from PUF plug using High volume air
sampler
46

• Water Sampling 100L
• High volume water sampler
• Quartz Micro Fiber for particulate
• Poly Urethane Foam for dissolved

47
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48
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49
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50
23478-PeCDF
2378-TCDD
75
135
75
209
123567-HxCN
34534-Co-PCB
51
PCDD/PCDF
Homologue Distribution and Source Estimation
Water and Sediment in River and Coastal Sea
52
PCDD/DF in Air from mainly combustion process
in Japan
PCDD/DF in Water from Impurity of Pesticide in
paddy soil
53
in Japan
Herbicide in the past

• CNP 1368- and 1379-TCDD
• (condensation of 2,4,6-TCP)
• PCP OCDD, HpCDD

still using

• 2,4-D 2,7- and 2,8- DiCDD

54
River water
Homologue Distribution
PCDF
PCDD
55
River sediment
Homologue Distribution
PCDF
PCDD
56
Homologue Distribution
River sediment
Incineration pattern
PCDD
PCDF
57
Homologue Distribution
River sediment
PCP
CNP
Pesticide pattern
PCP
Pesticide pattern
Incineration pattern
CNP
PCDD
PCDF
58
Homologue Distribution
Sea sediment
???
PCDD
PCDF
59
Importance of Low chlorinated DD/DF
Isomer distribution
formation mechanism
Biodegradation pathway
degradation mechanism
Important information
Source estimation
on site analysis
Monitoring of stack gas
MCDF gtgt TCDF
PCB PCN PCDD PCDF
Monitoring of Environment
Air, Water
60
Kako river
S100pg/L
S20pg/L
80
80
PCDF
PCDD
60
60
40
40
(pg/L)
(pg/L)
20
20
0
0
D2Cl
P5Cl
D2Cl
P5Cl
O8Cl
O8Cl
M1Cl
M1Cl
Tr3Cl
Te4Cl
Tr3Cl
Te4Cl
Hx6Cl
Hp7Cl
Hx6Cl
Hp7Cl
Homologue profiles of PCDD/Fs in river water
61
PCDF
PCDD
Homologue profiles of PCDD/Fs in river water
R. Lohmann et al (1999)
62
Kako river
S100pg/L
S20pg/L
80
80
PCDF
PCDD
60
60
40
40
(pg/L)
(pg/L)
20
20
0
0
D2Cl
P5Cl
D2Cl
P5Cl
O8Cl
O8Cl
M1Cl
M1Cl
Tr3Cl
Te4Cl
Tr3Cl
Te4Cl
Hx6Cl
Hp7Cl
Hx6Cl
Hp7Cl
Homologue profiles of PCDD/Fs in river water
63
River water
PCB
S100pg/L
Homologue profiles of PCBs in river water
64
River water
PCN
S20pg/L
Homologue profiles of PCNs in river water
65
PCB contamination in Sea sediment
66
????
Thermal
PCB???????????
PCB important index for Pollutant dispersion
???
chemical
??????????????
Stable in environment persistent
????
biological
????1020??????
Environmental loading 10-20 years
??? 209 ??????
209 congeners much information
?????PCB?????
Vertical distribution of PCB in sediment core
PCB??????????
Historical trend of PCB pollution
?????PCB?????
Horizontal distribution of PCB in sediment
PCB????????
Spatial migration of PCB
67
Production of N.C.P
PCB concentration
Sediment core
Annual production
Annual production and Vertical distribution in
sediment
68
(No Transcript)
69
Horizontal distribution in sea sediment
???
Harima nada
???
Osaka Bay
Independent area western and eastern part
??????????
?????????
like a soup dish
???????
Sea bottom and water depth
70
Horizontal distribution in sea sediment
Channel fast stream
sand
silt
silt
sand
Central part slow stream
Particle size in sea sediment
71
?????????????????
Before normalization by particle size
distribution
coast
High
Inmost part
High
Low
channel
High
???????
Low
Harima nada
??
Osaka Bay
Central part High
Horizontal distribution in sea sediment
72
????????????????
After normalization by particle size distribution

????????
Constant flow map and PCB distribution
??????????????
?????PCB?????
Horizontal distribution in sea sediment
73
?????????
Horizontal distribution in sea sediment
?????
Around Kobe port
???
Osaka bay
PCB???????
PCB concentration and Distance from source
74
ISOMER SPECIFIC ANALYSIS OF MONO- TO
TRICHLORINATED DIBENZO-DIOXINS AND DIBENZOFURANS -
T.NAKANO and R.WEBER
Organohalogen compounds,Vol.46, 558-561 (2000)
75
Precursor of PCDD/DF formation
76
4-MCP
1,2,8-TrCDF
3,4-DCP
2,3,8-TrCDF
77
O-
m-
2-MCP
3-MCP
1,4,9-TrCDF
1,4,6-TrCDF
2,5-DCP
1,4,7-TrCDF
4-MCP
1,4,8-TrCDF
Authentic standard (1,4,7- NMR)
p-
Synthesis of 1,4,X-T3CDF isomers from
chlorophenol
78
Authentic standard
H2 H3
H9
H8
H6
NMR 1,4,7-TrCDF
79
????
Ambient air
80
Ambient air
Incineration (flyash)
??????????(MCDFTrCDF)
Isomer distribution of ambient air(MCDF-TrCDF)
81
Ambient air
Incineration (flyash)
??????????(MCDDTrCDD)
Isomer distribution of ambient air(MCDD-TrCDD)
82
28-
2-
37-DiCDF
23-
27-DiCDF
27-
23-DiCDF
37-
28-DiCDF
128-TrCDF
238-
237-TrCDF
128-
238-TrCDF
237-
1278-TCDF
2378-TCDF
??????????????(MCDFTrCDF)
Isomer distribution of bleaching
process(MCDF-TrCDF)
83
238-
128-
28-
2-
237-
27-
??????????????(MCDFTrCDF)
Isomer distribution of bleaching
process(MCDF-TrCDF)
Ambient air
24-
124-
??????????(MCDFTrCDF)
Isomer distribution of ambient air(MCDF-TrCDF)
84
??CNP???????(MCDFTrCDF)
Isomer distribution of pesticide CNP (MCDF-TrCDF)
24-
248-
246-
pesticide CNP
Ambient air
24-
124-
??????????(MCDFTrCDF)
Isomer distribution of ambient air(MCDF-TrCDF)