The PCBs management in Japan: Pollution, Environmental risks , Analysis and control measure by Japanese Government

July 19th Hanoi

Yasuaki Maeda Osaka Prefecture University

Todays Talk
1) History of the regulation of PCB A: Stockholm Convention and Japanese Measure B: PCB as POPs 2) How PCB can be analyzed A: GC-MS B: simple method 3) The contamination of POPs in Vietnam and Japan and their emission sources 4) Treatment of PCB A: Chemical dechlorination B:Combusition C: Sonolysis
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Damaged Babies by PCB

What is POP
Stockholm Convention
international environmental treaty that aims to eliminate or restrict the production and use of persistent organic pollutants (POPs).

remain intact for exceptionally long periods of time (many years); become widely distributed throughout the environment as a result
of natural processes involving soil, water and, most notably, air;

accumulate in the fatty tissue of living organisms including humans,

and are found at higher concentrations at higher levels in the food chain; and are toxic to both humans and wildlife.
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Stockholm Convention
2001 May 23: Signed at Stockholm 2002 August: Japan 2004 May 17: Effective A: (Elimination) Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene, Mirex, Toxaphene, PCBs B: (Restriction) DDT C: (Unintentional Production) Polychlorinated dibenzo dioxins, dibenzofurans, PCBs, Hexachlorobenzene
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May 2009 New POPs

A: -Hexachlorocyclohexane, Hexachlorocyclohexane, Chlordecone, Hexabromobiphenyl , Hexabromodiphenyl ether, heptabromodiphenyl ether, Lindane, pentachlorobenzene(A and C), Tetrabromodiphenyl ether, pentabromo diphenyl ether B: (Restriction) Perfluorooctanesulfonic acid(PFOS) and its salts, perfluorooctanesulfonyl fluoride(PFOSF) C: Unintentional chemicals: Dioxins, Dibenzo furan Next candidates: PAHs
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Regulation in Japan
1) Stop the production and use: Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene, Mirex, Toxaphene, DDT, PCBs Stop the import and export of POPs 2) Unintentional POPs: 3) Develop the inventry and make the plan for the reduction of the emission( Dioxins, Dibenzo furan, HCB, PCB): 7680TEQ/ 1997, 372-400TEQ/2003 4) BAT/BEP: Best Available Technology/ Best Environmental Practice
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Japanese correspondence
1. General Technical Guidelines for the Environmentally Sound Management of Wastes consisting, containing or contaminated with Persistent Organic Pollutants 2. Technical Guidelines for Environmentally Sound Management of Wastes consisting, containing or contaminated with PCB, PCT or PBB 3. Draft Technical Guidelines for Environmentally Sound Management of Wastes consisting, containing or contaminated with PCDDs and PCDFs 4. Draft Technical Guidelines for Environmentally Sound Management of Wastes consisting, containing or contaminated with Aldrin, Dieldrin, Endrin, Chlordane, Heptachlor, HCB, Mirex and Toxaphene or with HCB as an industrial chemical 5. Draft Technical Guidelines for Environmentally Sound Management of Wastes consisting, containing or contaminated
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Japanese measure to POPs convention

Search of POPs contamination and correspondence to Stockholm convention 2001 5 committees

(1) POPs Agricultural chemicals (2) PCBs treatment committee (3) Treatment of waste contaminated with POPs (4) Inventory of HCBPCBs committee (5) POPs monitoring studying committee

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Technical Guideline(1)
Low POPs content in Waste [1] PCB [2] Dioxine [3] Agricultural Chemicals Aldrin, Chlordane, Dieldrin, Endrin, Heptachlor, Hexachlorobenzene, Mirex, Toxaphene (long term toxity)

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Regulation
Levels of destruction and irreversible transformation
DE(Destruction efficiency) POPs input-POPs output/ POPs total input DREDestruction removal efficiency): POPs input-POPs in exhaust gas/ POPs total input DE99.999%, DRE: 99.9999% Dioxin emission : lower than 0.14 ngTEQ/Nm3
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Treatment technology
1.Alkali metal reduction 2. Base catalyzed decomposition (BCD) 3. Cement kiln co-incineration 4. Gas phase chemical reduction (GPCR) 5. Hazardous waste incineration 6. Plascon (Plasma technology) 7. Super-critical water oxidation (SCWO) Subcriticalwater oxidation 8. Catalytic hydro-dechlorination (CHD) 9. Potassium tert-Butoxidemethod (t-BuOK) 10. The combined System of both photo-chemical dechlorination and catalytic dechlorination (PCD and 13 CD)

Inventory of HCB and PCB

Emission sources
Incinarator Cement kiln Pulp production Mettallurgy(Cu,Fe,Al ,Zn) Total Metallurgy(others) Petroleum burning Biomass burning Chemicals production Crematorium Electric cable burning Total Others Total

HCB emission (kg/y) PCB emission (kg/y)

44 11 0.08 30 85 100 0.38 0.034 0.24 0.16 0.42 100 1.9 190 15 350 5.7 82 450 100 0.84 0.28 0.031 0.44 0.084 100 5.1 560
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Transformer 50kVA:115kg PCB

Condenser 100kVA:35kgPCB
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Electric machine :few to ten 4500000 cable=1400km

Waste containing PCBs

Waste Stored numbers HV trans 15,430 HV condenser 240,002 LV trans. 34,679 LV condenser 1,796,644 Trans (electric pole) 1,974,106 Stabilizer 5,099,425 PCB 93t Oil with PCB 175,244t Copy paper 722t Sludge 19,611t Others 97,185 Using numbers 2,377 30,190 838 41,505 1,879,900 557,929 76kg 18kg 0 0 8,175 PCB concentration 60-70 % (KC-1000) 100%(Kc-300,400,500) 100%(KC-300,400,500) 100%(KC-300,400,500) few-ten ppm 100%(KC-300,400,500) 100%(KC-300,400,500) ppm-100% 3-5%

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Agricultural Chemicals
2001total 3680t174places Aldrin;51.85t, Dieldrin;18.885t, Endrin;39.076t,DDT;943.766tBHC;1808t, unknown; 818.117t recovered46.25t3 places Chlordane49t( stored in 1986 by Japanese Regulation)
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Treatment of Agricultural Chemicals

DE:>99.999% Emission gas: 0.1ngTEQ/m3 Waste water:10pgTEQ/L Ash:3ngTEQ/g Combustion over 1000oC Na method, super critical , Mechanochemical, Geomelt
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PCB treatment 5 places

Hokkaido

KItakyusyu Tokyo Toyota Osaka

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PCB Treatment system

Place Hokkaido (Na method) Tokyo ( Hydrothermal) Toyota (Na method) Osaka (Cat.Hydro.) Kitakyusyu (Na method) Treatment HV Trans Waste Trans, Condenser, waste HV Trans waste HV trans waste HV trans Waste,mud Amounts 1.8t/day 8.0t/day 2.0t/day 1.6t/day 2.0t/day Start 2008.May Not yet Finish 2016

2005, Nov. 2016 2005, Sep. 2016 2006, Oct. 2016

1.5t/day 2004, Dec. 2016 10.4t/day 2009,July

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Ultrasound
0 10 102 103 104 105 106 107

Bumble bee (150 Hz)

Middle C (256 Hz)

Mosquito (1500 Hz)

Grasshopper (7 kHz)

Upperrange bats (70 kHz)

Human hearing Conventional power ultrasound Exended range for Sonochemistry Diagnostic ultrasound

16 Hz 18 kHz 20 kHz 100 kHz 20 kHz 2 MHz 5 MHz 10 MHz

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Acoustic Pressure

Compression

Rarefaction
~ 5000 K ~ 2000 atm
150

Bubble radius ( m)

Implosion Growth Shock Wave Rapid Quenching

100

50

Formation
0 100 200

Hot Spot
300 400

500

Time ( sec)

FIGURE. Sound Motion and the Development and the Collapse of a Cavitation Bubble 25

Sonolytical Degradation of PCBs

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Decomposition and its acceleration

pH 11.0 11.5 12.0 12.5 [OH-] (mol L-1) 0.001 0.003 0.01 0.03 ultrasonic ksonic (min-1) 0.116 0.134 0.171 0.290 t1/2 (min) 6.0 5.2 4.1 2.4 non-ultrasonic (stirring) knon (min-1) 0.0022 0.0077 0.0157 0.0324 t1/2 (min) 315.1 90.0 44.1 21.4 accelerationb 52.5 17.4 10.9 8.9

0.002 0.012 0.019 0.016

0.0001 0.0007 0.0013 0.0008

a[DEP]

60 ; at 293 = 100 Comsumption or yield (M) 50

knon

1 K
DEP

bacceleration

= ksonic /

100 80 60 %

Mass balance Reaction with OH radical Hydrolysis

40 30 20 10 0 4 6 8 pH 10 12

DEP + tertBuOH

MEP

40 20 0 4 6

CO+CH4+C2H6+C2H4+C2H2

8 pH

10

12

Pyrolysis

FIGURE. Consumption of DEP and Formation of Products as a Function of pH on 5min Sonication.

FIGURE. Reaction Pathways of the Sonochemical Degradation of 28 DEP as a Function of pH.

PFOS degradation by Sonolysis

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HPLC-MS spectrum of Sonolytical Products of PFOS and PFOA

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Dioxines? PCDDPCDFDL-PCB

Chlorine at position 2,3,7,8

0 or 1 chorine at ortho position

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Toxic Equivalency Factors (TEF

PCDDs Isomers 2378-TetraCDD 12378-PentaCDD 123478-HexaCDD 123678-HexaCDD 123789-HexaCDD 1234678-HeptaCDD OctaCDD TEF 1 1 0.1 0.1 0.1 0.01
0.0001

PCDFs Isomers 2378-TetraCDF 12378-PentaCDF 23478-PentaCDF 123478-HexaCDF 123678-HexaCDF 123789-HexaCDF 234678-HexaCDF 1234678-HeptaCDF 1234789-HeptaCDF OctaCDF TEF 0.1 0.05 0.5 0.1 0.1 0.1 0.1 0.01 0.01
0.0001

DL-PCBs Isomers 3,4,4',5-TetraCB 3,3',4,4'-TetraCB 3,3',4,4',5-PentaCB 3,3',4,4',5,5'-HexaCB 2',3,4,4',5-PentaCB 2,3',4,4',5-PentaCB 2,3,3',4,4'-PentaCB 2,3,4,4',5-PentaCB 2,3',4,4',5,5'-HexaCB 2,3,3',4,4',5-HexaCB 2,3,3',4,4',5'-HexaCB
2,3,3',4,4',5,5'-HeptaCB

IUPAC No. #81 #77 #126 #169 #123 #118 #105 #114 #167 #156 #157 #189

TEF
0.0001 0.0001

0.1 0.01
0.0001 0.0001 0.0001 0.0005 0.00001 0.0005 0.0005 0.0001

Proposed by WHO in 1998

Concentrations of Dioxines Toxic Equivalency Quantity [TEQ]concn.TEF PentaCDFs

No TEF only add the total concentration

TetraCDDs TetraCDDsPentaCDDs PentaCDDsHexaCDDs HexaCDDs

for the estimation of emission sources

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Main emission source Herbiscide:agent orange

100 80 60 40

Combustion: incenerator
100 exhaust ga s 80 60 40 flyash

2,3,7,82,3,7,8-TetraCDD

Agent Orange
20 0

20 0

Herbicide at paddy field

100 80

Natural sources: forest fire

100 80

1,3,6,81,3,6,8-+1,3,7,9+1,3,7,9-TetraCDD
60 40 20 0

PentaCP CNP
60 40 20 0

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Nalysis of PCBs
Extract (Soxhlet or PLE)

MultiMulti-Layer SilicaSilica-gel

KOH

Active CarbonCarbon-Dispersed SilicaSilica-gel

Concentrate

HighHigh-resolution GC/highGC/high-resolution MS

Fig.1 Scheme of analytical procedure

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Results
120

Preexperiment : comparison of standrd sample

100 80

Recovery (%)

60

40

20

Recoveries of PCDD/PCDFs and DLDL-PCBs obtained by Soxhlet extraction (n=3).

Value Recovery Recovery Analized Authorized value

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Analtical results Scanning Mode

Total Ion Chromatogram TIC

Peak No.5

OctaCDF

Peak No.4

1,2,3,4,6,7,8-HeptaCDF

TIC of the extract of authentic OctaCDF using PLE, and mass spectra of Peak No. 4 and 5.
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Characteristics of the abundance of PCDDs, PCDFs, and dioxin-like PCBs in sediment samples from selected Asian regions in Can Gio, Southern Vietnam and Osaka, Japan.

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 Aloui

Agent orange spray

Bien Hoa

Survay of the Dioxines at south of Vietnam and Japan

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South South of Vietnam

Sampling points
Can Gio10 points Huerural area3 points HanoiUrban area 2 points

Can Gio

No.8 No.10 No.5 No.6

No.7 No.9

No.2 No.1 No.4

0

No.3

3.5

7 km

Fig.8 A map and photograph of Can Gio

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Osaka

Kanzaki river basin

monitored from2001
Urban points Rural and residential points

Banda Waterway R. Ina R. Ai

Location No. 23

R. Yodo

R. Kanzaki

Fig.9 A map and photographs of Osaka

Around Industrial solidsolid-waste incinerators

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PCDD/PCDFs PCDD/PCDFs
PCDD/PCDF PCDD/PCDF concentration Table Total PCDD/PCDF concentrations

Area Can Gio Hue Hanoi Osaka (Suburban area) Osaka (Urban area)

Average Concn. (ng/kg-dry weight [dw]) 386 1000 530 134 9203

Concentration Range (ng/kg-dw) 62 650 250 520 59 500 2300 540 830
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380000

PCDD/PCDFs PCDD/PCDFs emission sources at 3 palces in Vietnam

100 100 Average relative concn.
100 Average relative concn.

Can Gio
Average relative concn. 80 60 40 20 0
TeCDFs OCDF HxCDDs HxCDFs HpCDFs PeCDDs PeCDFs TeCDDs OCDD HpCDDs

Hue
80 60 40 20 0
TeCDFs HxCDDs HxCDFs HpCDDs HpCDFs PeCDDs TeCDDs PeCDFs OCDD OCDF

Hanoi
80 60 40 20 0
HxCDDs HpCDDs HxCDFs HpCDFs TeCDDs OCDD PeCDDs TeCDFs PeCDFs OCDF

PCDD/PCDF homologue

PCDD/PCDF homologue

PCDD/PCDF homologue

(a) Can Gio

(b) Hue

(c) Hanoi

Fig.10 Profiles of PCDD/PCDF homologues in sediment samples from from Vietnam.

OctaCDD + HeptaCDDsPentaCP or natural sources PCDFs combustion

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PCDD/PCDFsand PCDD/PCDFsand their emission sources in Osaka

100 Average relative concn. 80 60 40 20 0
TeCDFs HxCDDs TeCDDs PeCDDs HpCDDs HpCDFs HxCDFs PeCDFs OCDD OCDF

100 Average relative concn.

Suburban locations s, Osaka

Urban locations, Osaka

80 60 40 20 0
OCDD HxCDFs HxCDDs HpCDDs TeCDDs PeCDDs HpCDFs TeCDFs PeCDFs OCDF

PCDD/PCDF homologue

PCDD/PCDF homologue

(a) Suburban areas

(b) Urban areas

from m Osaka Fig.11 Profiles of PCDD/PCDF homologues in sediment samples fro

OctaCDD + HeptaCDDsPentaCP or Natural sources TetraCDDs 1,3,6,8-+1,3,7,9-TetraCDDs CNP PCDFsemitted from combustion process
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 emission sources of OctaCDD

Contaminated in Pentachlorophenol Japan until 1970 Virtnam :unknown

Cl Cl OH Cl Cl Cl

Cl Cl Cl Cl

Cl O

Cl Cl

HO Cl

Cl

Cl Cl

O Cl

Cl

Natural sources : forest fire 1Low concentration of PCDFs 223782378-substituted HexaCDDs 123789123789-HexaCDD 53% 53%123678123678-HexaCDD 30%
PentaCP

OctaCDD

Table 2 Ratios of 123789123789- or 123678123678-HexaCDDs to total 23782378substituted HexaCDDs

Area Can Gio Hue Hanoi Osaka 123789-HexaCDD 54% 55% 40% 38% 12378-HexaCDD 28% 28% 40% 42%

CanGip CanGip and Hue :Natural Osaka Osaka : :PentaCP PentaCP Hanoi: Hanoi: unkown

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DL DLDL-PCBs
DL DLDL-PCBs PCBs Table 3 Total DLDL-PCB concentrations
Area Can Gio Hue Hanoi Osaka (Suburban area) Osaka (Urban area) Average Concn. (ng/kg-dw) 250 260 13000 250 88000 Concentration Range (ng/kg-dw) 20 1100 100 12000 16 360

490 13000 700 370000

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DL DLDL-PCBs estimation of emission source

DLDL-PCBs

+ +

PCB materials materials combustion

Table 4 Ratios of (#126 + #169)/( #169)/(#77 )/(#77 + #126 + #169) #169)

Area

No.3 (near town) No.4 (near shrimp nursery) No.6 (near hotel) No.7 (near hotel)
Hue Hanoi Osaka (Suburban area) Osaka (Urban area)

Can Gio

Ratio 0.190.15 0.55 0.22 0.21 0.19 0.030.03 0.08 0.090.05 0.060.0 4

PCB PCB PCB PCB PCB PCB

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Sources

WHO WHOWHO-TEQ
WHO WHOWHO-TEQ Table 5 WHOWHO-TEQ values
Area Can Gio Hue Hanoi Osaka (Suburban area) Osaka (Urban area) WHO-TEQ (ng/kg-dw) 2.7 2.9 9.6 2.3 190 Range (ng/kg-dw) 0.42 0.92 9.3 0.18 1

Environmental Criteria of Japan: 150 ng/kg-dw

7.2 5.6 9.8 1.1 370

WHO-TEQ: TEQ obtained from TEF proposed by WHO in 1998.

Can Gio: same as other big cities in Vietnam City Center in Osaka: very high
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Conclusion
PCDD/PCDF Source Can Gio Hue Hanoi Suburban Osaka Urban Osaka
Natural Agent Orange Natural

DL-PCBs Source
Combustion PCB products PCB products

TEQ

Natural agent orange PCB products

Natural PCB products

Combustion Agricultural Chemicals Combustion Agricultural Chemicals Combustion

PCB products

PCB products

combustion

PCB products

Agricultural chem. =combustion =PCB products Combustion and PCB products

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PCB products

Thank you!

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