New Technologies for Site Measurement and Remediation

June 7th, 2006

Masaaki Hosomi

Tokyo University of Agriculture and Technology

Contents• Ground Air System (GAS) for Chlorinated

ethenes: Non-drilling Soil-gas Survey→ Kimitsu System Co. Ltd. & GAS Research Association

• Real-Time PCR Techniques Targeting 16S rDNA of Dehalococcoides for Bioremediation of Chlorinated ethenes→ Kanji Nakamura et al. & Kurita Water Industries Ltd.

Nakashima et al. (Kokusai Kogyo Co. Ltd.)

• Non-combustion technology for dioxin, PCB and POPs pesticides: Mechanochemical Process (MC)→ Radicalplanet Research Institute Co. Ltd.

Ground Air System (GAS)~ Non-drilling Soil Gas Survey ~

Copy Right: Kimitsu System Co.Ltd.http://www.gass.jp/index.html

http://gass.jp/index_kaimei.htmlhttp://www.kimitsu-system.com/

International Patentee: Suzuki Yoshikazu

(e-mail:info@kimitsu-system.com)

Ground Air System (GAS)

Sampling pump

Main pump-Vacuum pump-Blower

Soil gas detector

The soil-gas is extracted by the vacuumed pressure inside the GAS vessel.

GAS Vessel

: Soil gas air flow

Soil-gas surveyDrilling system Non-drilling system

The sampling pipe is set up under the soil.

The device is set up on the ground level.

Floor inside of factories and buildings under operating

Ground covered with concretedifficult

CostHigh Low

Possible

Searching hot-spot (a heavily polluted area)

by GAS

•High-efficiency •Low cost

Overview of soil gas survey by GAS

Soil Gas Sampling

pump

Gas detector

Vacuum pump

Blower

GAS Vessel

GAS VesselVacuum pump

Main pumpswitch cock

Blower

To Soil Gas

Sampling pump

Pressure gauge: Air flow

Sampling and Measuring by Gas Detector Tube

Sampling pump outlet

Gas detector tube

Connecting sampling port from GAS vesseland tetra-bag for soil gas sampling

Joint Research between GAS and my Laboratory

Extracted area of the soil-gas has not been understood with accuracy.

Estimate extracted area of the soil-gas by the GAS.

•Differential pressure (DP) test

•Tracer test

Differential pressure (DP) testEstimate extracted area by the main pump.

Main pump

Measure the DP between soil and atmospheric air.

Sampling pump

Manometer

Porous stone

Main pump

Measure the detection time of gas.

Sampling pump

Porous stone

Tracer test

He

Tracer gas

Estimate extracted area by the sampling pump.

He detector

Sandpit

200 cm

80 cm

Map of extracted area

Distribution of DP [kPa] Distribution of average transfer speed of tracer gas [cm/s]

Extent of the impact of GAS is about 40-50 cm vertical under GAS vessel.

Main pump：Vacuum pump

-50 -30 -20 -10 0 10 20 30 5070

60

50

40

30

20

10

Distance of center [cm ]

Depth [cm]

2-2.51.5-21-1.50.5-10-0.5

GAS

-50 -30 -20 -10 0 10 20 30 5070

60

50

40

30

20

10

Distance of center [cm ]

Depth [cm]

2-2.51.5-21-1.50.5-10-0.5

GASGAS

-50 -30 -20 -10 0 10 20 30 5070

60

50

40

30

20

10

Distance of center [cm ]

Depth [cm]

0-0.005 0.005-0.010.01-0.015 0.015-0.020.02-0.025 0.025-0.03

GAS

-50 -30 -20 -10 0 10 20 30 5070

60

50

40

30

20

10

Distance of center [cm ]

Depth [cm]

0-0.005 0.005-0.010.01-0.015 0.015-0.020.02-0.025 0.025-0.03

GASGAS

Measurement of GAS in a Factory under Operation（MOE：Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Photo:Provided by Mitsuya Industrial Co. Ltd. (2003-2004)

Measurement of GASS outside a Factory under Operation（MOE：Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Provided by Mitsuya Industrial Co. Ltd. (2003-2004)

1 m-depth Core Boring for Soil Gas Investigation Following the Soil Investigation Manual in a Factory under Operation（MOE：Demonstration Program for Low-cost and Low-loading type Soil Monitoring and Remediation Technologies Provided by Suzuki (2003-2004)

1 m-depth Core Boring for Soil Gas Investigation Following the Soil Investigation Manual(Provided by Mr. Kamisuna)

Measurement of GAS in a Factory under Operation（MOE：Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Provided by Suzuki (2003-2004)

68 70 72 74 76 78 80 82 84 86 88 90 92 94 96 98 100

46

48

50

52

54

56

58

60

62

64

66

68

70

72

74

76

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80

82

84

86

1.4 3.1 0 0.4 0.6 0 0.2

0.1 0 8.1 0 0.3 3.9

1.8 1 1 1.5 0.3 3.3 2.1

5.7 1.9

0 12 65 10 9.3 6.6 1.5

15 12

0.5 18 0.9

20 6.9 6.6 18

0.3 3.5 6 0.6 15 0.9

18 6

0 0.10

9 9 15 4.5 7.8 25 24 33 100 480

3.8 2.1 50 0.1

0.7 0.7 15 15

8.1 7.5 1.5

0.8 11 0.8 3.4 3 10.5 6 138 12

1 6.6 5.7

5 9 1.2 3 4 8.5 11 12.5 15 6.9

6 3 36 7.5

0 1 12 90 4 6

1.3 2 1 10 140 21 6 1.5 2.1

3 7 42 6

1 10 9 50 84 0

6 50 110 25100160 13 50 95 30 0.9 0.3

0 5 1.5 87 28 6 30 27 38 0

10 12.5 35 50 10

0 18 1 1515 105 6 21 36 18 24 0 0

115 200

82 240 60 30 21 35 51 15 3.6 0

50 60 125

2 5 66 15 21 15 30 15 51 12

42

0 30 0.2 7.5 0.5 2.4 3 2.6 0.4 6 1.2 0.8 0 0

0125101520304050608090100120140160180200220240260280300350400450480

Horizontal distribution of TCE in soil gas determined by GASwithout core boring（MOE：Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Provided by Suzuki (2003-2004)

Soil-gas survey by GAS

• System of searching a heavily polluted area

• Survey on floor inside of buildings and ground covered with concrete is possible.

• High-efficiency and low-cost system

• Rapid measurement (a few minutes)

Development of Real-Time PCR Techniques Targeting 16S rDNA of Dehalococcoides

for Bioremediationof Chlorinated ethenes-contaminated Sites

Kanji Nakamura (Tohoku Gakuin University)*Hiroaki Ishida (Kurita Water Industries Ltd.**)**

Masahiro Mizumoto (Kurita Water Industries Ltd.**)**

How to manage and control bioremediation

Field: Bioremediation of contaminated soil

Contaminants: Chlorinated ethenesTetrachloroethene (PCE)Trichlororethene (TCE)Dichloroethene (DCE)Vinyl chloride (VC)

Microbe: Dehalococcoides bacteria

Technology: Biostimulation

Pathway of anaerobic dechlorination

Proceed easily Dehalococcoides is needed

Ｈ

ＨＨ

ＨＣ Ｃ

Ｈ

ClCl

Ｈ

Ｃ Ｃ

Ｈ

ClＨ

Ｈ

Ｃ

Ｈ

ＨＨ

Ｈ Ｈ

ＨＨ

ＨＨ

ClCl

Ｈ Ｈ

ClCl

Ｈ Ｈ

ClＨ

Ｈ

Ｃ

Ｈ

ClＨ

ＨCl

ClCl

Ｈ Cl

ClCl

Ｈ Cl

ClCl

ＨＣ Ｃ

Cl

ClCl

Cl

ClCl

Cl

ClCl

ClＣ Ｃ

TCE ETHPCE c-DCE VC

Electron Donor：Ｈ２

Produced from added organics

Electron Acceptor: PCE, TCE, c-DCE, VC

Maymo-Gatell et al. (1997) : Dehalococcoides ethenogenesHendrickson et al. (2002): Classification of Dehalococcoides

TCE degradation in vials with soils from 14 different contaminated sites in Japan

SoilGW

7/147/14NMLKJIHGFEDCBA

Detection of Dehalococcoides 16S rDNA

Final ProductSoil Sample

Incubated 60 daysat 30℃

TCE with Na-acetate, N, P

Not detectedNot detectedNot detectedNot detectedNot detectedNot detectedNot detected

TCETCE

c-DCEc-DCEc-DCEc-DCEc-DCE

DetectedDetectedDetectedDetectedDetectedDetectedDetected

ETHETHETHETHETHETHETH

Dehalococcoides 16S rDNA cloned from 7 vials （PCR amplified w/ Bact27f/1492r）

GATGAACGCTAGCGGCGTGCCTTATGCATGCAAGTCGAACGGTCTTAAGCAATTAAGATAGTGGCGAACGGGTGAGTAACGCGTAAGTAACCTACCTCTAAGTGGGGGATAGCTTCGGGAAACTGAAGGTAATACCGCATGTGGTGGRCCGACATATGTTGGTTCACTAAAGCCGTAAGGCGCTTGGTGAGGGGCTTGCGTCCGATTAGCTAGTTGGTGGGGTAATGGCCTACCAAGGCTTCGATCGGTAGCTGGTCTGAGAGGATGATCAGCCACACTGGGACTGAGACACGGCCCAGACTCCTACGGGAGGCAGCAGCAAGGAATCTTGGGCAATGGGCGAAAGCCTGACCCAGCAACGCCGCGTGAGGGATGAAGGCTTTCGGGTTGTAAACCTCTTTTCATAGGGAAGAATAATGACGGTACCTGTGGAATAAGCTTCGGCTAACTACGTGCCAGCAGCCGCGGTAATACGTAGGAAGCAAGCGTTATCCGGATTTATTGGGCGTAAAGTGAGCGTAGGTGGTCTTTCAAGTTGGATGTGAAATTTCCCGGCTTAACCGGGACGAGTCATTCAATACTGTTGGACTAGAGTACAGCAGGAGAAAACGGAATTCCCGGTGTAGTGGTAAAATGCGTAGATATCGGGAGGAACACCAGAGGCGAAGGCGGTTTTCTAGGTTGTCACTGACACTGAGGCTCGAAAGCGTGGGGAGCGAACAGAATTAGATACTCTGGTAGTCCACGCCTTAAACTATGGACACTAGGTATAGGGAGTATCGACCCTCTCTGTGCCGAAGCTAACGCTTTAAGTGTCCCGCCTGGGGAGTACGGTCGCAAGGCTAAAACTCAAAGGAATTGACGGGGGCCCGCACAAGCAGCGGAGCGTGTGGTTTAATTCGATGCTACACGAAGAACCTTACCAAGATTTGACATGCATGTAGTAGTGAACTGAAAGGGGAACGACCTGTTAAGTCAGGAACTTGCACAGGTGCTGCATGGCTGTCGTCAGCTCGTGCCGTGAGGTGTTTGGTTAAGTCCTGCAACGAGCGCAACCCTTGTTGCTAGTTAAATTTTCTAGCGAGACTGCCCCGCGAAACGGGGAGGAAGGTGGGGATGACGTCAAGTCAGCATGGCCTTTATATCTTGGGCTACACACACGCTACAATGGACAGAACAATAGGTTGCAACAGTGCGAACTGGAGCTAATCCCCAAAGCTGTCCTCAGTTCGGATTGCAGGCTGAAACCCGCCTGCATGAAGTTGGAGTTGCTAGTAACCGCATATCAGCATGGTGCGGTGAATACGTTCTCGGGCCTTGTACACACCGCCCGTCACGTCATGAAAGCCGGTAACACTTGAAGTCGATGTGCCAACCGCAAGGAGGCAGTCGCCGAGGGTGGGACTGGTAATTGGGACG（Position１４８:ＡorＧ）

A dominant type of Dehalococcoides existing in Japan

Detection of Dehalococcoides 16S rDNAby block PCR

１ ２ ３ ４ ５ ６ ７ ８ ９

445 bp

Gro

undw

ater

ＡG

roun

dwat

er B

Gro

undw

ater

CG

roun

dwat

er D

Gro

undw

ater

ＡG

roun

dwat

er B

Gro

undw

ater

CG

roun

dwat

er D

628 bp

Primer pair B (De624f and De1232r)This study

Primer pair ALoffler et al. (2000).

15

20

25

30

35

40

101 102 103 104 105 106

PC

R C

ycle

Num

ber

that

am

plifi

ed a

cer

tain

am

ount

of D

NA

Dehalococcoides 16S rDNA concentration (copies/mL)

Real-Time PCR by LightCycler

Detection of Dehalococcoides 16S rDNAby Real-Time PCR

Chl

orin

ated

eth

enes

& E

then

e (m

g/L)

10８

10７

10６

10５

10４

10３

De-16S rDNA

De-

16S

rDN

A (c

opie

s/m

L)

0

1

2

3

4

5

6

7

0 10 20 30

c-DCE

VC

ETH

Time (days)

Full scale biostimulation

10

100

1000

10000

No.1 No.2 No.3 No.4 No.5 No.6 No.7 No.8

Deh

aloc

occo

ides

16S

rDN

A

(cop

ies/

mL)

Initial Dehalococcoides 16S rDNA concentrationsin groundwater at a contaminated site

Monitoring wells in bioremediation area

The result showed the feasibility of biostimulation

Change of De-16S rDNA concentrations in groundwaterIntermittent addition of organics and nutrients from multiple wells w/o circulation

Significant increase was observed in 3 months1.0E+08

16S

rDN

A(c

opie

s/m

L) 1.0E+07

1.0E+06

1.0E+05

1.0E+04

1.0E+03

1.0E+02

1.0E+01

1.0E+000 30 60 90 120 150 180 210 240 270 300

Time (days)

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

1.0E+07

1.0E+08Dehalococcoides

16S rDNA

(copies/mL)

De 16S rDNA

0 100 200 300 400 500

1

10

100

1000

10000

0 100 200 300 400 500

Time (days)

Chlorinated Ethenes (µg

/L)

TCE c-DCE VC

Target value for c-DCE

All field data showed this correlation

The increase of Dehalococcoides population ledthe decrease of chlorinated ethenes in the field

Conclusions

１．Dehalococcoides population was needed forcomplete dechlorination.

２．A certain type of Dehalococcoides was dominant in Japan.

３．Real-Time PCR targeting 16S rDNA of Dehalococcoides was successfully used to managethe full scale biostimulation.

Non-combustion technology for dioxin, PCB and POPs pesticides: Mechanochemical Process (MC)

Radicalplanet Research Institute Co. Ltd.& Hosomi Laboratory

Background for Non-combustion Technologies

• POPs Convention requires disposal techniques to be in environmentally sound manner and not produce other POPs by-products in the national implementation plan.

• Environmental and health concerns about release of POPs by-products like dioxins from incineration plants have triggered the development of alternative destruction technologies.

PCB problems in Japan• PCB wastes including transformers, capacitors and

carbonless copy paper have been stored for about 30 years because construction of incineration plant as PCB disposal facility has not been accepted publicly.

• In order to manage the risk of PCB release into the environment during long-term PCB storage, the central government established the evaluation system of emerging and alternative destruction technologies in 1996, i.e., non-combustion technologies.

Development of non-combustion technologies

• Private sectors have demonstrated the performance and effectiveness of non-combustion technologies for destruction of PCB wastes.

• Most of non-combustion technologies include chemical dehalogenation process with liquid phase reaction. (i.e., minimization of off-gas generated and easiness of verification of PCB degradation)

Definition of non-combustion technologies: alternative destruction technologies of incineration

Approval of non-combustion technologies

• The committees organized by the central government have reviewed these demonstration data in terms of treatment performance, by-products, final products, operation conditions and environmental concerns and confirmed several alternative technologies as officially approved PCB-disposal technologies.

Approved PCB Treatment TechnologiesDecomposition technologies of liquid PCB waste• Chemical dehalogenation

-Base catalyzed decomposition-Metallic sodium dispersion process-UV irradiation-Pd/C catalytic hydrogenation reduction-t-C4H9OK chemical extractive decomposition

• Molten metal decomposition• Plasma decomposition• Hydrothermal decomposition and Supercritical water

oxidation• Mechanochemical process

(officially granted by the notification (No.25, April 1, 2004)

Washing and separation technologies of PCB waste• Vacuum thermal separation• Solvent/oil washing

Why do we focus on MC process?

High Safety

Non-heating process Closed system

＋

On-site treatment by mobile equipment

Lower cost and remove anxietywithout transfer of pollutants

Community and Publicacceptance

MC is applicable to remediation of small site

RevolutionRevolution

RotationRotation

CaOCaO CaOCaO

(700rpm)

(700rpm)

steel balls

Targetsubstance

RevolutionRevolution

RotationRotation

CaOCaO CaOCaO

(700rpm)

(700rpm)

steel balls

Targetsubstance

Stainless steel pot

Rotating Disk

Ｍechanochemical (MC) treatment with a planetary ball mill

029.77

72.2399.72

100.599.5100

70.06

28.370 0 0

0

20

40

60

80

100

0 0.5 1 2 4 8Milling time (h)

Tota

l chl

orin

e ra

tio (％

)

Chloride ions ratio

Chlorine ratio in remaining 4CB

029.77

72.2399.72

100.599.5100

70.06

28.370 0 0

0

20

40

60

80

100

0 0.5 1 2 4 8Milling time (h)

Tota

l chl

orin

e ra

tio (％

)

Chloride ions ratio

Chlorine ratio in remaining 4CB

Chlorine balance during MC treatment of 4-chlorobiphenyl (4CB)

Time dependence of the molar ratio of degradation products during MC treatment of 4CB.

0 2 4 6 8Milling time [h]

Mol

ar ra

tio [%

]

100

0

20

40

60

80

100

0

20

40

60

804CBBiphenylCyclohexylbenzeneTerphenylQuarterphenylTotal

C l

D e c h l o r i n a t i o n

H y d r o g e n a t e - r e d u c t i o nP o l y m e r i z a t i o n

P o l y m e r i z a t i o n

D e c o m p o s i t i o n t o l o w e r m o l e c u l a r c o m p o u n d s

M i n e r a l i z a t i o n ？

H y d r o g e n a t e- r e d u c t i o n

P o l y m e r i z a t i o n

T e r p h e n y l s

Q u a t e r p h e n y l s* *

*

*

C lC l

-P o l y m e r i z a t i o n

P o l y m e r i z a t i o n

D e c o m p o s i t i o n t o l o w e r m o l e c u l a r c o m p o u n d s

M i n e r a l i z a t i o n ？

H y d r o g e n a t e- r e d u c t i o n

P o l y m e r i z a t i o n

T e r p h e n y l s

Q u a t e r p h e n y l s* *

*

*

・

・

*

*

R a d i c a l l y

R a d i c a l l y

C lC l

D e c h l o r i n a t i o n

H y d r o g e n a t e - r e d u c t i o nP o l y m e r i z a t i o n

P o l y m e r i z a t i o n

D e c o m p o s i t i o n t o l o w e r m o l e c u l a r c o m p o u n d s

M i n e r a l i z a t i o n ？

H y d r o g e n a t e- r e d u c t i o n

P o l y m e r i z a t i o n

T e r p h e n y l s

Q u a t e r p h e n y l s* *

*

*

C lC l

-P o l y m e r i z a t i o n

P o l y m e r i z a t i o n

D e c o m p o s i t i o n t o l o w e r m o l e c u l a r c o m p o u n d s

M i n e r a l i z a t i o n ？

H y d r o g e n a t e- r e d u c t i o n

P o l y m e r i z a t i o n

T e r p h e n y l s

Q u a t e r p h e n y l s* *

*

*

・・

・・

*

*

R a d i c a l l y

R a d i c a l l y

Proposed degradation pathways of 4CB by the MC treatment.(*, not detected; **, detected, but not confirmed by spike test

0

1000000

2000000

3000000

4000000

5000000

6000000

0 10 20 30 40 50 60

Milling time (min)

conc

. (pg

)

T4CDDsP5CDDsH6CDDs

H7CDDsO8CDD0

500

1000

1500

2000

2500

3000

0 10 20 30 40 50 60

0

1000000

2000000

3000000

4000000

5000000

6000000

0 10 20 30 40 50 60

Milling time (min)

conc

. (pg

)

T4CDDsP5CDDsH6CDDs

H7CDDsO8CDD0

500

1000

1500

2000

2500

3000

0 10 20 30 40 50 60

Degradation of OCDD and by-productsduring MC treatment of OCDD

0

1000000

2000000

3000000

4000000

5000000

6000000

0 10 20 30 40 50 60

Milling time (min)

T4CDFs

P5CDFs

H6CDFs

H7CDFs

O8CDF0

500

1000

1500

2000

2500

3000

0 10 20 30 40 50 60

0

1000000

2000000

3000000

4000000

5000000

6000000

0 10 20 30 40 50 60

Milling time (min)

T4CDFs

P5CDFs

H6CDFs

H7CDFs

O8CDF

T4CDFs

P5CDFs

H6CDFs

H7CDFs

O8CDF0

500

1000

1500

2000

2500

3000

0 10 20 30 40 50 60

Degradation of OCDF and by-productsduring MC treatment of OCDF

Dechlorination rates [%] based on analyses of chloride ions after MC treatment of OCDD and OCDF for 2 h showed 99.9% and 99.3%, respectively.

Nomura and Hosomi (2005) Elucidation of degradation mechanism of dioxins during mechanochemical treatment, Env. Sci. Tech., 39, 3799-3804.

Note that this is the first study to demonstrate 100% dechlorination of dioxins by measuring the amount of chloride ions produced during the MC treatment of OCDD/OCDF.

No remaining dioxins or no other organochlorine compounds were detected, which confirms the complete dechlorinationof OCDD/F.

What is Japanese Stockpile?

MOAFF put out the notice of collecting unused POPs pesticides in shed of end users through NOKYO and burying collected pesticides underground in 1972 because of their toxicity and adverse effects on human health.

Buried POPs pesticides are defined as Japanese Stockpile.MOAFF has started to identify quantity and location of buried

POPs pesticides since adoption of POPs convention and reported that total amount of buried POPs is about 4000 t and there are about 200 sites through sending out questionnaires to local governments and NOKYO.

Buried POPs pesticides mainly consist of BHC, DDT, Chlordane, Dieldrin, Endｒin, Aldrin, and Heptachlor.

Employed Technologies in MOAFF’s Project

• 2000 fiscal yearMechanochemical process

• 2001 fiscal yearHydrothermal decompositionVacuum thermal decompositionGeo-Melt vitrification

• 2002 fiscal yearMetallic sodium dispersion processBase catalyzed decompositionSupercritical water oxidation

Feasibility of treating POPs Pesticidesusing MC process

Target compounds for treatment

PCNB

Cl

ClCl

Cl

ClNO2

γ-HCH

Cl

ClCl

Cl

ClCl

H

HH

H

Cl

Cl

ClCl

ClCl

Cl

Heptachlor

additives CaO:2 gtarget compound: 50 mgRotational speed:700 rpmMilling time :2 h

Chloride ions extracted by hot water and ultrasonic cleaning for milled mixtures were measured by ion chromatography.

99.4 99.4 100.8

Heptachlor γ-HCH PCNBTarget compound

Dechlorination ratio（％）

( Dechlorination ratio: the amount of chloride ions / chlorine in a target compound added to the system )

・Dechlorination ratio reached 100 % in treatment of target compounds・No organochlorine compound was detected as degradation products by the GC-MS analysis

Degradation mechanism of γ-HCH during MC treamtment

Experimental condition

HCH and CaOAdditives :1:10 molar ratio with respect to chlorine bound γ- HCH to calcium as CaOAmounts :

Milling time : 120 min

Toward to elucidate the degradation behavior of γ- HCH

Ion chromatograph for analysis of chloride ions in milled mixtures

GC-MS for analysis of HCH and the degradation products in milled mixtures

Cl

Cl

ClCl

Cl

H

Cl Cl

Cl

ClCl

Cl

H H

H Cl

H

ClCl

Cl

Cl Cl

Cl

Cl ClCl

Cl

Cl

Cl

H Cl

H

ClCl

H

H Cl

H

ClH

Cl

HCH 2,3,4,5,6-pentachlorohexene（PCCH)

Degradation pathway of γ-HCH by MC treatmentDehydrochlorination (-HCl)

Dehydrochlorination (-HCl)

Dehydrochlorination (-HCl)

1,2,4-TriCB 1,3,5-TriCB

Cl Cl Cl

Cl

1,2,3-TriCB

1,4-DCB 1,3-DCB 1,3-DCB

>Major

dechlorination dechlorinationdechlorination

1,2-DCB 1,2-DCB

Cl

dechlorination

100% dechlorination accomplished, andDegraded to lower molecular compounds including Carbon !

Conclusions・Dechlorination ratio reached 100 % in treatment ofheptachlor, HCH and PCNB, and no organochlorine compound was detected by GC-MS analysis. These resultsconfirmed the feasibility of treating POPs pesticides.

・Dechlorination ratio in the MC treatment of HCH increasedwith milling time, and reached 100 % in 120 min.

・Chlorobenzenes and 2, 3, 4, 5, 6-pentachlorocyclohexene(PCCH) were identified as the major degradation productsof the MC treatment of HCH.

・The degradation of HCH proceeds via dehydrochlorinationand the dechlorination of degradation products .

Schematic Profile of Commercial MC plant

Radicalplanet Research Institute Co. Ltd.

motor

MC reactor Planet E-200

powder collecting equipment

Commercial MC plant owned by Radicalplanet Research Institute Co. Ltd.

E-200 Type

Produced by Sumitomo Heavy Industries Techno-Fort Co.,Ltd.

Transportability of MC Plant (Planet E-200)

“Radicalplanet process” consists of the Planet E-200, a motor and powder collecting equipment.These equipments are simple, compact , separated and are transportable by trailers.

Skematic Mechanochemical Plantby Radicalplanet Research Institute Co. Ltd.

Direction of Each Reaction Pot RotationTop Plate

Pot Axis

Reaction Pot

Base Axis

Base PlateDirection of Base Plate Rotation

Pot Plate

PCB-contaminated Soil Destruction Treatments

PCB-contaminated soil

PCB oil and mixed oil

T im e(hrs)P C B (m g/kg)0 1,28316 1.532 0.1264 N D (＜0.01)

PCDDｓ＋PCDFｓ Co- PCB Tot al0.00037 0.0041 0.0045

DXNｓ（ｐｇ－TEQ/ g)

PCB（Fluorescent Ballastcontaining PCB Oil） Destruction Treatments

T im e(hrs)P C B (m g/kg)0 1,26316 N D (＜0.01)32 N D (＜0.01)64 N D (＜0.01)

PCB oil and mixed oilFluorescent Ballast

PCDDｓ＋PCDFｓ Co- PCB Tot al0 0.00027 0.00027

DXNｓ（ｐｇ－TEQ/ g)

γ-BHC Destruction by MC Treatments

γ-BHC (liquid)

0

10,000

20,000

30,000

40,000

50,000

0 2 4 6 8 10TIM E（ｈｒs）

γ-BHC（ppm）

D Es(％) ＞99．999891D REｓ（％）＞99.99999996D XN s（pg-TEQ /g）＝0.031

10,146ppm

46,827ppm

PCP Destruction by MC Treatments

PCP (Pentachlorophenol)

0.02

-2,000

0

2,000

4,000

6,000

8,000

0 10 20 30 40

TIM E（ｈｒ）

PCP

（ppm）

D Es(％) ＞99．997949D R Es(％) ＞99.9999998D X N s（pg-TEQ /g）＝0.18

6,652ppm (67%P C P )

Chlordane Destruction by MC Treatments

0

1,000

2,000

3,000

4,000

5,000

0 10 20 30 40TIM E（ｈｒs）

Chlordan

e（ppm）

D es（％） ＞99．999521D REs（％） ＞99.99999954D XN s (pg-TEQ /g) ＝0.034

3,986ppm （40％)

Chlordane

Endrin

<0.001

<0.001

<0.001

<0.001

γ B H C

D D T

B H C

op' D D T

pp' D D T

pp' D D D

pp' D D E

α B H C

β B H C

δ B H C

8H rs A fter

<0.001

<0.001

<0.001

0.003

<0.001

(Unit：mg/ kg)

R esults of D istruction

POPs Wastes Weights : 20~80kg / Charge

BHC Powder

Admixture of Powder

DDT Powder

Endrin Powder

MC Destruction of Mixed Agricultural Chemicals

POPs Wastes Treated by MC (1)

Plastic MasksConcrete and Soil

Clothe and Work Gloves Protective clothing (Tyvex)

POPs Wastes Treated by MC (2)

Chipped Wood Cardboard

Pipes and Can made of MetalPieces of PP and PVC

Destruction Treatment of Mixed Wastes

MC Destruction

Powder after MC TreatmentMixed Wastes in Reaction Pot

Summary• GAS is very promising and time- and cost-saving

technology for soil gas survey in urban area including operating factory with concrete floor.

• High-sensitive real-time PCR techniques targeting 16S rDNA of Dehalococcoides give valuable information on applicability of biostimulation in small sites.

• MC process is applicable to remediation in small sites contaminated by pretty high-strength POPs.