Field Experience in Bioremediation Soil and Groundwater - - PowerPoint PPT Presentation

SLIDE 1

Field Experience in Bioremediation ｏ ｆ Soil and Groundwater Contaminated with Chlorinated solvents and Hexavalent Chromium in Japan

September 23, 2008

• ---- EcoCycle Corporation, Japan

SLIDE 2

EcoCycle Corporation

• Established in 1999
• Business: Environmental remediation, Bioinoculants for

agriculture, recycling of industrial effluents, EHS consultant

• Some of the clients are manufacturers of Car, electronic

equipment, electrical apparatus, dry cleaning facilities etc. (Hitachi Group, Mitsubishi group)

• Technological partnership with more than 40 engineering

companies in Japan, the USA (GZA Geoenvironmental, USA), Taiwan, Korea and growing.

SLIDE 3

Some Prominent Treatment Technologies today in the market

Soil vapor extraction and air sparging Dig and dispose Pump and Treat Chemical oxidation

SLIDE 4

N

• t

f

• r

g r

• u

n d w a t e r × ○ ○ × ○ M

• n

t h s

• f

e w y e a r s 5 ～1 5 K V e n t i n g H i g h c

• s

t / N

• t

f

• r

a c t i v e f a c i l i t y × ○ ○ ○ × W e e k s

• m
• n

t h s 1 5 ～ 4 K H

• t

s

• i

l C r 6 m a y r e l e a s e / N

• t

g

• d

u n d e r h i g h O C / K i l l u s e f u l m i c r

• r

g a n i s m s ○ ▲ ▲ × ○ F e w m

• n

t h s

• y

e a r s 5 ～2 K O x i d a n t s N

• t

f

• r

a c t i v e f a c i l i t y / A f f e c t h y d r

• g

e

• l
• g

y ○ ○ ▲ ○ × M

• n

t h s 3 K F e ( ) V e r y l

• n

g t i m e ○ × ○ × ○ T e n s

• f

y e a r s （ ※4 ） P u m p a n d T r e a t H i g h c

• s

t × ○ ○ ○ × W e e k s 4 ～ 6 K D i g a n d D i s p

• s

e C

• n

c e n t r a t i

• n

s a b

• v

e 4 m g / L a n d e x t r e m e p H ○ ▲

○： ～ 1 5 m g / L ▲ ： 1 5 m g / L ～

○ ○ 3 ～ 1 2 m

• n

t h s 5 ～1 5 K E D C b a s e d b i

• r

e m e d . L i m i t a t i

• n

s G r

• u

n d w a t e r V e d

• s

e Z

• n

e H i g h C

• n

c e n t r a t i

• n

L

• w

K s

• i

l A c t i v e F a c i l i t i e s T i m e s p a n R e m e d i a t i

• n

C

• s

t （ y e n / 1 ㎥） T e c h .

Comparison of Different Leading Remediation Technologies

• ○ =

G

• d

; × =

N

• t

G

• d

; ▲ = H a s s

• m

e d r a w b a c k s

• T

h e P r i c i n g i s i n J a p a n e s e Y e n ( 1 J P Y = U S $ 1 ) a s i n t h e J a p a n e s e m a r k e t

• P

r i c i n g v a r y w i t h s i t e h y d r

• g

e

• l
• g

y , c

• n

t a m i n a t i

• n

s i g n a t u r e e t c .

• I

t i s d i f f i c u l t t

• a

s s e s s t h e c

• s

t

• f

p u m p a n d t r e a t b e c a u s e i t w

• u

l d t a k e t e n s

• f

y e a r s t

• c

l e a n t h e s i t e

SLIDE 5

Biorem ediation

Exploiting ability of m icroorganism s to degrade/ detoxify contam inants

Bioaugm entation

I ntroducing m icrobes in the contam inated m edia

Biostim ulation

Stim ulating native m icrobes

Aerobic

Stim ulating m icrobes that use oxygen for respiration

Obligate anaerobic

Stim ulating m icrobes that live only w hen oxygen is absent ( EDC m ediated chlorinated solvent rem ediation)

Facultative anaerobic

Stim ulating m icrobes that live in presence or absence of oxygen ( EDC-M m ediated Cr( VI ) rem ediation

SLIDE 6

Target contaminants

Halogenated Aliphatic Hydrocarbons (CAHs): Perchloroethylene

(PCE), Trichloroethylene (TCE), Trichloroethane (TCA), Dichloromethane (DCM) which were being used as solvents and de- greasers in the industries like automobile, hardware, electronic equipments etc.

And their daughter products like Dichloroethylene (DCE),

Dichloroethane (DCA), Vinyl chloride (VC)

Hexavalent Chromium which has been used in Tanning, electroplating,

electrical apparatus etc.

Petroleum hydrocarbons, cyanide etc (Pilot test is a must) Other heavy metals like Lead, Manganese, Arsenic, Selenium etc.

(Pilot test is a must)

SLIDE 7

F

• r

C h l

• r

i n a t e d h y d r

• c

a r b

• n

s F

• r

C h l

• r

i n a t e d h y d r

• c

a r b

• n

s

E D C E D C E D C E D C

• E

E

F

• r

C y a n i d e a n d F

• r

C y a n i d e a n d p e t r

• l

e u m h y d r

• c

a r b

• n

s p e t r

• l

e u m h y d r

• c

a r b

• n

s

H A R H A R E D C E D C

• M

M

F

• r

H e x a v a l e n t c h r

• m

i u m F

• r

H e x a v a l e n t c h r

• m

i u m

Our in n

• s

i t u s i t u Bioremediation products

SLIDE 8

Want to clean the site in Want to clean the site in moderately short time moderately short time Pumping and treating the water for Pumping and treating the water for years without much success years without much success Large size of contamination Large size of contamination plume plume Want to save $ Want to save $ Deep and Deep and widespread widespread contamination contamination Moderately high Moderately high concentration concentration Running/active facility Running/active facility Facilities has large Facilities has large machines machines

EDC based in

n

• s

i t u s i t u

Bioremediation is for……….

SLIDE 9

W h a t i s s p e c i a l w i t h W h a t i s s p e c i a l w i t h i n i n

• s

i t u s i t u E D C b a s e d B i

• r

e m e d i a t i

• n

E D C b a s e d B i

• r

e m e d i a t i

• n

① S h

• r

t t i m e : C

• m

p l e t e r e m e d i a t i

• n

w i t h i n 3 ～1 2 m

• n

t h s a s c

• m

p a r e t

• 1

2

• 3

6 m

• n

t h s f

• r

m a y e x i s t i n g b i

• r

e m e d i a t i

• n

p r

• d

u c t s

② R e m e d i a t i

• n
• f

h i g h c

• n

c e n t r a t i

• n
• f

c

• n

t a m i n a t i

• n

（

• u

r e x p e r i e n c e : 7 5 m g / ℓ ) a

s c

• m

p a r e t

• <

2 m g / L f

• r

m a n y e x i s t i n g b i

• r

e m e d i a t i

• n

p r

• d

u c t s ③ High priority of safety issue: EDC is completely biodegradable into carbon dioxide and water

⑤Easy to apply on the site ④ Low cost technology: 1/3 to 1/5 of conventional methods

SLIDE 10

Remediation process

Site investigation (Hydrogeology, contamination details etc.) Microcosm experiment (optional) Pilot demonstration Remediation design Full scale injection Site closure

SLIDE 11

Site Investigation

Hydrogeology:

• Bore logs, Soil cross sections, Hydraulic conductivity, seepage

velocity, groundwater flow direction etc

• Contamination data
• Source, storage/usage points, pathways like drainage, type of

contamination, concentration, phase partition, extent of contamination by depth and area etc.

SLIDE 12

Soil cross section at a Hexavalent chromium contaminated site

K = 10-4 cm/sec K = 10-2 cm/sec K = 10-5 cm/sec

SLIDE 13

Contamination Pathway

UST Soil Gas

Sorbed Phase DNAPL

Dissolved phase

Free Phase DNAPL

SLIDE 14

Hexavalent Chromium Plume (two dimensional)

Ｃ ｕ ｒ ｔ ｓ ｙ ： Ｇ Ｚ Ａ

SLIDE 15

Ｃ ｕ ｒ ｔ ｓ ｙ ： Ｇ Ｚ Ａ

SLIDE 16

EDC Injection (Gravity feed)

I n j e c t i

• n

w e l l I n j e c t i

• n

U n i t Mixing tank M

• n

i t

• r

i n g w e l l

C

• n

t a m i n a t i

• n

SLIDE 17

GeoProbe 6 6 1 0 -DT track rig 2 .3 GPM capacity pum p, w ith pressures up to ~ 1 ,0 0 0 PSI

Wyman-Gordon Grafton, Massachusetts, USA

Injection with Direct push technology

Sturm Ruger, NH, USA

Ｃ ｕ ｒ ｔ ｓ ｙ ： Ｇ Ｚ Ａ

SLIDE 18

Double Packer Injection

SLIDE 19

• 2

4

• 2

2

• 5

+ 5 2 + 7 4 + 8 2 O R P ( m V ） Carbon Dioxide Sulfate Fe（ Ⅲ） Mn （ Ⅳ） Nitrate DO TEA Ⅵ Ⅴ Ⅳ Ⅲ Ⅱ Ⅰ

Aerobic Facultative anaerobic Obligate anaerobic P C E 、 T C E d e g r a d a t i

• n

D C E / V C d e g r a d a t i

• n

Preference for Terminal Electron Acceptors in Nature

C r ( 6 ) r e d u c t i

• n

SLIDE 20

Degradation Process

P C E D C E V C E t h y l e n e

無機塩

微生物 微生物A A B B A A Ｃ Ｃ A A Ｄ Ｄ A A Ｅ Ｅ

C

Cｌ Cｌ Cｌ

C H

Cｌ

• T

C E

Cｌ

• Cｌ
• Cｌ
• C

Cｌ Cｌ Cｌ

C

Cｌ

C

Cｌ Cｌ

H H C C

Cｌ

H H H C C H H H C H

SLIDE 21

Microbial degradation Chemical degradation Unknown Pathway

Degradation Pathway

P e r C h l

• r
• e

t h y l e n e C C l

2

= C C l

2

C a r b

• n

T e t r a c h l

• r

i d e C C l

4

T r i c h l

• r
• e

t h y l e n e （ T C E ） CCl2=CHCl T r i c h l

• r
• e

t h a n e （ 1 , 1 , 1

• T

C A ） T r i c h l

• r
• e

t h a n e （ 1 , 1 , 2

• T

C A ） C h l

• r
• f
• r

m C H C l

3

D i c h l

• r
• e

t h y l e n e ( c i s

• 1

, 2 ,

• D

C E ） D i c h l

• r
• e

t h y l e n e ( 1 , 1

• D

C E ） D i c h l

• r
• e

t h a n e （ 1 , 1

• D

C A ） D i c h l

• r
• e

t h a n e （ 1 , 2

• D

C A ） D i c h l

• r
• m

e t h a n e C H

2

C l

2

V i n y l e c h l

• r

i d e C H

2

= C H C l C h l

• r
• m

e t h a n e C H

3

C l E t h y l e n e C H

2

= C H

2

E t h a n e C H

3

• C

H

3

M e t h a n e C H

4

W a t e r , C h l

• r

i d e i

• n

s , C a r b

• n

d i

• x

i d e

C h l

• r
• e

t h a n e C H

3

• C

H

2

C l

SLIDE 22

Field Experience

C

• n

t a m i n a t i

• n

s : P C E , T C E , D C E , T C A , D C A , C T , D C M , C y a n i d e , B e n z e n e , C r ( 6 ) e t c .

J

a p a n , T h a i l a n d , t h e U S , I n d i a ……. .

H

i g h c

• n

c e n t r a t i

• n

: 7 5 m g / L

L

• w

K h y d r

• g

e

• l
• g

y : 1

• 6

c m / s e c

L

a r g e s t s i t e : 7 m i l l i

• n

㎥

S u c c e s s f u l l y a p p l i e d

• n

> 1 2 s i t e s C h l

• r

i n a t e d S

• l

v e n t s H e x a v a l e n t C h r

• m

i u m J a p a n E P A f u n d e d s i t e ( D e m

• n

s t r a t i

• n
• f

l

• w

c

• s

t , e n v i r

• n

m e n t a l l y f r i e n d l y t e c h n

• l
• g

y

SLIDE 23

Site A: Cell-phone parts manufacturer near Tokyo, 40,000 m2 X 12 m plume size

Ｃ ｕ ｒ ｔ ｓ ｙ ： Koa Kaihats

SLIDE 24

Hydrogeological modeling

SLIDE 25

SLIDE 26

Injection set-up

興亜開発株式会社 提供資料

Gravity Injection

SLIDE 27

EDC Propagation in the groundwater

SLIDE 28

2 4 . 1 . 3 ( B e f

• r

e i n j e c t i

• n

) 2 5 . 1 . 3 （ U n i t 1 r e m e d i a t i

• n

)

50000 100000 150000 200000 250000 300000 350000 400000 50000 100000 150000 200000 250000

50m 0.001 0.01 0.1 0.2 0.3 0.4 0.5 1 1.5 2 2.5

50000 100000 150000 200000 250000 300000 350000 400000 50000 100000 150000 200000 250000

50m 0.001 0.01 0.015 0.02

2 4 . 1 2 . 1 7 （ U n i t 3 r e m e d i a t i

• n

)

50000 100000 150000 200000 250000 300000 350000 400000 50000 100000 150000 200000 250000

50m 0.001 0.01 0.02 0.03 0.04 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45

興亜開発株式会社 提供資料

Bioremediation of TCE in the groundwater

SLIDE 29

50000 100000 150000 200000 250000 300000 350000 400000 50000 100000 150000 200000 250000

50m 0.01 0.04 0.08 0.12 0.16 0.2 0.24 0.28

50000 100000 150000 200000 250000 300000 350000 400000 50000 100000 150000 200000 250000

50m 0.004 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0.12

50000 100000 150000 200000 250000 300000 350000 400000 50000 100000 150000 200000 250000

50m 0.004 0.04 0.06 0.08 0.1 0.12

50000 100000 150000 200000 250000 300000 350000 400000 50000 100000 150000 200000 250000

50m

0.004 0.04 0.05 0.06

Bioremediation of cis-DCE in the groundwater

2 4 . 1 . 3 ( B e f

• r

e i n j e c t i

• n

) 2 4 . 1 2 . 1 7 （ U n i t 3 r e m e d i a t i

• n

) 2 5 . 1 . 3 （ U n i t 1 r e m e d i a t i

• n

) 2 5 . 1 . 3 （ U n i t 2 r e m e d i a t i

• n

)

SLIDE 30

Site B (near Nagoya): Change in ORP concentration of

groundwater

株式会社大林組 提供資料

Before EDC injection After injection After 1 week After 20 days

SLIDE 31

30 d post injection 75d post injection 60 d post injection Before Injection

TCE Degradation c-DCE Degradation

30 d post injection 75d post injection 60 d post injection Before Injection

SLIDE 32

Site C (North Kyushu)

新日本グラ ウト 工業株式会社 提供資料

SLIDE 33

Low Hydraulic conductivity

資料提供： 新日本グラ ウト 工業株式会社

Particle size analysis

4 . 5 ～5 m ： C l a y 1 . ～1 . 5 m : s a n d y s i l t 3 . 5 ～4 . m : G r a v e l w i t h s i l t 5 . 5 ～6 . m : G r a v e l w i t h c l a y

Special injection technique

SLIDE 34

Pump and Treat followed by Bioremediation

c i s

• 1

, 2

• D

C E

. 2 . 4 . 6 . 8 . 1 . 1 2

1 年 2 年 3 年 4 年 5 年

E n v i r

• n

. S t d . . 4 m g / ℓ

濃度［ m g / ℓ ］

T C E

. 5 1 . 1 . 5 2 . 2 . 5 3 .

P u m p a n d T r e a t

• f

5 8 , 2 4 9 . 6 ｍ3

g

r

• u

n d w a t e r E D C I n j e c t i

• n

B i

• r

e m e d i a t i

• n

P

• s

t r e m e d i a l m

• n

i t

• r

i n g ( 2 y r s . )

濃度［ m g / ℓ ］

SLIDE 35

Site D: High way authority, North Kyushu

資料提供： 新日本グラ ウト 工業株式会社 4 . ～4 . 5 m : s a n d y s i l t 2 . ～2 . 5 m : S a n d y s i l t 1 . ～1 . 5 m : G r a v e l + c l a y 3 . ～3 . 5 m ： C l a y e y G r a v e l 5 . ～5 . 5 m ： C l a y e y g r a v e l 7 . ～7 . 5 m ： C l a y e y s a n d 6 . ～6 . 5 m : C l a y

Particle size analysis

SLIDE 36

Tetrachloro ethylene degradation

Before Injection A f t e r 5 w e e k s A f t e r 4 w e e k s A f t e r 3 w e e k s A f t e r 2 w e e k s A f t e r 1 w e e k 新日本グラ ウト 工業株式会社 提供資料

SLIDE 37

. 1 . 1 . 1 1 1 初期値 5 週間後 1 4 週間後2 2 週間後2 9 週間後

観測期間（週） P C E （㎎/ ℓ ）

1

• 5

2

• 4

3

• 3

4

• 4

5

• 4

6

• 8

7

• 6

8

• 6

9

• 7

1

• 8

. 1 . 1 . 1 1 1 初期値 5 週間後 1 4 週間後 2 2 週間後 2 9 週間後

観測期間（週） T C E （㎎/ ℓ ）

. 1 . 1 . 1 1 1 初期値 5 週間後 1 4 週間後 2 2 週間後 2 9 週間後

観測期間（週） ｼｽ- 1 , 2

• D

C E （㎎/ ℓ ）

. 1 . 1 . 1 1 1 初期値 5 週間後 1 4 週間後 2 2 週間後 2 9 週間後

観測期間（週） 1 , 1

• D

C E （㎎/ ℓ ）

5 1 1 5 初期値 5 週間後 1 4 週間後 2 2 週間後 2 9 週間後 観測期間（週） T O C （ ㎎ / ℓ ）

Degradation of various VOCs

PCE TCE TOC cis- 1,2- DCE 1,1- DCE

SLIDE 38

Combination of Technologies: Heating, Soil gas venting and Bioremediation

＞ 1 m g / ℓ ～ 1 m g / ℓ ＞

C

• n

c e n t r a t i

• n

S

• i

l h e a t i n g a n d g a s v e n t i n g EDC b a s e d b i

• r

e m e d i a t i

• n

T e c h n

• l
• g

i e s

三井金属資源開発株式会社 提供資料

SLIDE 39

三井金属資源開発株式会社 提供資料

S t e p I : S u b s u r f a c e H e a t i n g a n d e x t r a c t i

• n
• f

l i q u i d a n d g a s p h a s e

L

• w

h y d r a u l i c c

• n

d u c t i v i t y / h i g h c

• n

c e n t r a t i

• n
• f

c

• n

t a m i n a t i

• n

Heating and extraction of groundwater and gas greatly increased extraction rate

Gas extraction Heaters Monitoring well Monitoring well 40-60oC zone Silty fine sand Sandy silt K= 10-6 cm/sec 80oC zone

SLIDE 40

0.001 0.01 0.1 1 10 100 1000 50 100 150

Days after EDC Injection

C

• n

c e n t r a t i

• n

(mg/L ）

TCE 1.1-DCE cis-DCE V C E t h y l e n e

実例紹介： 三井金属資源開発株式会社

EDC Based Bioremediation

SLIDE 41

Biostimulant Injection

Bio-Barrier for preventing the contamination from flowing out side the site

Microbial degradation zone Biostimulant propagation

No electricity required/no on site water treatment facility/no maintenance !!!!!!!

SLIDE 42

Hexavalent Chromium

Mainly used in industries like tanning, electroplating, electrical

apparatus etc.

Hexavalent chromium (Cr VI) is highly toxic where as trivalent

chromium (Cr III) is essential nutrient for humans

Cr (VI) is soluble in water and hence is highly mobile in groundwater

to reach potential receptors like drinking water wells where as, Cr (III) is insoluble in water hence do not move in groundwater.

The average soil concentration of Cr (III) in the world is 200 mg/Kg Predominant forms of Cr (VI) in soil : dichromate (Cr2O7

• 2), chromic

acid (H2Cr2O4), hydrogen chromate (HCrO4

• ) chromate ions (CrO4
• 2 )

SLIDE 43

Site A: Near Tokyo, Automobile parts manufacturer

C

• n

c e n t r a t i

• n

( m g / L ) Days after EDC-M injection

Cr (6) concentration 環境基準値

1 日 2 日 3 日 1 年 2 年

. 1 . 1 . 1 1 1 1 5 2 . 1 < . 5

A r e a : 1 , m

2

; D e p t h

• f

c

• n

t a m i n a t i

• n

: 5 m f r

• m

G L H y d r

• g

e

• l
• g

y : S a n d y L

• a

m ; G r a v e l G W l e v e l : 2

• 3

m f r

• m

t h e G L

Ｃ ｕ ｒ ｔ ｓ ｙ ： Hitachi Plant Service

SLIDE 44

1 日 2 日 3 日 検出下限値以下 11.8 4.17 11.2 0.06 0.34 0.32

2 4 6 8 10 12 14

D a y s a f t e r i n j e c t i

• n
• f

E D C

• M

( m g/ L) M

• n

i t

• r

i n g w e l l M

• n

i t

• r

i n g w e l l

Site B: Former Tanning site, India

Concentration

SLIDE 45

• Dr. PS Reddy/ Kuroda

EcoCycle Corporation 939-8064, Toyama city, Akada 694-2, Japan Tel: +81-76-420-3122 Fax: +81-76-420-3161 psreddy@ecocycle.co.jp K u r

• d

a @ e c

• c

y c l e . c

• .

j p

Contact

SLIDE 46

Memo