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Slide 1

In Situ Bioremediation at

FracRock Sites Mary F. deFlaun, PhD

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Slide 2

Overview

Two case studies of bioaugmentation in fractured rock:1. Naval Air Warfare Center in NJ

• fractured mudstones

2. Industrial facility near Nashville, TN

• karst

Common Features:– TCE at DNAPL concentrations

– treated using emulsified vegetable oil (EVO) as the electron donor and the anaerobic microbial consortia KB-1® (contains DHC bacteria)

• Co-author and instructor for the ITRC BioDNAPL Training

• Co-author for ITRC IDSS and Mass Flux guidance documents

•Guidance documents available atwww.itrcweb.org

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Slide 3

Collaborators:Naval Air Warfare Center, West Trenton, NJ

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Slide 4

GeoSyntec Consultants

Mercer County Airport

• Jet engine testing facility from 1950’s to 1990’s

• Est. 100,000 gals of TCE ‘lost’ from storage tanks-10,000 gals est. to gw(~200 ppm max conc.)

• Areas of coincident jet fuel contamination

• Daughter products-cis-DCE and VC present (16 & 1.2 ppm max)

• Triassic sedimentary rock – fractured sand and mudstones

• 60 gpm pump & treat system since 1993– no decrease in TCE since 1998

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Slide 5

Black Fissile MudstoneGrey Laminated and

Massive MudstoneRed Massive Mudstone

From Pierre Lacombe

Dipping Bedded Lockatong Mudstones

200 ft

Test area

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Slide 6

Implementation

• Utilize 4 existing wells-areal extent 9,000 ft2 up to 115’ bgs• 4 wells form a trapezoid 230 ft on the long side• Estimate 220 lbs TCE in pilot area (up to 16 ppm)• Inject EVO first to retain injected bacteria

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Slide 7

Pilot Test Injections

– Used the four wells as injection/extraction well pairs - extracted from one well of the pair while injecting into the other using flow proportional pump

– Pulled water from designated extraction well to make up 10% stock of EVO

– Injected the EVO stock with gw pulled from the extraction well to a final concentration of ~2%-until EVO visible in the extraction well

– Added 20 L KB-1 culture-DHC bacteria

– Injected the remainder of the EVO and flushed the well with at least 1 well volume of groundwater without amendments

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Slide 8

USGS Toxics Research Site

core hole 68 BR drilled downgradient

100 f

t

GW

Flo

w

Dire

ctio

n68

BR

47BR

38BR

41BR

16BR

BRP15

12

3

4

100 f

t

GW

Flo

w

Dire

ctio

n68

BR

47BR

38BR

41BR

16BR

BRP15

12

3

4

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Slide 9

0

1

2

3

4

5

6

7

8

9

31-M

ay-0

5

8-A

ug-0

5

22-A

ug-0

5

10-O

ct-0

5

19-D

ec-0

5

3-A

pr-0

6

7-Ju

n-06

28-A

ug-0

6

13-N

ov-0

6

19-F

eb-0

7

21-M

ay-0

7

5-M

ar-0

8

mic

rom

ole

s/l

iter

Date Sampled

Well 16BR CVOC Molar Concentrations: May 2005-March 2008

cis-DCE

TCE

VC

ethene

TCE= 288 ug/L

Injection Event

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Slide 10

0

20

40

60

80

100

120

140

31-M

ay-0

5

8-A

ug-0

5

22-A

ug-0

5

10-O

ct-0

5

19-D

ec-0

5

3-A

pr-0

6

7-Ju

n-06

28-A

ug-0

6

13-N

ov-0

6

19-F

eb-0

7

21-M

ay-0

7

5-M

ar-0

8

mic

rom

ole

s/l

iter

Date Sampled

Well 38BR CVOC Molar Concentrations: May 2005-March 2008

cis-DCE

TCE

VC

ethene

TCE = 15,800 ug/L

Injection Event

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Slide 11

Historical Concentrations at 38BR (μg/L)

1

1 0

1 0 0

1 ,0 0 0

1 0 ,0 0 0

1 0 0 ,0 0 0

9 0 9 1 9 2 9 3 9 4 9 5 9 6 9 7 9 8 9 9 0 0 0 1 0 2 0 3 0 4 0 5 0 6 0 7

TC E

D C E

V C

In n o c u la t io n

3 8 B R

From Pierre Lacombe, USGS, Feb. 2007

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Slide 12

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

31-M

ay-0

5

8-A

ug-0

5

22-A

ug-0

5

10-O

ct-0

5

19-D

ec-0

5

3-A

pr-0

6

7-Ju

n-06

28-A

ug-0

6

13-N

ov-0

6

19-F

eb-0

7

21-M

ay-0

7

5-M

ar-0

8

mic

rom

ole

s/l

iter

Date Sampled

Well BRP1 CVOC Molar Concentrations: May 2005-March 2008

cis-DCE

TCE

VC

ethene

TCE = 206 ug/L

Injection Event

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Slide 13

0

1

2

3

4

5

6

31-M

ay-0

5

8-A

ug-0

5

22-A

ug-0

5

10-O

ct-0

5

19-D

ec-0

5

6-M

ar-0

6

5-Ju

n-06

28-A

ug-0

6

13-N

ov-0

6

19-F

eb-0

7

21-M

ay-0

7

5-M

ar-0

8

mic

rom

ole

s/l

iter

Date Sampled

Well 41BR CVOC Molar Concentrations: May 2005-March 2008

cis-DCE

TCE

VC

ethene

TCE =674 ug/L

Injection Event

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Slide 14

Second Donor Injection

• 3 yrs after initial injection – July 2008

• EVO added at MW-30BR by gravity injection (dg-high concentration and very tight)

• EVO added at BRP-1 using MW-41BR as the extraction well

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Slide 15

2nd Injections and Downgradient Monitoring

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Slide 16

Injection Round 1 Injection Round 2

1.00E-01

1.00E+00

1.00E+01

1.00E+02

1.00E+03

Co

nce

ntr

atio

n (

mg/

L)

Total Organic Carbon Concentrations

BRP-1

16BR

30BR

38BR

41BR

74BR

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Slide 17

Injection Round 1 Injection Round 2

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1.00E+07

1.00E+08

1.00E+09

1.00E+10

1.00E+11

Co

nce

ntr

atio

n (

cells

/L)

DHC Cells

BRP-1

30BR

41BR

74BR

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Slide 18

Injection Round 1 Injection Round 2

1.00E-01

1.00E+00

1.00E+01

1.00E+02

1.00E+03

Co

nce

ntr

atio

n (

mg/

L)

Sulfate

BRP-1

16BR

30BR

38BR

41BR

74BR

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Slide 19

Injection Round 1 Injection Round 2

1

10

100

1,000

10,000

100,000

Co

nce

ntr

atio

n (

µg/

L)

Methane Concentrations

BRP-1

16BR

30BR

38BR

41BR

74BR

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Slide 20

0

5,000

10,000

15,000

20,000

25,000

30,000

35,000

40,000

Co

nce

ntr

atio

n (

µg/

L)

Concentrations of CVOCs at 30BR

TCE

cis-DCE

VC

Ethene

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Slide 21

Injection Round 1 Injection Round 2

0

2000

4000

6000

8000

10000

12000

14000

16000

Co

nce

ntr

atio

n (

µg/

L)

Concentrations of CVOCs at 38BR

TCE

cis-DCE

VC

Ethene

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Slide 22

Injection Round 1 Injection Round 2

1.00E-01

1.00E+00

1.00E+01

1.00E+02

Co

nce

ntr

atio

n (

mg/

L)

Total Organic Carbon Concentrations at 68BR

68BR-B

68BR-C

68BR-D

68BR-F

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Slide 23

Injection Round 1 Injection Round 2

1.00E-01

1.00E+00

1.00E+01

1.00E+02

1.00E+03

Co

nce

ntr

atio

n (

mg/

L)

Sulfate at 68BR

68BR-B

68BR-C

68BR-D

68BR-F

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Slide 24

Injection Round 1 Injection Round 2

1

10

100

1,000

10,000

100,000

Co

nce

ntr

atio

n (

µg/

L)

Methane Concentrations at 68BR

68BR-A

68BR-B

68BR-C

68BR-D

68BR-F

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Slide 25

0

500

1000

1500

2000

Co

nce

ntr

atio

n (

µg/

L)

Concentrations of CVOCs at 68BR-B

TCE

cis-DCE

VC

Ethene

Injection Round 1 Injection Round 2

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Slide 26

0

100

200

300

400

500

600

700

800

Co

nce

ntr

atio

n (

µg/

L)

Concentrations of CVOCs at 16BR

TCE

cis-DCE

VC

Ethene

Injection Round 1 Injection Round 2

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Slide 27

0

100

200

300

400

500

600

700

Co

nce

ntr

atio

n (

µg/

L)

Concentrations of CVOCs at 41BR

TCE

cis-DCE

VC

Ethene

Injection Round 1 Injection Round 2

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Slide 28

0

20

40

60

80

100

120

140

160

180

200

Co

nce

ntr

atio

n (

µg/

L)

Concentrations of CVOCs at BRP-1

TCE

cis-DCE

VC

Ethene

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Slide 29

Summary

• Fracture surface coating of EVO and bacteria an effective passive approach to bioaugmentation in fractured rock

• Bioaugment only once with donor replenishment yearly or less frequently

• Temporary recirculation using well pairs an effective distribution strategy for known connections

• Several wells in the pilot test area and dg are below GWQS for the first time in decades

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Slide 30

Site 2Active Manufacturing Plant

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Slide 31

BackgroundSite History

• Release of ~1500 pounds of TCE

• 5 to 10 ppm of TCE in clay

overburden and bedrock at the

source

• 3 ppm of TCE in DG bedrock

• Biodegradation daughter

products and DHC bacteria

present

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Slide 32

Challenges

• GEOLOGY!!

• TCE in clay overburden and fractured bedrock

• Expedited timeframe (3 months) for the initial

source treatment

• Bedrock groundwater (and VOCs) discharge

through seeps to an off-property stream; vinyl

chloride discharge is unacceptable

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Slide 33

– Injections at existing wells in source area –Nov-05, Nov-06, Jul-08

• EVO and KB-1® in Nov 05, EVO only thereafter to replenish electron donor

– Passive bioremediation as a biobarrier near the site boundary – Jun-07

• Addition of EVO and KB-1 at 7 locations using recirculation between groups of wells

Overburden

Bedrock

EEO KB-1

Approach – Full Scale

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Slide 34

Plume Treatment

– Pump between wells at least until EVO breakthrough

– Add KB-1™ during oil injection

– In one week, a 300’ biobarrier was constructed using 290 gallons of EVO and 40 liters of KB-1™

Full-Scale Biobarrier Application

(Down Gradient Plume)

Overburden

Bedrock

EEO KB-1

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Slide 35

Biobarrier Results

biobarriers

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Slide 36

TCEcDCE

VC

0

1000

2000

3000

4000

5000

6000

6/1/046/1/05

6/1/066/1/07

6/1/086/1/09

6/1/10

VO

C C

on

cen

trat

ion

(u

g/L)

TCE

cDCE

VC

Average Results at MW-09 Series Wells(Source Area)

Pump and Treat

Bioremediation

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Slide 37

TCEcDCE

VC

0

200

400

600

800

1000

1200

1400

6/1/046/1/05

6/1/066/1/07

6/1/086/1/09

6/1/10

VO

C C

on

cen

trat

ion

(u

g/L)

TCE

cDCE

VC

Average Results for MW-20 Series Wells(downgradient of biobarrier)

Pump and Treat

BiobarrierSource AreaBioremediation

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Slide 38

Full-Scale Biobarrier

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Slide 39

Questions?