cost effective leadership for a cleaner environment in situ ......april 7-10 24 ihdiv field pilot -...

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2003 SymposiumMay 15-172003 SymposiumMay 15-17

IN SITUIN SITU PERCHLORATE BIOREMEDIATION PERCHLORATE BIOREMEDIATIONAT IHDIV NSWC AT IHDIV NSWC

Paul B. Hatzinger, Ph.D.Envirogen, Inc.

Cost Effective Leadership for a Cleaner Environment

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NDIA SymposiumApril 7-10NDIA SymposiumApril 7-10

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Problem StatementProblem Statement

Perchlorate (ClO4-)

Use: Perchlorate salts have been used extensively by DoD, NASA, Aerospace Contractors during last 6 decades as fuel oxidants in rockets and missiles.

Contamination: Groundwater contamination in at least 14 states, including CA, NV, UT, TX, MD, MA. Greater than 15 million impacted.

Toxicology: Perchlorate inhibits thyroid function and influences metamorphosis. Effects of low level exposure are uncertain. California action level is now 4 ppb.

Characteristics: Anion, low volatility, high water solubility, chemically stable, persistent in environment for years.

Remediation: Traditional ex situ technologies (e.g., air stripping, carbon adsorption, filtration) are ineffective. Biological remediation is considered the most promising approach.

ClO4- ClO4

-

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Perchlorate BiodegradationPerchlorate Biodegradation

Cl- + H2O

Biomass + CO2 Substrate (electron donor)

ClO4-

ClO3-ClO2

-

* Highly Favorable Reaction (-801 kJ/mol acetate)

* Several Different Genera Isolated (Wolinella, Ideonella,Dechlorospirillum, Dechlorisoma, Dechlorimonas)


(electron acceptor)

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Fluidized Bed ReactorsFluidized Bed Reactors

> 7 BILLION GALLONS TREATED


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* What is the Natural Occurrence of Perchlorate Reducers?

* Can They be Stimulated to Degrade Perchlorate In Situ Using Electron Donor Addition? - Which Donors?

* What are Potential Inhibitory Factors?

Key Questions for In SituTreatment

Project CU- 11632000 - 2002


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SITES EVALUATED:(1) JET PROPULSION LABS (CA)

(2) INDIAN HEAD NSWC (MD) (2 Sites)

(3) THIOKOL PROPULSION (UT)

(4) SOUTH OYSTER (VA) (Pristine Site).

(5) LONGHORN AAP (TX) (3 Sites)

(6) BOEING CORP (CA) (2 Sites)

Potential for In SituRemediation

MICROCOSM AND COLUMN STUDIES:Occurrence of Perchlorate ReducersElectron DonorsAlternate Electron AcceptorsEnvironmental VariablesDeveloped Biodegradation Model


site water

sediments

N2

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CONCLUSIONS• Perchlorate-reducing bacteria are widelydistributed: soils, groundwater, sewage, etc.

• Biostimulation is a promising in situapproach, but most effective electron donor issite specific.

• Oxygen and nitrate must be biodegradedbefore perchlorate reduction will occur.

•Low pH (< 5.5) inhibits perchloratereduction.

• Other common electron acceptors such assulfate and ferric iron do not influenceperchlorate reduction.

SERDP LaboratoryStudies

Dechlorisoma suillum JPLRND

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INDIAN HEAD DIVISION, NAVAL SURFACEWARFARE CENTERFIELD DEMONSTRATIONJanuary 2002 - January 2003

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IndianHead

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Demonstration Site

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IHDIV - HOG OUT FACILITY

GP7 (35) GP8 (430) GP9 (73)

GP4 (57)GP1 (120)

GP11 (230)

GP5 (65)GP6 (280)

GP12 (55)

GP10 (300)

GP13 (230)

GP17 (< 5)

MW3 (1.6)

MW6 (142)

MW4 (181)

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Site CharacteristicsSite Characteristics

Groundwater Characteristics1. Depth 6 - 16 ft (BLS)2. Perchlorate 50-400 mg/L 3. pH < 5.0 4. Alkalinity ~20 mg/L5. Sulfate 50-200 mg/L6. Nitrate 2-12 mg/L(as N)7. Nitrite < 0.4 mg/L

8. Oxygen ~ 1 mg/L

Laboratory Results1. Perchlorate-Reducers Present.2. No degradation at Site pH.3. Degradation after Buffering.4. Acetate, Lactate effective in Buffered Sediments.

6’

10’

Soil and Backfill

Sand Stringers

Sandy Silt/Clayey Silt

Sand/Gravel

Gray Clay

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ApproachApproach

• Amend Aquifer with Sodium Lactate as Electron Donor(~ 350 mg/L) and a Bicarbonate/Carbonate Mixture asBuffer (~ 2500 mg/L).

• Design a Recirculation System to Ensure ThoroughMixing of Amendments with Perchlorate-ContaminatedGroundwater.

• Install Two Plots: A Test Plot that Receives Amendmentsand a Control Plot (No Amendments) to Monitor anyAbiotic Decline in Perchlorate Concentrations.

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Recirculation SystemCost Effective Leadership for a Cleaner Environment

Gravel layer

Electron Donor + Buffer

Injection Well

Clay layer

Sandy Silt/Clayey Silt

Extraction Well

Nested monitoring wells

Bioactive Zone

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Cost Effective Leadership for a Cleaner EnvironmentField Pilot Design

Injection Skid

Test PlotControl Plot

12’

10’

Groundwater flow

MW-1S,1D

MW-2S,2D MW-4S,4D

MW-3S,3D

Injection Well

Extraction Well

MW-5MW-5

MW-1S,1DMW-3S,3D

MW-2S,2DMW-4S,4D

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Pilot SystemCost Effective Leadership for a Cleaner Environment

Test PlotTest Plot

Buffer Tank

Control PlotControl PlotInjection Skid

Lactate Tank

TPMWs

EW

IW

EW

IW

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Injection Skid andControl Panel Cost Effective Leadership for a Cleaner Environment

Injection Skid

Control Panel

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IHDIV Field Pilot

• Begin Adding Buffer/Electron Donor 7/25/02.

• Performed 2 Baseline Sampling Events (5 wks, 1 wk before)

• Groundwater Sampling (2, 4, 7, 10, 15, 20 wks)

• Completed Sampling 12/12/2002

• DATA

PROJECT SCHEDULE

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Water RecirculationCost Effective Leadership for a Cleaner Environment

0

5000

10000

15000

20000

25000

0 25 50 75 100 125 150

Test PlotControl Plot

Wat

er P

umpe

d (g

als)

Days

shut down

Water Recirculated During the Field Demonstration

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IHDIV Field Pilot - pHCost Effective Leadership for a Cleaner Environment

3

3.5

4

4.5

5

5.5

6

6.5

7

-20 0 20 40 60 80 100 120 140

Influence of Buffer Addition on pH in DeepTest Plot Wells

TPMW-1dTPMW-2dTPMW-3dTPMW-4dTPMW-5

pH

Days (After Start-Up)

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3.5

4

4.5

5

5.5

6

6.5

7

7.5

-20 0 20 40 60 80 100 120 140

pH Values in Shallow Test Plot Wells During Buffer Addition

TPMW-1sTPMW-2sTPMW-3sTPMW-4s

pH


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3

3.5

4

4.5

5

5.5

6

6.5

7

-20 0 20 40 60 80 100 120

pH Values in Control Plot Wells CPMW-5CPMW-4dCPMW-4sCPMW-3dCPMW-3sCPMW-2dCPMW-2sCPMW-1dCPMW-1s

pH


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IHDIV Field Pilot - Lactate

PQL

0

100

200

300

400

500

600

0 25 50 75 100 125 150

Lactate Levels in Representative TPMWs

TPMW-3dTPMW-4dTPMW-5

Lac

tate

(mg/

L)

Days

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IHDIV Field Pilot - PerchlorateCost Effective Leadership for a Cleaner Environment

0

50

100

150

200

250

300

-50 -25 0 25 50 75 100 125 150

Perchlorate Levels in Shallow Test Plot Wells

TPMW-1sTPMW-2sTPMW-3sTPMW-4s

Perc

hlor

ate

(mg/

L)


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IHDIV Field Pilot -PerchlorateCost Effective Leadership for a Cleaner Environment

0

50

100

150

200

250

300

-50 -25 0 25 50 75 100 125 150

Perchlorate Levels in DeepTest Plot Wells


Per

chlo

rate

(mg/

L)


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IHDIV Field Pilot - Lactate

PQL

0

100

200

300

400

500

600

0 25 50 75 100 125 150

Lactate Levels in Deep TPMWs


Lac

tate

(m

g/L

)

Days

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IHDIV Field Pilot -PerchlorateCost Effective Leadership for a Cleaner Environment

0

50

100

150

200

250

300

-50 0 50 100 150

Perchlorate Levels in Control Plot Wells CPMW-5CPMW-4dCPMW-4sCPMW-3dCPMW-3sCPMW-2dCPMW-2sCPMW-1dCPMW-1s

Per

chlo

rate

(mg/

L)


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IHDIV Field PilotCost Effective Leadership for a Cleaner Environment

CONCLUSIONS:

1. The Recirculation System Effectively Delivered Bufferand Electron Donor Throughout the Test Plot.

2. Perchlorate and Nitrate Biodegradation Occurred Rapidly After the Amendments were Applied to theAquifer.

3. In Situ Treatment Using Electron Donor and Buffer Addition is a Viable Bioremediation Option for Perchlorate Treatment in Source Areas.

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Jay DieboldDarren EngbringMike CushmanMatt GiovanelliCharles Condee

Dr. Randy CramerCarey Yates

Pam Clemens

ACKNOWLEDGEMENTS


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QUESTIONS ?

Paul B. Hatzinger(609) [email protected]

Jay Diebold(242) [email protected]

cost effective leadership for a cleaner environment in situ ......april 7-10 24 ihdiv field pilot -...

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