1 Full Full- Scale Permanganate Remediation Scale Permanganate Remediation of a Solvent DNAPL Source Zone of a Solvent DNAPL Source Zone in a Sand Aquifer in a Sand Aquifer Beth L. Parker, Ph.D. Beth L. Parker, Ph.D. University of Waterloo Presented at the EPA Seminar: In Situ Treatment of Groundwater Contaminated With Non-Aqueous Phase Liquids Chicago December 11, 2002 1
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FullFull--Scale Permanganate Remediation Scale Permanganate Remediation of a Solvent DNAPL Source Zoneof a Solvent DNAPL Source Zone
in a Sand Aquiferin a Sand AquiferBeth L. Parker, Ph.D.Beth L. Parker, Ph.D.
University of Waterloo
Presented at the EPA Seminar:In Situ Treatment of Groundwater Contaminated
With Non-Aqueous Phase LiquidsChicago
December 11, 20021
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CollaboratorsCollaborators
� Tom Al, University of New Brunswick� Inorganic Geochemistry
� Ramon Aravena, University of Waterloo� Isotope Geochemistry
� John Cherry, University of Waterloo
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This Case Study Will Show:This Case Study Will Show:
� Density driven distribution of KMnO4 in sand
� Performance assessment with minimal uncertainty
� Nearly complete destruction of TCE and 1,1,1-TCA
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Two General ApproachesTwo General Approachesfor In Situ Oxidationfor In Situ Oxidation
� Inject-and-withdraw (active)Flushing
� Inject-and-leave (passive)Episodic Injection
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Injection
Addition of Treatment Chemicals
Withdrawal
The Active ApproachThe Active Approach
B.L.Parker
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The Waterloo Passive ApproachThe Waterloo Passive Approach
� Use density and dispersion effects to distribute permanganate solution
� Inject in a manner that minimizes groundwater displacement
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The Waterloo Passive ApproachThe Waterloo Passive Approach
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1
Sand aquifer
4KMnO ( high density )
Relies on density and dispersion effects
B.L.Parker, 1997
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1
2
3
4
time
C oncentrationand D en sity
Decrease
no lateral groundw ater flow
Evolution of a Single Disc in a Sand AquiferEvolution of a Single Disc in a Sand Aquifer
B.L. Parker, 19978
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Initial Proof Initial Proof -- of of -- ConceptConcept
Inject-and-Leave Field Trial in Borden Aquifer
Matthew Nelson M.Sc. Thesis (1999) Supervisors: Drs. Beth Parker and John Cherry
University of Waterloo
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Borden 9x9 m Sheet Pile Enclosure
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System Set-upat 9m Cell
Borden Site
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Density of Dissolved KMnODensity of Dissolved KMnO44 in Waterin Water
sea water
0 20 40 60
1.05
1.04
1.03
1.02
1.01
1
rela
tive
den
sity
grams per liter KMnO4
Typical Range Used
20 Co
10 Cosolubility
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sand
SETTINGSETTING
clay12 ft
0 ft1 ft
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Evidence for Density Induced FlowEvidence for Density Induced Flow
Day 1
Day 3
Day 8Day 23
Day 65
3.4
Dep
th (m
.b.g
.s.)
ML-1 First Injection
0 5 10KMnO 4 (g/l)
2.2
2.4
2.6
2.8
3.0
3.2
(Nelson, 1999)14
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The Waterloo Passive ApproachThe Waterloo Passive Approach
� Use density and dispersion effects to distribute permanganate solution
� Inject in a manner that minimizes groundwater displacement
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contaminatedwater
displaced byinjected fluid
dispersionzone
KMnO4
KMnO4
LongLong--Screen Injection Causes Large Screen Injection Causes Large Displacement of Contaminated WaterDisplacement of Contaminated Water
Parker, 1997
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d isplacedcontam inated
w ater1
2
3
KM nO 4
gap
gap
zon e treated by d ens ity flow
zone trea ted by density flow
Injection of Discs Leaving Gaps Minimizes Injection of Discs Leaving Gaps Minimizes Displacement of Contaminated WaterDisplacement of Contaminated Water
Parker, 1997
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KMnO4Stage 1
Sand aquifer
Initial disc
Injection of Multiple Discs Injection of Multiple Discs Using Direct Push DeviceUsing Direct Push Device
Parker, 1997
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Injection of Multiple Discs Using Injection of Multiple Discs Using Direct Push DeviceDirect Push Device
KMnO 4
Injection 1
In jection 2
Stage 2
Parker, 1997
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Stage 1: Inject Disc Above DNAPL on Aquitard
KMnO 4
aquita rd
Stage 1
sand aquifer
Initial disc
Parker, 1997
DNAPL
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Disc Sinks and Spreads
Parker, 1997
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aquitard
DNAPL
Injector withdrawn
Time
3
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Site
TCE and TCA source zone
Case Study in FloridaCase Study in Florida
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Ft. Lauderdale SiteFt. Lauderdale Site
Picture 0564
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Contamination Occurred RecentlyContamination Occurred Recentlylate 1996 to early 1997late 1996 to early 1997
� TCA used: 1995-96� Switch from TCA to TCE: Nov 1996 - April 1997� Conventional monitoring wells installed: 1997� Fenton�s treatment pilot study: 1998-1999� UW bundle multi-levels installed: 1999
� Fenton�s performance assessment� Permanganate selected as source removal action
for permanent remedy
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Site GeologySite Geology10
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30
40
50
60
70
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Water table
8-inch coarse sand layer57 ft bgs
Fine and medium grainedbeach sand withno visible layering
Increased frequency of gravel size carbonate rockfragments
Before Remediation Before Remediation �� February 2000February 2000
Plume
TCE µg/L
0 10 ftN
Parker, 2002
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Monitoring wellMultilevel systemGeoProbe sampling
TCE µg/LAfter Remediation After Remediation �� December 2000December 2000
TCE source zones>10,000Building
0 10 ftN
100
100
Parker, 2002
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Monitoring wellMultilevel systemGeoProbe sampling
TCE µg/LAfter Remediation After Remediation �� October 2002October 2002
Building
0 10 ftN
100
214
1,480
108
Parker, 2002
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Specific ConclusionsSpecific Conclusions� 99% reduction in contaminated volume
� Displacement avoided by limiting injection to <8%of treatment zone pore volume for each episode
� 1,1,1-TCA also disappeared
� No TCE or TCA rebound
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General ConclusionGeneral Conclusion
This case study showed thatpermanganate can be successful forcomplete remediation of the source if :
� The site conditions are suitable� The remedial design is tailored to the site
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Final StageFinal Stage
� Fourth injection occurred October 2002 to complete source zone remediation
� Performance assessment monitoring planned for February 2003
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AcknowledgementsAcknowledgementsFunding:� University Consortium Solvents-in-Groundwater Research Program� Canadian Natural Sciences and Engineering Research Council� Sun Belt Interplex, Inc.
Staff:� Matthew Nelson, MSc Hydrogeologist: Project Manager� Colin Meldrum, BASc: Field Activities and Data Display� Bob Ingleton, Paul Johnson, BSc: Injection System Design and Field Technical
Assistance� Martin Guilbeault, MSc, Matthew Whitney, BASc: Field Assistance� Maria Gorecka, MSc: Lab Analysis of VOC
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For information on this case study:For information on this case study:
Parker, B.L., J. A. Cherry and T. A. Al (2002).
Passive permanganate remediation of a solvent DNAPL source zone.
In proceedings for �The Third International Conference on Remediation of Chlorinated and Recalcitrant Compounds,� Monterey, California.