Full-Scale Permanganate Remediation of a Solvent DNAPL Source Zone in a Sand Aquifer

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Full-Scale Permanganate Remediation of a Solvent
DNAPL Source Zonein a Sand Aquifer

• 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

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Collaborators

• 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

• 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 Approachesfor In Situ Oxidation

• Inject-and-withdraw (active)
• Flushing
• Inject-and-leave (passive)
• Episodic Injection

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The Active Approach
Addition of Treatment Chemicals
Withdrawal
Injection
B.L.Parker
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The 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 Approach
Relies on density and dispersion effects
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S
a
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q
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B.L.Parker, 1997
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Evolution of a Single Disc in a Sand Aquifer
B.L. Parker, 1997
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Initial Proof - of - ConceptInject-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-up at 9m Cell Borden Site
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Density of Dissolved KMnO4 in Water
1.05
1.04
Typical Range Used
1.03
sea water
relative density
solubility
1.02
1.01
1
0 20 40
60
grams per liter KMnO4
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SETTING
0 ft
sand
1 ft
12 ft
clay
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Evidence for Density Induced Flow
(Nelson, 1999)
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The Waterloo Passive Approach

• Use density and dispersion effects to distribute
  permanganate solution
• Inject in a manner that minimizes groundwater
  displacement

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Long-Screen Injection Causes Large Displacement
of Contaminated Water
Parker, 1997
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Injection of Discs Leaving Gaps Minimizes
Displacement of Contaminated Water
Parker, 1997
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Injection of Multiple Discs Using Direct Push
Device
Parker, 1997
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Injection of Multiple Discs Using Direct Push
Device
Parker, 1997
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Stage 1 Inject Disc Above DNAPL on Aquitard
Stage 1
K
M
n
O
4
sand aquifer
Initial disc
DNAPL
Parker, 1997
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Disc Sinks and Spreads
Parker, 1997
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Case Study in Florida
TCE and TCA source zone
Site
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Ft. Lauderdale Site
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Contamination Occurred Recentlylate 1996 to
early 1997

• TCA used 1995-96
• Switch from TCA to TCE Nov 1996 - April 1997
• Conventional monitoring wells installed 1997
• Fentons treatment pilot study 1998-1999
• UW bundle multi-levels installed 1999
• Fentons performance assessment
• Permanganate selected as source removal action
• for permanent remedy

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Site Geology
Water table
Fine and medium grained beach sand with no
visible layering
8-inch coarse sand layer 57 ft bgs
Increased frequency of gravel size carbonate
rock fragments
Carbonate bedrock 85 ft bgs
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Monitoring Methods
Focus on depth-discrete methods

• Continuous Cores
• Bundle tube samplers
• Waterloo Profiler
• Conventional Monitoring Wells
• Micro-monitoring Wells

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Core Being Removed from Piston Core Barrel
Aluminum core tube inside core barrel
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Cutting the Aluminum Core Tube
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Subsampling Sand for VOC Analysis
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Installation of Bundle Tube Sampler 1999
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Bundle Tube Sampler
STEEL WELL COVER w/CONCRETE PAD
CONCRETE PAD
1/4 OD TEFLON TUBING IN 1/2 OD POLYETHYLENE
TUBING
1/2 OD POLYETHYLENE or 1/4 OD TEFLON TUBING
2-4 NITEX SCREENS
SET IN NATURAL FORMATION NO SAND PACK
¾ ID SCH 40 PVC PIPE CENTER STOCK
6-8 NITEX SCREEN OVER PIPE PERFORATIONS
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TCE Concentration Profile CW-L
0
10
Before Injection (February 2000)
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30
Depth (ft)
40
625,500 mg/L
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60
70
80
600000
TCE Concentration (mg/L)
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TCE Concentration Profile CW-K
0
10
Before Injection (February 2000)
20
30
Depth (ft)
40
21,574 ug/L
50
60
70
80
0
25000
5000
10000
15000
20000
TCE Concentration (mg/L)
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Conceptual Model of DNAPL Distribution
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Before Remediation
CW-L
TCE Source Zone gt10,000 µg/L
Building
100
TCE Plume
gt 100 µg/L
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The Waterloo Passive Approachfor Permanganate

1. Pre-injection delineation
2. Permanganate injection in targeted zones
3. Monitor results and design subsequent injection
4. Repeat steps until attain desired endpoint

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Full-Scale Permanganate Remediation in Ft.
Lauderdale, FL
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KMnO4 Mixing Tank
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(No Transcript)
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Stage 1 KMnO4 Injection at Several Depths
KMnO4 Feed Tank
Scaffolding
Direct Push Drill Rig
Pressure Tank 2
Pressure Tank 1
NO2 Tank
Asphalt Ground Surface
Sand Aquifer
Parker, 2000
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Stage 2 Spreading and Sinking by Density
KMnO4 Feed Tank
Scaffolding
Direct Push Drill Rig
Pressure Tank 2
Pressure Tank 1
NO2 Tank
Asphalt Ground Surface
Sand Aquifer
Parker, 2000
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Conceptual Model of DNAPL Distribution
Parker, 2000
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KMnO4 Target Treatment Zone
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Source Zone Wells
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KMnO4 Injection Coverage Episode 1
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KMnO4 Injection at Multiple Depths
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Passive Crew
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Effects of Density and Diffusion on Injected
KMnO4 Ellipsoids
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Project Timeline
UW Site Pre-Design Characterization
3rd Injection Episode
3rd Post-Treatment Monitoring
1st Injection Episode
1st Post-Treatment Monitoring
4th Injection Episode
2nd Post-Treatment Monitoring
2nd Injection Episode
0
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1
3
7
10
13
Time (months)
February 2000
October 2002
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Site Map X Sections
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TCE Distribution on B-B Feb 2000
Parker et al., 2000
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TCE Distribution on B-B Oct 2002
Parker et al., 2002
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TCE Concentration Profile CW-K
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TCE Concentration Profile CW-K Prior to 4th
Injection
17 ug/L
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TCE Distribution on C-C Feb 2000
Parker et al., 2000
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TCE Distribution on C-C Oct 2002
Parker et al., 2002
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TCE Concentration Profile CW-L
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TCE Concentration Profile CW-L Prior to 4th
Injection
Oct 2002
1, 480 ug/L
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TCE Distribution on D-D Feb 2000
Parker et al., 2000
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TCE Distribution on D-D Oct 2002
Parker et al., 2002
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TCA Distribution on C-C Feb 2000
Parker et al., 2000
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TCA Distribution on C-C Oct 2002
Parker et al., 2002
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Before Remediation February 2000
TCE µg/L
CW-L
Building
100
TCE source zone gt10,000
Plume
100
Parker, 2002
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After Remediation December 2000
TCE µg/L
TCE source zones gt10,000
Building
100
100
GeoProbe sampling
Parker, 2002
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After Remediation October 2002
TCE µg/L
Building
1,480
214
108
100
GeoProbe sampling
Parker, 2002
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Specific Conclusions

• 99 reduction in contaminated volume
• Displacement avoided by limiting injection to lt8
  of treatment zone pore volume for each episode
• 1,1,1-TCA also disappeared
• No TCE or TCA rebound

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General Conclusion

• This case study showed that
• permanganate can be successful for
• complete remediation of the source if
• The site conditions are suitable
• The remedial design is tailored to the site

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Final Stage

• Fourth injection occurred October 2002 to
  complete source zone remediation
• Performance assessment monitoring planned for
  February 2003

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Acknowledgements

• Funding
• 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
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.
Battelle 2002 Monterey Conference Proceedings