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Full-Scale Permanganate Remediation of a Solvent DNAPL Source Zone in 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. 1. Collaborators.

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full scale permanganate remediation of a solvent dnapl source zone in a sand aquifer

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

1

collaborators
Collaborators
  • Tom Al, University of New Brunswick
    • Inorganic Geochemistry
  • Ramon Aravena, University of Waterloo
    • Isotope Geochemistry
  • John Cherry, University of Waterloo
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
two general approaches for in situ oxidation
Two General Approachesfor In Situ Oxidation
  • Inject-and-withdraw (active)

Flushing

  • Inject-and-leave (passive)

Episodic Injection

slide5
The Active Approach

Addition of Treatment Chemicals

Withdrawal

Injection

B.L.Parker

the waterloo passive approach
The Waterloo Passive Approach
  • Use density and dispersion effects to distribute permanganate solution
  • Inject in a manner that minimizes groundwater displacement
slide7
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The Waterloo Passive Approach

Relies on density and dispersion effects

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B.L.Parker, 1997

evolution of a single disc in a sand aquifer
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Evolution of a Single Disc in a Sand Aquifer

B.L. Parker, 1997

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initial proof of concept inject and leave field trial in borden aquifer

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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slide11
System Set-up

at 9m Cell

Borden Site

11

density of dissolved kmno 4 in water
o

20 C

o

10 C

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

setting
SETTING

0 ft

sand

1 ft

12 ft

clay

evidence for density induced flow
(g/l)

KMnO

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0

5

10

2.2

ML-1 First Injection

2.4

2.6

Day 1

Day 3

Depth (m.b.g.s.)

2.8

Day 8

Day 23

3.0

Day 65

3.2

3.4

Evidence for Density Induced Flow

(Nelson, 1999)

14

the waterloo passive approach1
The Waterloo Passive Approach
  • Use density and dispersion effects to distribute permanganate solution
  • Inject in a manner that minimizes groundwater displacement
long screen injection causes large displacement of contaminated water
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Long-Screen Injection Causes Large Displacement of Contaminated Water

Parker, 1997

injection of discs leaving gaps minimizes displacement of contaminated water
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Injection of Discs Leaving Gaps Minimizes Displacement of Contaminated Water

Parker, 1997

injection of multiple discs using direct push device
Stage 1

KMnO4

Sand aquifer

Initial disc

Injection of Multiple Discs Using Direct Push Device

Parker, 1997

injection of multiple discs using direct push device1
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Injection of Multiple Discs Using Direct Push Device

Parker, 1997

stage 1 inject disc above dnapl on aquitard
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Stage 1: Inject Disc Above DNAPL on Aquitard

Stage 1

K

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sand aquifer

Initial disc

DNAPL

Parker, 1997

disc sinks and spreads
Injector withdrawn

Time

1

DNAPL

2

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aquitard

Disc Sinks and Spreads

Parker, 1997

case study in florida
Case Study in Florida

TCE and TCA

source zone

Site

22

contamination occurred recently late 1996 to early 1997
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
  • 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

site geology
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

monitoring methods
Monitoring Methods

Focus on depth-discrete methods

  • Continuous Cores
  • Bundle tube samplers
  • Waterloo Profiler
  • Conventional Monitoring Wells
  • Micro-monitoring Wells
core being removed from piston core barrel
Core Being Removed from Piston Core Barrel

Aluminum core tube

inside core barrel

bundle tube sampler
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

slide32
0

100000

200000

300000

400000

500000

700000

TCE Concentration Profile CW-L

0

10

Before Injection

(February 2000)

20

30

Depth (ft)

40

625,500 mg/L

50

60

70

80

600000

TCE Concentration (mg/L)

slide33
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)

slide35
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Monitoring well

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f

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Multilevel system

GeoProbe sampling

Before Remediation

CW-L

TCE Source Zone

>10,000 µg/L

Building

100

TCE Plume

> 100 µg/L

100

the waterloo passive approach for permanganate
The Waterloo Passive Approachfor Permanganate
  • Pre-injection delineation
  • Permanganate injection in targeted zones
  • Monitor results and design subsequent injection
  • Repeat steps until attain desired endpoint
slide37
Full-Scale Permanganate Remediation

in Ft. Lauderdale, FL

37

slide40
Drill

Rods

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

slide41
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

project timeline
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

32

1

3

7

10

13

Time (months)

February 2000

October 2002

tce concentration profile cw k
Feb 2000

May 2000

Jul 2000

Dec 2000

Oct 2002

TCE Concentration Profile CW-K
tce concentration profile cw l
Feb 2000

May 2000

Jul 2000

Dec 2000

Oct 2002

TCE Concentration Profile CW-L
slide63
Before Remediation – February 2000

N

Monitoring well

0

1

0

f

t

Multilevel system

GeoProbe sampling

TCE µg/L

CW-L

Building

100

TCE source zone

>10,000

Plume

100

Parker, 2002

slide64
After Remediation – December 2000

Monitoring well

Multilevel system

N

0

1

0

f

t

TCE µg/L

TCE source zones

>10,000

Building

100

100

GeoProbe sampling

Parker, 2002

slide65
After Remediation – October 2002

Monitoring well

Multilevel system

N

0

1

0

f

t

TCE µg/L

Building

1,480

214

108

100

GeoProbe sampling

Parker, 2002

specific conclusions
Specific 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
general conclusion
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
final stage
Final Stage
  • Fourth injection occurred October 2002 to complete source zone remediation
  • Performance assessment monitoring planned for February 2003
acknowledgements
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
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.

Battelle 2002 Monterey Conference Proceedings

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