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 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 Source Zone

  • 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: Source Zone

  • 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 Approaches Source Zonefor In Situ Oxidation

  • Inject-and-withdraw (active)

    Flushing

  • Inject-and-leave (passive)

    Episodic Injection


The Active Approach Source Zone

Addition of Treatment Chemicals

Withdrawal

Injection

B.L.Parker


The waterloo passive approach
The Waterloo Passive Approach Source Zone

  • Use density and dispersion effects to distribute permanganate solution

  • Inject in a manner that minimizes groundwater displacement


( Source Zone

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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 - Concept Source ZoneInject-and-Leave Field Trial in Borden Aquifer

Matthew Nelson M.Sc. Thesis (1999)

Supervisors: Drs. Beth Parker and John Cherry

University of Waterloo

9



System Set-up Source Zone

at 9m Cell

Borden Site

11


Density of dissolved kmno 4 in water

o Source Zone

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 Source Zone

0 ft

sand

1 ft

12 ft

clay


Evidence for density induced flow

(g/l) Source Zone

KMnO

4

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 Source Zone

  • 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

K Source Zone

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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

d Source Zone

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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 Source Zone

KMnO4

Sand aquifer

Initial disc

Injection of Multiple Discs Using Direct Push Device

Parker, 1997


Injection of multiple discs using direct push device1

K Source Zone

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Stage 2

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Injection of Multiple Discs Using Direct Push Device

Parker, 1997


Stage 1 inject disc above dnapl on aquitard

a Source Zone

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Stage 1: Inject Disc Above DNAPL on Aquitard

Stage 1

K

M

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sand aquifer

Initial disc

DNAPL

Parker, 1997


Disc sinks and spreads

Injector withdrawn Source Zone

Time

1

DNAPL

2

3

aquitard

Disc Sinks and Spreads

Parker, 1997


Case study in florida
Case Study in Florida Source Zone

TCE and TCA

source zone

Site

22


Ft. Lauderdale Site Source Zone


Contamination occurred recently late 1996 to early 1997
Contamination Occurred Recently Source Zonelate 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 Source Zone

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 Source Zone

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 Source Zone Piston Core Barrel

Aluminum core tube

inside core barrel





Bundle tube sampler
Bundle Tube Sampler Source Zone

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


0 Source Zone

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)


TCE Concentration Profile CW-K Source Zone

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)



N Source Zone

Monitoring well

0

1

0

f

t

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 Approach Source Zonefor Permanganate

  • Pre-injection delineation

  • Permanganate injection in targeted zones

  • Monitor results and design subsequent injection

  • Repeat steps until attain desired endpoint


Full-Scale Permanganate Remediation Source Zone

in Ft. Lauderdale, FL

37


KMnO Source Zone4 Mixing Tank

38


Drill Source Zone

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


Stage 2: Spreading and Sinking by Density Source Zone

KMnO4

Feed Tank

Scaffolding

Direct Push Drill Rig

Pressure

Tank

#2

Pressure

Tank

#1

NO2

Tank

Asphalt Ground Surface

Sand Aquifer

Parker, 2000


Conceptual model of dnapl distribution1
Conceptual Model of DNAPL Distribution Source Zone

Parker, 2000


Kmno 4 target treatment zone
KMnO Source Zone4 Target Treatment Zone


Source Zone Wells Source Zone


Kmno 4 injection coverage episode 1
KMnO Source Zone4 Injection Coverage Episode 1


Kmno 4 injection at multiple depths
KMnO Source Zone4 Injection at Multiple Depths


Passive Crew Source Zone

47



Project timeline
Project Timeline Source Zone

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 distribution on b b feb 2000
TCE Distribution on B-B’ – Feb 2000 Source Zone

Parker et al., 2000


Tce distribution on b b oct 2002
TCE Distribution on B-B’ – Oct 2002 Source Zone

Parker et al., 2002


Tce concentration profile cw k

Feb 2000 Source Zone

May 2000

Jul 2000

Dec 2000

Oct 2002

TCE Concentration Profile CW-K


Tce concentration profile cw k prior to 4 th injection

Oct 2002 Source Zone

TCE Concentration Profile CW-K Prior to 4th Injection

17 ug/L


Tce distribution on c c feb 2000
TCE Distribution on C-C’ – Feb 2000 Source Zone

Parker et al., 2000


Tce distribution on c c oct 2002
TCE Distribution on C-C’ – Oct 2002 Source Zone

Parker et al., 2002


Tce concentration profile cw l

Feb 2000 Source Zone

May 2000

Jul 2000

Dec 2000

Oct 2002

TCE Concentration Profile CW-L


Tce concentration profile cw l prior to 4 th injection
TCE Concentration Profile CW-L Source Zone Prior to 4th Injection

Oct 2002

1, 480 ug/L


Tce distribution on d d feb 2000
TCE Distribution on D-D’ – Feb 2000 Source Zone

Parker et al., 2000


Tce distribution on d d oct 2002
TCE Distribution on D-D’ – Oct 2002 Source Zone

Parker et al., 2002


Tca distribution on c c feb 2000
TCA Distribution on C-C’ – Feb 2000 Source Zone

Parker et al., 2000


Tca distribution on c c oct 2002
TCA Distribution on C-C’ – Oct 2002 Source Zone

Parker et al., 2002


Before Remediation – February 2000 Source Zone

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


After Remediation – December 2000 Source Zone

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


After Remediation – October 2002 Source Zone

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 Source Zone

  • 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 Source Zone

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 Source Zone

  • Fourth injection occurred October 2002 to complete source zone remediation

  • Performance assessment monitoring planned for February 2003


Acknowledgements
Acknowledgements Source Zone

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: Source Zone

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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