Full-Scale Permanganate Remediation of a Solvent DNAPL ...Full-Scale Permanganate Remediation of a...

1

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

2

2

CollaboratorsCollaborators

� Tom Al, University of New Brunswick� Inorganic Geochemistry

� Ramon Aravena, University of Waterloo� Isotope Geochemistry

� John Cherry, University of Waterloo

3

3

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

4

4

Two General ApproachesTwo General Approachesfor In Situ Oxidationfor In Situ Oxidation

� Inject-and-withdraw (active)Flushing

� Inject-and-leave (passive)Episodic Injection

5

5

Injection

Addition of Treatment Chemicals

Withdrawal

The Active ApproachThe Active Approach

B.L.Parker

6

6

The Waterloo Passive ApproachThe Waterloo Passive Approach

� Use density and dispersion effects to distribute permanganate solution

� Inject in a manner that minimizes groundwater displacement

7

7


23

1

Sand aquifer

4KMnO ( high density )

Relies on density and dispersion effects

B.L.Parker, 1997

8

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

9

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

9

10

Borden 9x9 m Sheet Pile Enclosure

10

11

System Set-upat 9m Cell

Borden Site

11

12

12

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

13

13

sand

SETTINGSETTING

clay12 ft

0 ft1 ft

14

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

15

15


� Use density and dispersion effects to distribute permanganate solution

� Inject in a manner that minimizes groundwater displacement

16

16

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

17

17

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

18

18

KMnO4Stage 1

Sand aquifer

Initial disc

Injection of Multiple Discs Injection of Multiple Discs Using Direct Push DeviceUsing Direct Push Device

Parker, 1997

19

19

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

20

20

Stage 1: Inject Disc Above DNAPL on Aquitard

KMnO 4

aquita rd

Stage 1

sand aquifer

Initial disc

Parker, 1997

DNAPL

21

21

Disc Sinks and Spreads

Parker, 1997

12

aquitard

DNAPL

Injector withdrawn

Time

3

22

Site

TCE and TCA source zone

Case Study in FloridaCase Study in Florida

22

23

23

Ft. Lauderdale SiteFt. Lauderdale Site

Picture 0564

24

24

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

25

25

Site GeologySite Geology10

20

30

40

50

60

70

80

90

Water table

8-inch coarse sand layer57 ft bgs

Fine and medium grainedbeach sand withno visible layering

Increased frequency of gravel size carbonate rockfragments

Carbonate bedrock85 ft bgs

26

26

Monitoring MethodsMonitoring Methods

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

Focus on depth-discrete methods

27

27

Aluminum core tubeinside core barrel

Core Being Removed fromCore Being Removed fromPiston Core BarrelPiston Core Barrel

28

28

Cutting the Aluminum Core TubeCutting the Aluminum Core Tube

29

29

Subsampling Sand for VOC AnalysisSubsampling Sand for VOC Analysis

30

30

Installation of Bundle Tube Sampler: 1999Installation of Bundle Tube Sampler: 1999

31

31

Bundle Tube SamplerBundle Tube Sampler

SET IN NATURAL

FORMATIONNO SAND PACK

¾� ID SCH 40 PVC PIPE CENTER

STOCK

1/2� OD POLYETHYLENE or

1/4� OD TEFLON TUBING

6-8� NITEX SCREEN OVER PIPE

PERFORATIONS

2-4� NITEX SCREENS

CONCRETE PAD

1/4� OD TEFLON TUBING IN 1/2� OD POLYETHYLENE

TUBING

STEEL WELL COVER w/CONCRETE PAD

32

32

TCE Concentration Profile CWTCE Concentration Profile CW--LL0

10

20

30

40

50

60

70

806000000 100000 200000 300000 400000 500000 700000

TCE Concentration (µg/L)

Dep

th (f

t)

Before InjectionBefore Injection(February 2000)

625,500 µg/L

33

33

TCE Concentration Profile CWTCE Concentration Profile CW--KK0

10

20

30

40

50

60

70

80250000 5000 10000 15000 20000

TCE Concentration (µg/L)

Dep

th (f

t)

Before InjectionBefore Injection(February 2000)

21,574 ug/L

34

34

Conceptual Model of DNAPL DistributionConceptual Model of DNAPL DistributionBuilding

DNAPL Zone

?

?

?

20

10

30

40

50

60

Dep

th (F

eet)

DNAPL Residual Trail

70

???

Suspected Release

Area

DNAPL Plume

35

35

100

100Monitoring wellMultilevel systemGeoProbe sampling

Building

CW-L TCE Source Zone>10,000 µg/L

Before RemediationBefore Remediation

TCE Plume> 100 µg/L

0 10 ftN

36

36

The Waterloo Passive ApproachThe Waterloo Passive Approachfor Permanganatefor 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

37

37

Full-Scale Permanganate Remediationin Ft. Lauderdale, FL

37

38

38

KMnO4 Mixing Tank

38

39

39

40

40

Asphalt Ground Surface

Sand Aquifer

Direct Push Drill RigScaffolding

NO2Tank

PressureTank

#2

PressureTank

#1

KMnO4Feed Tank

Stage 1: KMnO4 Injection at Several Depths

DrillRods

Parker, 2000

41

41

Asphalt Ground Surface

Sand Aquifer

Direct Push Drill RigScaffolding

NO2Tank

PressureTank

#2

PressureTank

#1

KMnO4Feed Tank

Stage 2: Spreading and Sinking by Density

Parker, 2000

42

42

Conceptual Model of DNAPL DistributionConceptual Model of DNAPL DistributionBuilding

DNAPL Zone

?

?

?

20

10

30

40

50

60

Dep

th (F

eet)

DNAPL Residual Trail

70

???

Suspected Release

Area

DNAPL Plume

Parker, 2000

43

43

KMnOKMnO44 Target Treatment ZoneTarget Treatment Zone

N

Building

50 10Feet

Monitoring Well

MMW-6D

MW-2MW-3

MW-1MW-7D

MW-10D

Cluster WellCW-C CW-D

CW-ICW-H

CW-G

CW-B

CW-F

CW-K

CW-JCW-M CW-L

Target Zone

44

44

Source Zone WellsSource Zone Wells

Picture 0569

45

45

N

Building

50 10Feet

Minimum Injection Radius Estimated from

Injection Volumes based on an ellipsoid with 3:1

spherical shape

Estimated Coverage

Determined from Sampling

Monitoring Well

MMW-6D

MW-2MW-3

MW-1MW-7D

Cluster Well

CW-C CW-D

CW-ICW-H

CW-G

CW-B

CW-F

KMnO Injection Location4

UW-4

UW-2UW-5

UW-3

UW-1

UW-6

CW-K

CW-JCW-M CW-L

New Cluster Well Location

KMnOKMnO44 Injection Coverage Injection Coverage Episode 1Episode 1

46

46

Ground

10

50

20

30

40

60

Dep

th (f

eet)

Horizontal Exaggeration 2xEllipsoid size based on 30% porosity and a height to width ratio of 3:1.

UW

-4

UW

-5

UW

-1

7.5' 6.5'

KMnOKMnO44 Injection at Multiple DepthsInjection at Multiple Depths

47

47

Passive Crew

47

48

48

Ground

10

50

20

30

40

60

Dep

th (f

eet)

Horizontal Exaggeration 2xEllipsoid size based on 30% porosity and a height to width ratio of 3:1.

UW

-4

UW

-5

UW

-1

7.5' 6.5'

Effects of Density and Diffusion on Injected KMnOEffects of Density and Diffusion on Injected KMnO44 EllipsoidsEllipsoids

49

49

Project TimelineProject Timeline

Time (months)

0

UW Site Pre-DesignCharacterization

1st InjectionEpisode

1

2nd InjectionEpisode

3

3rd InjectionEpisode

7

1st Post-Treatment Monitoring

10

2nd Post-Treatment Monitoring

13

February 2000

32

4th Injection Episode

3rd Post-Treatment Monitoring

October 2002

50

50

Site Map Site Map �� X SectionsX Sections

N

Building 50 10 15Feet

Fence

MMW-6D

MW-8D

MW-5D

Monitoring Well (MW, MMW)

MW-7DMW-1

MW-3 MW-2

MW-4D

MMW-12DMMW-13D

MW-10D

MMW-9DMMW-11D

CW-CCW-D

CW-I

CW-H

CW-B

CW-GCW-F

CW-A

CW-E

CW-K

CW-JCW-M

CW-L

Cluster Well (CW)

C

C�B�

D�

D

B

KMnO Treatment Zone4

Spigots

UWP2

UWP1

Profiles

UWP3

51

51

TCE Distribution on BTCE Distribution on B--B� B� �� Feb 2000Feb 2000

16

12

11

15

22

59

58

26

53

152

107

77

5

249

3101

31775

135300

252900

1000

37

19

11

26

12

3111

118

22

19

794

1413

533

2746

11161

17079

5181

10262

1769

1934

5595

21574

28

18

193.4 (May, 00)1 (July, 00)

TCE ug/L

50 000

0

100

1000

10 000

100 000

Ground

10

50

20

30

40

60

Dep

th (f

eet)

CW

-B

20.5'

CW

-C

70

BSouth North

B�

CW

-D

CW

-K

4.0�2.5�

MW

-3

7.5�

MW

-2

7.5�


Parker et al., 2000

52

52

TCE Distribution on BTCE Distribution on B--B� B� �� Oct 2002Oct 2002

2

<1

<1

<1

<1

2

<1.5

<1

<1

<1

<1

<1

<1

<1

<1

33

186

214

2

<1

<1

<1.5

<1

<1

<1

<1

<1

17

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

2

<1

<1

<1.5

<151165

TCE ug/L

<1.5

<1

<1<1

<1<1<1

UW

P3

3 (MCL)

50 000

0

100

1000

10 000

100 000

Ground

10

50

20

30

40

60

Dep

th (f

eet)

CW

-B

20.5'

CW

-C

70

BSouth North

B�

CW

-D

CW

-K

4.0�2.5�

MW

-3

7.5�

MW

-2

7.5�


Parker et al., 2002

53

53

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000

Conce ntration (ug/L)

Dep

th (f

t)

Feb 20000

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)

May 2000

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)Jul 2000

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)Dec 2000

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)

Oct 2002

TCE Concentration Profile CW-K

54

54

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)

Oct 2002

TCE Concentration Profile CWTCE Concentration Profile CW--KKPrior to 4Prior to 4thth InjectionInjection

17 ug/L

55

55

TCE Distribution on CTCE Distribution on C--C� C� �� Feb 2000Feb 2000

<1.5

2

25

103

115

161

261

813

860

2631

3505

1790

946

12453

12352

15110

19160

162

135

133

142

918

658

282

914

117110

186638

1040

69296

5181

10494

48036

625500

58

38

36

31

25

33

35

140

94

95

172

321

190

101

102

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

33 (May, 00)

21

58

32

11

<1.5

<1.5

<1.5

<1.5

<1.5

8

6.4 (May, 00)

39

31

38

36

42

51

29

40

6 (May, 00)

TCE ug/LTCE ug/L0

100

1000

10 000

100 000

50 000

GroundSurface

10

50

20

30

40

60

Dep

th (f

eet)

CW

-E12.5'7.3'

CW

-I

CW

-M

CW

-A

CW

-J

CW

-L

19.4' 6�

70

C C�

MM

W-6

D

MW

-4D

16.8' 7.6' 35.9'9.9'

South North

MW

-5D


MW

-10D

5.3�

Parker et al., 2000

56

56

TCE Distribution on CTCE Distribution on C--C� C� �� Oct 2002Oct 2002

<1.5

6

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

18

22

108

2

2

2

<1

<1

<1

<1

<1

<1

<1

61

<1

<1

4

38

1480

147

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1.5

<1

<1

4

<1

<1

9

<1

<1

21

<1

<1

<1

<1

<1

<1

<1

<1

<1.5

<1.5

<1.5

<1

<1.5

<1

<1

<1

TCE ug/L<1

<1

<1

<1

0

100

1000

10 000

100 000

50 000

15

3 (MCL)

GroundSurface

10

50

20

30

40

60

Dep

th (f

eet)

CW

-E12.5'7.3'

CW

-I

CW

-M

CW

-A

CW

-J

CW

-L

19.4' 6�

70

C C�

MM

W-6

D

MW

-4D

16.8' 7.6' 35.9'9.9'

South North

MW

-5D


MW

-10D

5.3�

Parker et al., 2002

57

57

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)

Feb 20000

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)

May 2000

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)Jul 2000

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)Dec 2000

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)

Oct 2002

TCE Concentration Profile CW-L

58

58

0

10

20

30

40

50

60

70

801 10 100 1000 10000 100000 1000000


Dep

th (f

t)

TCE Concentration Profile CWTCE Concentration Profile CW--LLPrior to 4Prior to 4thth InjectionInjection

1, 480 ug/L

Oct 2002

59

59

TCE Distribution on DTCE Distribution on D--D� D� �� Feb 2000Feb 2000

102 (March, 00)

6

10

165

10

9

8

8

9

2141

2606

440

136

152

239

96

796

1.5 (July, 00)

39

31

38

36

42

50

29

40

742

381

940

302

12

10

9

10

10

16

12

18

245

3091

3560 (March, 00)

6 (May, 00)

TCE ug/L0

100

1000

10 000

100 000

50 000

MW

-8D

GroundSurface

10

50

20

30

40

60

Dep

th (f

eet)

11.5'

CW

-H

CW-F

16'

70

D D�

6�13'

CW

-G

MW

-1

9.2'

CW-I

South North

MW

-7D

KMnO Treatment Zone4North

2.6�

MW

-4D

35.9�

Parker et al., 2000

60

60

TCE Distribution on DTCE Distribution on D--D� D� �� Oct 2002Oct 2002

38

<1

<1.5

<1

<1.5

<1.5

<1

<1

<1

<1

<1

<1

<1

<1

<1

35

<1

<1

<1

<1.5

<1.5

<1.5

<1

<1.5

<1

<1

<1

1.5

<1

<1

<1

<1

<1

<1

<1

<1.5

<1

<1

<1

<1

<1.5

<1

0

100

1000

10 000

100 000

50 000

TCE ug/L

<1

<1

<1

<1

<1

4616

82108

UW

P2

3 (MCL)

MW

-8D

GroundSurface

10

50

20

30

40

60

Dep

th (f

eet)

11.5'

CW

-H

CW-F

16'

70

D D�

6�13'

CW

-G

MW

-1

9.2'

CW-I

South North

MW

-7D

KMnO Treatment Zone4North

2.6�

MW

-4D

35.9�

Parker et al., 2002

61

61

TCA Distribution on CTCA Distribution on C--C� C� �� Feb 2000Feb 2000

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

24

136

159

90

257

143

56

566

559

776

1742

<1.5

<1.5

<1.5

<1.5

35

45

8

20

3535

8141

111

1263

294

494

2207

9908

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5 (May, 00)

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5 (May, 00)

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5

<1.5(May, 00)

1,1,1-TCA ug/L0

100

1000

10 000

100 000

50 000

GroundSurface

10

50

20

30

40

60

Dep

th (f

eet)

CW

-E12.5'7.3'

CW

-I

CW

-M

CW

-A

CW

-J

CW

-L

19.4' 6�

70

C C�

MM

W-6

D

MW

-4D

16.8' 7.6' 35.9'9.9'

South North

MW

-5D


MW

-10D

5.3�

Parker et al., 2000

62

62

TCA Distribution on CTCA Distribution on C--C� C� �� Oct 2002Oct 2002

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

6

<1.5

<1

<1

<1

<1

<1

<1

<1

<1.5

13

30

3

6

4

6

135

56

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

<1

TCA ug/L<1

<1

<1

<1

0

100

1000

10 000

100 000

50 000

64

GroundSurface

10

50

20

30

40

60

Dep

th (f

eet)

CW

-E12.5'7.3'

CW

-I

CW

-M

CW

-A

CW

-J

CW

-L

19.4' 6�

70

C C�

MM

W-6

D

MW

-4D

16.8' 7.6' 35.9'9.9'

South North

MW

-5D


MW

-10D

5.3�

Parker et al., 2002

63

63

100

100Monitoring wellMultilevel systemGeoProbe sampling

BuildingCW-L

TCE source zone>10,000

Before Remediation Before Remediation �� February 2000February 2000

Plume

TCE µg/L

0 10 ftN

Parker, 2002

64

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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

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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

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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.

Battelle 2002 Monterey Conference Proceedings

Full-Scale Permanganate Remediation of a Solvent DNAPL ...Full-Scale Permanganate Remediation of a...

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