full-scale permanganate remediation of a solvent dnapl ...full-scale permanganate remediation of a...
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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
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
The Waterloo Passive ApproachThe Waterloo Passive Approach
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
The Waterloo Passive ApproachThe Waterloo Passive Approach
� 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�
KMnO Treatment Zone4
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�
KMnO Treatment Zone4
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
Conce ntration (ug/L)
Dep
th (f
t)
May 2000
0
10
20
30
40
50
60
70
801 10 100 1000 10000 100000 1000000
Conce ntration (ug/L)
Dep
th (f
t)Jul 2000
0
10
20
30
40
50
60
70
801 10 100 1000 10000 100000 1000000
Conce ntration (ug/L)
Dep
th (f
t)Dec 2000
0
10
20
30
40
50
60
70
801 10 100 1000 10000 100000 1000000
Conce ntration (ug/L)
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
Conce ntration (ug/L)
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
KMnO Treatment Zone4
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
KMnO Treatment Zone4
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
Conce ntration (ug/L)
Dep
th (f
t)
Feb 20000
10
20
30
40
50
60
70
801 10 100 1000 10000 100000 1000000
Conce ntration (ug/L)
Dep
th (f
t)
May 2000
0
10
20
30
40
50
60
70
801 10 100 1000 10000 100000 1000000
Conce ntration (ug/L)
Dep
th (f
t)Jul 2000
0
10
20
30
40
50
60
70
801 10 100 1000 10000 100000 1000000
Conce ntration (ug/L)
Dep
th (f
t)Dec 2000
0
10
20
30
40
50
60
70
801 10 100 1000 10000 100000 1000000
Conce ntration (ug/L)
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
Conce ntration (ug/L)
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
KMnO Treatment Zone4
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
KMnO Treatment Zone4
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
64
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
65
65
Monitoring wellMultilevel systemGeoProbe sampling
TCE µg/LAfter Remediation After Remediation �� October 2002October 2002
Building
0 10 ftN
100
214
1,480
108
Parker, 2002
66
66
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
67
67
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
68
68
Final StageFinal Stage
� Fourth injection occurred October 2002 to complete source zone remediation
� Performance assessment monitoring planned for February 2003
69
69
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
70
70
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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