coupled chemical oxidation and enhanced … · 2016. 1. 22. · 3stantec consulting, calgary,...
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COUPLED CHEMICAL OXIDATION AND ENHANCED BIOREMEDIATION
PILOT TESTPETROLEUM HYDROCARBON PLUME
MIGRATING IN FRACTURED ROCK
Brett Yeske, MSc., P.Eng.1 , James E. Studer 2, Steve Sterling3, Barry Nevokshonoff4 and Ben Ellard1
1UFA Co-operative Ltd., Calgary, Alberta, Canada;2InfraSUR, LLC, Albuquerque, NM USA;
3Stantec Consulting, Calgary, Alberta, Canada4Sequoia Environmental Remediation Inc., Calgary, Alberta, Canada
REMTEC 2007
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OutlineOutline
••Project ObjectivesProject Objectives
••Project BackgroundProject Background
••Proposed Remedial StrategyProposed Remedial Strategy
••Site Conceptual Model Driven CharacterizationSite Conceptual Model Driven Characterization
••Pilot Test StrategyPilot Test Strategy
••Pilot Test ResultsPilot Test Results
••ConclusionsConclusions
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Project ObjectivesProject Objectives
••Enhance Site Conceptual ModelEnhance Site Conceptual Model
••Test Hydraulic Characteristics Under InjectionTest Hydraulic Characteristics Under Injection
••Determine Geochemical Effects of Chemical InjectionDetermine Geochemical Effects of Chemical Injection
••Evaluate the Efficacy of the Proposed Remedial StrategyEvaluate the Efficacy of the Proposed Remedial Strategy
••Collect Data for Full Scale DesignCollect Data for Full Scale Design
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Proposed Remedial StrategyProposed Remedial Strategy• Based on SCM developed and refined through 2005 Based on SCM developed and refined through 2005 ––2006, NAPL and dissolved2006, NAPL and dissolved--phase PHC migration to south is phase PHC migration to south is most urgent remedial driver.most urgent remedial driver.
•• SCM suggests plume stabilization strategy consisting of SCM suggests plume stabilization strategy consisting of integrated physical removal, ISCO and BIO attenuation integrated physical removal, ISCO and BIO attenuation zones will be effective.zones will be effective.
•• Success depends on understanding the fractured bedrock Success depends on understanding the fractured bedrock hydrogeology, contaminant presence and migration and the hydrogeology, contaminant presence and migration and the effect of injected materials.effect of injected materials.
•• Therefore, a pilot test program was designed to Therefore, a pilot test program was designed to demonstrate the efficacy of the proposed remedial strategy.demonstrate the efficacy of the proposed remedial strategy.
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Injection ChemicalsInjection ChemicalsPermeOxPermeOx®® PlusPlus
Timed Oxygen Release Product consisting of Engineered Timed Oxygen Release Product consisting of Engineered Calcium Peroxide and manufactured by FMC Corporation.Calcium Peroxide and manufactured by FMC Corporation.
KlozurKlozur®® OBCOBCManufactured by FMC Corporation.Manufactured by FMC Corporation.Klozur brand sodium persulfate activation by iron, hydrogen Klozur brand sodium persulfate activation by iron, hydrogen peroxide, heat and other alkaline agents. peroxide, heat and other alkaline agents. Based on alkaline activation of Klozur sodium persulfate using Based on alkaline activation of Klozur sodium persulfate using PermeOx Plus which imparts alkalinity.PermeOx Plus which imparts alkalinity.Oxygen from PermeOx Plus activator component of the product Oxygen from PermeOx Plus activator component of the product is available as electron acceptor for aerobic metabolism.is available as electron acceptor for aerobic metabolism.
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Key AdvantagesKey Advantages
InIn--situ treatment avoids groundwater production and situ treatment avoids groundwater production and management issuesmanagement issuesCan be conducted in winterCan be conducted in winterPersulfate anion is relatively stable with relatively low Persulfate anion is relatively stable with relatively low Soil Oxidant DemandSoil Oxidant DemandOxidationOxidation--Reduction Potential is 2.1 VReduction Potential is 2.1 VPotential for Sulfate Radical is 2.6 VPotential for Sulfate Radical is 2.6 VMore stable than hydroxyl radicalMore stable than hydroxyl radicalOxygen is produced for bioOxygen is produced for bio--enhancementenhancement
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Proposed Pilot TestProposed Pilot Test
Installation of additional monitoring points and collection of Installation of additional monitoring points and collection of baseline characterization information.baseline characterization information.
Bench scale testing of core materials for oxidant demand.Bench scale testing of core materials for oxidant demand.
Injection of Injection of KlozurKlozur®® OBCOBC and and PermeOxPermeOx®® Plus.Plus.
Process monitoring during injection phase.Process monitoring during injection phase.
Performance monitoring over three months following Performance monitoring over three months following injections.injections.
Analysis.Analysis.
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Pilot Test CharacterizationPilot Test Characterization
NorthNorth--South Hydrogeologic ProfileSouth Hydrogeologic Profile
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Unit 4 (Zone A) CoreUnit 4 (Zone A) Core
Ø
1212MLS-95 from 21 to 22 ft (6.4 to 6.7 m bg)
970.865 m 970.555 m
PHC impacts observed in gradational sequences.
Siltstone
Zone C Core (Upper Unit 7)Zone C Core (Upper Unit 7)
1313
Weathered fracture with oxidation banding
Sandstone
956.228 m 955.924 mMLS-95 from 69 to 70 ft (21.0 m to 21.3 m bg)
1414
KlozurKlozur®® OBC Total Oxidant Demand TestOBC Total Oxidant Demand Test
1515
92A – 1045 L 20% OBC92B – 68 L 20% Permeox92C – 1278 L 10% Permeox, 234 L 20% Permeox
93A – 1057 L 20% OBC93B – 148 L 10% Permeox93C – Impermeable
Continuous monitoring
94A – 820 L 20% OBC94B – 966 L 20% OBC94C – 1082 L 20% OBC
Pilot Test InjectionsPilot Test Injections
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Process Monitoring Process Monitoring -- Hydraulic ResponseHydraulic Response
•• Transport through fracture bedrock networkTransport through fracture bedrock network
•• Injections into 94A started at 9:35amInjections into 94A started at 9:35am
•• Day lighting observed at MLS95Day lighting observed at MLS95--2 (Unit 4 Zone A 2 (Unit 4 Zone A Sandstone) at 10:16am.Sandstone) at 10:16am.
•• MLS95MLS95--2 approximately 3 m south of INJ2 approximately 3 m south of INJ--94A94A
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MLS95-2 Process Data - Field Parameters
0
2
4
6
8
10
12
1411
:23
AM
1:25
PM
4:56
PM
10:3
7 AM
12:1
5 PM
3:25
PM
2-May-07 2-May-07 2-May-07 3-May-07 10-May-07 17-May-07
0
50
100
150
200
250
300
350
400
450
Ph DO (mg/l) Persulphate (mg/l)
INJ94A - 173gal
INJ94B - 212gal
INJ94C - 221gal
Process Monitoring Process Monitoring -- GeochemistryGeochemistry
RW85 Process Data - Field Parameters
0
1
2
3
4
5
6
7
8
9
11:4
0 AM
1:08
PM
2:45
PM
9:30
AM
1:40
PM
5:50
PM
2:25
PM
1:00
PM
12:1
2 PM
2-May-07 2-May-07 2-May-07 3-May-07 3-May-07 3-May-07 8-May-07 10-May-07 17-May-07
-10
0
10
20
30
40
50
60
Ph DO (mg/l) Persulphate (mg/l)
INJ94A - 173gal
INJ94B - 212gal
INJ94C - 221gal
1818
Injection Start Time
Injection Stop Time
Precipitation
Performance Monitoring Performance Monitoring ––Hydraulic ResponseHydraulic Response
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Performance Monitoring Performance Monitoring –– GeochemistryGeochemistry
RW85 Performance Data - Field Parameters
-5.00
0.00
5.00
10.00
15.00
20.00
25.00A
pr-0
7
May
-07
Jun-
07
Jul-0
7
Aug-
07
pH DO (mg/L) Persulfate (mg/L)
RW85 Performance Data - Hydrocarbons
020406080
100120140160180
Apr
-07
May
-07
Jun-
07
Jul-0
7
Aug-
07
Benzene (mg/L)x100 Toluene (mg/L)x100 Ethylbenzene (mg/L)x100 Xylene (mg/L)x100 F1 (mg/L) F2 (mg/L)
20% Klozur OBC Injection
MLS95-2 Performance Data - Hydrocarbons
00.10.20.30.40.50.60.70.80.9
Apr
-07
May
-07
Jun-
07
Jul-0
7
Benzene Toluene Ethylbenzene Xylene F1 F2
2020
Performance Monitoring Performance Monitoring –– GeochemistryGeochemistry
RW82 Performance Data - Hydrocarbons
0100200300400500600700800900
1000A
pr-0
7
May
-07
Jun-
07
Jul-0
7
Aug-
07
Benzene (mg/L)x100 Toluene (mg/L)x100 Ethylbenzene (mg/L)x100 Xylene (mg/L)x100 F1 (mg/L) F2 (mg/L)
20% Klozur OBC
RW84 Performance Data - Hydrocarbons
0
20
40
60
80
100
120
140A
pr-0
7
May
-07
Jun-
07
Jul-0
7
Aug-
07
Benzene (mg/L)x100 Toluene (mg/L)x100 Ethylbenzene (mg/L)x100 Xylene (mg/L)x100 F1 (mg/L) F2 (mg/L)
20% Klozur OBC Injection
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BioTrap Incubation BioTrap Incubation -- Baseline and PostBaseline and Post--Injection LocationsInjection Locations
BL = Baseline (Not Shown is MW13 ~78 m North of MW33)
PI = Post Injection (Not Shown is MW70A ~40 m east of RW06-91)
PI, PI, PIBL + PI
BL + PI
BL
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PLFA Results PLFA Results -- Viable Cells/Bead and Viable Cells/Bead and Percent ProteobacteriaPercent Proteobacteria
WellWell 1313 3737 3838 6868 96A96A 96B96B 96C96C 70A70A
UnitUnit NAPLNAPL NAPLNAPL NAPLNAPL D.PD.P D.PD.P D.PD.P D.PD.P NoneNone
33 5.7E6 5.7E6 cell/bcell/b
4 4 (A)(A) 50 %50 % 2.7E6 2.7E6 71 %71 %
1.1E7 1.1E7 78 %78 %
3.4E5 3.4E5 74 %74 %
1.2E51.2E5
5 5 (B)(B) 4.2E5 4.2E5 70 %70 %
1.4E5 1.4E5 64 %64 %
2.9E62.9E6 1.6E5 1.6E5 50 %50 %
52 %52 %
66 82 %82 %
7 7 (C)(C) 9.3E4 9.3E4 45 %45 %
NAPL = inside Non-Aqueous Phase Liquid zone; D.P. = inside Dissolved Phase Plume; None = outside Plume
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Relative Percent of Total PLFA Structural Relative Percent of Total PLFA Structural GroupsGroups
MW96A MW96CMW70AMW38MW37
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Benzene Utilization and Functional GenesBenzene Utilization and Functional Genes
Not Shown is MW70A ~40 m east of RW06-91
0.98%0.023 mg/day
3.7%TOD PHE NAH
1.04%0.026 mg/day
3.9%PHE TOD
0.83%0.038 mg/day
3.6%TOD PHE NAH1.2%
0.038 mg/day5.0%
TOD PHE bssA
A
1.1%0.043 mg/day
3.42%PHE
0.38%0.038 mg/day
4.2%All < 5E01
C
B
70A
37
38
96
Percent 13C in biomass1st Order Rate Constant, mg/d
Percent 13C in DICFunctional Genes in Order
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ConclusionsConclusions
••Bench scale testing was a valuable first step.Bench scale testing was a valuable first step.
••Hydraulic effect was local and short lived.Hydraulic effect was local and short lived.
••Geochemical effect was broad and long lived.Geochemical effect was broad and long lived.
••Biological effect was broad and long lived.Biological effect was broad and long lived.
••Injection of Injection of KlozurKlozur®® OBCOBC and and PermeOxPermeOx®® PlusPlus was was effective in reducing contaminant concentrationseffective in reducing contaminant concentrations..
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Did we meet our Objectives?Did we meet our Objectives?
••The data collected has improved the SCM.The data collected has improved the SCM.
••Hydraulic effects were observed and recorded.Hydraulic effects were observed and recorded.
••Positive geochemical effects were apparent.Positive geochemical effects were apparent.
••Results indicate destruction of contaminants.Results indicate destruction of contaminants.
••Full scale design is underway.Full scale design is underway.