11

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

22

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

33

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

44

55

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.

77

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.

77

88

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

88

99

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.

1010

Pilot Test CharacterizationPilot Test Characterization

NorthNorth--South Hydrogeologic ProfileSouth Hydrogeologic Profile

1111

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

1616

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

1717

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

1919

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

2121

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

2222

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

2323

Relative Percent of Total PLFA Structural Relative Percent of Total PLFA Structural GroupsGroups

MW96A MW96CMW70AMW38MW37

2424

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

2525

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..

2626

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.