Cosolvent Flushing and Enhanced Bioremediation

at a Dry Cleaner SiteBy

Michael D. AnnableDepartment of Environmental Engineering Sciences

1

2

Project Team

University of Florida• Mike Annable, James Jawitz, Mike Brooks• Suresh Rao, Irene Poyer (Purdue)

USEPA-NRMRL-SPRD-Ada• Guy W. Sewell, Lynn Wood, Susan Mravik • Frank Beck, Ken Jewell, Tony Lee, Steve Acree, Randal Ross

LFR Levine-Fricke• Kevin Warner• Randy Sillan

MSU• James M. Tiedje, Shannon Flynn

Project Funding – State of Florida, EPA-TIO, Florida Center for

Soild and Hazardous Waste Management, SERDP (FIBRC-WES)

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Brief Cosolvent Flushing History•Before 1980 Cosolvents theory - Pharmaceuticals•Mid 1980s Cosolvents used to study transport of hydrophobic compounds in soils•Early 1990s Cosolvents investigated for remediation•1995 First Cosolvent Flood at Hill AFB (Florida)•1996 Second Cosolvent Flood at Hill AFB (Clemson)•1998 Cosolvent Flood at a Dry Cleaner Site (LFR, Sages)•1999 Cosolvent Flood at Dover AFB•2001 2nd Cosolvent Flood at Dover AFB (Clemson)•2002-3 Full-Scale Flood at Sages (Others?)

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Sages Dry Cleaner SiteJacksonville, Florida

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Pilot test at Jacksonville, FL (Sages): • Dry Cleaner PCE source zone• 8 to 9.5 m below ground surface• 7 m long by 3 m wide• Performanced based cores and tracers

6

Sages Site

Easting (ft)

MLS-1MLS-1MLS-2MLS-2

MLS-3MLS-3

MLS-4MLS-4

MLS-5MLS-5MLS-6MLS-6MLS-7MLS-7

466510 466514 466518 466522 466526 466530 466534 4665382193136

2193140

2193144

2193148

RW002RW002

RW003RW003RW004RW004

RW005RW005

RW006RW006RW007RW007

IW001IW001IW002IW002

IW003IW003

Nor

thin

g (f

t)• 3 Injection Wells (IWs)• 6 Recovery Wells (RWs)• 7 Multi-Level Samplers (MLSs)

7

26

27

28

29

30

31

32

Dep

th B

GS

(ft)

0 20000 40000 mg PCE/L MeCl

IW002 25

26

27

28

29

30

31 D

epth

BG

S (ft

)0 1000 2000 3000 4000 5000

mg PCE/L MeCl

RW007

High Frequency Soil Sampling at Sages

Thin lenses of DNAPL on

minor permeability

contrasts

8

Sages Well Layout

Injectionwells

Recoverywells

9

Sages Site

Partitioning Tracer Test:SN = 0.26 %VPCE 50 L

0.0001

0.001

0.01

0.1

1

0 20 40 60 80 100

methanol

2-ethyl-1-hexanol

Volume (kL)

C/C

0

0.0001

0.001

0.01

0.1

1

0 1 2 3 4 5 6

Time (d)

SN = 1.0 %RW007 MLS-4 Red

10

Sages Site

0

0.2

0.4

0.6

0.8

1

Flo

wra

te (

gpm

)

0

2

4

6

8

10

Packer

Heig

ht

(ft)

0 0.5 1 1.5 2 2.5 3 3.5 Time (days)

Cosolvent Flushing

95 % consumablegrade ethanol

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Cosolvent Flushing

Total PCETotal PCERemovedRemoved67.4 kg67.4 kg41.5 L41.5 L

0

40

80

120

160

200

PC

E (

mg

/L)

0

4

8

12

16

20

Eth

an

ol

(%)

0 5 10 15 20 25 30 35 Volume (kL)

PCE

ethanol

RW002

0

200

400

600

800

1000

1200

PC

E (

mg

/L)

0

10

20

30

40

50

60

Eth

an

ol

(%)

0 10 20 30 40 50 Volume (kL)

PCE

ethanol

RW003

12

Sages Site

Waste Treatment: Air Stripping Macro Porous Polymer (MPP)

PCE recovered from effluentTrailer-mounted MPP system

13

Summary Results

Cosolvent Extraction:43 L PCE Removed (Mass Recovery)

~63 % PCE Removed (Partitioning Tracer)65% Removal based on Soil Core Data

14

Concentration (or Flux) Reduction in the Source Zone

0

10

20

30

40

50

60

0.00 1.00 2.00 3.00 4.00 5.00

Post-Remediation Time (Years)

Ave

rage

Con

c. o

f PC

E (

mg/

L) Average = 49 mg/L

Average = 26 mg/L

Mass Reduction = 64% : Flux Reduction = 47%n = 35 sampling locations

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Solvent Extraction Residual Biotreatment(source management)

• Remove more accessible fraction of DNAPL, lower dissolved concentrations/flux. Reduce time/distance needed to meet GW quality objectives.

• Activate reductive bio-transformations in high redox environments.

• Insure supply of e- donor, accelerate process and reduce uncertainty.

• Meet regulatory requirements.

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Pre-Cosolvent Flush Site Characterization

• Aerobic Conditions

• Low levels of daughter products (TCE)

• DNAPL contamination identified at 26 to 31 ft. bgs

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GW Flow

90%+ Mass Removal

Cosolvent ExtractionInjection WellEthanol Flush

RecoveryWell

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PCE

Ethanol Mixed

Restoration?, Risk Reduction?

GW Flow

Residual Contaminants

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Bioremediation

Bioactive Zone

FNA, Dissolution < Assimilative Capacity

GW Flow

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Sage’s Dry Cleaner SiteJacksonville, Florida

RW-006RW-007

C1C2

C3C4MW-505

MW-506

MW-507MW-508

MW-509MW-510

MW-511

MW-512MW-513MW-514

RW-002

RW-003RW-004

RW-005

CONCRETESLAB

ASPHALT

DNAPLAREA

0 ft. 20 ft. 40 ft. 60 ft. 80 ft.

MLS

21

PCEPCE

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~1 M onth P ost-F lush

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~2.5 M onths P ost-F lush

C ON C RE TES LAB

A SP H ALT

AS PH ALT

AS PH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10 / 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~4 M onths P ost-F lush

0 ug/L

10000 ug/L

20000 ug/L

30000 ug/L

40000 ug/L

50000 ug/L

60000 ug/L

70000 ug/L

80000 ug/L

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

Pre-E thanol F lush (w ith D ay 29 data)

80,000 µg/l = 480 µM

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PCEPCE

0 ug/L

10000 ug/L

20000 ug/L

30000 ug/L

40000 ug/L

50000 ug/L

60000 ug/L

70000 ug/L

80000 ug/L

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10 / 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~25 M onths Post-F lush

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10 / 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~28 M onths Post-F lush

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C 1/ 16 / 1 7 / 18C2 / 14

C3 / 15C4

C7 / 20

C10 / 19

C5 / 1 1

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~31 M onths Post-F lush

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cis-DCEcis-DCE

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~1 M onth P ost-F lush

C ON C RE TES LAB

A SP H ALT

AS PH ALT

AS PH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~2.5 M onths P ost-F lush

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~4 M onths P ost-F lush

0 ug/L

2000 ug/L

4000 ug/L

6000 ug/L

8000 ug/L

10000 ug/L

12000 ug/L

14000 ug/L

16000 ug/L

C ON C RE TES LAB

A SP H ALT

AS PH ALT

AS PH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10 / 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

Pre-E thanol F lush (w ith D ay 29 data)

16,000 µg/l = 165 µM

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cis-DCEcis-DCE

0 ug/L

2000 ug/L

4000 ug/L

6000 ug/L

8000 ug/L

10000 ug/L

12000 ug/L

14000 ug/L

16000 ug/L

C ON C RE TES LAB

A SP H ALT

AS PH ALT

AS PH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~25 M onths Post-F lush

C ON C RE TES LAB

A SP H ALT

AS PH ALT

AS PH ALT

DNAPLAREA

C1/ 16 / 17 / 18C2 / 14

C3 / 15C4

C7/ 20

C10/ 19

C5/ 11

M W-505

M W-506

M W-507M W-508

M W-509M W-510

M W-511

M W-512M W-513M W-514

M W1

M W2

M W3

~28 M onths Post-F lush

CONCRETESLAB

ASPHALT

ASPHALT

ASPH ALT

DNAPLAREA

C 1/ 16 / 1 7 / 18C2 / 14

C3 / 15C4

C7 / 20

C10 / 1 9

C5 / 1 1

M W-505

M W-5 06

M W-50 7M W-508

M W-509M W-510

M W-511

M W-51 2M W-513M W-514

M W1

M W2

M W3

~31 M onths Post-F lush

Next look at flux across a multilevel sampler transect

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Total Plume Mass Load

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0.00 1.00 2.00 3.00 4.00 5.00

Post-Remediation Time (years)

Mas

s Lo

ad (

g/da

y)

PCE

TCE

c-DCE

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Molar Based Total Load

0

2

4

6

8

10

12

14

16

18

0.00 1.00 2.00 3.00 4.00 5.00

Post-Remediation Time (years)

Mo

lar

Mas

s L

oad

(m

mo

les/

day

)

PCE

TCE

c-DCE

Total

Increased mass flux caused by enhanced dissolution?

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SUMMARYSolvent Extraction:

43 L PCE Removed (Mass Recovery)~64 % PCE Removed

Source Zone Flux47% reduction in PCE concentration in

the source zone multilevel sampler network

PCE Daughter Product FormationSignificant increase in cis-DCE mass

For additional indications of Biological ActivitySee the Sages Poster

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What’s Next?

Full Scale Remediation at Sages (early 2003)

Monitoring Mass Flux from the Source Zone and in the Plume?