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Approaches to Integrating Source and Plume Treatment Strategies for Long-Term Dilute Plume Management Kent S. Sorenson, Jr., PhD, PE June 20, 2012 Presentation Overview Background Potential degradation mechanisms Strategies for

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SLIDE 1

Approaches to Integrating Source and Plume Treatment Strategies for Long-Term Dilute Plume Management

June 20, 2012

Kent S. Sorenson, Jr., PhD, PE

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SLIDE 2

Presentation Overview

  • Background
  • Potential degradation mechanisms
  • Strategies for technology integration
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SLIDE 3

BACKGROUND

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SLIDE 4

Test Area North

  • 1.5-mi TCE plume
  • 200 ft to water
  • 200-ft

contaminated thickness

  • Sludge injection

well at source

  • 1995 ROD

– Pump and treat – 100-year cleanup

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SLIDE 5

Fringe and Core Hypothesis (Cherry, 1996)

  • Generic chlorinated solvent plume conceptual model

CORE FRINGE

  • 102 m,
  • 103 µg/L
  • 103 m, • 102 µg/L

Mass Flux

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SLIDE 6

POTENTIAL DEGRADATION MECHANISMS

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SLIDE 7

Anaerobic Reductive Dechlorination

C I

PCE

C C C C H

TCE

C C H H

cis - 1,2 - DCE

H C C H H

Vinyl Chloride

H H C C H H

Ethene

H H C C H H

Ethane

H H H C C H

1,1 - DCE

H C C H

trans - 1,2 - DCE

O O C

Complete Mineralization

O H H C I C H

Chlorine Atom Carbon Atom Hydrogen Atom Single Chemical Bond Double Chemical Bond

Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl

Modified from Wiedemeier et al., 1996

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SLIDE 8

Anaerobic Reductive Dechlorination

TCE DCE + VC VC + Ethene

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SLIDE 9

Anaerobic Reductive Dechlorination

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SLIDE 10

Anaerobic Reductive Dechlorination

DCE Stall Not Always Bad

10 20 30 40 50 60 70 80 2 4 6 8 10 12 Time (months) Concentration (ppb)

TCE (ppb) DCE (ppb)

DCE MCL TCE MCL

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SLIDE 11

Aerobic Cometabolism

  • Axial

concentration ratios

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SLIDE 12

Aerobic Cometabolism

  • Aerobic TCE degradation half-life: 12-15 years (3H)
  • Aerobic DCE degradation half-life: 8-9 years (3H)

Sorenson et al., 2000; Wymore et al., 2007; Lee et al., 2008

ln(TCE/PCE) Distance, , from Well TSF-05 (m) x ln(TCE/tritium)

y = -1.3E-03x - 1.4E+00 R2 = 8.0E-01 y = -8.1E-04x + 3.2E+00 R2 = 9.2E-01 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 500 1000 1500 2000 2500 3000

  • 5.0
  • 4.5
  • 4.0
  • 3.5
  • 3.0
  • 2.5
  • 2.0
  • 1.5
  • 1.0
  • 0.5

0.0 TCE/PCE TCE/Tritium

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SLIDE 13

Aerobic Degradation

  • 9 plumes evaluated at 4 DOE sites

– Brookhaven National Laboratory – Paducah Gaseous Diffusion Plant – Savannah River Site – Rocky Flats

  • Aerobic TCE degradation rates evident at 8 out of 9
  • Degradation half-life range: 0.85 – 12 years

Koelsch et al., 2005

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SLIDE 14

Biogeochemical Reduction by Iron Minerals

  • Twin Cities Army Ammunition Plant
  • TCE & DCE half-lives < 2.5 years

Ferrey et al., 2004

1 10 100 1000 10000 100 300 500 700 900 Time of Incubation (days) Concentration of cis-DCE (µg/liter) Live Microcosms Autoclaved Controls Container Controls

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SLIDE 15

Biogeochemical Reduction by Iron Minerals

  • Resources

EPA, 2009; ESTCP, 2008

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SLIDE 16

STRATEGIES FOR TECHNOLOGY INTEGRATION

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SLIDE 17

Prerequisites

  • Identification of intrinsic degradation mechanism
  • Estimate of intrinsic degradation rate (separate from dispersion)
  • Reasonable assurance of longevity of mechanism

Sorenson et al., 2000

y = -0.020t + 38 R2 = 1.0 y = -0.14t + 280 R2 = 0.99

  • 5
  • 4.5
  • 4
  • 3.5
  • 3
  • 2.5
  • 2
  • 1.5
  • 1
  • 0.5

1990 2000 2010 2020 2030 2040 2050 2060 2070 2080 2090 2100

ln(TCE/TCE )

  • Year, t
  • 4.5
  • 4
  • 3.5
  • 3
  • 2.5
  • 2
  • 1.5
  • 1
  • 0.5

2 4 6 8 10 12 14 Time ln(C /C )

max

  • Baetsle (1969)

Analytical Model

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SLIDE 18

Fringe Types

  • Active Treatment Fringe (ATF)

– Fringe Concentration > MNA capacity

  • Bountiful
  • Intrinsic Treatment Fringe (ITF)

– Fringe Concentration ≤ MNA capacity

  • TAN
  • Well 12A
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SLIDE 19

Active Treatment Fringe

  • Source removed/contained
  • Active treatment required in fringe to meet cleanup goals

Mass Flux

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SLIDE 20

Bountiful/Woods Cross Superfund Site

Source Treatment Biobarrier Fringe Treatment

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SLIDE 21

Bountiful (cont.)

  • Source treatment (anaerobic reductive dechlorination) started 2008
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SLIDE 22

Bountiful (cont.)

  • Source flux stopped, downgradient biobarriers installed
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SLIDE 23

Intrinsic Treatment Fringe

  • Source removed/contained
  • Intrinsic degradation in fringe sufficient to meet cleanup

goals

Mass Flux

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SLIDE 24

Test Area North, OU 1-07B

Bioremediation Pump & Treat MNA

  • 1997 TCE

Distribution

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SLIDE 25

Test Area North, OU 1-07B

  • 2009 TCE

Distribution

DOE, 2012

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SLIDE 26

Test Area North, OU 1-07B

DOE, 2012

  • 2011 TCE

Distribution

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SLIDE 27

Test Area North, OU 1-07B

DOE, 2012

  • MNA performance

monitoring

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SLIDE 28

Test Area North, OU 1-07B

DOE, 2012

  • Zone 1
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SLIDE 29

Test Area North, OU 1-07B

DOE, 2012

  • Zone 2
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Test Area North, OU 1-07B

DOE, 2012

  • Zone 3

– Up to 30% temporary plume expansion allowed – Actual expansion 8.5% to 15% – Performance appears right on track!

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SLIDE 31

Well 12A Superfund Site

  • Tacoma water supply
  • Significant residual

source material

  • Large, dilute plume
  • Estimated intrinsic

degradation limit: 300 µg/L Core Fringe

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SLIDE 32

Well 12A Superfund Site

  • RAOs:

– 90% mass discharge reduction from core – ARARs at designated points

  • f compliance

– Determine if MNA can meet ARARs in fringe

Core Fringe

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SLIDE 33

Well 12A Superfund Site

  • Detailed 3D source

characterization for remedy design to stop mass discharge

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SLIDE 34

Well 12A Superfund Site

  • Performance monitoring

transects established for source treatment

  • MNA evaluation and

performance monitoring underway

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SLIDE 35

Acknowledgments

  • Kira Lynch (EPA)
  • John Wilson (EPA)
  • Sam Garcia (EPA)
  • Lee Nelson (Idaho National Laboratory)
  • Tamzen Macbeth (CDM Smith)
  • Nathan Smith (CDM Smith)
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SLIDE 36

References

  • Baetsle, L.H. 1969. “Migration of Radionuclides in Porous Media.” In: A. M. F. Duhamel

(Ed.), Progress in Nuclear Energy Series XII, Health Physics, pp. 707-730. Pergamon Press, Elmsford, NY.

  • Cherry, J. A. 1996. “Conceptual Models for Chlorinated Solvent Plumes and Their

Relevance for Intrinsic Remediation.” In: Symposium on Natural Attenuation of Chlorinated Organics in Ground Water, pp. 29-30. Office of Research and Development, U.S. Environmental Protection Agency, Washington, DC, EPA/540/R-96/509.

  • DOE. 2012. Annual Report for the Final Groundwater Remediation, Test Area North,

Operable Unit 1-07B, Fiscal Year 2011. DOE/ID-11464, Revision 0. 81 pp.

  • EPA. 2009. Identification and Characterization Methods for Reactive Minerals Responsible

for Natural Attenuation of Chlorinated Organic Compounds in Ground Water. EPA 600/R-09/115. December.

  • ESTCP. 2008. Workshop on In Situ Biogeochemical Transformation of Chlorinated Solvents.

February.

  • Ferrey, M. L., R. T. Wilkin, R. G. Ford, and J. T. Wilson. 2004. “Nonbiological Removal of cis-

Dichloroethylene and 1,1-Dichloroethylene in Aquifer Sediment Containing Magnetite.” Environmental Science &Technology. 38(6):1746-1752.

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SLIDE 37

References (cont.)

  • Koelsch, M., R. C. Starr, and K. S. Sorenson, Jr. 2005. “Assessing Aerobic Natural

Attenuation of Trichloroethene at Four DOE Sites.” Proceedings of the Waste Management 2005 Conference, Tucson, AZ.

  • Lee, M. H., S. C. Clingenpeel, O. P. Leiser, R. A. Wymore, K. S. Sorenson, Jr., and M. E.
  • Watwood. 2008. “Activity-Dependent Labeling of Oxygenase Enzymes in a

Trichloroethene-Contaminated Groundwater Site.” Environmental Pollution. 153(1):238-

  • 246. 2009.
  • Sorenson, K. S., Jr., L. N. Peterson, R. E. Hinchee, and R. L. Ely. 2000. An Evaluation of

Aerobic Trichloroethene Attenuation Using First-Order Rate Estimation. Bioremediation Journal, 4(4):337-357. 2000.

  • Wymore, R. A., M. H. Lee, W. K. Keener, A. R. Miller, F. S. Colwell, M. E. Watwood, and K. S.

Sorenson, Jr. 2007. “Field Evidence for Intrinsic Aerobic Chlorinated Ethene Cometabolism by Methanotrophs Expressing Soluble Methane Monooxygenase.” Bioremediation Journal. 11(3):125-139. 2007.