1. Cleanup of Small Dry Cleaner Using Multiple Technologies: Sages Dry Cleaner Site NATO/CCMS Pilot Study Meeting, June 2006 Guy W. Sewell, Ph.D. Professor of Environmental Health Sciences Robert S. Kerr Endowed Chair East Central University

2. LargeSmall Waste TypeMixedPH/CH Access Issuesflexibleless Boundary Issuessomemany NA-applicableyesless likely OwnershipGov./Corp.Private Time IssuesVaries Limited by economics Site Size Issues Small Urban Sites are more likely to require source zone treatment to meet remedial time limitations and coordinated remedial approaches to address both source zone and dissolved phase contaminants.

3. Field Evaluation of the Solvent Extraction Residual Biotreatment (SERB) Technology Project Team USEPA-NRMRL-SPRD-Ada Guy W. Sewell, PI, Biological Processes Lynn Wood, Physical Processes Susan Mravik, Site Coordinator Ann Keeley, Norma Duran (Lab Studies) Site Contractor Levine-Fricke Recon UF Mike Annable, PI Solvent Extraction MSU James M. Tiedje, PI Microbial Ecology Shannon Flynn, Rebekah Helton, Frank Loeffler (Lab Studies) Project Funding- SERDP(FIBRC-WES), EPA-TIO, State of Florida

4. OBJECTIVE Integrate Remediation Technologies into a Treatment Train for Comprehensive Site Restoration Target DNAPL Source Zone Decrease Remediation Costs LIMITATIONS Geology Source Zone Delineation Time (?)

5. CONTAMINANT OF INTEREST: Tetrachloroethene (PCE) TECHNOLOGICAL BASIS: Cosolvent Extraction (Ethanol) Biodegradation (Reductive Dechlorination)

6. DNAPL GW Flow Residual & Separate Phase Material PCE Spill

7. GW Flow 90%+ Mass Removal Cosolvent Extraction Injection Well Ethanol Flush Recovery Well

8. PCE Ethanol Mixed Restoration?, Risk Reduction? GW Flow Residual Contaminants

9. Bioremediation Bioactive Zone FNA, Dissolution < Assimilative Capacity GW Flow

10. Why SERB (Source Control) Remove more mobile fraction of DNAPL, lower dissolved concentrations. 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. Regulatory requirement.

11. Biotransformations for Chloroethenes PCE cis -DCE trans -DCE Vinyl Chloride Ethene TCE 1,1-DCE CO 2 2 Ethane CO 2 X X Some field evidence No evidence but -  G No evidence but -  G Reductive Transformation Oxidative Catabolism

12. ANAEROBIC OXIDATION-REDUCTION Electron Acceptors Electron Donors Organic Compound EtOH, H 2 Partially Oxidized Compound(s) acetate CO 2 3 NO - SO 4 = Fe 3+ HCO 3 - R-Cl x N 2 (NH 4 + ) H 2 S Fe 2+ CH 4 R-Cl x SEWELL, '95 Reduced Electron Acceptors

13. Chloroethene Sites Plume TypeBio-attenuationStable Parent DominantNoYes (PCE or TCE) VC/cis DCEYesNo Dominant Ethene FormingYes?

14. Field Test of the SERB Technology Sages Dry Cleaner Site Results and Discussion

15. Field Test Table of Events July, 1998Site Characterization, Ground Water Monitoring, & Partitioning Tracer Test Aug. 9-15, 1998Ethanol Flush (9000 gallons) Aug. 15, 1998Partitioning Tracer Test Start Hydraulic Containment Aug. 25, 1998End Hydraulic Containment Ethanol < 10,000 mg/L

16. Sage’s Dry Cleaner Site Jacksonville, Florida RW-006RW-007 C1 C2 C3 C4 MW-505 MW-506 MW-507 MW-508 MW-509 MW-510 MW-511 MW-512 MW-513MW-514 RW-002 RW-003 RW-004 RW-005 CONCRETE SLAB ASPHALT DNAPL AREA 0 ft.20 ft.40 ft.60 ft.80 ft.

17. Pre-Cosolvent Flush Site Characterization Aerobic Conditions Low levels of daughter products (TCE) DNAPL contamination identified at 26 to 31 ft. bgs

18. Figure 1. PCE and ethanol concentrations during co-solvent flood at Sages Site in recovery well RW-001.

19. Cosolvent Flush Performance Pre-Cosolvent Flush Partitioning Tracer44.3 L (PCE) Post-Cosolvent Flush Partitioning Tracer13.9 L (PCE) Estimated Recovery Based on Partitioning Tracer Tests30.4 L (PCE) (70%) Mass Recovery Based on PCE Concentrations in Recovery Wells41.5 L (PCE)

20. 0.003 0.006 0.009 0.008 0.003 0.001 0.006 0.004 0.0002 - 0.001 0.002 0.001 0.009 Ground Water (Avg) Canal

21. Ethanol 0 mM 50 mM 100 mM 150 mM 200 mM 250 mM 300 mM 350 mM 350 mM = 16 g/L = 1.6 %

22. Ethanol 0 mM 50 mM 100 mM 150 mM 200 mM 250 mM 300 mM 350 mM 350 mM = 16 g/L = 1.6 %

23. Ethanol 1000 mM = 4.6 g/L = 0.46 % 0 mM 25 mM 50 mM 75 mM 100 mM

24. Ethanol 1000 mM = 4.6 g/L = 0.46 % 0 mM 25 mM 50 mM 75 mM 100 mM

25. PCE 0 uM 50 uM 100 uM 150 uM 200 uM 250 uM 300 uM 350 uM 400 uM 450 uM 500 uM 500 uM = 83 mg/L

26. PCE 0 uM 50 uM 100 uM 150 uM 200 uM 250 uM 300 uM 350 uM 400 uM 450 uM 500 uM 500 uM = 83 mg/L

27. PCE 0 uM 50 uM 100 uM 150 uM 200 uM 250 uM 300 uM 350 uM 400 uM 450 uM 500 uM 500 uM = 83 mg/L

28. PCE 0 uM 50 uM 100 uM 150 uM 200 uM 250 uM 300 uM 350 uM 400 uM 450 uM 500 uM 500 uM = 83 mg/L

29. TCE 0 uM 10 uM 20 uM 30 uM 40 uM 50 uM 60 uM 70 uM 80 uM 90 uM 100 uM 100 uM = 13 mg/L

30. TCE 0 uM 10 uM 20 uM 30 uM 40 uM 50 uM 60 uM 70 uM 80 uM 90 uM 100 uM 100 uM = 13 mg/L

31. TCE 0 uM 10 uM 20 uM 30 uM 40 uM 50 uM 60 uM 70 uM 80 uM 90 uM 100 uM 100 uM = 13 mg/L

32. cis-DCE 0 uM 25 uM 50 uM 75 uM 100 uM 125 uM 150 uM 175 uM 175 uM = 17 mg/L

33. cis-DCE 0 uM 25 uM 50 uM 75 uM 100 uM 125 uM 150 uM 175 uM 175 uM = 17 mg/L

34. cis-DCE 0 uM 25 uM 50 uM 75 uM 100 uM 125 uM 150 uM 175 uM 175 uM = 17 mg/L

35. Vinyl Chloride 2.0 uM = 125 ug/L 0.0 uM 0.2 uM 0.4 uM 0.6 uM 0.8 uM 1.0 uM 1.2 uM 1.4 uM 1.6 uM 1.8 uM 2.0 uM

36. Vinyl Chloride 2.0 uM = 125 ug/L 0.0 uM 0.2 uM 0.4 uM 0.6 uM 0.8 uM 1.0 uM 1.2 uM 1.4 uM 1.6 uM 1.8 uM 2.0 uM

37. Vinyl Chloride 2.0 uM = 125 ug/L 0.0 uM 0.2 uM 0.4 uM 0.6 uM 0.8 uM 1.0 uM 1.2 uM 1.4 uM 1.6 uM 1.8 uM 2.0 uM

38. Ethene 0.0 uM 0.1 uM 0.2 uM 0.3 uM 0.4 uM 0.5 uM 0.5 uM = 14 ug/L

39. Chloride 0 uM 250 uM 500 uM 750 uM 1000 uM 1250 uM 1500 uM 1750 uM 2000 uM 2250 uM 2250 uM = 80 mg/L

40. Acetic Acid 0 uM 200 uM 400 uM 600 uM 800 uM 1000 uM 1200 uM 1400 uM 1600 uM 1600 uM = 96 mg/L

41. Sulfate 0 uM 100 uM 200 uM 300 uM 400 uM 500 uM 600 uM 700 uM 800 uM 900 uM 900 uM = 86 ug/L

42. Methane 0 uM 100 uM 200 uM 300 uM 400 uM 500 uM 600 uM 700 uM 800 uM 900 uM 1000 uM 1100 uM 1100 uM = 18 mg/L

43. Methane 0 uM 100 uM 200 uM 300 uM 400 uM 500 uM 600 uM 700 uM 800 uM 900 uM 1000 uM 1100 uM 1100 uM = 18 mg/L

44. SUMMARY Solvent Extraction: 41.5 L PCE Removed (Mass Recovery) ~70 % PCE Removed (Partitioning Tracer) PCE Daughter Product Formation TCE, cis-DCE, VC, ethene, methane (?) Change in Geochemistry Dissolved Oxygen, Sulfate, and Redox Indications of Biological Activity Methane, Volatile Fatty Acid, and Hydrogen

45. Partial Oxidation of Ethanol: CH 3 CH 2 OH + H 2 O -----> CH 3 COOH + 2 H 2 Complete Oxidation of Ethanol: CH 3 CH 2 OH + 3H 2 O -----> 2CO 2 + 6 H 2 Dechlorination of PCE: C 2 Cl X + H 2 -----> C 2 Cl x-1 + H + + Cl - Complete Dechlorination of PCE Requires 1-2 Moles of Ethanol (excluding competing processes)

46. Source Area = 40 ft. diameter X 5 ft. depth Assume Porosity = 0.4 Pore Volume = 70,000 L Concentrations: Average Ethanol = 8,000 mg/L Average PCE = 50,000 ug/L Total Mass: Ethanol - 570 Kg or 12,350 Moles PCE - 3.6 Kg or 21.5 Moles Theoretically, we have >250 times the amount of ethanol present for complete dechlorination of the estimated remaining PCE. 38.8 times the amount needed to degrade the 157.1 moles of the (estimated) PCE in the source zone (136 moles residual PCE + 21.1 moles dissolved PCE). While this estimate assumes no competing terminal oxidation processes such as methanogenesis or sulfate reduction, an efficiency greater that 2% would still meet the theoretical demand.

48. First Order Degradation Rates (Based on Total Mass) Ethanol -0.33 year -1 (R 2 0.53)t ½ = 2.1 yrs PCE -0.56 year -1 (R 2 0.82)t ½ = 1.2 yrs cis-DCE 0.81 year -1 (R 2 0.82)t ½ = 0.9 yrs

50. Currently the system remains biologically active and the dechlorination products are accumulating. High levels of dissolved methane and hydrogen have also been detected in the treatment zone. The maximum and minimum observed rate of dechlorination (based on cis-DCE production) are approximately 43.6 and 4.2 ug/liter/day, respectively. These rates can be extrapolated to a multi-step, concurrent, dechlorination process to predict that the dissolved phase PCE could be removed in 3 to 30 years, and that the total source zone PCE could be transformed in 24 to 240 years.

51. Publications Sewell, G.W. et al. 2005. Chlorinated Solvent Contaminated Soil and Ground Water: Field Application of the Solvent Extraction Residual Biotreatment Technology, Chapter 5. In Bioremediation of Recalcitrant Compounds. Taylor & Francis Publishers, Boca Raton. Pp 59-149. Mravik, S., R.K.Sillan, A.L. Wood, and G.W. Sewell. 2003. Field Evaluation of the Solvent Extraction Residual Biotreatment (SERB) Technology. Environ. Sci. Technol. 37: 5040- 5049. Jawitz, J., R.K. Sillan, M.D. Annable, P.S.C. Rao and K. Warner. 2000. In-Situ Alcohol Flushing of a DNAPL Source Zone at a Dry Cleaner Site. Environ. Sci. Technol. 34: 3722-- 3729.

52. Questions Questions?