1. Full-Scale Permanganate Remediation of a Solvent DNAPL Source Zone in a Sand Aquifer Beth L. Parker, Ph.D. University of Waterloo Presented at the EPA Seminar: In Situ Treatment of Groundwater Contaminated With Non-Aqueous Phase Liquids Chicago December 11, 2002 1

2. 2 Collaborators Tom Al, University of New Brunswick –Inorganic Geochemistry Ramon Aravena, University of Waterloo –Isotope Geochemistry John Cherry, University of Waterloo

3. 3 This Case Study Will Show: Density driven distribution of KMnO 4 in sand Performance assessment with minimal uncertainty Nearly complete destruction of TCE and 1,1,1-TCA

4. 4 Two General Approaches for In Situ Oxidation Inject-and-withdraw (active) Flushing Inject-and-leave (passive) Episodic Injection

5. 5 Injection Addition of Treatment Chemicals Withdrawal The Active Approach B.L.Parker

6. 6 The Waterloo Passive Approach Use density and dispersion effects to distribute permanganate solution Inject in a manner that minimizes groundwater displacement

7. 7 The Waterloo Passive Approach 2 3 1 Sandaquifer 4 KMnO (highdensity) Relies on density and dispersion effects B.L.Parker, 1997

8. 1 2 3 4 t i m e Concentration andDensity Decrease nolateralgroundwaterflow Evolution of a Single Disc in a Sand Aquifer B.L. Parker, 1997 8

9. Initial Proof - of - Concept Initial Proof - of - Concept Inject-and-Leave Field Trial in Borden Aquifer Matthew Nelson M.Sc. Thesis (1999) Supervisors: Drs. Beth Parker and John Cherry University of Waterloo 9

10. Borden 9x9 m Sheet Pile Enclosure 10

11. System Set-up at 9m Cell Borden Site 11

12. 12 Density of Dissolved KMnO 4 in Water sea water 0 20 40 60 1.05 1.04 1.03 1.02 1.01 1 relative density grams per liter KMnO 4 Typical Range Used 20 C o 10 C o solubility

13. 13 sand SETTING clay 12 ft 0 ft 1 ft

14. Evidence for Density Induced Flow (Nelson, 1999) 14

15. 15 The Waterloo Passive Approach Use density and dispersion effects to distribute permanganate solution Inject in a manner that minimizes groundwater displacement

16. 16 Long-Screen Injection Causes Large Displacement of Contaminated Water Parker, 1997

17. 17 Injection of Discs Leaving Gaps Minimizes Displacement of Contaminated Water Parker, 1997

18. 18 KMnO 4 Stage 1 Sand aquifer Initial disc Injection of Multiple Discs Using Direct Push Device Parker, 1997

19. 19 Injection of Multiple Discs Using Direct Push Device KMnO 4 Injection1 Injection2 Stage 2 Parker, 1997

20. 20 Stage 1: Inject Disc Above DNAPL on Aquitard KMnO 4 aquitard Stage 1 sand aquifer Initial disc Parker, 1997 DNAPL

21. 21 Disc Sinks and Spreads Parker, 1997 1 2 aquitard DNAPL Injector withdrawn Time 3

22. Site TCE and TCA source zone Case Study in Florida 22

23. 23 Ft. Lauderdale Site

24. 24 Contamination Occurred Recently late 1996 to early 1997 TCA used: 1995-96 Switch from TCA to TCE: Nov 1996 - April 1997 Conventional monitoring wells installed: 1997 Fenton’s treatment pilot study: 1998-1999 UW bundle multi-levels installed: 1999 –Fenton’s performance assessment Permanganate selected as source removal action for permanent remedy

25. 25 Site Geology Water table 8-inch coarse sand layer 57 ft bgs Fine and medium grained beach sand with no visible layering Increased frequency of gravel size carbonate rock fragments Carbonate bedrock 85 ft bgs

26. 26 Monitoring Methods Continuous Cores Bundle tube samplers Waterloo Profiler Conventional Monitoring Wells Micro-monitoring Wells Focus on depth-discrete methods

27. 27 Aluminum core tube inside core barrel Core Being Removed from Piston Core Barrel

28. 28 Cutting the Aluminum Core Tube

29. 29 Subsampling Sand for VOC Analysis

30. 30 Installation of Bundle Tube Sampler: 1999

31. 31 Bundle Tube Sampler SET IN NATURAL FORMATION NO SAND PACK ¾” ID SCH 40 PVC PIPE CENTER STOCK 1/2” OD POLYETHYLENE or 1/4” OD TEFLON TUBING 6-8” NITEX SCREEN OVER PIPE PERFORATIONS 2-4” NITEX SCREENS CONCRETE PAD 1/4” OD TEFLON TUBING IN 1/2” OD POLYETHYLENE TUBING STEEL WELL COVER w/CONCRETE PAD

32. 32 TCE Concentration Profile CW-L 0 10 20 30 40 50 60 70 80 600000 0 100000200000300000400000500000700000 TCE Concentration (  g/L) Depth (ft) Before Injection (February 2000) 625,500  g/L

33. 33 TCE Concentration Profile CW-K 0 10 20 30 40 50 60 70 80 25000 0 5000100001500020000 TCE Concentration (  g/L) Depth (ft) Before Injection (February 2000) 21,574 ug/L

34. 34 Conceptual Model of DNAPL Distribution

35. 35 100 Monitoring well Multilevel system GeoProbe sampling Building CW-L TCE Source Zone >10,000 µg/L Before Remediation TCE Plume > 100 µg/L 010ft N

36. 36 The Waterloo Passive Approach for Permanganate 1.Pre-injection delineation 2.Permanganate injection in targeted zones 3.Monitor results and design subsequent injection 4.Repeat steps until attain desired endpoint

37. 37 Full-Scale Permanganate Remediation in Ft. Lauderdale, FL 37

38. 38 KMnO 4 Mixing Tank 38

39. 39

40. 40 Asphalt Ground Surface Sand Aquifer Direct Push Drill Rig Scaffolding NO 2 Tank Pressure Tank #2 Pressure Tank #1 KMnO 4 Feed Tank Stage 1: KMnO 4 Injection at Several Depths Drill Rods Parker, 2000

41. 41 Asphalt Ground Surface Sand Aquifer Direct Push Drill Rig Scaffolding NO 2 Tank Pressure Tank #2 Pressure Tank #1 KMnO 4 Feed Tank Stage 2: Spreading and Sinking by Density Parker, 2000

42. 42 Conceptual Model of DNAPL Distribution Parker, 2000

43. 43 KMnO 4 Target Treatment Zone

44. 44 Source Zone Wells

45. 45 KMnO 4 Injection Coverage Episode 1

46. 46 KMnO 4 Injection at Multiple Depths

47. 47 Passive Crew 47

48. 48 Effects of Density and Diffusion on Injected KMnO 4 Ellipsoids

49. 49 Project Timeline Time (months) 0 UW Site Pre-Design Characterization 1 st Injection Episode 1 2 nd Injection Episode 3 3 rd Injection Episode 7 1 st Post- Treatment Monitoring 10 2 nd Post- Treatment Monitoring 13 February 2000 32 4 th Injection Episode 3 rd Post- Treatment Monitoring October 2002

50. 50 Site Map – X Sections

51. 51 TCE Distribution on B-B’ – Feb 2000 Parker et al., 2000

52. 52 TCE Distribution on B-B’ – Oct 2002 Parker et al., 2002

53. 53 Feb 2000 May 2000 Jul 2000 Dec 2000 Oct 2002 TCE Concentration Profile CW-K

54. 54 Oct 2002 TCE Concentration Profile CW-K Prior to 4 th Injection 17 ug/L

55. 55 TCE Distribution on C-C’ – Feb 2000 Parker et al., 2000

56. 56 TCE Distribution on C-C’ – Oct 2002 Parker et al., 2002

57. 57 Feb 2000 May 2000 Jul 2000 Dec 2000 Oct 2002 TCE Concentration Profile CW-L

58. 58 TCE Concentration Profile CW-L Prior to 4 th Injection 1, 480 ug/L Oct 2002

59. 59 TCE Distribution on D-D’ – Feb 2000 Parker et al., 2000

60. 60 TCE Distribution on D-D’ – Oct 2002 Parker et al., 2002

61. 61 TCA Distribution on C-C’ – Feb 2000 Parker et al., 2000

62. 62 TCA Distribution on C-C’ – Oct 2002 Parker et al., 2002

63. 63 100 Monitoring well Multilevel system GeoProbe sampling Building CW-L TCE source zone >10,000 Before Remediation – February 2000 Plume TCE µg/L 010ft N Parker, 2002

64. 64 Monitoring well Multilevel system GeoProbe sampling TCE µg/L After Remediation – December 2000 TCE source zones >10,000 Building 010ft N 100 Parker, 2002

65. 65 Monitoring well Multilevel system GeoProbe sampling TCE µg/L After Remediation – October 2002 Building 010ft N 100 214 1,480 108 Parker, 2002

66. 66 Specific Conclusions 99% reduction in contaminated volume Displacement avoided by limiting injection to <8% of treatment zone pore volume for each episode 1,1,1-TCA also disappeared No TCE or TCA rebound

67. 67 General Conclusion This case study showed that permanganate can be successful for complete remediation of the source if : The site conditions are suitable The remedial design is tailored to the site

68. 68 Final Stage Fourth injection occurred October 2002 to complete source zone remediation Performance assessment monitoring planned for February 2003

69. 69 Acknowledgements Funding: University Consortium Solvents-in-Groundwater Research Program Canadian Natural Sciences and Engineering Research Council Sun Belt Interplex, Inc. Staff: Matthew Nelson, MSc Hydrogeologist: Project Manager Colin Meldrum, BASc: Field Activities and Data Display Bob Ingleton, Paul Johnson, BSc: Injection System Design and Field Technical Assistance Martin Guilbeault, MSc, Matthew Whitney, BASc: Field Assistance Maria Gorecka, MSc: Lab Analysis of VOC

70. 70 For information on this case study: Parker, B.L., J. A. Cherry and T. A. Al (2002). Passive permanganate remediation of a solvent DNAPL source zone. In proceedings for “The Third International Conference on Remediation of Chlorinated and Recalcitrant Compounds,” Monterey, California. Battelle 2002 Monterey Conference Proceedings