In-Situ Thermal Remediation of Soil Contaminated with Organic Chemicals

1. In-Situ Thermal Remediation of Soil Contaminated with Organic Chemicals Ralph S. Baker, Ph.D. TerraTherm, Inc. Fitchburg, Massachusetts USA NATO/CCMS Pilot Study Prevention and Remediation in Selected Industrial Sectors: Small Sites in Urban Areas Athens, Greece 7 June 2006

2. Overview • Introduction to In Situ Thermal Remediation (ISTD) • Steam-Enhanced Extraction • Electrical Resistance Heating • Thermal Conduction Heating • Representative Field Projects and Results • SEE – Aalborg, Denmark • TCH – Richmond, California, USA • Conclusion • Supplemental Data

3. 20-80 20-100 20-300 20-300 2000 Changes in Physical Properties with Heating (to 120°C) Udell (1989, 1991, 1993, 1996) Davis (1997, 1999) Imhoff et al. (1997) Sleep and Ma (1997) Heron et al. (1998, 2000) Stegemeier and Vinegar (2001) Note: Abiotic and biological reactions not listed

4. Consider In-Situ Thermal Remediation (ISTR): • For Source Remediation of Organic Contaminants (e.g., DNAPL) • To Facilitate a Brownfields Cleanup • To Achieve Rapid Site Closure • As part of overall optimization of an existing system, especially where additional source control/removal would significantly shorten the duration of a long-term pump and treat, SVE, or Multi-Phase Extraction system.

5. Steam, upper Extraction well Steam, lower Steam Enhanced Extraction (SEE)

6. Electrical Resistance Heating (ERH) Recovery • Six-Phase Heating: Electrical current moves between the 6 electrodes on the outside diameter and the central neutral. Vertical Heated Zone • Three-Phase heating is another option Courtesy of CES Horizontal Heated Zone Slightly LargerThan Array Diameter

7. Thermal Conduction Heating (TCH) Combined with Vacuum: In-Situ Thermal Desorption (ISTD)

8. NIRÁS SEE Project, Aalborg, Denmark Former dry cleaning facility  50 years of dry cleaning activity (~ 1936-1985) Perchloroethylene (PCE) and turpentine (stoddard solvent) as cleaning fluid (Courtesy Tom Heron, NIRÁS)

9. j e v s d n u l e n i l o r a K Site layout and treatment wells Østerbro 24-26. Aalborg Appartments Former dry cleaner Shed Ware house Garages Railroad Shop Extraction well Steam Injection well

10. Fillings Sand Clay PCE Turpentine Contaminant distribution Former dry cleaning facility 1,0 m.b.g. 1,7 m.b.g. 3,7 m.b.g.

11. Source zone & estimated mass area 1 area 2 area 3

12. Extraction well Injection well Remediation strategy ~ day 1-2 Ground water Soil vapor Steam Steam Former dry cleaning facility Submerged pump Fillings Steam zone Sand Clay Steam zone

13. Remediation strategy ~ day 15 Ground water /free phase Soil vapor /steam Steam Steam Former dry cleaning facility Submerged pump Fillings Steam zone Sand Extraction well Clay Injection well Steam zone

14. T3 T2 T1 Continous operation Temperature distribution3,0m.b.g. after41days

15. Clean up results • Removed ~ 900 - 1.000 kg of PCE/turpentine • Remaining contamination in cold spots: ~ 5 - 8 kg • PCE in soil: 0,04 - 37 mg/kg • PCE in air: 1,2 - 600 mg/m3 • PCE in water 0,57 - 62 µg/l • Efficiency: 98-99 % • Remediation goal achieved: Threat to in- and outdoor air quality significantly reduced

16. Terminal One Project,San Francisco Bay Area, California

17. Target Treatment Zone

18. Areas To Be Cleaned Up in Southwestern Tank Farm

19. Richmond Site Cross-Section 5400 m3 CVOCs: PCE, TCE, DCE, and VC NAPL TTZ Fill 0-1 m Bay Mud Target Treatment Zone (TTZ) 0 – 6.1 m Cross-Section Not to Scale

20. – 126 – 12

21. Fiberglass Manifold Pipe Horizontal SVE Well HV Well HO Well

22. Heater-Vacuum (HV) Well Sub Slab Vapor Collection Point Fiberglass Manifold Pipe TC Pressure Monitoring Point Heater-Only (HO) Well

23. Richmond Results 34,222 17,000 6,650 1,055 932 2,000 2,000 230 12 < RL 65 5 Reductions: 99.96% 99.63% 99.03% 99.49% Results are based on 17 pre-treatment samples and 64 post-treatment samples. Post-treatment samples were collected from centroids (i.e., coolest locations) at random and biased depths (15 or 23% were collected between 18 and 20 ft bgs).

24. Richmond Results 510,000 57,000 6,500 6,500 2,000 17,000 2,000 230 1,500 44 24 < RL Reductions: 99.96% 99.63% 99.03% 99.49% Richmond results are based on 17 pre-treatment samples and 64 post-treatment samples. Post-treatment samples were collected from centroids (i.e., coolest locations) at random and biased depths (15 or 23% were collected between 5.5 and 6.1 m bgs).

25. Projected Post Redevelopment View 350 Condominium Residential Area and Waterfront Park Planned for Site

26. Project completed on time and on budget 7 months for construction and treatment Total TT project cost: ~$1.7M Cost of power: $250K Post-development value: ~$300M - Performance guaranteed - Remedial goals achieved

27. PCBs 23 TerraTherm, Inc. Shell TerraTherm Shell R&D 1980’s through 2000’s 1 2006 CVOCs 21 CVOCs 22 Chlorinated Benzenes, PAH, BTEX CVOCs 19 ISTD Development and Deployment 2005 20 CVOCs 18 CVOCs 17 MGP 16 PAHs, Dioxins 15 2004 CVOCs 14 11 2003 CVOCs/SVOCs, radionuclides 13 7 Chlorinated Pesticides 2 16 20 13 19 12 2002 Chlorinated Benzenes 9 8 11 10 PAHs 14 4 5 CVOCs 9 18 2001 12 23 3 15 21 22 17 2000 10 1999 1 PCBs 8 GRO/DRO, Benzene 7 PCBs Saipan 6 1998 CVOCs 4 PCBs 5 PCBs 3 1997 PCBs 2 1996

28. 1D 2D TCH Research (Ongoing) • 1D tests to select and characterize soils for large-scale experiments • 2D experiments on heat front propagation and DNAPL mobilization • Large-scale (150 m3) 3-D container experiments of TCH treatment of DNAPL under saturated conditions • Accompanying numerical simulations 3D Upper Footprint of Container at VEGAS

29. Reerslev, Denmark Municipal Well Field Threatened by nearby DNAPL source area, which is currently being considerated for ISTD.

30. Concluding Remarks • ISTR can be Tailored to the Needs of the Remediation Project • ISTR is Well-Suited to Small Urban Sites • ISTR is Rapid, Certain and Thorough, without the Drawbacks of Excavation • Clean to Residential Standards if Desired • Low Impacts to Neighbors • Cost-Competitive • Guarantees Available • Turn a Liability into an Asset!

31. About TerraTherm, Inc. • Exclusive licensee of ISTD technology: • Within the U.S., from the Univ. of Texas at Austin. Protected by 24 U.S. patents. • Outside the U.S., from Shell Oil Co. Protected by 8 patents, and patents pending. • Sublicensees in Denmark and Sweden (Krüger A/S); U.K. (AIG Engineering Group, Ltd.) • International Partners in Denmark (NIRÁS); Germany (reconsite GmbH; VEGAS); and Japan (SheGoTec Japan, Inc.) • For more information, please visit www.terratherm.com

32. Supplemental DataDocumented Results of Representative SEE, ERH and TCH Projects

33. Representative Steam Enhanced Extraction (SEE) Results (Courtesy of G. Heron)

34. Representative Electrical Resistance Heating (ERH) Results (Peacock et al. 2004; Cacciatore et al. 2004; Beyke et al. 2004; Hayes and Borochaner, 2004; Hoenig et al. 2004; Peterson et al. 2004)

35. Representative Thermal Conduction Heating (TCH) Results *All remedial goals met (Stegemeier and Vinegar 2001; LaChance et al. 2004, 2006; Bierschenk et al. 2004)