Fitchburg, Massachusetts USA 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

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

Changes in Physical Properties with Heating (to 120°C) 20-100 20-80 20-300 2000 Thermal remediation has many beneficial effects that aid in the removal of creosote DNAPL and associated PAHs. These thermal remediation mechanisms have been described in detail by Udell (1996), Davis (1997), Imhoff et al. (1997), Sleep and Ma (1997), Heron et al. (1998a,b,c), and Stegemeier and Vinegar (2001). A brief summary is listed below: Note: Per Stegemeier and Vinegar (2001), Vapor pressure increase factors should be: for oil based LNAPL: n-C16H24 and n-C29H60) ~8-80; for chlorinated solvents: ~15; for naphthalene ~300; for PCBs 1242 and 1260: 1000-2000. Note also: only VOCs and light NAPL constituents (e.g., n-C16H24 and naphthalene) become volatile enough below 120C to be amenable to SVE.) Ask Gorm: Why are some values in red and others in black? Conclude that for VOCs, vaporization is the dominant process, and capture of vapors and condensate is crucial – therefore complete heating and hydraulic and pneumatic control must be achieved 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

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.

Steam Enhanced Extraction (SEE) Steam, upper Steam, lower Extraction well Example of steam flow and zone governed by low-K zone at 5-6 m depth. Monitoring and adjustments during heat-up important and expensive. Modeling for Fort Lewis proposal.

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 Courtesy of CES Three-Phase heating is another option Horizontal Heated Zone Slightly Larger Than Array Diameter

Thermal Conduction Heating (TCH) Combined with Vacuum: In-Situ Thermal Desorption (ISTD) Heater Wells Are Spaced 6 to 25 Feet Apart and Operate at 1500°F - To Remediate Recalcitrant SVOCs, Thermal Conduction Can Raise the Temperature Between Wells to 400°C when the Wells are Close Together - If VOCs are to be Remediated, Well Spacing Can Be Much Farther Apart - The Well Spacing Determines the Project Length 6 Feet ~ 45 Days (SVOCs), 25 Feet ~ 8 Months (VOCs) Benzo(a)Pyrene BP 481° C Can Be Vaporized; Clays and Buried Cement are Not a Problem

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)

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

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

Source zone & estimated mass area 1 area 2 area 3

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

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

Continous operation Temperature distribution 3,0 m.b.g. after 41 days T3 T2 T1

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

Terminal One Project, San Francisco Bay Area, California

Target Treatment Zone

Areas To Be Cleaned Up in Southwestern Tank Farm

Cross-Section Not to Scale 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

– 126 – 12

Fiberglass Manifold Pipe Horizontal SVE Well HV Well HO Well

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

Richmond Results Reductions: 99.96% 99.63% 99.03% 99.49% 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).

Richmond Results Reductions: 99.96% 99.63% 99.03% 99.49% 510,000 57,000 6,500 6,500 2,000 2,000 17,000 230 44 < RL 1,500 24 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).

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

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

ISTD Development and Deployment PCBs 23 2006 CVOCs CVOCs 22 21 CVOCs 19 Chlorinated Benzenes, PAH, BTEX 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 2 Chlorinated Pesticides 13 19 16 20 12 2002 8 9 Chlorinated Benzenes 11 14 PAHs 10 5 4 CVOCs 9 18 12 23 2001 Shell TerraTherm TerraTherm, Inc. 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 Shell R&D 1980’s through 2000’s 1 PCBs 2 1996

TCH Research (Ongoing) 1D 2D 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

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

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!

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

Supplemental Data Documented Results of Representative SEE, ERH and TCH Projects

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

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)

Representative Thermal Conduction Heating (TCH) Results Site Major COCs Depth (m) Volume (m3) Initial Max. Concentration (mg/kg) Final Concentration (mg/kg)* Cost ($/m3) Confidential Mfg Site, OH TCE 4.6 8800 4,130 < 0.07 180 Terminal One, Richmond, CA PCE 6.1 5350 610 0.012 350 Shell Fuel Terminal, Eugene, OR Benzene Gasoline/ Diesel 3.7 13800 3.3 < 2.4 m free product < 0.044 free product removed 260 Naval Facility Centerville Beach, Ferndale, CA PCB 1180 800 < 0.17 550 National Grid, N. Adams, MA Naphthalene B[a]P 5.5 780 679 20 5.7 0.33 1090 Southern California Edison, Alhambra, CA PAH (B[a]P Eq.) Dioxins (TEQ) 30 12400 30.6 0.018 0.059 0.00011 570 Can meet more stringent goals than SEE or ERH *All remedial goals met (Stegemeier and Vinegar 2001; LaChance et al. 2004, 2006; Bierschenk et al. 2004)