In-Situ Thermal Remediation of Soil Contaminated with Organic

In-Situ Thermal Remediation of Soil Contaminated with Organic Chemicals Ralph S. Baker, Ph. D. Terra. Therm, 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) u u u Steam-Enhanced Extraction Electrical Resistance Heating Thermal Conduction Heating § Representative Field Projects and Results u u SEE – Aalborg, Denmark TCH – Richmond, California, USA § Conclusion § Supplemental Data

Changes in Physical Properties with Heating (to 120°C) 20 -80 20 -100 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) 20 -300 2000 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 Extraction well Steam, lower

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

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

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 Shed Shop oad Railr Gar age s Ware house K a ro line lu n d s ve j Former dry cleaner Extraction well Steam Injection well

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

Source zone & estimated mass area 1 area 2 area 3

Remediation strategy ~ day 1 -2 So il v Steam apor Former dry cleaning facility Steam zone Extraction well Injection well r te wa nd ou Steam Gr Fillings Submerged pump Sand Clay Steam zone

Remediation strategy ~ day 15 Steam Former dry cleaning facility Steam zone Extraction well Injection well Soil va /stea por m r wate nd Grou phase /free Steam Submerged pump Fillings Sand Clay Steam zone

Continous operation Temperature distribution 3, 0 m. b. g. after 41 days T 3 T 2 T 1

Clean up results § Removed ~ 900 - 1. 000 kg of PCE/turpentine § Remaining contamination in cold spots: ~ 5 - 8 kg u PCE in soil: 0, 04 - 37 mg/kg u PCE in air: 1, 2 - 600 mg/m 3 u 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

Richmond Site Cross-Section TTZ 5400 m 3 CVOCs: PCE, TCE, DCE, and VC NAPL 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

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

Richmond Results 34, 222 17, 000 6, 650 1, 055 2, 000 12 Reductions: 99. 96% 932 230 < RL 99. 63% 99. 03% 65 5 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 510, 000 57, 000 6, 500 2, 000 44 Reductions: 99. 96% 1, 500 < RL 99. 63% 17, 000 99. 03% 230 24 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 - Performance guaranteed - Remedial goals achieved 7 months for construction and treatment Total TT project cost: ~$1. 7 M Cost of power: $250 K Post-development value: ~$300 M

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

TCH Research (Ongoing) 1 D 2 D • 1 D tests to select and characterize soils for large-scale experiments • 2 D experiments on heat front propagation and DNAPL mobilization • Large-scale (150 m 3) 3 -D container experiments of TCH treatment of DNAPL under saturated conditions • Accompanying numerical simulations 3 D 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 Ø Clean to Residential Standards Ø Low Impacts to Neighbors Ø Cost-Competitive Ø Guarantees Available if Desired § Turn a Liability into an Asset!

About Terra. Therm, Inc. § Exclusive licensee of ISTD technology: u u 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 Gmb. H; VEGAS); and Japan (She. Go. Tec 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 Confidential Mfg Site, OH TCE Terminal One, Richmond, CA PCE Shell Fuel Terminal, Eugene, OR Benzene Gasoline/ Diesel Naval Facility Centerville PCB Beach, Ferndale, CA National Grid, N. Adams, MA Depth (m) Volume (m 3) Initial Max. Concentration (mg/kg) Final Concentration (mg/kg)* Cost ($/m 3) 4. 6 8800 4, 130 < 0. 07 180 6. 1 5350 610 0. 012 350 3. 3 < 0. 044 3. 7 13800 < 2. 4 m free product removed 260 4. 6 1180 800 < 0. 17 550 679 5. 7 Naphthalene 5. 5 780 B[a]P Southern California Edison, Alhambra, CA 20 30 0. 33 30. 6 PAH (B[a]P Eq. ) Dioxins (TEQ) 1090 0. 059 12400 570 0. 018 (Stegemeier and Vinegar 2001; La. Chance et al. 2004, 2006; Bierschenk et al. 2004) 0. 00011 *All remedial goals met