1. Surfactant Flushing 2009 Pilot Study Fueling Point – Military Site Northeastern USA Jeffrey H. Harwell Asahi Glass Chair of Chemical Engineering The University of Oklahoma Principal Surbec Environmental, LLC

2. Background Jet fuel spill discovered in 2006 Jet fuel spill discovered in 2006 Probably happened in 2001 Probably happened in 2001 Depth to water 44 ft Depth to water 44 ft Sandy aquifer - 20% silt Sandy aquifer - 20% silt Drinking water wells within ¼ mile but in deeper aquifer Drinking water wells within ¼ mile but in deeper aquifer Estimated 350,000 to 700,000 gal spill Estimated 350,000 to 700,000 gal spill

3. Pilot Study Objectives Surfactant Enhanced Aquifer Remediation (SEAR ) Evaluate effectiveness and efficiency Demonstrate chemical/hydraulic control Generate design for full-scale implementation

4. Within the LNAPL plume generally up-gradient minimize recontamination No impact to existing soil vapor extraction system Pilot Study Location

5. Treatability Study Surfactant system design Surfactant system design Provide proof of concept Provide proof of concept Geochemistry considerations Geochemistry considerations Heterogeneity issues Heterogeneity issues Optimization of injection strategy Optimization of injection strategy

6. Step 1: Formulate Microemulsion Monomer Organic Contaminant Micelle Increasing Salinity IIIIII

7. Vials Surf. A (wt%) Surf. B (wt%) Salt A (wt%) Salt B (wt%) Middle Phase Aqueous Phase NAPL Phase Winsor Type BA-10.750.191.50.06NoHazyYellowI BA-20.750.191.50.10YesClearYellowIII BA-30.750.191.20.10YesClearYellowIII BA-40.750.191.30.10YesClearYellowIII BA-50.750.191.40.10YesClearYellowIII BA-60.750.191.60.10YesClearYellowIII BA-70.750.191.70.10YesClearYellowIII BA-80.750.191.80.10YesClearYellowIII BA-90.750.191.90.10YesClearYellowIII BA-100.750.192.00.10YesClearYellowIII BA-110.750.192.10.10YesClearYellowIII BA-120.750.192.20.10YesClear Hazy Yellow III BA-130.750.190.80.10NoHazyYellowI BA-140.750.191.50.10YesClearYellowIII BA-150.750.191.60.10YesClearYellowIII BA-160.750.191.70.10YesClearYellowIII BA-170.750.192.50.10YesClearYellowIII Table 1 Microemulsion Phase Behavior Step 1: Formulate Microemulsion Mixture of food grade anionic surfactants

8. Table 2 Sorption Studies Step 2: Verify Adsorption Losses are Reasonable Very sandy soil; very low adsorption

9. Sample [Surf. A] [Surf. B] [Salt A][Salt B] [Calcium Chloride] Presence of Precipitate Presence of Separation IDwt% ppmYes/No P-00.750.191.6 0.1 0NoYes* P-1000.750.191.6 0.1 100NoYes* P-3000.750.191.6 0.1 300NoYes P-5000.750.191.6 0.1 500NoYes P-8000.750.191.6 0.1 800NoYes Table 3 Precipitation and Phase Separation Tests Note: * No phase separation within the first day of observation Step 3: Examine Sensitivity to Phase Separation

10. Solution Polymerμ (Average) (ppm)(cp) NAPL -1.4181 Surfactant/Polymer (S/P) Solution 01.4046 1001.6949 3001.9367 5002.7654 8003.3162 1,5003.7507 Surfactant/Polymer/Alkaline (S/P/A) Solution 01.4046 3002.0927 5002.6748 5002.6748 8003.9592 1,5004.2944 Table 4 Viscosity of Different Solutions Note:  (average) is the average viscosity shown in the unit of centipoise (cp) Step 4: Mobility Ratio

11. Column Test #Description% RecoveryNote 1Surfactant only99.49Observed some surfactant retardation 22PV Surfactant/Polymer99.93 Mobilization started on the second PV of surfactant injection 32PV Surfactant/Polymer/Alkaline99.94 Mobilization started on the second PV of surfactant injection 4 0.2PV P/A, 1PV S/P/A, 0.2PV P/A at 1500 ppm polymer* 99.93 More mobilized NAPL in the first PV of mobilization 5 0.2PV P/A, 1PV S/P, 0.2PV P/A at 500 ppm polymer 99.93 More solubilization observed when compared to column test #6 6 0.2PV P/A, 1PV S/P/A, 0.2PV P/A at 500 ppm polymer 99.94 More mobilization observed when compared to column test #5 7 0.05PV P/A, 1PV S/P, 0.05 PV P/A at 500 ppm polymer 99.93 When compared to column 8, less amount of NAPL mobilized and more solubilized NAPL 8 0.05PV P/A, 1PV S/P/A, 0.05 PV P/A at 500 ppm polymer 99.93** The NAPL was mobilized out from the column 3-5 minutes before column test #7 and there was a higher amount of NAPL mobilized out from column when compared to column test #7 9 0.05PV P/A, 1PV S/P, 0.2 PV P/A at 100 ppm polymer 94.6 Less amount of mobilized oil when compared to 500 ppm polymer 10 0.05PV P/A, 1PV S/P/A, 0.05 PV P/A at 100 ppm polymer 90.29 Less amount of mobilized oil when compared to 500 ppm polymer 111 PV S/A, no polymer92.97 Solubilization mechanism is dominant Table 5 Summary of 1-D Column Tests *S: surfactant, P: polymer, A: alkaline; PV = pore volume **yellow highlighted: the optimal surfactant candidate based on the performance of NAPL recovery and the recovery mechanism (mainly mobilization) Step 5: Optimize Injection Sequence

12. Pilot Study Overview Footprint was < 1/8 acre; well spacing of 25 ft. 2 pore volumes of surfactant at 0.94 wt % 2 nine-spot patterns Submersible pumps recover NAPL/water/surfactant Process equipment oil/water separator injection mixing tanks/pumps injection/extraction manifolds influent/effluent pumps carbon vessels

13. Mixing & Holding Tanks, O/W Separator, GAC Canisters

14. Site Map

15. Timeline Pre-Flush – 1 pore volume – 31 Aug 09 – 6 Sep 09 – Set BioTraps on 3 Sep 09 – Tracer (NaBr) injected 4 – 5 Sep 09 Surfactant Flush – 2 pore volumes – 6 – 21 Sep 09 – Groundwater sampled on 10 and 17 Sep 09 – Surfactant first observed – EX-02 and OWS on 20 Sep 09 – EX-01 on 23 Sep 09

16. Timeline Post Flush - 5 pore volumes – 21 Sep 09 – 1 Nov 09 – Applied vacuum on extraction wells on 25 Sep 09 – Reconfigured injection/extraction on 20 Oct 09 – Groundwater sampled on 1 Oct 09 and 2 Nov 09 – BioTraps 7 Oct 09 – Injected remaining treated water 3 – 6 Nov 09 to empty tanks

17. Size: 18,000 Gallons Transfer Pump Mixing Tanks

18. Size: 18,000 Gallons Mixer with propeller

19. Injection Manifold

20. Flow Meter Flow Control Unit Flow Meters and Flow Controllers

21. Remediation and Monitoring Wells

22. Oil/Water Separator 45 min. Residence Time

23. Surfactant Concentrate 330 Gallon Totes

24. Added Manually to Mixing Tank

25. Phase Behavior Test 2.5 min 3 min NaCl: 0.3-1.7% with 0.1% increment Quality Control Check

26. Phase Behavior Test 1 hour NaCl: 0.3-1.7% with 0.1% increment

27. Data Assessment Pre-Pilot Conditions – API Model estimated 2,300 gal LNAPL Results – Total LNAPL Recovery was 2,740 gal – API Model estimated140 gal remained

28. LNAPL Thickness/Distribution

29. API Model

30. Soil Sampling Results - Upper

31. Soil Sampling Results - Middle

32. Soil Sampling Results - Lower

33. LNAPL Recovery

34. Extraction Well - Partial Plugging

35. Key Findings Motivation for full-scale implementation – Significant LNAPL removal - 2,740 gal – Significant reduction in LNAPL thickness – Significant reduction in soil TPH-DRO – Hydraulic control achieved and maintained – No increase in dissolved-phase concentrations – Optimized surfactant formulation

36. Key Findings Lessons learned as a result of the pilot study – Heterogeneous NAPL thickness along perimeter – Heterogeneous stratigraphy – Mobilization of fine sand – Emulsification within process equipment Fixes – Better placement of well screens – Improved well locations – Improved surfactant formulation – Longer residence times in oil/water separator

37. Full Scale Implementation Final review with State Regulatory Agency, Military Base Groups on November 12 th Final review with State Regulatory Agency, Military Base Groups on November 12 th Decision for full scale (3.6 acres) made - RFP issued Decision for full scale (3.6 acres) made - RFP issued Implementing in 3 parcels of 1.2 acres each Implementing in 3 parcels of 1.2 acres each System installation in May 2010 System installation in May 2010 Surfactant injection in June 2010 Surfactant injection in June 2010 Post surfactant flush to be finished November 2010 Post surfactant flush to be finished November 2010