1. ETHANOL DERAILMENT SITES’ IMPACT ON GROUNDWATER QUALITY Presentation for Governors’ Coalition on Ethanol February 28, 2007

2. Five Derailments With Large Ethanol Releases Have Occurred Since 2005 July 27, 2005. 60,000 gallon release. Balaton, Minnesota August 31, 2005. 28,000 gallon release. South Hutchinson, Kansas June 17, 2006. 12,000 gallon release. Missoula, Montana October 20, 2006. > 100,000 gallon release. New Brighton, Pennsylvania November 22, 2006. 30,000 gallon release. Courtland, Minnesota

3. New Brighton, PA 23 ethanol tank cars derailed Several tankers ended up in the Beaver River Nine derailed tankers burned for 2 days 150 nearby residents were evacuated

4. New Brighton, PA About 365,000 gallons were released Much of the ethanol/fuel burned. Water 500 yards downstream was initially clear of gasoline contaminants as were downgradient PS intakes. Ethanol springs from park soils at various locations. Monitoring wells have been installed.

5. Courtland, Minnesota Pumped remaining ethanol from 7 derailed tank cars on 82 year-old track. Ethanol ponded in dry creek bed and was not removed. Cleanup dependent on natural attenuation – no excavation and no NAPL removal. Groundwater is 1.5 to 6 feet below surface. Ethanol (0.15 to 2.6%) and BTEX (2 mg/L) present in MW samples (at least 6 MWs).

6. Balaton, Minnesota Release prompted an evacuation of nearby residents. Accident considered human error at track switch control. Release contained soybean oil and denatured ethanol. Spill threatened recreational Lake Balaton. Pooled ethanol was pumped into an aerated sewage lagoon. MWs indicate that the 2.5-year old plume has moved about 380 feet.

7. Missoula, MT Release on coarse-textured soils Foamed the area to prevent ignition Over-excavated the saturated soils to a depth of 17 ft. and installed SVE in one area with residual ethanol. No detections in MWs beneath release site or downgradient of release site. Site manager is ready to close site.

8. Tanker held 28,488 gallons of ethanol of which 28,000 gallons were released on 8/31/05. South Hutchinson, Kansas

9. RESPONSE Strong ethanol fumes caused the evacuation of nearby homes, the Hutchinson Mental Health Facility and a middle school. Sand and foam were spread on the ethanol to prevent ignition. Haz-Mat Response Inc. personnel managed the cleanup.

10. CLEANUP The majority of the ethanol (~18 inches deep) was contained in a 0.5-mile long ditch adjacent to the track. Some ethanol drained into a pond and flowed beneath a trestle to a larger lake before earthen dams could be constructed. Sumps were dug along the ditch so that the ethanol could be collected and pumped into portable tanks. Approximately 20,000 gallons were recovered.

11. Observations on the Residue Approximately 8,000 gallons were not recovered. Ethanol was continuously volatilized from the soils as noted by a strong odor of ethanol during summer 2006. Soil cores from the site were characterized as smelling like sewage.

12. Vapor Pressure (mm Hg) If vapor pressure > 100 mm Hg Volatilization from free phase (NAPL) Vaporization of residual product from dry soil Law of Partial Pressure P total = P MTBE + P other constituents P MTBE = X MTBE P o MTBE P i (mm Hg) 27–28 0.8–0.9 2.8 0.2 0.7–0.8 Gasoline Constituent MTBE Benzene Toluene Ethylbenzene Xylenes 11% 1% 10% 2% 10% (NSTC, OSTP Report, June 1997) Arulanantham et al., 1999 Iso-octane (49) % by Volume Ethanol (49 - 57)

14. 28,000-gallon ethanol spill location H-1 H-3 H-6 H-4 H-5 H-2 H-1C H-1H-2H-3H-4H-5H-6 12 ft 0.7% 5 ft 2.4% 5 ft 0.6% 5 ft 4.8% 5 ft 1.6% 5 ft 0.6% 8.5 ft 5.6% 9.5 ft 4.0% 8.5 ft 2% 9 ft 0.8% 10 ft 4.8% 9 ft 4.2% Vadose zone methane concentrations

15. 03060 90120 Ethanol conc. (ug L -1 ) -12 -14 -16 -18 -20 -22 -24 -26 -28 Methane Ethylene Ethane Toluene Total Xylenes Ethanol 02468 Concentration (ug L -1 ) Geoprobe site H-2 Depth (ft)

16. 02468 Methane Toluene Total Xylenes Ethanol Ethylene Ethane 10 -12 -14 -16 -18 -20 Depth (ft) -22 -24 -26 -28 -30 Concentration (ug L -1 ) Geoprobe site H-5 0 200600400800 Ethanol Conc. (ug L -1 )

17. Field Measurements pH DO ORP Conductance Fe Mn Alkalinity

18. PHASE 2 RESULTS Collected unsaturated zone cores for the determination of hydraulic conductivity, microbial consortia (Mike Hyman), and flow and transport dynamics (Bill Rixey). Triangulated direction of groundwater flow. Installed 10 MWs with KDHE support. Completed two rounds of sampling and analysis of monitoring wells.

19. 0’ 20’ 30’ 40’ 10’ coarse sand and gravel medium sand clay fine to medium sand Screen Depths for Monitoring Wells 16-19’ 23-26’ 29-32’ 3-4’, 1.3x10 -8 cm/sec 6-7’, 5x10 -10 cm/sec 8-9’ 1.7x10 -9 cm/sec 10-12’, 1.2x10 -2 cm/sec 12-14’, 1.5x10 -2 cm/sec 18-20’, 2.5x10 -2 cm/sec 20-22’, 1.0x10 -1 cm/sec 28-30’, 1.9x10 -1 cm/sec 0’ 20’ 30’ 40’ 10’ coarse sand and gravel medium sand clay fine to medium sand 16-19’ 23-26’ 29-32’ 3-4’, 1.3x10 -8 cm/sec 6-7’, 5x10 -10 cm/sec 8-9’ 1.7x10 -9 cm/sec 20-22’, 1.0x10 -1 cm/sec 28-30’, 1.9x10 -1 cm/sec 12-32’ 10-12’, 1.2x10 -2 cm/sec 12-14’, 1.5x10 -2 cm/sec 18-20’, 2.5x10 -2 cm/sec

20. Groundwater Flow Shallow Groundwater Properties N W Average gradient: 0.005 ft/ft H c : 0.02 cm/sec v: 0.5 ft/day Direction: North-Northeast towards Arkansas River S E

22. Water Table gasoline and/or ethanol water Groundwater Contaminant spreading in capillary fringe due to decreased surface and interfacial tension. Predominately anaerobic microbial degradation of ethanol within the capillary fringe and conversion to methane. Attenuation of Contaminants within the Capillary Fringe Powers(2001)

23. 3 2 1 DISSOLVED OXYGEN (mg/L)

24. ETHANOL (  g/L) 25

25. 3 4 5 10 DISSOLVED ORGANIC CARBON (mg/L)

26. BENZENE (  g/L) 0.5 4 15

27. Phase 2: Preliminary Site Results Small amounts of ethanol entered the aquifer at 1 well location directly beneath the release. The unsaturated zone is actively degrading ethanol in the capillary fringe and methane is present in the underlying shallow groundwater. Most ethanol degradation appears confined to the immediate vicinity of the derailment. Soil-generated methane is likely partitioned into the shallow groundwater. Although DO and nitrate concentrations are low in the shallow groundwater, sulfate is unaffected which suggests that methanogenesis is not occurring.

28. Behavior of Ethanol Residual ethanol and BTEX ponded on the tight, wet ditch soils and was partially volatilized. Leachates to the capillary fringe appeared spatially limited to sloped areas beneath the derailed tankers. The high-clay content dry soils commonly are cracked and may have allowed preferential flow to infiltrate beneath the spill area. Small amounts of ethanol and BTEX were detected in the groundwater and are likely being consumed by degraders.

29. Preliminary Conclusions Robust emergency response to denatured ethanol releases at derailment sites lessens the likelihood of groundwater contamination. Excavation and SVE work well in gravelly soils. Spills on tight soils like those at S. Hutchinson, KS were primarily attenuated through volatilization. At sites that are not considered a threat to drinking water, natural attenuation has been allowed to run its course and ethanol and gasoline-contaminated groundwater has resulted.

30. Preliminary Conclusions Rail transport of ethanol is predicted to increase from ~6 billion gallons in 2006 to ~10 billion gallons in 2010 (minimum of 7.5 billion gallons – RFA of 2005). At least 4 of the 5 derailments discussed occurred on tracks that needed repairs. To reduce the risk of derailment many railroad spurs to rural towns in the Midwest corn belt need upgrading for increased traffic.

31. Recommendations Resample at S. Hutchinson in July Work jointly with Pinnacle Engineering Inc. Maple Grove, MN Study the consulting reports from the Balaton and Courtland sites Better understand the persistence of ethanol and BTEX in the capillary fringe Gain knowledge of the dynamics of the microbial consortia in the plumes Suggest a spectrum of remediation alternatives applicable to ethanol derailment sites with different risk levels.

32. Acknowledgments Bruce Bauman, American Petroleum Institute Todd Sneller, Nebraska Ethanol Board Eric Mork, ICM, Inc. Greg Hattan, co-PI KDHE Kenny Simmons, HAZ-MAT Response, Inc. Jeff Toavs, Technologist Mary Exner, co-PI UNL Michael Hyman, co-PI NCSU