Period Covered by Report: September 4, 2002 to January 4, 2003
Date of Report: January 16, 2003
EPA Grant Number: 14-2-1201270-94843
Title: A Continuation: Humate-Induced Remediation of Petroleum Contaminated Surface Soils
Investigators: Mark A. Nanny, R. Paul Philp, Vlad E. Andrus, and Glenn
Ulrich
Institutions: University of Oklahoma, Surbec-ART Environmental
EPA Project Officer: Bala Krishnan
Project Period: September 4, 2002 to September 3, 2003
Project Amount: $133,136
Research Category: Bioremediation of oil spills
The objectives of this proposed research are: 1) to measure the biodegradation and bioavailability of 14C-labeled heptadecane that is strongly adsorbed to humate, 2) to examine the adsorption of gasoline, gasoline oxygenates as a part of gasoline itself, and diesel fuel to humates, as well as their biodegradation in soil microcosms, and 3) to assess humate-induced remediation on a pilot-scale by conducting ex-situ tests of soils contaminated with crude oil, diesel fuel, and gasoline.
Many attempts were undertaken within this quarter for reconnaissance of the site which meets the requirements of the current project. Several trips with extensive sample collecting were performed at the Sunoco refinery at Tulsa. More than twenty samples of contaminated soils were collected there with the assistance of Sunoco personnel, followed by analyses of dichloromethane-acetone extracts with gas-chromatography and gas- chromatography-mass-spectrometry methods. Unfortunately, no samples contaminated with relatively new spills of crude oil or refined petroleum products were found. Such unexpected obstacle caused a delay in deploying both pilot-scale field test and microcosm experiment.
Nevertheless, with Surbec-ART's assistance, we found an old refinery site in Texas that contains several sites with gasoline and diesel contamination. The Waggoner refinery site contains all three types of moderately aged gasoline, diesel fuel, and crude oil-contaminated soils. This site has service to a backhoe and also has ample space for windrow construction.
The adsorption of diesel fuel to Earthgree Menefee humate (Cuba, New Mexico), which will be used in all our experiments during this project, was analyzed using a gravimetric method. The total amount of adsorbed diesel fuel was calculated as a difference between final loss for humate contaminated with diesel fuel and final loss for humate itself after complete dichloromethane and dichloromethane-methanol extractions. Results of this experiment demonstrated that neither freeze-dried humate (freeze- dried to remove surface moisture), nor "as is" humate retained hydrocarbons of diesel fuel range. This conclusion was also supported by pyrolysis-GC study of n-alkane and n-alkene concentrations in the solid residues of humate after extraction. The ratios of n-alkanes to n-alkenes did not show its increase for none of the eight samples studied.
Nanny, M.A., Andrus, V.E., Philp, R.P. (2002) "Evidence for Adsorption and Biodegradation Mechanisms Facilitating Humate-Induced Remediation of Petroleum-Contaminated Surface Soils", Extended Abstracts of the 21st International Meeting on Organic Geochemistry, Krakow, Poland , September 2003 (submitted).
Mark A. Nanny, Vlad E. Andrus, R. Paul Philp (2002) "Humate-enhanced remediation of crude oil-contaminated surface soils: Adsorption studies and microcosm results", Extended Abstracts for the Environmental Chemistry Division, American Chemical Society, 225th American Chemical Society National Meeting, New Orleans, March 2003 (accepted).
Collecting soils contaminated with diesel fuel, gasoline, and crude at Waggoner refinery site to set-up and start microcosm experiment. Implementation of pilot-scale ex-situ test consisting of fifteen windrows of soils contaminated with gasoline, diesel fuel, and crude oil at Waggoner refinery site.
Initiation of gas-chromatographic analyses of microcosm and windrow extracts for identification of biodegradation and/or adsorption processes, as well as Rock- Eval and pyrolysis-GC analyses of microcosm and windrow residues after solvent extraction.
gasoline, diesel fuel, crude oil, microcosm, humate, adsorption