United States Environmental Protection Agency Hazardous Waste Engineering Research Laboratory Cincinnati OH 45268 Research and Development EPA/600/S2-87'110 Feb. 1988 Project Summary Field Studies of In Situ Soil Washing James H. Nash The EPA and U.S. Air Force conducted a research test program to demonstrate the removal of hydrocarbons and chlorinated hydrocarbons from a sandy soil by in situ soil washing using surfactants. Contaminated soil from the fire training area of Volk Air National Guard Base, Wisconsin, was first taken to a laboratory for characterization. At the laboratory the soil was recompacted into glass columns creating a simulated in situ environment. Under gravity flow, 12 pore volumes of aqueous surfactant solutions were passed through each of the columns. Gas chromatograph (GC) analyses were used on the washing effluent and soil to determine removal efficiency (RE). The results of these tests were highly encouraging. RE's of field tests run at the fire training area were evaluated by GC, total organic carbon (TOC) and oil and grease data. Ten one foot deep holes were dug in the surface of the fire pit. Surfactant solutions were applied to each hole at a rate of 1.9 gallons per square foot per day. Soil samples, taken from the undisturbed layers beneath each hole, were analyzed for residual contamination. Samples experiencing a flow through of nine to fourteen pore volumes of surfactant solution still had contaminant levels comparable to 5,000-10,000 ng/g prewash conditions. The field study also included the development of a groundwater treatment process. Measurements of TOC, VOA and biochemical oxygen demand (BOD5) were decreased by 50%, 99%, and 50%, respectively. Treated effluent was discharged directly to the on-base aerobic treatment lagoons. This Project Summary was developed by EPA's Hazardous Waste Engineering Research Laboratory, Cincinnati, OH, to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction Surface and near-surface contamination often serve as the source for groundwater contamination Percolation of rainwater through spill sites quickly carries soluble and semi-soluble contaminants away from the point of origin Contaminants considered "insoluble" above parts per million nevertheless migrate more slowly. Gross contaminant sources supply pure product that over many years, flows deeply through unsaturated soils. Part of the EPA's Superfund site cleanup research has been directed at washing such contaminated soil with the aid of aqueous surfactant solutions. The research takes two directions. The first is to excavate the soil and mix it m a wash solution. The second research objective concentrates on the application or injection of a surfactant solution into undisturbed soil in situ. A segment of this in situ research is the subject of this project summary. This demonstration effort grew out of mutual need between the EPA and the U.S. Air Force. From 1982 to 1985 the EPA researched soil washing technology using surfactants in laboratory studies. Recompacted soils were used in these studies to simulate in situ conditions ------- Truly undisturbed contaminated soil was not tested up to that time. The U.S. Air Force, as part of its Installation Restoration Program, was seeking processes to clean up 128 fire training pits at Air Force installations. The Air Force selected the Air National Guard Base in Camp Douglas, Wisconsin, as a candidate site for the EPA to test either excavated or in situ soil washing. The EPA and the Air Force representatives chose in situ washing after further consideration. The Laboratory Study Previous laboratory work identified a 50/50 blend of two commercially available surfactants that work well in removing contaminants from soil. They are Adsee 799 and Hyonic PE-90, sold by Witco Chemical and Diamond Shamrock, respectively To determine if this same blend would work at the Volk Field fire training pit, contaminated soil samples were collected Five physical tests characterized the soil. They were: grain size, TOC, cation exchange capacity (CEC), mineralogy by x-ray diffraction, and permeability The grain size of the contaminated soil was 98% sand. By x-ray diffraction, alpha- quartz comprises the major portion of the soil with a minor amount of feldspar being present. TOC was as high as 14,900 ng/g. The cation exchange capacity of 5 milliequivalents.100 g was not significant to the contamination levels, however, it did support the x-ray diffraction mineralogic findings. The permeability of the fire pit soil, at 10-3 and 10'4 cm/sec, was one to two orders of magnitude less than adjacent uncontaminated soil Chlorinated hydrocarbons were part of the volatile contamination. Dichloromethane, chloroform, 1,1,1- trichloroethane (TCA), and trichloroethylene (TCE) at concentrations up to 3 ppm and total chlorinated solvents up to 3.5 ppm were determined by the VOA procedure. Other hydrocarbons are aliphatic, aromatic and polar constituents. The level of hydrocarbon contamination is in the hundreds of ng/g based on the laboratory analysis. Contaminated groundwater, a significant problem, from the aquifer below the fire training pit, was also characterized in the lab study. VOA, TOC, and ultraviolet spectroscopy (UV) was used. The investigations determined that the groundwater contains chlorinated and non-chlorinated hydrocarbons in excess of 300 ppm The soil adsorption constant (K) is a measure of a pollutant's tendency to adsorb and stay on soil. A value of 2,000 for PCB's indicates a two-hundred-fold greater adsorption (holding power) than benzene at K=10. Benzo(a)pyrene, a toxic substance, and oil have similar values - K = 30,000 - 40,000. Grouping contaminants according to a K value and evaluating removal efficiencies (RE) gives order to an otherwise complex collection of chemical classes. This is a report of the EPA's and the U.S. Air Force's field evaluation of in situ soil washing of compounds having K values between 101 and 106 The Field Study The field study was conducted by laying out ten 2' x 2' x 1' pits, dug into the contaminated surface of the fire training area, which served as reservoirs that held various surfactant solutions. Field technicians applied wash solutions into the holes at the maximum rate of 1 9 gallons per square foot per day The daily dosage was applied m four increments Since each hole percolated the solutions at different rates, the time interval between doses varied from hole to hole. Testing in three of the pits stopped when the time intervals for the next application approached ten hours indicating unacceptable permeabilities being created. Following seven days of washing, the pits received rinses with local, potable well water A combination of infrared spectroscopy (IR) and gravimetric determinations of soil extracts was used to evaluate "before and after" contaminant concentrations. To determine contaminant concentration, soil samples were taken after the rinse process, extracted with carbon tetrachlonde, and analyzed by IR spectrophotometer for spectral absorbance by the carbon hydrogen bond The extracts were then air dried and weighed to determine gravimetrically the contaminant concentration (non- volatile). The contaminant concentration before soil washing was based on the extracts of soil samples taken adjacent to the test holes No samples were taken directly from the test holes before washing in order not to bias permeation rates Based on both the gravimetric and IR determinations of contaminant concentrations, there was no measurable decrease in contaminants following as many as 14 pore volumes of soil washing in the field tests. In addition to the soil washing, field crew conducted a bench-s> groundwater treatment study. From study a treatment system was asseml and operated which successfully redi TOC, VOA and BOD5, by 50, 99, 50%, respectively. At these effh levels, discharge to the local aen sewage lagoon was below the Wisco Department of Natural Resources' pe limits A total of 320,000 L of c tammated groundwater was treatec rates of 15,000 to 45,000 Lday. The bench-scale study investig, the use of lime, alum, ferric sulf hydrogen peroxide, polymeric elec lytes and mineral acids. The apphce of these chemicals was guided conventions appropriate to wastew treatment plants. The resulting w treatment process (shown in Figure was based on the addition of lime ; g;L. The lime created a flocculatior iron oxides and organics. " contaminant plume contained up to mg/L iron. Particulate sedimentation clanfier, followed by additional reside time in a holding lagoon, reduced TOC, BOD5, and VOA to accept; discharge levels. A final polishing of volatiles m an air stripper was the I step in the process Table 1 i: summary of the analytical data Conclusions 1. In situ soil washing of the Volk Fi fire training pit with aquec surfactant solutions was r measurably effective It is likely t this same ineffectiveness would oc at other chronic spill sites that h; contaminants with high soil-sorpt values (K >1Q3). 2. In situ soil washing requires groui water treatment. Groundwa treatment at this site was ve successful with the simple addition lime Air stripping effectively remov the volatile organics. Advantages this site were its remoteness workable air emission limits tl facilitated groundwater treatrm operations and a local sewa treatment system owned by t responsible party TOC levels of recovered groundwater were reduc to one half the initial values precipitation with lime which allow for direct discharge to the aerol treatment lagoons. Obviously, not waste sites have these favorai conditions Other fire pit sites w lower effluent limits would requ systems with greater retention time: ------- Volatiles Lime 2 I t * — Flash Mix < JB1 ~~ta Clarifier ^ Lagoon Air To Aerobic Lagoon Well Figure 1. Volk Field pilot treatment for water. Table 1 Pt No. Analytical Tests and Sampling Points for the Water Treatment Process Description Tests Performed Approximate Values, Average or Range 1 Individual we/I head 2 Well field effluent 3 Flash mixer effluent 4 Clarifier effluent 5 Air stripper feed 6 Air stripper effluent 7 Clarifier 8 Clarifier bottom 9 Soil volatile organic total organic chemical oxygen demand oil and grease pH volatile organic total organic iron pH chemical oxygen demand flow rate total organic (dissolved) suspended solids pH flow rate total organic suspended solids pH flow rate volatile organic total organic temperature flow rate (water) oil and grease volatile organic total organic flow rate (air) oil and grease biochemical oxygen demand chemical oxygen demand suspended solids suspended solids oil and grease 70-20 mgiliter 60-760 mgiliter 6-500 mgiliter 0 2-46 mgiliter 5.7-62 70-20 mgiliter 250 ± 14% mgiliter 32 mglliter 6.0 ± 0.2 41 mgiliter .25 - 2 Mer.sec 7 60 mg 'liter 350 mgtliter 68-9.7 .5 - 2 liter'sec 205 ± 7% mgiliter 13 6-W4 mgiliter 76 .5 - 2 liter,'sec 3.5 - 7.0 mgiliter 151 ± 73% mgiliter 6-I5"C 95 - 7 26 /ifer/sec 3.6 mgiliter 0.3-05 pgMer 146 mgiliter 101 //sec 3.6 mgiliter 2.5 mgiliter 180 mgfliter 4.4 mgiliter 2331 mgiliter 800-16000 mgikg ------- James H. Nash is with Mason and Hanger-Silas Mason Co., Inc., Leonardo, New Jersey 07737 Richard P. Traver is the EPA Project Officer (see below). The complete report, entitled "Field Studies of InSitu So/7 Washing" (Order No. PB 88-1468081 AS; Cost: $14.95, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Releases Control Branch Hazardous Waste Engineering Research Laboratory-Cincinnati U.S. Environmental Protection Agency Edison, NJ 08837 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 Official Business Penalty for Private Use $300 EPA/600/S2-87/110 0000329 PS U S mn* PROTECTION U.S OFFiCIAL M/ *} O 2 L 6i"-OIC9, , „ II U 11 411 H *U'S- GPO 548-013* ------- |