PB88-146808 Ep 1.23/2; 600/2-87/110 >8 FIELD STUDIES OF SITU SOIL WASHING MASON & HANGER, SILAS-MASON COMPANY LEONARDO, NJ DEC 87 U.S. DEPARTMENT OF COMMERCE National Technical Information Service LIBRARY OF THE UNIVERSITY OF ILLINOIS AT URBANA-CHAMPAIGN NOTICE: According to Sec. 19 (a) of the University Statutes, all books and other library materials acquired in any man¬ ner by the University belong to the University Library. When this item is no longer needed by the department, it should be returned to the Acquisition Department, University Library. TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing) 1. REPORT NO. 2. EPA/600/2-87/110 3 PB38-146808 4. TITLE AND SUBTITLE Field Studies of In Situ Soil Washing 6. REPORT DATF December 1987 6. PERFORMING ORGANIZATION CODE 7. AUTHOR(S) James H. Nash 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS Mason & Hanger, Silas-Mason Co., Inc. Post Office Box 117 Leonardo, New Jersey 07737 10. PROGRAM ELEMENT NO. 11. CONTRACT/GRANT NO. Contract No. 68-03-3203 12. SPONSORING AGENCY NAME AND ADDRESS Hazardous Waste Engineering Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 13. TYPE OF REPORT AND PERIOD COVERED 14. SPONSORING AGENCY CODE EPA-600/12 15. SUPPLEMENTARY NOTES 16. ABSTRACT The EPA and US 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, WI, was first taken to a laboratory for characterization. At the laboratory, the soil was recorapacted 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 wash¬ ing 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 gal per sq ft per day. Soil samples, taken from the undisturbed layers beneath each hole, were analyzed for residual contamina¬ tion. Samples experiencing a flow-through of 9 to 14 pore volumes of surfactant solu¬ tion still had contaminant levels comparable to 5,000-10,000 ppm prewash conditions. The field study also Included the development of a groundwater treatment process. Measurements of TOC, VOA, and biochemical oxygen demand (BOD 5 ) were decreased by 50%, 99%, and 50%, respectively. Treated effluent was discharged directly to the on-base aerobic treatment lagoons. 17. KEY WORDS AND DOCUMENT ANALYSIS a. DESCRIPTORS b.lDENTIFIERS/OPEN ENDED TERMS c. COSATi Ficld/Group RfPTODUCEO BY NATlOh INFORM U.S. DEP SPR ^AL TECHNICAL ATION SERVICE ARTMENI OF COMMERCE NGFIEID. VA. 22161 18. DISTRIBUTION STATEMENT Release to Public 19. SECURITY CLASS (This Report) UNCLASSIFIED 21. NO. OF PAGES 67 20. SECURITY CLASS (This page) UNCLASSIFIED 22. PRICE EPA Form 2220-1 i Digitized by the Internet Archive in 2018 with funding from University of Illinois Urbana-Champaign Alternates https://archive.org/details/fieldstudiesofinOOnash FIELD STUDIES OF IN SITU SOIL WASHING EPA/600/2-87/110 December 1987 PB88-14d808 'by James H. Nash Mason & Hanger-Silas Mason Co., Inc. P.O. Box 117 Leonardo, New Jersey 0TT3T Contract No. 68-03-3203 Project Officer Richard P. Traver P.E. Releases Control Branch Land Pollution Control Division Edison, New Jersey 08837 HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO U5268 \ - 0-- NOTICE The information in this document has heen funded hy the U.S. Environmen¬ tal Protection Agency and the U.S. Air Force under Contract No. 68-03-3203 to Mason & Hanger-Silas Mason Co., Inc. It has heen subjected to the Agency's peer and administrative review, and it has been approved for publication as a USEPA document. The mention of trade names or commercial products does not constitute endorsement or recommendation for use. ii FOREWORD Today’s rapidly developing and chemging technologies and industrial products and practices frequently carry with them the increased generation of solid and hazardous wastes. These materials, if improperly dealt with, can threaten both public health and the environment. Abandoned waste sites and accidental releases of toxic and hazardous substances to the environ¬ ment also have important environmental and public health implications. The Hazardous Waste Engineering Research Laboratory assists in providing an authoritative and defensible engineering basis for assessing and solving these problems. Its products support the policies, programs, and regula¬ tions of the Environmental Protection Agency; the permitting and other responsibilities of State and local governments; and the needs of both large and small businesses in heindling their wastes responsibly and economically. This report describes field activities undertaken to evaluate at pilot-scale, techniques for sxirfactant-enhanced in situ soil washing. The information in this report is useful to those who develop, select, or evaluate equipment for cleanup of spills or waste sites or for the protec¬ tion of response personnel and equipment. For further information, please contact the Land Pollution Control Division of the Hazardous Waste Engineering Research Laboratory. Thomas R. Hauser, Director Hazardous Waste Engineering Research Laboratory iii ABSTRACT The U.S. Environmental Protection Agency Releases Control Branch and the U.S. Air Force Engineering and Services Center engaged in a joint project focused on in situ washing of a fire training pit at Volk Air National Guard (ANG) Base, Camp Douglas, Wisconsin. The washing fluids were solutions of commercially available surfactants in water. Of partic¬ ular interest was a blend of Adsee 799 and Hyonic PE90. This blend had previously proved successful in laboratory studies involving the cleaning of organic contaminants from soil. A second objective was to treat contam¬ inated groundwater underlying the test site. The fire training pit had served as a site for firefighting training as early as World War II up until deactivation in 1979. The subsurface soil was determined to be 85-95% sand and 5-15% fines. The contamination was principally a medium weight oil (2,000-25,000 mg/kg) with some vola¬ tiles (VOA analysis 5-10 mg/kg). The unconfined aquifer at 12 feet depth is reported to be continuous to 700 feet. The same aquifer serves as the water supply for the Camp Douglas. No contamination has been detected in the wells supplying the base nor private wells adjacent to the base. However, organic carbon levels in the groundwater under, and adjacent to, the pit were measured as high as 700 mg/liter. Small areas of the pit (ten squares that were one or two feet on a side) were isolated and surfactant solutions applied at a rate of 77 L/m^ per day for seven days. Cleaning efficiencies were determined based on before and after oil and grease measurements. Full scale air stripping and pilot flushing operations reduced the total organic carbon by as much as 60%. Volatiles in the groundwater were reduced by 99%. iv CONTENTS Foreword. iii Abstract. iv Figures. vl Tables. viii Abbreviations and Symbols. ix 1. Introduction. 1 2. Conclusions . 6 3. Recommendations . T it. Site Characteristics. 8 Soil characteristics. 8 Rainfall. 8 Hydrologic properties . 8 Determination of soil contamination. 11 Contaminants at the site. ih Electromagnetic survey of the fire pit area . . l8 Sanitary wastewater treatment at Volk Field . . 21 5. In Situ Washing. 22 Establishing a pre-test baseline. 22 Test Cell Layout. 22 Wash solutions. 23 Washing procedures. 23 Sampling and analysis. 25 Discussion. 27 6. Groundwater Control and Treatment . 30 Requirement for groundwater treatment . 30 Well field specification & performance. 30 Groxindwater treatment system. 35 T. Analytical Methods and QA/QC Report . U5 8. References. 50 Appendix. 52 V FIGUEES Number Page 1. Location of Volk Field. 3 2. Site map showing the fire training pit and shallow monitoring wells installed in I 98 I (see Table l). 3 . Spring 1985 Site Study Map. 9 U. Soil particle size distribution of soil taken at four depths (under the fire pit). 10 5 . Groundwater equipotential lines around the fire pit area. 12 6. Oil and grease values were highest near the fire pit surface. 13 7 . Gas Chromatogram of hydrocarbons from a composite of Volk Field fire training pit soil. 15 8. Graphs of split spoon consolidation (blows per foot) and vapor analysis (peak height counts) during monitoring well drilling. IT 9 . The contaminant plume as determined by TOC measurements of water samples at the water table. 19 10. EM Survey Plot showing equi-conductivity lines (units are millimhos/meter). 20 11. Volk Field Test Site for in situ soil washing and groundwater treatment. 2h 12. Soil Wash O&G Data. 26 13 . Proposed model of preferential path development in organic oil spill. 28 lU. Well field layout for groundwater discharge to the treatment system. 31 vi FIGURES (c ontinued) Number Page 15 . Equipotential lines during pumping . 3^ 16 . Volk Field pilot treatment for water. 36 IT. EPA's Mobile Independent Chemical/Physical Treatment plant. 38 18 . Air Stripping Tower. 19 . Five sets of data show the reduction in volatiles brought about by the water treatment process. Ul 20. The measured value for total organic carbon from each of the six production wells and total well flow. ... U3 21. Effect of water treatment on TOC for four data sets. UU vii Nvcnber TABLES Page 1. Chemicals Found in Shallow Wells. 5 2. Preliminary Laboratory VOA Characterization of Volk AFB Site of Opportunity. l6 3. Volatile Hydrocarbon Characterization of Volk AFB Site of Opportiinity Soils. l6 U. Oil and Grease Measurements of Samples Taken at 0.9 m (3 ft) Depth and 0.9 m Spacing. 22 5. Wash Solution Volumes and Concentrations for Volk Field Soil Wash Pilot Study - September 1985 . 25 6. Pumping Test of Production Well. 33 T. Analytical Tests and Sampling Points Table. 37 8. QA Siommary. Uj 9. Comparison of Coefficients of Variation for API and Volk Field Collocated Samples . U 9 A-1 Hazardous Parameters of Hydrophobic Organics. 5^ A-2 Hazardous Parameters of Hydrophilic Organics. 55 A-3 Hazardous Parameters of Hydrophilic Organics. 56 viii LIST OF CONVERSIONS METRIC TO ENGLISH To convert from to Multiply by Celsius degree Fahrenheit 1.8 T ^+32 joule erg 1,000 E+OT joule foot-pound-force 7 . 37 U E-01 kilogram povind-mass (ibm avoir) 2.205 E+00 meter foot 3.281 E +00 meter inch 3.937 E+01 meter^ foot^ 1.076 E +01 meter^ inch® I. 5 U 9 E+03 meter^ gallon (U.S. liquid) 2 . 6 U 2 E +02 meter^ litre 1.000 E+03 meter/second foot/minute 1.969 E +02 meter/second knot I. 9 UI+ E+00 meter^/second centistoke 1.000 E +06 meter^/second foot®/minute 2.119 E+03 meter^/second gallon (U.S. liquid)/minute 1.587 E+OU newton pound-force (ihf avoir) 2 . 2 U 8 E-01 watt horsepower (550 ft Ihf/s) 1.3^1 E-03 ENGLISH TO METRIC centistoke meter®/second 1.000 E -06 degree Fahrenheit Celsius (Tp-32)/1.8 erg joule 1.000 E-OT foot meter 3 .OU 8 E -01 foot® meter® 9.290 E-02 foot/minute meter/second 5.080 E-03 foot®/minute meter®/second U .719 E-Oh foot-pound-force joule 1.356 E+00 gallon (U.S. liquid) meter^ 3.785 E-03 gallon (U.S. liquid)/minute meter^/second 6.309 E -05 horsepower (550 ft Ibf/s) watt 7.457 E+02 inch meter 2.540 E-02 inch® meter® 6.542 E-04 knot (international) meter/second 5.144 e-01 litre meter^ 1.000 E-03 pound force (ibf avoir) newton 4.448 E+00 poiand-mass (ibm avoir) kilogram 4.535 E-01 pound/foot® pascal 4.788 E+01 ix Ct. TcT ^ •/Kf-«t BHQIBHavlOO to T8U %. • iz'.cAry ;X4aK» •xors' VQA CtacnM^i«ritof %’oll. S.i?^ Mt.« . ♦ • < . •C-^a 000,1 ICM ■:» £*-*'ci' *•# y>*t ?03,S1 -f ^■T*‘i *f i\n* r iffrf *ii iM f iaiJOHj. * • • • » ^•3 lOS, £ „ ^ I'^t TCVvS >*»*♦’ 'g«umretwifit4 * *r!*fc**» XC^-i dT0*.5 ^ if \* t) r. »etS3*f ' - • • < * « eo^i pi -■uialy io> ' i ’>S f T*«* of ?|^oti,.ltlO»’ . . . • ^ . >’•1 0^.»0,i 9ifoJii! •>>1 '^•*'* ttfKi -•J&yrtk’,'*>b^V «- T8?.1 * Tijatit'\tJbtirpll .a,U) notlA^ . >4J< syi-. . {o2onn*-‘5rfXjf^99^ot-JEvjim>f»9fr r* * ' * ’'■ - •S.'i0ftt.9 a' ^CCP In—ilfa Pjl^O KHUSHX OT o^jrraw m-fl rtarmod oT ’ wrtACoO -arjjS « s ♦ , • 3i>-a 00«,i ,r.\ ;j :• - ? H.I\ I"-,- ^iio.e so.-*:' 009Ui^«r>! I**?! • » iif^^ ■ • • ' • •r^ ' oupcaH 0rc«xdft*« *. “ * •IifOt iSi ' * •ll3«aa *T5*#»* (>is>o*s\* ‘b:SOO«B\l baoi»«9\*’iLf9a Bn6wlmV:pf9m &a099«\*tiV'SJ> ‘ * aoJt^ss Sitm ssMata *■ j tO-T Q^iO, P !>aOO»«\T9.t9« 0/VO?99\*99J«» oo+a £0-2 e6''.£ *Ttr>’tar eo-- \ oz.'^ sa-»i i^«9 C#^.> x>-s cO-S ..1 ffotmo X’-W tr>s 8Pr, «i U»»4q erlalftO pytfTT ir|r»: - *, »♦ » 7Bi9« 0y#4*ijr«. <* t o T» -IS oiuolM^fgl •oidt^Omroq^^oot (£iJupl;I,^.V) ooXXiQi ^fu&lm\(Biafftl iU.O) ooll^a (aX-Stfl ft 0??) twoqmoB t(x>aX ^ *if9al 1 X4riof^«un .foi) ^oat tif ) i fBfoq > •jonO\jKiiK>q; SECTION 1 INTRODUCTION Within reasonable economic limits, pollutants that adsorb well to soil are difficult to remove from the soil. Paradoxically, these pol¬ lutants can leach into groundwater at concentrations above drinking water limits. Trichlorophenol, polychlorinated biphenyls (PCB), and polynuclear aromatics (PNA) are among the presently infamous pollutants that have rela¬ tively high soil adsorption characteristics. These also have EPA water quality criteria less than parts per billion. (See Appendix A.) The U.S. Environmental Protection Agency (EPA) is researching remedial methods to remove pollutants from soil. Accelerating the natural leaching process by flushing contaminated soil in situ with an aqueous sur¬ factant solution and recovering the wash effluent from the aquifer is one method being investigated. The soil adsorption constant (k) is a measure of a pollutant’s tendency to adsorb and stay on soil (see Appendix A). A value of 2,000 for PCB's indicates a two hundredfold 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 ac¬ cording to a K value and evaluating removal, efficiencies (RE) gives order to an otherwise complex collection of chemical classes. Through this and other ongoing research new, better and more economic remedial methods are being pvirsued. This is a report of the EPA's and the U.S. Air Force’s field evalua¬ tion of in situ soil washing of compoiinds having K values between 10^ and 10 . From 1982 to 1985 the EPA developed soil washing technology using surfactants. The work was conducted in laboratory studies.^ Although con¬ sidered in situ washing of soil, the technique was not used on undisturbed rocesses to This mutual contaminated soil in the field. The Air Force was seeking clean-up 128 fire training pits at Air Force installations, interest led to a pilot field test of in situ soil washing using surfac¬ tants . The primary objective of this joint project was to evaluate in situ soil washing using surfactant solutions. A secondary objective was to provide information to the Air Force that would help develop a comprehen¬ sive decontamination strategy for fire training areas of all Department of Defense (DoD) installations. In October of 1984 the Air National Guard (ANG) Bureau in Washington, DC and the Base Civil Engineer at Volk Field, ANG Base Camp 1 Douglas, Wisconsin were contacted concerning the possible use of the fire training area at Volk for the demonstration of either in situ surfactant flushing or soil washing (see Figure l). The enthusiastic responses led to a November 198^1 meeting with the Wisconsin Department of National Resources (WDNR) in which WDNR also indicated strong support for the research project. In May 1985, the WDNR received a more in-depth project briefing and continued to show their cooperation and full support for the project. With this assurance a detailed site investigation was initiated in early Jtme.^ In September 1985 two pilot studies were carried out to determine the effectiveness of treating contaminated groundwater and the effective¬ ness of in situ washing with surfactants. Historical data indicate that the fire training area was established in World War II and routinely received waste solvents, used lubrication oil, and JP-U fuel (see Figure 2). The total liquid waste deposited at the site was as much as 260,000 gallons. An estimated 80 percent of these wastes burned in fire training exercises, leaving approximately 52,000 gal¬ lons to leach into the soil.^ In 1981 , because of concerns over the pollution potential of this site, ANG engineers conducted an exploratory site survey and sampling project. Twelve shallow well samples were analyzed for purgable organics using EPA Methods 60 I and 602. Table 1 summarizes the I 98 I findings. The average water table depth is 12 feet below grade. Both chlorinated sol¬ vents and fuel components entered the shallow groundwater. Soils beneath the site contain similar contamination. This report is in eight sections including the Introduction. Before undertaking the field operation, laboratory tests were conducted by SAIC Inc., La Jolla, California. Section U, Site Characteristics, is based on information obtained diiring the laboratory study as well as two field studies and a literature review. Knowing the site characteristics is im¬ portant to understand the setting for this specific work. The reader should be able to contrast or compare this work to other sites. The in situ washing field work is described and discussed in Section 5. At this particTilar site (and most likely any site having significant vadose zone contamination above an unconfined aquifer) groundwater control and treat¬ ment is an integral part of in situ soil washing. The development of a treatment process from bench scale testing at the site through operation of the treatment system is given in Section 6. The quality evaluation of the data obtained during the field study is provided Section 7. Conclusions and recommendations are in Sections 2 and 3. These are based on the bench and full scale work done in the field to determine a suitable grovindwater treatment process and the in situ soil washing. References are given in Section 8. 2 Figure 1. Location of Volk Field 3 o Q-17 Scale in Feet 25 0 25 50 75 Legend 1 1 1- Boundary of Training Area Bore Hole Location Groundwater Flow Direction Figure 2. Site map showing the fire training pit and shallow monitoring wells installed in 1981 (see Table 1). 4 TABLE 1. CHEMICALS FOUND IN SHALLOW WELLS (A-1 to P-l6) Volk Field 1981 (in micrograms per liter) I.D. Nximber EPA Method 601 EPA Method 602 Chloro¬ form ®TCA ^TCE Benzene Toluene Ethyl Benzene A-1 2.3 < 1.0 < 1.0 U500.0 2700.0 270.0 B-2 2.3 < 1.0 < 1.0 10.0 100.0 10.0 D-U 1.5 7.8 22.0 510.0 2100.0 190.0 F-6 1.1 39.0 100.0 lUOOO.O 8000.0 950.0 G-T 59.0 36.0 k2.0 31000.0 36000.0 6800.0 H-8 130.0 < 1.0 < 1.0 1900.0 5700.0 200.0 J-10 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 K-11 1.3 < 1.0 < 1.0 < 1.0 h.6 < 1.0 L-12 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 N-lU 50.0 < 1.0 < 1.0 8.5 < 1.0 2.9 0-15 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 < 1.0 P-l6 120.0 < 10.0 < 10.0 Uooo.o < 50.0 1000.0 (a) trichloroethane (b) trichloroethylene 5 SECTION 2 CONCLUSIONS 1. In situ soil washing of the Volk Field fire training pit with aqueous surfactant solutions is not measurably effective. It is likely that this same ineffectiveness would occur at other chronic spill sites that have contaminants with high soil-sorption values (K >10^). 2. In situ soil washing requires groundwater treatment and washing ef¬ fluent treatment. Groiondwater treatment at this site was successful with the simple addition of lime. Air stripping removes the volatile organics. Advantages at this site that facilitated groxindwater treatment operations were its remoteness for workable air emission limits and a local sewage treatment system (aerobic lagoons) owned by the responsible party. TOC levels were reduced to one half the ini¬ tial values by precipitation with lime to allow direct discharge to the aerobic treatment lagoons. These favorable conditions are not expected at all sites. 6 SECTION 3 RECOMMENDATIONS Based on the findings of this study the following recommendations are made: 1. Regarding the technology of surfactant-enhanced in situ soil washing, a study should he conducted to identify the reasons why surfactant washing of vindisturbed Volk field soil failed. (a possible reason is presented in Section 5 and Figure 13 of this report.) 2. Regarding the cleanup of the specific Volk Field Fire Training Pit, a. The present well field shoiild be pumped to remove the contamination in the aquifer. The water should be pvimped directly to the existing treatment lagoons on the base. b. To remove contamination from the Volk Field fire pit soil, the pit should be bermed and a fluid distribution system should be placed over the pit for recharge. The natural leaching of the soil should be accelerated by recycling a portion of the gro\indwater. additional withdrawal wells should be drilled further down gradient of the pit. They shovild be drilled deeper than 35 feet to give the screened sections of the wells more exposure in the plume. c. The excavation and washing of the soil in a system such as the EPA’s Mobile Soil Washing System shoTild be evaluated. The basic effect would be to isolate the con¬ tamination predominantly associated with the fines of the soil. 7 SECTION U SITE CHARACTERISTICS Before the pilot scale treatment studies that are reported here Mason & Hanger made a field study for the Air Force in May of 1985. The study determined the extent and type of contamination at the fire training pit (see Figure 3). The work performed at that time included: drilling and sampling in shallow bore holes, installing seven monitoring wells to Uo feet (12.2 meters) depth, the determining of the water table height and gradient, determination of permeability, and sampling and analyzing soil and water samples for volatiles and total organic carbon.^* SOIL CHARACTERISTICS The soil beneath the fire training pit is contaminated with waste oils, JP-1+ jet fuel, and solvents used in maintenance around the base. The effect of such contamination on the soil is obvious when compared with adjacent clean soil. The most obvious difference is color and lack of vegetation. The surface and near-surface soil of the pit is black, cohe¬ sive, and free of any grass except at the edges. The pit emits an odor of fuel oil, and the soil has enough residual contamination to feel oily. The local soil has a thin natviral organic layer that supports a grass cover. It is sandy, non-cohesive, and light brown in color below the top soil. The grain size distribution of the soil in the vadose zone \inder the pit is 95 percent sand with 5 percent by weight finer them sand. The local soil is also sand but with 10 to 15 percent finer particles (see Figure h). Mineralogically both soils are at least 98 percent alpha quartz and have no clay as determined by x-ray diffraction. The top of the fire pit was covered with a U-inch layer of 60/k0 gravel/sand. Under¬ lying oil eind vapors have infiltrated upward and contaminated the cover. RAINFALL The average annual rainfall over the last 29 years is 29.08 inches. The highest 2U-hour rainfall was inches. This was in 19T6. Fluctua¬ tions in the water table from 3.5 feet to 10.5 feet were measured in a nearby upgradient drinking water well between 1950 and 1966. HYDROLOGIC PROPERTIES The soil type at Volk Field is Boone fine sand. According to the Soil Conservation Service Engineering Field Manual , this is in hydrologic soil group A. Group A has high infiltration rates and low runoff poten- 8 9 Figure 3. Spring 1985 Site Study Map. PERCENT FINER THAN SPLIT SPOON SAMPLES FROM ETT-S Figure 4. Soil particle size distribution of soil taken at four depths under the fire pit. 10 tial. Standing-water after a rainfall demonstrates the fire pit has a low infiltration rate. Runoff through a drain hole in the berm has spread contaminants to surface soil adjacent to the pit. -3 The water table is in a highly weathered sandstone, and the aquifer extends to a depth of TOO feet. In terms of permeability the soil of the vinsaturated zone below the pit has a laboratory measured value of U x 10 to 5 X 10“^ cm/sec. The permeability of the xinconfined aquifer is 5 x 10 ^ cm/sec.^ According to measurements of water table elevations made at the site, natiiral groundwater flow increases in speed compared to the background flow as it passes under the pit (see Figure 5). This is con¬ sistent with the measured lack of fines at the water table. The mobilized contaonination leaves the site via the groiindwater in an initially easterly direction and then turns to travel northeast. The volume of soil and groundwater directly involved in this study was ap¬ proximately U,600 cubic yards. The pores of the soil contain ap¬ proximately 230,000 gallons of contaminated water. Indirect measurements using an electromagnetic (EM) survey technique indicate a large plume leaving the site. In addition, the total, volvime of contaminated water pumped from beneath the pit between September 7 and November lU, 1985 was U6U,000 gallons. This is more than twice the volume of water contained in the study volume. Analytical data shows the contamination levels from the well field were not significantly lower after pumping. DETERMINATION OF SOIL CONTAMINATION To determine the concentration of non volatile contamination, oil and grease (O&G) tests were run on 36 soil samples taken at various depths and locations over the area of the pit. The oil and grease test requires the soil sample be air dried for 2k to 36 hours before extraction with carbon tetrachloride (CClj^). Volatiles in the soil were therefore not contributing to the mass of extract obtained. The quantity of oil and grease extracted was measured two ways. The first was by infrared absor¬ bance at a wave number of 2910 cm”^. This is equivalent to a wavelength of 3.U36 microns. Because the O&G values were so high for most of the samples it was possible to evaporate the carbon tetrachloride on a steam bath and weigh the residue in a beaker. Agreement between these two methods was quite good. As expected, the concentrations determined after evaporation from the steam bath were slightly less than those calculated from the infrared method. Figure 6 shows the overall distribution of CCljj extractable oil and grease as a function of depth. Oil and grease values were highest near the fire pit surface, decreased in soil that was deeper and then increased in soil that was slightly below the water table. Work conducted in November of I 98 U measured chromatagraphable aliphatics, aromatics and "unresolved" compounds. These values were an order of mag¬ nitude lower than the O&G measurements. The total amount of extractable material in the pit soil was calcu¬ lated by segmenting the soil column below the pit into 10 equal thicknesses; determine the average concentration of the 10 imaginary slabs 11 12 Figure 5. Groundwater equipotential lines around the fire pit area from September treatment study before pumping. IxJ U U. z I h- Q. LJ Q (spuDsnom) (6>i/6ai) 3SV3a9 ^ 310 13 Figure 6. Oil and grease values were highest near the fire pit surface. of soil; and then, inultiply the average by the veight of the soil. Using this approach and referring to Figure 6 for the concentrations, the total extractable hydrocarbons is 1,700 gallons. CONTAMINANTS AT THE SITE Much of the vadose zone contamination at the fire pit is lubrica¬ tion oil (see Figure 7). Comparatively smaller quajatities of volatile or¬ ganics and oxidized hydrocarbons are present. Early in the project the contamination of the aquifer was thought to be a floating layer. This is not the case. The contaminants in the aquifer are water soluble and have penetrated the aquifer. A possible explanation for this is intense biological activity in the soil that could have been brought about by the firefighting foam used in the training exercises.° The non-volatile chemicals, principally the oil and grease on the soil, comprise the majority of the contamination in the unsaturated zone (5,000 to 20,000 mg/kg). The oil and grease, a carbon tetrachloride (CC1|^) extraction of the soil, contains oxidized oils and greases indicat¬ ing weathering. The oxidized forms are more water soluble than the non oxidized forms and are in greater abiindance deeper in the water table. Not all the hydrocarbon contamination is extractable with CCLj^. The total organic carbon measurement on a contaminated water sample was 760 mg/liter. Oil and grease on the same sample was only 20 mg/liter. The depth of contamination into the aquifer is not known. However, monitoring well (ET-6) was drilled to UO feet (30 feet into the aqmfer). Samples from the bottom of this well were contaminated (see Figure 5). The chemical species vary with depth and distance from the pit.^ Chlorinated volatile organic compounds are low in concentration at the pit surface. As depth increases, the measured level of volatiles increases (600-3500 ppb). Chlorinated volatiles detected in the soils are: dichloromethane, chloroform, 1,1,1, trichloroethane, trichloroethylene. Chemicals indicative of long term weathering, isoprenoid compovinds, were measured. Non-chlorinated chemicals in the groundwater include benzene, toluene, xylene, and ethylbenzene which are all principal components of jet fuel (see Tables 2 and 3). The groundwater has a soluble organic con¬ tent of up to 760 mg/liter carbon. In the absence of oxygen within the aquifer, the organic material remains soluble. Along with a high quantity of iron in the water the organic material is partially flocculated into an organic-iron complex when exposed to air. Also on exposure to air the volatile organics will begin to volatilize from 10 or 20 mg/liter to 2 or 3 mg/liter in a few hours. pH for the well field effluent is 5.5 to 6.0. After a few hours of exposure to the atmosphere pH will rise to 7.5 or 8 . 0 . During the installation of monitoring wells the driller's boring- log was supplemented with gas chromatography (GC) measurements of the "head space" of soil samples. Given in units of total counts of peak height, the GC values represent a rough estimate of the distribution of volatiles. Figure 8 shows foxir such logs. The first log is from an 14 15 Figure 7. Gas Chromotogram of hydrocarbons from a composite of Volk Field fire training pit soil. 03 t-3 M o 03 5m Eh Eh K O Pu Oh O o w Eh M 03 e i-q o > o s o M Eh M PS O O < o > >H PS < M s M m) W PS PL, CM W t-3 Eh 'O P o cO P< c a. VO UN on w • « h O « H p h- rH O H on ^ 0 \ UN _j -3 .3 o " Os Os 1 a rH ^ “H^ on -3 UN > 3 3 CO C > E- 4> a 4) >» J3 P 4) VO p • VO Q P 0 z o on a S S 5 2 U rH rH o rH O o •H Eh 4) a cd pp* O P a 4^ a O ^w' fl O rH VO -3 CM • • • on-3 H Q o GO 0 •H 4J 2 o VO o CO on S 0} fH H -3 Z \0 UN Eh CTs P • c rH CM • 4^ 0> O r-i □ p O fH o T3 q B 3 o U O a B o o u P Q (3 f- 0\ O CO -3 o O 2: 5z VD 00 2 l/V-3 rH rH rH rH CM O o 4) Q q jO P 4) GO a q -3 GO o p • G -3 H o B5 <7s 2 CM O o m on GO UN SO rH GO -3 ja CM on o iH Q rH CM rH CM N—" '>M«' P P P q y y y y y O o y ♦J P o y y a q q 4 h y y 0} 4h 4-4 4-» >-( y y 4-4 a 4) Ih UN 4-t 4-4 Jh UN UN 3 3* 3 • • ( CO CO rH on UN CO CM CM ^ ^ ^ V rH rH rH rH rH rH CM CM r -H a ^ ^ ^ ^ ^ ^ & p 4J 4^ 4J 4^ P P P CO T* ’H 'jH a a a o o 0/ 4J 4) Q •P O V) lU V a] O C •H g ■3 O O GO VC OO VO On Os O lf\ *H ITS -If CVJ ^ 0\ 0\ VO CVJ ITS ITS • • • • * CD GO CD -sr iH CVJ H m -If- • • • • • OCMmcJt^ CO ^ rn CO CVJ H CO GO c\j 00-3- m H (\j iH on iH CM VO H CM 4) 0) Af ly CO CO iH on ITS •H H *H H ^ ^ •P p 4J V 4^ ^ ;W .H •H ‘W &4 (i< O. O. cu i/N W^aO r-i CM if UN t*- VO CO Os UN-3 on o o CM o on VO -3 CO VO t-i on o on P-» UN CO t-vo P P 4> y U 4) 4) OJ 4 h UN UN 3 • • CO CM CM CM CM CM P P P •p* "H a« pu. £ 16 to Figure 8. Graphs of split spoon consolidation (blows per foot) and vapor analysis (peak height counts) during monitoring well drilling. upgradient well, the rest, from highly contaminated wells. Note that the Covints scale is a log scale. Before installing monitoring wells, bore holes were made in and aroxind the fire pit. These are half darkened circles in Figure 3. Water samples, taken from each bore hole at the water table, were analyzed for total organic carbon (TOC). Figure 9 is a plot of the pltome at the top of the water table based on these TOC measurements. ELECTROMAGNETIC SURVEY OF THE FIRE PIT AREA Because of work reported by the New Jersey Geological Survey it was felt that axi electromagnetic (EM) survey had a potential for success at Volk Field."^ By using an induced electromagnetic field in soil or rock structure it is possible to measure differences in the conductivity of the soil or rock.° More precisely the difference arise more from conductive solutions in the pore spaces. In the case of the work done at a Naval air station in New Jersey, residual fuel, left over from fire training, had entered an unconfined sandy aquifer. The plume was mapped by the EM sur¬ vey. Since organic contaminants seldom alter the conductivity of grotindwater it was a svirprise when measurable differences in conductivity in the aquifer mapped out in the form of a reasonable plume. The reason for the conductivity was attributed to the fire fighting foam ’’AFFF." An electromagnetic survey was conducted around the Volk pit area. The survey included. The instrument used was ein EM-3^ manufactured by Geonic Ltd. Mississaugua Ontario, Canada. The EM 1 - 3 H consists of a 2-foot diameter coil of wire that transmits a bvirst of electromagnetic energy at a low frequency. This induces electromagnetic excitation in conductive or semiconductive material. A second coil spaced at 10, 20 or UO meters from the transmitter receives the initial burst from the transmitter and the induced signal from the grovmd. These received signals are electronically transformed into a conductivity value for the "half space" between the coils. This technique maps large soil structure and not small targets such as 55 gallon drtams. By moving the coils over an area of land in a grid pattern conductivities of half spaces are measured and plotted on a map. The coil spacing used on the survey that produced Figxire 10 was 20 meters. This results in a 30-meter depth of penetration of the induced signal. For an explanation of how the coil spacing affects the depth see Reference 8 . Figure 10 is the resulting conductivity map near the pit. The ini¬ tial easterly path of the plume is different from local groundwater motion which is to the northeast. Examination of the drilling logs reveals a less consolidated sandstone (fewer blows per foot) in that area, affording the plume an easier route to the east. A turn to the north is required to get the overall path of the plume on the northeast course. A piece of data to help support the possibility of the plume reaching the point marked with an "S" in the figure is analytical data on soil taken from the drip line of an environmenteilly stressed (dying) tree. The sample was taken from a depth of 12 feet ( 3.7 meters) using a 2 -inch diameter hand 18 19 Figure 9. The contaminant plume as determined by TOC measurements (shovm in mg/1 on the lines) of water samples at the water table. Figure 10. EM Survey Plot showing equi-conductivity lines (units are millihos/meter). 20 auger. The analysis shows an oil and grease content in the 100 mg/kg range. An infrared spectrum trace indicated the presence of slightly oxidized oil (like the oil and grease found in the well field). No AFFF was analytically identified in the plume.Iron is up to 150 times more concentrated in plume water than background water. The conductivity differences are likely due to dissolved iron in the plume. SANITAEY WASTEWATER TREATMENT AT VOLK FIELD Treated water from the fire pit was discharged to the base sewage treatment system. The Wisconsin Air National Guard at Volk Field under the control of the Base Civil Engineer maintains two aerobic lagoons con¬ taining a combined 20 million gallons to treat domestic sewage generated at the base. In addition, the town of Camp Douglas has its sewage treated at the base. Twice a year, the second of the two lagoons is discharged into a tributary of the Lemonwier River. The WDNR discharge permit requires the following effluent limitations: BOD 5 Suspended Solids pH Ammonia Nitrogen Dissolved Oxygen 17 mg/1 IT mg/1 6 . 0 - 9.0 3.0 mg/1 6.0 mg/l minimum The use of Volk Field as a training school is seasonal. The heaviest usage is in the simmer when "The Guardsmen" are doing their two weeks of ac¬ tive duty. Sewage pumped from the first to the second lagoons is recorded daily and can be as much as 300,000 gallons per day (GPD) at a BOD^ of up to 120 mg/liter. During periods of low activity pumping is around 80,000 GPD. The WDNR placed a limit on the effluent sent from the fire pit treatment to the base lagoons. The limit was 60 pounds per day BODc. Since BODc requires 5 days to determine it was necessary to anticipate what will happen in 5 days to maintain continuous pumping. An attempt was made to correlate total organic carbon measurements with BOD^. There is a positive correlation but a specific relationship between the two could not be demonstrated. 21 SECTION 5 IN SITU WASHING TESTS ESTABLISHING A PRE-TEST BASELINE It was important for the test that the soil washed in situ he undis¬ turbed. The wash fluid’s path could not he influenced hy pre-test sam¬ pling methods that created preferred hydraulic paths. To establish the level of contamination for the specific test cells, six samples were taken adjacent to the test cells to establish pre-wash levels. The measured O&G values appear in Table h. These concentrations varied as much as -73% and +50% from the average. Since coefficients of variation for replicate O&G measurements average 12^, this variability, -73% to 50%^ for pre-wash levels is significantly troublesome when analyzing the post-wash data. This is all within a 10-foot square section of the pit {2.5% of the pit area). TABLE U. OIL AND GREASE MEASUREMENTS OF SAMPLES TAKEN AT 3 FT DEPTH AND 3 FT SPACING Sample No. 1+055 U 056 1+057 1;058 1+059 U 060 O&G mg/kg 5 I+OO 1850 5800 5050 1050 1^060 TEST CELL LAYOUT A photograph of the test site is in Figure 11. The well field to withdraw contaminated groundwater is in the foregrotind of Figure 11. In the right center of the picture are the test cells used in the soil wash¬ ing evaluation. The EPA's Mobile Independent Chemical/Physical Treatment Unit is in the background. The Air Force’s Air Stripping Tower is to the left. Both are being used to treat contaminated groundwater. Test holes were dug in the fire pit to determine the soil washing ability of a nxjmber of surfactant solutions. The locations of the holes were chosen to provide as near a uniform contamination level as could be predicted from oil and grease measurements and elevation observations of the surface of the pit. Ten holes were dug. Five of the holes measured 2 foot X 2 foot X 1 foot deep and five of the holes were 1 foot x 1 foot x 1 22 foot (see Figrore 11). The depth of the holes matched the planned depth of soil that would be scraped off the surface of the pit prior to full scale remedial washing. One foot is the depth below which the carbonized oil layer is located and at a depth where suitable percolation rates were measured.^ WASH SOLUTIONS Two terms describe the surfactants used, "synthetic," and "natural." The synthetic surfactants are those that have been man-made by chemical processes and are available commercially. The natural surfactants are those that have their origin at the fire training pit itself, and are by¬ products of biological activity. The synthetic surfactants used for the pilot treatment study were: 1. Surfactant 1 (Sl). A mixture of ethoxylated fatty acids sold by Witco Chemical Corporation. Used in agriculture as a soil penetrant. 2. Surfactant 2 (S2). An ethoxylated alkyl phenol sold by Diamond Shamrock. 3. Surfactant 3 (S3). An anionic sulfonated alkyl ester sold by Diamond Shamrock. The nattiral surfactants are described as: 1. Old natural surfactant - from the first 10,000 gallons pumped from the well field. 2. New natural surfactant - from the well field after pumping 20,000 gallons, lower in suspended solid than the old natural surfactant. 3. Clarifier effluent - lime treated well field effluent lower in iron and therefore less likely to plug the soil pores with precipitates. WASHING PROCEDURES The rate of addition of wash solution was 3 inches per day. This corresponds to 1.87 gallon per day for the one square foot test holes and T.U8 gallon per day for the four square foot test holes. Wash solution was added four times a day for either U or 6 days depending on the availability of the solution. Percolation in two test holes stopped after the first day. Tests in these holes were abandoned. A third hole was abandoned two days later for the same reason. The remaining seven holes were then rinsed with only two or seven gallons of clean, upgradient, well water after the washing. Before finishing the rinse period, U inches of rain fell over a 3-day period. The test holes offered significantly less resistance to percolation of the runoff than the rest of the fire pit. 23 2A Figure 11. Volk Field Test Site for in situ soil washing, and groundwater treatment. Rainwater penetrated the surface layer of gravel fill and flowed laterally to the test holes. Attempts to keep the holes from filling up with runoff using herms at the surface were ineffective. Approximately 1100 cubic feet of rainwater fell on the fire pit diiring the 3-day rain. Not all of it went throu^ the test holes, but some fraction of it was seen flowing down the walls of the holes from above the black layer of oil. If 5 per¬ cent of the rain that fell on the pit flowed into the test holes that would be equivalent to 33 inches of rain in each of the holes. Therefore, the rinse phase of the pilot study was extensive. The mobility of contamination from other areas of the pit to the test holes is unknown. The 0.25 inch deposit of fine soil at the bottom of each hole was distinctly darker than the soil originally at the bottom. It was sharply defined by text\ire and O&G, and was easily parted from the soil directly below. Table 5 lists the total volume of wash solution used in each test hole, the identity of the wash solution, and its concentration. TABLE 5. WASH SOLUTION VOLUMES AND CONCENTRATIONS FOR VOLK FIELD SOIL WASH PILOT STUDY - SEPTEMBER I 985 Pit if Wash Solution Concentration {% WT) Total Volume Gallons Pore Volumes 1 natural surfactant +S3 0.025/S 84 plugged T 2 new natural surfactant O.O 2 U 122 10 3 old natural surfactant O.O 2 U 168 14 h new natural surfactant 0.024 112 9 5 old natiiral surfactant 0.024 112 plugged 9 6 * clarifier effluent 0.015 28 9 T* S3 0.5 42 l4 8 * 50/50 S1/S2 1.5 42 l4 9* clarifier effluent 0.015 28 9 10 0 plugged 0 *1 sq ft cross section holes SAMPLING AND ANALYSIS After washing and rinsing the soil below each of the test holes, samples were taken of: the surface of fine material at the bottom of each hole, soil from 2-U inches and soil 12-lU inches below the bottom of the hole. The samples were placed in wide mouth glass jars. The jars were then placed in cartons for transportation to the analytical lab at the EPA's Oil and Hazardous Materials Simulated Environmental Test Tank (OHMSETT) facility in Leonardo, New Jersey. At OHMSETT the soil samples were extracted to determine oil and grease and the extracted fluids were analyzed using an infrared spectrophotometer. The bar charts in Figure 12 25 2" TO 4" OiScG VALUES TAKEN AFTER WASHING 1 2" TO 1 4" 0 CO C Jj C bO O C •H T-l •u a o D. 3 1 -c ”3 iJ 3 4-1 J-I CO (U J= ■I-J CO & TO O C JO to CO J-I CO (u ■u 4-J CO CO T3 a TO C4_l c O 3 O CO J., bo cu CO (U j: (U 4-J > •H >^ CLi jb (O' <1) J4 3 bO 41 fluent samples. Figiore 20 is a graph of the TOC values measured for the six wells in the well field between September 9 and 27, 1985 and measured TOC values for the entire well field. Although the individual wells main¬ tained a near constant level of TOC over the 380 hour time span the collec¬ tive effect was a lower average TOC from the well field. This can be ex¬ plained if there was a shift in the balance of the wells and some of the less contaminated wells started yielding more fluid. After withdrawal from the well field the groundwater was mixed with lime in a flash mixer. As was stated earlier in this section and reported in the bench study, the addition of lime brought about the formation of a brown precipitate. The precipitate consisted of organic matter and an iron hydroxide. On September 19 samples were taken from the flash mixer. The process flow was lU gpm. pH in the flash mixer varied between 6.3 and 9.^ by changing the lime dosage. Water coming into the flash mixer had a TOC value of 270 mg/liter and a pH between 5.8 and 6.1. The TOC of the super¬ natant (clear water phase) coming out of the flash mixer was 2l;0 mg/liter at a pH of 6.7. A pH of 9.^ was attained when lime was overdosed. The TOC dropped to lii5 mg/liter. After reconciling the difference in time a slug of fluid passes the various process stages, four sets of data were prepared in a bar chart to show the change in TOC. The chart shows the well field effluent, the clarifier effluent, the air stripper feed and finally the air stripper ef¬ fluent to the sewer (see Figure 21). The second bar in each set is the clarifier effluent. The organic content in each set decreased between the time the fluid left the clarifier and entered the air stripper (third bar). It is during this time the fluid is in the l6,000 gallon lagoon. Precipitation and volatilization continue in the lagoon. It was only a period of 6 hours at a flow rate of 9 gpm that this pH was maintained. Comparing the difference between TOC change in the air stripper with the change in volatiles content from the gas chromatography test shows a rather weak correlation. 42 TOC (parts per million carbon) ^ TOC (mg/IHer) 360 340 320 300 280 260 240 220 200 1 80 1 60 1 40 1 20 1 00 250 270 290 310 330 350 370 390 410 LAPSED TIME (hours) Figure 20. The measured value for total organic carbon from each of the six production wells (top) and the average TOC (bottom). T-1-1-1-T-1-1-1-1-1-1-1-1-1-r 43 »ow«F B > O* < a« 4; Q* I CO t> o* ► Ck < w CS o ^ Q • 4) O H B 5 ? a < Pi •0 •0 •o •0 •0 © © © © © © © © © hJ 4 -> 4 H 4 H 4 ^ d d d d d d d d d 0 u 0 0 0 0 0 0 © 0 0 0 0 0 0 0 0 0 rH rH rH r< rH rH rH rH rH rH rH ^H rH rH rH 0 0 0 0 0 0 0 0 0 0 0 0 0 u 0 0 0 < o. w '3’3'a •O *0 -o CJ CM CVI 41 o cw 4> OS o « o I I I m VN O CM CM CM O ^ h- CM ^ \o t~ neo CM u\ \o CM CM o o a 3 ^ O 3 £(S CM CM II CM o cn III I I III o a 4 ) P N O CD P ^ <4J «J © 4 ; a V o ia c a © a © w © © 1 ^ 3©a^*^»43X P-*^*r4 d © C#-«J3 ^©4^©C3©04-> PS fU n Eh U3 U d d d •p ■o *3 I I I VO iH -S- ITV O o O O CM fH i-i CM VO VO O • • • 000 I I I u © p< Pi U CO I 4 v4 < I I I © a © N a © © -- c ^ © © «H K 3 >» C rH J3 W © O 4J © CQ Eh M U, d d d ■O *0 *0 m * J3 I © O , n E-> w VO o CM as III I III I III I I I cn I I I I CM VO lA CM rH rH I I CM I m I I rH fH irx iH 4f\ O UN CM CM f-l I I I CO cn c^ cn o Ov CM UN cn cn o CM I I I I I I Ov C »o o S3 © £ >« rH -JV d < os < s i-H as (u u © P* P« 4J P Pi ^ a © "H ^ © ^ V v< d (b ki cd o <: c 8 47 Tyndall Collocated In claiming that the objectives were over ambitious reference is made to the American Petrolem Institute report Refinery Wastewater Priority Pol¬ lutant Study - Sample Analysis and Evaluation of Data .^^ Analytical data for that report was obtained from three laboratories (two private and one EPA con¬ tract lab). A comparison of the CV*s from that study and the Volk Field work appears in Table 9. In all but one listing — Lab A's VOA - the field data at Volk Field has a lower coefficient of variation than the other seven listings. 48 TABLE 9. COMPAEISON OF COEFFICIENTS OF VARIATION FOR API AND VOLK FIELD COLLOCATED SAMPLES API Refinery Study Volk Field Study Lab A Lab B EPA OHMSETT VOA 2k% 1195^ lhk% 12% TOC 35 69 13 Oil & Grease 112 - liT 38 49 SECTION 8 REFERENCES 1. Ellis, W. D. and J. R. Payne. Treatment of Contaminated Soils With Aqueous Surfactants (Draft Interim Report) to EPA Releases Control Branch, September I 985 . EPA-600/2-85/129, NTIS PB 86-122 561 /REB. 2. Hazardous Materials Technical Center, Installation Restoration Program Records Search prepared for 820i+th Field Training Site, Wis¬ consin Air National Guard, Volk Field, Camp Douglas, Wisconsin, August 1984. 3. Mason & Hanger-Silas Mason Co., Inc. Field Study of the Fire Train¬ ing Area, Volk Field ANG Draft Report, July IT, 1985 to EPA Releases Control Branch.(Internal Report to EPA) 4. McNahb, G. D. et al.. Chemical Countermeasure Application at Volk Field Site of Opportiuaity . EPA report September 19, 1985. (internal report to EPA) 5 . Bradbiary, K. R. and E. R. Rothchild, "A Computerized Technique for Estimating the Hydraulic Conductivity of Aquifer From Specific Capacity Data,” Ground Water Vol 23, No. 2, March-April 1985. 6. Guire, P. E., et al., "Production and Characterization of Emvilsify- ing Factors From Hydrocarbonoclastic Yeast and Bacteria," Microbial Degradation of Oil Pollutants . Pub. No. LSU-SG-73-01 Louisiana State University, Baton Rouge, LA. 19T2 7. Andres, K. G. and R. Crance, Proceedings of the NWWA/API Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water , "Use of the Electrical Resistivity Technique to Delineate a Hydrocarbon Spill in the Coastal Plain Deposits of New Jersey." November 5-7, 1984, NWWA & API. 8. Technical Note TN-6 "Electromagnetic Terrain Conductivity Measure¬ ment at Low Induction Numbers." Geonics Limited Mississauga Ontario Canada. October I 98 O. 9 . Chan, D. B., Analytical Method of Aqueous Film Forming Foam (AFFF) , September 1978. Civil Engineering Laboratory, Naval Construction Battalion Center, Port Hueneme, California 93043, TM No. M-54-78-08. 50 10. Fink, P. T., Aqueous Film Forming Foam Treatability . 1978 Civil and Environmental Engineering Development Office (Air Force Systems Command), Tyndall Air Force Base, Florida 32^03 11. Keely and Tsang. A Handbook for the Use of Mathematical Models for Subsvirface Contaminant Transport Assessment . Earth Sciences Divi¬ sion, Lawrence Berkeley Labortory, University of California, Berkeley, CA 9^720 report to the USEPA, January 1983, lAG #AD89F ZA 175 12. Mason & Hanger-Silas Mason Co., Inc. Volk Field Contaminated Grovindvater Bench Scale Treatability Studies, September 198^ . Draft report. November 1985 to EPA Releases Control Branch. 13. Stallings, R. L., T. N. Rogers, Packed-Tower Aeration Study to Remove Volatile Organics from Groundwater at Wurtsmith Air Force Base, Michigan , June 1985. Engineering & Services Laboratory, Air Force Engineering & Services Center, Tyndall Air Force Base, Florida 321+03. lU. Radian Corporation, Refinery Wastewater Priority Pollutant Study - Sample Analysis and Evaluation of Data . December I 98 I to American Petroleum Institute, Environmental Affairs Department 2101 L Street, Washington DC 20037 51 APPENDIX The categories of organic compounds in Tables A-1 to A-3 were based on the logarithm of the octanol/water partition coefficients (log P) of the com¬ pounds, as follows: . Hydrophobic organics: log P 3.00 . Slightly hydrophilic organics: log P 1.00, 3.00 . Hydrophilic organics: log P 1.00 The log P is a measure of the tendency of a compound to dissolve in hydrocar¬ bons, fats, or the organic component of soil rather than in water. For in¬ stance, many hydrophobics, some slightly hydrophilics, and no hydrophilics were detected in soil, which contains organic components that tend to adsorb other organics; only groundwater samples contained any hydrophilics (see Table U) [table not included]. This does not mean that only hydrophobics and slightly hydrophilics are fo\and in soil, but they are normally found more than hydrophilics are. Not only is the log P a measure of the tendency of a compound to dis¬ solve in octanol, fat, or oils, it can also be used to estimate the tendency of an organic compotind to become (or remain) adsorbed in soil. Several re¬ searchers have published regression equations relating log P to the soil ab¬ sorption constant, or K (Lyman et al. 1982). The partitioning of a com¬ pound between the organic components of soil and a water solution is expressed as follows: K oc g adsorbed/g organic carbon g/ml solution The adsorption tendency is mainly dependent on the weight of organic carbon (oc) in the soil. If the organic carbon content of a soil is known, then the soil adsorption constant (K) can be derived from (Lyman et al. 1982): K % organic carbon 100 ) K g adsorbed/g soil g/mL solution 1. Taken from report Chemical Countermeasures for In Situ Treatment of Hazard¬ ous Material Releases by JHB Associates, 8U00 Westpark Drive, McLean, Vir- ginia. EPA Contract No. 68-01-3113, Task No. 29, JPB project No. 2-81T-03- 956 - 29 . pp. ^-10 to I 4 -IU. 52 Thus, K can be used to estimate what fraction of a compound will be adsorbed on soil and what fraction will remain dissolved in water when the soil and water are in equilibrium with each other. The K values for the waste compovinds foTind in soil and groxindwater at Superfund sites are presented in Tables A-1 through A-3 [original Tables 6 through 8) for hydrophobic organics, slightly hydrophilic organics, and hydrophilic organics, respectively. They were obtained from published data (Lyman et al., I 982 ) or calculated from log P values (Hansch and Leo, 1979). Besides the IT hydrophobic compounds found in soil, another T hydrophobic compounds were found in groundwater near the Superfund sites. These compounds may have been found in the soil if analyses were made, but groundwater samples are analyzed more often than soil samples in Field Inves¬ tigation Team investigations. The same is time for the IT slightly hydrophilic organics and the 10 inorganic contaminants measured in groundwater but not in soil. h.1.2 Significant Human Health Hazard The substances for which countermeasures are most needed are those likely to cause significant adverse health effects in the exposed population. Several measures of the human health risk are available, and the EPA Water Quality Criteria are most appropriate. A large proportion of the chemicals reported at Superfund sites are carcinogenic or at least acutely toxic. The EPA Water Quality Criteria for carcinogens are expressed as levels presenting a known increase in risk, rather than as safe levels. These are presented in Tables A-1 through A-3, [original 6 through 9-9 not included] along with median acute lethal dose data (LDcq's) for rats, and whenever available, lowest carcinogenic dose data (TDLo’s) for all listed carcinogens. Clearly, althou^ both are carcinogenic, the carcinogenic potency of PCB's (TDLo: 1220 mg/kg is much less than that of dioxin (TDLo: 0.0011^; mg/kg), and the TDLo values allow one to assess relative carcinogenic hazard. 53 TABLE A-1. HAZARD PARAMETERS OF HYDROPHOBIC ORGANICS Substance Soil Adsorption Constant EPA Water Quality Criteria (ppm) Chlordane 200 U .6x10"'^* Dieldrin 200 - Anthracene TOO Benzo(a)anthracene 60,000 2.8x10"^* Benzo(a)pyrene U0,000 2.8x10“°* Fluoranthene 8,000 O.OU 2 Pyrene 2,000 2.8x10“°* DDT 10,000 2.UxlO“®* Bis(2-ethylhexyl)phthalat e 20,000 15 Di-n-butyl phthalate 100 3h o-Dichlorobenzene TO O.h PCBs 2,000 T.9xl0“'^* Dioxin 2,000,000 - Naphthalene 6oo - Oil (30,000) ** - Grease (5,000,000) *** - 1,2,U-Trichlorobenzene 200 Hexachlorobutadiene 200 U.5xl0“^* Trichlorophenol 2,000 - Ethyl benzene 50 1.1+ Bis(2-ethylhexyl)Adipat e 90,000 - Cyclohexane TO Benzo(b)pyrene U0,000 2.8x10“°* 1.1,2-Trichlorotrifluorethane 60 * Corresponds to an incremental increase in cancer risk of 10“^ ** Estimated based on n-C^^ *** Estimated based on n-C 2 ^ 54 TABLE A-2. HAZAED PARAMETERS OF HYDROPHILIC ORGANICS Substance Soil Adsorption Constant Water Quality Criteria (ppm) Xylene 30 Phenol 20 3.5 Carbon Tetrachloride 20 O.OOU Methylene Chloride 5 - Perchlorethylene 20 0.008 Toluene 30 ll|.3 Trichloroethylene 20 0.0027 Dichlorophenol 50 l.h Methyl Chloroform 20 - Vinylidene Chloride 10 Chloroform 10 1.9x10”^ Ethyl Chloride 6 Fluorotrichloromethane 20 Ethylene Dichloride 6 9.i+xl0”^* Methyl Isobutyl Ketone 5 Vinyl Chloride 6 0.002 Benzene 10 6.6x10” * 1,2-Dichloroethylene 10 1,2-Diphenylhydrazine 20 U.2xl0”^* Tetrahydropyran h - 1,1-Dichloroethane 6 - Chlorobenzene 20 0.U9 2-Ethyl-ij—me thyl-1,3, -di oxolane 10 - Isopropyl Ether 9 * Corresponds to an incremental increase in cancer risk of 10”° 55 TABLE A-3. HAZARD PARAMETERS OF HYDROPHILIC ORGANICS Substance Soil Adsorption Constant EPA Water Quality Criteria (ppm) Acetone O.T Methyl Ethyl Ketone 1 - Acrolein 0.8 0.32 Tetrahydro furan 2 - l,U-Dioxane 1 - Acrylonitrile O.U 5.8x10"5* Isobutanol 2 2-Propanol 1 * Corresponds to an incremental increase in cancer risk of 10”^ 56