development of the integrated, in-situ remediation

~ 9 7 o o ~ l s b

DOE/MC/3 1185 -- 5375

Development of the Integrated, in-Situ Remediation Technology Large Scale Field Test of the Lasagna Process, Tasks 8 and 10 Laboratory and Pilot Scale Experiments of

the Lasagna Process

Topical Report

September 26) 1 f?y-May 25,1996

Work Performed Under Contract No.: DE-AR21-94MC3 11 85

For U.S. Department of Energy Office of Environmental Management Office of Technology Development 1000 Independence Avenue Washington, DC 20585

1J.S. Department of Energy Office of Fossil Energy Morgantown Energy Technology Center P.O. Box 880 Morgantown, West Virginia 26507-0880

BY Monsanto Company

800 N. Lindbergh Boulevard St. Louis, Missouri 63167

Disclaimer

This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or use- fulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

DISUAIMER

Portions of this document m y be illegible in electronic image products. huge are produced from the best available original dOl?ument.

A. Executive Summarv

Development of an Integrated in-situ Remediation Technology

DOE Contract Number: DE-AR21-94MC31185

Topical Report for Tasks #8 and # I O entitled: “Laboratory -- - and Pilot Scale Experiments of LasaanalM Process”

Authors: Sa V. Ho, Christopher J. Athmer and P. Wayne Sheridan

Monsanto Company 800 N. Lindbergh Blvd St. Louis, MO 63167

and

Andrew P. Shapiro

General Electric Company GE Corporate Research and Development River Road at Van Antwerp Road Building K-I , Room 3C21 Schenectady, NY 12301

Submitted by:

Monsanto Company St. Louis, 11110

Abstract: Contamination in low permeability soils poses a significant technical challenge to in-situ remediation effods. Poor acCeSSibility to the contaminants and difficulty in delivery of treatment reagents have rendered existing ii)-situ freatments such as biommdiation, vapor exfraction, pump and treat rather ineffisdve when applied to low penneability soils ptesent at many contaminated sites. This technology is an integrated in-situ treatment in which established geotechnical methods are used to install degradation zones directly in the contaminated soil and el&-osmsis is utilized to move the contaminants back and forth thmugh those zones until the treatment is completed. This topical aport summarizes the results of the lab and pilot sized Lasagnam experiments conducted at Monsanto.

A- 1

A. Executive Summary (cont'dl

Expeninents were conducted with kaolinite and an actual Paducah soil in units ranging from bench-scale containing kgquantity of soil to pilot-scale containing about half a ton of soil having various treatment zone configurations. The obtained data support the feasibility of scaling up this technology with respect to electrokinetic parameters as well as removal of organic contaminants. A mathematical model was developed that was successful in predicting the temperature rises in the soil. The infomation and experience gained from these experiments along with the modeling effort enabled us to successfully design and operate a /arger field experiment at a DO€ TC€antaminated clay site.

A-2

B. Acronvms and Abbreviations

- A ADAC A/D C c, DC, dc DOE e- E, EPA ESC Fe Feo Fe2+ GAC GE H+ H20 HPLC I ID i k k, kb ki L P MMES n N d NaOH 02 OH ORNL PC PGDP PH

approximately area (cross sectional) brand name of the computer input card analog to digital computer input card specific heat of the soil specific heat of the pore water direct current Department of Energy electrons electrochemical reduction potential Environmental Protection Agency Monsanto's Environmental Sciences Center Iron Iron metal oxidized iron (ferrous ion) granular activated carbon General Electric hydrogen ion water high performance liquid chromatography current (amps) internal diameter voltage gradient thermal conductivity coefficient of electroosmotic conductivity coefficient of hydraulic conductivity coefficient of electroosmotic efficiency dimension of length viscosity of pore water Martin Marietta Energy Systems soil porosity sodium ion sodium hydroxide oxygen hydroxide anion Oak Ridge National Laboratory personal computer Paducah Gaseous Dfision Plant measure of acid content

B-1

B. Acroavms and Abbreviations (cont’d)

PNP PV

Q P P w ROA 0

t T TCE

WKWMA Q,

U

paranitrop henol pore volumes volumetric flow rate density of the soil density of the pore water Research Opportunity Announcement electrical conductivity time temperature trichloroethylene velocity of the pore fluid Western Kentucky Wildlife Management Area electrical potential

B-2

C. Units

amps "C cm &gm hr in, " ka kwh L m mA mg mho ml P P8 N nm PPb PPm s, sec V wt%

amperes Celsius, degrees Celsius centimeters grams hours inches

kilowatt-hours liters meters milliamps milligrams semens or l/ohms milliiters microsemens micrograms equivalents per liter (normal or normality) nanometers parts per billion (pgkg) parts per million (mag) seconds volts percent by weight

kilograms

c-1

D. Table of Contents

Section Etle

A. a C D. E

F.

Executive Summay Acronyms and Abbreviations Units Table of Contents Background

Statement of the Problem The Solution Consortium Descdption Management Plan Technical Deliverables

Topical Report for Tasks #8 and #I 0 Introduction Materials and Methods Results and Discussion

Kaolin Clay Paducah Soil

Summary and Conclusions Acknowledgments References

Appendix A. Pilot Run #I Data Appendix a Pilot Run #2 Data Appendix C Pilot Run #3 Data Appendix D. Pilot Run #4 Data Appendix E. Pilot Run #5 Data

Page

A-1 &I GI D-1 E-I E-1 El El E-2 E-2 F-I F-1 F-2 F-5 F-5 F-6 F-11 F-12 F-12

F-31 F-34 FA0 F-44 F-52

D- 1

D. Table of Contents (Cont'd)

Table El Table E2

Table I Table 2

Table 3

Table 4

Figure 1 Figure 2 Figure 3 Figure 4

Figure 5

Figure 6 Figure 7

Figure 8 Figure 9

Figure 10 Figure 11

Figure 12

Figure 13

List of Tables List of Tusks and Responsible Company List of Topical Reports and Responsible Company

Characteristics of Kaolin Clay and Paducah Soil Comparison of Pilot Unit to Benchtop Units for Kaolin Clay Comparion of pilot Unit to Benchtop Units for Paducah Soil Model Parameters

List of Figures

Lasagna Configurations Lasagna Laboratory Experimental Setup pilot Unit Setup Residual Concentratiins of PNP afler 1 pore volume for pilot run #2 Voltage Gradients andpHprofile for Paducah Soil with Two GAC Treatment Zones Flow Rate and current vs. Time for Pilot Run #4 Cation Concentration and Specific Conductance of Cathode Zone Fluid pH vs. T i m for pilot Run #5 Effect of Voltage Gradient on Electroosmotic Flow Rate for Paducah Soil "Hot Spot" Temperare Bofile Model Rediction of the Maximum Soil Temperatures for Three Voltage Gradients MOM A.ediction of Pmer Input vs. ? h e for Three Voltage Gradients Effect of Heating on Electroosmotic Flow as a Function of Pmer Input

E-3 E-3

F-14 F-15

F-14

F-17

F-18 F-19 F-20 F-21

F-22

F-23 F-24

F-25 F-26

F-27 F-28

F-29

F-30

D-2

E. Background

Statement of the Problem Contamination in low permeability soils poses a significant technical challenge to in-situ remediation

dorts. Poor accessibity to the contaminants and dif5cult-y in delivery of treatment reagents have rendered existing in-situ treatments such as bioremediation, vapor extraction, and pump and treat., rather ineffective when applied to low penneabiity soils present at many contaminated sites.

The Solution The proposed technology combmes electro-osmosis with treatment mnes that are installed directly in

the contaminated soils to form an integrated in-situ remedial process. Electro-osmosis is an old civil engineering technique and is well known for its effectiveness in moving water d o d y through low- permeability soils with very low power consumption.

Conceptually, the integrated technology could treat organic and inorganic contamhation, as well as mixed wastes. Once developed, the technology will have tremendous benefits over existing ones in many aspects including environmd impacts, cost effectiveness, waste generation, treatment flexibility, and breadth of applications.

Consortium Description A Consortium has been formed consisting of Monsanto, E. I. du Pont de Nemom & Co., Inc.

w o n t ) and General Electric (GE), with participation fiom the Environmental Protection Agency @PA) Of€ice of Research and Development and the Department of Energy (DOE) Environmental Management Oilice of Science and Technology. The five members of this group are leaders in their represented technologies and hold si@& patents and intellectual property which, in concert, may form an integrated solution for soil treatment. The Consortium's activities are being fbditated by Clean Sites, Inc., under a Cooperative Agreement with EPA's Technology Innovation Oflice. A schematic diagram of the government/iidustq consortium is shown on the fiont page of this topical report.

E-1

E. Background (Cont'd)

Management Plan

A Management Plan for this project was prepared by Monsanto and submitted on November 30, 1994. That plan summaflzed . the work plan which was developed in conjunction with Wont, GE, EPA's Risk Reduction Engineering Laboratory (RREL), Martin Marietta Energy Systems (MMES), and the Department of Energy. The DOE Gaseous Diffusion Plant in Paducah, Kentucky, was chosen as the site for the initial field tests.

CDM Federal Programs Corporation was chosen to provide the on-sie support of the field tests which were installed at the DOE site in November 1994. This experiment tested the combination of elecko-osmosis and in-situ sorption in the treatment zones. In 1994 and 1995, technology development was carried out under the present contract by Monsanto, Wont , and GE. These studies evaluated various degradation processes and their integration into the overall treatment scheme at bench and pilot scales.

Technical Deliverables Tables El and E2 Summarize the 13 technical tasks and the 8 topical reports which will be written

describing the results obtained in the technical tasks. These two tables show which organization is primarily responsible for the tasks and for preparing the topical reports. The present topical report s u m the results of tasks 8 and 10,

E-2

E. Backmound (Cont'd)

MMES Monsanto/DuPont/ Nilex

MonsantoKDM Task 12 - Design and Fabrication of Large-Scale Lasagna Process Task 13 - Large-Scale Field Test of Lasagna Process

Table El. List of Tasks and Responsible Company

'Task 1 - Evaluation of Treatment Zone Formation Options Tasks 2 - 4 Electrokinetic Modeling Task 5 - Cost Analvsis

DuPont GE

W o n t Task 6 - Laboratory-Scale Microbial Degradation Tasks 7 - Lab-Scale Electrokinetic and Microbial Degradation

DuPont Monsanto

Table E2. List of Topical Reports and Responsible Company

Tasks 8 and 10 - Bench and Pilot Scale Tests of Lasama Process Monsanto ?asks 9 - TCE Degradation Using Non-Biological Methods Task 11 - Contamination Analysis, Before and After Treatment Tasks 12 and 13 - Large-Scale Field Test of Lasama Process

GE Monsanto Monsanto

E-3

F. TOD ical ReDort o f Tasks 8 & 10

INTRODUCTION

We have been developing a novel in situ technology aimed at cleaning up contamination in low- perm- soils or heterogeneous soils containing low-permeability zones. Our approach involves the synergistic coupling of electrokinetics (1-9) with in situ treatment processes. The general concept is to use electrokinetics to transport contamimnts h m the soil into ‘treatment zones77 where the con taminants are removed fiom the pore water by sorption, immobilization or degradation. This integrated technology has been described elsewhere (10). Briefly, it consists of the following components:

a) create permeable zones in close proximity sectioned through the contaminated soil region, and turn them into sorptioddegradation mnes by introducing appropriate materials (sorbents, catalytic agents, microbes, oxidants, buffers, etc.).

b) utilize electrokinetics to transport contaminants from the soil into the treatment zones.

c) periodic reversal of the electro-osmotic flow and recycle of the cathode effluent back to the anode side can be utilized to minimize complications associated with long-term operation of uni- directional electrokinetic processes.

Electrodes and treatment u lna can be of any orientation depending upon the emplacement technofogy used and the sitdcontambnt characteristics. Schematic diagrams of two typical configurations, horizontal and vertical, are shown in Figure 1. The process has been d e d ‘Lasagnam’(lO-ll) due to the layered configuration of electrodes and treatment zones.

Conceptually, the Lasagnam technology exhiiits a high degree of flexiidity in the treatment process used, which can incorporate mixtures of different treatment materials in the same treatment mne or utilize functionally distinct treatment zones. The technology can thus be potentially efktive for treating organic (e.g., chlorinated solvents) or inorganic (e.g., heavy metals) contamination as well as mixed wastes. With electrokinetics as the mechanism fix contamman ’ t transport, the technology is well suited for treating contaminated low permeabiity soils (clayey, silty soils) or heterogeneous soils (clay lens in permeable soils). Hydrofhcturhg (12) is a particularly attractive tool for installing horizontal electrodes and treatment zones to handle deep contamination, but does require overconsolidated soils to be effective. For shallow contamination (< 50 feet) and especially ifthe soil is not overcomlidated, vertical treatment approach using sheet piling or trenching may be more appropriate.

A consortium of industry and federal agencies has been formed to combine expertise and resources for accelerating the development of this technology. A field test of the process was successfidly completed at a DOE site in Paducah, KY, which has clayey soil mntaminated with trichloroethylene (TCE). In support of this program, we studied the movement of water and contaminants through kaolin clay and

F- 1

F. Topical Repart of Tasks 8 & 10 (Cont'd)

Paducah soil using the Lasagnam process. The process was extensively studied at the bench level, then scaled up in a laboratory pilot unit. The pilot scale experiments played an important role in the development of models and designs for the field tests. Electrokinetic characteristics, soil temperature, cathode efEIuent pH and conductivity, and ion electromigration were evaluated under controlled conditions. This paper focuses on the scale-up aspects of the Lasagnam process fiom bench to pilot scale. Bench-scale study of various Lasagnam configurations including heterogeneous soil matrices and coupling electrokinetics with in-situ biotreatment has been reported elsewhere (1 0).

MATERIALSANDMETHODS

Bench Scale

The bench scaie unit has been described in detail elsewhere (10). Briefly, the electrokinetic cell was made fiom clear plastic tube, 10 cm ID ( 81 cm2 cross-sectional area). Kaolinite or Paducah soil was sandwiched between sand andor granular activatedl carbon 'treatment zones': The outermost treatment zones functioned pmady as the hydraulic input and output zones. Well water or recycled cathode fluid was introduced at the anode treatment zone under constant head using a Marriotte bottle. The cathode fluid was expelled at the top of the cathode treatment zone and put into the Maniotte

bottle. A plug of glass wool in the inletloutlet fittings prevented solid material fiom leaving the unit. The center treatment zones contained some mixture of sand and GAC. The center 'bntaminated soil" Section was approximately 6.5 cm long and outer soil zones were approximately 4.6 cm long. The electrodes were made of 1/4"steel plates with stainless steel rods screwed into the edge of the steel plates for connections to the power supply. The distance between the plate electrodes was 18 cm. Figure 2 shows a diagram of the bench-scale electrokinetic cell.

Pilot Scale

A pilot-scale Lasagna'TM unit (Figure 3) was constructed fiom a Nalgenm polyethylene tub (120 cm long by 60 wide by 60 deep) to simulate the vertical Lasagnam wnfiguration to be used at the DOE Paducah site. Electrodes were made of 1/4 in. steel plate 59.5 cm wide by 51 cm tall. These electrodes were placed at each end of the polyethylene tub and were connected to the power leads by 12 gauge wire. Immediately in fi-ont of each electrode was a permeable zone to allow inflow and outflow of liquid to the electrode region. The permeable zones were wnstructed the same way as the treatment zones described below.

Treatment zones were constn~cted in three con@urations. In the kaolinite experiments, each treatment zone consisted of 13.6 kg of medium sand and 100 grams of granular activated carbon (GAC). Sand and carbon were contained between sheets of 0.3 cm thick porous polypropylene measuring 59.5 cm wide by 51 cm tall and approximately 2.5 cm apart. There were a total of four treatment zones, two in the cater of the bed and two in fiont of the electrodes. The distance between the two adjacent treatment zones was 35.6 cm.

F- 2

F. Topical Report of Tasks 8 & 10 (Cont'd)

Subsequent runs used treatment zones constructed by Wickdrain Inc. These treatment zones were made by gluing egg-crate polyethylene sheets to steel hmes which had holes drilled to allow water passage. The wickdrain was then wrapped with a geotextile and filled with 100% GAC. These zones were placed 35.6 cm apart and were 59.5 cm wide by 60 tall. The last Paducah soil pilot experiment used Monsanto Hydraway@ construction wickhg material filled with GAC and had a single treatment zone in the center in order to increase the treatment zone spacing to 53 cm.

Once the treatment zones were installed in the unit, Georgia kaolinite clay (air-dried, air-floated kaolinite obtained fiom Thiele Kaolinite Co., Wrens, GA) or Paducah soil was placed in the Unit between the treatment zones. The first 2 pilot runs were prepared with kaolin clay packed to a depth of 43 cm. Kaolin powder was hydrated with tap water in a wheelbarrow to a water content of 37.5 wt%. AU other pilot runs used Paducah soil obtained fiom the Western Kentuclq Wildlife Management Area (WKWMA), adjacent to the DOE Paducah Plant site where the field trial was conducted. Some characteristics of kaolinite and the Paducah soil are listed in Table 1. The Paducah soil is classified as clay loam, with M y low organic content and much higher cation exchange capacity thanblinite.

After the soil was packed in the unit fix the fist pilot run, holes were drilled into the side of the tub to allow access to the treatment zones for sampling and to allow water to recycle ftom the cathode zone back to the anode zone. Plumbing consisted of stainless steel tubing fittings and 1/4 in. polyethylene tubing.

For studying contaminant transport, five sausage-like units of paranitrophenol (PNP) contambated clay were placed in the center section of the pilot unit. The sausages, approxunakly 25 cm long and 3.8 cm in diameter, were uniformly contaminated to 370 pg PNP/g wet soil for a total of 0.94 gram PNP. Dialysis membrane was used to encase the PNP contaminated clay for convenient r e t x i d and analysis during and after the test. Four of the five sausages were placed horizontally in the center clay zone reaching nearly ftom treatment zone to treatment zone and centered in the four quadrants (looking at a cross sectional fhce). The fifth sausage was placed vertically in the unit, in the center of the middle clay zone.

A type "J" thermocouple was installed near the center of the unit to monitor temperature effects on the last Paducah soil test. The temperature was read using a hand held digital thermometer @&e Model 5 1) caliirated at the ice point (0 oC).

Analytical and Data System

The pilot unit was powered by a Sorenson DCR 3W9B power supply capable of 300 volts dc and 10 amp output. The voltage, current and various incremental voltages of the pilot unit were monitored

F- 3

l and logged manually as well as with a data acquisition unit featuring a personal computer running LabTech Notebook sohare and a ADAC AD voltage measurement card and line isolators.

The pore fluid fiom the treatment zones was analyzed periodically for specific conductance and pH. Conductance was measured using a Cole Parmer model 19101 specific conductance meter. A Corning model 140 meter and Orion model 91 series electrode were used to measure pH.

The analysis of the model organic contamhint PNP involved extracting PNP fi-om clay samples with 0.1N NaOH solution and measuring the level of PNP in solution by spectrophotometric absorption at 400 nm or by high pdormance liquid chromatography (HPLC). One extracton was sufficient to remove all PNP fiom clay. For carbon, which binds PNP much more tightly, the extraction solution contained 0.1N NaOH and 2 wt?! methylene chloride, and repeated extractions were carried out to msudmizePNP recovery.

Electroamotic flow rate for the kaolinite experiments was measured by diverting the recycle flow into a graduated cyftnder or flask. A Turbo model Magmeter MG911lF3 flow meter was installed m the recycle line for the Paducah soil m. The meter controller unit was equipped with a 0-5 volt dc output which was comected to the data system. The meter calibration was checked in the lab at flow rates of OY60 and 500 mVhr.

Electrokinetic Parameters For each run, the electro-osmotic permeability can be calculated using the following equation:

I Q = k c i A (1) I where;

Q : volumetric flow rate by electro-osmosis (~rn:~/sec) k, : cmefiicient ofelectro-osmotic permeability (cm2/vo~-sec) i, : voltage gradient applied across the soil mass (volt/cm) A : cross-sectional area perpendicularto flow (cm?

Note that the electro-osmotic flow is proportional to the applied voltage &at, and that the electro- osmotic permeability has the units of velocity over field strength ( d s e e over volt/cm). The CoeEcient of electro-osmotic transport efficiency, ky is by definition:

ki = Q / I where 1:current (amp) (2)

Combined with equation 1 and with simple rearrangement, equation 2 becomes: I

F- 4


where h is the conductivity of the soil colm (mho/m). The transport efficiency ki has the units of cm3/mp-sec and reflects the efficiency of current usage for pumping water through the soil column.

RESULTS AND DISCUSSION Scale-up experiments using the pilot unit were carried out ht with kaolinite as the model soil whose electrokinetic characteristics have been well studied in our laboratoq as well as by other researchers. Subsequent studies were then conducted using the actual Paducah soil.

KAOLINCLAY

Electrokinetic Characteristics - BenWPiIot Comparison. A large number of experiments were conducted with bench-top electrossmosis units to provide data for designing the pilot unit. Bench- scale for kaolinite have been reported elsewhere (10). The pilot unit was 6 t imes longery 32 times larger in cross sectional area, and 197 times more volume between the two treatment zones.

The kaolinite pilot Unit was o p t e d at constant voltage for 36 days with one pol- reverSa. In the first pass, liquid flow equivalent to 0.87 pore volume of the center zone was obtained in 19 days. The polarity was then reversed for 17 days passing 1.0 pore volume. The results are shown in Table 2, which also lists the corresponding data for a typical benchtop run for comparison. Average liquid flow rate for the entire pilot run was 120 mvhr, equivalent to an average electro-osmotic permeability &) of 1.7 x 10-~ r rn2N-se~ .

The average transport efficiency (14) was 0.46 cm3/amp-sec; and the total power consumption was 51 bWm3 per pore volume (pv) of liquid. Note that the power consumption in kwh/m3-pv should be proportional to the treatment zone spacing, which explains the 5x increase in the power usage for the pilot unit vs. bench due to the corresponding &fold increase in the zone spacing. Table 2 shows that electro-osmosis in the -m configuration scales up reasonably we^ for kaolinite clay.

PNP Removal. The eEztiveness of the Lasagnam process for removing PNP as the model organic contaminant fi-om clay in the pilot unit was studied. Five sausage-like units of PNP contaminated clay were placed in the center section of the pilot unit, four horizontally and one vertically as described in the Experimental section.

The unit was operated for 14 days in one direction resulting in a 0.94 pore volume of water exchange in the center clay section. A single hoxizontal PNP contaminated sausage and some kaolinite soil surrounding the sausage were removed and analyzed for PNP. The results showed that over 98% of the PNP loaded had been removed fiom the sausage h this single pass. Only 15 mg/kg PNP was detected at the downstream end, with decreasing PNP concentration toward the upstream end, which contained no PNP @igure 4).

F-E;


The PNP contaminated sausage was returned to the unit. Electrid polarity was then reversed and maintained for 25 days sweeping an additional 1.6 pore volume. After that, all sausages, as well as representative samples from the center clay zone and the complete sandcarbon treatment zones were extracted and analyzed for PNP. No detectable (<lo ppb) amount of PNP was found in any clay samples. All the PNP recovered was €tom the carbon in the center treatment zones. Ofthe PNP recovered, 91% was found in the downstream treatment zone illustrating the efficiency of the first pass. However, only 55% of the estimated PNP loaded was recovered in the treatment zones. Although close to 1Wh PNP recovery was common in bench scale units, where PNP loading was typidy at 100 mg PNP/g carbon, it is more diilicult to extract all the adsorbed PNP when the PNP to carbon ratio is as low as it was in the pilot unit (-3 mg PNP/g carbon). Despite the low mass balance, the fhct that PNP was un%ody and completely removed from the clay zones is indicative of the effectveness of the technology for cleanup of organic contaminants like PNP. Due to the extremely low vapor pressure of PNP, it is uniilcely the PNP loses were due to volatilization.

PAJlUCAH SOIL

Electrokinetic Characteristics - BencbRilot Comparison. Paducah soil was used to study the electrokinetic characteristics of a real soil. As with kaolinite, many benchtop experiments were conducted prior to the pilot runs described here. Parametefs monitored during these runs include soil temperature, pH, conductivity, and ions profiles. Witpl two treatment zones in the center, the Paducah soil pilot unit was nearly 7 times longer, 37 times larger in cross sectional area, and 250 times more pore volume per soil zone than the bench scale unit (Table 3). Prefihicated treatment zones contained 1Wh granular activated carbon (GAC) instead of a mixture of sand and carbon as in the kaolinite experiments.

The Paducah soil pilot unit was operated at constant voltage for a total of 44 days with one polarity reversal. In the first pass, liquid equivalent to 0.71 pore volume of the center zone flowed in 21 days. The polarity was then reversed for 23 days passing 1.5 pore volumes. The average electro-osmotic permeability &) for the first pass was 5.6 x lo4 un2/V-s, comparable to the bench-scale data, but was much higher (10.6 x lo4 cm2/V-s) for the revefsed pass. The reason for this large difference is not clear. We suspected that the increased soil moisture content of this fsirly dry soil (19% moisture) may have played a major role in the observed discrepancy. The average transport efEciency (k) was 0.22 cm3/amp-sec, and the total power consumption was 200 kwh/m3 per pore volume of liquid, about 4 times that of kaolinite. Table 3 shows that the Paducah soil appears to scale up reasonably well with respect to power consumption, which should be proportional to the treatment zone spacing.

Bipolar Effects. With the treatment zones containing loOO! activated carbon, which is electrically conducting, there was the possibility of them acting 8s bipolar electrodes due to the applied electric field. That is, the side of the carbon zone %g the anode could behave like a cathode (which would generate OH and release hydrogen), and the other side of the carbon may behave like an anode (which

F- 6

F. Topical Report of Tasks 8 & 10 (Cont’d)

would generate K‘ and release oxygen). Evidence for bipolar effects in terms of voltage distribution and pH are shown in Figures 5. Voltage drop typically tends to be higher near the cathode and lower near the anode (lo), a pattern observed for the two treatment zones in this case. The pH’s of the soil on the %node” sides of the treatment zones were low, and those on the ‘bathode” sides were high, consistent with pH characteristics ofthe eIectrodes.

Larger Treatment Zone Spacing.The pilot unit was packed with fiesh Paducah soil and the Monsanto Hydraway0 treatment zones in a configuration that closely resembled the field design. A single treatment zone in the center of the unit and two electrode treatment zones were used. The Hydraway@ zones were now spaced 53.3 cm apart. The unit was initially operated at 0.5 V/cm, which ran stable in one direction for 105 days with an average electro-osmotic permeabiity ( k ~ ) of 1.1 x 1 o - ~ cm’/volt-sec. Apparently, at this low voltage gmbent the recycle of the cathode efnuent back to the anode side was suf€icient to s tab i i the electro-osmosis process without the need for polarity reversal. Figure 6 shows the values for flowrate and current during the three months of operation.

Conductivity and pH. The pH and specific conductance of the cathode duent and of the water in the treatment zones were monitored during the course of op t ion . Within a few days, the specific conductance of the fluid in the cathode zone rose sharply. Ions analysis showed that this increase in solution conductivity was due to the presence of Na” (Figure 7). Sodium ion apparently moved M e r than the water and accumulated in the cathode region. The advantage of the water recycle scheme of the Lasagnam process is evident here: cations transported by electromigration to the cathode were brought back to the anode zone where they could be reintroduced into the soil. Mer a fkw days of operation, the anode pH decreased fiom near neufrality to about 6 while the cathode pH &uent increased to over 12. The near neutral pH at the anode is thought to be partially due to the oxidation of the iron anode taking place preferentiayl over the electrolysis of water acwrding to the following reactions:

Fe” - 2e’ Fe* E, = a.44 volts

E, = -123 volts

This is consistent with the presence of rust in the anode solution. The pH of the anode solution was also neutcalized by the high pH of the recycled cathode &uent. The pH in the center treatment zones did not vary much after the initial decreasehm the starting pH of about 8 to a pH between 6 and 7 (Figure 8). The specific conductance of water in the treatment zones showed some fluctuations between 300 to 500 ws/cm.

EffectsofVoltageGradient. The relationship between the applied voltage gradient and the corresponding electro-osmotic flowrate was studied fiom about 1 V/cm down to below 0.1 Vim. The electro-osmotic flowrate was found to vary quite linearly with the applied voltage gradient (Figure 9). Extrapolation of the fitted line shows that the flow would stop at a voltage gradient of 0.06 V/cm,

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or an overall voltage of about 7 volts. This threshold voltage is the sum of the voltages required to drive the electrode reactions and the overvoltages associated with our particular experimental setup. The results suggest that fbr a much larger setup (field-scale) where the o v d voltage applied will be much higher than 7 volts, electro-osmosis can be operated &ciently at very low voltage gradients. For example, a 0.1 V/cm gradient for a 10 m electrode spacing would result in a total voltage of 100 V. The low voltage gradient is attractive in field operations due to less energy consumption per unit of water transported electro-osmotically. Another benefit of low voltage gradient operations is less severe soil heating, as addressed below.

Soil Heating. Soil heating will occur in the use of electrokinetics for soil remediation due to the electrical input. While heating has not been an issue in laboratory studies, our modeling work discussed in the next section suggests that in field scale applications thermal effects of Joule heating will be significant. Under steady-state conditions, the energy supplied to the soil by Joule heating is balanced by thermal conduction of the energy to the boundaries of the soil system. As the size of the treated soil increases, the surface area to volume ratio decreases, and the characteristic length for heat conduction increases. This leads to a maximum steady-state temperature rise in the soil that varies with the square of the characteristic length of the region. Therdore, field experiments, wbich may easily be a factor of ten larger than laboratory experiments, might be expected to have temperature rises on the order of 100-fold larger than the similar laboratory expeximent. Tempemture rises as a function of the voltage gradient applied were measured to assess the importance of this effect and to provide data for the modeling eBort.

figure 10 shows the core soil temperatme of the pilot unit (at the center of the soil mass) as a function of the applied voltage Merit. At 0.5 V/cm, the core temperature only went up to almost 2SoC, an average of 1.1 degree above the ambient temperature of 23.7OC. When the voltage gradient was increased to 1.0 V/cm, the core temperature increased over several days to an average of 4.8"c over ambient. The voltage gradient was then doubled again to 2.0 V/cm. This caused a dramatic increase in soil core temperatme, which within one week was approaching 53*C, a temperature rise of almost 3OoC! The temperature rise appears to be roughly proportional to the square of the voltage gradient, consistent with the power input varying with the square of the applied voltage.

An increase in soil temperatwe could have an impact on volatile matter in the soil as well as electrokinetic effects. If the contaminant of interest is volatile, provisions should be made to monitor the air space above the treated area and control options evaluated.

Modeling of Thermal Effects

The significant temperature rises observed in the pilot experiments prompted the development of the followhg mathematical model describing Joule heating and heat transfer by conduction and convectiun (13).

F-8

F. Topical Report of Tasks 8 L 10 (Cont'd)

The coupled equations describing the electric and temperature fields are:

Charge conservation:

v a(T)Vq5 := 0

Electro-osmotic and hydraulic flow through porous media:

Energy consemtion:

(4)

where Q is the electric potential, athe electrical conductivity, u the pore fluid velocity, k, the soil electro-osmotic permeabii, kh the soil hydraulic pemeabihty, p the pore water viscosity, n the soil porosity, Tthesoiltemperature,pthesoildensity,cthespecificheatofthesoil,p,theporewater density, &the pore water specific heat, and kthe t h d conductivity.

Equation 4 makes several sixnpliijhg assumptions regding charge tramport in the soil. First, there are no capacitive effects, which should be the case with a DC electric field. Second, charge is tramfkd predominantly by ionic migration, so that convection in the charged double layer at the soil particldpore liquid i n t h and current carried by difksion of ions are negligible. And third, the electrical conductivity, to first order, is only a function of tempatwe. Several investigatorS (2,1418) have examined the transport of ions in electrokinetic applications, both experimentally and theoretically, and have shown that electrical conductivity becomes a strong function of position as ions get redistributed by the electric field and electrode reactions. However in soils with moderate buffering capacity it can be shown that this effect can be neglected in certain cases, including the laborato~~ tests simulated in this work.

F-9

F. ToDid Rebort of Task 8 & 10 (Cont'd)

Because both fluid viscosity and electrical conductivity are very sensitive to temperature, their temperature dependence has been incorporated in this model. The viscosity dependence is reflected by the electro-osmotic permeability, ke, which varies inversely with viscosity, according to the Helmholtz-Smoluchowski equation (19). That is, the effects of temperature on the zeta potential, dielectric constant, and solub~ty of species are ignored. The following expression for the temperature dependence of viscosity of water (20) was used to estimate the temperature dependence of the electro- osmotic permeability:

Laboratory experiments determined that the temperature dependence of soil electrical conductivity can also be expressed as a function of fluid viscosity (13). The inverse relation between electrical conductivity and fluid viscosity is consistent with the behavior of ionic aqueous solutions (21). Thus the temperature dependence of conductivity was also expressed in terms of fluid viscosity as

A two dimensional rectangular geometry (1.1 m x 0.45 m) was used to represent the experimental apparatus used in these experiments. The left side of the rectangle was the anode and the right side was the cathode. The boundary conditions for the electric field were #(anode)=k (60, 120 or 240 V) and ~cathode)=o. The top and bottom sides of the rectangle was electrically insulated. The thermal boundary conditions are constant temperature of 23.7OC at all four sides of the domain. The parameters used in the example computer simulation are given in Table 4.

The thermal model was run for three applied voltages, 60, 120, and 240 V. Three cases are analyzed for maximum mil temperature, power and flow rate. The calculaM maximum temperatures for these cases are shown in Figure 11. For this geometry, the warmest region lies in the center of the domain, and fiom the symmetry of the temperature field, it can be concluded that electro-osmotic convection is unimportant in heat transfix. This may not be the case if arrays of cylindrical electrodes are used. In such cases, maximum temperature may occur near the electrodes where the ament is concentrated.

F- 3.0

F. Topical Report of Tasks 8 & IO (Cont'd)

From Figure 11 it can be observed that the temperature rises begin relatively rapidly and then converge toward a steady value after about 7 days. The time scale for thermal d i i o n across the narrow dimension of the geometry (L2pc/k) is 7.2 days. In field applications in which the characteristic dimension is, for example, 10 m, the steady state temperatures would not be reached until 3500 days, or well after the remediation was completed. The steady state temperature rises were 1.4, 6.6, and 30.3"C for the 60, 120, and 240 V cases respectively. This compares well with experimental measurements of 1.3, 4.9, and -30°C for the respective conditions. The fact that the measured temperature rises are slightly d e r than the model predictions may be attributable to inaccwacies in input properties (the thermal conductivity was chosen to achieve a good fit with experimental data; other properties were measure independently), and the fact that a two-dimensional model was used to represent a three-dimensional experiment, and therefore the model had less &dive heat transfer area. The &or of 4.7 between the temperature rise for the 120 V case and the 60 V case is slightly higher than the order of magnitude scaling which predicts that the temperature rise will be proportional to the electric field squared. The nonlinearity of the system, however, is more apparent when comparing the 60 V and 240 V cases. The ratio of temperature rises predicted in the simulations was 21.6 (the ratio of the corresponding temperatwe rises in the experiments was 23.1) compared to the factor of 16 that would be expected in a linear system.

The increased temperature rise at higher voltages is attributable to the temperature dependency of the electrical conductivity. As the conductivity increases, the V2/R losses increase, because the system resistance goes down. Therdore the power supplied to the soil increases with time as shown in Figure 12. The transient behavior of the applied power is clearly dependent on the control strategy. instead of constant voltage, a constant current were maintained, the power (12R) would decrease with time as a result of decreasing resistance. In fhct., operating at constant current in field scale applications has the important advantage of heating the soil relatively quickly early in the process, and approaching the steady state operating conditions h t e r than a constant voltage control system.

The effect of heating on the electro-osmotic flow rate is shown in Figure 13. The pore volumes as defined in Figure 13 refer to one-half of the total pore volume between the electrodes, because in the test there was one activated carbon treatment zone between the electrodes. As with the temperature rise, nonlinearity is seen in the relation between applied voltage and electro-osmotic flow. The ratio of the flow rate in the 240 V case to the 60 V case is 5.5, or 38% larger than if the electro-osmotic permeabiity were independent of temperature.

SUMMARY AND CONCLUSIONS

A novel integrated in situ remediation technology, called Lasagnam, is being developed coupling electro-osmosis with in situ treatment zones. Experiments were conducted with kaolinite and an actual soil in units ranging fiom bench-scale containing kgquantity of soil to a pilot-de containing about halfa ton of soil having various treatment mne configurations. The obtained data support the fmibility of scaling up this technology with respect to electrokinetic parameters as well as removal of

F- 1 1

F. Topical Report of Tasks 8 & 10 (Cont’d)

organic contaminants. A mathematical model was developed that was successl h predicting the temperature rises in the soil. The information and experience gained fkom these experiments along with the modeling effort had enabled us to successfully design and operate a larger field expehent at a DOE TCE-contaminated clay site.

ACKNOWLEDGMENTS

The authors would like to express their appreciation to Dr. Edward Griffith for his valuable inputs on electrokinetics; Jay Wendling for PNP WLC and ion chromatography analysis; Andy Shapiro for thermal modeling of the pilot unit. Special thanks go to the following members of the Monsanto shop servjces and instrument support for their help in coIlstructing the pilot unit and data system: Kevin Deppermann, Alan Jackon, John Matthews, and Marvin Denison.

REFERENCES

1. L. J. Casagrande, BSCE, 3951-83 (1952). 2. AP. Shapiro, P. Renaud, and R Probstein, ‘hlimimy Studies on the Runoval of Chemical

Species fiom Saturated Porous Media by Electro-osmosis” In Physicochemical Hydrodynamics, Vol. 11, NO. 5/6, pp, 785-802 (1989). J.Hamed, Y.B. A~andRJ.Gale, ASCE,Vol. 112, pp. 241-271,Febn~~ (1991). 3.

4. C. J. Bruell, and B. AS& J . Environ f i g , Val. 118, No. 1, pp. 68-83, J&eb 1992. 5. B. ASegall, and C. J. Bruell, J . Mron . Eng., Vol. 118, No. 1, pp. 84-100, JanlFeb 1992. 6. YB. Acar,H. Li, and RJ. GaIe,ASCEsVol. 118,No. 11, pp. 1837-1852,November 1992. 7. AP. Shapiro, and RF. Probstein, EMrm Sci. Technol. 27, pp. 283-291, 8. R Lag- ‘Electroreclatnation - Applications in The Nethdands” Emirwz. Sci. TechZ., pp

26480, Vol. 27, No. 13, 1993. 9. Y. B. Acar and A N. Alshawabkeh, ‘Principle of Electrokinetic Remediation” Mmn.

SCiTechnol., pp. 2638-47, VoI. 27, No. 13, 1993. 10. S. V. Ho, P. W. Sheridan, C. J. Athmer,, M. A Hehkamp, J. M. Bmkin, D. Weber, and P. H.

Brodsky ‘Integrated In Situ Soil Remediation Technology - The Lasagna procesS,” Emtiron. Sci. Technol., 1995,29( lo), 2528-2534.

11. P.H. Brodsky and S.V. Ho, U.S. Patent No. 5,398,756, March 1995. The term Lasagna is a trademark of Monsanto Company.

12. L. Murdoch, ‘Some Recent Development in Delivery and Recovery: Hydraulic Fracturing and Directional Drilling” Prmeedngs of EEX’92 - 9% 2nd Annual E;Mtronmental Technology Eqnmtion catd Conjierence, Wash., DC, USA, April 79,1992.

13. Shapiro, AP.; Schdtz, D.S. Emerging Techloglees in H m a b u s W@eMmtagment W, 1995 Extended Abstracts for the Special Symposium, Atlanta, GAY American Chemical Society, p 457.

14. Alshawabkeh, AN.; Acar, Y.B.,J Ernirofi ki. Health, 1992, A27(7), 1835. 15. Eykholt, G.R.; Daniel, D.E. J Geotechnicalfig. 1994,120(5), 797. 16. Jacobs, RA; et al. .l Wren. Sci. Health, 1994, A29(9), 1933.

1993.

F-12


17 18 19

20

21

. ,

. .

Hicks, RE.; Tondorfj S. Mrm. Si. T e c h & 1994,28(12), 2203. Jacobs, Rk; et al. AICHe Probstein, RF., P~~cochemica l l~odymmics , An Intrduction, 1994,2nd edition, John Wdey & Sons, Inc., New York, p. 197. Weast, RC., ed. Haradbook of Chemisfry and Physics, 1972, The Chemical Rubber Co., Cleveland, p F-36. Gurney, RW. Ionic Processes in Solution, 1953, Dover Publications, New York, p 69.

F-13

Table 1. Characteristics of Kaolin Clay and Paducah Soil

Parameter Units Kaolinite Paducah Soil Type clay clay loam

Sand Silt Clay

Bulk Density Porosity noisture Cation Exchange Capacity Organic Carbon Content

Y O 0 Y O 0 YO 100

1.65 CCICC 0.62 YO 37.5

meq/100g 1.1 YO 0

22 46 32 2.0 0.4 20

13.4 0.2

Estimated Hydraulic cm/s 1 o-8 10"- io4 Conductivity

Table 2. Comparison of Pilot Unit to Benchtop Units for Kaolin Clay. Both units had 2 steel electrodedsand-carbon zones and 2 sand-carbon treatment zones evenly spaced between the electrodes.

Parameter Units Benchton Pilot Ratio

Pilo t/Bench

Length (include sand zones) Cross Section Area Pore Volume / Zone Treatment Zone Spacing

Voltage Gradient 'Current Density EO Conductivity (ke) Power Consumption Resistivity

cm cm2 cm3 cm

V/cm A/m2

cm2/sec-v kwhr/m3-pv

ohm-cm

18 81

300 6

1 0.57

10 19100

2.5 x 10-~

118.1 2600 56000 35.56

1 0.37

51 27300

1.7 1 0 - ~

7 32 187 6

1 0.7 0.68 5.1 1.4

1

Table 3. Comparison of Pilot Unit to Benchtop Units for Paducah Soil. Configurations: 2 Steel electrodes/GAC zones

2 GAC treatment zones evenly spaced between the electrodes

~~

Ratio Para meter Units Benchtop Pilot Pilot/Benc h

Length (include carbon zones) Cross Section Area Pore Volume / Soil Zone Treatment Zone Spacing

Voltage Gradient Current Density EO Conductivity (kJ Power Consumption Resistivity

cm cm2 cm3 cm

V/cm A/m2

cm2/sec-v kwhr/m’-pv

ohm-cm

18 81 173 6

118 3,030 43,130

36

1 1 1.1 2.0

5.0 x lo6 5.6-10.6 x

24 200 4,700 5,100

6.6 37 249

6

1 1.8

1.1-2.1 8.3 1.1 ~


T a b l e 4 . Model Parameters

Parameter Value

porosity, n 0.4

thermal conductivity, k 1.2 w rn-lK'

electrical conductivity, so (20OC) 0.024 S m-l

Pore fluid viscosity, m ( 2 0 ° C ) 0.001 kg rn-l s-' soil density, r 1970 kg rn-' soil heat capacity, c 1870 J kg''R'

water density, r,, 1000 kg rn-3

water heat capacity, c, 4180 J kg-'K-l

electro-osmotic permeability, k, (20OC) 1.2 x 10" m2 s-l

F-1'7

F. Topical Report oFTasksC3 & 10 (bnt'd)

Figure 1..

Horizontal Confi,pration

borehole

ground surface r s 4 Granular Electrode

I I Degradation Zone

A

I

Vertical Configuration

Degradation contaminated Degradation Zone soil Zone

&&: electroosmotic flow is reversed upon switching electrical polarity.

F-18

Y 'I+

$ . E c I *z

' 0 c F P

I I I I I I I I I I I

tr 3

I I I I I I I I I I I

I N W

0

I

r 5-

I t

b ' I C

+E 1 I

3 i)


Figure 3. Pilot unit showing two steel plate electrodes with sand/carbon zones in front and two sandcarbon zones in the middle of the unit.

SandKarbon Zones I / I I

17.5" + I I

1/4" Steel Plate

Electrode

1/4" Steel Plate Electrode

F-2 0


F-2 1

Figure 5. Voltage Gradients and pH Profile for Paducah Soil with Two GAC Treatment Zones

Distance from Anode (in)


(p) WJJW

s .c,

51 E

t3

W E cp

0 0 o m * M

0 0 M

0 0 0 m o m m c u -

0 0 d

0 m o

E 't; 0

n

v! 0

0

0 0 0

0 0 0 0 0 0 0 0 0 1 O o ~ ~ m T l =

0 0 0 0 m m -

F-23

0 0 d

0 00

0 c\l

0

Figure 7. Cation Concentrations and Specific Conductance of Cathode Zone Flu

a -6000 E - 5000 d 3

Q € e o - 4000 0 -+ o m 3 0- -3000 a-

yl u

-2000 m

600 700 T c e 0 'I 500 3

Sodium

Calcium

Potassium

-t- Conductiv

a d

Htt 0 J . m d d

. . . . . . . . . . I .

v m h m d d d d

8000

[ 7000

t roo Water Exchange - Pore Volumes

Figure 8. pH vs Time for Pilot Run with 1 GAC Treatment Zone

13.k

+Zone A (Amode)

+Zone C (Treatment Zone)

+Zone E (Cathode)

+Effluent 8.

7.

6.

5. c

4.d I I I I I I I I

I I I I I I I I t

0 10 20 30 40 50

Time (Days) 60 70 80 90

n L c u 2

B ii 0

Figure 9. Effect of Voltage Gradient on Electroosmotic Flow Rate for Paducah Soil

90

70 60 50 40 30 20 I O 0

ao

0.0 0.2 0.4 0.6 Vo I tag e G rad ie n t (vk m)

0.8

F. ToDical Rmrt of Tasks 8 & 10 (Cont'd)

c1 0 Q m 0 z 0

c1

F

a 3 L

0 cc)

i i=

m ii

F-27

60

50 0

Y 40

8 10

Figure 11. Model prediction of the maximum soil temperatures for three voltage gradients

T

t -60 V/m -+I20 V/m +240 V/m

o ! I I I I I I I

0 40 80 120 160 Time (days)

Figure 12. Model prediction of power input vs time for three . voltage gradients

600

500

- 400 3 L +60 V/m

-t- 120 V/m 0 4 - 2 4 0 V/m

300-9 ‘;J h) to a 2 0 0 -

I 0 0 Irl A I A

0 o t v I I I I I I

0 4 0 8 0 1 2 0 1 6 0

Time (days)

v)

J 0 >

0

i! I.

7 W 0 2

n

30

25

20

15

10

5

0 0

Figure 13. Effect of heating on electroosmotic flow as a .function of power input.

-60 V/m -+- 120 V/m +240 V/m

50 100

Time (days)

150 200

F. Topical Report &Tasks 8&10 Appendix A

Appendix A. Pilot Run #l Data

F-31

EO-1.N.S

F. Topical Report of Tasks 8&10 Appendix A

11/17/93 1315 11117193 1533

11/18/93 11:OS 11/18/93 1530 11/19/93 730 11119/93 1310 11/19/93 18:OO 1112w93 1005 11/22/93 710 11/22/93 13:lO 11/22/93 l e 0 0 11/23/93 8:15 11/23/93 1215 11/24/03 745 11/24/93 810 1 llW93 11 :25 11/24/93 1EOO 11/27/93 1423 11/29/93 7:30 11/30/93 730 11/30/93 1305 11/30/93 1430 12/1/93 1O:W 1 2 / w 725 12/2/93 9:15 12/2/93 1630 12/3/93 a00 12/-3 E00 lU(vo3 e 0 0 12/11193 1030 12/7/93 1330 12/8/93 8:30 12/8/93 1030 12/9/93 715 12/9193 l e 4 5 12/10/93 9:30 12110193 1430 12/11/93 9:30

12/15/93 11:00 12/16/93 1000 12/17/93 1515 12/20/93 lW45

12/21/93 1 1 : s 12/22/93 1215 12/23/93 13:40

11118193 730

12/13/93 lorn

iam/s3 1415

M 0.09 80 0.76 77 0.91 BB.6 1 .09 92.7 1.76 70.9 2.00 85.1 2.20 143 2.87 42.5 4.75 106.3 5.00 130.2 5.11 141.8 5.79 127.6 5.96 114 8.77 0 8.78 110.8 6.82 187 7.20 138 10.05 145 11.76 109

12.99 37.2 13.05 129.7

'13.88 111.6 14.76 81.5 14.83 143 15.14 s9.5 15.78 121 18.78 106.3

12.78 04.6

0.09 1.35 1 .e4 2.04 3.35 3.79 4.35 5.84 9.18 s.9

10.29 12.47 12.86 14.07 14.08 14.59 15.7

25.37 30.59 33.01 33.4

33.51 35.87 37.93 38.14 38.87 40.27 48.46

18.82 nvlrr-hH*

18.89 104.2 20.01 68

20.89 191 21.75 21.3 22.15 159 22.80 117 23.05 106 23.84 128 25.68 86.8 27.91 100 28.88 100 30.08 215 32.90 160 33.04 155 33.94 137 34.86 181

20.84 19.1

0.16 2.46 3.35 3.46 5.66 6.52

9.36 11.58 17.07 n.88 24.16 28.77 41.42 41.97 45.12 48.76

am

0.00 0.02 0.03 0.04 0.06 0.07 0.08 0.10 0.16 0.18 0.18 0.22 0.23 0.25 0.25 0.26 0.28 0.45 0.55 0.59 0 . 0 0 . 0 0.64 0.68 0.68 0.70 0.72 0.87

0.00 0.04 0.06 0.06 0.10 0.12 0.16 0.17 0.21 0.31 0.39 0.43 0.52 0.74 0.75 0.81 0.87

118.1 118.3 118.4 118 118

118.2 117.7 117.6 117.6 117.6 117.8 117.7 117.8 118.2 118.2 118.3 118.7 117.5 117.5 117.4 11 7.4 11 7.4 117.5 11 8.4 118.6 118.6 118.5 117.2 117.6 117.6 11 7.5 117.5 117.3 117.8 118.7 117.9 117.7 118

118.2 118.5 118.8

11 8.5 118.7

1187

117.9 117.9

149 88 84 82 97 102 10s 117 87 116 109 78 75 85 132 109 121 86 80 83 81

1 07 82 81 a% 92 e9 88

eo 40 87 66

95 93 83 88 (01 (01 $5 92 92 86 88

m

0.53 3.02 3.43 3.91 5.79 6.53 7.18 9.52 15.52 16.32 16.74 18.74 19.14 20.93 20.98 21.50 22.49 32.23 38.95 39.51 40.10 40.28 42.68 44.97 45.18 46.09 48.04 50.86

0.21 3.13 4.44 4.53 8.74 7.74 9.69 10.43 12.75 18.46 24.14 26.90 30.49 38.81 39.23 41.79 44.57

8.54E-OB 8.21E-08 9.43E-06 9.8oE-06 7.57E-OB 9.W-06 1.53E-05 4.56E-06 1.14E-05 l.loE-05 1.52E-05 1.37E-05 1.22E-05

O.OOE+OO 1.18E-05 2.1OE-05 1.47E-05 1.56€-05 1.17E.05 1.02E.05 3.89E-06 1.m-05 1.2DE-05 8.8BE-06 1 .%?€-os 6.32E-06 1.X-05 1.14E-OS

1.12E-05 7.3oE.06 2.oM-08 2.05E-05 2.s-06 l.WE-05 1.2sE-05 1.14E-05 1.37E-05 1.03E.05 1.0gE-05 1.06E-05 2.rn-05 1.7oE-05 1 . a - 0 5 1 .a-05

0.149 0.243 0.293 0.314

0.232 0.378 0.101 0.339 0.312 0.361 0.449 0.422 O.Oo0 0.233 0.502 0.317 0.420 0.378 0.317 0.128 0.337 0.378 0.279 0.405 0.180 0.340 0.336

0.273 0.315 0.133 0.547 0.090 0.470 0.342 0.317 0.382 0.313 0.305 0.305 0.629 0.483 0.468 0.432

0.203

0 16.92 95.92

108.78 124.04 183.70

228.04 302.43 490.03 519.40 532.69 588.33 609.16 666.04 667.75 m . 0 7 715.61

1024.76 1175.52 1257.02 1276.10 1281.05 1358.43 1431.16 1437.89 1466.69 1528.37 1808.87

0 6.63

100.00 141 .67 144.52 214.86 248.05 308.67 332.17 405.79 587.90 787.36 854.57 967.91

1230.86 1244.30 1325.23

207.20

1.72E-05 0.520 1413.74 36.02 167 52.93 0.85 117.5 85 47.41 1.7s-05 0.546 1504.28

I I 107.51 128.26 1176s mvh

I I I

F-32

PlVoLTS.xLS

F. Topical Report of Tasks 8&10 Appendix B

Appendix B. Pilot Run #2 Data

PNP Movement Experiment

F-34

PILOTZ.XJ.0

Rl PILOT WIT R FLOW DATA

P O m Rl cwml ud cm&d. ImAl O*lrlm31 bmllro*v) 187.0 112.0

Aor M b

InMV) .cn 33.6 102.4 83.0 117.3 177.2 18.0 lW.2 187.3 210.0 100.0 100.7 aM.0

o&l W.8 113.9 92.9 101.4 107.2 107.2

04.0 111.2 100.6 116.7 126.7

w.3 114.8 1m.2 110.1 133.9 1m.9 128.1 06.0 zoo. 4 1W.O 211.1 186.4 wan 1W.O lQ.4 110.8 101.9

PH

C

.1

8.4

8.4 8.6

6.4

6.9

0.3

0.4

I - I

I

I

I

I

8.3 I

.L

9. 2 ... I

I

8.1

8.4 I

n ... I

I

8.4

8.3

8. 1

n

8.8

8.8 8.8

8.6

-w IUSlCm) Pm.

V a . p .

119.6 110.7 119.9 117.0 117.3 117.2 117.6 117.2 117.4 118.1 116.6 116.7 116.4

110.0 117.0 119.1 118.1 118.0 117.8

117.0 111.9 116.3 110.7

121.9 110.7 119.2 119.1 110.2 118.3 118.3 118.1 119.4 110.7 118.7 110.1 118.9 119.2 110.3 110.0 118.4

E

i

u)8

642 i

mz 1

861 1

476 1

w

267 1

m

1

161 1

1

333 n 1

1

128

78 1

1

1

1

1

i ie 1

662

840

636

728 872

341

me nm 1120194 1C30 1120194 13:m 1127194 16:30 1120194 le16 1131191 em 111194 1216 U m b 1130 1E11011216 ?NIo1 labs 218194 1*00 117194 e30 MloI la46 M194830

1 1 1 m e00 U 1 W 1816 1111194 1600 1112194 1230

11lu81 e30 i l 1 W e30 1116f94~bs 2/1619411:46 1118194E00 U17f94800 ulwoIo:l6

1110194 10:40 11?woI 11:40 11- 12:lO U21194 e:& U21191 846 1123191846 112bmb 1200 2l?wo4 13:00 wmm e26 WlI(L(I46 311191 e00 313101 13:m 3fw E30 317194 e36 37194 1240 3mob e30 319194E16 3 1 m 1GU 3111191 1C66

ui3m i3:m

aiom 830

n m ( 0 4

0.13 1.21

4.96 8.07 7.01 8.07 9.01 11.16

13.01 13.02

r- 0.30 1.26 2.16 3.17 4.02 I02 6.43 6.11 6.00 8.W 8.01 8.W 9.40 10.11 10.13 11.45 1l.W

14.13 16.11 10.02

m.OO 21.19 21.01 26.02 26.16 2e.M 21.01 28.07 29.08

1.m

11.00

1a.m

i8.m

N(kmc

I

I

I

9.2 10.2

10.4 I

I I

I

10.9

11.3 I

I

II.

I n * L

I

-. I

I

I

I

I

11.2 m

I

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F. ToDid R m r t of Tasks 8&10 ADDendix B

PNP Analysis for Contaminated Clod After 1 Pore Volume

ug PNP/ g wet Sample N e w PS PNP clay % removal 0" I .04 0.0000 0.00 100.00%

0.54 0.38 0.47 0.28 0.35 0.24 0.26 0.35 0.85

Average 98.44%

1 2l 3" 4' 5" 6 7" 8" 9"

0.0000 0.6453 1.6234 1.2697 I .0790 2.0788 3.2263 5.431 3 7.1452

0.00 1.70 3.45 4.53 3.08 8.66 12.41 15.52 8.41

100.00% 99.54% 99.07% 98.77% 99.1 7% 97.66% 96.65% 95.8 1 % 97.73%

C interface Zone D 2" down Zone 04" down

B @ C # I B @ C # 2

0.57 0.75 0.8 0.44 0.6

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F-39

F. Topical Report of Tasks 8&10 Appendix C

Appendix C. Pilot Run #3 Data

Paducah Soil, 1 Voltlcm

F-40

F. Topical Report of Tasks 8&10 Appendix C

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F. Topical Report of Tasks 8B10 Appendix C

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F-45

F. Topical Report of Tasks 8&10 Appendix D

Appendix D. Pilot Run #4 Data

Paducah Soil, 1/2 Volt/cm

F-4 6

PILOT4.XLS

6/7/94 925 m94 7:45 6/9/94 750 6/10/94 7:40 6/13/94 810 6/14/94 1455 6/15/94 8:00 6/17/94 900 6/2m 8:00 6/29/94 1325 6/22/94 900 6tz3/94 8:H) 6/24/94715 6/27/94 800 6n8/94 800 6/29/94 11:00 m/94 855 7/1/94 720 7/5/94 13:00 7/6/94 9 00 7 n m 630

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60.5 R 3 84.0 25.5 25.0 15.0 50.0 15.0 20.0

15.0 10.0 10.0 15.0

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0.04 59.9 350.3 0.07 59.9 345.3 0.11 59.4 338.5 0.14 59.7 335.5 0.19 60.2 325.7 0.20 59.8 322.7 0.21 59.9 322.7 0.25 60.0 3227 0.28 60.3 320.7 0.29 59.9 305.0 0.30 60.2 295.2 0.31 60.3 287.3 0.31 60.2 284.3

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0.33 60.3 277.5

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70.4

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7/8/94 700 31.98 50.0 24.25 0.56 60.7 284.3 131.2 8.92E-06 0.049

I d rebav DI*M anldy) (m)

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0

Tsmp. (acre) 23.2 24.1 24.4 24.4 24.6 24.4 24.5 23.4 24.8 24.7 23.4 22.1 20.9 20.5 19.5 20.5 21.8 22.1 22.1 24.1 24.5 24.1 23.9

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574 233 1415 1219 400

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670 245 1805 711 76 - 250 2190 675 80 - 288 1965 518 120

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1080 424 867 167 474

703 488 758 279 451

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F. Topical Report &Tasks 8&10 Appendix D

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Time (days)

F. Topical Report of Tasks 8&10 Appendix E

Appendix E. Pilot Run #5 Data

Paducah Soil, 1 Treatment Zone

F-52

a s 1.34 1.74 2.23 2.78 3.38 4.12 8.97 6.10 9.63 11.02 12.82 16.M 16.W 17.91 16.87 20.39 22.67 23.00 26.13

27.66

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88.78

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296.9 289.8 301.8 312.3 316.7 319.0 323.0 3m.7

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development of the integrated, in-situ remediation

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