Short Course

BASICS AND APPLICATIONS OF
ELECTROKINETIC REMEDIATION
Handouts Prepared for a

Short Course
Universidade Federal do Rio de Janeiro (COPPE-UFRJ)

Federal University of Rio de Janeiro
By
Akram N. Alshawabkeh, Ph.D., PE
Department of Civil and Environmental Engineering
400 Snell Engineering Center
Northeastern University
360 Huntington Avenue
Boston, MA 02115
Phone (617) 373-3994
Fax (617) 373-4419
Email: aalsha@neu.edu
19-20 November 2001

Rio de Janeiro, Brazil
1
Short Course
Basics and Applications of Electrokinetic Remediation
Akram N. Alshawabkeh, Ph.D., PE
TABLE OF CONTENTS
SECTION 1: INTRODUCTION AND OVERVIEW 3
SECTION 2: THEORETICAL BASIS FOR

ELECTROKINETIC REMEDIATION 18
SECTION 3: PRACTICAL ASPECTS OF 1D AND 2D

ELECTROKINETIC REMEDIATION 35
SECTION 4: FIELD DEMONSTRATION 59
SECTION 5: POTENTIAL ENHANCEMENT OF BIOREMEDIATION

BY ELECTROCHEMICAL METHODS 75
LIST OF REFERENCES:
2
SECTION 1
INTRODUCTION AND OVERVIEW
The use of electric fields is an innovative method for in situ restoration of contaminated hazardous
waste sites. Direct currents (DC) are applied across electrodes inserted in the soil to generate an
electric field for mobilization and extraction of contaminants and for bio-geochemical modifications
of polluted soils and slurries. The driving mechanisms for this technique, known as electrokinetic
remediation, are transport under electric fields (in particular electroosmosis and ionic migration)
coupled with electrolysis and geochemical reactions. Extraction and removal are generally achieved
by electrodeposition, precipitation or ion exchange (for heavy metals) and collection and treatment
of organics in external systems. Contaminants that could be treated by electric field applications
include inorganic, organic, and radioactive compounds that are charged (ionic) or non-charged (polar
and non-polar). The major advantages of the technology include: (a) it can be implemented in situ
with minimal disruption, (b) it is well suited for fine-grained, heterogeneous media, where other
techniques such as pump-and-treat can be ineffective, and (c) accelerated rates of contaminant
transport and extraction may be obtained.
This short course provides a review of the fundamentals and applications of electrokinetic
remediation. The course describes the role of clay mineralogy, general electrokinetic and transport
phenomena in soil under electric fields, followed by identification of electrolysis and geochemical
reactions associated with application of electric fields in soils. Current technology status and
considerations for practical implementation of the technology are presented. The short course also
describes the potential for enhancing bioremediation of organic contaminants by eletrochemical
methods
Soil and Groundwater Contamination in the US
Soil contamination is a major threat to groundwater resources in the US and around the world. Soil
and groundwater contamination is a result of decades on misuse and mishandling of earth resources.
Many federal and state agencies, and private companies have contributed to the problem. In the US,
activities by the Department of Defense and the Department of Energy caused significant soil
contamination with organics (such as chlorinated solvents), heavy metal (such lead and chromium),
and radionuclides. Contamination problems caused by other parties include pesticides, heavy metals
and petroleum contamination among others. It estimated that there are more than 40,000
contaminated sites in the US, out of which, about 1,450 sites are listed on the National Priority List.
The estimated cost for remediation is more than $ 350 Billion and the estimated cost for cleaning
the NPL sites is about $ 40 Billion. Management and remediation of is challenging due to the
difficulties in locating contamination, site characterization, evaluation of the extent of
contamination, and risk assessment.
In situ remediation of low permeability clayey soils that exhibit sorption capacity is a difficult task
in managing contaminated sites. The low permeability of such soils limits extraction of the pore fluid
or contaminants by hydraulic gradients. The sorption capacity prevents solubilizaion of the
contaminants and therefore their bioavalibility or their transport. The microstructure and
composition controls transport and reactive processes of contaminants in clays. A brief description
3
of clay mineralogy and its impact on transport and contaminant fate in the subsurface is provided.
Clay Mineralogy
Clay minerals occur in small particle size and are formed of repetitive layers of unit cells. The cells
consist of 2,3 or 4 structured sheets of tetrahedral and octahedral units. The sheets are stacked on
top of each other such that the stacking is repetitive in each layer. The two basic units (Figure 1.1)
of layer silicates are (a) Silica Tetrahedron – a silicon ion is tetrahedrally coordinated with four
oxygens, and (b) Aluminum (Al) or Magnesium (Mg) Octahedron – Al or Mg ion is octahedrally
coordinated with 6 oxygens or hydroxyls. Table 1.1 lists properties of three common minerals
(kaolinite, montmorillonite and illite) in geotechnical engineering. Generally, three criteria can be
considered for classification of clay minerals:
1. The height of the unit cell or “thickness of layer”
2. Composition, whether “dioctahedral” or “trioctahedral” and ionic content of layer.
3. Stacking segments of layers and degree of orderliness of stacking.
Factors that define the geoenvironmental engineering behavior of clays include fabric/structure,
cation exchange capacity, organic content and specific surface area. Fabric is the arrangement of
particles, particle groups and pore spaces in a soil. Structure is the combined effect of fabric,
composition and interparticle forces. For example, the variation of the hydraulic conductivity of clay
is an outcome of the type of clay microstructure.
Generally, discrete clay particles have a negative surface charge that influences and controls the
particle environment. This surface electric charge can be developed in different ways, including the
presence of broken bonds and due to isomorphous substitution1 (Mitchell 1993). The quantity of this
surface charge varies from mineral to mineral and is affected by pore fluid environment. Figure 1.2
displays the effect of pH on the surface charge of kaolinite and montmoriloonite. Decreasing the pH
reduces the value of the negative surface charge (and may also cause surface charge reversal).
The clay particle-water-electrolyte system is usually considered to consist of three different zones;
the clay particle with negatively charged surface, pore fluid with excess positive charge, and the free
pore fluid with zero net charge. The net negative charge on the clay particle surfaces requires an
excess positive charge (or exchangeable cations) distributed in the fluid zone adjacent to the clay
surface forming the diffuse double layer (Figure 1.3). The quantity of these exchangeable cations
required to balance the charge deficiency of clay is termed the cation exchange capacity (CEC), and
expressed in milliequivalents per 100 grams of dry clay.
Several theories have been proposed for modeling charge distribution adjacent to clay surface. The
Gouy-Chapman diffuse double layer theory has been widely accepted and applied to describe clay
behavior. A detailed description of the diffuse double layer theories for a single flat plate is found
1 Isomorphous substitution is the substitution of ions of one kind by ions of another type, with the same or different
valence, but with retention of the same crystal structure. (e.g., Al in place of Si; Mg instead of Al and Fe(II) for Mg)
(Mitchell 1993)
4
in Hunter (1981), Stumm (1992), Mitchell (1993), and Yeung (1993). The Gouy-Chapman theory
(1910-1913) is considered the most successful theory that describes the diffused double layer. A
brief description of the theory is provided.
Poisson equation describes the relationship between the potential and charge, given by
d2
=−
dx 2
Where x is the distance from the surface (m), ψ is the electric potential (V), ρ is charge density
(C/m2) and ε is the dielectric constant of the medium (C2 J-1 m-1). The charge density of the ions in
the double layer is
= e ∑ zi n i
where e is the electronic charge (1.6 x 10-19 C), zi and ni are the charge and concentration of ith ion,
respectively. The concentration of the cations and anions in the double layer is given Boltzmann
distribution,
ze
−( )
n + = n 0e kT
ze
( )
n − = n 0e kT
where no: ionic concentration (ions/m3) in the free pore fluid,

k: Boltzmann Coefficient (1.38x10-23 J ko)
T: Temperature (ko)
Accordingly, for a simple case of monovalent ions,
  − e   e   e 
= en 0 e  kT  − e  kT   = −2 en 0 sinh  
   kT 
Substituting ρ into the Poisson Equation,
d2 2n e e 
= 0 sinh  
 kT 
2
dx
Solving the potential distribution equation for boundaries (ψ=ψ0 at x=0 and ψ =0 as x →∞) and then
5
simplifying yields the following distribution,
= 0 e (− Kx )
which is known as the Debye-Huckel Equation and the normalized value of (1/K) represents the
characteristic thickness of the double layer (known as Debye Length),
1/ 2
1  N7 
=  
K  8 Q o z 2 e 2 
The Debye length is inversely related to the cations valence and concentration of free pore fluid. As
shown in Figure 1.4, cations of higher valence will reduce the thickness of the double layer (Debye
length). Also increasing the pore fluid electrolyte concentration will reduce the Debye length
(Figure 1.5). Stern (1924) evaluated the impact of ion size and pH on the double layer thickness.
As pH increases, the thickness (1/K) increases. As ion size increases, (1/K) increases.
An important characteristic of the double layer is the value of plane of shear potential, known as zeta
potential (Figure 1.6). The value of zeta is less than the surface potential of the particle and
represents the value at the slip plane, which located at a small unknown distance from the clay
surface.
Electrokinetic Phenomena in Soils
Electrokinetics is defined as the physicochemical transport of charge, action of charged particles,

and effects of applied electric potentials on formation and fluid transport in porous media. The
presence of the diffuse double layer gives rise to several electrokinetic phenomena in soil, which
may result from either the movement of different phases with respect to each other including
transport of charge, or the movement of different phases relative to each other due to the application
of electric field. The electrokinetic phenomena include electroosmosis, electrophoresis, streaming
potential, and sedimentation potential. Electroosmosis is defined as fluid movement with respect to
a solid wall as a result of an applied electric potential gradient. In other words, if the soil is placed
between two electrodes in a fluid, the fluid will move from one side to the other when an
electromotive force is applied. Electrophoresis is the movement of solids suspended in a liquid due
to application of an electric potential gradient. Streaming potential is the reverse of electroosmosis.
It defines the generation of an electric potential difference due to fluid flow in soils. Sedimentation
(or migration) potential, known as Dorn effect (Kruyt 1952), is an electric potential generated by the
movement of particles suspended in a liquid. Figure 1.7 displays the electrokinetic phenomena in
soils.
6
Under certain conditions (such as presence of appropriate mineral, high water content and low ionic
strength of pore fluid), electroosmosis will have a significant role in electrokinetic soil remediation.
Several theories are established to describe and evaluate water flow by electroosmosis including
Helmholtz-Smoluchowski theory, Schmid theory, Spiegler friction model, and ion hydration theory.
Descriptions of these theories are given in Gray and Mitchell (1967) and Mitchell (1993).
Helmholtz-Smoluchowski model is the most common theoretical description of electroosmosis and
is based on the assumption of fluid transport in the soil pores due to transport of the excess positive
charge in the diffuse double layer towards the cathode. The rate of electro-osmotic flow is controlled
by the coefficient of electro-osmotic permeability of the soil (ke), which is a measure of the fluid flux
per unit area of the soil per unit electric gradient.
The value of ke is assumed to be a function of the zeta potential of the soil-pore fluid interface, the
viscosity of the pore fluid, soil porosity, and soil electrical permittivity. When the soil pores are
treated as capillary tubes, the coefficient of electroosmotic permeability is given by,
ke = n
where ζ is the zeta potential (V), n is the porosity, and η is the viscosity (FT/L2). While hydraulic
conductivity, kh, is significantly influenced by the pore size and distribution in the medium (Acar
and Olivieri 1989), the electroosmotic coefficient of permeability, ke, according to the Helmholtz--
Smoluchowski theory is dependent mainly on porosity and zeta potential. The value of ke has been
assumed to be constant during the electrokinetic process as long as there is no change in the
concentration of ions or pH of the pore fluid.
Extensive research has been carried out on the zeta potential of the glass-water interface. There is
a good qualitative agreement in the results of different studies. Hunter (1981) in a detailed
description of theoretical and experimental treatise of the zeta potential in colloid science, displays
the effect of pH and ion concentration in the pore fluid on zeta potential.. The effect of electrolyte
chemistry on zeta potential could therefore represented by (Kruyt 1952),
= A - B log C o
where A, and B are two constants that are evaluated experimentally, and Co (M/L3) is the total
electrolyte concentration.
It is hypothesized that the drop in pH of the soil due to electrokinetic processing will cause a
decrease in the coefficient of electro-osmotic permeability associated with the drop in zeta potential;
hence, the electroosmotic flow will start to decrease and eventually stop at later stages of the
process. The results of Acar et al. (1989), Hamed et al. (1991), and Acar et al. (1993) demonstrate
the decrease and cessation of electroosmosis upon continued testing. Consequently, the ke value
determined in one--dimensional tests is time--dependent and controlled by the chemistry generated
at the electrodes.
7
Vane and Zang (1997) investigated the effect of pore fluid properties on electroosmostic
permeability. The results displayed that the effect of pH on zeta potential and electroosmostic flow
vary significantly depending upon the mineral type. Lockhart (1983) demonstrated that high
electrolyte concentration in the pore fluid causes strong electrolyte polarization which limits
electroosmotic flow. At a certain pH value and pore fluid ionic strength, the soil surface charge
could drop to zero rendering a zero zeta potential or what is called the iso-electric point (Lorenz
1969). Negative surface charge of clay particles (negative zeta potential) causes electroosmosis to
occur from anode to cathode while positive surface charge causes electroosmosis to occur from
cathode to anode (Eykholt 1992; Eykholt and Daniel 1994). The electro-osmotic flow can virtually
be eliminated at the iso-electric point.
Ion Migration
Electric currents occur in soils due to ion migration, which is the transport of charged ions in the
pore fluid toward the electrode opposite in polarity. The ionic mobility is a term used to describe the
rate of migration of a specific ion under a unit electric field. A similar term is used in soils, but to
account for soil porosity and tortuosity, the term is modified to “effective” ionic mobility. Rates of
contaminant extraction and removal from soils by electric fields are dependent upon the values of
the effective ionic mobilities of contaminants. Heavy metal ionic mobilities at infinite dilution are
in the range of 10-4 cm2/Vs. Accounting for soil porosity and tortuosity, the effective ionic mobilities
are in the range of 10-4 to 10-5 cm2/Vs. Accordingly, the rate of heavy metals transport in clayey soil
is about few centimeters per day under a unit electric gradient (1 V/cm). As a result of ion migration
in the soil pores, cations are collected at the cathode and anions at the anode.
In summary, application of electric gradients in soil will result in two significant transport
mechanisms; electroosmosis and ion migration. Electroosmosis draws contaminants with the flowing
water under electric fields. Ion migration transports ions to the electrode opposite in polarity under
electric fields. Electroosmosis and any other hydraulic flow will usually carry all types of solutes
from one location to another, depending on flow direction. However, ion migration separates
negatively and positively charged ions and cause their migration to opposite electrodes.
Consequently, hydraulic flow might enhance the migration of certain ions, but retard migration of
other ions (with opposite charge). The relative contribution of electroosmosis and migration to ion
transport under electric fields varies for different soil types, water content, type of ion, pore fluid
chemistry, and boundary conditions.
Electrolysis
Application of direct electric current through electrodes immersed in water induces electrolysis
reactions at the electrodes. Oxidation of water at the anode generates an acid front while reduction
at the cathode produces a base front as described by the following electrolysis reactions,
2H2O - 4e- O2 + 4H+ (anode)

4H2O + 4e- 2H2 + 4OH- (cathode)
The prevailing of electrolysis reactions at the electrodes depends on the availability of chemical
8
species and the electrochemical potentials of these reactions. Although some secondary reactions
might be favored at the cathode because of their lower electrochemical potential, the water reduction
half reaction (H2O/H2) is dominant at early stages of the process. Within the first few days of
processing, electrolysis reactions drops the pH at the anode to below 2 and increase it at the cathode
to above 10, depending upon the total current applied (Acar et al., 1989; Acar et al., 1990; Acar and
Alshawabkeh 1993). Studies (Hamed et al., 1991; Probstein and Hicks 1993; Eykholt and Daniel,
1994; Yeung and Datla, 1995) showed that while acid production enhances the process development
of a high pH zone at the cathode adversely impacts extraction of heavy metals from soils.
Soil pH and Geochemical Reactions
While the acid generated at the anode advances through the soil toward the cathode by ionic
migration and electroosmosis, the base developed at the cathode initially advances toward the anode
by diffusion and ionic migration. However, the counterflow due to electroosmosis retards the
back-diffusion and migration of the base front. The advance of this front is slower than the advance
of the acid front because of the counteracting electro-osmotic flow and also because the ionic
mobility of H+ is about 1.76 times that of OH-. As a consequence, the acid front dominates the
chemistry across the specimen except for small sections close to the cathode (Acar et al., 1990;
Alshawabkeh and Acar 1992; Probstein and Hicks 1993; Acar and Alshawabkeh 1994).
Geochemical reactions in the soil pores significantly impact electrokinetic remediation and can
enhance or retard the process. Precipitation and sorption of heavy metals prevent their transport and
thus limit extraction. Complexation could reverse the charge of the ion and might reverse direction
of migration. These geochemical reactions, including precipitation/dissolution, sorption, redox and
complexation reactions are highly dependent upon the pH condition generated by the process. The
advance of the acid front from anode toward the cathode assists in desorption and dissolution of
metal precipitates. However, formation of the high pH zone near the cathode results in
immobilization to precipitation of metal hydroxides. Limitations of electrokinetic remediation due
to catholyte high pH required seeking innovative methods to enhance the technique and prevent
immobilization of metals close to the cathode.
9
Table 1.1. Characteristics of Kaolinite, Illite and Montmorillonite
Kaolinite (1:1 mineral)

Octahedral Sheet: Gibbsite (dioctahedral, Al)
Bonding: Hydrogen bond and Van der waals bond
Basal Spacing: 7.2 D
Particle size: ~ 0.2 – 2 micrometer
Cation Exchange Capacity: 3 – 15 meq/100g
Specific Surface Area: 10 – 20 m2/g
Shape: 6-sided thick (bulk) plates
Atterberg Limits LL (30 – 110); PL (25 – 40)
Compression Index (Cc): 0.19 – 0.28
Coeff. of Consolidation (Cv) 12 – 90 x 104 cm2/s
Occurrence: Common
Isomorphous Substitution: One Si in each 400 by Al
Smectite (Montmorillonite) (2:1 mineral)

Bonding: Van der waals bond and exchangeable cations
Basal Spacing: 9.6 - 4 D
Particle size: ~ 0.1 micrometer
Cation Exchange Capacity: 80 – 150 meq/100g
Specific Surface Area: up to 700-840 m2/g
Shape: Thin flakes like films
Atterberg Limits LL (100 – 900); PL (50 – 100)
Coeff. of Consolidation (Cv) 0.06 – 0.3 x 104 cm2/s
Occurrence: Common
Isomorphous Substitution: In every 6 Al by one Mg; In 15% of Si by Al
Illite (2:1 mineral)

Bonding: K ions (R= 1.33 D, R. of Hexagonal hole = 1.32 D)
Basal Spacing: ~ 10 D
Particle size: ~ 0.1 – 0.2 micrometer
Cation Exchange Capacity: 10 – 40; if no K: up to 150 meq/100g
Specific Surface Area: 65 - 100 m2/g
Shape: Flakes
Atterberg Limits LL (60 – 120); PL ( 30 – 60)
Coeff. of Consolidation (Cv) 0.3 – 2.4 x 104 cm2/s
Occurrence: Common
Isomorphous Substitution: 1/4 Si replaced by Al; charge is balanced by K; 9-10% K2O
10
Figure 1.1 Basic Unit of Layer Silicates (Mitchell, 1993)
11
pH
0 2 4 6 8
0.2
Montmorillonite
Kaolinite
0.1
Surface Charge (C/m2)
-0.1
-0.2
Figure 1.2 Effect of pH on the Surface Charge of Montmorillonite and Kaolinite
12
++-
Clay +-+-+
Particle
surface
++-+-
+++-+
+-++-
++-+
Double layer
Conc. thickness
Cations
Anions
Distance from clay surface
Figure 1.3 A Schematic of Charge Distribution at the Clay Surface
13
Figure 1.4 Effect of Cation Valence on Charge Distribution in the Diffuse Layer
14
Figure 1.5 Effect of Free Pore Fluid Concentration on the Double Layer Potential Distribution
15
Moving
Potential (mV) particle
plane
ψ0
ζ
Distance
Figure 1.6 Potential Distribution Showing the Slipping Plane (Zeta) Potential
16
E ( DC ) E ( DC )
Saturated Saturated
Clay Clay
(a) Electric Gradient (c) Electrical Gradient

Induces Water Flow Induces Particle Movement
Particle
Movement
E E
Saturated
Clay
(b) Water Flow Induces (d) Particle Movement

Electric Potential E Induces Electric Potential
Figure 1.7 Electrokinetic Phenomena in Soil
17
SECTION 2
THEORETICAL BASIS FOR ELECTROKINETIC REMEDIATION
Theoretical understanding and simulation of the electrokinetic treatment demand a grasp of the
mathematical formulation of transport processes, which are controlled by such variables as
electrolysis reactions at the electrodes, pH and soil-surface chemistry, equilibrium chemistry of the
aqueous system, electrochemistry of the contaminants, and geotechnical/hydrological characteristics
of the porous medium. The complexity of transport processes necessitates simplifying assumptions
which would allow adequate numerical simulation. The following assumptions are employed in the
theoretical development presented in this section: (1) The soil medium is isotropic and saturated, (2)
The porous medium is a solid framework of cation exchange surfaces with the pore space occupied
by chemically reactive species in aqueous solution, (3) All fluxes are linear homogeneous functions
of all driving forces (or potential gradients), (4) Isothermal conditions prevail (coupled heat transfer
is neglected), (5)All the applied voltage is effective in fluid and charge transport, (6) Electrophoresis
is not present,(7) The chemicoosmotic coupling is negligible, (8) Soil particles are treated as
electrically nonconductive (insulators), (11) Surface conductance and streaming potential are
negligible. Based on the assumptions, theoretical formulations are provided for transport
mechanisms under electric fields. Contaminant transport mechanisms include hydraulic or fluid
flow, species or mass transport, and charge transport. Following is a description of these transport
mechanisms.
Fluid Flux
Fluid flux result from application of a hydraulic gradient (Darcy’s law), an electric gradient
(electroosmosis) and/or a chemical gradient (chemicoosmosis). Chemicoosmosis could be neglected
because it is significant only in the presence of large chain molecules and in very active clay deposits
(activity describes plasticity of the soil and equals plasticity index divided by clay fraction in
percentage). Fluid flux per unit area of the porous medium due to hydraulic and electric gradients,
Jw (L3L-2T-1), is given by,
J w = k h ∇(− h) + k e ∇(−Φ)
where kh is the coefficient of hydraulic conductivity (LT-1), ke the coefficient of electroosmotic

permeability (L2 V-1 T-1KLVWKHK\GUDXOLFKHDG/DQG LVWKHHOHFWULFSRWHQWLDO9
Extensive research has been carried out on the hydraulic conductivity of fine-grained soils with a
relatively good understanding of the fundamental factors affecting its value (Mitchell 1956; Olson
and Daniel 1981; Boynton and Daniel 1985; Acar and Olivieri 1989; Daniel 1989). These studies
indicate that microstructure and fabric are the factors that highly influence fluid transport in
fine-grained deposits. Other factors affect kh include soil porosity and pore size distribution.
Presence of uniformly distributed fine size pores result in lower hydraulic conductivity while
presence of few macro pores result in higher hydraulic conductivity even if soil porosity is the same
18
in both cases. Figure 2.1 shows two different microstructures and pore size distributions that
produce two different hydraulic conductivities even at the same porosity.
Electrokinetic soil remediation induces changes in the pore fluid chemistry, diffuse double layer, soil
fabric and consequently the hydraulic conductivity. Furthermore, electroosmotic consolidation is
expected to take place and influence the hydraulic conductivity value. In attempting to provide a
mathematical formulation of electrokinetic soil remediation, hydraulic conductivities are generally
assumed to be constant in time and space because; (a) there is no clear mathematical formalism that
can describe the effect of pore fluid chemistry on soil fabric and consequently the hydraulic
conductivity, and (b) the uncertainties in evaluating the hydraulic conductivities are more significant
than the changes expected in its values.
Contribution of each component due to hydraulic and electric gradients is dependent upon the ratio
of coefficient of electroosmotic permeability relative to hydraulic conductivity (ke/kh). Soil type,
microstructure, and pore fluid conditions are the factors that impact this ratio. In course-grained soils
this ratio is very small and goes to zero due to almost nonexisting electroosmotic flow and relatively
high hydraulic conductivities ( > 10-3 cm/sec) of such soils. On the other hand, in soft, fine-grained
soils the ratio of (ke/kh) becomes significant as ke is usually in the order of 10-5 cm2/V.sec while kh
is less than 10-5 cm/sec (10-7 cm/sec for clayey soils).
Mass Flux
Mass flux of different chemical species relative to pore fluid is a result of different coupled potential
gradients. Hydrodynamic dispersion is mass transport due to a chemical concentration gradient.
Migrational mass flux is mass transport of charged species to electrode opposite in polarity due to
an electric potential gradient. Filtration or ion sieving is mass transport due to a hydraulic gradient.
Total mass flux of dissolved species also includes the advective component due to species transport
by the flowing fluid.
Hydrodynamic dispersion is a result of two basic phenomena; mechanical dispersion and molecular
diffusion. While mechanical dispersion occurs as a result of velocity variation within the porous
medium, molecular diffusion is mass transport due to the difference in thermal kinetic energy of
the molecules. Mechanical dispersion is a significant mechanism in contaminant transport in ground
water (Perkins and Johnston 1963, Bear 1972) because of the relatively high hydraulic conductivity
and advective hydraulic flow in such deposits (higher than 10-5 cm/sec). On the other hand,
molecular diffusion is the primary process that controls hydrodynamic dispersion in clay deposits
due to the low advective hydraulic flow in these deposits. Therefore, only molecular diffusion is
considered in mass transport under concentration gradients.
The total mass transport of chemical species per unit cross-sectional in a saturated soil medium
under hydraulic, electric and chemical concentration gradients is described by,
J i = Di ∇(- ci ) + ci (u i + k e) ∇(-Φ ) + ci k h ∇(- h)

* *
19
where Ji (ML-2T-1) is the total mass flux of the ith chemical species per unit cross sectional area of
the porous medium, ci (ML-3) is the molar concentration of the ith chemical species, Di* (L2T-1) is
the effective diffusion coefficient of the ith chemical species, ui* (L2 T V-1) is the effective ionic
mobility of the ith species. Transport mechanisms included in are diffusion, ion migration,
electroosmotic advection and hydraulic advection. A schematic of mass transport of cationic and
anionic species is provided in Figure 2.2. Transport profiles are based on the assumptions that water
advection components (electroosmosis and hydraulic) act from anode to cathode. The advective flow
enhances transport of cationic species, which migrates from anode to cathode, and retards transport
of anionic species, which migrates from cathode to anode.
The effective diffusion coefficient in the porous medium, Di*, is related to the respective diffusion
coefficient in free solution, Di, by (Bear, 1972; Gillham and Cherry, 1982; Shackelford and Daniel,
1991),
*
Di = Di n
ZKHUH GLPHQVLRQOHVVLVDQHPSLULFDOFRHIILFLHQWDFFRXQWLQJIRUWKHtortuosity of the medium.

9DOXHVRI VSDQRYHUDZLGHUDQJHIRUdifferent saturated and unsaturated soils. Experiments are
often necessary to determine its value for a specific soil type. Shackelford and Daniel (1991)
VXPPDUL]HUHSRUWHG YDOXHVIRUGLIIHUHQWVRLOW\SHV7KHVHYDOXHVare as low as 0.01 and as high as
0.84, mostly ranging between 0.2 to 0.5. Diffusion coefficient for different ions at infinite dilution
are available in most electrochemistry handbooks and references. These values represent the
maximum values attained under ideal conditions. Many factors might affect the molecular diffusion
coefficient such as the electroneutrality requirement, concentration, and electrolyte strength
(Shackelford, 1991). Shackelford and Daniel (1991) investigate the effective diffusion coefficients,
D*, of different inorganic chemicals in compacted clay. Their results demonstrate that molding water
content and compaction methods have little effect, if any, on the effective diffusion coefficients.
Generally, changing molding water content in compaction tests result in significant changes in the
compacted soil microstructure (Mitchell 1993). According to results of Shackelford and Daniel
(1991) the change in compacted clay microstructure due to different molding water contents will
have little effect on the effective diffusion coefficient of different chemicals.
The effective ionic mobility, ui*, define the velocity of the ion in soil pores under unit electric field.
There is no method yet devised to measure the effective ionic mobility (Koryta 1982); however, ui*
can be theoretically estimated by assuming that Nernst-Townsend-Einstein relation between Di, the
molecular diffusion coefficient, and ui, holds for ions in the pore fluid of soils (Holmes, 1962);
*
* Di zi F
u = n ui =
i
RT
where ui is the ionic mobility of species i at infinite dilution, zi is the charge of the ith species, F is
Faraday’s constant (96,485 C/mol electrons), R is the universal gas constant (8.3144 J/K.mol), and
T is the absolute temperature. Note that each of ui in this case has a value and a sign that reflects the
20
charge of species i (i.e. the ionic mobilities and effective ionic mobilities, ui and ui* will have
negative values for anions and positive values for cations). The signs are included in the ionic
mobilities of cations and anions to simplify the mathematical equations.
Mass transport equation demonstrates that electrical gradient results in two mass transport
mechanisms, ion migration and electroosmotic advection. The relative contribution of these
components to species transport depends upon soil and contaminant characteristics. Both
mechanisms require high degree of saturation. However, electroosmosis require specific conditions,
including presence of clay minerals. It is also affected by pore fluid ionic strength and pH. Acidic
pore fluid conditions could reverse the charge on the clay mineral surface, and consequently the
electroosmostic flow (Lorenz 1969; Hunter 1981; Stumm 1992; Eykholt and Daniel 1994). At
specific pH, the soil could have a zero net charge (pzc: point of zero charge, Stumm 1992) and
electroosmosis could cease. Ionic migration on the other hand, occurs in all soil types, including
course grained soils (sand and gravel). Acar and Alshawabkeh (1993) compared the role of
electroosmosis and ionic migration for different conditions. The results showed that in most cases
ionic migration is more significant than electroosmosis. Best conditions for electroosmosis can result
in a flow in the order of 10-5 cm/sec per unit voltage gradient (V/cm). Average effective ionic
migration rates of different ions are usually in the order of 10-5 cm/sec, but also could be in the order
of 10-4 cm/sec.
Charge Flux
Applying a DC current through a soil-water-electrolyte medium generates an electric field causing

charge transport. It is assumed that the soil pore fluid has a relatively high ionic strength that makes
the contribution of the free pore fluid dominate the other charge transport mechanisms. Therefore,
the contribution of the soil solids and the diffuse double layer ions on charge transport is neglected.
The simplest form of electrical conductance of the soil is governed by Ohm’s law describing the
current density (charge transport) in the pore fluid due to electrical gradients,
I= *

where I is the electric current density (CL-2T-1DQG LVWKHHIIHFWLYHHOHFWULFDOFRQGXFWLYLW\RIWKH
soil. However, charge flux has another component due to ion diffusion. Therefore, the total charge
flux can be evaluated by using Faraday’s law for equivalence of mass flux and charge flux,
N
I = ∑ zj F Jj
j=1
substituting the value of Ji, the total charge flux is given by,
21
N
I = F ∑ z j D*j c j) + *

j=1
ZKHUHWKHHIIHFWLYHHOHFWULFDOFRQGXFWLYLW\ RIWKHVRLOEXONGXHWRFKDUJHIOX[LVJLYHQE\
N
*
= ∑Fz
i =1
i
*
u i ci
It should be noted that the advective components (electroosmosis and hydraulic advection) of species
mass flux will not result in any charge flux due to preservation of the electrical neutrality of free
pore fluid, given by,
∑c z =0
j=1
j j
Conservation of Mass and Charge
To evaluate changes per unit pore volume of the soil, it will necessary to apply the conservation
equations to transport equations. Conservation of mass and charge in a unit volume of the soil under
the set of assumptions employed require that,
∂ v ∂h
= mv = − ∇ Jw
∂t ∂t
w
∂ n ci
= − ∇ Ji + n R i i = 1,2,..., N
∂t
∂ Te ∂
= Cp = − ∇I
∂t ∂t
where v is the volumetric strain of the soil mass, mv is the coefficient of volume compressibility of
the soil (L2F-1); Te is the volumetric charge density of the soil medium (CL-3); Cp is the electrical
capacitance per unit volume (farad L-3); Ri (ML-3T-1) is the production/consumption rate of the ith
aqueous chemical species per unit fluid volume due to geochemical reactions. The consolidation
equation describes change in hydraulic head due to soil volume change. This equation becomes
significant in the case where hydraulic gradients are used to enhance transport under electric
22
gradients. Significant changes in the hydraulic head and development of negative pore water
pressure (suction) could occur due to nonuniform pH and voltage gradient distributions. The mass
conservation equation describes transient reactive transport of i chemical species under hydraulic,
electric and chemical concentration gradients. For zero electrical gradients, this equation will render
the advective-diffusive equation. The last PDE of the system describes conservation of charge in the
porous medium. The equation describes the rate of change in the electrical potential required to
maintain electrical neutrality of the medium. For zero net change in charge, one should assume zero
electric capacitance (Cp) of the soil.
Geochemical Reactions
Reactive transport of charged species is controlled by rates of geochemical reactions (Ri).

Electrolysis reactions at the electrodes usually produce extreme pH and chemistry conditions at the
boundaries (unless amendments are used). The chemistry boundary conditions results in a complex
system of geochemical reactions that include sorption (surface complexation and ion exchange),
redox and precipitation-dissolution reactions. The term Ri could then be expanded to account for
each reaction type, e.g.,
s aq p
Ri = Ri + Ri + Ri
where Ris is a term for sorption, similarly Riaq is a term for aqueous reactions and Rip for
precipitation/dissolution reactions. Two approaches have been developed and used to describe
chemical reactions; instantaneous equilibrium approach and kinetics approach. In instantaneous
equilibrium reactions species concentrations reach equilibrium instantaneously whereby in kinetic
reactions approach concentrations in solution vary with time till they reach equilibrium. For several
species, chemical reactions, e.g., dissolution, sorption and redox, have been found to vary with time
before reaching equilibrium. Kinetics approach is expected to be more realistic for modeling these
reactions. However, one could assume chemical reactions reach equilibrium at a very short time
(relative to transport time) and can use equilibrium. Geochemical models (using kinetics or
equilibrium) exist and one could incorporate these models for predicting rates of geochemical
reactions during electric field applications. However, an overview of these reactions is provided as
most modelers attempt to develop their own geochemical codes.
Sorption Reaction
The following general term has been considered for sorption evaluation:
s ∂ si ∂ si ∂ ci
Ri = = i = 1,2,..., N
n ∂ t n ∂ ci ∂ t
ZKHUH LVWKHEXONGU\GHQVLW\RIWKHVRLOsi is the adsorbed concentration of the component j per

unit mass of the soil solids (MM-1). The reversible term (∂si / ∂t) is often used to describe the
23
sorption rate. The equilibrium partitioning between the adsorbed phase and the aqueous phase of
the chemical components are commonly measured under controlled temperature and applied
pressure, and the resulting correlations of si versus ci are called adsorption isotherms. Several
equilibrium models (linear, Freundlich, and Langmuir models) have been used to describe sorption
of heavy metals on soils. Assuming instantaneous equilibrium in sorption reactions and linear
isotherms,
∂ si
= K di
∂ ci
where Kdi is called the distribution coefficient, Kd, of species i. A retardation factor, Rdi, have been
introduced and used in modeling species transport accounting for linear sorption as,
K di
R di = 1 +
n
The retardation factors of species i, Rdi, define the relative rate of transport of a nonsorped species
to that of a sorped species. For a nonsorped species, Rdi = 1.
Simple isotherm sorption models ignore the potential effects of variations in pH, solute composition
and ionic strength, redox potential, or processes such as competitive adsorption. Alternative, more
robust (and complicated) sorption models include ion- or ligand-exchange, mass action models, and
surface complexation models as described by Langmuir (1997), Kirkner and Reeves (1988), Yeh
and Tripathi (1989) Davis and Kent (1990), Stumm and Morgan (1995), Bethke (1996).
Aqueous Reactions
In aqueous phase reactions, any complex j is the product of i’s reactant components, i.e.:
Nc
∑a
i =1
ji ci ↔ x j j = 1,...., N x
where c‘i is the chemical formula for component i, x‘j is the chemical formula for the complex j, aji
is the stoichiometric coefficient in complex j for component i. The law of mass action implies that:
Nc
x j = K j ∏ cia ji
eq
j = 1,...., N x
i =1
where Kjaq is the equilibrium constant for aqueous reaction j. The rate of accumulation of component
i due to aqueous reaction j, Rjiaq, is:
24
aq
R ji = a ji R j
The total rate of accumulation of component i due to all aqueous reactions is:
Nx Nx
R = ∑ R ji = ∑a
aq aq
i ji Rj
j=1 j=1
Precipitation/Dissolution Reactions
It is necessary to account for the precipitation/dissolution reactions in the formulation of mass

transport equations. In precipitation reactions, the chemical components are assumed to be composed
of products,
Nc
pj → ∑b i =1
ji ci j = 1,...., N p
where p‘j is the chemical formula for precipitate j, bji is the stoichiometric coefficient in precipitate
j for component i, and Np is the number of precipitates for component i. The production of the
precipitate will not occur until the solution is saturated. Therefore, the law of mass action is written
as,
Nc
K j ≥ ∏ cib ji
sp
j = 1,...., N p
i =1
where Kjsp is the solubility product equilibrium constant for precipitate j. By the same rationalization
of previous formulations, the total rate of production of component i due to precipitation/dissolution
reactions, Rip, is,
Np Np
R = ∑ R ij = ∑b
p p p
i ji Rj
j=1 j=1
where Rjp is the rate of production of precipitate j.
General System for Modeling Transport
The theoretical formalism results in a mathematical system of equations describing the transient
reactive multi-component species transport under hydraulic, electric, and chemical gradients. The
resulting system consists of partial differential equations for transport and algebraic equations for
geochemical reactions. The transport PDEs are divided into three types. The first consists of one
equation that describes transient fluid flow. The second consists of N number for equations that
25
describe reactive transport of N species. The third type is described by one equation for charge
transport.
Substituting fluid flux into volume change equation results in the electroosmotic consolidation
given by,
∂h
= cv ∇ 2 h + k e ∇2 Φ
∂t mv γ w
This equation is necessary to describe changes in the hydraulic head across the soil, which
impacts the advective component of mass transport. The transient reactive PDEs for mass
transport are derived by substituting mass flux equation into mass conservation equation,
∂ n ci
= D*i ∇ 2 ci + ∇(ci [ (u*i + k e) ∇Φ + k h ∇ h ]) + n R i
∂t
where i=1,2,.....,N. Note that for the case of nonreactive solute transport (Ri=0), steady state
fluid flux ( ∂h/ ∂x =const.) and no electrical gradient, the equation becomes the advective-
diffusive solute transport equation widely used to describe nonreactive solute transport,
∂ n ci
= D*i ∇ 2 ci - v ∇ ci
∂t
where v = - kh ∇ h.
Changes in the electric potential distribution across the soil as a result of changes in the
geochemistry is formulated by substituting the charge flux equation in the charge conservation
equation,
∂Φ N
Cp = F ∑ z j D*j ∇2 c j + ∇ (σ * ∇Φ )
∂t j=1
The total number of differential equations described for this system are N+2 which are N
equations for mass transport, one equation for charge conservation, and one equation for fluid
flow. The unknowns described in this system are N species concentrations, ci, one electric
SRWHQWLDO RQHK\GUDXOLFSRWHQWLDOKDQG1XQNQRZQVIRUWKHUDWHRIi chemical reactions.
Therefore 2n+2 unknowns are described by N+2 differential equations. The other N number of
equations required for this system are the mass balance equations for the chemical reactions.
26
Preservation of Electrical Neutrality
The following derivation is used to demonstrate that the charge transport equation preserves the
electrical neutrality of the porous medium. For a unit volume of the soil, the rate of change in the
electric charge equals the total rate of change of chemical species concentrations multiplied by
their charge and Faraday’s constant, i.e.,
N
∂ n cj
rate of change in electric charge = ∑ z j F
j=1 ∂t
Preservation of electrical neutrality requires that the total change in electric charge per unit
volume equals zero.
N
∂ n cj N N
∑ zj F
j=1 ∂t
= ∑ z j F ∇(− J j) + n ∑ z j F R j
j=1 j=1
The total rate of change of all chemical species under chemical reactions times their charge is
zero,
N
∑z R
j=1
j j =0
In other words, consider the following chemical reaction,
A ↔ m B+ l + l D m
one mole of A will produce m moles of B+l and l moles of D+m. The total change in B+l concentration
times its charge is m moles of B+l * (+l) = ml. The total change in D+m concentration times its charge
is l moles of D+m * (-m) = -ml. Therefore, the total change in each one concentration times its charge
is ml-ml=0.
Substituting flux equations into charge conservation equation:
N
∂ n cj N N
∑ zj F
j=1 ∂t
= ∑ z j F D*j ∆ 2 c j + ∑ z j F ∆ (c j [ (u*j + k e ) ∆Φ + k h ∆ h ] )
j=1 j=1
Simplifying and substituting Σ zj cj = 0,
N
∂ n cj N N
∑ F zj
j=1 ∂t
= ∑ F z j D*j ∇2 c j + ∑ F z j ∇ ( c j u*j ∇Φ )
j=1 j=1
Accordingly, for Cp=0, we get:
27
N
∂ n cj
∑z F
j=1
j
∂t
=0
Boundary Conditions
Boundary conditions are required for hydraulic head, N chemical species concentrations, and electric
potential. Usually hydraulic heads are controlled either to provide constant head difference or
constant flow rates. Thus, hydraulic head boundary conditions are easily identified. In most cases,
zero head difference is applied between the cathodes and anodes. Boundary conditions for this case
are,
h |S1 = h |S 2 = 0
where S1 is the boundary surface at the anode and S2 is the boundary surface at the cathode.
Boundary conditions for charge conservation equation are developed from the current value at
the boundary. Two type of boundary conditions could be applied. If the voltage difference is kept
constant between the anode and cathode (current density changes depending upon electric
conductivity) then the following boundary conditions are used,
Φ |S1 = Φ max Φ |S 2 = 0
However, if the current is maintained constant (voltage changes depending upon electric
conductivity), then the following boundary conditions are used,
N
[ F ∑ z j D*j∇ c j + *
∇ ] |S1 = I
j=1
|S 2 = 0
Identifying boundary conditions for the partial differential equations describing species transport is
calculated based on electrolysis reactions at the electrodes. When inert electrodes are used in
groundwater, oxidation of water at the anode generates an acid front, while reduction at the cathode
produces a base front by the following electrolysis reactions:
2 H 2 O - 4 e- - > 4 H + + O 2 Anode
2 H2 O + 2 e- - > 2 OH- + H 2 Cathode
While these electrolysis reactions are the most likely to occur (if no amendments are used), the
prevailing electrolysis reactions at the electrodes depend upon the availability of other species, pH,
28
and the electrochemical potentials of their reactions. In the presence of multi-species at the cathode
or anode, electrolysis reactions will occur depending on the electrochemical potential of each
reaction. It is necessary to evaluate these potentials for different species. In general, the overall
electrolysis (cell) reaction comprises two independent half-reactions at the anode and at the cathode.
Consider the following half-cell reaction
vo O + n e → v r R
-
where O is the oxidized form, R is the reduced form, and vo and vr are the stoichiometric
coefficients. From basics of thermodynamics, the free energy of this cell reaction is given by
(R )vr
∆ G = ∆ G o + RT ln
(O )vo
where G is the Gibbs free energy and parenthesis represent activities. Since ∆G = - nFE
RT (O )vo
E = Eo + ln
nF (R )vr
This is the Nernst Equation (Bard and Faulkner 1980) and it provides the potential of the O/R
electrode verses the natural hydrogen electrode (NHE) as a function of the activities of O and R.
Equation 42 is useful in identification of the type of electrolysis reactions expected at the anode and
at the cathode in the presence of multi-species. The electrolysis reaction that has the highest positive
E will occur at the cathode, while the electrolysis reaction with the most negative E will occur at the
anode. As a result of these electrolysis reactions, the chemistry at the electrodes will undergo
continuous changes. These changes either enhance the electrokinetic process (e.g., generation of acid
at the anode) or retard the process (e.g., generation of the base at the cathode). Chemical reagents
are introduced at the electrodes to enhance electrokinetic process.
Once the type of electrolysis reactions are identified, then the boundary conditions can be evaluated
from mass equilibrium in electrodes compartments. The rate of concentration change of a specific
species i in the electrode compartment will be equal to the net mass flow rate of the species. Figure
2.3 displays a schematic of the anode well showing the mass fluxes of a specific species, i. The in
and out fluxes of species i in this well are (1) generation or electroplating at the electrode due to
electrolysis reactions, (2) in/out flux at the soil boundary due to transport, (3) injection of any
enhancement agent in the compartment, (4) extraction of the anolyte from the electrode well and (5)
chemical reactions of species i. Accordingly, the rate of change of species i concentration in the
anode well is given by,
∂ cia ~
= Ji dS - q E cia + q A CiA ± R iA V a ± R ielect Va
∂t ∫
a
V
SA
29
where Va is the volume of water in the anode well, cia is the concentration of species i in the anode
well, Ji is the flux of species i in/out of the anode/soil boundary, SA is the boundary surface area of
the soil/anode well, qE is the flow rate of fluid extracted from the anode, qA is the flow rate of the
(enhancement) fluid injected into the anode well, CiA is the concentration of species i in the
enhancement fluid, RiA is the production/sink rate of species i in the anode well due to chemical
reactions, Rielect is the production/sink rate specie i due to electrolysis reactions at the electrode.
.
Numerical Strategies
Three approaches for numerical simulation are encountered for the developed system of
differential and algebraic equations:
1. Differential and Algebraic Equations Approach (DAE): this approach consists of providing a
solution to the mixed differential and algebraic equations in which the transport equations and
chemical equilibrium reactions are solved simultaneously as a system (Miller and Benson 1983;
Lichtner 1985).
2. Direct Substitution Approach (DSA): this approach consists of direct substitution of the algebraic
chemical equilibrium equations into the differential transport equations to form a highly nonlinear
system of partial differential equations (Vallocchi et al. 1981; Jennings et al. 1982; Rubin 1983;
Lewis et al. 1987).
3. Sequential Iteration Approach (SIA): this approach consists of iterating between the sequentially
solved differential and algebraic equations (Kirkner et al. 1984, 1985; Yeh and Tripathi 1991).
Electrokinetic Remediation Models
Researchers have attempted to model contaminant transport under electrical gradients. Shapiro et
al. (1989) and Shapiro and Probstein (1993) describe a 1-D model accounting for species transport
under electric fields. The model accounts for ion diffusion, migration, and electroosmotic advection
in predicting species transport rate. The model solves the charge flux equation in order to evaluate
the nonlinear electric field distribution. The model assumes incompressible soil medium and thus
constant hydraulic head distribution. Water electrolysis reactions are used to calculate constant flux
boundary conditions for hydrogen ion at the anode and hydroxyl ion at the cathode. A steady state
electroosmotic flux is calculated by averaging the electrical gradient and zeta potential across the
soil sample. The results are compared with the experiments for the case of acetic acid extraction with
constant voltage at the boundaries. Species incorporated in the code include acetate, hydrogen,
hydroxyl, sodium, and calcium ions. Geochemical reactions include are first order sorption and
water and acetic acid dissociation. Numerical solution is achieved using finite element method in
the spatial domain and Adams-Bashforth integration in time. Comparisons show good agreement
in one case of acetic acid removal from 0.4 m length kaolinite sample.
Jacobs et al. (1994) followed the model described in Shapiro and Probstein to predict 1-D transport
30
of zinc under electric fields. The model uses an averages electroosmotic flow rate across the soil (i.e.
electroosmotic flow is assumed independent of location). The model accounts for zinc precipitation
and dissolution reactions and demonstrated the role of background ion concentrations on the process.
Jacobs and Probstein (1996) further modify the code to model 2-D species transport under electric
fields. They applied the 2-D code for the case of electroosmotic extraction of phenol from kaolinite.
The model solves three PDEs for transport of phenol, sodium ion, and chloride ion. Hydrogen and
Hydroxyl ion concentrations were calculated using zero net charge equation and water equilibrium
equation. The model demonstrates 2-D phenol between one anode and one cathode. Limited
geochemical reactions were incorporated (water and phenol dissociation) due to the complex 2-D
simulation of the process.
Mitchell and Yeung (1991) propose a model in a study of the feasibility of using electrical gradients
to retard or stop migration of contaminants across earthen barriers. Principles of irreversible
thermodynamics are employed and a one dimensional model is developed for transport of
contaminants across the liner. Integral finite difference method was used to solve the problem and
the model reasonably predicted the transport of sodium and chloride ions across the liner.
Geochemical reactions were not incorporated in this model. Eykholt (1992) attempts to model the
pH distribution during the process using mass conservation equation accompanied by empirical
relations to account for the nonlinearity in the parameters controlling the process. One transport
differential equation is formed assuming that hydrogen and hydroxyl ions have the same diffusion
coefficients and ionic mobilities. In this model, the development of negative pore water pressure is
modeled using the modified Smoluchoweski equation of Anderson and Idol (1986); and the
complexity in electrical potential distribution is modeled using proposed empirical relations. Haran
et al. (1997) present a 1-D model for extraction of hexavalent chromium from soils using electric
fields. The model accounts for transport of H+, OH-, CrO4-2, K+, Na+, and SO4-.Geochemical
reactions included sorption (described by a retardation coefficient) and water equilibrium.
Acar et al. (1988) and Acar et al. (1989) present a one dimensional model to estimate pH distribution
during electrokinetic soil processing. The model demonstrates the impact of electrolysis reactions
on pH distribution during electrokinetic remediation. Alshawabkeh and Acar (1992) describe a
modified formulation and present a system of differential/algebraic equations for the process and
accounting for the chemical reactions of adsorption/desorption, precipitation/dissolution, and
acid/base reactions. Acar and Alshawabkeh (1994) model the change in soil and effluent pH during
electrokinetic soil processing. Two transient transport equations for hydrogen and hydroxyl ions are
used together with water autoionizaion equation. This attempt assumes linear electric and hydraulic
gradients throughout the process and disregards the coupling of these components. Alshawabkeh and
Acar (1996) and Acar and Alshawabkeh (1996) enhance the model and modify the code for
stimulating reactive extraction of heavy metals by electric fields. The model predicts reactive
transport of hydrogen, lead, hydroxyl, and nitrate ions. The charge conservation equation is used to
solve for electric field distribution and electroosmotic consolidation equation is used for predicting
hydraulic head profile. The model accounts for lead hydroxide precipitation-dissolution, lead
sorption (assuming linear pH dependent isotherm) and water equilibrium reactions.
31
Frequency (%)
0.01 0.1 1 10
Pore Diameter (µm) Wet of optimum

Dry of optimum
Figure 2.1 A schematic of microstructure and pore size distribution of clay at wet and dry of
optimum
32
Co
nc
ent Initial Concentration
Co
rati
2
on An Cat
ode 1 3 4 ho
de
Distance
Xh Xe Xm
1. Hydraulic Advection X1 = (kh ih) T 2. Diffusion

3. ElectroosmosisXe = (ke ie) T 4. Ion MigrationXm = (u* ie) T
Concentration
Xm
Initial Concentration
Co
2
Cathode
Anode
1 4 3
Distance
Xh Xe
1. Hydraulic Advection X1 = (kh ih) T 2. Diffusion

3. Electroosmosis Xe = (ke ie) T 4. Ion Migration Xm = (u* ie) T
Figure 2.2 Transport Mechanisms of (a) cations and (b) anions
33
Boundary S1
OH-
OH-
OH-
OH-
OH-
Figure 3.2
Figure 3.2 Boundary condition at the anode
34
SECTION 3
PRACTICAL ASPECTS OF 1D AND 2D ELECTROKINETIC REMEDIATION
Although significant research has been conducted in the 80’s and 90’s on electrokinetic remediation,
one can argue that the fundamentals of the process are not yet well understood. The reason is that
the objective of most of these studies was to demonstrate the feasibility of the remediation process
and not to investigate the fundamental physicochemical and geochemical processes. For example,
rates of electroosmosis and ionic migration in soils under heterogeneous, anisotropic, and partially
saturated soils are not easy to establish. Even in homogenous and saturated conditions, the complex
geochemical reactions make it difficult to predict transport rates. In most cases these reactions are
assumed instantaneous while in fact they are time dependent and their rates significantly impact time
and energy requirements. In any case, a discussion is provided for practical applications of the
process based on the current understandings of the process. Few studies have looked into practical
considerations for field implementations. Schultz (1997) provided an economic modeling and
calculations of optimum spacings, time and energy requirements of one dimensional field
applications based on electroosmotic transport.
Soil type
Bench-scale and pilot-scale tests indicated that the technology can be successful in clayey to fine
sandy soils. However, contaminant transport rates and the efficiency of the process depend heavily
on soil type, mineral composition and pore fluid conditions. Reddy et al. (1997) demonstrated that
presence of iron oxides in glacial till creates complex geochemical conditions that retards Cr(VI)
transport. On the other hand, the same study showed that presence of iron oxides in kaolinite and
Na-montmorillonite did not seem to significantly impact Cr(VI) extraction. Pamukcu and Wittle
(1992) and Wittle and Pamukcu (1993) demonstrated removal of Cd2+, Co2+, Ni2+, and Sr2+ from
different soil types at variable efficiencies. The results showed that kaolinite, among different types
of soils, had the highest removal efficiency followed by sand with 10% Na-montmorillonite, while
Na-montmorillonite showed the lowest removal efficiency. The results indicated that soils of high
water content, high degree of saturation, low ionic strength and low activity (soil activity describes
soil plasticity and equals plasticity index divided by % fines, clay and silt, in the soil) provide the
most favorable conditions for transport of contaminants by electroosmotic advection and ionic
migration. Highly plastic soils, such as illite, montmorillonite, or soils that exhibit high acid/base
buffer capacity require excessive acid and/or enhancement agents to desorb and solubilize
contaminants before they can be transported through the subsurface and removed (Alshawabkeh et
al., 1997), thus requiring excessive energy.
Hydraulic conductivities of different soil types can vary many orders of magnitude within a
heterogeneous deposit. Consider a contaminated deposit containing interlayers of sand and clay,
typical values of hydraulic conductivities of these soils are 1x10-3 and 1x10-9 m/s, respectively. If
pump-and-treat is used to remediate such a heterogeneous deposit, most of the fluid flow induced
will occur in the sandy layer and the clayey layer will be practically untreated. On the other hand,
electric conductivities of these soils are within an order of magnitude. As a result, the electric field
strengths in the different soil layers will be similar when an externally electric potential is applied
across the deposit. Similar ionic migration rates of contaminant transport can be generated in
35
different soil layers within the heterogeneous deposit resulting in a more homogeneous cleanup. The
ability to remove contaminants uniformly from a heterogeneous natural deposit is another distinct
advantage of the technology. A combination of hydraulic and electric gradients could also enhance
the process. Runnells and Wahli (1993) showed the use of ion migration combined with soil washing
for removal of Cu2+ and SO42- from fine sands. A field study reported by Banerjee et al. (1990) also
investigated the feasibility to use electrokinetics in conjunction with pumping to decontaminate a
site from chromium. While soil chromium profiles were not evaluated in this study, the results
showed increase in effluent chromium concentrations.
One of the factors that should be considered carefully is the degree of saturation. Depending upon
the target transport mechanism, the degree of saturation impacts both electroosmosis and ionic
migration.
Contaminants type and concentrations
Studies showed that removal of heavy metals, radionuclides, and selected organics by electrokinetics
is feasible. Hamed (1990) and Hamed et al. (1991) demonstrated electrokinetic remediation using
kaolinite samples mixed with Pb2+ at various concentrations below and above the soil cation
exchange capacity. The process removed 75% to 95% of lead at concentrations of up to 1,500 mg/kg
across the test specimens at reported energy expenditure of 29 to 60 kWh/m3 of soil processed.
However, since no enhancement procedure was used, most of the removed lead was found deposited
at section close the cathode. Acar et al. (1994) demonstrated 90% to 95% removal of Cd2+ from
kaolinite specimens with initial concentration of 99-114 mg/kg. Other laboratory studies reported
by Runnels and Larson (1986), Lageman et al. (1989), Eykholt (1992), and Acar et al.(1993) further
substantiate the applicability of the technique to a wide range of heavy metals in soils. The process
can potentially remove radionuclides from clayey soil samples (Ugaz et al., 1994). Bench-scale tests
displayed that uranium at 1,000 pCi/g of activity is efficiently removed from kaolinite. A yellow
uranium hydroxide precipitate was found in sections close to cathode. Enhanced electrokinetic
processing showed that 0.05M acetic acid was enough to neutralize the cathode reaction and
overcome uranium precipitation in the soil. Other radionuclides such as thorium and radium showed
limited removal (Acar et al., 1992). In the case of thorium, it was postulated that precipitation of
these radionuclides at their hydroxide solubility limits at the cathode region formed a gel that
prevented their transport and extraction. Limited removal of radium is believed to be either due to
precipitation of radium sulfate or because radium strongly binds to the soil minerals causing its
immobilization (Acar et al., 1992).
Lageman et al. (1989) showed that the process can migrate a mixture of different contaminants in
soil simultaneously. Lageman (1993) reported 73% removal of Pb at a concentration of 9000 mg/kg
from fine argillaceous sand, 90% removal of As at 300 mg/kg from clay and varying removal rates
ranging between 50% to 91% of Cr, Ni, Pb, Hg, Cu, and Zn from fine argillaceous sand. Cd, Cu, Pb,
Ni, Zn, Cr, Hg, and As at concentrations of 10 to 173 mg/kg also were removed from a river sludge
at efficiencies of 50 to 71%. The energy expenditures ranged between 60 to 220 kWh/m3 of soil
processed. Therefore, one can conclude that the type of contaminant does not pose a significant
limitation on the technology provided it does not exist in an immobile form, e.g., sorbed on the soil
particle surface or precipitated in the soil pore.
36
Regarding contaminant concentrations, existing experimental data indicate that removal of Cu(II)
of concentration up to 10,000 mg/kg of soil and Pb(II) concentration up to 5,000 mg/kg are possible.
Acar and Alshawabkeh (1996) demonstrated extraction of lead at 5300 mg/kg from pilot-scale
kaolinite samples. However, high ion concentrations in the pore fluid increase the electrical
conductivity of the soil and thus reduce the efficiency of electroosmotic fluid flow (Gray and
Mitchell 1967; and Lockhart 1983). Moreover, the strength of electric field applied may have to be
reduced to prevent excessive power consumption and heat generation during the process. The results
of Hamed (1990), Pamukcu and Wittle (1992) and Wittle and Pamukcu (1993) demonstrated that
lower initial concentrations of cadmium result in higher electro-osmotic efficiency; however,
removal efficiencies were higher for samples with higher initial concentrations. Alshawabkeh et al.
1997 investigated electrokinetic extraction of heavy metals from clay samples retrieved from a
contaminated Army Ammunition site. The soil contained cations at the following concentrations:
calcium: 19,670 mg/kg; iron: 11,840 mg/kg; copper: 10,940 mg/kg; chromium: 9,930 mg/kg; zinc:
6,330 mg/kg; and lead: 1,990 mg/kg. The high calcium concentration hindered extraction of the
metals. However, the results showed that metals with higher initial concentration, less sorption
affinities, higher solubilities, higher ionic mobilities are transported and extracted faster than other
metals.
Electrokinetic remediation is also effective for the removal of organic pollutants such as phenol,
gasoline hydrocarbons, and TCE from contaminated soils. Successful application of the process has
been demonstrated for extraction of the BTEX (benzene, toluene, ethylene and m-xylene)
compounds and trichloroethylene from kaolinite specimens at concentrations below the solubility
limit of these compounds (Bruell et al., 1992; Segal and Bruell, 1992). High degrees of removal of
phenol and acetic acid (up to 94%) were also achieved by the process (Shapiro et al., 1989; Shapiro
and Probstein 1993). Acar et al. (1992) reported removal of phenol from saturated kaolinite by the
technique. Two pore volumes were sufficient to remove 85% to 95% of phenol at an energy
expenditure of 19 to 39 kWh/m3. Wittle and Pamukcu (1993) investigated the feasibility of removal
of organics from different synthetic soil types. Tests were conducted on kaolinite,
Na-montmorillonite, and sand samples mixed with different organics. Their results showed the
transport and migration of acetic acid and acetone towards the cathode. Samples mixed with
hexachlorobenzene and phenol are reported to show accumulation at the center of each samples. The
results of some of these experiments were inconclusive, either because contaminant concentrations
were below detection limits or because the samples were processed for only 24 hrs, which might not
be sufficient to demonstrate any feasibility in electrokinetic soil remediation. Recently, the
Department of Energy (DOE), Environmental Protection Agency (EPA), Monsanto, General
Electric, and Dupont have also applied electric fields for electroosmotic extraction using layered
horizontal electrodes in what is called the "Lasagna" process. Ho et al. (1997) reported successful
extraction of TCE from a site in Paducah, Kentucky using the LasagnaJ process. They also reported
98% removal efficiency of p-nitrophenol, as a model organic compound, from soil in a pilot-study.
Although removal of free phase non-polar organics is questionable, Mitchell (1991) stated that this
could be possible if they would be present as small bubbles (emulsions) that could be swept along
with the water moving by electroosmosis. Acar et al. (1993) stated that unenhanced electrokinetic
remediation of kaolinite samples loaded up to 1,000 mg/kg hexachlorobutadiene has been
unsuccessful. However, Acar et al. (1993) reported that hexachlorobutadiene transport was detected
only when surfactants were used.
37
Electrolyte Enhancement
Several procedures have been proposed to enhance electrokinetic remediation of heavy metals and
radionuclides. Some of these procedures attempt to control production of hydroxyl ions at the
cathode. Other procedures attempt to enhance complexation of heavy metals to enhance extraction
at the anode. Some of these procedures are presented.
Catholyte neutralization
One way on controlling the catholyte pH is to neutralize the hydroxyl ions produced by electrolysis
using weak acids or catholyte rinsing. The advantages of using weak acids include (a) they form
soluble metal salts; (b) their low solubility and migration rates will not increase the electric
conductivity of the soil; and (c) they are biodegradable and, if properly selected, environmentally
safe. However, improper selection of some acids may pose a health hazard. For example, the use
of hydrochloric acid may pose a health hazard because: (a) it may increase the chloride concentration
in the groundwater; (b) it may promote the formation of some insoluble chloride salts, e.g., lead
chloride; and (c) if it reaches the anode compartment, chlorine gas will be generated by electrolysis.
Rødsand et al. (1995) and Puppala et al. (1997) demonstrated that neutralization of the cathode
reaction by acetic acid can enhance electrokinetic extraction of lead. Hicks and Tondorf (1994)
indicated that development of a pH front could cause isoelectric focusing, which retards ions
transport under electric fields. They showed that this problem can be prevented simply by rinsing
away the hydroxyl ions generated at the cathode. They demonstrated 95% zinc removal from
kaolinite samples by using the catholyte rinsing procedure.
Ion-selective membranes
Another procedure to control hydroxyl ions and enhance metals transport toward the cathode is the
use of membranes. Ion selective membranes, which are impermeable to hydroxyl ions, could be used
to separate the catholyte from the soil and thus prevent or minimize the transport of hydroxyl ions
into the soil. These membranes are insoluble in most solvents and chemically resistant to strong
oxidizing agents and strong bases. Rødsand et al. (1995) and Puppala et al. (1997) showed that this
technique has limited success when compared to catholyte neutralization. The reason is that heavy
metals accumulate and precipitate on these membranes resulting in a significant increase in the
electrical resistivity of membrane. Unless these membranes are continuously rinsed and cleaned, the
energy cost of this technique will substantially increase.
Chelating or complexing agents
An acid front may not develop in soils of high buffer capacity and in soils that produce reverse
electroosmosis, i.e., from the cathode toward the anode (Yeung et al., 1996). Reddy et al. (1997)
showed that soils that contain high carbonate buffers, such as glacial till, hinder the development and
advance of the acid front. On the other hand, acid advance in soils with low buffering capacity may
cause uncontrolled dissolution of soil minerals resulting in an excessive release of some of their
constituents, such as Al and Si. Under these circumstances, it is necessary to use enhancement
agents to solubilize the contaminants without acidification. Chelating or complexing agents, such
as citric acid and EDTA, have been demonstrated to be feasible for the extraction of different types
38
of metal contaminants from fine-grained soils. The enhancement agents should form charged
soluble complexes with the metal contaminants. Cox et al. (1996) demonstrated the feasibility of
using iodine/iodide lixivant to remediate mercury-contaminated soil. The use of EDTA as an
enhancement agent has also been demonstrated for the removal of lead from kaolinite (Yeung et al.,
1996) and lead from sand (Wong et al., 1997).
Enhancement of anolyte pH
While acidification of the soil causes dissolution of the soil minerals, it also increases the ionic
strength and electric conductivity of the soil, which may hinder contaminant transport (Acar and
Alshawabkeh 1993). If hydrogen ion generation and supply at the anode is not controlled, most of
the energy may be consumed by generation and migration of this ion between the electrodes rather
than the transport of charged contaminants. Therefore, it may be necessary to neutralize the anode
reaction and/or control acid production and introduction into the soil mass.
Voltage and current levels
Electric current intensities used in most reported studies are in the order of a few Amps per square
meter. Although high current levels generate more acid that will work for the process, it increases
the total ionic concentration that will decrease the overall electroosmotic flow. Selection of the most
appropriate current density and voltage gradients depends on the soil electrochemical properties,
especially electric conductivity. Soils with higher electric conductivities require more charge and
higher currents than lower conductivity soils. A voltage gradient in the order of 100 V/m can be used
as an initial estimate for initial processing. Increasing the current densities (or voltage gradients) will
increase transport rates under ionic migration. However, increasing current densities will increase
energy expenditure and cost of the process. An optimum current density or voltage gradient could
be appropriately selected based on the soil properties, electrode spacing, and time requirements of
the process. A procedure is provided for selection of appropriate current densities.
Electrode Requirements
The number of electrodes required for 1-D applications depends upon spacing between electrodes
of the same-polarity (e.g. anode-anode or cathode-cathode spacing). Decreasing spacing between
same-polarity electrodes minimizes the area of inactive electric field, but increases the cost of the
process. The same situation applies for 2-D configurations. In general, the goal of 2-D applications
of electric fields is to achieve axi-symmetrical (or radial) flow towards a center electrode. The
derivations will focus on extraction of positively charged heavy metals, thus locating the cathode
as the center electrode allows accumulation of the cationic contaminants in a smaller zone around
the cathode. Outer electrodes (anodes) are placed at specific distances from the center cathode to
achieve relatively radial flow. The electrodes can be placed in a hexagonal or square configuration.
Hexagonal (honeycomb) electrode configuration consists of cells, each contains a cathode
surrounded by six anodes. The square configuration consists of a cathode and four (or possibly eight)
anodes surrounding the cathode. Hexagonal and square grids generate two-dimensional, non-linear
electric fields. Areas of inactive electric fields will develop depending on the configuration selected.
Since this impacts the cost of electrodes, it will be necessary to select the configuration with the
39
optimum number of electrodes per unit area while minimizing the area of the ineffective electric
fields.
Table 3.1 provides a comparison of number of electrodes required per unit surface area for 1-D, 2-D
hexagonal, and 2-D square configurations. Three cases are provided for 1-D arrangement where the
same-polarity electrode spacing equals (a) the anode-cathode spacing, (b) one half the anode-cathode
spacing, and (c) one third the anode-cathode spacing. Number of electrodes is calculated based on
a unit surface (plane) area. For each configuration, the number of electrodes per unit area is
calculated considering a unit cell. Accordingly, the number of electrodes required per unit plane area
of site can be given by,
F1 F1
N ' [ ]1D flow ' [ ]
2 2 2D flow
LE RE
where N (L-2) is the number of electrodes per unit surface area of site to be treated, LE (L) and RE
(L) are 1-D and 2-D anode-cathode spacing, respectively, and F1 (dimensionless) is a shape factor
depending on electrode configuration. F1 is calculated by adding the number of electrodes serving
a unit area (or a unit cell). If an electrode is serving more than one cell, then a fraction of the
electrode is serving each cell. Table 1 shows the values of F1 for selected configurations. The results
show that 1-D configurations with same-polarity electrode spacings of one half and one third anode-
cathode spacings require 100% and 200% increase in number of electrodes, respectively, when
compared to the 1-D case of equal electrode spacings. Hexagonal configuration requires 15%
increase in number of electrodes when compared to 2-D square configuration. Electrode
requirements clearly affect the uniformity of electric fields and development of ineffective areas.
Thus, it is necessary to evaluate the impact of increasing the electrodes on the development of
ineffective spots.
Electric Field Distribution
Numerical simulations of contaminant transport under electric fields use nonlinear, 1-D electric-field
distributions for predicting species transport (Alshawabkeh and Acar, 1992; Shapiro and Probstein,
1993; Alshawabkeh and Acar, 1996, Jacobs et al., 1996). Similar numerical procedure can be used
for 2-D applications. One also could assume uniform steady-state conditions and use the Laplace
equation to describe the 2-D electric-field distribution. Analytical solutions, numerical methods, or
conformal mapping can be used for solving the Laplace equation. However, these solutions do not
provide a mechanism for comparing the effectiveness of different configurations. An approximate
and practical approach is adopted in this paper for evaluating the area of ineffective electric fields.
Electric field distributions show that the ineffective area for each cell has the shape of a curvilinear
triangle with the base being the distance between electrodes of the same polarity (Figure 3.1). The
height of this triangular area is approximate and depends on processing time, electrode spacings and
alignment. The height of this triangle is expected to be larger in the case of 1-D compared to 2-D
applications due to electrode alignment. This height is assumed as half the length of the triangle
base for 1-D applications and a quarter the length of the base for 2-D applications. This assumption
40
provides a practical method for comparing the efficiency of different configurations.
Figure 3.1 shows approximate distributions of the resulting inactive spots for 1-D (Figure 3.1a) and
2-D (Figure 3.1b) configurations. Approximate calculations of the percentage of ineffective area
for each configuration are summarized in Table 1. For the 1-D configurations, the ineffective area
is half the total area when the same-polarity electrode spacing equals the anode-cathode spacing.
Thus, it is not practical to use such a scheme unless remediation is implemented in two stages where
electrode polarity can be changed. This is also the case for the 2-D square arrangement.
Electrode configuration and time requirements
1-D Transport
Electric currents could be applied in soils to generate one-dimensional (1D) or two dimensional
electric fields. 1D electric fields could be generated by electrode sheets with specific spacing
between the anodes and cathodes. Using sheets requires trenches and is not expected to be cost-
effective in most cases. Placing electrodes in bore holes is expected to provide an optimum and cost
effective method for in situ application of electric fields. However, problems associated with bore
hole configuration include development of inactive (dead) electric field spots between the anodes
and between the cathodes.
Several factors will affect electrode configuration, spacing and time requirements for electrokinetic
remediation. These factors include (a) location and size of any inactive electric field spots, (b)
number and costs of electrodes per unit area to be treated, and (c) time requirements of the designed
remediation process. Large electrode spacings reduce the number of boreholes and installation costs,
but increase the processing time and operation costs. It will be necessary to assess these variables
prior to selecting the required configuration and spacing.
In general, the processing time required is a function of the rate of transport and electrode spacing.
As electroosmotic advection and ionic migration are the prominent transport mechanisms,
hydrodynamic dispersion and retardation can be neglected in preliminary analysis. Accordingly, rate
of species transport under an electric field is given by,
v = ( u* + k e ) (- )
where v = rate of species transport (or velocity) assuming the soil is a homogeneous medium (m/s);
u* = effective ionic mobility of the ion (m2/V-s); ke = coefficient of electroosmotic conductivity
(m29VDQG LVWKHHOHFWULFSRWHQWLDO9ROW,IWKHVSDFLQJEHWZHHQHOHFWURGHVRIRSSRVLWHSRODULW\
is chosen to be L, the time (T) required for remediation can be estimated by dividing the spacing (L)
over the velocity of species transport (v), i.e.,
L
T = *
( u + k e ) (- )
Where T is the time required for clean-up. However, this is a simplified estimation of time
requirements where the contaminant of interest is assumed to be readily available for transport in
41
the soil pore fluid. This is probably the exception rather than the rule in real-life field
implementation of the technology. Heavy metals are usually either sorbed on the soil particle
surface or precipitated in the soil pore. Therefore, their transport is retarded by sorption and
precipitation. A delaying factor similar to the retardation factor in advection-dispersion contaminant
transport can be introduced to account for the extra time required for acid transport, metal desorption
and dissolution, etc. Therefor, total time requirements should account for this retardation and can
then be modified to
T = Rd L
*
( u + k e ) (- )
where Rd = delaying factor (dimensionless). The value of Rd depends on soil type, pH, and type of
contaminant. Sorption retardation factor can be used as an initial estimate of Rd and it equals unity
for non-reactive contaminants which are readily available for transport. If enhancement agents are
used to solubilize heavy metals, this factor should be modified accordingly. Alshawabkeh et al.
GHILQHGDQHZSDUDPHWHU WRFDOFXODWHWKHUHDFWLYHWUDQVSRUWUDWHRIDVSHFLHVUHODWLYHWRWKH
electric conductivity of a medium, i.e.
*
u + ke
= *
Rd
:KHUH LVWKHHIIHFWLYHHOHFWULFFRQGXFWLYLW\RIWKHVRLOPHGLXP$FFRUGLQJO\WKHWLPH
required for remediation in 1D applications is given by,
1 L
T = *
(- )
This equation indicates that for a given electric field strength, the time required for remediation
is linearly related to the spacing between the electrodes. If time is to be calculated using current
1 LE
TR ' (1)
Id
density, then we get,

where Id (Amps L-2) is the electric current density.
2-D Radial Transport
The approach provided below for 2-D applications assumes radial electric fields distribution (Figure
3.2). Rw represents the radius of center well (assumed cathode), RE represents the cathode-anode
spacing, and Z is the depth of the site. The difference between this case and the 1-D case is that the
current density in radial flow is a function of the radial distance (r); however, in both cases the total
42
current is constant. The electric current per unit depth for the radial transport is given by,
Iz ' (2 r) ( ir (1)
where Iz (amp L-1) is the current per unit depth and ir (VL-1) is the radial voltage gradient.
Contaminant transport rate is dependent upon the voltage gradient, which is a nonlinear function of
the radial distance. Ignoring diffusion and accounting for ion migration and electroosmosis, the
radial velocity of ions transport is given by
( u ( % ke )
v(r) ' ir (1)
Rt
where v(r) ( L T-1) is the velocity of species transport. Substituting ir leads to,
IZ
v(r) ' (1)
2 r
The velocity of contaminant transport is a nonlinear function of the radial distance (even if the soil
is homogeneous and isotropic). The time required for the contaminants to transport from the outside
anodes to the center cathode is calculated by integrating dt = dr / v(r) from RW to RE, leading to
2 2
(RE & RW)
TR ' (1)
IZ
Since (RW)2<< (RE)2, this equation can be simplified as,

2
RE
T' (1)
IZ
In order to provide time evaluation as a function of the voltage, a modified variable (rN) is introduced
to simplify the formulation,
43
r dr
r ) ' ln dr ) ' (1)
RW r
The transformed voltage gradient with respect to rN (irN) is independent of rN, and is given by,
Iz
ir '
) (1)
2 (
Substituting the value of Iz from,
2
1 RE
TR ' (1)
( i)
r
The form of this equation for radial transport is similar to the equation of for 1-D transport. In both
cases, $ and F* are soil properties and the gradients ie and irN are constants. However, comparing the
two equations shows that while T is a function of the linear distance between the electrodes for 1-D
case, it is a function of square the radial distance for 2-D applications. This is important for selection
of electrode spacings. Selection of radial spacing for 2-D radial cases is much more critical than for
1-D cases as time and cost of remediation will significantly increase with increased radial spacing.
Energy expenditure
Several factors impact energy requirements and cost for electrokinetic remediation at a specific site.
These factors include soil properties, contaminant properties, electrode configuration and processing
time. Energy consumption changes during processing due to changes in electric conductivity.
However, energy calculations could by simplified by averaging soil electrical conductivity
throughout the process. Accordingly, energy expenditure per unit volume of
max I d T R max IZ TR
W ' ( )1D&flow ' ( )radial&flow (1)
L 2
(RE&RW)
2
contaminated soil is given by the following equation for both 1-D and radial applications
where W (J L-3) is energy expenditure per unit volume of soil and Nmax (V) is the applied voltage.
Substituting the equations for TR results in the following equation for both 1-D and radial cases,
44
W ' max
(1)
This equation shows that same energy expenditure is expected for both 1-D and radial applications,
assuming that same total voltage is applied and each case is processed for specific required time.
This indicates that energy requirement could be considered independent of electrode configuration
if energy source (maximum voltage) is the controlling factor. In other words, two 1-D schemes (for
one specific site) with different spacings should result in same energy expenditure if same total
voltage was used in both schemes. The difference between the two schemes would be in terms of
time requirements. However, electrode configuration is a design factor if the energy source is not
the limiting factor.
Cost
The total costs for full-scale in situ implementation of electrokinetic remediation can be divided into
five major components (Alshawabkeh et al., 1999): (1) cost of electric energy,(2) cost for fabrication
and installation of electrodes, (3) cost of enhancement agents, if necessary, (4) costs of any post-
treatment, if necessary, and (5) fixed costs. Impacts of electrode configuration and spacing on these
cost components are addressed separately.
Electric energy cost
Based on energy expenditure evaluation, the following energy cost equation provided by
C2
Cenergy ' max
(1)
3,600,000
Alshawabkeh et al. (1999) for 1-D conditions is also valid for 2-D, radial conditions,
where Cenergy ($ L-3) is electric energy cost per unit volume of soil treated, and C2 ($/kWh) is electric
energy cost.
Costs for fabrication and installation of electrodes
If acid production at the anode is not controlled, then inert electrodes, such as graphite or coated
titanium, should be used to prevent dissolution of the electrode and generation of undesirable
corrosion products in an acidic environment. If necessary, sacrificial electrodes can also be used as
anode. Any conductive materials that do not corrode in a neutral or basic environment can be used
as cathode. Important considerations for the choice of electrode material are (Alshawabkeh et al.,
1999): (1) electrical conduction properties of the material, (2) availability of the material, (3) ease
of fabrication to the form required for the process, (4) ease of installation in the field, and (5)
45
material, fabrication, and installation costs. The electrodes can be installed horizontally or vertically.
The costs of each electrode depend on the material used, complexity of installation, and dimensions.
The number of electrodes per unit volume of soil to be treated depends on electrode configuration
and spacing. The installation costs depend on the method of installation, depth of the electrodes to
be installed, and number of electrodes to be installed. The total electrode costs per unit volume of
soil to be treated can be calculated by evaluating the number of electrodes per unit cell of an area,
i.e,
Celectrode ' C1 N (1)
where Celectrode ($ L-3) is electrode costs per unit soil volume, N ( L-2) is the number of electrodes per
unit surface area, and C1 ($ L-1) is the cost of electrodes per unit length. Values for N are provided
in Table 3.1 for different configurations. Increasing electrode spacings decreases the value of N and
hence decreases total electrode costs. For the 1-D case, spacings between electrodes of same
polarities significantly impact this cost component.
Cost for enhancement agent
Enhancement agents and chemicals are used to improve the efficiency of electrokinetic remediation
Chemicals cost is a significant component of the total cost of the processes. Chemicals are used for
either neutralizing pH conditions, or enhancing solubility of target contaminants, or both. The cost
of chemicals required for pH neutralizing is considered in this evaluation. This cost is dependent
upon the electric current and is given by the following equations,
Id MW
Cn&chemical ' C3 TR for 1&D (1)
L F
Iz MW
Cn&chemical ' C3 TR for Radial (2)
2 2
(RE&RW) F
where Cn-chemical ($ L-3) is the cost of chemicals required to neutralize electrolytes per unit soil
volume, C3 ($ M-1) is the cost of the chemical agent, MW (MM-1) is the molecular weight of the
neutralizing chemical, " (dimensionless) is a factor depending upon the stoichiometry of the
neutralizing reaction, and F is Faraday’s constant (96,485 C/mol-electron). Substituting the time
required for remediation in both 1-D and radial cases will result in the following equation;
46
C3 MW
Cn&chemical ' (1)
F
Accordingly, the chemicals cost is independent of electric current or spacing and is dependent on
soil characteristics. This is due to the fact that electric current and electrode spacings impact time
requirements. For example, increasing the current will decrease the time required for remediation,
such that the same total charge is introduced for any electric current value.
Cost of post-treatment
Post treatment costs should also be considered if effluent treatment is required. These costs are
highly site and contaminant specific. An estimate of effluent treatment costs could be evaluated per
unit volume of the soil for 1D case as follows,
k e T
Cpost-treat = C4
(L/n)
where Cpost-treat is the post treatment cost per unit volume of the soil ($ L-3) and C4 is the cost of
treatment per unit volume of the electrolyte (effluent) collected ($ L-3). Substituting for the value of
T (time required for remediation), then effluent treatment cost is given by;
n ke n R d ke
Cpost- treat = C4 *
= C4 *
u + ke
Derivations for radial transport post treatment costs also result in similar equation. Volume and cost
of effluent treatment depends on the ratio of transport under electroosmosis relative to total transport
rate. In order to minimize the volume collected, it is necessary to maximize transport by ionic
migration and minimize transport by electroosmosis. If contaminant transport occurs only due to
migration then this cost component will be zero and one needs only to treat electrolyte in electrode
well. However, if electroosmosis is the only mechanism used for contaminant transport (e.g., for non
charged contaminants) then cost of treatment will be equal to (C4 n Rd) which, indicates that the cost
depends upon the number of pore volumes required for remediation. If the contaminant is readily
available for transport, then Rd =1 and one pore volume is enough for remediation. However, if
extraction is retarded due to geochemical reactions then it is obvious that the pore volumes required
will increase depending upon the value of Rd. Sometimes catholyte recycling is used which will add
another component that should be considered for evaluation of total volume of water collected.
47
Other fixed and variable costs
Other costs for full-scale implementation include mobilization and demobilization costs of various
equipment, site preparation, security, progress monitoring, insurance, labor, contingency, and
miscellaneous expenses. The equipment will not be consumed in a particular project. However,
there are capital, depreciation, or rental costs involved. These cost components will be divided into
fixed (e.g. mobilization and demobilization) and variable (e.g. monitoring, insurance, rentals)
components. Variable costs are simply evaluated by multiplying the cost rate by the total time
required for remediation, i.e.
C5 L
Cvariable ' for 1&D (1)
(i
e
2
C5 RE
Cvariable ' for radial (1)
( i)
r
where Cvariable ($ L-3) is the total variable cost per unit soil volume, and C5 ($ L-3 T-1) is the variable
cost rate per unit soil volume. C5 is evaluated by estimating the variable daily cost (for monitoring,
insurance, rentals, ... etc) and dividing by the total volume of site. C5 is highly dependent upon the
size of the site and decreases as volume of contaminated soil increases.
Total costs
The total costs per unit volume of soil to be treated are thus given by
Ctotal = Celectrode + Cenergy + Cchemical + Cpost- treat + Cfixed + Cvariable
where Ctotal = total costs per unit volume of soil to be treated ($ L-3); and Cfixed = fixed costs per
unit volume of soil to be treated ($ L-3). Cost evaluation indicates that electrode configuration
will impact electrode, energy, and variable costs. Other costs (chemicals, fixed, and post-
treatment) independent on electrode configuration and spacing.
Optimum Electrode Spacing
1D Applications
Assuming post-treatment, chemicals, and fixed costs are independent of electrode spacing, the
optimum electrode spacing can be obtained for 1D applications by equating the partial derivative
of Ctotal with respect to L to zero, which renders the following equation,
48
*
3 7,200,000 C1 F1
L optimum =
3,600,000 C5 + C2 (∇ )2 *
where Loptimum = optimum electrode spacing (L). This equation provides an estimate for the
optimum electrode spacing that minimizes the total costs of 1D applications as a function of the
properties of the contaminated soil and electric field strength. The optimum spacing is also
dependent upon electrode costs (C1), energy costs (C2), variable costs (C5) and electrode
configuration (F1). This equation demonstrates the impact of the cost ratios C2/C1 (energy cost /
electrodes cost) and C5/C1 (variable cost / electrodes cost) on optimum electrode spacing.
In some cases, time requirements might be the limiting factor where remediation needs to be
FRPSOHWHGZLWKLQDVSHFLILFWLPHSHULRG)RUVXFKFDVHVRQHFDQVXEVWLWXWHWKHYDOXHVRI VRWKDW
the optimum electrode spacing could be evaluated based on time requirement by the following
equation for 1D applications,
2 7,200,000 2 C1 F1 * T
L optimum =
3,600,000 * 2 T 2 C5 + C2 Loptimum
2
Thus, the procedure for design of field implementation is to decide whether the limiting factor is
time or energy.
Radial Applications
Assuming post-treatment, chemicals, and fixed costs are independent of electrode spacing, the
optimum electrode spacing can be obtained for 2-D applications by equating the partial
derivative of Ctotal with respect to RE to zero, which renders the following equation,
7,200,000 C1 F1 ir (
)
RE2&opt ' (1)

3,600,000 C5 RE2&opt % C2 ir2 (
)
This equation provides an estimate for the optimum electrode spacing that minimizes the total
costs of 2-D applications as a function of the properties of the contaminated soil and electric field
strength. The optimum spacing is also dependent upon electrode costs (C1), energy costs (C2),
variable costs (C5) and electrode configuration (F1). The optimum spacing equation provides a
formulation that demonstrates the impact of the cost ratios C2/C1 (energy cost / electrodes cost)
and C5/C1 (variable cost / electrodes cost) on optimum electrode spacings.
If time is the limiting factor, then substituting the value of irN yields the following equation,
49
7,200,000 2
C1 F1 ( TR
RE2&opt ' (1)
3,600,000 ( 2
T 2 C5 % C2 RE2&opt
Thus, the procedure for design of field implementation is to decide whether the limiting factor is
time or energy.
Example Cost Evaluations
The following example is considered to show the role of each cost component. In this example, a
contaminated area of 30m × 60m is assumed. The depth of contamination is assumed to be 3 m.
The soil is a saturated, silty clay. The porosity, tortuosity factor, electrical conductivity, and
coefficient of electroosmotic permeability of the soil are determined from preliminary laboratory
analyses to be 0.4, 0.3, 0.02 S/m, and 2×10-9 m2/V-s, respectively. The ionic mobilities of target
contaminants are taken to be 5×10-8 m2/V-s. The value of Rt is assumed to be 4 and the value of $
is thus calculated to be 1 ×10-7 m3/C.
The mobilization cost of a drilling rig and the labor cost of a two-man operating crew are taken to
be $1000 per day to evaluate C1 (Alshawabkeh et al., 1999). For boreholes to be drilled without
installation of casing and sampling, a continuous flight auger can achieve approximately 65 m a day.
Therefore, the drilling cost is estimated to be $15 per linear meter. Costs for fabrication and
installation of electrodes are approximately $5 per linear meter as the electrodes are reusable.
Therefore, C1 is taken to $20 per linear meter. The electricity cost C2 is assumed $0.04 per kWh.
Cost of enhancement reagent (molecular weight assumed 100 g/mole) is taken as $ 2 / kg. Variable
cost rate is calculated based on two-man crew, 14 hours per week, at a rate of 25 $/ man-hr.
Accordingly, the variable rate will be around 0.001 $/m3-hr, including 30% increase for insurance.
Total cost of other components, including post treatment and fixed costs, is taken as $25 / m3.
Two configurations will be considered: (a) 1-D, where the same-polarity electrode spacing equals
one-third the anode-cathode spacing and (b) 2-D hexagonal configuration. In both cases F1 = 3.
Impact of electrode spacing on electrode, energy and variable costs is demonstrated in Figure 3.3
for the 1-D configuration and in Figure 3.4 for the hexagonal configuration. In these figures, a 1-D
electric gradient ie of 100 V/m and a transformed radial electric gradient irN of 100 volt are assumed
for cost evaluations. For the two schemes provided, increasing electrode spacing showed a
significant decrease in electrode costs. For 1-D case, increasing electrode spacing from 1 m to 2 m
resulted in a more than 80% decrease (from $60 /m3 to about $10 /m3) in electrode costs. However,
increasing electrode spacing beyond 2 m did not result in a comparable decrease in electrodes cost.
Similar behavior is noted in the hexagonal case.
Increasing electrode spacing results in a linear increase in energy and variable costs in the 1-D case.
As indicated earlier, increasing electrode spacing will increase the total voltage applied (assuming
constant voltage gradient), increase energy expenditure and cost. Similarly, increasing electrode
50
spacing increases time requirements and, consequently, variable costs. For the hexagonal case, the
increase of energy and variable costs is a nonlinear function of electrode spacing, as shown in
Figure 3.4.
Impact of electrode spacing on total costs and time requirements for both the 1-D and hexagonal
cases is displayed in Figures 3.5 and 3.6, respectively. Increasing electrode spacing has more
impact on the time requirements for the hexagonal case when compared to the 1-D case. This is
again because time requirements are related to square of the radial electrode spacing. Accordingly,
selection of the optimum electrode spacing is more critical for 2-D applications when compared to
1-D applications. A minimum exists in the cost versus electrode spacings relationship. It is necessary
to provide a mechanism for selecting the optimum electrode spacing that will minimize cost, time,
or both.
51
Table 3.1. Impact of configuration on electrode requirements and size of ineffective areas
Config. Electrode spacing No. of Area of cell No. of electrodes per unit area Ineffective Area
Electrodes (Acell)
per cell (F1)
Opp. Charge Same N % increase Aineff % of
charge Acell
1-D LE LE 1 LE2 1/LE2 0 LE2/2 50%
1-D LE LE/2 2 LE2 2/LE2 100% LE2/4 25%
1-D LE LE/3 3 LE2 3/LE2 200% LE2/6 17 %
Square RE ¥5E 2 2 RE2 1/R2 0 RE 2 50%
Hex. RE RE 3 3(¥5E2/2 ¥5E2 15.5% 3RE2/4 29%
52
LE LE
4 6
LE
2
LE
LE
2 LE
LE
4
6
LE
LE LE LE LE LE
2 2 3 3 3
Area of Cell = L2E Area of Cell = L2E Area of Cell = L2E

2
L2 L L2E
Ineffective Area = E Ineffective Area = E
Ineffective Area =
6 4 6
(a)
2R E
RE 4
RE
2R E RE
2R E RE
4
3 3R 2E
Area of Cell =
Area of Cell = 2R 2 2
E
3R 2E
Ineffective Area = R 2E Ineffective Area =
4
(b)
Area of effective electric field Cathode
Area of ineffective electric field Anode
Figure 1. Approximate evaluation of ineffective areas for (a) 1-D and (b) 2-D
electrode configurations.
53
A r RE A
RW
DE
r
Z
Section A-A
N(r) N max
Anode Cathode Anode

(+) (-) (+)
Figure 3.2 A schematic showing radial electric field distributions.
54
Figure 3.3
55
Figure 3.4
56
Figure 3.5
57
FIGURE 3.6
58
SECTION 4
FIELD DEMONSTRATION
Field demonstration of electrokietic remediation is site specific and the design, implementation and
performance varies from site to site. Successful field studies at various conditions are needed to
support the hypothesis and laboratory experiments that claim the potential of the processes. The
objective of this study is to evaluate the potential of electrokinetic remediation of chromium at
representative field conditions. In particular, this section evaluates the effect of saline water on the
efficiency of chromium extraction by EK under field conditions. The demonstration was conducted
by the Environmental Laboratory of the Engineering Research and Development Center (EL-
ERDC), US Army Corps of Engineers.
Description of Site, Equipment and EK Testing System
The study is conducted at NAS Point Mugu, which is located in Ventura County, California
approximately 50 miles northwest of Los Angeles. Established in 1944, the main base comprises
approximately 4,500 acres. NAS Point Mugu is bordered by Highway 1 on the north and east, the
Pacific Ocean on the south and west, and a Ventura County game reserve on the West and
Northwest. The Old Area 6 shops are located along Beach Road just west of the south end of Laguna
Road (Figure 4.1). Site 5 is a large area where electroplating and metal finishing operations disposed
of their effluent. The waste disposal locations are less than one acre in size. They are the result of
lab and shop waste disposal practices in the Old Area 6 shops between 1947 and 1978.
The area of initial study is approximately ½ acre in and around two former waste lagoons located
in the center of the site. The lagoons were unlined and were used between 1947 and 1978 to receive
wastewater discharge from the electroplating and metal finishing activities. The largest waste
generator in the area was plating shop, which reportedly disposed of up to 95 million gallons of
plating rinsate between 1948 in 1965. In the late 1940's and early 1950's, the photo and rocket fuel
chemical shops disposed of waste photo fixer and developer, organic solvents, chemical wastes, and
rocket fuel into septic tanks which eventually emptied into Mugu Lagoon. In 1994, an emergency
removal action was performed during which approximately 117 cubic yards of material were
excavated from the waste lagoons. The removal action was executed to limit exposure of several
residential and migratory birds and to reduce the source of contamination that could impact surface
and groundwater.
The initial EK test site consists of the two waste lagoons (pits) and its adjacent tidal marsh area. The
original demonstration/validation (Dem/Val) plan was to address the heavy metals contamination
in the lagoon area with an additional EK cleanup effort in the adjacent tidal marsh (Figure 4.2) thick
by approximately 18-ft deep high density polyethylene (HDPE) barrier wall was installed
surrounding the two waste lagoons. This area was given the designation of Test Cell #1 (TC1) while
the adjacent salt water march area was designated Test Cell # 2 (TC2). The barrier was installed to
limit tidal influences and groundwater flow into and out of the demonstration area. It would also
prevent the movement of mobile species outside of the test cell treatment area in the event the EK
59
process could not control the movement of mobilized metals. Because of the presence of the light-
footed clapper rail, a federally- and state-listed endangered species, a 7-ft high frame covered with
a dark mesh screen was installed to enclose the site. This enclosure served to shield the site from
access by the bird. It also allowed free movement by personnel inside the enclosure for normal
system operations without disturbing the bird.
However, due to technical difficulties, particularly the effect of brackish water on conductivity and
transport, the study was transitioned from a Dem/Val to a pilot-scale project. The transition and the
pilot-study were operated by ERDC EL (WES) at the end of October 1998. ERDC EL (WES)
restarted the EK system with a reduced electrode well field in January 1999. Figure 4.2 shows the
location of the original Dem/Val study (Cell # 1) and the area for the pilot-study. This paper focuses
on the results of the pilot study to demonstrate the potential for chromium and cadmium removal
from the site by the application of EK technology.
The main EK system components are: a process control trailer, power supplies, electrode wells,
chemical storage tanks, and fluid control and distribution system. The electrokinetic remediation
system consists of an array of electrodes, a power distribution and control system, automated process
monitoring equipment, and process piping to distribute chemical amendments to the electrode wells
and to extract contaminants from the electrode wells. Other equipment necessary to support system
operations due to the site conditions at NAS Point Mugu included off-gas extraction and treatment
equipment to treat the gases that were generated in the electrode wells during system operation. A
pH control system was used at the cathode wells by regulating the addition of citric acid to the
cathode wells. The pH control system contains several pumps and solenoids that are controlled and
operated via the computer program. If there is a failure in the pH system, the system shuts itself
down. Operation is suspended until a technician corrects the problem. Citric acid was selected
because it is inexpensive and environmentally acceptable. The EK system operation required
electricity (220-volt, 100 amp, 3-phase power), freshwater supply, and telephone lines to be installed
at the site. The electrical supply was needed to provide power to energize the field of electrodes,
pumps, and other control equipment. The fresh water was required for make up water for the
electrode wells. The two telephone lines were for voice communication and system
monitoring/remote control.
The distance between the anode and cathode wells was 15 feet. The anode and cathode wells were
10 feet deep. The distance between like electrode wells was 5 feet. The electrodes were labeled
Anode Well (AW#) and Cathode Well (CW#), depending on the electrode type and its location
(Figure 4.2). ERDC EL (WES) operated the pilot-scale study at reduced electrode field in the north
end of Pit 1 (electrodes AW9-11, AW18-20 and CW8-10). The anode electrode, which operate
under highly corrosive conditions, consisted of 3 feet long, 1-in. diameter titanium hollow tubes
(Eltech) with an iridium oxide coating. The cathode electrodes were constructed of 1/8 inch x 2-inch
x 10-feet long stainless steel mesh. The anode and cathode wells were capped with PVC couplings
for easy removal. The anode wells were sealed with a system attached to vent the gases produced
during system operation (e.g., chlorine and oxygen,). Gas from the wells passed through the
scrubber unit prior to release to the atmosphere. At first, the cathode wells were vented to the
atmosphere, since only small volumes of hydrogen sulfide gas were expected to be produced.
During the demonstration at NAS Point Mugu, hydrogen sulfide gas (H2S) was detected in the
60
cathode wells. Upon determination that H2S was being produced during system operation, the
cathode wells were sealed and the gases were vented to a scrubber unit prior to release to the
atmosphere. The wells were installed using standard well drilling and casing installation practices.
The only notable exception was the extra care required installing the cathode well ceramic casings.
These casings are brittle and easily broken.
Electrical power is applied to the electrode array via three 10 kilowatt (kW) power supplies (EMI
part number ESS 30-333). Each of these power supplies is capable of delivering up to 30 volts (V)
at up to 333 amps (A). The power supplies were wired in series to deliver up to 90 V at up to 333
A. Application of the electric power to the electrode array was controlled by an on-site computer
system with customized LabView 4.0 software. ERDC EL (WES) operated the system with constant
voltage beginning in January 1999. The applied current fluctuated with the varying resistivity of the
soil in the treatment area. The total power supply current as well as each individual electrode well
current was logged by the computer system. The data were collected by computer data
acquisition/control and manually recorded by hand. The data were stored in four separate file types
in text from and are viewable with most spreadsheet software. The data from the field (electrode
wells and other sensors) and the power supplies were collected approximately every 30 minutes to
multiple computer files.
Frequent and extensive monitoring of the electrokinetic remediation process was necessary. To
conduct this monitoring, 18 two-inch diameter piezometer wells were installed in and around the test
cells. A series of piezometer wells were also installed between AW10 and CW9 to determine
transport profiles and pH front (acid front) development. The wells were screened at various depths
and located in positions where contaminant transport or electric field effects would most likely occur
if the electrokinetic process control could not be maintained. The installation data for the wells are
shown in Figure 4.2.
Sampling and chemical analysis were conducted by an independent certified laboratory. Soil cores
were taken from 20 coring points to a depth of 12 feet in TC1 for baseline analysis. The sampling
analysis results are presented in isopleths by depth. The baseline data presented in this section were
extracted from the isopleths by creating a transparency grid overlay for the reduced treatment area
at the north end of TC1 Pit 1. Metal analysis included Cr, Cd, Pb, Cu, and Zn. No significant
concentrations of Pb, Cu, and Zn in the liquid or the soil were detected. The two major soil
contaminants, chromium and cadmium, are presented here.
Processing conditions are summarized in Table 4.1. The volume of the treated soil is estimated
about 64 m3. Initially a total voltage of 60 volts was applied, but it was reduced to 45 volts after 20
days of processing. The reason was the difficulty in controlling the catholyte pH under 60 volt
application. After 118 days of processing, the electrodes were shortened to 4 ft to facilitate extraction
at shallow depths. Further discussion regarding the changes is provided in the results section.
61
Results and discussion
pH profile and Control
The piezometers were sampled before treatment and each month with the regulatory compliance
sampling. Figure 4.3 shows the pH contours before processing (Figure 4.3a) and after 4 months of
treatment (Figure 4.3b) across wells AW10 and CW9. The figure shows the development and
advance of the acid front from the anode towards the cathode. Acidification seems to occur at lower
depths (below 70 in.) and moves towards the cathode. The first few inches close to the cathode were
acidified because of citric acid injection to control the cathode pH at 4. The upper middle section
in the cathode side showed a relatively high pH (6.5 - 7.5).
In the first 20 days, the pH in CW9 was difficult to maintain below 4.0 with electric power applied
at 60 volts and 50 amps. The current level at this applied power resulted in the citric acid cathode
amendment being consumed faster than it could be physically pumped into the cathode wells. To
maintain a pH of 4.0 in CW9, the applied voltage was lowered to 45 V where it remained until the
June suspension of treatment. Occasional pH spikes (pH 12) occurred when the computer failed to
respond to the software or when the software is turned off (Figure 4.4). This action trips the fail-
safe relay circuit that allows a power supply to maintain 9 volts in the test area. Since no citric acid
is being pumped into the cathode wells, the well pH increases. Maintaining electrical energy to the
field was considered a safety precaution to prevent soluble chromium from migrating outside the
confined test area.
Chromium Extraction
The results from the baseline soil characterization indicate that the majority of the chromium
contaminant is located in the top sections of soil nearest the cathode (Figure 4.5a). The lowest
chromium concentration (180 mg/kg) was located near the anode at a depth of 5-ft. This analysis
shows that the entire soil volume in pilot treatment area was completely contaminated with
chromium from the surface to a depth of 10 ft. The initial average contaminant mass of chromium
in the treatment area was estimated to be 2,319 grams.
The soil sampling results after treatment indicate that most of the chromium contamination has
moved upward toward the cathode (Figure 4.5b). The chromium movement in the direction of the
cathode was expected because positively charged trivalent chromium is attracted to the cathode.
Figure 4.5b reveals that the chromium contaminant was not detected or was below the natural Point
Mugu background levels (109 mg/kg) in the sections closest to the anode to over 8-ft toward the
cathode. The total mass of chromium remaining in the soil was estimated to be 1,621 grams.
62
Extracted chromium was measured in the effluent storage tank and in the electrode wells. At the end
of the treatment, the effluent storage tank held approximately 800 gallons of liquid collected from
the anode wells plus some rinse water from the NAS water distribution system. NAS water was
used to rinse out the well fluid from the field pumps, pipes, and valves. The effluent liquid
contained 12 mg/L of chromium. This corresponds to a total of 33 grams of chromium removed
from the site.
Figure 4.6 illustrates the cumulative total chromium concentration with time from the cathode
(Figure 4.6a) and the anode wells (Figure 4.6b). These wells were sampled monthly and quarterly.
The highest concentrations of chromium were discovered in the anode wells not in the cathode
wells. This indicates that a fraction chromium may have existed in negatively charged Cr(VI)
oxyanions. The slope of the chromium concentration lines was flat after the process was terminated.
A total mass of 126 grams of chromium was moved from the soil into the electrode well liquid.
After 4 weeks of treatment, the soil sampling analysis along the piezometer profile between AW10
and CW9 indicated that most of the chromium contamination had risen to shallower depths near the
cathode. The chromium movement can be seen when comparing the pretreatment seen in Figure
4.5a to post treatment seen in Figure 4.5b. The upward movement can be attributed to the electrode
modifications. The field data results reveal that approximately five percent of the chromium mass
had been removed from the soil to the electrode wells. The soil sampling results indicate that 78
percent of the soil volume has been cleared of the chromium contaminant or treated below the Point
Mugu natural background levels. The mass balance error or chromium removal was 24.7 percent.
Cadmium Extraction
The baseline characterization indicates that the majority of the cadmium contaminant was located
in the top sections of soil evenly distributed between the anode and the cathode (Figure 4.7a). The
minimum cadmium concentrations were 5 mg/kg, located at 5-ft and 10 ft depths. The maximum
cadmium concentrations were approximately 20 mg/kg, near the surface. This analysis illustrates
that the entire soil volume was contaminated with cadmium. The initial average cadmium mass in
the treatment area was estimated to be 70.9 grams. Soil sampling results after treatment indicates
that most of the cadmium contamination has moved upward toward the cathode. Figure 4.7b
reveals that cadmium was not detected in most of the sections closest to the anode to over 7 feet
toward the cathode. The total calculated mass of cadmium remaining in the treatment area was
estimated to be 36.8 grams. These results follow the same pattern as the chromium analysis. EK
treatment is effective in removing the cadmium contaminant from the soil. However, additional
testing is required to achieve the study goals of removing the cadmium contaminant from the soil
at Site 5.
In comparing the pretreated cadmium analysis in to post treatment cadmium analysis in Figure 4.7,
the results show that most of the cadmium contamination had moved toward the cathode and was
rising to shallower depths. The analysis revealed that beginning from AW10 to over 7 feet toward
CW9 the soil was cleaned of cadmium contamination or treated below the natural background level.
The data analysis from the six-month sampling revealed that approximately two percent of the
cadmium mass had been moved from the soil to the electrode well liquid. The mass balance error
63
for cadmium removal was 46.3 percent. The analysis indicates that 70 percent of the soil between
AW10 and CW9 had been cleared of cadmium contamination. The bulk of the remaining chromium
and cadmium contaminants are located in the upper soil sections closest to the cathode wells. This
data conclusively verifies the effectiveness of electrokinetic treatment at NAS Point Mugu Site 5.
Electric Current and Energy Expended
The current density reached a peak of 1.79 mA/cm2 on the 17th day of operation. At 60 volts, the
current in AW-11 went to a high of 45 amps. This current level consumed the citric acid cathode
amendment faster than it could be physically pumped into the wells. When the voltage was dropped
to 45 volts, the total current density was 0.97 mA/cm2. Assuming a linear voltage gradient of 9.8
V/m, the apparent electric conductivity of the soil between the electrodes is about 1 S/m. This is a
very high electric conductivity, which is reflective of the site’s saline water.
The total cumulative energy expended was collected from two different sources, the electric energy
meter to the site and the calculated energy expended at the electrodes (Figure 4.8). The readings
from the electric meter represent the total energy supplied to the site while the calculated energy
represents the energy expended at the electrodes to treat the contaminated soil. The cumulative
energy from the electric power meter was 25,798 kWh (208 kWh/m3), and the reading from the data
acquisition system was 24,978 kWh (200 kWh/m3). The difference between the meter and the data
acquisition was 820 kWh. The energy applied to the electrode field was not as high as the total
energy supplied to the site. The computer controlled hardware (pumps, sensors, solenoids, lights,
and refrigerator) consumed energy that contributes to the total energy supplied to the site. To provide
a conservative cost estimate of the energy expended, the higher cumulative energy number was
employed. At a cost rate of $0.08 per kWhour, the total energy expended from January through June
1999 was $2064 ($16.5/m3). For comparison, the difference in cost between the two cumulative
energy calculations was $66.
Impact of Brackish Condition
A critical component of this study is to assess the impact of brackish water on transport of
contaminants. In general, the total current is carried by species in the solution depending upon their
concentrations and mobilities. The total current can be divided into positive charge current and
negative charge current: I = I+ + I-, where I+ is the fraction of the current carried by positively
charged ions and I- is the fraction of the current carried by negatively charged ions. To simplify, and
using conservation of electrical neutrality, I+ should be equal to I-. Which means that half the
current is carried by the positively charged ions and half is carried by the negatively charged ions
in solution. The positively charged ions carrying the charge include calcium, hydrogen, chromium,
cadmium, lead, ... etc. The negatively charge species carrying the current include chloride, hydroxyl,
chromium complexes, etc. Accordingly, a fraction of the current is used for chromium (or cadmium)
transport. This fraction will depend upon chromium form, concentration and mobility relative to
electric conductivity of the medium. Increasing specific ion concentration and mobility will increase
its impact on current. However, increasing electric conductivity of the soil will minimize the amount
of charge carried by this specific species. The high ionic strength and electric conductivity at Point
Mugu significantly decreases the contribution of chromium transport in total electric current. To
64
overcome this problem, a relatively high current density (~ 10 A/m2) was used in this project. The
high electric conductivity of the soil rendered a relatively small voltage gradient (~ 10 V/m). The
outcome is a reasonable energy expenditure (~ 400 kWh/m3) and efficient extraction of chromium
(Figure 4.5b) and cadmium (Figure 4.7b).
65
Table 4.1. Testing Conditions at Point Mugu Site
Cathode:Anode Spacing: 4.57 m (15 ft)

Same Electrode Spacing: 1.5 m (5 ft)
Electrode length: 3 m (10 ft shortened to 4 ft after 118 days)
Soil Volume: 9.14 m x 4.57 m x 3 m = 125 m3 (30 ft x 15 ft x 10 ft)
Initial Conditions
Initial Cr: 180 to 1100 mg/kg
Initial Cd: 5 to 20 mg/kg
Initial pH: 4 to 8
Electric Energy: (Constant voltage, varying current)

Day 1: 60 volts
Day 20: 45 volts
Day 118: 45 Volts Electrode lengths were shortened to 4 ft.
66
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Scale in Feet
Site 20th St. 1
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LEGEND
Water Drainage Ditch
LB&M ASSOCIATES, INC.
Private/Public Lands Base Property
Source: Modified from Fugro-McClelland, 1991
Figure 4.1. NAS Point Mugu General Location Map
67
Figure 4.2. TC1 Electrode Well Field
68
Figure 4.3a. Pilot Study Initial pH Profile Results between AW10 and CW9
Figure 4.3b. Pilot Study pH Profile Results after Treatment
69
14
12
10
Cathode Well 9 (CW9) pH
CW9 pH
6
0
0 20 40 60 80 100 120 140 160 180
Time Since January 1999 Restart (Days)
Figure 4.4. CW9 pH changes during processing
70
15 feet
(+) (-)
200 240 260 300 300 340 370 400 650 800 850 900 900 950 1000 1100
185 190 190 190 200 215 230 245 260 285 300 320 340 360 380 400
180 185 190 190 195 200 215 230 250 275 300 325 350 375 400 410
550 560 580 600 600 600 600 600 600 575 550 525 500 490 485 475
200 210 210 200 200 200 200 205 205 205 210 210 215 215 220 220
10 feet
Concentration > 109 mg/kg from 1997 Natural Pt. Mugu Background Levels
Concentration < 109 mg/kg from 1997 Natural Pt. Mugu Background Levels
Figure 4.5a. Pilot Study Initial Site Characterization Chromium Results.
15 feet
(+) (-)
1 0 0 0 147 5 0 0 318 1351 1935 3222 5163 5052 8226 2072
0 0 90 0 25 0 0 0 236 122 340 510 216 278 344 2419
0 0 0 0 0 0 0 0 37 0 0 47 30 79 0 58
76 0 0 0 0 0 0 0 0 0 0 0 40 33 0 0
43 0 13 0 13 0 542 81 35 1 8 0 14 2 0 0
10 feet
Concentration > 109 mg/kg from 1997 Natural Pt. Mugu Background Levels
Concentration < 109 mg/kg from 1997 Natural Pt. Mugu Background Levels
Figure 4.5b. Pilot Study Soil Chromium Results after Treatment
71
160
Cumulative Total Chromium Concentration (mg/L)
CW8
140
CW9
CW10
120
100
Cathode Wells
80
60
40
20
0
13-Jan-99 12-Feb-99 14-Mar-99 13-Apr-99 13-May-99 12-Jun-99 12-Jul-99 11-Aug-99 10-Sep-99
Date
Figure 4.6a. Pilot Study Cumulative Total Chromium in Cathode Wells
300
AW09
Cumulative Total Chromium Concentration (mg/L)
AW10
AW11
250
AW18
AW19
AW20
200
Anode Wells
150
100
50
0
13-Jan-99 12-Feb-99 14-Mar-99 13-Apr-99 13-May-99 12-Jun-99 12-Jul-99 11-Aug-99 10-Sep-99
Date
Figure 4.6b. Pilot Study Cumulative Total Chromium in Anode Wells
72
15 feet
(+) (-)
20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
5 5 5 5 5 5 5 6 7 8 9 10 10 12 13 14
20 19 18 16 15 15 16 16 16 15 15 14 13 12 12 11
5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5
10 feet
Concentration > 3.1 mg/kg from 1998 N atural Background Levels
_ 3.1 mg/kg from 1998 N atural Background Levels

Concentration <
Figure 4.7a. Pilot Study Cadmium Results from Initial Site Characterization
15 feet
(+) (-)
0 0 2 0 3 0 0 0 0 12 27 44 0 49 78 36
0 0 1 0 0 1 0 0 0 4 14 32 8 13 17 47
0 0 0 0 0 3.5 0 0 0 0 0 2 4 4 4 16
0 0 0 0 0 0 0 0 0 2 0 0 3.3 3.4 3 0
2 1 0 0 0 0 28 0 0 1 0 0 4 5 2 3
10 feet
Concentration > 3.1 mg/kg from 1998 Natural P t. Mugu Background Levels
Concentration <_ 3.1mg/kg from 1998 Natural P t. Mugu Background Levels
Figure 4.7b. Pilot Study Soil Cadmium Results after Treatment
73
30,000
pH Controller
Pumps Clogged
Maintance and Adjustments

for Better pH Control
From Acid Tank

With Biomass
25,000 Voltage Lowered
Failure
to Offgas System
Cummulative Energy (kWh)
20,000
15,000
10,000
Electric Meter
Data Acquistion
5,000
0
0 20 40 60 80 100 120 140 160
Time Since January Restart (days)
Figure 4.8. Pilot Study Cumulative Energy Used
74
SECTION 5
POTENTIAL ENHANCEMENT OF BIOREMEDIATION
BY ELECTROCHEMICAL METHODS
Organic contaminants have been known to be present in many hazardous waste sites (USEPA, 1991;
DOE, 1995; Kelsh and Parsons, 1997). Economical restoration of these contaminated sites to
environmentally acceptable conditions is an important challenge facing the scientific and technical
community. Current in situ soil remediation technologies depend on hydraulic and air flow for
effective remediation of soils and are not as effective in the clean-up of lower hydraulic conductivity
soils (less than 10-5 cm/sec) such as fine sands, silts and clays. In situ bioremediation is an attractive
and often cost-effective option to remediate soil and groundwater contaminated with organics.
Successful implementation of in situ bioremediation is dependent upon presence, or effective
injection, of electron acceptors and nutrients into the porous medium. Microbial processes require
an electron donor, macronutrients (e.g, nitrogen and phosphates), micronutrients, trace nutrients and
an electron acceptor. Microbially-mediated cometabolite transformations require an additional
external electron donor as well. In some cases, inducers may be needed to trigger the microbial
transformation reaction. Effective introduction and transport of these additives is hindered by low
soil permeability, preferential flow paths (channeling), biological utilization, and chemical reactions
in the soil. Complications of site geohydrology, additive transport and associated reactions, coupled
with the observed inefficiency in the field, have been mostly approached by gross overinjection of
the additives. Excessive dosing coupled with the shortcomings of the hydraulically-driven transport
processes can result in nutrient rich areas with excessive biological growth (biofouling). Biofouling
adversely impacts system implementation due to reduced conductivity by microbial growth plugging
the flow paths. Several surveys have concluded that ineffective transport of remediation additives
is the primary cause of system failure for some in situ bioremediation efforts (Zappi et al., 1993;
NRC 1993).
A technology for uniform introduction of nutrients and electron acceptors/donors has been the
principal bottleneck in the successful field implementation of in situ bioremediation (Suflita and
Sewell, 1991; Zappi et al., 1993). An emerging technology for treating such hazardous waste sites
using in situ bioremediation methods is through the application of electric fields to transport the
nutrients as well as bacteria. Electric fields could be used to overcome problems associated with
additives injection into heterogeneous and/or low permeability soils. Uniform and accelerated
delivery of nutrients, and electron acceptors may be achieved using electric injection instead of
hydraulic injection. Uniform transport of ions under electrical fields is controlled by the charge and
ionic mobility of available species in the pore fluid. Accelerated and uniform transport rates of
nutrients, electron acceptors and microorganisms could be achieved in heterogeneous or low
hydraulic conductivity soils by electric fields. The technique could also employ electroosmotic flow
into fine-grained soils to enhance additive injection. This method can be used to stimulate
bioremediation under aerobic or anaerobic conditions.
The conditions generated under dc electric fields and their impact on the porous media are discussed.
This section describes the effect of dc fields on ions transport in soils, electrolysis and geochemical
75
reactions, microbial adhesion and transport, and microbial activity. The interest in these in these
processes is derived from the potential to develop strategies to enhance in situ bioremediation. A
review of ion transport mechanism in porous media under dc fields is provided to address the
potential of injecting and transporting nutrients and biostimulants by ion injection and
electroosmosis and also the possibility of injecting bioaugmentation innoculants by electrophoresis.
A discussion is provided for electrolysis reactions and their effects on pH and dissolved oxygen
(DO) values, which in turn affect microbial survival. Electrolysis reactions are also important as they
cause the production of oxygen and hydrogen and also may cause abiotic degradation of
contaminants. A discussion is provided for the factors that may impact microbial adhesion and
transport under dc fields. A review of studies that investigate electrokinetic extraction of organic
contaminants is also provided. Finally, the results of studies that evaluate the general impacts of
electric fields on anaerobic and aerobic cultures are summarized.
Nutrients Transport under Electric Fields
Injection and transport of bioremediation additives by electric fields are controlled by electrokinetic
transport mechanisms in an ion exchange medium. These transport mechanisms include
electroosmotic advection (or electroosmosis), electromigration (or ionic migration), electrophoresis
and to a lesser extent diffusion.
Acar et al. (1996; 1997) showed that ionic migration could be used for injection and transport of
anionic and cationic additives. In a bench-scale experimental setup, ammonium hydroxide (NH4OH)
was introduced at the anode compartment and sulfuric acid (H2SO4) at the cathode compartment.
The electric field caused migration of nitrate ion from anode towards the cathode and sulfate ion
from cathode towards the anode. The study reported transport rates of 5 to 20 cm/day in fine sand
and kaolinite soil specimens and consequent soil saturation of ammonium and sulfate ions. The study
concluded that ion migration under dc fields can be used to inject nutrients, electron
acceptors/donors to enhance in situ bioremediation.
Redox by Electrolysis
Application of direct electric currents in saturated soils results in redox reactions at the electrodes.
If inert electrodes (such as graphite) are used, water oxidation generates an acid (H+) and oxygen gas
at the anode while water reduction produces a base (OH-) and hydrogen gas at the cathode (Acar and
Alshawabkeh, 1993). Based on Faraday’s law for equivalence of mass and charge, the rate of
electrolysis reactions depends on the total current applied. For a specific reaction, e.g., water
oxidation at the anode, the rate of electrolysis is given by,
I
J=
zi F
where J is the rate of oxidation or reduction by electrolysis (MT-1), I is the current (A), z is the
76
charge of the ion (for hydrogen z = 1) and F is Faraday’s constant (96,485 C / mole). Assuming that
water electrolysis occurs at the electrodes with 100% efficiency, one amp current will oxidize 1/2F
mole H2O into 1/F mole of H+ and 1/4F mole O2 at the anode per second. The same current will
reduce 1/F mole H2O into 1/F mole OH- and 1/2F mole H2 per second at the cathode. It should be
indicated that other electrolysis reactions may occur and limit the water electrolysis reaction. The
type of electrolysis reaction depends upon the chemistry of the electrolyte, pH and the standard
electrode potential for ions in the electrolyte.
Oxidation and reduction generate complex boundary conditions at the electrodes that can either
enhance or retard microbial activity and contaminant degradation. Oxidation at the anode generates
oxygen that stimulates aerobic degradation. An acid (H+) is also produced, which could drop the pH
at the anode to below 2. The acid migrates under the applied electric field toward the cathode and
may acidify the soil. The soil resistance to pH changes depends upon the soil buffering capacity.
However, a pH drop is not favored for microbial growth. Optimum pH for bacterial growth is near
neutrality with minimum and maximum pH values for growth near 5 and 9, respectively (Gaudy and
Gaudy, 1988). A relatively neutral pH is needed to optimize biological activity in the soil. Soil
acidification may also cause dissolution of the soil minerals. Electrolytes conditioning that neutralize
acid generation and enhance delivery of proper additives for bioremediation should be considered.
As an example, the use of ammonium hydroxide at the anode and sulfuric acid at the cathode was
successful in (a) neutralizing the acid and base at the anode and cathode and (b) injection of
ammonium and sulfate ions into the soil (Acar et al. 1996).
Oxygen production is another critical boundary condition generated at the anode. The oxygenated
water at the anode may be introduced into the soil at efficient rates by electroosmotic flow to
enhance aerobic conditions. Preliminary results indicated that the efficiency of gas production by
electrolysis is 75%. Other mechanisms, such as air sparging, in-well aeration, hydrogen peroxide,
oxygen releasing solid compounds, or even cryogenic oxygen generators, can be used to supplement
oxygen requirement. However, the advantage of dc fields is that they serve for both oxygen
generation and transport in low hydraulic conductivity soils. It should be noted that while this
oxygen will enhance conditions for aerobic microorganisms, it is likely to adversely impact the
anaerobic microorganisms. If anaerobic bioremediation is the target treatment method, measures
to remove oxygen at the anode using chemical scavengers or gas-stripping (eg. nitrogen gas) are
needed to prevent adverse impacts on anaerobic microorganisms. Alternatively, an aerobic-anaerobic
treatment could be designed to take advantage of the availability of oxygen in a limited subsurface
zone
Organics Extraction by dc Fields
Electric fields have been used for extraction of the contaminants from the subsurface. Bench-scale
tests and limited field studies demonstrated the use of electric fields for extraction of heavy metal
and radionuclides from soils (Lageman et al., 1989; Hamed et al., 1991; Pamukcu and Wittle, 1992;
Acar and Alshawabkeh, 1993; Probstein and Hicks, 1993; Runnels and Wahli, 1993; Eykholt and
Daniel, 1994; Alshawabkeh and Acar, 1996; Pamukcu et al., 1997). Electric fields have also been
used for electroosmotic extraction of organic contaminants from soils (Shapiro et al., 1989; Acar et
77
al., 1992; Bruell et al., 1992). Recently, the Department of Energy, Environmental Protection
Agency (EPA), Monsanto, General Electric, and Dupont applied electric fields for electroosmotic
extraction of TCE from a site in Paducah, Kentucky using layered horizontal electrodes by the
“Lasagna” process (Ho et al., 1997; 1999a; 1999b). The Lasagna process uses mainly
electroosmosis for extraction of TCE out of the soil into electrode or treatment wells.
Electric fields use in soil restoration has been focused on contaminant extraction by their transport
under electroosmosis and ionic migration. Contaminant extraction by electric fields is a successful
technique for removal of ionic or mobile contaminants in the subsurface. However, this technique
might not be effective in treatment of soils contaminated with immobile and/or trapped organics,
such as dense non aqueous phase liquids (DNAPLs). For such organics, it is possible to use electric
fields to stimulate in situ biodegradation under either aerobic or anaerobic conditions. It is necessary
to evaluate the impact of dc electric fields on the biogeochemical interactions prior to application
of the technique. It is not clear yet how dc electric fields will impact microbial adhesion and
transport in the subsurface. Further, the effect of dc fields on the activity of microorganisms in a soil
matrix is not yet well understood.
Microbial Adhesion and Transport
The presence of appropriate microorganisms (depending on electron-acceptor and nutrient

availability) at the actual site of contamination (sometimes at a micro-scale) has long been
recognized as a key factor in determining if biodegradation/biotransformation will occur, as well as
in influencing the rate of biodegradation. Microorganisms can be present in the subsurface in
suspension (in the pore fluid), as microcolonies or as a biofilm. Bacterial adhesion to porous media
often influences the nature and extent of colonization of a subsurface medium. The biofilm
development model (Characklis and Wilderer, 1988), summarized below, can provide some
understanding into bacterial transport and adhesion in subsurface environments. The "first three
steps" in biofilm development are: (1) Surface conditioning, (2) Transport of microoganisms to the
conditioned surface and, (3) Sorption of microorganisms to the surface. In biofilm literature, it is
recognized that the nature of the bacterial cell surface is a key parameter in determining its adhesion
to any media and eventually the biofilm architecture (Reynolds et al., 1989; Characklis and
Wilderer, 1988; van Loosdrecht et al., 1987). The sorption of microorganisms is due to reversible
sorption (governed by charge/electrostatic interactions) and irreversible sorption (due to production
of extracellular exoploymers and formation of matrix). The dependency of reversible sorption of
bacteria on charge/electrostatic interactions indicates that an applied electric field may play a
significant role in bacterial adhesion and transport in subsurface environments. Further, the role of
bacterial surface (eg., lipid content and surface charge) itself could influence the electrophoretic
mobility of bacteria in porous media. Data available in literature indicate that the presence of heavy
metals alter the electrokinetic properties of bacteria, although the context of these researchers was
not hazardous waste decontamination (Collins and Stotzky, 1992). The imposed dc electric field is
also expected to affect the electrokinetic properties, adhesion and transport of microorganisms. It
is not clear what will be the extent of this effect; however, the authors noted that microorganisms
tend to stick and attach themselves to the electrodes in experiments conducted using diluted sludge
samples under dc fields. The type or activity of microorganisms attached to the electrodes was not
78
evaluated. Electrode polarity did not seem to have an effect on adhesion as microorganisms were
attached not only to the anode but also to the cathode. This might indicate that the adhesion to
electrode surface is not necessarily due to the electric attraction between the negatively charge
microrganisms and the positively charged anode. Further evaluation is needed to verify if this
adhesion is due to reversible sorption, irreversible sorption, or due to electrode charge.
Electric fields will not only impact microorganisms adhesion but will also affect their transport in
porous media. As microbes are generally negatively charged, dc fields will cause their transport
towards the anode. DeFlaun and Condee, (1997) demonstrated electrokinetic transport of a pure
bacterial culture in bench-scale soil samples. Generally, the rate of transport is related to the
effective electrophoretic mobility in soils and is affected by soil physical parameters such as
porosity, pore size distribution and tortousity. The results of DeFlaun and Condee (1997)
demonstrate the potential of using microorganisms electrophoresis for the purpose of
bioaugmentation to enhance in situ bioremeidation. It is also necessary to note that microorganisms
transport in porous media under electric field might not be strictly governed by electrophoresis
alone, since microbes, as living entities, may be subject to other influences or "attractors" and also
tend to form colonies and attach to the soil particle surface.
Microbial Activity under dc Fields
Recently, there has been an increasing interest in the bioelectrochemical processes in medicine and
biosensor fields. Studies showed that low level ac (alternating currents) and dc electric fields (in the
range of volts/cm and up to few hundred Hz) stimulate the metabolic processes (Berg and Zhang,
1993; McLeod et al., 1992, Blank et al., 1992) in a nonlinear way so that only a specific range (or
so-called window) of field strength and frequencies can cause a significant impact (Tsong, 1992;
Fologea et al., 1998). This “electrostimulation” process has been explored in areas that include
enzyme activation, biopolymer synthesis, membrane transport, and proliferation (Berg, 1993).
Furthermore, bioelectrochemical devices (or biosensors) are being developed for manipulation of
bacteria, viruses and genetic material using sophisticated microelectrodes (Buerk, 1993; Ramsey,
1998). Electrostimulation and biosensors research fields are at the micro-scale (might reach the
nano-meter) level, focus on ac fields, and have not yet been employed in the soil bioremediation
area. It is necessary to evaluate the dc field intensities that microorganisms can sustain and also the
“window” of dc fields that may stimulate microbial activity.
Electric fields also introduce environmental changes that affect microbial growth. As discussed
earlier, electrolysis reaction impact pH, Dissolved Oxygen (DO) and other geochemical conditions.
Furthermore, electric fields may produce an increase in temperature. Most microorganisms grow
rapidly at temperatures between 20 and 45 oC and are capable of growing over a range of 30 to 40oC
(Gaudy and Gaudy, 1988). Temperature increase to above 45 oC will significantly limit the growth
of most microbes (some could survive high temperatures). Temperature increase due to current
application will depend upon field strength and resistivity of the medium. Acar and Alshawabkeh
(1996) reported 10 oC increase in temperature in an unenhanced (no additives were used to control
electrolyte pH) large-scale test on extraction of lead from kaolinite.
79
Anaerobic Microbial Activity
The impact of electric current on the environmental conditions and the anaerobic microbial activity
in completely mixed fed-batch reactors was studied at various electric field strengths (Maillacheruvu
and Alshawabkeh, 1999). Experiments were conducted in bio-electrokinetic (BioEK) reactors, which
consist of plexiglass boxes with titanium-coated mesh electrodes mounted at both ends. Electric
fields of 1.5 V/cm through 6 V/cm were applied. Unacclimated anaerobic cultures obtained from
a mesophilic anaerobic digester were used in these experiments.
Limited pH changes may occur if water electrolysis reactions (Equations 3 and 4) occur at the same
rate and efficiency. In a completely mixed reactor, the proton produced at the anode should
neutralize the hydroxyl ion produced at the cathode. However, the results indicated that the pH
decreased to less than 5.5 even under completely mixed conditions in fed-batch reactors. The pH
drop indicate less hydroxyl production at the cathode, either because different electrolysis reactions
occurred (other than Equation 4) or because of biochemical reactions in the reactor. The type and
concentrations of ions in the solution will impact the pH changes and require further investigation.
Sodium bicarbonate was used and was effective in buffering the system for the range of electric field
strengths studied.
Dissolved oxygen was produced in the experimental reactors, proportional to electric field strength
used, where no oxygen scavengers were used. Dissolved oxygen was, however, controlled by
addition of sodium sulfite to the system. In an actual soil, there may exist niches, which are devoid
of oxygen where anaerobic bacteria may survive even if some dissolved oxygen was produced and
not eliminated completely using oxygen scavengers. Further studies in soils are needed to evaluate
this hypothesis. Some anaerobic bacteria (particularly sulfate-reducing bacteria or SRB) may indeed
have survived even in the presence of relatively high concentrations of oxygen.
Electric current in the reactor generally increased slightly with time (5% at 1.5 V/cm to about 15%-
18% at 4.5 V/cm for an exposure period of about 140 hours) at different electric field strengths.
While this suggests that the ionic composition of the electrolyte medium changed over time, results
from this preliminary study indicate that dissolved organic carbon (DOC) removal efficiency and
microbial activity do not appear to be significant, especially at the lower end of electric field
strengths.
Microbial activity was estimated as the capacity of the culture to recover from exposure to electric
currents. Microbial activity was measured as a function of the ability of the anaerobic
microorganisms to consume readily degradable acetate (measured as DOC). A sample of culture
was withdrawn from a fed-batch experimental reactor at regular intervals. One part of the sample
was immediately analyzed (designated the "to sample") for DOC concentration while the other part
allowed to "recover" for a period of 24 hours in an evacuated glass vial to preserve anaerobic
conditions. After 24 hours had elapsed the DOC was measured again. The second part of the
sample was designated the "t24 sample". If the t24 sample shows a decrease in DOC as compared
to the to sample, it is indicative of an active culture. Figure 5.1 shows the microbial activity data
for experiments at electric field strengths of 1.5 V/cm and 4.5 V/cm. These data indicate that, before
80
the electric current was applied, the t24 sample showed more removal (about 20%) of DOC than the
to sample -- indicative of an active culture as noted earlier. From Figure 5.1, it is apparent that the
initial "shock" exposure to the electric current results in a decrease in activity for the t24 sample as
compared to the to sample. This trend continued for several hours during which period the total
DOC percent removal in the experimental reactor also dropped by about 10 to 20% in all the
experiments tested. However, after a period of several hours of exposure, the t24 sample gradually
showed an increase in microbial activity by exhibiting higher DOC removal than the to sample --
even during the application of the electric field. This is an interesting phenomenon since it indicates
a certain degree of acclimation of the culture to electric current, and a tendency for the anaerobic
culture to recover from the initial shock load in terms of changes in environmental conditions due
to application of the electric current. Once the electric current application was stopped, the rate of
DOC percent removal in the experimental reactors gradually improved. Eventually, after the
removal of the electric current, the 24 hour sample showed about 20% higher removal of DOC as
compared to the to sample. These data also suggested that there was essentially no difference in
recover of microbial activity 1.5 V/cm and 4.5 V/cm experiments. Results from 3.0 V/cm and 6.0
V/cm showed the same trends.
Aerobic Microbial Activity
Another preliminary study was conducted to evaluate the impact of dc fields on aerobic
microbial activity in a completely mixed and aerated reactor. The study used a sludge sample
from the aeration tank of Deer Island Wastewater Treatment Plant, MA. The sludge was placed
in two identical polyethylene carboys and aerated by gas diffusing stones connected to an air
source. A batch-fed system was used to maintain the sludge. Percent increment of volatile
suspended solids (VSS) was used to measure growth rate and the sludge was maintained until
steady state growth rates were achieved after about 20 days. Samples were then taken from the
sludge and placed in Bioelectrokinetic (BioEK) reactors (Figure 5.2). The reactors consist of
acrylic boxes (14-cm length × 14-cm width × 10-cm height), which have two holes on the top:
one was used for sampling and for measurement probes (DO, pH, conductivity and temperature
probes), while the other hole was used for the aeration tubing. Two titanium-coated mesh
electrodes were fixed on the inner side of the box as anode and cathode (Fig. 3).
Samples were then taken from the sludge and placed in the BioEK reactors (Figure 5.2). The
reactors were modified to allow aeration of sludge. Electric dc fields of 4, 8, and 16 volts, which
reflect 0.28, 0.57, and 1.14 V/cm dc electric fields, respectively, were applied. These electric
field strengths were less than those used in the anaerobic tests, which makes it easier to control
the environmental changes, such as pH, produced by electrolysis. Initial testing conditions are
summarized in Table 5.1.
Complete aeration and mixing maintained dissolved oxygen around saturation during exposure to
electricity. Temperature measurements did not show any significant change during testing. Although
there was a slight decrease in pH, sludge mixing allowed electrolysis reactions at the electrodes to
neutralize each other, thus minimizing significant pH changes. Anaerobic tests showed a drop in the
pH to about 5.5. The slight drop in pH in the aerobic tests compared to the anaerobic tests may be
81
related to the difference in processing time (which was shorter in the aerobic tests) and the
constituents of the anaerobic and aerobic cultures. It is possible that another electrolysis reaction,
other than water reduction, has occurred at the cathode in the anaerobic tests thus limiting OH-
production. Another possible reason is that the currents used in the aerobic tests are smaller than
those used in the anaerobic tests, which may limit the changes due to electrolysis in the aerobic tests
when compared to the anaerobic tests. In any case, this is an issue that needs further evaluation.
With most variables (pH, DO and temperature) were controlled, any changes in microbial activity
can only be attributed to electric currents. Percent change in chemical oxygen demand (COD) of the
sludge was used as an indication of microbial activity. Other measures of substrate utilization may
be used, such as TOC, DOC, BOD, and/or VSS. However, COD was used because it is easier and
faster than some of these measures and because of our interest in the general response. Some
concerns may rise because microorganisms are organic in nature and COD might not accurately
reflect microbial activity. However, microorganisms consume more organic matter than they
synthesize and the ratio of consumed to synthesized organic matter is about 10:1 under normal
aerobic condition (Gaudy and Gaudy, 1988). Therefore, COD values provide a good indication of
microbial activity. Furthermore, COD values were used for comparison with control test (no electric
field) results and not as absolute values.
Average COD changes are summarized in Figure 5.3. The behavior can be divided into 2 groups:
one describing the low voltage (LV) of 0 and 4 V tests and the other describing high voltage (HV)
of 8 and 16 V tests. After 24 hours, the LV group showed less drop (about 17% difference) in COD,
when compared to the HV group. This is an indication that tests with higher voltage gradients (8 and
16 V) resulted in more degradation of the organic matter. After 48 hours of exposure to electricity,
both LV tests showed the same behavior, where COD dropped to around 42-45% of the initial value.
This is an indication that application of 4 volts (0.28 V/cm) may not be high enough to produce any
changes, when compared to tests with no electricity. On the other hand, the test with 8 volts seems
to cause the most significant drop in the COD value (61% after 48 hours exposure). The impact of
the highest voltage (16 V) seems to diminish after the first 24 hours. While the 16 V tests showed
less COD drop when compared to the 8 V test, it still showed more COD drop when compared to
the LV tests. The change in COD drop between the tests may be attributed to an increased microbial
activity.
The results indicate that dc electric fields (up to 1.14 V/cm) do not have an adverse effect on mixed
aerobic cultures. In fact, an increase in the degradation rate may occur due to increasing the voltage
gradient up to a certain value (0.58 V/cm in this study), beyond which this increase may diminish.
This behavior is similar to electrostimulation by ac electric fields reported in the bioelectrochemistry
research area (Fologea et al., 1998). For the conditions of the preliminary study, the window of
significant response of bacteria stimulation is somewhere between 0.27 and 1.14 V/cm. Further, the
results show that this window of dc range is also affected by time of exposure. This can be
concluded as the impact of the 1.14 V/cm field diminished after 24 hours. However, to confirm this
conclusion, it is necessary to separate the effects of any abiotic processes.
The tests were conducted in an open, mixed and aerated reactor to maintain constant values of pH,
DO, and temperature. Thus the difference in COD drop may not be related to pH, temperature.
82
Aeration and mixing maintained DO around saturation in all tests, thus the effect of oxygen
production at the anode is minimized. The only other process (other than microbial activity) that may
relate to COD drop is abiotic transformation by electrolysis reactions at the electrodes. If abiotic
redox of the organic content occurs in this study, then increasing the current density should increase
the COD drop. The results do not show this pattern, but show a peak followed by a decrease in COD
drop with increasing current density (Figure 5.3). Accordingly, microbial activity may be the major
factor in the difference in COD drop obtained in tests with different current densities.
83
Table 5.1. Initial testing conditions for aerobic tests.
Sludge Volume ~ 1.5L

Volatile Suspended Solids (VSS) ~ 280 mg/l
Chemical Oxygen Demand (COD) 390~414 mg/l
Dissolved Oxygen (DO) ~ 8 mg/l
pH ~8
Conductivity 0.5~1.0 mS/cm
Voltage 0 (3); 4V (3); 8V
(No. of Tests) (2); 16V (2)
84
50
40 EF Applied
30
20 EF Removed
10
%
Removal 0
-10
1.5 V/cm + Sulfite
-20
4.5 V/cm + Sulfite
-30
-40
-50
0 100 200 300 400 500 600
Time (Hours)
Figure 5.1. Variation in anaerobic microbial activity under electric fields (Maillacheruvu and
Alshawabkeh, 1999).
Aeration dc Power Supply

Tubing
Air
Probe
Electrode
Electrode
Sludge
Reactor Sample
Porous Stone
Magnetic Stirrer Stir Bar
Figure 5.2. A schematic of BioEK reactor
85
70
0V
60 4V
8V
% Drop of COD
50
16 V
40
30
20
10
0
0 20 40 60
Time (hour)
Figure 5.3. Average COD drop in aerobic tests

(electrode spacing =14 cm)
86
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BASICS AND APPLICATIONS OF

Handouts Prepared for a

Universidade Federal do Rio de Janeiro (COPPE-UFRJ)

19-20 November 2001

SECTION 1: INTRODUCTION AND OVERVIEW 3

SECTION 2: THEORETICAL BASIS FOR

SECTION 3: PRACTICAL ASPECTS OF 1D AND 2D

SECTION 4: FIELD DEMONSTRATION 59

SECTION 5: POTENTIAL ENHANCEMENT OF BIOREMEDIATION

Soil and Groundwater Contamination in the US

where no: ionic concentration (ions/m3) in the free pore fluid,

Accordingly, for a simple case of monovalent ions,

Substituting ρ into the Poisson Equation,

Electrokinetic Phenomena in Soils

Electrokinetics is defined as the physicochemical transport of charge, action of charged particles,

2H2O - 4e- O2 + 4H+ (anode)

Soil pH and Geochemical Reactions

Kaolinite (1:1 mineral)

Smectite (Montmorillonite) (2:1 mineral)

Illite (2:1 mineral)

Figure 1.2 Effect of pH on the Surface Charge of Montmorillonite and Kaolinite

Distance from clay surface

Figure 1.3 A Schematic of Charge Distribution at the Clay Surface

(a) Electric Gradient (c) Electrical Gradient

(b) Water Flow Induces (d) Particle Movement

Figure 1.7 Electrokinetic Phenomena in Soil

where kh is the coefficient of hydraulic conductivity (LT-1), ke the coefficient of electroosmotic

J i = Di ∇(- ci ) + ci (u i + k e) ∇(-Φ ) + ci k h ∇(- h)

ZKHUH GLPHQVLRQOHVV LVDQHPSLULFDOFRHIILFLHQWDFFRXQWLQJIRUWKHtortuosity of the medium.

Applying a DC current through a soil-water-electrolyte medium generates an electric field causing

Conservation of Mass and Charge

Reactive transport of charged species is controlled by rates of geochemical reactions (Ri).

ZKHUH LVWKHEXONGU\GHQVLW\RIWKHVRLOsi is the adsorbed concentration of the component j per

It is necessary to account for the precipitation/dissolution reactions in the formulation of mass

where Rjp is the rate of production of precipitate j.

General System for Modeling Transport

In other words, consider the following chemical reaction,

Substituting flux equations into charge conservation equation:

Simplifying and substituting Σ zj cj = 0,

Accordingly, for Cp=0, we get:

Electrokinetic Remediation Models

Pore Diameter (µm) Wet of optimum

1. Hydraulic Advection X1 = (kh ih) T 2. Diffusion

1. Hydraulic Advection X1 = (kh ih) T 2. Diffusion

Figure 2.2 Transport Mechanisms of (a) cations and (b) anions

Figure 3.2 Boundary condition at the anode

Contaminants type and concentrations

Chelating or complexing agents

Voltage and current levels

Electric Field Distribution

Electrode configuration and time requirements

density, then we get,

2-D Radial Transport

Since (RW)2<< (RE)2, this equation can be simplified as,

Substituting the value of Iz from,

Electric energy cost

Costs for fabrication and installation of electrodes

Celectrode ' C1 N (1)

Cost for enhancement agent

Ctotal = Celectrode + Cenergy + Cchemical + Cpost- treat + Cfixed + Cvariable

Optimum Electrode Spacing

RE2&opt ' (1)

Example Cost Evaluations

ZKHUH GLPHQVLRQOHVVLVDQHPSLULFDOFRHIILFLHQWDFFRXQWLQJIRUWKHtortuosity of the medium.

ZKHUH LVWKHEXONGU\GHQVLW\RIWKHVRLOsi is the adsorbed concentration of the component j per