Environ. Sci. Technol.
1997, 31, 1191-1197
Soil Chemistry Effects and Flow
Prediction in Electroremediation of
Soil
JOHN M. DZENITIS*
Department of Mechanical Engineering, Massachusetts
Institute of Technology, Cambridge, Massachusetts 02139
This work addresses processes occurring during the
removal of contaminants from soils using electric fields.
Laboratory experiments and mathematical modeling are used
to study the changes in the flows of ions and pore liquid
during the process; these flows are directly related to the
removal of charged and uncharged contaminants by elec-
tromigration and electroosmosis, respectively. Soil properties
are explored by electrophoresis measurements, acid/
base titrations, and elemental analyses of pore solutions,
then incorporated into an electrochemical transport model,
and compared to electroremediation experiments. It is found
that a soil chemistry model involving cation exchange and
aluminum chemistry must be included to describe the
process accurately. Varying electroosmotic flow is suc-
cessfully predicted, but only until the development of a
low ionic strength region in the medium. The insight gained
allows the mechanisms of electroosmotic flow reversal
and cessation to be identified. As importantly, this investigation
finds the low ionic strength region to be an undesirable
but likely occurrence with or without significant effects from
soil chemistry and shows how controlling the system
chemistry makes the electroremediation technique more
robust in practice.
Introduction
Electroremediation is an innovative method for removing
contaminants from soil using in situ, low power, dc electric
fields. Like other in situ methods such as bioremediation,
vapor extraction, and soil flushing, electroremediation has
advantages in avoiding high costs and human health risks of
excavation. Additionally, electroremediation is well-suited
to heavy metal contaminants, unlike bioremediation and
vapor extraction, and it is applicable to contaminants in
heterogeneous and low-permeability soils, unlike soil flushing.
Charged contaminants such as heavy metals in solution are
primarily moved by electromigration, and uncharged con-
taminants such as soluble organic molecules can be moved
with the bulk liquid in the presence of charged soil surfaces
by electroosmosis (1, 2). Once the contaminants reach the
electrode reservoirs, the solutions can be easily pumped out
and treated.
Laboratory experiments (3-11) and limited field work (12,
13) have proven that it is possible to achieve nearly complete
removal of contaminants using electric fields. However, these
studies have also shown that the approach can fail when flow
of charge (current) or flow of mass (convection) are not
maintained. Determining the causes of decrease in these
* Present address: Monsanto Company U4E, 800 North Lindbergh
Boulevard, Saint Louis, MO 63167; telephone: 314-694-8696; fax: 314-
694-1531; e-mail address: jmdzen@ccmail.monsanto.com.
S0013-936X(96)00707-9 CCC: $14.00  1997 American Chemical Society
flows is thus of great importance. For electromigration, Hicks
and Tondorf (10) showed how products of electrode reactions
could halt the removal of heavy metal contaminants by
affecting the metal speciation. By controlling the cathode’s
product, OH-, they achieved removals of over 95%. For
electroosmosis, Shapiro and Probstein (6, 8) showed that in
some cases convective flow ceased before high removal
percentages were reached. They found that by using a basic
purge solution to limit the anode’s product, H+, they could
promote flow toward the cathode. The specific mechanism
for electroosmotic flow cessation has not been as conclusively
identified as in the electromigration case, largely because of
the complexity of the multispecies electrochemical transport.
The most physically realistic model of electroremediation
transport was introduced by Shapiro et al. (5) and extended
and generalized by Jacobs et al. (14) and Jacobs and Probstein
(15). Despite the detail of this model, the electroosmotic
flow velocity is based on the measured flow rate, so the model
is not predictive in terms of convective velocity. In particular,
the causes of varying flow rate and flow cessation, so important
to contaminant removal by electroosmosis, cannot be
determined. Eykholt was the first to include dependencies
required to model changing electroosmotic flow during
electroremediation (16-18). His model did show varying flow
rate, and he was able to predict a change in the direction of
electroosmotic flow when acid was added to the cathode
reservoir. However, there was not quantitative agreement
between his experiments and numerical simulations. In this
paper, we develop the first quantitatively accurate predictions
of varying charge and mass flow during electroremediation.
Insights into the mechanisms of flow cessation are uncovered
in the process.
Experimental Section
Electroremediation Experiments. The apparatus used for
the one-dimensional electroremediation experiments is
shown schematically in Figure 1 and described in detail in
ref 19. The soil mixture with length ≈150 mm was contained
in a clear PVC tube with an inner diameter of 54 mm. The
ends of the soil were held by filter paper against a stainless
steel screen that acted as a mechanical support and voltage
probe. Electrode reservoirs on either side of the soil contained
carbon fiber electrodes (Fiber Materials Inc., Biddeford, MA)
across which the voltage was applied. The cathode reservoir
(165 mL) was connected to a tank on a scale, and the anode
reservoir was part of a gravity-fed recirculation system (total
volume of 4500 mL) using a return pump with wetted surfaces
of polypropylene. This large volume gave the anode reservoir
a high chemical capacitance, useful for controlling the system
chemistry as described below. The pressure at the ends of
the cell was balanced by adjusting the feed tank height, so
all of the measured mass flow resulted from electroosmosis
(2). The dc power supply was adjusted throughout the
experiment to maintain 15 V across the 150 mm soil length.
Measurements of current, applied voltage, effluent mass,
applied soil matrix stress, and local voltage and pressure in
the soil were made with a digital data acquisition system.
The soil used was an acidic form of a nearly pure kaolin
clay (Albion Sperse 100, Albion Kaolin Co., Hephzibah, GA).
A barely-liquid mixture was made by gradually stirring the
dry clay into a 10 mM NaCl solution until a solid:liquid mass
ratio of 1:1 was reached. The loading piston was used to
gradually consolidate this mixture in the test cell to assure
a tight seal with the walls.
To investigate the effect of chemical changes on the
process, two electroremediation experiments are presented
here. In the first experiment (untreated), the main electrode
VOL. 31, NO. 4, 1997 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1191
FIGURE 1. Apparatus used for electroremediation experiments. Measurements of current i, voltage distribution V, effluent mass m, and
soil matrix stress s are indicated.

products, H+ and OH-, were not controlled. As the experi-

ment progressed, the pH at the anode reservoir dropped to
2, and the pH at the cathode reservoir increased to 11. In the
second experiment (base addition), the anode product H+
was replaced with Na+ by periodically adding concentrated
NaOH to the reservoir, which kept the anode pH above 9.
This approach is similar to that taken by Shapiro and Probstein
(6, 8).
The electroosmotic flow rate through the medium can be
characterized with an average electroosmotic permeability
ka ) u/Ea (m2 V-1 s-1), where u is the volumetric flow per unit
area per unit time or average interstitial velocity (m s-1) and
Ea is the applied electric field (V m-1). In one dimension, Ea
is the voltage drop across the medium divided by its length.
The use of ka for flow of mass emphasizes that the flow results
solely from the electric field and forms a useful analogue
with average conductivity and flow of charge later. The initial
conditions are uniform, and if the charged double layer at
the solid/liquid interface is thin as compared to the inter- FIGURE 2. Electroosmotic flow rate in terms of average electroos-
particle distance, the electroosmotic permeability is given by motic permeability ka ) u/Ea for experiments with and without base
addition at the anode. At 7 days, the untreated experiment has
ζ displaced approximately 1 pore volume and shows flow cessation,
ka ≈ - at t ) 0 (1) while the base addition experiment has displaced over 2.2 pore
µτ2
volumes and is increasing.
where  is the permittivity of the liquid (6.93 × 10-10 C V-1
m-1 in 298 K water), µ is the viscosity (kg m-1 s-1), τ is the of the pore solution modified by the tortuosity factor:
dimensionless porous medium tortuosity, and ζ is the
F2
ζ-potential (V), which is identified with the electric potential
at the soil/liquid interface (2). The tortuosity is a constant
σa ≈ ∑z ν c
τ2
2
j j j at t ) 0 (2)
(g1) introduced to account for the indirect path through the
porous medium. As the experiment progresses, the average where F is Faraday’s constant (96 487 C mol-1), zj is the charge
electroosmotic permeability involves a spatial average because number of the species j, νj is the mobility (mol s kg-1), and
conditions in the medium become non-uniform (5, 8). cj is the concentration (mol m-3 or mM). When the chemical
Equation 1 no longer applies, but the experimental definition composition changes, σa becomes a complicated spatial
ka ) u/Ea still holds. The experimental electroosmotic average involving varying concentrations, diffusion, local
permeability is plotted in Figure 2. The initial behavior of electric field effects, and the surface conductivity (5). The
the two experiments was identical, but the flows diverged experimental definition σa ) i/Ea still holds at these later times,
after 2 days. The experiment with base addition showed and these results are shown in Figure 3. The initial behavior
increasing flow rate while the untreated experiment’s flow of the two experiments was again identical up to 2 days and
began to cease at 7 days. At this point, the experiment with then diverged as the conductivity of the base addition
base addition had displaced over 2.2 pore volumes while the experiment began to rise dramatically at about 4 days.
untreated experiment had displaced only 1. Soil Medium Transport Properties. To determine why
The charge flow analogue to the mass flow above is mass and current flow decreased in the first case and dropped
interstitial current density i, which is movement of charge but later increased in the second case, a detailed numerical
per unit area per unit time (A m-2). As above, the porous model was used to track the multispecies transport including
medium’s condition can be represented by a single value, in electromigration, electroosmotic convection, diffusion, and
this case the average electrical conductivity σa ) i/Ea (S m-1). chemical reactions. In this work, we used a one-dimensional
Initially the concentrations are uniform and surface con- version of the model introduced by Shapiro et al. (5) and
ductivity can be neglected, so σa is simply the conductivity extended by Jacobs et al. (14) and Jacobs and Probstein (15).

1192 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 31, NO. 4, 1997

FIGURE 3. Charge flow rate in terms of average electrical
conductivity σa ) i/Ea for experiments with and without base addition
at the anode. Both experiments show an initial drop in conductivity,
but the base addition experiment’s conductivity begins to rise
dramatically at ≈4 days.
The deviations and details are not reproduced here. The
required solvent properties (density, viscosity, permittivity)
were taken to be those of pure water, and the solute properties
(diffusion coefficient, mobility, chemical equilibrium coef-
ficients) were taken to be those of the infinitely dilute species
in water. The porous medium properties (porosity, tortuosity,
hydraulic permeability, surface conductivity, surface poten-
tial, chemical behavior) depend on the specific soil and local
conditions in the medium, so these properties were deter-
mined separately. The results are summarized below, and
more details can be found in ref 19.
A porosity of 0.54 was measured from consolidation tests,
and a tortuosity of 1.65 was calculated from eq 2 using an
initial conductivity measurement. The hydraulic permeability
was measured to be 4 × 10-16 m2 at the initial conditions, and
a surface conductivity of 10-3 S m-1 measured by Shapiro (6)
for the same clay was used.
The ζ-potential of the surface seen in eq 1 is a property
depending on complex physicochemical interactions (20).
Given the scale of the transport problem and the complex
composition of soils, empirical data and major simplifications
are required. Microelectrophoresis measurements of the
kaolin clay’s ζ-potential were made with a Zeta-Meter 3.0+
(Zeta-Meter Inc., Long Island, NY) in hydrosols of various
composition. Since pH, ionic strength I ) 1/2∑z2j cj, and
exchangeable cation concentration are key parameters in
determining ζ-potential, the solutions were designed to
explore these dependencies. The pH was varied with HCl
and NaOH because NaCl was used as a background electrolyte
in the electroremediation experiments; it can be shown that
the electroremediation process effectively forms this acid and
base by separating the salt’s ions (19). The initial ionic
strength and cation concentration were varied by adding
NaCl to each of the solutions so they had one of three Na+
concentrations: 0.1, 10, or 200 mM. Measurements at 1 and
6 days showed that there was generally little change in
ζ-potential over this period.
The measured ζ-potentials are shown in Figure 4 together
with a simple empirical fit of the data. The pH had a great
effect on the clay, resulting in ζ-potentials from +10 mV to
-45 mV. Sodium concentration had an effect only for pH >
6. In this range, the ionic strength is equal to the sodium
concentration, so there was a decrease in ζ-potential mag-
nitude for higher ionic strengths. This behavior is consistent
with more extensive work on clays and metal oxides (20, 21).
The empirical fit shown in Figure 4 was based on depend-
encies seen in these works; we assumed a point of zero net
charge at pH 6 and linear dependence on pH and log I. The
FIGURE 4. ζ-potential measurements and empirical fit for varying
pH and at three Na+ concentrations. The model assumes a point
of zero net charge at pH 6 and linear dependence on pH and the
logarithm of ionic strength.
form can be physically justified, but the number of data points
used here is really insufficient for the curve fit. This is certainly
an area that could bear further work. The pH dependence
is similar to the measurements of Lorentz (22), which had
less variation in ionic strength. Eykholt and Daniel (17) used
Lorenz’s data to include ζ-potential dependence on pH.
Soil Chemical Behavior. The chemical properties of the
soil medium were the final part of the system to be
characterized. Chemical behavior is important because it
determines the species that are present, the electric field
distribution (via the conductivity distribution), and the soil
surface charge; in other words, chemical interactions deter-
mine what is present and how it moves. Despite its
importance, the issue of soil chemistry has been avoided in
electroremediation work because of its complexity. Here,
soil chemistry was tackled in a manner similar to that used
for the surface potential above. The key, again, is to realize
that electromigration separates the background electrolyte
ions and replaces them with electrode products, so that acid/
base (HCl/NaOH) titration is the appropriate way to explore
the soil’s chemical behavior.
Alkalinity is the concentration of strong base minus the
concentration of strong acid in a solution. For a system with
only H+, OH-, Na+, and Cl-, the alkalinity is given by Alk )
[Na+] - [Cl-]. In this case, the concentrations of all species
are known when alkalinity and ionic strength are given if
electroneutrality, ∑zjcj ) 0, and water equilibrium, [H+][OH-]
) Kw, are assumed to always hold (23). The titrations were
performed with initial alkalinity -100 e Alki e 100 mM using
NaOH for positive Alki and HCl for negative values. Instead
of trying to completely cover the two-dimensional alkalinity/
ionic strength space, two extremes were taken in the titrations:
(a) Constant initial ionic strength with NaCl added as
necessary to make Ii ) 100 mM.
(b) Minimum initial ionic strength with no NaCl added so
Ii ≈ |Alki|.
In making the soil mixtures, a compromise was struck
between reproducing the electroremediation test conditions
and having a workable mixture. A solid:liquid mass ratio of
1.5:1 was selected for the initial pH experiments because the
resulting slurry could still be stirred but was close to the
concentration in the electroremediation experiments (2.2:1).
The concentration effect was incorporated later.
The pH electrode measurements after 24 h are shown in
Figure 5 versus initial liquid alkalinity. The pH curve for a
solution without weak acid or base is also plotted for reference.
The relative flatness of the experimental curves represents a
buffering resistance to pH change. The clay shows some
VOL. 31, NO. 4, 1997 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1193
FIGURE 5. Experimental titration of kaolin clay showing buffering
to both acid and base relative to a solution with no weak acid/base
behavior. There is little difference between the constant and varying
ionic strength paths.

buffering of acid and more pronounced buffering of base,

which is expected because this particular clay is in acidic
(H+) form. The acidic nature of the clay is seen as well as in
fact that with no added alkalinity, the initial pH is less than
7.
Ionic strength had little effect on the titration curve. This
is an unexpected result in some ways because surface
chemistry models usually include ionic strength dependence,
and simple ion exchange models would predict a dependence
on sodium concentration. On the other hand, the relative
insensitivity to background electrolyte compared to H+ is
common and is the same sort of behavior seen for the surface
potential. There is some deviation between the two curves
for small positive alkalinities in Figure 5, and those differences
are consistent with higher Na+ concentration displacing more
H+ from the clay surface. The differences are small on the
overall scale, however, and the dependence on ionic strength
will be neglected from now on.
Since the clay was seen to have a significant chemical
effect, another series of titrations was performed together
with elemental analyses of the resulting pore solutions. A
slightly lower solid:liquid mass ratio (1.2:1) was used to make
it easier to obtain liquid for the analysis, and only the constant
ionic strength titration was performed. The mixtures were
prepared as before, and 24 h later pore liquid samples were
separated from the mixtures by centrifuging through tubes
with internal membranes (Ultrafree CL 0.45 µm, Millipore
Inc., Bedford, MA). The pore solutions were analyzed for Na,
Cl, Al, Ca, Fe, K, and Mg using inductively coupled plasma
(ICP) spectroscopy in a Perkin-Elmer Plasma 40 (Norwalk,
CT). Since Cl cannot be detected with this device, its
concentration was determined indirectly by AgCl precipita-
tion. In retrospect, since kaolinite is an aluminosilicate, silicon
should have been added to the elements analyzed. The clay
behavior can be modeled without silicon, but better results
might have been possible had it been included.
The results of the elemental analyses are shown as changes
in pore liquid concentration multiplied by magnitude of the
ion charge in Figure 6. Presenting the data in this way weights
the elements according to their charge contribution. This is
not strictly true for aluminum, however, since Al(OH)4- will
form at high pH. The major trend seen is consumption of
Na+ in the positive alkalinity range. This mechanism can
explain the buffering to base (NaOH) seen in Figure 5, as will
be discussed below. The changes in Cl- and in Na+ near zero
alkalinity may not be significant; in this range, [NaCl] ≈ 100
mM and the accuracy of the analysis are probably not better
than 10% for Cl- and 5% for Na+.
FIGURE 6. Clay chemical effect in titrations in terms of measured
change in pore liquid concentration. Significant consumption of
sodium (a) and release of aluminum (b) are seen.
Changes in Al, Ca, Fe, K, and Mg are only seen as releases
since none of these species were present in the liquid initially.
The greatest effect was from Al release at both negative
and positive alkalinities. In addition, Ca and Mg were
released in similar amounts in negative alkalinity. There was
no change in Fe or K concentration. All of these measured
clay element responses are consistent with the pH results;
they are changes that buffer the system pH to both base and
acid addition.
It is clear that the clay’s reactive concentration range (≈100
mM) is significant on the scale of the initial electrolyte
concentration (10 mM). What is not clear is how the soil
affects electroremediation and how the soil behavior should
be incorporated in the transport model for predictive
purposes. The simplest means of incorporating soil chemistry
would be to use the mineral’s equilibrium equations, but it
can be shown that the measured species and concentrations
do not correspond to kaolinite equilibrium. This is not
surprising given natural impurities and the long time scale
of mineral equilibrium. Creating artificial equilibrium models
can be successful, however, because the time scale of simple
surface reactions [minutes (23)] is short as compared to the
time scale of electroremediation. Three different models of
the soil behavior were constructed for use in numerical
simulations of the electroremediation experiments. These
models are briefly introduced below, then included in the
electroremediation model, and compared to the data in the
section Applications of Models to Experiments.
When soil chemistry is ignored here, the species present
are H+, OH-, Na+, and Cl-; the chemical reactions are water
electrolysis at the electrodes and water equilibrium through-
out the liquid. Soil chemistry is included by introducing
additional species and chemical equilibrium reactions to the

1194 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 31, NO. 4, 1997

chemical system. The simplest model of the measured
buffering behavior (Figure 5) is an amphiprotic acid/base
site XH capable of accepting or donating a proton. The solid
then acts as a weak acid and a weak base, buffering the
medium to additions of base and acid through the reactions

XH + Na+ + OH- ) X- + Na+ + H2O

(3)
XH + H+ + Cl- ) XH2+ + Cl-

A partitioning function fit to the measured pH response was

used. This was taken to be a function of pH only because the
next likely dependence, ionic strength, was seen to have little
effect in the titration.
The acid/base site model is designed to match the
experimental pH response, but it ignores the ion consumption
and release seen in Figure 6. Ion exchange behavior is well
known in the field of soil chemistry (see, e.g, ref 24) and can
be used to reproduce the cation consumption and release
seen in the elemental analysis results. Since Na+ was the
major participant, a sodium ion exchange site is used in the
second soil chemistry model, giving buffering reactions:

XH + Na+ + OH- ) XNa + H2O

(4)
XNa + H+ + Cl- ) XH + Na+ + Cl-

Since H+ and Na+ are the only cations in this model, Na+
release serves as a substitute for the actual release of Al3+,
Ca2+, and Mg2+. Again, the partitioning function was made
to fit the data in Figure 5.
The third soil chemistry model reproduces the experi-
mental aluminum release by including solid aluminum
hydroxide Al(OH)3(s) as a species. This is largely insoluble
at zero alkalinity, but dissolves when sufficient amounts of
acid or base is added, which approximates the aluminum
release seen in Figure 6. The initial amount of Al(OH)3(s)
was based on the maximum dissolved concentration, and
literature values (23) were used for the solubility product and
equilibrium constants of the dominant dissolved species, Al3+
and Al(OH)4-. As above, sodium ion exchange was used to
give the Na+ consumption behavior and match the experi-
mental titration pH.
Applications of Models to Experiments
Simulations of electroremediation transport were run without
soil chemistry and with soil chemistry models based on acid/
base, ion exchange, and ion exchange/aluminum hydroxide
reactions. The first set of simulations focused on soil
chemistry effects, and the experimental electroosmotic
permeability (Figure 2) was used as an input. All other
parameters were either determined from independent ex-
periments or calculated in the simulation. Even using the
experimental electroosmotic permeability, the transport
problem is quite complex: the concentration and electric
potential distributions must be found, and the migration,
diffusion, and chemical reactions of all species must be
determined as they progress in time and space. The soil
surface species (XH, XNa, X-, XH2+) and solid aluminum
hydroxide are immobile, but their local concentrations change
as the transport shifts the mobile species in solution.
Comparisons between the simulations and experiments can
be made in terms of the medium’s local and average
conductivity.
Figure 7 shows the average conductivity for experiments
and simulations with experimental mass flow as an input.
The average conductivity involves a spatial integration of the
species’ concentrations throughout the medium (related to
eq 2), and the poor agreement in Figure 7a shows that the
composition of the pore solution was not properly predicted.
FIGURE 7. Average conductivity for experiments and (a) NaCl
simulations (ignoring soil chemistry) and (b) ion exchange/aluminum
hydroxide soil model simulations with experimental mass flow as
an input. The poor agreement in panel a and the success in panel
b shows that the medium chemistry is not properly predicted without
including soil effects.
Better results were obtained using the acid/base and cation
exchange soil models, but close agreement in both conduc-
tivity and voltage distribution required the ion exchange/
aluminum hydroxide model (Figure 7b).
In the next set of simulations, the single “free” input to
the runs abovesthe electroosmotic flow velocityswas no
longer specified. Instead, the empirical surface potential
model shown in Figure 4 was used in determining the local
contributions to the electroosmotic flow. The inputs were
all determined from independent experiments, and the
evolution in time was determined solely by the numerical
model. Figure 8 shows the flow rate as average electroosmotic
permeability for experiments and simulations with and
without soil chemistry. As expected from the conductivity
results, the case ignoring soil chemistry (Figure 8a) could not
predict the electroosmotic flow accurately. The ion exchange/
aluminum hydroxide model gave much better results (Figure
8b), properly predicting initially negative flow (towards the
anode), early increase, and subsequent plateaus. Once the
flow models diverged significantly from the experiments, the
species’ distributions became incorrect, and the simulated
system became unstable. The instability of the system and
the divergence of both experimental and modeled flow around
1.7 days will be discussed below.
Because the empirical surface potential model (Figure 4)
was a weak link in the analysis, another simulation based on
Lorenz’s data (22, 17) was run. This showed a faster initial
increase and higher plateau than seen in Figure 8b, but gave
a similar overall behavior.

VOL. 31, NO. 4, 1997 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1195


FIGURE 8. Electroosmotic flow rate in terms of electroosmotic
permeability ka ) u/Ea for experiments and (a) NaCl simulations
(ignoring soil chemistry) and (b) ion exchange/aluminum hydroxide
soil model simulations with no free inputs. A soil chemistry model
is necessary for quantitative predictions, and even then experiment
and model diverge at ≈1.7 days.
Discussion
Quantitative prediction of electric and electroosmotic flow is
important in improving understanding of the processes
occurring during electroremediation. One phenomenon that
can now be better understood is electroosmotic flow initiation.
Negative initial flow is not surprising given that (1) the
electroosmotic permeability can be negative (ζ > 0) for acidic
pH and (2) clays that give an acidic initial pH are often used
in laboratory work. The more interesting question is why the
flow becomes positive. The answer is that the local electric
field becomes large precisely where the local electroosmotic
permeability takes on significantly positive values, increasing
the flow toward the cathode. This is predicted even in the
absence of soil chemistry because the NaOH solutions formed
near the cathode have lower electrical conductivity (hence
higher field) than the HCl solutions created near the anode.
A related but more pronounced effect is seen when the proper
soil chemistry model is included; the soil reaction near the
cathode (eq 4a) removes charged species and markedly
decreases the local conductivity. This makes a small region
near the cathode (10-20% of the total medium length) develop
a large electric field and provide virtually all of the positive
pumping power.
Another phenomenon, at least as important as electroos-
motic flow initiation, is the electroosmotic flow cessation
seen in this and other experimental work. The most prevalent
qualitative explanation of flow cessation involves the soil’s
point of zero net charge (pH0, where ζ ) 0). However, it is
1196 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 31, NO. 4, 1997
unlikely that the pH in the high field region is exactly pH0.
Although the model here did not predict flow cessation, the
reason for its occurrence is indicated. The fundamental
physicochemical effect is the development of large Debye
length (thickness of the charged liquid layer adjacent to the
charged clay solid) in the low ionic strength region formed
near the cathode. An analysis with simplified geometry (25)
shows that the electroosmotic permeability (e.g., eq 1) should
be multiplied by a factor that decreases as ionic strength
decreases; for the smaller ionic strengths in these simulations
(I < 0.1 mM), the attenuation factor can be less than 0.4,
which would explain discrepancies such as those seen in
Figure 8b. Eykholt (16) includes this effect, but does not
emphasize the results. Simplified corrections involve as-
sumptions that are not quantitatively applicable to our
situation, but the general concept applies. Low ionic strength
is related to low conductivity and the high field region, which
means that most of the electrical effort is being applied right
where it is least effective. Also, there is a positive feedback
effect where the low ionic strength causes higher electric field
strength, which accelerates the deionization. The resulting
attenuation factor could reduce the flow by orders of
magnitude. One important conclusion is that significant flow
reductions or cessation can occur even in soils that do not
show zero ζ-potential behavior.
The low ionic strength region explains two types of
deviations seen at about 1.7 days in Figure 8b: (1) the
experimental cases’ flow rates diverge because the base
addition begins to have an effect on the low ionic strength
region, and (2) the simulations diverge from the experiments
because the model does not take into account the electroos-
motic attenuation. The absence of this attenuation also leads
to the instability seen in the simulations.
There is also a mechanical effect that may play a role in
some observations: the high field region creates low pressure
and large pressure gradients, which may not be supportable
in some apparatuses. Low pressures can cause external leaks,
and large pressure gradients can cause “short-circuiting” of
the liquid flow along the walls of a test cell. The apparatus
and in-cell consolidation used here prevented these effects
from being a problem, but they are likely to occur in other
setups. Low pressures and high pressure gradients in the
field may cause uneven velocity distributions and channeling,
which could lead to expending energy to move liquid that is
not contaminated. Low pressure could also cause evolution
of dissolved gases, breaking the ionic conductance in the
region.
Electromigration is an important transport mechanism in
electroremediation whether electroosmosis is the primary
mechanism for contaminant removal or not. The changes
in conductivity seen here are driven mainly by electromi-
gration transport, with shifting of the distributions from
convective movement. The early drop in overall conductivity
seen in Figure 7 is a result of the local conductivity changes
discussed above; the drop occurs before there is much
convective displacement. The low ionic strength region can
also form when there is no flow of the pore liquid at all, with
undesirable effects for electromigration transport itself. First,
the region is often associated with a jump in pH that can
change the sign of the charge of the dominant heavy metal
species, leading to focusing of the contaminant within the
medium (1, 10). Second, low conductivity means that the
overall movement of ions by electromigration is slow, so the
remediation process would take a great deal of time.
Controlling the system chemistry is the key to avoiding
the formation of the low ionic strength region. The region
results from reactions that eliminate charge-carrying ions
(e.g., H+ and OH-), in interactions either with each other or
with the soil surface. By substituting less reactive species at
one or both electrodes, this eliminating reaction is avoided.
The resulting electric field distribution is more even, and flow
of charge and mass are maintained. If soil chemistry is
negligible, the added ions can have an immediate and strong
effect, as is seen in Figure 7a. If the soil participates
significantly in reactions with the background electrolyte or
the added chemicals, the effect of the chemical addition may
be delayed, as shown in Figure 7b.
Some soil types (e.g., sandy ones) may have little chemical
capacitance compared to the background electrolyte and
could be ignored in the system’s chemical model; others (e.g.,
those rich in humates, clays with smaller particle size) may
have significantly higher reactive concentrations than those
observed here. The specific soil model constructed here will
not be applicable for most natural soils, but the framework
and procedure used will be useful and should be included as
part of site characterization and process design. It is
important to first understand how electroremediation could
change the chemical composition throughout the medium
and then explore the soil response to the expected changes
in batch experiments. A simplified soil chemistry model can
then be constructed and used to further refine the chemical
control and process design.
Acknowledgments
The author thanks R. F. Probstein and R. E. Hicks for their
guidance during the time this work was performed. Financial
support was provided in part by the Office of Science and
Technology within the U.S. Department of Energy’s Office of
Environmental Restoration and Waste Management under
the Contaminant Plumes Containment and Remediation
Focus Area, by the U.S. Environmental Protection Agency
Northeast Hazardous Substance Research Center at New
Jersey Institute of Technology, and by MIT’s John Hennessy
Fellowship for Environmental Studies.
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Received for review August 16, 1996. Revised manuscript
received November 22, 1996. Accepted December 6, 1996.X
ES960707E
X Abstract published in Advance ACS Abstracts, February 15, 1997.
VOL. 31, NO. 4, 1997 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1197