NITRATE POLLUTION CONTROL IN DIFFERENT

SOILS BY ELECTROKINETIC TECHNOLOGY

X. Jia, D. L. Larson, W. S. Zimmt, J. L. Walworth

ABSTRACT. Previous studies found that a small DC electrical current could attract anions to the anode in sandy soil, even with
solute flow towards the cathode. Laboratory experiments were conducted in a vertical, partially saturated column with
different soils to determine if nitrate transport could similarly be controlled using electrokinetic (EK) technology. Nitrate
concentration, pH value, electrical potential difference, and soil water content were measured for three soils at selected times
at different distances from the anode. Constant electrical current was applied to the system for 9 h, and measurements
continued for a total of 48 h. The results demonstrated that nitrate can be strongly retained near the anode against gravity
in sandy soil with an 80 mA (0.5 mA/cm2) current input. When the percentage of clay in the soil was increased, the EK effect
on ion movement decreased; the transport of both ions and water were inhibited by fine clay particles. The loamy soil showed
a slight increase in nitrate concentration near the anode, but the clayey soil showed no change. An increase in pH near the
cathode was seen in all soils. Water content for sandy soil was higher at the bottom of the column and lower at the top of the
column, but for loam and clay soils, the lowest water content was found above the cathode near the bottom of the column.
Electrical potential difference between the two electrodes showed that the sandy soil required the highest electrical potential
difference to obtain the desired current level; loamy and clayey soils required less. For sandy soil, the highest potential
difference was found near the top of the column, but for loam and clay soils, the highest electrical potential difference was
measured near the bottom, next to the cathode, suggesting that these locations were the critical zones limiting electrical ion
transport.
Keywords. Electric potential, Electrokinetic, Nitrate control, pH, Water content.

lectrokinetic remediation, using a small DC current

to cause chemical and physical changes in a soil
volume, has been a focused study for over fifteen
years. The primary chemical reaction at the electrodes is electrolysis, with hydrogen ions (H+) produced at the
anode and hydroxyl ions (OH-) at the cathode. Hydrogen ions
then move through the bulk volume of the system, constituting an acid front. When the acid front moves, oppositely
charged ions (anions) are attracted to the anode (Acar et al.,
1995; Eid et al., 1999, 2000).
Many studies have reported that electrokinetics (EK) can
be used to remove heavy metals, radionuclides, organic
components, and inorganic wastes from water and aqueous
slurries, as well as saturated and unsaturated soils (Acar et al.,
1995; Probstein and Hicks, 1993). Until now, EK technology
has been largely limited to laboratory or small-scale

Article was submitted for review in September 2004; approved for

publication by the Soil & Water Division of ASAE in June 2005.
The authors are Xinhua Jia, ASAE Member Engineer, Postdoctoral
Research Associate, Department of Agricultural and Biological
Engineering, University of Florida, Gainesville, Florida; Dennis L.
Larson, ASAE Member Engineer, Associate Professor, and Werner S.
Zimmt, Adjunct Professor, Department of Agricultural and Biosystems
Engineering, University of Arizona, Tucson, Arizona; and James L.
Walworth, Associate Professor, Department of Soil, Water and
Environmental Science, University of Arizona, Tucson, Arizona.
Corresponding author: Dennis L. Larson, Department of Agricultural and
Biosystems Engineering, University of Arizona, Room 403, Shantz Bldg
#38, Tucson, AZ 85721; phone: 520-621-1248; fax: 520-621-3963; e-mail:
larson@ag.arizona.edu.

experiments, although some large field applications have

been attempted (Cairo et al., 1996; Jia et al., 2005).
The major reasons limiting greater application of EK
technology are the complexity of soil properties (Yu and
Neretnieks, 1997; Grundl and Reese, 1997) and lack of
understanding of EK process control factors (Shang and Lo,
1997). When an electrical field is imposed on a soil, the
reactions may include electrolysis, electroosmosis, and
electromigration, as well as ion diffusion, ion exchange, pH
gradient changes, gas generation, soil physical property
changes, water loss, precipitation of salts, hydrolysis,
oxidation and reduction, and sorption and adsorption (Yeung
et al. 1997; Mitchell, 1993; Grundl and Reese, 1997).
Electrokinetic effects in four sediments (natural and
undisturbed glacial till, reconstituted glacial till, pure
kaolinite, and pure montmorillonite) were examined by
Grundl and Reese (1997). They found that the tills containing
high calcium (Ca) concentration and smectite clay experienced little pH change because Ca buffered the soil pH and
flow of water was inversely related to the smectite content.
The montmorillonite experienced color changes caused by
the reduction of Fe3+ (ferric) to Fe2+ (ferrous), shrinkage,
cracks filled with gas (although the surrounding soils still
allowed water flow), and 10% water loss. The kaolinite,
which has little buffering capacity, showed a pH change due
to electrolysis, and a much higher current flow (63 mA)
resulted from the application of an 80 V/m voltage. The
recorded current with all other sediments with an 80 V/m
input voltage was only 7.5 mA.
The application receiving greatest attention may be the
use of EK to remove heavy metals from contaminated soils.

Transactions of the ASAE

Vol. 48(4): 13431352

E 2005 American Society of Agricultural Engineers ISSN 00012351

1343

Complete removal of chromium (Cr) and arsenic (As) from

three soils (a kaolinite contaminated with Cr and As, a soil
artificially polluted with trivalent Cr, and an industrial site
having soil contaminated with As) using an experimental
process involving injection of hypochlorite and control of
alkalinity and pH was reported by Le Hecho et al. (1998).
EK decontamination efficiency has been found to be
highly dependent on the sorption and diffusion parameters of
the soil. In a bentonite soil, which contains a large amount of
smectite, the removal of cesium (Cs) and strontium (Sr) from
a 3 m soil column was achieved by the application of
100 VDC and flushing of the soil with saline water to reduce
sorption and thus shorten the treatment time (Yu and
Neretnieks, 1997). In a one-dimensional lab experiment,
65% of Cr and 57% of uranium (U) were removed from soil
with 10% water content in 10 days using controlled pH
conditions and a gel polymer matrix and cation exchange
resin to promote chemical circulation with an electrical input
of 20 to 25 V and 2 mA (Bibler et al., 1993).
A second application of substantial interest has been the
removal of organic chemicals from contaminated soils. In a
batch-scale column test, 43% of phenanthrene was removed
from glacial till clay in 127 days by EK and the addition of
a co-solvent (such as n-butylamine) at the anode (Li et al.,
2000). Electrokinetic removal of a polycyclic aromatic
hydrocarbon (PAH) from kaolinite was improved by controlling pH (using 0.01 M NaOH) at the anode to offset the
electrolysis reaction. Higher electroosmotic flow was
achieved using deionized water with pH control, but the
deposition of contaminant near the cathode reduced removal
efficiency (Saichek and Reddy, 2003).
Agriculturally related electrokinetic research has principally focused on management of saline soils and retention of
nitrates in the plant root zone. Increased soil salinity has
reduced crop yields in many irrigated fields; nitrate pollution
of surface and ground waters is a major concern in
agricultural areas where nitrate fertilizer is applied extensively. This study compared the effectiveness of electrokinetics in attracting and retaining nitrates in different soils. Prior
Arizona research yielded variable results in the evaluation of
electrokinetics to control nitrate movement under a variety of
laboratory, lysimeter, and field conditions.
In a field lysimeter experiment with a loamy soil,
horizontal drainage tubing, parallel electrodes, and sprinkler
irrigation, Cairo et al. (1996) found that nitrate concentration
was initially highest near the cathode, located near the buried
drainage tube, due to a strong hydraulic gradient. However,
significant nitrate movement towards the anode located near
the soil surface occurred after water movement ceased. In
laboratory experiments with a saturated sandy soil, Eid et al.
(1999) found that EK could effectively concentrate and retain
nitrate close to the anode, even against a hydraulic gradient.
Nitrate movement to the anode was directly dependent on the
current density (current per cross-sectional area) and duration of current application. Higher current application, closer
spacing of electrodes, or longer electrical application time
yielded higher nitrate migration.
The promising results of prior Arizona research lead to a
series of field lysimeter and small field plot experiments
(Al Rawahy et al., 2003; Jia, 2004; Jia et al., 2005). In 2001,
a strip of Sudan grass was planted across the middle of a 1 m2
lysimeter filled with a local loam soil. A subsurface drip
irrigation tube and anode were buried below the grass, and

1344

parallel cathodes were inserted at the lysimeter sides.

Replicated comparisons of 11.2 V and no electrical input
treatments found that nitrate concentration, EC values, and
Ca and Na (sodium) concentrations all increased near the
anode during electrical current application. However, results
were inconsistent, and Sudan grass yield differences were
insignificant.
A number of studies have led to conclusions that some of
the nitrate is transformed to other substances by an electrical
input. Manokararajah and Sri Ranjan (2003) concluded that
nitrification occurred as a result of EK treatments with a
loamy soil. In laboratory experiments in field soils having
three different NH4-N concentrations, Elektorowicz and
Boeva (1996) found that NH4-N was uniformly distributed
after application of an electrical field for 27 days. However,
NO3- was generated and accumulated near the anode,
indicating that nitrification was induced in the process. In a
saturated artificial soil composed of sand and clay, Chew and
Zhang (1999) reported that 95% of the nitrate was transformed to nitrogen gas and ammonia gas by EK application.
However, in experiments without any electrical current
application, the nitrate concentration was reduced at the
bottom of the root zone before reaching the water table,
indicating that natural denitrification in the soil profile is
responsible for part of the nitrate decrease (Meek et al.,
1969).
Nitrate movement in soils has been simulated under
dynamic environmental, irrigation scheduling, and inorganic
N conditions. Antonopoulos (2001) reported significant
agreement between modeled and measured values of water
content and inorganic N at different soil depths and the
cumulative N uptake by plants. A one-dimensional model
was used successfully by Eid et al. (2000) to predict nitrate
movement due to an electrical input. Another model,
Hydrus-2d, has been used to simulate two-dimensional solute
transport by numerically solving the Richards equation for
saturated-unsaturated water flow and the convection-dispersion equation for solute transport (Simunek et al., 1999).
To address the EK effect in different soils and obtain data
for future field applications, laboratory experiments were
conducted with three different soils (sand, loam, and clay).
The study was designed to quantify the effectiveness of EK
in controlling nitrate movement in natural soil conditions.
Thus, there was no pH control or fluid enhancement near the
electrodes. The experimental design was intended to model
application to a subsurface drip irrigated field, with simultaneous insertion of electrode wires and drip irrigation tubing
by drip tube insertion equipment envisioned.

PROCEDURES
SOIL PREPARATION
The soils used for this study were Vinton sand, taken from
a riverbed in Tucson, Arizona, and Green Illite, purchased
from a commercial medical product company (Naprodis,
Inc., Poway, Cal.). The Vinton sand contained 97.0% sand,
1.2% clay, and 1.8% silt (Zou, 1999). The sand was sieved
through a 2 mm screen and air dried. The Green Illite
consisted of 75% illite and 15% kaolinite. Illite was selected
as the primary clay mineral principally because it is one of the
predominant minerals at the experimental site near Tucson
and has a low cation exchange capacity. This makes

TRANSACTIONS OF THE ASAE

plasticity, swelling, and shrink-swell capacity less intense

than in smectite. In the study, the sandy soil consisted of
100% Vinton sand, the loamy soil was 83% Vinton sand and
17% Green Illite, and the clay soil was 75% Vinton sand and
25% Green Illite. A cement mixer was used to mix the sand
and clay for the three soils to ensure high uniformity. After
the soils were well mixed, they were bagged and then stored
at room temperature until used.
INFLUENT PREPARATION
The influent contained 50 mg/L of N (221 mg/L of NO3-)
in tests with all three soils. The concentration selection was
based on the assumption that a typical field application is
about 200 kg/ha of N in a season, equivalent to 100 mg/L of
N in the root zone (30 cm deep), and that N is introduced in
two applications. NaNO3 was chosen as the nitrogen source
for two reasons: soil pH was neutralized by Na+ and NO3,
and Na has little interaction with soil particles. Other cations,
such as potassium (K+) and Ca2+, are more commonly added
nutrients, but might interact with soil particles and complicate interpretation of results (Tan, 1998).
For sandy soil, the NaNO3 was dissolved in nitrate-free tap
water and then applied to the top of the column through a drip
system. When the nitrate concentration in the drainage
equaled the influent concentration, the experiment was
started as soon as surface water was no longer visible. The
saturated conductivity of Vinton sand was 1.8 105 m/s,
and it took several days to achieve homogenous concentration in the column. However, for loamy and clay soils, the
hydraulic conductivities and the infiltration rates were
extremely low (<1.1 108 m/s), and flushing of chemicals
from soils was impossible to achieve. So, nitrate solution
(2.5 L containing 45 mg/L N) was mixed with the loam or
clay soil with continuous stirring, and the resulting wet paste
was then transferred into the test column.
To minimize denitrification processes in the system, 1%
1 M boric acid in its metaboric acid (HBO2) form was added
as a biocide in all loamy and clayey soil experiments to

eliminate living microorganisms, as recommended in the

Orion 9307 nitrate electrode manual (Thermo Electron
Corp.). According to the Nernst-Townsend-Einstein relationship, ionic transport due to electromigration is proportional
to ionic mobility (Acar and Alshawaabkeh, 1993). In this
system, both the nitrate concentration and nitrate ionic
mobility were higher than metaboric acid.
SOIL COLUMN PREPARATION
An acrylic cylinder, 38 cm in height and 14 cm in
diameter, was used in all experiments. Two electrodes,
spaced 25 cm apart, were placed in the column, the anode at
the top of the column and the cathode at the bottom, as shown
in figure 1. The electrodes were perforated stainless steel
disks 1 mm thick by 12.6 cm in diameter. The electrodes were
encased in the soil by placing thin layers of soil below the
cathode and atop the anode and connected to an external
adjustable, constant-current electrical power supply (model
6035A, Agilent Technologies, Inc.).
Sandy soil was inserted into the column in small
increments and packed layer by layer to a predetermined bulk
density limit of 1.52 g/cm3. Loam and clay soils, with
measured bulk densities of 1.42 and 1.38 g/cm3, respectively,
were mixed with NaNO3 solution. A layer of large-particle
silica sand (20/30 mesh, 0.5 to 0.75 mm diameter) was placed
at the bottom of the soil column just above a drainage port to
permit effluent drainage to an open container. No suction was
applied in the tests to enhance fluid movement, in order to
simulate future field applications and ensure that all tests
started with the same hydraulic gradient.
ELECTRICAL CELL
Current is defined as the increment of charge flowing
across a plane per unit of time. A constant current application
ensures a uniform electric field across the electrodes with a
fixed space, while a constant voltage gives a variable electric
field (Jia, 2004). In this experiment, constant current was
applied, and the current level was determined by preliminary

Figure 1. Schematic diagram of laboratory setup.

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1345

experiments. The current level was determined by visible

electrolysis reaction and pH changes in the soils after 3 h
(irrigation cycle) of applied electrical current. Temperature
increase and safety concerns motivated inputting minimal
current. The results suggested that 80 mA constant current
(0.5 mA/cm2) be used for sandy soil and 60 mA (0.4 mA/cm2)
for loam and clay soils. Measurement wires were inserted at
7.5 cm and 17.5 cm distances from the anode so that voltage
changes across the entire column and the top (0 to 7.5 cm),
middle (7.5 to 17.5 cm), and bottom (17.5 to 25 cm) sectors
could all be recorded by a datalogger (model CR23X,
Campbell Scientific, Inc.). A voltage divider, a device to
decrease/increase voltage proportionally, was connected
between the wires and the datalogger to ensure that the
recorded voltages were within the datalogger range (5 V).
A multimeter was also used to measure the voltages.
EXPERIMENTS
Nine experiments were conducted (three for each soil),
with constant current applied for 9 h. For the experiment with
sandy soil, the soil was packed in the column, washed with
nitrate-free tap water, and then saturated with the 50 mg/L N
solution. The electrical input was initiated when the effluent
concentration was equal to the influent concentration. As
described above for loam and clay soils, the mixed slurries
were transferred into the column layer by layer. The columns
were allowed to equilibrate overnight prior to starting the
tests. Sampling, concentration, and voltage measurements
continued for two days to monitor changes occurring after
termination of electrical input.
SAMPLING
Sampling ports were spaced 5 cm apart with the top ports
located 2.5 cm below the anode and the bottom (fifth) ports
2.5 cm above the cathode. Four 1.3 cm diameter sampling
holes were drilled through the column wall at each layer. The
holes were closed by rubber septa except when opened to
collect soil samples or later to release generated gas. A small
20 cm tube was used to collect soil samples from the edge to
the column interior, yielding a fan-shaped sampling area
under unsaturated conditions. Tensiometers were inserted
into each layer for soil water status measurement, and the
results were recorded by a CR23X datalogger (Campbell
Scientific, Inc.).
SOIL NITRATE ANALYSIS AND pH MEASUREMENT
Soil samples were taken at each sampling layer at
predetermined sampling times. Soils were oven dried, and
the soil moisture content was determined gravimetrically.
Deionized (DI) water was added to a soil sample, and the
resulting slurry was mixed and shaken at low speed for 1 h.
The soil was then filtered, and 5 mL of the liquid was used
for nitrate analysis by ion chromatography (BioLC, Dionex
Inc.). The pH was measured with pH paper immediately after
soil samples were taken.
Because this experiment was intended to provide guidance for future field applications, changes in nitrate concentration throughout the column during application of
electricity, as well as nitrate redistribution after the electricity
stopped, were evaluated. Soil samples were collected at the
beginning of the experiment, after 3, 6, and 9 h of applied
current, and then 2 h after turning off the electricity.

1346

Additional samples were collected at 24 and 48 h after the

beginning of the experiment.

RESULTS AND DISCUSSION

All the tests were conducted for 48 h (9 h at constant
electrical current, followed by 39 h of observation). Soil
water content and voltage changes were measured and
recorded by a datalogger; multimeter voltage measurements
were taken, and soil samples were periodically removed for
gravimetric water content analysis. Nitrate concentration
was determined at specified times at various distances from
the anode, and pH near the cathode was determined every 3 h
while the current was applied.
Attempts to establish a nitrate mass balance in sandy soil
indicated a loss of 15% of the nitrate in a control column with
no electrical input, suggesting that natural denitrification was
occurring. About 30% of the original nitrate could not be
accounted for after 9 h of electrical input. Therefore, 1% of
1 M HBO2 was added to all loam and clay soil used in
experiments to control the denitrification process, and mass
balances are not included in this article. In addition, due to the
lack of equipment for capturing gas samples and analyzing
other forms of nitrogen, only the NO3 content of soil samples
was quantified.
NITRATE
Figure 2 shows the change in nitrate concentration in
sandy soils versus time after application of an 80 mA input
current. It is clear that the electrical input caused a strong
migration of nitrate ions toward the top of the column (the
anode). The average initial nitrate concentration was
235 mg/L with a standard deviation of 11 mg/L. The
difference between the solution nitrate concentration of
221 mg/L and the measured initial soil column value of
235 mg/L probably is due to prior adsorption of the nitrate on
the sandy soil, which contained 1.2% clay. Because quantifying nitrate concentration changes was the test objective, the
measured value was used as the initial concentration in the
column, rather than the input solution concentration value.
During the 9 h of constant 80 mA electrical input, the NO3
content in soil 2.5 cm distant from the anode increased for the
first 6 h, but then decreased to well below the initial
concentration. The lowest nitrate concentration in soil near
the anode was observed between 6 and 12 h after the start of
the test. Even 2 h after the electricity was turned off, the soil
2.5 cm below the anode contained less nitrate. However, soil
samples taken 2.5 cm below the anode 24 and 48 h after test
start contained over 900 mg/L of NO3. To attempt to explain
these observations, the sampling process was modified in
later tests to determine nitrate content directly adjacent to the
electrodes as well as 2.5 cm distant.
The nitrate concentration in soil 12.5 and 22.5 cm below
the anode decreased initially, and then increased slightly after
the electricity was turned off. This result was expected;
nitrate concentrated at the top of the column slowly diffused
downward due to the high concentration gradient after
termination of the electrical attraction. As shown in figure 2,
the final nitrate concentration decreased continuously from
column top to bottom.
The change in nitrate concentration in loamy soils with 9 h
of 60 mA constant current application is shown in figure 3.

TRANSACTIONS OF THE ASAE

1000
End of current

NO3 (mg/L)

800

600
2.5 cm
12.5 cm

400

22.5 cm
200

0
0

12

18

24

30

36

42

48

Elasped Time (h)

Figure 2. Nitrate concentration vs. time at 2.5, 12.5, and 22.5 cm below the anode with constant current of 80 mA for 9 h in sandy soil.

The average initial nitrate concentration was 210 mg/L with

a standard deviation of 13 mg/L. The changes in concentration are obviously much smaller than those seen in the sandy
soil. The concentration scale in the sandy soil graph (fig. 2)
is 0 to 1000 mg/L, while the scale is 0 to 350 mg/L for the
loamy soil results (fig. 3). After 9 h of electrical input, the
nitrate concentration at the top of the column near the anode
was higher than near the bottom (99 mg/L), but only slightly
greater than the influent nitrate concentration. After the
electricity was stopped, the nitrate concentration in soil
350

2.5 cm distance from the anode increased to 291 mg/L, and

the nitrate concentrations in all other layers decreased to
below the influent nitrate concentration. At the end of the
experiment, a sharp difference in nitrate concentration can be
observed between the 2.5 cm sampling port and the lower
ports (12.5 and 22.5 cm).
There were no distinct nitrate distribution changes in the
clayey soil column due to application of 60 mA of electrical
current for 9 h, as shown in figure 4. However, nitrate
concentration changes were observed at the end of the

End of current

300

NO3 (mg/L)

250
200
150
100

2.5 cm
12.5 cm

50

22.5 cm
0
0

12

18

24

30

36

42

48

Elasped Time (h)

Figure 3. Nitrate concentration vs. time at 2.5, 12.5, and 22.5 cm below the anode with constant current of 60 mA for 9 h in loamy soil.
400

2.5 cm
12.5 cm

End of current

22.5 cm

NO3 (mg/L)

350

300

250

200
0

12

18

24

30

36

42

48

Elapsed Time (h)

Figure 4. Nitrate concentration vs. time at 2.5, 12.5, and 22.5 cm below the anode with constant current of 60 mA for 9 h in clayey soil.

Vol. 48(4): 13431352

1347

10000
Sand
Loam

NO3 (mg/L)

Clay
1000

100

10
0

10

15

20

25

Distance from the anode (cm)

Figure 5. Comparison of the NO3 distribution in the three soils at the end of the experiment.

experiment. Leached nitrate concentration was higher than

influent concentration in soil 2.5 cm below the anode, indicating
that nitrate may have been retained near the anode and then
diffused downward to the 2.5 cm level. At the 12.5 and 22.5 cm
sampling ports, the nitrate concentration at test termination was
about equal to the influent nitrate concentration.
COMPARISON OF NO3 EFFECT IN THE THREE SOILS
The NO3 concentration distributions at the end of the 48 h
experiments with the three different soils are compared in
figure 5. The figure includes data obtained between the
2.5 cm port and the electrodes; note that a log scale is used
to show nitrate concentration. In the sandy soil, the highest
concentration is 2000 mg/L adjacent to the anode (0.25 cm),
and the concentration drops to 38 mg/L next to the cathode
(24.75 cm). This suggests that nitrate ion movement was
highly influenced by the EK input. In the loamy soil, the
highest nitrate concentration is 634 mg/L next to the anode
(0.25 cm from the anode), and the lowest is 104 mg/L next
to the cathode.
The nitrate distribution in the clayey soil apparently was
unaffected by the 60 mA input. The nitrate concentration in
soil 2.0 cm from the anode is unexplainably lower than that
at the 2.5 cm port; perhaps this was due to sampling

procedures. Within 1 h after the start of the clayey soil

experiment, gas generation caused a large crack, filled with
gases, to form in the soil near the bottom of the column just
above the cathode. The required electrical voltage rose
correspondingly. The crack grew until the septum next to the
cathode was opened to release the pressure. Subsequently, the
septum was left open when the current was applied; the soil
fissure disappeared, and the required voltage decreased.
EFFECT OF pH
Because the three soils had different buffering capacities,
their pH response was expected to be quite different. The pH
values near the anode at the top of the column changed very
little with any of the soils during the electrical input.
However, the pH changes next to the cathode during input of
the electrical current were significant for all three soils
(fig. 6). A very rapid pH increase was observed in the clayey
soil following the application of current; the pH near the
cathode increased less in the sandy and the loamy soils. The
pH for clayey soil almost reached 14, and the pH near the
cathode in the sandy soil rose to 12.5 by the end of the
electrical input. The increased alkalinity is attributed to
electrolysis, which appears to have occurred from the
beginning until termination of the electrical input.

14

pH

12

10
Sand
Loam

Clay

6
0

Time (h)
Figure 6. The pH distribution adjacent to the cathode in the three soils due to the electrical current application.

1348

TRANSACTIONS OF THE ASAE

40
2.5 cm

Water Content (%, g/g)

35

12.5 cm
30

22.5 cm

25
20
15
10
5
0
0

12

18

24

30

36

42

48

Elasped Time (h)

Figure 7. Changes in water content at top, middle, and bottom of the soil column filled with sandy soil exposed to an 80 mA electrical input during the
first 9 h.

WATER CONTENT
During the electrical application (the first 9 h in fig. 7),
sandy soil water content fluctuated, indicating water flow
may have been influenced by the EK treatment. Water
content generally declined during electrical input; the lowest
water content was measured 2 h after the current was turned
off. Dewatering in the system has been suggested by other
researchers (Shang and Lo, 1997), and electrolysis of water
must have occurred at the electrode/soil solution interface
because the maximum pH change was observed adjacent to
the cathode. After the electrical input was terminated, the soil
water tended to redistribute due to gravity. At the end of the
experiment, the lowest water content was measured at the top
of the column and the highest content was measured at the
bottom.
The water content in the different layers of the loamy soil
varied from 25% to 34%, with the highest water content at the
top of the column at the beginning of the experiment (fig. 8).
While electricity was applied, the lowest water content was
observed at the bottom. After the end of the 9 h of electrical
input, the water seemed to redistribute, and while the water
content at top and bottom ports remained constant, the water
content in the middle of the system increased. Overall, there
was some decrease in total water content.

Figure 9 shows that the water content changes for clayey

soil were similar to, but smaller than, those in loamy soil. At
the end of the experiment, the highest water content was
found in the middle of the column, and the lowest water
content was found at the bottom of the column.
ELECTRICAL POTENTIAL DIFFERENCE
Figure 10 shows the electrical potential differences taken
during tests with the three soils. The total values of electrical
potential difference reflect the measurement across the entire
25 cm column, the top value is the potential difference
from the anode to the sampling port 7.5 cm below, the
middle reading is the potential difference between ports
7.5 and 17.5 cm distant from the anode, and the bottom
value was measured between the port located 17.5 cm below
the anode and the cathode. A small electrical potential
gradient is desired because the undesired temperature
increase is proportional to the squared electrical potential
(Ho et al., 1997). For sandy soil, with constant 80 mA current,
the total voltage averaged 97 V (3.9 V/cm) across the 25 cm
column. Electrical resistance is affected both by water
content and nitrate concentration. The highest voltage, at the
top of the column for sandy soil, corresponded to the highest
nitrate retention, but also the lowest water content. The

40

Water Content (%, g/g)

35
30
25
20
15
2.5 cm

10

12.5 cm
22.5 cm

5
0
0

12

18

24

30

36

42

48

Elasped Time (h)

Figure 8. Changes in water content at top, middle, and bottom of the soil column filled with loamy soil exposed to a 60 mA electrical input during the
first 9 h.

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40

Water Content (%, g/g)

35
30
25
20
15

2.5 cm

10

12.5 cm
22.5 cm

5
0
0

12

18

24

30

36

42

48

Elasped Time (h)

Figure 9. Changes in water content at top, middle, and bottom of the soil column filled with clayey soil exposed to a 60 mA electrical input during the
first 9 h.

potential difference near the bottom was higher than that in

the middle, which is opposite to patterns of measured nitrate
concentration and water content. This was probably caused
by the gas-generated soil voids near the bottom of the column
that increased the electrical resistance. For both loamy and
clayey soils, the total potentials were much lower. The
electrical potential difference was 0.7 V/cm for loamy soil
and 0.6 V/cm for clayey soil with constant 60 mA current.
The highest potential difference was measured near the
bottom next to the cathode.

SUMMARY AND DISCUSSION

The application of an electrical current caused different
ion concentration and pH changes in sandy, loamy, and
clayey soils. The differences could be caused by heterogeneity of soil properties as well as differences in solute transport.
Hydrus-2D was used to simulate water and solute transport
after electrical current input using prior measured values as
initial conditions. The simulated results were compared with
measured results, and the differences were considered to be
caused by electrokinetics. This comparison indicated that
there should have been very high nitrate content adjacent to
the anode and served as impetus for additional soil sampling
very near the anode in subsequent tests.
The application of current caused electrolysis of water at
the electrodes, and the generated OH increased the pH near

the cathode, as observed in all soils. As a coupling effect, H+

must be generated near the anode. However, due to the high
soil buffering capacity, lower pH values were not observed in
loamy and clayey soils near the anode. Tests failed to detect
any pH changes due to addition of 0.1 M of [H+] to either
loamy or clayey soils (Jia, 2004).
In sandy soil, ions were easily moved due to lack of
adsorption of the ions on the soil particles, and migration was
evident even against a hydraulic gradient (gravity and
drain-permitted water flow toward the bottom of the
column). Very high nitrate migration rates were observed in
sandy soil; the nitrate concentration next to the anode
increased to nearly ten times greater than the influent nitrate
concentration. After the current was stopped, nitrate next to
the anode started to migrate away, and increased nitrate
concentration was observed 2.5 cm below the anode.
However, the diffusion process was very slow, and the higher
nitrate concentration was not detected until the much later 24
and 48 h tests, instead of 2 h after the electrical current was
stopped.
In the loamy soil, although pH increased near the cathode,
indicating electrolysis, nitrate was moved slowly and less
effectively than in the sand. Acidity generated by the
electrical current apparently was neutralized by soil buffering capacity, since only a small pH change was detected near
the anode. The reactions at the cathode generated gas, and a
soil void section about 0.5 cm deep was formed just above the
cathode. This result was not expected, so the gas was not

Electrical Potential (V/cm)

7
6
5
4
3
2
1
0

Sand

Loam

Total
Top
Middle
Bottom

Clay

Figure 10. Electrical potential difference (V/cm) across the top, middle, and lower sections and the entire column for sandy, loamy, and clayey soils.

1350

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collected and analyzed, but merely released by opening

column side ports to permit water and ion movement.
However, the expected gas might be hydrogen due to
electrolysis (Jia, 2004).
In the clayey soil, the observed electrokinetic effect on
nitrate movement was minimal. This result is in agreement
with tests and analysis reported by Acar et al. (1995), who
found that hundreds of hours were required to move ions
through 1 cm of the soil using the maximal electroosmotic
flux. Their explanation noted that negatively charged clay
particles attract cations at the surface to neutralize the applied
charge and that electroosmotic flux is decreased by high
activity clays, low water content, and high electrolyte
concentration. Therefore, it is not surprising that nitrate
movement was not observed in the clayey soil with 9 h of
electrical input.
It may be concluded that the EK effect is strongly related
to soil type, or inversely related to the percentage of clay in
the soil. The electrical input yielded high nitrate attraction
and retention to the anode in the sandy soil, less increase in
nitrate content near the anode in loamy soil, and no
measurable change in nitrate content near the anode in clayey
soil. Large pH changes were observed near the cathode in all
soils.
The electrical currents applied to the three soils (0.5 mA/
cm2 for sand, and 0.4 mA/cm2 for loam and clay) were the
lowest currents across the 25 cm column to cause measurable
electrolysis after 3 h electrical input. A neuromuscular
electrical stimulation test reported that 100 mA was the
individual tolerance to electricity used to increase strength of
skeletal muscle without causing discomfort (Richard et al.,
2002). In this research, the highest current level was set to
100 mA to minimize the potential harmful effects to living
creatures.
Soil water content in the column decreased during all
experiments. In sandy soil, the lowest water content was at
the top and the highest at the bottom of the column. This
suggests that water movement due to gravity, leading to
drainage at the bottom of the system, might dominate the
process. In loamy and clayey soils, the driest region was at the
bottom of the column, probably due to electrolysis and slow
capillary water movement. This suggests that control of
nitrate movement by electrokinetics in field applications will
be most effective only when both water content and the
potential contamination threat are high.
The highest electrical gradient occurred at the top of the
column with sandy soil, probably due to the accumulation of
nitrate and lower water content near the anode. For the loamy
soil, the highest electrical gradients were at the bottom of the
column close to the cathode. This location corresponded with
the region with low water content and soil void caused by gas
accumulation. Generated gases probably will be vented in
field applications, and moisture content is expected to be the
dominant factor determining electrical resistance and required potential.
Design and management of an electrokinetic system to
control movement of nitrate and other ions must be based on
an understanding of soil, soil moisture, and chemical
concentrations. A good application based on this study may
be prevention of nitrate pollution from coarse soils with a
shallow water table or near a riparian ecosystem. An
electrical barrier could either gather nitrate near the anode or

Vol. 48(4): 13431352

promote gas formation and venting. The process would be

triggered by an automatic control system when water content
is high enough to create a contamination threat.

CONCLUSIONS
Electrokinetics can effectively attract nitrates to and
retain them near the surface of a sandy soil, even with water
movement downward toward the cathode under unsaturated
soil water conditions. Both the ion transport and soil water
movement were decreased following the increase of clay
percentage in the soil. EK treatment of loamy and clayey soils
was minimally effective in altering nitrate migration with the
electrical current application used in this study. Gas generation and pH increase near the cathode were seen for all soils.
The electrical input can yield substantial hydrolysis and
nitrification, changing the pH near the electrodes and
releasing nitrogen and hydrogen gases. Adding acid to the
soil in the plant root zone could make trace elements more
available in basic Arizona soils. Additional testing is
required to quantify both gasification and acidification
effects in different soils. An automatic flow control device
that can trigger the EK process is necessary to ensure that EK
occurs only when it is needed under natural soil conditions.
ACKNOWLEDGEMENT
The authors wish to acknowledge the support of this
research project provided by the USDA-NRIGP National
Water Quality Program (CREES Award 2001-3510209878).

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