Environ Geochem Health

DOI 10.1007/s10653-007-9100-6

ORIGINAL PAPER

Desorption characteristics of kaolin clay contaminated

with zinc from electrokinetic soil processing
Myung Ho Lee Æ Masashi Kamon Æ Soo Sam Kim Æ
Jai-Young Lee Æ Ha Ik Chung

Ó Springer Science+Business Media B.V. 2007

Abstract A number of bench scale laboratory
column tests were carried out using a newly designed
and developed electrokinetic cell to investigate the
fundamental behavior of zinc-spiked kaolin clay
subjected to an electric field. Laboratory investiga-
tions focused on (i) zinc migration by the combined
effects of electromigration and electro-osmosis and
(ii) the electrically induced desorption characteristics
of zinc-contaminated kaolin that occurred during
processing. The correlations of the applied voltage
gradient, electro-osmotic flow rate, and the develop-
ment of a pH gradient were examined and evaluated.
M. H. Lee (&)
Department of Civil & Environmental Engineering,
Hanyang University, 1271, Sa1-Dong, Sangnok-Ku,
Ansan, Kyungki-Do 426-791, Republic of Korea
e-mail: mhleecok@paran.com
M. Kamon
Graduate School of Global Environmental Studies,
Kyoto University, Kyoto, Japan
S. S. Kim
Department of Civil & Environmental Engineering,
Hanyang University, Ansan, Republic of Korea
J.-Y. Lee
Department of Environmental Engineering,
The University of Seoul, Seoul, Korea
H. I. Chung
Geotechnical Engineering Research, Korea Institute
of Construction Technology (KICT), Koyang-Si,
Republic of Korea
The results showed that the removal efficiency was
high during the early stage of processing due to rapid
desorption by electrokinetic effects in the cathode
region. However, the majority of zinc migrating from
the anode was precipitated due to the high pH
environment in the cathode region.
Keywords Desorption
Electrokinetics
Kaolin

pH
Removal efficiency
Zinc
Introduction
In recent years, heavy metal contamination of soil
and water has increased due to the application of
metal working and plating products, metal-based
pesticides and fertilizers, heavy metal-based paints
and coatings, metal-coated power lines and railways,
and the use of leaded gasoline (Vangronsveld and
Cunningham 1998). Many remediation methods have
been developed and are available for use on contam-
inated land. However, relatively few are applicable to
soils polluted with heavy metals; some of the low-
cost options available for the remediation of organic
pollutants (e.g., thermal and biological processes) are
not available for metal-contaminated soils (Wood
1997). Since the discovery of the electrokinetic (EK)
phenomenon by Reuss in 1808, and the initial
practical application in the field by Casagrande in
1939, the technique has been used for the de-watering

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 Environ Geochem Health

of soils and sludges. In recent years, since the report Table 1 Summary of conditions imposed in the electrokinetic
by Segall et al. (1980) on the detection of various (EK) column tests
pollutants in the drained fluid from electrically Parameter K1 K2 K3
treated dredged sludge, EK soil processing has been
intensively investigated as a remediation method for Soil type Kaolin
contaminated soils. Sample diameter (mm) 60
The EK remediation technology is a relatively new Sample length (mm) 150
method, which involves passing a low-level DC Applied electric field strength (V) 45
electrical current between electrode pairs embedded EK processing time (h) 2 4 8
in the contaminated ground for the removal of Electrolyte solution 0.01 M
NaCl
subsurface contaminants in an open flow arrangement
Initial soil pH 5.38 5.29 5.49
(Acar and Alshawabkeh 1993). This technology can
Initial zinc contamination (mg/kg) 574.6 569.9 578.6
be directly applied in-situ, with the advantage of
being effective for low-permeability soils, in which
hydrodynamic techniques would be unsuitable. The
Testing materials
fundamental processes of EK remediation are the
transport of ionic species and water through porous
Kaolin clay was selected because its electrochemical
media, based on the phenomena known as electro-
and mechanical properties are well known. The
migration (EM), electrophoresis (EP) and electro-
experiments were performed to investigate interac-
osmosis (EO), as well as other related effects,
tions between inorganic pollutants and clay particles
including dissolution/precipitation, electrolysis, and
on the removal efficiency during EK processing. The
the resultant acid/base fronts (Rødsand et al. 1995).
chemical content and typical properties of kaolin are
Ground improvement and remediation schemes
presented in Table 2.
using electrokinetics are often difficult, as a result of
For safety reasons, zinc nitrate (Zn(NO3)2
6H2O)
the development of a chemical gradient between a
was chosen to produce a model metal-contaminated
system of electrodes due to electrolytic reactions and
soil in the laboratory remediation studies; zinc is
acid/base fronts. For example, migrating metal ions
moderately toxic to humans. Sodium chloride (NaCl)
may precipitate in a zone where the soil pH has
was used to produce the electrolyte solution. De-
increased during the EK treatment, which eventually
ionized water was used as a flushing fluid, which was
limits the remediation efficacy. The research purpose
introduced from the anode side, and as a purging
was to investigate several variables affecting EK
solution for the cathode chamber.
processing, such as the effects of contamination level,
intensity of the applied electric field, and the drainage
Testing apparatus and procedure
boundary condition on the migration of inorganic
pollutants through a porous medium. Correlations
A schematic diagram of the EK reactor is presented
between the electric current, EO fluid flow, and pH
in Fig. 1. A zinc-spiked kaolin specimen was
gradient were demonstrated in the presence of a DC
electric field. The characteristic features of desorp-
tion, migration and precipitation of heavy metals Table 2 Physicochemical properties of kaolin clay. Compo-
during the EK processing were also examined and sitions of various oxides: 38.5% Al2O3, 45.4% SiO2, 0.2%
Na2O, 0.5% Fe2O3, 0.02% MgO, and 0.1% K2O
evaluated.
Typical properties ASP-170 kaolin clay

Specific gravity 2.58

Methodology Average grain size (mm) 0.4
pH 6.0*8.0
The experimental conditions, including the applied Liquid limit (%) 68
electrical intensity, EK processing time, initial soil
Plastic limit (%) 31
pH, and initial zinc concentration, are summarized in
Loss on ignition (%) 13.6
Table 1.

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Environ Geochem Health

significant power loss due to the increase in the

To
Power supply
resistance under a constant electrical current condi-
Anode tion (Yeung et al. 1997). Each test was continued
(stainless steel)
until the monitored electrical current became less
than 10 mA. The volumetric EO flow, electrical
Inlet for current, and local potential difference were continu-
water supply
ously monitored during the test. The soil pH and zinc
Voltage pin concentration were measured after the experiment.
lin
Kao y Sand filter
Cla
Results and discussion
pH port Outlet for EO flow
Outlet for gas vent
Electric current and volumetric
Porous disc electro-osmosis (EO) flow
Inlet for
gas flushing Figure 2 shows the electric current and corresponding
Inlet for
gas flushing EO flow through the specimen. As shown, the electric
Cathode
(stainless steel)
To current initially increased during the first 3 h, then
Power supply
stabilized at approximately 75 mA for about 3 h, and
Fig. 1 Schematic diagram of electrokinetic (EK) reactor thereafter decreased. The corresponding EO flow
rapidly increased with increasing electric current, but
became slower with the reduction of current passing
prepared by mixing the required mass of dry soil and through the specimen. Clay particles initially contain
zinc nitrate powder, with a background solution of cations on their particle surfaces, and a larger amount
0.01 M NaCl, using a reciprocating shaker (SR-1 of pore fluid can be transported by those surplus
Taitec) operated at 2000 ± 2 rpm. The mixing period cations, together with the additional metal contami-
was approximately 3 h prior to the start of each run to nant (i.e.,Zn2+) adsorbed onto the clay particles.
promote a uniform mixture and to achieve chemical
equilibrium; the preliminary sorption kinetics exper- Voltage and pH profiles
iments indicated that a period of 1 h was sufficient to
attain chemical equilibrium. The zinc-spiked kaolin Figure 3 presents a typical example of the voltage
was then introduced into the testing cell through 30- profiles as a function of the sample distance from the
mm i.d. tubing.
After sample placement, the anode assembly was 100 200
connected to the column, and all the inlet/outlet ports
were connected, either to the Hydraulic Head Equal-
Volumetric EO flow, ml
Electrical current, mA

izer (HHE) or a plastic bottle using 4-mm i.d. tubing. 75 150

The water level in the EK reactor was kept constant

by the HHE, and the gases generated at the cathode 50 100
were also flushed out of the cathode compartment by
the HHE during EK processing. At the end of each
25 50
test, the clay specimen was divided into small
portions and centrifuged for 30 min at
3000 ± 2 rpm. The supernatant collected from the 0 0
0 1 2 3 4 5 6 7 8
centrifuge tube was analyzed to determine the zinc
Time, hr
concentration.
Electrical current EO flow
All the experiments were conducted under a
constant electric field to avoid the premature termi- Fig. 2 Electric current and the corresponding volumetric
nation of the experiment, which might result from a electro-osmosis (EO) flow: test K3

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60
55
Voltage, V
50
45
40
35
0 30 60 90
Distance from cathode, mm
1hr 3hr 4hr 5hr
Fig. 3 Voltage profiles: test K3
cathode by measuring local potential differences
along the specimen. As shown, an electrical potential
loss occurred from the beginning of the test, probably
due to the sand filter installed in the cathode region
(Fig. 1), so that the initial local voltage gradient was
approximately 0.3 V/cm. The voltage gradient
increased during the first 3 h, but the voltage dropped
after 4 h of the EK processing. It appears that the H+
ions generated at the anode by electrolytic reactions
migrate toward the cathode, together with Zn2+ ions
from the anode compartment, and meet the migrating
OH ions from the cathode in the middle of the soil
sample. This process of ion migration, known as acid/
base fronts (Acar and Alshawabkeh 1993), resulted in
the formation of water due to neutralization as well as
the precipitation of zinc (e.g., Zn(OH)2) in the zone
where the voltage drop occurred.
Final soil pH profiles, measured after 2, 4, and 8 h
of the EK treatment, are shown in Fig. 4. The initial
pH value of the soil specimen was approximately 6.
After EK processing, the anode solution became
acidic and the pH of the cathode solution and sand
filter increased to 13. It has been reported that the
acid front generated at the anode by electrolytic
reactions advances toward the cathode and eventually
flushes across the specimen by advection, migration,
and diffusion (Hamed et al. 1991). The soil pH on the
anode side decreased to about 2 and that in the
cathode half remained at the initial value for the first
2 h of EK processing. After 4 h, most of the specimen
became acidic on the anode side due to the effect of
an acid front sweeping across the specimen, with the
pH values in between 2 and 4. In Fig. 3, the zone of
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Environ Geochem Health
14
12
10
8
pH
6
4
2
120 150 0
-30 0 30 60 90 120 150 180
7hr 8hr Distance from cathode, mm
Initial pH K1 : 2 hr K2 : 4 hr K3 : 8 hr
Fig. 4 Final pH profiles: tests K1, K2, and K3
stiff pH gradient was noted to correspond to the place
where the local voltage drop occurred. The factors
influencing the acid/base fronts across the porous
medium would significantly affect the flow, the flow
efficiency and the extent of ion migration and
removal during EK soil processing (Acar et al. 1994).
Zinc migration
The specimen was sampled after EK processing;
post-chemical analysis was also performed. The soil
section of each experiment collected for the mea-
surements of soil pH and zinc concentration is shown
schematically in Fig. 5. The label of each section
(e.g., A-* and C-*) denotes the region close to each
electrode: A-* in the anode region and C-* in the
cathode region. The location of each section (e.g., A-
1: 0.88) was calculated from the normalized distance
from the cathode (i.e., from 0 at the cathode end to 1
at the anode end) due to the volume reduction of the
specimen with processing time.
The mass balance of zinc before and after EK
processing, calculated using tests K1, K2, and K3, is
given in Table 3. The batch shaker test and the acid
digestion method were used for the determination of
the aqueous zinc concentration in the liquid phase
and the total adsorbed zinc in the solid phase,
respectively (USEPA 1986, 1987).
Figure 6 presents the final distribution of total
adsorbed or retained zinc concentrations (i.e., either
adsorbed onto the soil particles or precipitated in the
pore space) as a function of the normalized distance
Environ Geochem Health

1200

Flow In

Adsorbed zinc conc., mg/kg

1000

Anode 800
1
A-1 600
(0.88)
400

Normalised distance
A-2 200
(0.63)
0
0 0.2 0.4 0.6 0.8 1
Normalised distance from cathode, x/L
C-2
(0.38) Initial adsorbed zinc 2 hr 4 hr 8 hr

Fig. 6 Adsorbed zinc concentration after electrokinetic (EK)

C-1 processes as a function of the normalized distance from the
(0.13) cathode: tests K1, K2, and K3

0
Cathode
Flow Out
Fig. 5 Schematic diagram of the soil section
from the cathode. The initial concentration of total
adsorbed zinc was about 570 mg/kg. As seen, the
concentration near the anode was reduced to approx-
imately 100 mg/kg after 2 h of EK processing. The
EK removal of zinc in the middle of the specimen
appeared to commence after 4 h of EK treatment. It
should be noted that the concentration near the
cathode was elevated to 900 mg/kg after 4 h of
treatment, which became higher than 1,000 mg/kg
after 8 h of processing. This elevation near to the
cathode indicates that the zinc ions transported from
the anode were precipitated in the pore space due to
the high pH environment. After 8 h, the zinc
concentration became less than 200 mg/kg in most
of the specimen.
The final aqueous zinc concentration in the pore
space is shown in Fig. 7 as a function of the
normalized distance from the cathode. Note that the
initial aqueous zinc concentration was about 230 mg/
l. The zinc concentration in the cathode decreased by
half, but the level near the anode increased after 2 h
of EK treatment. After 4 h, the zinc concentration
near the cathode was significantly reduced to less
than 50 mg/l, whereas those in the middle of the
specimen increased; the zinc concentration near the
anode was slightly reduced. After 8 h, the zinc
concentration near the anode was reduced to approx-
imately 100 mg/l, whereas that near to the cathode
increased from about 30–200 mg/l.

Table 3 Mass balance calculations

Parameter K1: 2 h EK processing K2: 4 h EK processing K3: 8 h EK processing

C-1 C-2 M A-2 A-1 C-1 C-2 A-2 A-1 C-1 C-2 A-2 A-1
a
Total zinc in the specimen (mg) 182.1 182.3 182.1
Aqueous zinc in the pore (mg) 80.9 80.5 79.8
Adsorbed zinc mass (mg) 101.2 101.8 102.3
Initial void ratio, ei 5.21 5.13 5.19
Final aqueous zinc conc. (mg/l) 122.6 197.8 201.2 306.8 285.9 31.0 276.6 332.3 234.6 205.6 331.8 260.4 117.6
Final adsorbed zinc conc. (mg/kg) 634.4 486.5 475.3 290.1 124.7 909.2 308.7 160.8 107.3 1063 195.0 92.1 53.9
a
Calculated mass of Zn from the initial volume of specimen

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 Environ Geochem Health

350 1.6

Aqueous concentration, C/Co

300 1.4
Aqueous zinc conc., mg/L

1.2
250
1
200
0.8
150
0.6
100
0.4
50
0.2

0 0
0 0.2 0.4 0.6 0.8 1 0 2 4 6 8 10
Normalised distance from cathode, x/L Time, hr
Initial aqueous zinc 2 hr 4 hr 8 hr
C-1 C-2 A-2 A-1

Fig. 7 Aqueous zinc concentration after electokinetic (EK) Fig. 9 Migration of zinc ions through kaolin clay during
processes as a function of the normalized distance from the electrokinetic (EK) processes: tests K1, K2, and K3
cathode: tests K1, K2, and K3

Removal efficiency the total adsorbed zinc concentration in most of the

soil specimen was decreased within 2 h of EK
Electrically induced desorption, migration, and pre- treatment, as shown in Fig. 8. Consequently, by that
cipitation of zinc in the specimen for each of tests K1, time, the aqueous zinc concentration in the anode
K2, and K3 during EK soil processing as a function region (e.g., A-1 and A-2) had increased due to
of time are shown in Figs. 8 and 9. The zinc removal desorption of zinc from clay particles. Desorption and
efficiency estimated from tests K1, K2, and K3 is dissolution may occur simultaneously, with a similar
given in Table 4. It is interesting to note the amount of ionic zinc species going into the pore
simultaneous variation in the total adsorbed zinc solution. Those soluble zinc ions in the cathode
concentration with the change of aqueous zinc region were able to escape from the specimen
concentration. On the application of electricity, the through the open cathode; hence, the aqueous zinc
adsorbed zinc appears to initially dissolve into concentration was first reduced in the cathode region.
the pore solution due to the effects of EM. Therefore, However, those ions in the anode region migrated to
the next section of the specimen toward the cathode,
and rendered an increase in total aqueous zinc in that
region along with zinc ions being desorbed from the
2
soil particles. This may be related to the effectiveness
1.8
Adsorbed concentration, C/Co

of EK flushing during the process.

1.6
The removal of approximately 80% of adsorbed
1.4
1.2
zinc in section A-1 was achieved during the first 2 h
1
of EK processing, with a slight reduction shown after
0.8
4 h of processing (see A-1 in Fig. 8). Therefore, it
0.6
appears that the aqueous zinc in section A-1 was
0.4 transported toward the cathode by the effects of EM,
0.2 together with the EO force, between 2 and 4 h of
0 processing, and hence the reduction of aqueous zinc
0 2 4 6 8 10
concentration (as shown in Fig. 9). The reduction of
Time, hr
aqueous zinc in section A-1 continued during the rest
C-1 C-2 A-2 A-1
of the test, increasing the removal efficiency of
Fig. 8 Desorption and precipitation of zinc in kaolin clay adsorbed and aqueous zinc by up to approximately
during electrokinetic (EK) processes: tests K1, K2, and K3 90%.

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Environ Geochem Health

Table 4 Calculations of the zinc removal efficiency

Parameter K1: 2 h EK processing K2: 4 h EK processing K3: 8 h EK processing

C-1 C-2 M A-2 A-1 C-1 C-2 A-2 A-1 C-1 C-2 A-2 A-1

Final void ratio after EK process ef 3.54 5.16 6.07 5.57 5.26 2.47 4.51 4.70 5.12 1.95 2.30 3.77 5.48
Final aqueous Zn conc., C/Co 0.50 0.87 0.91 1.37 0.84 0.09 0.96 1.15 0.83 0.48 0.82 0.73 0.35
Zn removal efficiency (%) 50 13 9 – 16 91 4 – 17 52 18 27 65
Final insoluble Zn conc., C/Co 1.53 0.84 0.79 0.49 0.14 2.30 0.49 0.23 0.15 2.57 0.42 0.14 0.06
Zn removal efficiency (%) – 16 21 51 86 – 51 77 85 – 58 86 94
Total removal efficiency (%) 17.9 22.3 29.1
Removal efficiency: aqueous zinc (%) 10.3 24.4 40.4
Removal efficiency: adsorbed zinc (%) 24.0 20.6 20.3

A similar pattern can be seen in section A-2; the
removal efficiency and rate are slightly different from
those observed in section A-1. However, the adsorbed
zinc concentration significantly increased in section
C-1 between 2 and 4 h of the EK processing, as
shown in Fig. 8. Therefore, the migrating zinc ions
from the anode side may be either precipitated in the
pore space or re-adsorbed onto the soil particles in the
cathode region. Some of the aqueous zinc ions were
successfully extracted from the specimen or precip-
itated in the highly alkaline pore solution, so that the
aqueous zinc concentration was significantly de-
creased by 4 h of processing as also shown in Fig. 9.
It should be noted that the maximum processing
time was 8 h, and any type of enhancing techniques,
such as conditioning the anode and cathode compart-
ment or installation of an ion-selective membrane
were not used for tests K1, K2, and K3. Therefore,
although the removal efficiency in most parts of the
specimen ranged from 58 to 94%, the overall removal
efficiency was less than 30%, due to the zinc
precipitation close to the cathode in the high pH
environment. It was also noted that the migrating
heavy metal contaminants under the effects of EM
were unable to penetrate the zone of neutralization
due to the precipitation of ions.
in pore space, and their dissolution/precipitation
under different pH environment. The following
conclusions can be drawn from the experimental
results.
On the application of a DC electric field, both EM
and EO occurred, and the migrating cations were
either enhanced or hindered by the advective flow
toward the cathode due to the effects of EO and/or the
opposite hydraulic flow toward the anode. The
amount of zinc in the system had a direct effect on
the electrically induced fluid flow.
Metal contaminants can be removed from soft clay
with high moisture content using the EK remediation
technology; the removal efficiency of adsorbed zinc
was up to 94% in the anode region. However, most of
the migrating metal contaminants were precipitated
in the cathode region due to the neutralization that
occurred during EK processing, resulting in a low
overall efficiency of metal removal.
Acknowledgements The authors thank Mr. H. Shimizu for
his helpful assistance during the laboratory tests at the Disaster
Prevention Research Institute (DPRI), Kyoto University.
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