Chemosphere 63 (2006) 1667–1676

www.elsevier.com/locate/chemosphere

Effect of soil chemical properties on the remediation

of phenanthrene-contaminated soil
by electrokinetic-Fenton process
a,*
Jung-Hwan Kim , Sang-Jae Han b, Soo-Sam Kim b, Ji-Won Yang c

a
Environment Energy Engineering (En3), 4th Floor, Dongcheon Building, 267-2 Nonhyun-Dong, Kangnam-Ku,
Seoul 135-010, South Korea
b
Department of Civil and Environmental Engineering, Hanyang University, 1271 sa-1 dong, Aansan,
Kyunggi-do 425-791, South Korea
c
National Research Laboratory for Environmental Remediation, Department of Chemical and Biomolecular Engineering,
Korea Advanced Institute of Science and Technology (Kaist), 373-1 Geseong-dong, Yuseong-gu, Daejeon 305-701, South Korea

Received 14 February 2005; received in revised form 5 October 2005; accepted 5 October 2005
Available online 28 November 2005

Abstract

The electrokinetic-Fenton (EK-Fenton) remediation of soil contaminated with phenanthrene was studied. Two dif-
ferent soils were chosen to investigate the effects of chemical properties, such as Fe oxide contents and acid soil buffer
capacity. The H2O2 concentrations in pore water, the electrical potential distributions and the electrical currents were
monitored to assess the electrochemical effect in relation to the soil properties. Hadong caly had high acid buffer capac-
ity, and thus the amount of electroosmotic flow was lager in the experiment with Hadong clay than with EPK kaolin.
The major mechanism of phenanthrene removal was a degradation in the experiment with EPK Kaolin, while it was a
simple transport away from the system in experiment with Hadong clay. It was mainly because of the lower acid buf-
fering capacity and better H2O2 stability in case with EPK Kaolin than with Hadong clay.
 2005 Published by Elsevier Ltd.

Keywords: Electrokinetic-Fenton process; HOCs; Fe oxide; Acid buffer capacity

1. Introduction bilities and slow desorption rates, PAHs are difficult to

Polycyclic aromatic hydrocarbons (PAHs) are
organic contaminants commonly found in subsurface
(Warman, 1985). These chemicals not only result in tox-
icity, but also are carcinogens and endocrine disrupters
(Sullivan and Krieger, 1992). Because of their low solu-
*
Corresponding author. Tel.: +82 2 540 3910; fax: +82 2 540
0935.
E-mail address: genkjh@wm.cau.ac.kr (J.-H. Kim).
be removed from subsurface environments.
Among various technologies employed for the reme-
diation of soils contaminated with organic chemicals,
Fenton process is one of the most widely used and stud-
ied, in which hydroxyl radicals are produced by the reac-
tion of hydrogen peroxide and ferrous ion. Hydroxyl
radicals are non-specific oxidants that react with most
organic contaminants at rates close to their theoretical
limit, which is near the diffusion-controlled rate in water
(109–1010 M1 s1) (Walling, 1975). However, they are

0045-6535/$ - see front matter  2005 Published by Elsevier Ltd.

doi:10.1016/j.chemosphere.2005.10.008
1668 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676
effective only at low pH values, which require pH adjust-
ment during the remediation (Valentine and Wang,
1998).
Application of the modified FentonÕs reagent has
been effective in degrading contaminants and included
the use of high concentrations of H2O2 and iron oxides
as catalysts (Tyre et al., 1991). Soil-bound contaminants
are more resistant to oxidative attack during chemical
treatments than contaminants in solution (Watts et al.,
1993; Watts and Dilly, 1996). The effects of sorption
on contaminant degradability can be minimized with
high H2O2 additions, which results in the generation of
non-hydroxyl radical transient oxygen species, such as
perhydroxyl radicals (HO2 ), superoxide radical anions
(O2 ) and hydroperoxide anion (HO 2 ), which are capa-
ble of oxidizing sorbed contaminants (Watts and Stan-
ton, 1999). In the following equations, –Fe3+ and
–Fe2+ represent liganded iron or occupying sites at an
oxide surface:
H O þ –Fe2þ ! OH þ OH þ –Fe3þ
2 2 ð1Þ
H2 O2 þ OH ! HO2 þ H2 O
HO2 $ O2 þ Hþ ; pK a ¼ 4:8
HO2 þ –Fe2þ ! HO 3þ
2 þ –Fe
HO þ O ! HO þ O
2 2 2 2
However, the modified Fenton method has difficulties
in treating heterogeneous subsurface environments that
contains clayey soil with low permeability. Electrokinetic
remediation of soil possessing low permeability repre-
sents a technology for both heavy metals and organics
removal (Hamed et al., 1991; Acar et al., 1992). Recently,
it has been demonstrated that the removal efficiency can
be improved by combined application of an electrical
field and supplementary reagents for organic removal
(Yang and Long, 1999; Reddy and Saichek, 2003). An
H2O2 & H2O2 stabilizer Supply In-let
Anode
Ground level
Water flow
H2 O2
Soil surface
Radical species
desorption, degradation and removal
of contaminants
Hydrogen ion
Fig. 1. Schematic diagram of the electrokinetic-Fenton process catalyzed by minerals in the subsurface.
innovative remediation technique known as the electr-
okinetically enhanced in situ Fenton oxidation method
(Yang and Long, 1999) employs a high H2O2 concentra-
tions as the anode purging solution, which demonstrates
a potential to treat contaminants sorbed onto soils pos-
sessing low permeability. The H2O2 introduced from
the anode chamber is transferred toward the cathode
by electroosmotic flow, which is accompanied by the
decomposition of contaminants on the mineral surface,
where the anions (O2 , HO 2 ) may move towards the
anode due to electromigration (Fig. 1). The electrolysis
of water produces hydrogen ions at the anode, which in
turn generates an acid front, thus affects the contaminant
remediation and H2O2 stabilization, which may have
direct influences from soil properties.
Thus the purpose of the present study is to examine
the effect of soil chemical properties, such as buffer
capacity and iron contents, on the EK-Fenton process.
A bench-scale experiments of the EK-Fenton process
were conducted using two soils spiked with phenanthrene
as the representative PAH and a low concentration acid
ð2Þ (0.01 N H2SO4) as the anode purging solution for pH
ð3Þ control. Electrical current, electrical potential distribu-
tion and electroosmotic flow, as well as the pH, were
ð4Þ
measured. The residual H2O2 and phenanthrene concen-
ð5Þ
trations that existed in the soil at the end of each experi-
ment were also detected.
2. Experimental
2.1. Materials
The soils selected for the present study were EPK
(EdgerÕs Plastic Kaolin from Florida) kaolin and
Hadong clay. EPK kaolin was purchased from the
Cathode
Soil
Organic contaminants
- -
Anions HO2 O2
Hydroxide ion
 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676 1669

Feldspar Corporation and the Hadong clay was an
actual soil in Hadong, Korea. Table 1 shows that the
mineralogy, physical and chemical properties of these
soils differ significantly. As seen in the table, the major
mineral of EPK kaolin was kaolinite whereas the
Hadong clay soil was largely composed of quartz, kaoli-
nite and halloysite. The two soils had negligible amounts
of organic carbon. The concentrations of extractable
NO 2
3 and SO4 in the soil were determined by 0.01 M
HCl extraction, and the soluble Cl concentration in
the soil by de-ionized water, but the salts in the two soils
were only in trace amount.
Table 2 shows that the Fe, Mn and Ca concentration,
in different forms, were determined by the sequential
extraction procedure proposed by the Commission of
the European Communities Bureau of (Tokalioğlu
et al., 2000). The two soils possessed much lesser amounts
of Mn, and the Fe concentration in the EPK kaolin was
higher than that in Hadong clay, while the concentration
of Ca indicated contrary tendency.
Phenanthrene was selected to be a representative
PAH compound, and has an aqueous solubility of
1.1 mg l1 and a log Kow of 4.57 at 25 C (Schwarzen-
bach et al., 1993). The electrolyte was supplied from
the anode part and composed of 0.01 N H2SO4 for pH
control and 7% H2O2 for oxidation.
2.2. Electrokinetic reactor
The electrokinetic reactor was set up as shown in
Fig. 2. The reactor was divided into four parts: two elec-
trode chambers, an electrolyte reservoirs and a soil cell.
The electrokinetic cell used for the tests was 8 cm in dia-
meter and 20 cm long, and made of Plexiglas. Seven pas-
sive electrodes were inserted into the soil cell and graphite
electrodes of disk shape were placed in contact with the
chambers. The electrodes were located at each end of
the cell so that the electrolyte solution was only in contact
with one face of each electrode. A filter paper was placed
at the end of the soil cell. Each electrolyte chamber occu-
pied the space between a porous stone and an electrode.
PVC valves were used to control the inflow and outflow
of the solution. The inlet at the bottom of the anode cham-
ber was connected to a reservoir containing 2000 ml of

Table 1
Chemical and physical characteristics of soils
Parameter EPK kaolin Hadong clay
Major mineral component (XRD) Kaolinite Quartz, kaolinite, halloysite
Specific gravity of solid particles (ASTM D 854)a 2.65 2.62
Composition (%) (ASTM D 422)a
Clay 97 55
Silt 3 23
Sand 0 22
Specific surface area (m2 g1) 24.3 25.1
Organic carbon content (%) (Walkley and Black, 1934) <0.1 <0.1
Cation exchange capacity (%) (US Soil Conservation Service, 1972) 5.5–6 10.1–10.6
Extractable salts concentration (mg kg1)
SO2
4 (extracted with 0.01 M HCl) 42 13
NO 3 (extracted with 0.01 M HCl) 13 44
Cl (soluble with de-ionized water) ND ND
CaO (%) (XRF) 0.18 2.16
Hydraulic conductivity (cm s1) 2 · 108 7 · 108
Initial soil pH (500%, water–solid) 5.6 7
a
ASTM (1996).

Table 2
Distribution of different iron, manganese and calcium fractions in soils
Fraction EPK kaolin (mg kg1) Hadong clayey soil (mg kg1)
Fe Mn Ca Fe Mn Ca
Exchangeable and bound to carbonates 69 2 1244 33 15 1249
Bound to Fe- and Mn-oxides 185 0.2 187 89 11 222
Bound to organic substances 44 0.2 64 51 1 319
Residual fraction 3866 7 712 2976 18 9857
Total 4163 10 2208 3147 45 11646
1670 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676
Fig. 2. Schematic diagram of the electrokinetic apparatus.
anolyte solution, which was circulated by a peristaltic
pump. A graduated cylinder (2000 ml volume) was used
as the catholyte reservoir to measure the water volume
transported. Gas vents were provided in the electrode
chambers for the escape of any gases resulting from the
electrolysis reactions.
2.3. Methods
2.3.1. Preparations of test specimen and reactor
For all the electrokinetic tests, phenanthrene dis-
solved in hexane was mixed with the soil to obtain the
required concentration of 200 mg kg1 of dry soil, and
then the hexane was allowed to evaporate in a fume
hood. A little heterogeneity below 5% through this pro-
cedure was generated. The soil was then made up to a
moisture content of 75–80% with de-ionized water.
The soil was then statically compacted into a cell
using an air pressure of 150 kPa for 7 d. The cell was,
then, inserted into the main testing chamber. Once the
soil was fully packed into the cell, the peripheral equip-
ment was attached to the reactor. At the start of testing,
the cathode chamber was filled with de-ionized water
and the anode compartment and reservoir were filled
with the appropriate electrolyte solution.
2.3.2. Operating conditions
The test conditions are summarized in Table 3. A
constant electrical potential between electrodes was
applied throughout the experiments. The tests with
EPK kaolin and Hadong clay were abbreviated in the
prefix by K1,2,3 and H1,2,3, respectively. Seven percent
of H2O2 was used as the anode purging solution for all
the tests.
In K1&2 and H1&2, only H2O2 was used as the
anode purging solution, and K2 and H2 were a long-
term experiments of K1 and H1, respectively. H2SO4
(10 mN) along with H2O2 were used in the anode purg-
ing solution in K3 and H3. Thus test 2&3 in both K&H
experiment were performed until the effluent volume was
reduced or stabilized.
2.3.3. Chemical analysis
At the end of each experiment, the cell filling was
sliced into layers of approximately 2 cm, and each sec-
tioned sample was well mixed and was measured for
pH and moisture content.
The phenanthrene in the liquid samples was extracted
by triple liquid–liquid extraction, using a total of about
50 ml dichloromethane. To extract the phenanthrene
from the soil, the soil sample (2.5 g) was transferred to
a 10 ml borosilicate screw-top tube. 7.5 ml of a 1:1
dichloromethane:methanol mixture was added to the
soil, and the soil–solvent suspension was shaken (200
rpm) for 72 h at 30 C. The tube was then centrifuged
for 15 min, and the solvent mixture was transferred to
a 10 ml test tube. One gram of anhydrous sodium sulfate
was mixed with the phenanthrene containing solvent to
completely remove residual water. The phenanthrene
concentration was determined using a HPLC (Gibson
 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676 1671

Table 3
Summary of test conditions
Parameter K1 K2 K3 H1 H2 H3
Applied electrical 30
potential (V)
Area (cm2) 50.24
Length of sample (cm) 20
Initial concentration 200
of spiked phenanthrene
(mg kg1)
Fluid at the cathode chamber De-ionized water
Permeating fluid at H2O2 H2O2 H2O2 (7%) H2O2 H2O2 H2O2 (7%)
the anode chamber (7%) (7%) H2SO4 (10 mN) (7%) (7%) H2SO4 (10 mN)
Duration (h) 240 486 312 240 528 240
Initial water content (%) 42.1 42.3 42.5 38.5 39.2 40.2

305 system) equipped with UV and Fluorescence detec- 8

tors. A mixture of water and methanol, 20:80, was used 7 Blank
as the mobile phase, with a constant flow rate of EPK
6
1.0 ml min1. The detector wavelength was set at Hadong
254 nm. Using this procedure, 75–80% of the phenan- pH 5
threne spiked into EPK kaolin and Hadong clay was 4
recovered. This result indicates that some irreversible
3
sorption/partitioning of the phenanthrene into clay
might have occurred, due to EPK kaolin and Hadong 2
clay possessing soil properties of a small particle size 1
and high soil surface area. After the phenanthrene con-
0
centration of the 10-sectional samples had been analyzed 0 100 200 300 400 500 600 700
+
800 900 1000
by HPLC, the average value of the adjacent parts was Acid added (mmol H /kg soil)
used as the representative phenanthrene concentration. Fig. 3. Titration curves of soils.
After the soil had been diluted and centrifuged, the
residual H2O2 concentration in the supernatant was ana-
lyzed by an iodometric titration method (Kolthoff et al.,
1969). higher than that in EPK Kaolin. Therefore, the resis-
tance to pH change in the Hadong clay might be due
to the neutralization of H+ by the calcium carbonates
3. Results and discussion in the soil.

3.1. Soil buffer capacity of two soils 3.2. Electrical current and electrical potential distribution

The method of Yong and Warkentin (1990) was
adapted in the present study to construct a titration
curve of the soil buffer capacity. The acid solutions were
prepared at the concentration of 0, 0.001, 0.002, to
0.01 M. The acid solutions were then added to the soil
at a ratio of 1:10 for soil:acid solution, using 4 g of
dry soil and 40 ml of acid solution. Blank test without
soil was conducted. The titration curves of pH vs acid
inputs for the EPK kaolin, Hadong clay and blank are
shown in Fig. 3.
The titration curves show that the Hadong clay was
resistant to pH change, while the EPK kaolin seemed
to have no significant resistance to pH changes. Gee
et al. (2001) proposed that soil buffer capacity increased
as the amount of Ca in the soil increased. In Tables 1
and 2, Ca content in Hadong clay was significantly
Fig. 4 shows the current increased rapidly and
reached a peak within 1–24 h, and then decreased and
remained nearly constant when H2SO4 was used for
pH control. The peak at the very beginning was because
the quantity of ions was the greatest due to the dissolu-
tion of salts associated with the dry soil particles (Mitch-
ell, 1993). Wada and Umegaki (2001) proposed, when
NaCl was introduced from the anode chamber, that
the anions in the pore water were Cl ions, and the
major cations balancing the anionic charge were H+,
Na+ and Al3+. Namely, based on the principle of electri-
cal neutrality, the ionic concentrations was proportional
to the amount of salts released from soil surface and
introduced from the anode. The increase of these salts
concentration resulted in an increase of the electrical
conductivity and current.
1672 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676

20 H2 SO4 þ CaCO3 þ H2 O
K1 (7% Hydrogen peroxide)
18
H1 (7% Hydrogen peroxide)
$ 2Hþ þ SO2
4 þ Ca
2þ
þ CO2
3 þ H2 O
16
K3 (7% Hydrogen peroxide,10mN Sulfuric acid) $ CaSO4  2H2 O ðGypsumÞ þ CO2 ð6Þ
14 H3 (7% Hydrogen peroxide,10mN Sulfuric acid)
Current (mA)

12 Therefore, when H2SO4 was used in addition to H2O2

10 as the purging solution, major salts during the early
stage of tests with Hadong clayey soil were HCO and
8
CO2 along with SO2
, O  and HO in tests3 with
6 3 4 2 2

4
EPK kaolin.
Fig. 5 shows the normalized electrical potential
2
(V/Vmax) distribution. In K1 and H1 that used H2O2
0
0 50 100 150 200 250 300 350 as the only purging solution, the electrical potential dif-
Elapsed time (h) ference between the 2 cm and anode end of soil specimen
was higher than in the other regions during the 240 h.
Fig. 4. Comparison of current in EPK kaolin and Hadong
These results signify that the difference of the electrical
clayey soil.
conductivity in this region was higher than that in the
other regions, and was maintained as time elapsed.
Therefore, these phenomenon might have resulted from
Table 1 shows that salts, such as SO2 
4 , NO3 and Cl ,

the concentration gradient of ionic species, O2 and
released from the soils were at very trace levels. Hadong HO 2 generated during the H2O2 decomposition as well
clay, however, contains a significant amount of soluble as HCO 2
3 and CO3 released from the soil.
carbonate (Tables 1 and 2) that reacts with sulfuric acid. On the contrary, in K3 and H3 using H2O2 and
And as time elapsed, ionic concentration decreased with H2SO4 as the anode purging solution, the potential gra-
the solids produced according to the following equation dient in the regions near the anode was much lower than
(Lindsay, 1979): in the other tests, and a very low potential gradient

1
1
Normalized electrical potential

Normalized electrical potential

0.5h 0.5h
0.8 0.8
24h 24h
72h 72h
0.6 240h 240h
(V/Vmax)

0.6
(V/Vmax)

0.4 0.4

0.2 0.2

0 0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Distance from anode (cm) Distance from anode (cm)
(a) K1 (7% H2O2) (b) K3 (7% H2O2, 10mN H2SO4)
1 1
0.5h
Normalized electrical potential
Normalized electrical potential

0.5h 24h
0.8 0.8
24h 72h
72h 240h
0.6 0.6
(V/V max)
(V/Vmax)

240h
0.4 0.4

0.2 0.2

0 0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Distance from anode (cm) Distance from anode (cm)
(c) H1 (7% H2O2) (d) H3 (7% H2O2, 10mN H2SO4)

Fig. 5. Development of electrical potential profile (Vmax indicate that electrical potential was measured by the passive electrode,
inserted at both ends of the soil specimen).
 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676 1673

region gradually developed from the anode end toward dient. When only H2O2 was used, the electrical potential
the cathode as time elapsed. drop near anode resulted in non-linear profile, and thus
This phenomenon has been confirmed by Wada and electroosmotic flow was retarded.
Umegaki (2001) that Cl ions were gradually speeded In addition, the cumulative electroosmotic flow with
toward the cathode, due to the electroosmotic flow, Hadong clay was higher than that with EPK kaolin.
when NaCl was injected from the anode chamber. Based Generally, according to the Helmholtz–Smoluchowski
on this result, the main cause of the potential flattening theory, the electroosmotic flow rate increases with the
was the transportation of SO2
4 ions towards the cathode increase of negative zeta potential and electric-field
due to the electroosmotic flow. strength, and then the amount of the negative zeta
potential in the soil surface is proportional to the pH
3.3. Electroosmotic flow and electrical potential increase in the soil. Based on this theory, carbonate min-
distribution erals in the Hadong clay buffered the acid generated at
the anode and maintained the pH high (Fig. 7). Thus
Fig. 6 shows the cumulative electroosmotic flow. The the zeta potential is relatively unchanged, which keeps
results indicate that the differences in the anode reagent the cumulative electroosmotic flow in Hadong clay
and soil properties had a significant effect on the cumu- higher than in EPK kaolin with a low buffering capacity.
lative electroosmotic flow. When H2SO4 was addition- Consequently, electroosmotic flows were dependent
ally used with H2O2 as an anode purging solution, the on linearity of electrical potential distribution and zeta
electroosmotic flow rate was higher than that in the tests potential according to soil chemical property.
using only H2O2. The cumulative electroosmotic flow is
closely related to the linearity of electrical potential gra- 3.4. pH and residual concentration of H2O2 after tests

1800 Fig. 7 shows the distribution of the residual H2O2

Cumulative volume of effluent (ml)

K2 (7% Hydrogen peroxide) concentration and the pH of the soil specimen after
1600 H2 (7% Hydrogen peroxide)
K3 (7% Hydrogen peroxide, 0.01 N Sulfuric acid)
tests. The pH values were ranged from 3.4 to 7.2 in
1400 H3 (7% Hydrogen peroxide, 0.01 N Sulfuric acid) K1 and from 3.8 to 10.5 in H1. These results indicate
1200 that the initial pH and acid buffer capacity of the soil
1000
affected the transportation of the acid and base front.
Namely, since the EPK kaolin possessed a low initial
800
pH and low acid buffer capacity, the pH in the soil
600 was lower than that in the Hadong clay. The residual
400 H2O2 concentrations in the Z = 0.05–0.15 regions were
higher in H1 than in K1, while that in the other regions
200
showed the contrary tendency (Z = normalized distance
0 from the anode end in the soil column; i.e., Z = z/L,
0 100 200 300 400 500 600
where z = distance from anode end in the soil column
Elapsed time (h)
and L = soil column length).
Fig. 6. Cumulative volume of effluent plotted against elapsed Generally, the H2O2 decomposition rate is propor-
time. tional to the increase in the pH and amount of Fe oxide

4.5 12 4.5 12
K1 (Hydrogen peroxide) K2 (Hydrogen peroxide)
H 2O2 concentration (%)

H2O2 concentration (%)

4 H1 (Hydrogen peroxide) 4 H2 (Hydrogen peroxide)

K1 (pH) 10 K2 (pH) 10
3.5 H1 (pH) 3.5 H2 (pH)

3 8 3 8

2.5 2.5
pH

pH

6 6
2 2

1.5 4 1.5 4

1 1
2 2
0.5 0.5

0 0 0 0
0.05 0.15 0.25 0.35 0.45 0.55 0.65 0.75 0.85 0.95 0.05 0.15 0.25 0.35 0.45 0.55 0.65 0.75 0.85 0.95
Normalized distance from anode Normalized distance from anode
(a) K1 and H1 (b) K2 and H2

Fig. 7. Residual H2O2 and pH distribution in the soil specimens after the tests.
1674 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676

in the soil (Watts et al., 1999a). A higher residual H2O2 than in K2, it is evident that the treatment efficiencies
concentration in Z = 0.05–0.25 regions and a lower in tests using EPK kaolin were higher than in Hadong
residual H2O2 concentration in the other regions were clay.
found for H1 compared with K1. Since the amount of Since the Fe content and soil buffer capacity in EPK
Fe oxide in Hadong clayey soil was lower than that in kaolin were, respectively, higher and lower than those in
EPK kaolin, the residual H2O2 concentration in Hadong clay, a higher removal efficiency and improve-
Z = 0.05–0.25 regions were higher in EPK kaolin than ment of H2O2 stabilization were found in tests with
in Hadong clay. On the other hand, in H1, due to the EPK kaolin compared with those in Hadong clay. Par-
high acid buffer capacity of Hadong clay, the decompo- ticularly, in K3 with EPK kaolin as well as H2O2 and
sition rate of H2O2 increased rapidly as the distance H2SO4 as the anode purging solution, the efficiency of
from the anode increased. phenanthrene increased significantly compared to other
In addition, although the test period were longer and tests. This result indicates that the low buffer capacity
cumulative electroosmotic flow were higher in H2 than of EPK kaolin and addition of 0.01 N H2SO4 resulted
in K2, the residual concentration of H2O2 in the entire in increase of advancement rate of acid front, and then
soil specimen was lower in H2 than in K2. The lower sta- the oxidation of phenanthrene with Fenton-like reaction
bility of H2O2 in H1 and H2 also resulted from the increased.
higher acid buffer capacity. The mechanism of phenanthrene treatment was influ-
enced by the soil properties (Fig. 8). In the tests with
3.5. Residual concentration of H2O2 and phenanthrene Hadong clay, the residual concentration of the phenan-
threne in the regions near cathode increased compared
Although the test period and amount of electroos- to the initial phenanthrene concentration. These results
motic flow in H2 were longer and larger, respectively, indicate that desorption of the phenanthrene in the

1.2 5 1.2 5 1.2 5

4.5 4.5
Phenanthrene concentration (C C )

Phenanthrene concentration (C C0 )

4.5
-1

Phenanthrene concentration (C C0-1)

-1
0

1 1 1
4 4 4

H2O2 concentration (%)

H2O2 concentration (%)

H2O2 concentration (%)

3.5 3.5 3.5

0.8 0.8 0.8
3 3 3
0.6 2.5 0.6 2.5 0.6 2.5
2 2 2
0.4 0.4 0.4
1.5 1.5 1.5
1 1 1
0.2 0.2 0.2
0.5 0.5 0.5
0 0 0 0 0
2 6 10 14 18 0
2 6 10 14 18 2 6 10 14 18
Distance from the anode (cm) Distance from the anode (cm) Distance from the anode (cm)
(a) K1 (b) K2 (c) K3
5 5
5 1.2
1.2
1.2 4.5 4.5
4.5
Phenanthrene concentration (C C0-1)
Phenanthrene concentration (C C0 )
Phenanthrene concentration (C C )

-1
-1

4
0

1 4 1
1 4
3.5 3.5
H2O2 concentration (%)

H2O2 concentration (%)

H2O2 concentration (%)

3.5
0.8 0.8 3
0.8 3 3

2.5 2.5
2.5 0.6 0.6
0.6
2 2
2
0.4 1.5 0.4 1.5
0.4 1.5
1 1
1 0.2 0.2
0.2
0.5 0.5
0.5
0 0 0 0
0 0
2 6 10 14 18 2 6 10 14 18 2 6 10 14 18
Distance from the anode (cm) Distance from the anode (cm) Distance from the anode (cm)
(d) H1 (e) H2 (f) H3

-1 Hydrogen peroxide concentration (%)

Relative phenanthrene concentration (C C0 )

Fig. 8. The distribution of residual phenanthrene and hydrogen peroxide in the soil specimens after the tests.
 J.-H. Kim et al. / Chemosphere 63 (2006) 1667–1676
regions near anode occurred and then most of the des-
orbed phenanthrene was transported toward the cath-
ode due to the electroosmotic flow. Namely, since the
transportation rate toward the cathode was faster than
the degradation rate, the major mechanism of the phen-
anthrene treatment were desorption and transportation.
However, in the tests with EPK kaolin, the increase of
the relative phenanthrene concentration in the regions
near cathode did not occur, except in K2. These results
indicate that the degradation rate of phenanthrene was
as fast as the desorption rate at the soil surface.
Watts et al. (1999b) suggested that the reductants,
such as O2 and HO2 , were responsible for the desorp-
tion of the sorbed contaminants during the vigorous
Fenton-like reactions. Kawahara et al. (1995) also pro-
posed that, in the Fenton reaction with high H2O2 con-
centration, a significant increase in the extractability of
the PAHs occurred after 1 h of treatment. It was because
of the release mechanism of tightly held PAHs due to
electron exchange by the structural iron in the clay min-
erals and the swelling of the layers. The present result
also supports the mechanism: the degradation and
removal with transportation of desorbed phenanthrene
after the desorption of phenanthrene sorbed in the soil
during the EK-Fenton process.
4. Summary and conclusions
The objective of this investigation was to examine the
electrochemical phenomenon, H2O2 stabilization and
treatment mechanism in relation to the soil properties
during the EK-Fenton process for phenanthrene
removal. The experiments employed two clay soils,
EPK kaolin and Hadong clay soil, to compare the effects
caused by different soil types. The parameters measured
during the test were the electrical current, electrical
potential gradient distribution, and cumulative electro-
osmotic flow. At the end of each test, the pH and resid-
ual phenanthrene concentrations in the soils were also
measured. The following conclusions could be drawn
from this study:
As was stated by the principle of electrical neutrality,
the electrochemical variation (current and potential gra-
dient) during the EK-Fenton process depended on the
amount and distribution of salts in the soil specimen.
3
The major salts were CO2 3 and HCO released from
  Willians and Wilkins, Baltimore, MD.
the soil, O2 and HO2 generated with H2O2 decomposi-
tion, and SO2
4 introduced from the anode.
The electroosmotic flow was closely related to the
profile of electrical potential gradient during the experi-
ment. The more linear profile it resulted, the larger
cumulative electroosmotic flow was obtained. In addi-
tion, the departure from the linearity indicates a higher
electrical resistance due to a shortage of ionic species,
which resulted in an undesirably bigger electrical poten-
1675
tial difference within a short distance. Furthermore, the
amount of cumulative electroosmotic flow was lager in
the test with Hadong clay than with EPK kaolinite
due to a high acid soil buffer capacity of Hadong clay.
The major mechanism of phenanthrene treatment
was degradation due to a suitable condition for the Fen-
ton-like reaction in the test with EPK kaolinite possess-
ing a low acid buffer capacity and high iron content. The
high carbonate content in Hadong clay, however,
resulted in a large acid buffer capacity, and thus resulted
in the decrease of H+ concentration. Carbonates appear
to reduce the H2O2 stabilization and treatment efficiency
of phenanthrene by the Fenton-like reaction.
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