Separation and Purification Technology 190 (2018) 297–306

Contents lists available at ScienceDirect

Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Exchange electrode-electrokinetic remediation of Cr-contaminated soil using MARK

solar energy
⁎
Ming Zhou , Jingming Xu, Shufa Zhu, Yajing Wang, Hui Gao
School of Chemical Engineering and Pharmaceutics, Henan University of Science and Technology, Luoyang 471023, China

A R T I C L E I N F O A B S T R A C T

Keywords: The present work focused on analyzing the effects of solar energy on the electrokinetic remediation (EKR) of Cr-
Solar energy contaminated soil, compared to direct current (DC) power supply. Meanwhile, to control the remedied soil pH
Soil remediation and focusing phenomena, the exchange electrode-EKR (EE-EKR) has also been employed. Four runs of tests were
Chromium conducted using DC power supply with the conventional EKR (run A, run D), DC power supply with EE-EKR (run
Electrokinetic
B) and solar energy with EE-EKR (run C) respectively. Important electrokinetic parameters such as electrical
Exchange electrode
voltage and current, electroosmotic flow, soil pH, the remediation efficiency of total Cr, Cr(VI), Cr(III) and cost
analysis were investigated to evaluate EE-EKR using solar energy. The results show that run B had the highest
removal efficiency of total Cr (43.65%), Cr(VI) (91.88%), and Cr(III) (19.32%), and run C, run A, run D follo-
w in turn. It was proved that EE-EKR could increase the removal efficiency of Cr, especially Cr(III) from con-
taminated soil, because it could reduce focusing phenomena and enhance electrical current. Meanwhile, the
experimental results also indicated that the combination of electrokinetics and solar energy was feasible and
effective to some extent for the remediation of Cr-contaminated soil.

1. Introduction Nowadays, electrokinetic remediation (EKR) had been proved as the

Soil pollution in China, caused by rapid urbanization and economic
development, had become an increasingly serious threat to public
health and the environment. In 2014, the
Ministry of Land and Resources and the Ministry of Environmental
Protection of the People's Republic of China jointly issued the first-ever
results of a nationwide soil pollution survey that took place from April
2005 to December 2013 [1]. The report admits that the situation of
overall national soil environment in China is not optimistic. The 16.1%
of soil in the Chinese mainland is contaminated, and more seriously,
19.4% of farming soil is contaminated. Inorganic soil pollutants are the
major pollutants in China’s soil, including cadmium, mercury, arsenic,
copper, lead, chromium, zinc and nickel from high to low. Among these
heavy metal pollutants, chromium (Cr) has been recognized as one of
the most hazardous pollutants, unfortunately the standard-ex-
ceeding rate of Cr is 1.1% in soil based on the soil pollution bulletin.
The toxic Cr in contaminated soil is a serious pollution problem af-
fecting soil and underground water qualities, therefore presenting a
direct hazard to human health. The release of Cr will can cause chronic
alterations in the nervous system and gastrointestinal tract as well as
renal dysfunction [2–4]. So decontamination of the Cr-contaminated
soil is one of the most important challenges.
relatively cheap, effective and environmentally friendly technology for
simultaneous removal multi-heavy metals in polluted soil [5]. During
the EKR process, under the driving force of direct current (DC) electric
field, heavy metals and organic pollutants can be migrated from soil
towards electrode wells by electroosmosis, electromigration and other
processes (such as electrophoresis). Electroosmosis (Electroosmotic
flow) is the movement of liquid in the porous soil under an electric
field, which mobilizes the organics and neutral molecules along with
pore fluid. And electromigration is the transport of charged ions to-
wards opposite charge of the electrode due to the applied electric field.
Electrophoresis is the motion of dispersed particles relative to a fluid
under the influence of a spatially uniform electric field. Ad-
vantages of this technology are: in-situ/ex-situ remediation, the ap-
plicability to a wide range of pollutants, and so on [6–9]. Because of
these advantages, EKR has been successfully applied, alone or in com-
bination, to remove a wide range of pollutants, such as a variety of
heavy meals, organic pollutants from the contaminated soil, sew-
age sludge and dredged sediments [10–18].
However, compared to other soil remediation technologies, there
are still many difficulties to carry out the soil remediation by EKR.
Some of which are electrical energy consumption of EKR, focusing
phenomena in the remediation process and adverse effects of EKR on

⁎
Corresponding author.
E-mail address: axore@163.com (M. Zhou).

http://dx.doi.org/10.1016/j.seppur.2017.09.006
Received 24 October 2016; Received in revised form 2 September 2017; Accepted 4 September 2017
Available online 06 September 2017
1383-5866/ © 2017 Elsevier B.V. All rights reserved.
M. Zhou et al.
soil properties (such as soil pH) [19–21]. So, in this study, instead of DC
power, we tried using solar cell to resolve the energy supply and
study its possibility [22–24]. The focusing phenomena is occasionally
observed only in the soil near electrodes during the EKR of heavy metal
contaminated soil, due to chemical precipitation near cathode [25,26],
which has become a limitation for the extraction or removal of heavy
metal pollutants. In order to decrease the focusing effect of the EKR and
improve the efficiency of Cr removal, we tried to use EKR with the
exchange electrode method (EE-EKR). M. Pazos et al. reported the
“polarity exchange” method that the technique can avoid the negative
effect of OH− on metal transportation and improve the metal removal
from contaminated soil by EKR [27]. EE-EKR can neutralize the hy-
droxide ion in the cathode region and reduce the precipitation of
chromic hydroxide by exchanging the anion and cathode in the electric
field. However, there are few literatures on EE-EKR of Cr-contaminated
soil, especially with regard to solar energy being used as the power
supply [28,29]. So the objective of this study was to investigate the
possible use EE-EKR with solar energy for removal of Cr from con-
taminated soil and explored the major factors influencing the re-
mediation process.
2. Materials and methods
2.1. Sample preparation and its characterization
The experimental soils are primarily silty loam, collected at the
chromium slag piled field located in Sanmenxia City, China's Henan
province, at depth between 0 and 20 cm. The total Cr and Cr(VI)
average concentration, organic matter content, pH, cation exchange
capacity, redox potential of soil samples were 1858 mg/kg, 623 mg/kg,
4.12%, 8.13, 21.3 cmol/kg, 332.6 mv respectively. The soil samples
were air dried, homogenized and sieved to remove the coarse particles
by the 2 mm nylon sieve prior to experiments.
2.2. Laboratory-scale electrokinetic experiments
Four runs of tests were carried out using DC power supply with the
conventional EKR, DC power supply with EE-EKR and solar cell with
EE-EKR respectively. The details of experimental conditions are de-
scribed in Table 1. The sketch map of the EKR experimental system is
shown in Fig. 1. The EKR experimental system was divided into the
following major parts: the soil cell (an inner length of 14 cm, a width of
8 cm, and a height of 6 cm), two electrode chambers (an inner length of
4 cm, a width of 8 cm, and a height of 6 cm), two electrolyte reservoirs,
four channels dispensing peristaltic pump (DG-4/BT00-300T, Long-
erpump, China) and a digital DC power supply (GPC6030D, GW Instek,
China) or solar cell. Graphite sheet electrodes were used as the working
electrodes in the experimental system (an inner length of 1 cm, a width
of 8 cm, and a height of 6 cm). To prevent soil leakage from the soil cell
to the electrode chambers, two non-woven fabrics were used.
The solar cell panel was made of monocrystalline silicon with a
length of 35.5 cm, a width of 25 cm, and a thickness of 2.5 cm. The
nominal voltage, nominal peak power and photoelectric conversion
Table 1
Electrokinetic experimental conditions.
Run Electrolyte Voltage (V) Treatment Energy Exchange of
concentration time (h) electrode
(KCl mol/L)
A 0.1 22 144 DC power 0
B 0.1 22 144 DC power At the 72th
hour
C 0.1 – 144 Solar cell At the 72th
hour
D Distilled water 22 144 DC power 0 voltage in run A, B, D were different from that in run C. In run A, B and
298
Separation and Purification Technology 190 (2018) 297–306
efficiency, are 22 V, 10 W and 18%, respectively. In this study, the solar
cell panel was installed on the balcony (the sixth floor, about 18 m
height) and the longitude and latitude of experimental site is E
112.4237 and N 34.6042, respectively. The side of monocrystalline si-
licon was faced to sunlight. Because in darkness, the output potential of
solar cell is zero, so run C worked nine hours a day (8:00 am to
5:00 pm) (total 144 h in 16 days, in March 2016). In the 16-day EKR
experiment, it included ten sunny days and six cloudy days, and daily
air temperature fluctuated from 8 °C to 26 °C.
In every experiment, 675 g of soil sample mixed with 225 mL of
distilled water were placed in the soil cell. At the flow rate of 15 mL/
min, the four channels dispensing peristaltic pump was cycled to re-
fresh anolyte and catholyte in electrode compartments. In run A, B and
C, electrolyte was circulated as 0.1 mol/L KCl solution and the initial
pH and conductivity of electrolyte is 6.95 and 1.074 s/m respectively.
By using KCl solution as electrolyte, the electrical conductivity of
the electrolyte has been improved and meanwhile KCl is the fertilizer to
soil. For the comparison, in run D, electrolyte was circulated as distilled
water, other conditions are consistent with run A. Each electrolyte so-
lution was refreshed every 9 h and the cumulative amount of total Cr
and Cr (VI) in each electrolyte during the processing was measured.
After the EKR experiment, the soil sample was taken out from the soil
cell and was sectioned into ten equal parts from left to right and each
part was used to analyze for the total Cr, Cr(VI) concentration and pH
respectively.
2.3. Analytical methods
The Cr(VI) concentration in the electrolyte was quantified based on
the diphenylcarbazide colorimetric method using a UV–vis spectro-
photometer at 540 nm (Metash UV-5200PC, China). The detection limit
of Cr6+ is 0.2 µg and 0.004 mg/L by the method. The total Cr con-
centration in the electrolyte was determined on the diphenylcarbazide
colorimetric method after oxidating Cr(III) into Cr(VI) with excess po-
tassium permanganate. The Cr(VI) concentration in the soil was de-
termined by selectively extracting Cr(VI) according to the EPA Method
3060A (alkaline digestion procedure by 0.28 mol/L Na2CO3 and
0.5 mol/L NaOH), and the Cr(VI) concentration was quantified in the
digestion solution by the same method (diphenylcarbazide colori-
metric). The total Cr concentration in the soil was determined by an
atomic absorbance spectrometer (Varian AA240, USA) after digesting
with aqua regia. The detection limit of total Cr in soil is 0.3 mg/kg by
the method. The Cr(III) concentration need be obtained during the
experiment. Its concentration can be calculated from the difference
between the total Cr and Cr(VI) concentrations.
Soil pH was monitored using the pH meter (pHS3C, SPSIC, China) in
the slurries with soil to distilled water ratio of 1:2.5. The soil organic
matter content was measured by the PE-2400 elemental analyzer
(Perkinelmer, USA). Redox potential of soil was determined by poten-
tial method. The CEC (cationic interchange capacity) of soil was mea-
sured by the ammonium acetate extraction method (EPA 9080).
Electrical current and voltage through the soil cell was measured by the
multimeter (F15B+, Fluke, USA) in the EKR process. To ensure data
quality, all chemical analyses were performed in duplicate.
The recovery experiments by adding standard Cr samples were carried
out, the average recovery ratio was 98.29%.
3. Results and discussion
3.1. Electrical voltage and current during the experiment
Electrical voltage is one of the key factors in the EKR of con-
taminated soil. During the EKR, the variation trends of electrical vol-
tage are given in Fig. 2. Fig. 2 shows that the variations of electrical
D, electrical voltage fluctuated very slightly, and was maintained
M. Zhou et al. Separation and Purification Technology 190 (2018) 297–306

Fig. 1. A schematic view of the lab-scale electrokinetic re-

actor. (The electrode compartment, soil cell, and electrolyte
reservoir are made of organic glass). 1. The DC power
supply (GPC6030D, Gw instek, China); 2. Solar cell panel; 3,
4. Working electrode; 5. The soil cell; 6, 7. Non-wo-
ven fabrics; 8, 9. The electrode compartment; 10, 11. The
electrolyte reservoir; 12, 17. Simple flow regulator; 13–16.
4-Channel peristaltic pump (BT00-300T/DG-4, longerpump,
China); 18, 19. Gas vent.

constant because of using regulated DC power supply, so there was o-
verlap between run A, run B and run D. Electrical voltage of run C was
influenced significantly by the weather condition of experiment [24]. In
the run, electrical voltage fluctuated sharply with time and had the
periodical variations. In one working cycle (8:00 am to 5:00 pm),
electrical voltage increased firstly, reached the maximum value
(12:00–3:00 pm) and then decreased. Because of cloudy weather con-
ditions (the fifth day, the sixth day, the seventh day, the eleventh day,
the twelfth day and the fourteenth day), so electrical voltage in the
period was relatively lower during the EKR experiment.
Electrical current through soil is strongly correlated with the con-
centration of mobile ions in the EKR process [6]. So, electrical current is
an important indicator to measure the amount of ion electromigration.
In this study, the variations of electrical current through soil cell for run
A, B, C and D are given in Fig. 3. From the figure, electrical current of
four runs showed the different trend. In run A and D, electrical current
increased firstly, reached the peak (113.2 mA and 99.7 mA), then
slowly decreased and stabilized in the constant value. The main reason
is that when electric field was established, first the electrical current
was low because it took some time for anolyte and catholyte to enter
contaminated soil and for soil mineral and pollutants to dissolve and
desorb from the soil. About 5–6 h later, electrical current reached the
peak due to the electromigration of pollutants and minerals to electrode
and high ion concentrations in the pore fluid. Then electrical current

24

22

20

18

16

14
Voltage (V)

12

10

6 run A
run B
4
run C
2 run D

0
0 9 18 27 36 45 54 63 72 81 90 99 108 117 126 135 144
Time (hours)
Fig. 2. Variations of voltage across the soil cell.

299
M. Zhou et al.
120
100
80
Current (mA)
60
40
20
0
0 9 18 27 36 45 54
Fig. 3. Variations of current across the soil cell.
began to decline because of the decrease in the migration of anion and
cation in soil-pore fluid and the forming of Cr(OH)3 in the cathode
region. Furthermore, OH− ion electromigrating to anode can be neu-
tralized by H+ ion electromigrating to cathode, hence forming water
and decreasing the ion concentration in the EKR system. Compared to
run D, run A exhibited higher electrical current, because of adding
0.1 mol/L KCl solution.
In run B, in the beginning the variations of electrical current across
the soil cell were consistent with run A. The current also firstly in-
creased, reached a peak, then declined due to the same reason of run A.
But at the 72th hours, cathode has been exchanged with anode, the
trend of electrical current of run B changed. Electrical current firstly
decreased, then began to increase after some time, then gradually de-
creased and stayed at the constant value. In comparison to run A, an
obvious process of decrease and increase of electrical current could be
present after 72 h. The reasons of this phenomenon are following. The
soil pH in the anode region became acidic and that in the cathode re-
gion became alkaline after the 72 h EKR. At the 72th hours, anode has
been exchanged with cathode, new H+ generated by electrolysis reac-
tion moving towards cathode can be neutralized by OH− in the original
cathode region, new OH− generated by electrolysis reaction moving
towards anode can be neutralized by H+ in the original anode region,
hence forming water and decreasing the ion concentration in the
system. So electrical current began to decrease, due to the decrease in
the migration of OH− and H+ in pore fluid. Then because the dissolving
of Cr(OH)3 in the anode region (the original cathode region) by the H+,
so electrical current began to increase due to the increase in the mi-
gration of ions in pore fluid. In general, compared with the run A, run B
exhibited higher electrical current at this stage (72–144 h).
In run C, just like the variations of electrical voltage, electric current
was strongly influenced by the weather conditions and had the peri-
odical variations. In one working cycle (8:00 am to 5:00 pm), electric
current through the soil cell firstly increased, reached a maximum and
then decreased. Unlike run B, an obvious process of decrease and in-
crease of electrical current could not be obvious after 72 h because
electric current of run C was significantly influenced by the weather
conditions.
The current experimental result suggests that there are more
charged ions during the EKR process of run B and run C, especially run
Separation and Purification Technology 190 (2018) 297–306
run A
run B
run C
run D
63 72 81 90 99 108 117 126 135 144
Time (hours)
B, which can in part explain the probable reason of higher Cr removal in
run B.
3.2. Electroosmotic flow during electrokinetic experiment
Electroosmotic flow is the motion of liquid induced by applying an
electric voltage across a porous soil [30,31]. Some soluble chro-
mium compounds in the contaminated soil could be removed by elec-
troosmotic flow. At a basic pH, the surface charge of soil particles is
negative and electroosmotic flow is towards cathode. During EKR ex-
periments, electroosmotic flow was calculated by measuring the vo-
lume change in the catholyte, and Fig. 4 showed the cumulative amount
of electroosmotic flow during the process. From the figure, electro-
osmotic flow in run B was also higher than that in run A, C and D.
Electroosmotic flow of EKR can be calculated by the following equation
[32]:
Qeof = K eoPA (1)
where Qeof (cm /s) is the electroosmotic flow, Keo (cm /Vs) is the
3 2
coefficient of electroosmotic permeability, P is the electrical potential
gradient (V/cm), and A (cm2) is the cross-sectional area of the soil.
According to the equation, electroosmotic flow is directly proportional
to the electrical potential gradient under the assumptions of constant
porosity and a constant coefficient of electroosmotic permeability.
From Fig. 2, run A, B and D exhibited the maximum and stable elec-
trical potential gradient in both ends of soil cell, therefore run A, B and
D had the larger Qeof compared to run C. Compared run A with run B,
EE-EKR can reduce the precipitation of chromic hydroxide, which help
to get the large cross-sectional area, so run B had the largest Qeof.
Compared run A with run D, the cumulative amount of electroosmotic
flow was basically the same.
3.3. Soil pH
Variations of soil pH are presented in Fig. 5. It has been well known
that EKR can strongly influence soil pH. In typical EKR, H+ generated
by electrolysis reaction at the anode move from anode to cathode; ac-
cordingly, OH− produced by electrolysis reaction at the cathode move
from cathode to anode. So, the anode soil region become acidic, while
300
M. Zhou et al. Separation and Purification Technology 190 (2018) 297–306

700

600
Electroosmotic flow accumulation (mL)

500

400

300

200
run A

run B
100
run C

run D

0
0 9 18 27 36 45 54 63 72 81 90 99 108 117 126 135 144
Time (hours)
Fig. 4. The cumulative amount of electroosmotic flow during electrokinetic treatment.

the cathode soil region is alkaline. In run A and D, soil pH in treated soil
also showed the distribution caused by the EKR. The experimental re-
sults suggested that some amendments should be performed to return
the soil pH to its initial condition after typical EKR.
There was a significant difference of soil pH between run A, D and
run B, C. Fig. 5 shows EKR with the exchange of electrode had a mi-
nor effect on the pH of experimental soil, including the soil of the anode
region and the cathode region. The reason is that H+, OH− produced
by electrolysis reaction in the soil can be partly neutralized after the
exchange of electrode. So EE-EKR can solve to some extent the adverse
effects of EKR on soil pH. Soil pH had a significant impact on the Cr(VI)
reduction and Cr(III) oxidation, generally high pH enhanced the oxi-
dative power while low pH enhanced reduction reactions. After the
experiment, EE-EKR (run B, C) had higher soil pH which led to oxidise
more Cr(III) to Cr(VI), and mobility of chromium was enhanced which
can also in part explain the probable reason of higher Cr removal in run
B and run C.
3.4. Removal of Cr
Figs. 6–8 show the residual concentration of total Cr, Cr(VI) and Cr
(III) in soil after EKR, and the cumulative amount of total Cr, Cr(VI) and

10

6
pH

Initial soil
3
run A
2 run B

run C
1
run D

0
1 2 3 4 5 6 7 8 9 10
Soil sections
Fig. 5. Variations of pH in soil sections after electrokinetic remediation.

301
M. Zhou et al. Separation and Purification Technology 190 (2018) 297–306

2000

1800

1600
Total Cr concentration (mg/kg)

1400

1200

1000

800

Initial soil
600
run A

400 run B

run C
200
run D

0
1 2 3 4 5 6 7 8 9 10
Soil sections
Fig. 6. Residual total Cr in treated soil after electrokinetic treatment.

Cr(III) transferred to electrolyte and electrode are presented in
Figs. 9–12 during the EKR process. Table 2 shows the mass balance of
Cr in the experiments.
After remediation, the total Cr and Cr(VI) remaining in the soil was
determined, and the average value of chromium in the ten sections was
calculated as the content of chromium in the whole soil cell. The re-
moval efficiency of chromium was calculated on the basis of the
average content of chromium in the soil before and after EKR. From
Figs. 6 and 7, compared to the initial concentration, the concentration
of total Cr and Cr(VI) in treated soil all decreased (run A–D), especially
Cr(VI). Chromium desorbed from the soil was moved to the anode and
cathode by electromigration. Meanwhile, chromium could also be
removed as soluble chromium complexes by electroosmosis. The com-
bination of electroosmosis and electromigration removed chromium
from contaminated soil, so the concentration of chromium in treated
soil decreased. Meanwhile, it was apparent that run B had the highest
removal efficiency of total Cr (43.65% which was calculated based on
the residual total Cr in treated soil after EKR), the highest removal ef-
ficiency of Cr(VI) (91.88%), and the highest removal efficiency of Cr
(III) (19.32%) than those of run A, C and D, because of the highest and
stable input voltage and current and the advantage of exchange elec-
trode method. As Cr(VI) in the soil occur mainly as CrO42− and HcrO4−
[33], Cr(VI) can be easily treated and Cr(III) can be hardly treated re-
latively by EKR. The experimental results are consistent with other

700

600

500
Cr (VI) concentration (mg/kg)

Initial soil
400 run A

run B

300 run C

run D

200

100

0
1 2 3 4 5 6 7 8 9 10
Soil sections
Fig. 7. Residual Cr (VI) in treated soil after electrokinetic treatment.

302
M. Zhou et al. Separation and Purification Technology 190 (2018) 297–306

1400

1200

1000
Cr (III) concentration (mg/kg)

800

600

Initial soil
400
run A

run B

200 run C

run D

0
1 2 3 4 5 6 7 8 9 10
Soil sections
Fig. 8. Residual Cr (III) in treated soil after electrokinetic treatment.

350

300

250
Total Cr in the anolyte and anode
Cr accumulation (mg)

Total Cr in the catholyte and cathode

200
Cr(VI) in the anolyte and anode
Cr(VI) in the catholyte and cathode
150
Cr(III) in the anolyte and anode
Cr(III) in the catholyte and cathode
100

50

0
0 9 18 27 36 45 54 63 72 81 90 99 108 117 126 135 144
Time (hours)
Fig. 9. Cumulative mass of Cr in the electrolyte and electrode in run A.

report [34].
Compared run A with run B, experimental results showed that EE-
EKR was a more effective method to eliminate chromium in con-
taminated soils because of higher electric current quickly to migrate
chromium to the electrode. Meanwhile, in the conventional EKR (run
A), the nearer to the cathode region, the higher are the OH− con-
centration and pH value in soil, which can hinder the desorption of Cr
from contaminated soil and lead to the precipitation of chromic hydr-
oxide. In the run B, the removal efficiency of total chromium and Cr(III)
increased, because of the dissolving of Cr(OH)3 in the original cathode
region by the H+ generated from the exchanged electrode.
Compared run A with run D, experimental results showed that using
KCl as electrolyte was a more effective method to eliminate chromium
in contaminated soils because the electrical conductivity of electrolyte
has been improved and higher electric current quickly to migrate
chromium to the electrode.
Compared run B with run C, experimental results showed that EE-
EKR with the DC power had a slightly higher removal efficiency under

303
M. Zhou et al. Separation and Purification Technology 190 (2018) 297–306

400

Total Cr in the anolyte and anode

350 Total Cr in the catholyte and cathode
Cr(VI) in the anolyte and anode
300 Cr(VI) in the catholyte and cathode
Cr(III) in the anolyte and anode
Cr accumulation (mg)

250
Cr(III) in the catholyte and cathode

200

150

100

50

0
0 9 18 27 36 45 54 63 72 81 90 99 108 117 126 135 144
Time (hours)
Fig. 10. Cumulative mass of Cr in the electrolyte and electrode in run B.

400

Total Cr in the anolyte and anode

350 Total Cr in the catholyte and cathode
Cr(VI) in the anolyte and anode
300
Cr(VI) in the catholyte and cathode
Cr(III) in the anolyte and anode
Cr accumulation (mg)

250
Cr(III) in the catholyte and cathode

200

150

100

50

0
0 9 18 27 36 45 54 63 72 81 90 99 108 117 126 135 144
Time (hours)
Fig. 11. Cumulative mass of Cr in the electrolyte and electrode in run C.

the weather conditions of this experiment, because of the stable and
continuous input. Although the removal efficiency of Cr of run C was
slightly lower (total Cr: 41.55%, Cr(VI): 89.42%, Cr(III): 17.40%),
however in contrast with the cost of energy consumption, the difference
of removal efficiency maybe was not important. From Table 2, by
comparison, it was more reasonable that the removal efficiency of Cr
was calculated based on the concentration of residual Cr in soil after
EKR experiment.
In this technology, an electric field was utilised to promote the
movement of Cr contaminants towards the electrode. However there is
no selectivity in the conventional EKR process, other native ions that
are present in the soil can also be mobilised. In our previous research,
experimental results showed that EKR had an impact on the distribution
and concentrations of soil native ions [35]. After the electrokinetic
experiment (EKR of fluorine-contaminated soil), in the treated soil, the
average value of available nitrogen was raised from 69.53 to 74.23 mg/
kg, the average value of available phosphorus and potassium were re-
duced from 20.05 to 10.39 mg/kg, from 61.31 to 51.58 mg/kg re-
spectively. So some steps should be taken to offset the impacts, after
electrokinetic treatment.
3.5. Cost analysis
The main cost of EKR using solar energy is resulted from the cost of
solar cell. Now, in China, the market price of monocrystalline silicon
solar cell is about US$ 0.6 (Parameters: power: 4.4 W; size:
156 × 156 mm; efficiency: 17.2–19%) [36]. EKR of contaminated soil
need require about 500 kWh/m3 of power consumption [30]. On the
basis of the average power consumption and the 144 h remediation
time (based on this study, the removal efficiency of total Cr was

304
M. Zhou et al. Separation and Purification Technology 190 (2018) 297–306

350

Total Cr in the anolyte and anode

300 Total Cr in the catholyte and cathode

Cr(VI) in the anolyte and anode

Cr(VI) in the catholyte and cathode

250
Cr(III) in the anolyte and anode
Cr accumulation (mg)

Cr(III) in the catholyte and cathode

200

150

100

50

0
0 9 18 27 36 45 54 63 72 81 90 99 108 117 126 135 144
Time (hours)
Fig. 12. Cumulative mass of Cr in the electrolyte and electrode in run D.

Table 2
The mass balance of Cr in the experiments.

Initial Cr in soil samples (mg) Residual Cr in treated soil (mg) Cumulative mass of Cr in the electrolyte and electrode (mg) Mass balance (%)

Run Total Cr Cr(VI) Cr(III) Total Cr Cr(VI) Cr(III) Total Cr Cr(VI) Cr(III) Total Cr Cr(VI) Cr(III)

Run A 1254.15 420.53 833.62 834.3 61.22 773.08 407.24 352.05 55.19 98.99 98.27 99.36
Run B 1254.15 420.53 833.62 706.73 34.16 672.57 531.94 379.55 152.39 98.77 98.38 98.96
Run C 1254.15 420.53 833.62 733.05 44.48 688.57 506.27 372.55 133.72 98.82 99.17 98.64
Run D 1254.15 420.53 833.62 881.75 89.78 791.97 355.66 318.55 37.11 98.67 97.10 99.46

41.55%, after the 16 days (9 h/d, 144 h) EE-EKR using solar energy),
the EKR power consumption can be calculated (500,000/
144 = 3472.2 W/m3). So, the cost of solar cell is US$ 473.5/m3
((3472.2/4.4) × 0.6). Monocrystalline silicon solar cell has a life span
of twenty years, so the running cost need be calculated by the division
of capital by the life span [24], and the final calculation result is US$
1.04/m3 (473.5/(20 × 365/16)). Now, China's electricity price is about
8.4 USD cent/kWh (¥0.56/kWh, 6.670 Chinese Yuan to US Dollar Ex-
change Rate in Sep 2016), so the running cost of EKR by DC power is US
$ 42/m3 (0.084 × 500), which is much higher than the running cost of
using solar cell (US$ 1.04/m3). Of course, the calculation method of
cost analysis is idealistic, for example that it doesn't take into account
the actual weather conditions, but even so, the running cost of using
solar cell is satisfactory.
4. Conclusions
In this paper, experimental results showed that EE-EKR was a con-
siderable and potential technology to eliminate Cr in contaminated
soils. In the same intensity of electric field (for example, run A and run
B), it could improve the removal efficiency of Cr than the conventional
EKR, because it could reduce focusing phenomena and enhance elec-
trical current, etc. And EE-EKR can solve to some extent the adverse
effects of EKR on soil pH. Experimental results also showed that Cr
could be removed from contaminated soil by EE-EKR driven by solar
energy under the weather conditions of this experiment. Meanwhile, in
EE-EKR experiments (normal power supply and solar-powered system)
are not so different between them under the better weather conditions.
After electrokinetic remediation, the chromium in the soil was mainly
found in trivalent, its toxic effects to the organism and influence on
human health were greatly reduced.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (No. 41471256) and Key Scientific Research
Project of Henan Province Universities and Colleges (No. 15A610003).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.seppur.2017.09.006.
References
[1] H. Angel, M. William, Pollution in China Still a State Secret [Infographic], 2014,
Available: < http://blogs.scientificamerican.com/guest-blog/soil-pollution-in-
china-still-a-state-secret-infographic/ > .
[2] Y.P. Liao, X.B. Min, Z.H. Yang, L.Y. Chai, S.J. Zhang, Y.Y. Wang, Physicochemical
and biological quality of soil in hexavalent chromium-contaminated soils as af-
fected by chemical and microbial remediation, Environ. Sci. Pollut. R. 21 (2014)
379–388.
[3] S.M. Lotfy, A.Z. Mostafa, Phytoremediation of contaminated soil with cobalt and
chromium, J. Geochem. Explor. 144 (2014) 367–373.
[4] M. Megharaj, S. Avudainayagam, R. Naidu, Toxicity of hexavalent chromium andits
reduction by bacteria isolated from soil contaminated with tannery waste, Curr.
Microbiol. 47 (2003) 51–54.

305
M. Zhou et al.
[5] L.Z. Yuan, X.J. Xu, H.Y. Li, N.N. Wang, N. Guo, H.W. Yu, Development of novel
assisting agents for the electrokinetic remediation of heavy metal-contaminated
kaolin, Electrochimi. Acta 218 (2016) 140–148.
[6] Y.B. Acar, A.N. Alshawabkeh, Principles of electrokinetic remediation, Environ. Sci.
Technol. 27 (1993) 2638–2647.
[7] Y.B. Acar, R.J. Gale, A.N. Alshawabkeh, R.E. Marks, S. Puppala, M. Bricka,
R. Parker, Electrokinetic remediation-basiscs and technology status, J. Hazard.
Mater. 40 (1995) 117–137.
[8] K. Baek, D.H. Kim, S.W. Park, B.G. Ryu, T. Bajargal, J.S. Yang, Electrolyte con-
ditioning- enhanced electrokinetic remediation of arsenic-contaminated mine
tailing, J. Hazard. Mater. 161 (2009) 457–462.
[9] V. Jurate, S. Mika, L. Petri, Electrokinetic soil remediation-critical overview, Sci.
Total. Environ. 289 (2002) 97–121.
[10] N. Habibul, Y. Hu, G.P. Sheng, Microbial fuel cell driving electrokinetic remediation
of toxic metal contaminated soils, J. Hazard. Mater. 318 (2016) 9–14.
[11] E. Mena, J. Villaseñor, M.A. Rodrigo, P. Cañizares, Electrokinetic remediation of
soil polluted with insoluble organics using biological permeable reactive barriers:
effect of periodic polarity reversal and voltage gradient, Chem. Eng. J. 299 (2016)
30–36.
[12] F. Rozas, M. Castellote, Selecting enhancing solutions for electrokinetic remediation
of dredged sediments polluted with fuel, J. Environ. Manage. 151 (2015) 153–159.
[13] M.T. Ammami, F. Portet-Koltalo, A. Benamar, C. Duclairoir-Poc, H. Wang, F. Le
Derf, Application of biosurfactants and periodic voltage gradient for enhanced
electrokinetic remediation of metals and PAHs in dredged marine sediments,
Chemosphere 125 (2015) 1–8.
[14] I. Robles, M.J. Lozano, S. Solís, G. Hernández, M.V. Paz, M.G. Olvera, E. Bustos,
Electrokinetic treatment of mercury-polluted soil facilitated by ethylenediamine-
tetraacetic acid coupled with a reactor with a permeable reactive barrier of iron to
recover mercury (II) from water, Electrochim. Acta 181 (2015) 68–72.
[15] M.O. Boulakradeche, D.E. Akretche, C. Cameselle, N. Hamidi, Enhanced electro-
kinetic remediation of hydrophobic organics contaminated soils by the combination
of non-ionic and ionic surfactants, Electrochimi. Acta 174 (2015) 1057–1066.
[16] C. Risco, S. Rodrigo, R. López-Vizcaíno, A. Yustres, C. Sáez, P. Cañizares,
V. Navarro, M.A. Rodrigo, Electrochemically assisted fences for the electro-
remediation of soils polluted with 2,4-D: a case study in a pilot plant, Sep. Purif.
Technol. 156 (2015) 234–241.
[17] A. Giannis, D. Pentari, J.Y. Wang, E. Gidarakos, Application of sequential extraction
analysis to electrokinetic remediation of cadmium, nickel and zinc from con-
taminated soils, J. Hazard. Mater. 184 (2010) 547–554.
[18] V.R. Ouhadi, R.N. Yong, N. Shariatmadari, S. Saeidijama, A.R. Goodarzia, M. Safari-
Zanjania, Impact of carbonate on the efficiency of heavy metal removal from
kaolinite soil by the electrokinetic soil remediation method, J. Hazard. Mater. 173
(2010) 87–94.
[19] E.K. Jeon, S.R. Ryu, K. Baek, Application of solar-cells in the electrokinetic re-
mediation of As-contaminated soil, Electrochim. Acta 181 (2015) 160–166.
[20] D.W. Li, T. Huang, K.X. Liu, Near-anode focusing phenomenon caused by the
306
Separation and Purification Technology 190 (2018) 297–306
coupling effect of early precipitation and backward electromigration in electro-
kinetic remediation of MSWI fly ashes, Environ. Technol. 37 (2016) 216–227.
[21] M. Pazos, A. Plaza, M. Martín, M.C. Lobo, The impact of electrokinetic treatment on
a loamy-sand soil properties, Chem. Eng. J. 183 (2012) 231–237.
[22] I. Hassan, E. Mohamedelhassan, E.K. Yanful, Solar powered electrokinetic re-
mediation of Cu polluted soil using a novel anode configuration, Electrochim. Acta
181 (2015) 58–67.
[23] F.L. Souza, C. Saéz, J. Llanos, M.R.V. Lanza, P. Cañizares, M.A. Rodrigo, Solar-
powered electrokinetic remediation for the treatment of soil polluted with the
herbicide 2,4-D, Electrochimi. Acta 190 (2016) 371–377.
[24] S.H. Yuan, Z.H. Zheng, J. Chen, X.H. Lu, Use of solar cell in electrokinetic re-
mediation of cadmium-contaminated soil, J. Hazard. Mater. 162 (2009)
1583–1587.
[25] D. Li, Y.Y. Niu, M. Fan, D.L. Xu, P. Xu, Focusing phenomenon caused by soil con-
ductance heterogeneityin the electrokinetic remediation of chromium (VI)-con-
taminated soil, Sep. Purif. Technol. 120 (2013) 52–58.
[26] A. Altin, M. Degirmenci, Lead (II) removal from natural soils by enhanced elec-
trokinetic remediation, Sci. Total. Environ. 337 (2005) 1–10.
[27] M. Pazos, M.A. Sanromán, C. Cameselle, Improvement in electrokinetic remediation
of heavy metal spiked kaolin with the polarity exchange technique, Chemosphere
62 (2006) 817–822.
[28] P. Lu, Q.Y. Feng, Q.J. Meng, T. Yuan, Electrokinetic remediation of chromium- and
cadmium-contaminated soil from abandoned industrial site, Sep. Purif. Technol. 98
(2012) 216–220.
[29] R.B. Fu, D.D. Wen, X.Q. Xia, W. Zhang, Y.Y. Gu, Electrokinetic remediation of
chromium (Cr)-contaminated soil with citric acid (CA) and polyaspartic acid (PASP)
as electrolytes, Chem. Eng. J. 316 (2017) 601–608.
[30] J. Virkutyte, M. Sillanpaa, P. Latostenmaa, Electrokinetic soil remediation-critical
overview, Sci. Total. Environ. 289 (2002) 97–121.
[31] M.M. Page, C.L. Page, Electroremediation of contaminated soils, J. Environ. Eng.
128 (2002) 208–219.
[32] J. Hamed, Y.B. Acar, R.J. Gale, Pb(II) removal from kaolinite by electrokinetics, J.
Geotech. Eng. 117 (1990) 241–271.
[33] B. Dhal, H.N. Thatoi, N.N. Das, B.D. Pandey, Chemical and microbial remediation of
hexavalent chromium from contaminated soil and mining/metallurgical solid
waste: a review, J. Hazard. Mater. 250–251 (2013) 272–291.
[34] G. Li, S.H. Guo, S.C. Li, L.Y. Zhang, S.S. Wang, Comparison of approaching and fixed
anodes for avoiding the ‘focusing’ effect during electrokinetic remediation of
chromium-contaminated soil, Chem. Eng. J. 203 (2012) 231–238.
[35] M. Zhou, H. Wang, S.F. Zhu, Y.N. Liu, J.M. Xu, Electrokinetic remediation of
fluorine- contaminated soil and its impact on soil fertility, Environ. Sci. Pollut. R 22
(2015) 16907–16913.
[36] Alibaba Group, Monocrystalline Silicon Mono Solar Cell Price in China, 2016,
Available: < https://www.alibaba.com/product-detail/156x156-monocrystalline-
silicon-mono-solar-cell_60396130674.html?spm=a2700.7724857.0.0.4oTtC4 > .