Chemical Engineering Journal 316 (2017) 601–608

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Chemical Engineering Journal

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

Electrokinetic remediation of chromium (Cr)-contaminated soil with

citric acid (CA) and polyaspartic acid (PASP) as electrolytes
Rongbing Fu b,⇑, Dongdong Wen a, Xiaoqian Xia a, Wei Zhang a,⇑, Yingying Gu c
a
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resource and Environmental Engineering, East
China University of Science and Technology, Shanghai 200237, China
b
College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
c
College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China

h i g h l i g h t s

Distribution mechanism of temperature in soil cell was revealed in EKR process.

Utilization efficiency and allocation mechanism of energy were uncovered in EKR process.
6+

Transformation mechanism between Cr and Cr3+ was explored in EKR process.

Cr fractionation in soil changing regularity was discussed in EKR process.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the electrokinetic (EK) remediation of industrial soil contaminated by chromium (Cr) was
Received 4 November 2016 explored using two electrolytes, citric acid (CA) and polyaspartic acid (PASP). All of the EK experiments
Received in revised form 10 January 2017 were conducted in a 2-L soil cell reactor with a moisture level of 23.1% blended with a total Cr of
Accepted 22 January 2017
11.20 ± 1.03 mg g1 under a constant voltage gradient (2 V cm1) for 7 d. The experimental results
Available online 25 January 2017
showed that electric energy was wasted to heat up the soil in EK remediation as the soil temperature
increased. The temperature difference in soil-cell positions was likely caused by a variety of soil charac-
Keywords:
teristics, such as ionic strength. Compared with deionized water (DW), using CA in the contaminated soil
Electrokinetic remediation
Chromium (Cr)
was found to effectively improve the removal efficiencies of both the total Cr and Cr6+. However, using
Electrolytes PASP only improved the Cr6+ removal efficiency, mainly because the CA and PASP could restore Cr6+ to
Temperature Cr3+. When using both CA and PASP as electrolytes, the a-OH and –COOH groups play a key role in chro-
Fractionation mium reduction. In the EK experiment, the relatively lower removal efficiency of the total Cr with PASP
was partially due to the transformation of the exchangeable portion of Cr into carbon-bounded Cr.
Carbon-bounded Cr has a lower migration rate than that of the exchangeable portion. Compared with
the addition of DW, additional energy consumption was increased in the EK remediation after adding
the two electrolytes to reach the same removal rates of Cr. Consequently, utilization efficiency of the
accumulated electrical energy consumption decreased.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
Chromium (Cr) soil pollution is a prevalent environmental issue
worldwide. Serious chromium contamination has been found in
many abandoned industrial sites predominantly due to the impro-
per disposal and accidental spillage of chromium waste [1,2]. Hex-

avalent chromium Cr6+ forms oxyanions (e.g., CrO2 4 , HCrO4 , and
⇑ Corresponding authors.
E-mail addresses: rongermmfu@163.com (R. Fu), wzhang@ecust.edu.cn (W.
Zhang).
Cr2O2
7 ) and is highly mobile in soil and groundwater, which poses
the risk of toxicity and carcinogenicity. Thus, remediation of Cr6+ in
soils has recently gained attention [3,4]. Because of its strong
adsorption into soils and the formation of insoluble Cr hydroxides
in aqueous solutions, Cr3+ is relatively immobile and nontoxic com-
pared with Cr6+. In the U.S., about 11% of the sites on the National
Priority List for the treatment of soil contamination have been
contaminated by Cr, and 14% of the contaminated sites in Japan
that exceed environmental quality standards are contaminated
by Cr6+ [5]. About 0.21% of arable land in China could be abandoned
due to serious Cr pollution, with 1.39% of such land rated to have a

http://dx.doi.org/10.1016/j.cej.2017.01.092
1385-8947/Ó 2017 Elsevier B.V. All rights reserved.
602 R. Fu et al. / Chemical Engineering Journal 316 (2017) 601–608
high Cr risk [6,7]. Therefore, remediation of Cr-contaminated soils
is among the top priorities in many countries for environmental
protection and restoration [8]. Accordingly, effective technologies
for such soil remediation are urgently needed.
Until now, many techniques have been used for remedial treat-
ment of contaminated sites and include physical separation [9–11],
immobilization [12,13], and extraction [14,15]. In particular, elec-
trokinetic (EK) remediation is considered one of the emerging tech-
niques that holds a promising potential for in-situ soil remediation
[2,10]. Compared with other techniques, EK remediation has high
efficiency and reliability, as well as competitive economic viability.
EK technologies can be scaled to meet different treatment require-
ments and can handle a wide range of pollutants, such as toxic
metals and organic pollutants [16–20]. EK remediation involves
the application of a low, direct electric-voltage gradient (0–
2 V cm1) or a low direct current (0–1 A) across electrodes inserted
into the contaminated soil to move contaminants towards the elec-
trodes. The main transport mechanisms of contaminants in EK
remediation are electromigration, electroosmosis and elec-
trophoresis, coupled with electrolysis and geochemical reactions.
For instance, toxic metal ions are mainly transported by electromi-
gration, which is the migration of ions towards an oppositely
charged electrode [7,21,22]. In the EK process, water at the anode
is primarily oxidized (2H2O ? 4H++4e + O2), undergoing a reduc-
tion reaction (2H2O + 2e?H2 + 2OH) at the cathode [21]. H+ and
OH- are transported through the soil through electrolysis. Soil acid-
ification may occur, which could result in toxic metals desorption
from the soil. Conversely, soil alkalization may occur at high pH
values, which causes a precipitation of toxic metals inside the soil
[7,23]. Interestingly, Cr6+ adsorption increases with a decreasing
pH, whereas Cr3+ desorption is most significant at a low pH [24].
Thus, EK remediation of Cr from soil is difficult to achieve without
enhancement.
Complexants and chelators form soluble metal-chelate com-
plexes and coordination complexes with toxic metals that can
enhance the removal of toxic metals in soil by electrokinetics
[7,25,26]. For example, ethylenediaminetetraacetic acid (EDTA),
nitrilotriacetic acid (NTA), diethylenetriamine pentaacetic acid
(DTPA), and ethyleneglycoltetraacetic acid (EGTA) are commonly
used to enhance EK remediation of Cd, Pb, and Cu [27]. However,
because such complexants and chelators are costly and have high
solubility and persistence in the soil, which increases potential tox-
icity to plants, they are hardly used in practical site remediation
[26]. Searching for environmentally friendly and economically
viable alternatives is imperative. Citric acid (CA), a chelating agent,
has been used to improve the removal of metals from soil because
it is commercially available, relatively inexpensive, and environ-
mentally benign. However, CA has rarely been used in EK remedi-
ation of industrial soil contaminated by Cr [28–30]. Similarly,
although polyaspartic acid (PASP) is a non-phosphorus-based
biodegradable polyamino acid that has been used as an environ-
mentally friendly scale and corrosion inhibitor because it can coor-
dinate various toxic metals with its carboxylic groups [31,32], its
application as an electrolyte in the EK process has not been
explored. Both CA and PASP share similar properties and hold the
potential to be used as excellent electrolytes in EK remediation.
Furthermore, the changes in the soil temperature because of elec-
trical heating and the electrical energy consumption in EK remedi-
ation processes have been reported [33–35], but the differential
distribution of soil temperature in soil cell and the effective energy
consumption in EK remediation with different electrolytes have
not been raised as an issue.
This study aims to investigate the influences of these two elec-
trolytes (CA and PASP) on EK soil remediation. The specific tasks
are (1) to compare the Cr removal efficiency in remediated soil
using the two electrolytes; (2) to evaluate the energy utilization
efficiency in different EK experiments using a rational evaluation
method that considers the energy utilization efficiency; (3) to
explore the transformation mechanism between Cr6+ and Cr3+ dur-
ing EK remediation processes; (4) to reveal the Cr fractionation or
speciation changes during the EK remediation processes; and (5) to
investigate the soil temperature variation during the EK remedia-
tion processes to better develop effective operation plans that
avoid heat energy loss in EK soil remediation. The related findings
will be helpful for the optimization and selection of electrolytes for
effective EK remediation of Cr-contaminated on-site soil.
2. Materials and methods
2.1. Chemicals and soils
PASP (purity > 99.0%) was obtained from Shandong Hong Mei
Water Technology Co., Ltd. (Shandong, China). Sinopharm Chemi-
cal Reagent Co., Ltd., (Shanghai, China) supplied the diphenylcarbo-
hydrazide, C7H8O8-H2O, HNO3, HCl, HF, and HClO4. All
experimental chemicals used in the experiments were of analytical
grade.
The contaminated soil used in this experiment was obtained
from an industrial site, Fuzhou Ming Yang Transportation Equip-
ment Co., Ltd, located in Fujian Province, China. Because the top
20 cm over the polluted area is the main concentration area of Cr
at industrial site, soil samples were manually collected from the
top 20 cm over the polluted area. Before use, the samples were
air-dried for 48 h, ground, and sieved using a 2-mm mesh, then
stored in room-temperature hermetic containers. Table 1 shows
a summary of the basic characteristics of soil, including Cr concen-
trations, pH, and water content of soil, oxidation-reduction poten-
tial (ORP) and electrical conductivity (lS cm1).
2.2. Experimental setup
Fig. 1 shows a schematic diagram of the experimental reactor
for the EK remediation used in this study. The system was com-
posed of one plexiglass reactor used as a soil cell
(L  W  H = 20 cm  10 cm  10 cm), two electrode compart-
ments (L  W  H = 5 cm  10 cm  10 cm), one pair of cathode
and anode made of stainless steel electrodes (304, 0Cr18Ni9,
L = 12 cm, £ = 1 mm), one DC power supply (HB17601SL2A,
China), one multimeter (VC830L, China), two peristaltic pumps
(KPP-B08DA, China), and two working solution reservoirs. Two
pieces of cellulose filter paper (20 lm and /11 cm; Hangzhou Spe-
cial Paper Co., Ltd.) were placed in the soil cell between the two
electrode compartments to separate the treated soil and working
fluids. The DC power supply was applied to the EK system at speci-
fic constant voltage gradients. The multimeter was connected in
the circuit series to monitor the real-time electric current. A peri-
staltic pump was used to circulate the electrolyte solution from
reservoirs to maintain a constant level in electrode compartments,
and the electrolyte solution was replenished in the anode reservoir
every 12 h to maintain the continuous operation of experiments
and ensure the regularity of electrolyte addition. To ensure that
Table 1
Properties of contaminated soil used in the experiments.
Properties Result
pH 4.10
Moisture content (%) 23.1
Electrical conductivity (lS cm1) 1620
Oxidation-reduction potential (mV) 558
Cr6+ (mg g1) 8.25 ± 0.30
Total Cr (mg g1) 11.20 ± 1.03
 R. Fu et al. / Chemical Engineering Journal 316 (2017) 601–608
Fig. 1. A schematic diagram of the experimental reactor for EK remediation (a) and sampling area distribution for the EK remediation (b). V: DC power supply (HB17601SL2A,
China); A: Multimeter (VC830L, China); P: Peristaltic pumps (KPP-B08DA, China); T: Mercury thermometer; E: Electrolyte; R: Electrolyte reservoirs; SE: Stainless steel
electrode.
the electrolytes were thoroughly mixed in the electrolytic com-
partment, an upward flow was generated through a silicone tube
(2.5  4.5 mm) that was inserted into the pipe center of the stain-
less steel electrode. Five mercury thermometers were evenly
inserted into the soil cell at a depth of 4 cm with intervals of
4 cm to monitor the temperature changes in the local soil sections
(e.g., S1–S5, from anode to cathode, as marked in Fig. 1), respec-
tively, in the EK remediation process. To reduce the impact of
external temperature variation on the soil cell, as well as on the
EK processes, the external walls of the plexiglass reactor were
wrapped in a 1-cm-thick foam polyethylene heat shield (1  2 m;
Shanghai Yingfu New Material Technology Co., Ltd.).
2.3. Electrokinetic remediation
Each soil cell was filled with about 3.0 kg (dry weight) of satu-
rated contaminated soil for each EK experiment. 1 L of the elec-
trolyte solution was added to the two reservoirs respectively
with 0.4 L of the electrolyte solution to the anode and cathode
compartments. It was then necessary to wait 12 h to allow for
the full saturation of electrolytes in the tested soils before begin-
ning the EK experiments. All of the EK experiments were con-
ducted under a constant voltage gradient (2 V cm1) for 7 days.
Three sets of EK experiments were run with DW, CA and PASP,
respectively. At the end of each experiment, the soil specimen
was removed from the cell and was equally divided into 5 sections
from anode to cathode (S1–S5). A soil sample of each section was
analyzed for pH, electric conductivity, moisture content, Cr6+ con-
centrations, and total Cr concentrations.
603
2.4. Chemical analysis
First, an appropriate amount of the soil sample was used to ana-
lyze moisture content, which was measured by weight loss after
heating the sample to 105 °C for 8 h. The other soil samples were
vacuum freeze-dried using a freeze dryer machine (FD-1A-50),
and then ground and sieved using a 2-mm mesh. The soil pH of
the 5 different sections was measured in a 1:2.5 (soil: water) sus-
pension using a pH meter (DELTA320).
The Cr6+ in soil was extracted according to the national standard
(HJ 687-2014, China). Briefly, 2.5 g of soil samples, 50-mL alkaline
aqueous solution (0.28 mol/L Na2CO3 + 0.5 mol/L NaOH), 400-mg
MgCl2, and 50-mL buffer solution (0.5 mol/L K2HPO4 + 0.5 mol/L
KH2PO4) were added to a 250-mL Erlenmeyer flask and thoroughly
mixed with a polyethylene film to seal the flask. The mixture was
shaken on a rotating shaker for 5 min at the room temperature, and
then shaken at 90–95 °C. at for 60 min. After cooling to room tem-
perature, the supernatant in the mixture was collected with the
suction filtration using a 0.45-lm membrane filter (/7 cm; Hang-
zhou Special Paper Co., Ltd.), and the pH was adjusted to
9.0 ± 0.2. The properly diluted filtrate using DW first reacted with
diphenylcarbohydrazide, and the absorbance of the purple product
in the reaction solution was then measured at a wavelength of
540 nm with a UV trophotometer (LP UV1102) to determine the
concentration of Cr6+ according to the national standard (GB/T
15555.4-1995, China).
The total Cr in soil samples was extracted by acid digestion in
accordance with the China Standard HJ 491-2009. Briefly, 6 mL
HNO3 and 2 mL HF were mixed with 0.5 g soil and the mixture
604 R. Fu et al. / Chemical Engineering Journal 316 (2017) 601–608

was placed in a microwave digestion instrument (Milestone ETHOS (a)

A). After the microwave digestion (1500 W for 60 min), the mix- 0.45
EK1
ture was transferred to 50-mL Teflon crucible with the addition EK2
0.40
of 2-mL HClO4 (analytical grade, 70.0–72.0%). The mixture was EK3
then heated at 150 °C until it became sticky. Three mL of 0.35

Electric current (A)

hydrochloric acid solution (v:v, 1:1) were added to the mixture
to dissolve soluble residue in the mixture, which was then trans- 0.30
ferred to a volumetric flask with additions of 5-mL 10% NH4Cl solu-
0.25
tion and DW to a constant volume of 100-mL. The total Cr
concentration in the digested soil samples solution was deter- 0.20
mined by atomic adsorption spectrometry (AAS, nov AA400, Ana-
lytik Jena AG). 0.15
To determine the binding forms of Cr with soil samples before
0.10
and after EK remediation, the selective sequential extraction
(SSE) approach was adapted from the Tessier method [36]. The 0.05
metal species in soil are sorted into the following fractions: (a)
EXCH: exchangeable (metals leached from soaking soil in 1 M of 0 1 2 3 4 5 6 7 8
MgCl2, pH 7); (b) CAR: carbonate-bound (1 M of NaOAc, pH 5); Time (d)
(c) FeMnOX: Fe-Mn oxide-bound (0.04 M of NH2OHHCl in 25%
(v/v) HOAc, pH 2 and heated at 96 °C); (d) OMB: organic matter-
(b)

Accumulated energy consumption (KWh)

bound (0.02 M HNO3 in 30% H2O2, pH 2); and (e) RES: the residual EK1
2.0 EK2
(digested with a HCl-HNO3-HF-HClO4 mixture). After applying SSE,
the Cr concentrations in these five fractions were determined by EK3
atomic adsorption spectrometry (AAS, nov AA400).
1.5

2.5. Calculations of energy consumption and Cr removal efficiency

1.0
The accumulated energy consumption (W) in the EK remedia-
tion was calculated as:
Z t
0.5
W¼ UIdt ; ð1Þ
0

where U is the voltage between the electrodes (V), I is the electric

0.0
current (A), and t is the remediation time (h).
The Cr removal efficiency, g was calculated as follows:
0 1 2 3 4 5 6 7 8
C0  Ct
g  100% ð2Þ Time (d)
Ct
Fig. 2. The variation of electrical current (a) and accumulated energy consumption
where Ct is the Cr concentration (mg g1) at time t and C0 is the ini-
(b) in the seven-day EK experiments.
tial Cr concentration (mg g1).

2.6. Statistical analysis

All statistical analyses were carried out using Origin 9.1 for
Windows. The presented results are mean values ± standard devi-
ation from three independent samples with an experimental error
below 10%. All the EK experiments were carried out at same room
temperature (20 ± 3 °C).
3. Results and discussion
3.1. Changes in electric current and energy consumption
Fig. 2a and b shows the changes of the electrical current and the
accumulated energy consumption versus the elapsed time in the
three EK experiment groups. Electric current was found to decrease
in the order of EK2 (0.1 M citric acid) > EK3 (1% PASP) > EK1 (DW)
as shown in Fig. 2a. The current decreased almost linearly from
approximately 0.36 to 0.05–0.06 A within 2.5 d and reached a pla-
teau at about 0.06 A in EK1. Similar current variations were found
in the EK2 and EK3 groups with a stable level of about 0.33 A in
EK2 and about 0.08 A in EK3. The differences in the three groups’
electric-current magnitude and changes were mainly attributed
to variations in conductive capacity and the ability of the three
mobile liquid phases to extract metal ions from the soil. Since
the electric current in the EK experiments is highly related to the
concentration of mobile ions in soil cells [21,37], the decrease of
electric current over time may have been caused by the depletion

Table 2
Results of the electrokinetic experiments.

Experiment Electrolyte Total power consumption (kWh) Removal efficiency of the total Cr (%) Removal efficiency of Cr6+ (%) The value of b
EK1 DW 0.628 29.24 ± 5.01 37.45 ± 2.78 46.51 ± 7.96
EK2 CA 2.038 49.54 ± 5.09 94.27 ± 0.51 24.32 ± 2.50
EK3 PASP 0.859 25.33 ± 7.33 93.26 ± 0.49 29.48 ± 8.53

Average Ct = R per sample Ct/5.

Average removal efficiency of total Cr in whole soil cell = [(C0  average Ct)  100%]/C0.
Average removal efficiency of Cr6+ in whole soil cell = [(C0  average Ct)  100%]/C0.
 R. Fu et al. / Chemical Engineering Journal 316 (2017) 601–608
Fig. 3. Three-dimensional maps of the soil temperature during EK remediation of
an industrial soil polluted with Cr: (a) EK1; (b) EK2; and (c) EK3.
605
of mobile ions in the soil that can also indicate the migration and
removal of free toxic metals.
Fig. 2b shows that the accumulated energy consumption in all
of the EK experiments had a monotonic increase within seven days,
which agrees with many relevant studies [38]. The accumulated
energy consumption ranked as WEK2 = 2.038 kWh > WEK3 = 0.859 -
kWh > WEK1 = 0.628 kWh. In the initial two days, the accumulated
energy consumption of the three experiments was mostly similar
at the level of 0.3–0.5 kWh. After two days, the accumulated
energy consumption in the EK2 experiments (0.1-M citric acid)
began to increase significantly and became much greater than
the other two conditions.
In addition to the energy needed for the migration of toxic met-
als complexed with the electrolytes, the energy loss due to the
heating effect and water electrolysis is evident. Currently, no
method exists to assess the effective energy consumption in EK
remediation. In this study, a decontamination parameter (b) is pro-
posed and calculated in Eq. (3) to evaluate the energy utilization
efficiency. A relative ratio of the removal efficiency of toxic metals
and the total energy consumption is b. Clearly, as the value of b
increases, the greater the energy utilization efficiency:
g
b¼ ð3Þ
W0
where g is the EK removal efficiency, and W is the power consump-
tion in the EK remediation, which is calculated in Eq. (1). Table 2
compares the b values in the different EK experiments are com-
pared. Obviously, b values varied with the different EK processes
in the order of bEK1 = 46.51 ± 7.96 > bEK3 = 29.48 ± 8.53 > -
bEK2 = 24.32 ± 2.50. Although the removal efficiency was improved
by adding the electrolytes, additional energy consumption was
increased due to more energy loss from the heating effect, water
electrolysis, and ion migrations (migration of non-target ions),
which lowered the energy utilization rate.
3.2. Changes in the temperature of the soil cell and the distribution
mechanism
Fig. 3 shows the 3D mapping of temperature profiles at different
sampling sections (S1–S5) versus the elapsed time in all of the EK
experiments. In general, the temperature reached a peak within
12 h of the operation and then gradually decreased in all of the
experiments. This increase may be related to the higher current
at the early experiment stage. The average temperatures at differ-
ent sampling sections are plotted in Fig. 4d, which positively corre-
late with the observed accumulated energy consumption orders
(EK2 > EK3 > EK1); thus, the potential energy consumption or loss
could be due to the heating up of the soil [35].
Fig. 3 also indicates that the temperature became higher in the
soil at/near the cathode as opposed to at/near the anode. There was
a region (S5) of low temperatures near the electrodes, which may
have been due to the cooling effect from the electrolyte additions
[38]. The temperature increase is primarily dependent on the elec-
tric current and the resistance of the soil, which is a function of the
moisture and salt concentration [38]. Different electrolytes led to
the difference in desorption levels and fractionation distribution
of toxic metals in the soil that changed the soluble salt concentra-
tion; thus the soil resistance could have changed in the three
groups of EK experiments.
Some soil characteristics changed during the EK process. Fig. 4
presents data of the moisture content and pH in different soil cell
positions at the end of the experiments. The experiments’ average
temperature was calculated by dividing the sum of temperature
606 R. Fu et al. / Chemical Engineering Journal 316 (2017) 601–608

42 (a)

Moisture content (%)

40

38

36

34

32
8 (b)
7
6
5
pH

4
3
2
1
38
Average temperature ( C)

36 (c)
34
32
30
28
26
24
22

S1 S2 S3 S4 S5

Fig. 4. (a) Moisture content, (b) pH, and (c) average temperature in different soil cells positions in the EK experiments.

values measured at different time periods to measuring numbers.
For example, the moisture gradually decreased from the anode side
(41.9%) to the lowest section level S4 (35.1%) near the cathode
where the moisture level bounced back to 40.8% due to the elec-
trolyte refill in the EK1 experiments. Similar results were also
observed in EK2 and EK3. The low moisture appears to be related
to the high temperature, as shown in Fig. 3, which may promote
water loss by evaporation. The soil pH gradually increased from
the anode (1.77) to the cathode (6.83) primarily because of the
respective water oxidation and reduction reactions at the anode
and cathode as previously introduced in the EK1 experiments.
Similar results were also observed in EK2 and EK3. The electric
conductivity near the cathode gets lower because of the hydroxide
precipitation (Mn+ + nOH = M(OH) n;) and carbonate precipitation
(HCO 
3 + OH ? CO3
2
and Mn+ + (n/2)CO2
3 = M(CO3)n/2;) near the
cathode at high pH [38], which also means the electric resistance
of the soil was increased, subsequently causing more energy con-
sumption to heat the soil during the EK process. The distribution
differences of soil resistance in the soil cell may be caused by
hydroxide precipitation of toxic metals and migration of soil salt
in the processes of EK remediation. This different distribution of
soil resistance may lead to distinguished water loss, generated by
differentiated soil heat buildup and temperature rise. Moreover,
the evaporation process could change the local moisture. The lower
moisture, accordingly, results in higher electric resistance of the
soil, leading to the gradual amplification of the distribution
difference phenomenon.
3.3. Cr removal and the transformation between Cr6+ and Cr3+
The total concentration of Cr and Cr6+ and their distribution in
the soil after the experiments are shown in Fig. 5. In EK1, the total
Cr concentration was lower near the cathode, which is opposite to
what is observed in EK2 and EK3. The highest total Cr concentra-
tion appears to be near the anode for EK1 and near the cathode
for EK2 and EK3. The total concentration of Cr was (11.20 ± 1.03)
mg g1 in test soil and the concentration of Cr6+ was (8.25 ± 0.30)
mg g1. And in the EK experiments, Cr6+ in the soil migrated
towards the anode, and Cr3+ migrated towards the cathode. The
total distribution of total Cr in EK1, EK2, and EK3 were different
because of the extent of the Cr6+ conversion into Cr3+ in the pres-
ence of CA and PASP.

As shown in Fig. 5b, obviously, Cr6+ (e.g., CrO2 4 , HCrO4 , and
Cr2O27 ) in the soil migrates toward the anode, which is consistent
with the result in EK1, as Cr6+ had the highest accumulation near
the anode. For EK2 and EK3, there was no clear distribution pattern
of Cr6+. Comparing the data of the total Cr and Cr6+ for EK2 and EK3
experiments, we can determine that the Cr6+ in the soil cell was
transformed to Cr3+. For example, the average Cr6+ concentration
in the soil cell in EK2 was 0.47 ± 0.04 mg g1, whereas the total
Cr had an average concentration of 5.65 ± 0.57 mg g1. As the
cationic Cr3+ migrated to the cathode during the EK process, the
higher total Cr distribution at the cathode could be attributed to
the conversion of Cr6+ to Cr3+ and the migration of Cr3+ toward
the cathode. The numbers of a-OH and –COOH groups in organic
acids play key roles in the reduction [39–41]. CA with one a–OH
group and three –COOH groups and PASP with multiple –COOH
groups are thought to be capable of reducing Cr6+ to Cr3+ in the soil
cell. Moreover, the presence of other trace metals such as Mn(II),
Cu(II), Al(III), Fe(II), or Fe(III) can dramatically catalyze the Cr6+
reduction [39–41].
The removal efficiencies of the total Cr and Cr6+ in the different
EK experiments are compared in Table 2. Compared with EK1, the
removal efficiencies of Cr6+ in EK2 and EK3 are all considerably
enhanced at (94.27 ± 0.51)% and (93.26 ± 0.49)%, respectively. The
removal efficiency of the total Cr in EK2 was significantly improved
to (49.54 ± 5.09)% when compared to the EK1 result (29.24%). In
EK3, the total Cr removal rate was not enhanced but reduced to
 R. Fu et al. / Chemical Engineering Journal 316 (2017) 601–608 607

(a) 13 (a) EK1

S5 12
Initial
S4 11

Cr distribution in soil (mg/g)

S3 10
S2 9
EK3 S1 8
7
6
5
EK2
4
3
2
EK1 1
0
Initial S1 S2 S3 S4 S5
0 2 4 6 8 10 12 14 16
13 (b) EK2
Residue total Cr (mg/g)
12
11

Cr distribution in soil (mg/g)

(b) 10
S5 9
Initial
S4 8
S3 7
S2 6
EK3 S1 5
4
3
2
EK2
1
0
Initial S1 S2 S3 S4 S5

EK1
13 (c) EK3
12
11
Cr distribution in soil (mg/g)

0 1 2 4 5 8 9 11 12
6+ 10
Residue Cr (mg/g)
9
Fig. 5. Distribution of (a) the total Cr and (b) Cr6+ in the industrial contaminated soil 8
before and after EK experiments (indicates the area where Cr has obviously 7
accumulated).
6
5
4
(25.33 ± 7.32)%, probably because of the transformation of the 3
exchangeable portion of Cr into carbon-bounded Cr (see Fig. 6c). 2
1
0
3.4. Fractionation changes Initial S1 S2 S3 S4 S5

As shown in Fig. 6, a five-step sequential extraction was con-

ducted to analyze residue Cr speciation in soil samples. In EK1,
the ‘‘EXCH” Cr fraction was mainly removed with a maximum
removal rate up to 97.57% in S5. There is also an obvious removal
for the ‘‘CAR” fraction in EK1 with a maximum removal rate up to
68.64% in S4. Other fractions, such as FeMnOX, OMB, and RES, were
hardly removed. In EK2, there was significant removal of both
EXCH and CAR with the maximum removal rates 86.09% and
93.03%, respectively, in S1. A small removal rate of FeMnOX in
EK2 was achieved in S1 with a removal rate of 29.85%. However,
the removal of OMB and RES was not observed in EK2. In EK3, FeM-
nOX, OMB, and RES had no obvious changes that were similar to
EK1 in terms of an apparent reduction in EXCH, which was likely
converted to CAR. Two possible sources of carbonate may come
from: (1) bicarbonate may transformed carbonate (HCO 
3 + OH ?
CO3 ) at the cathode [38]; and (2) the oxidation of PASP by Cr6+.
2
Fig. 6. Fractionation change of Cr after EK experiments: (a) EK1; (b) EK2; and (c)
EK3.
4. Conclusions
This study explored the EK remediation of industrial chromium
(Cr)-contaminated soil using two different electrolytes. Compared
to deionized water, more additional energy was consumed in EK
remediation with CA and PASP electrolytes due to heat loss, water
electrolysis, and Cr or other non-target ions migration. The soil
temperature was directly related to the electric current. The tem-
perature rise of the soil cell depended on the soil characteristics
(e.g., moisture, pH and electric conductivity). Cr6+ was reduced in
608 R. Fu et al. / Chemical Engineering Journal 316 (2017) 601–608
the presence of CA and PASP in EK remediation, whereas total Cr
removal was only effectively achieved with CA as the electrolyte.
As possible reason is that the EXCH Cr portion was transformed
into the CRA portion in EK3, in which PASP was the electrolyte.
The CAR migration ability was lower than the EXCH.
Acknowledgments
This research was supported by projects of the National Natural
Science Foundation of China (41372262, 41371467, 41201303),
and the Shanghai Pujiang Program (15PJD013).
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