ARTICLE IN PRESS

Journal of Environmental Management 81 (2006) 384391

www.elsevier.com/locate/jenvman

Optimization of the electrocoagulation process for the removal of

copper, lead and cadmium in natural waters and simulated wastewater
Claudio Escobara, Cesar Soto-Salazarb,, M. Ines Torala
a

Laboratory of Analytical Chemistry, Department of Chemistry, Faculty of Sciences, University of Chile, Las Palmeras 3425, P.O. Box 653, Santiago, Chile
b
Department of Analytical and Inorganic Chemistry, Faculty of Chemical Sciences, University of Concepcion, P.O. Box 160C,
Concepcion Edmundo Larenas 129, Concepcion, Chile
Received 10 December 2004; received in revised form 4 November 2005; accepted 10 November 2005
Available online 17 April 2006

Abstract
Chemical, electrochemical and ow variables were optimized to examine the effectiveness of the electrocoagulation process for the
removal of copper, lead and cadmium. The electrochemical process, which uses electrodes of commercial laminate steel, was applied to
simulated wastewater containing 12 mg dm
3 of copper, 4 mg dm
3 of lead and 4 mg dm
3 of cadmium. The optimum conditions for the
process were identied as pH 7, ow rate 6.3 cm3 min
1 and a current density between 31 and 54 A m
2. When the electrode
geometric area and time of electrolysis reached critical values, the copper removal reached a maximum value of 80%. A linear
relationship was identied between the current density and the mass of generated sludge. In addition, a linear relationship was found
between specic energy consumption and current density. The results of this investigation provide important data for the development of
an industrial-scale electrolytic reactor.
r 2006 Elsevier Ltd. All rights reserved.
Keywords: Electrocoagulation; Copper; Lead and cadmium removal; Optimization conditions for electrocoagulation

1. Introduction
Historical efuent discharges from a variety of anthropogenic activities have resulted in contamination of rivers,
lakes and other water-bodies. The explosive population
growth and expansion of urban areas has exacerbated the
adverse impacts on water resources. Since growing
populations result in signicant increases in wastewater
volume, there is an urgent need to develop innovative,
effective and inexpensive technologies to treat wastewater.
To address this problem, technologies such as ion
exchange, ultraltration, reverse osmosis and chemical
precipitation have been developed. Each treatment method
has advantages and disadvantages. Ion exchange, for
example, while highly effective in removal of certain
charged contaminants, requires resin regeneration or
replacement at a high cost. Ultraltration and reverse
Corresponding author.

E-mail address: cesarsoto@udec.cl (C. Soto-Salazar).

0301-4797/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2005.11.012

osmosis are clean processes, but can be prohibitively

expensive. While chemical precipitation is a simple process,
it does generate a high volume of sludge.
An effective technology that meets the requirements of
process cleanliness, ease of manipulation, and low operational and investment costs is electrocoagulation. This
technology was rst employed in the 19th century to treat
wastewater on ships, and has recently been utilized as an
alternative to more conventional treatment processes. The
electrocoagulation technologies are essentially electrolytic
processes that involve the destabilization of suspended,
emulsied or dissolved pollutants in an aqueous medium,
by the application of an electric current. In electrocoagulation (a process similar to chemical coagulation), there is a
reduction of the net surface charge to a point where the
colloidal particles can approach closely enough for Van der
Waals forces to hold them together and allow aggregation
to take place. The surface charge reduction is a consequence of the decrease of the repulsive potential of the
electrical double layer by the presence of an electrolyte

ARTICLE IN PRESS
C. Escobar et al. / Journal of Environmental Management 81 (2006) 384391

having an opposite charge. This mechanism corresponds to

the destabilization of colloidal particles (Hiemenz and
Rajagopalan, 1997).
During electrocoagulation, the coagulant is generated in
situ by electrolytic oxidation of an anode of appropriate
material. Charged ionic species are removed from wastewater by allowing ions to react with oppositely charged
ions, or with ocs of metallic hydroxides generated within
the efuent (Mollah et al., 2001).
Optimization of color removal in wastewater (Ibanez et
al., 1998), treatment of wastewater with oils (Ibanez et al.,
1995) and destruction of organic residuals has been
accomplished using electrocoagulation (Ibanez et al.,
1997). Vik et al. (1984) studied the efcacy of electrocoagulation in removal of humic acid from potable water.
This technology has also been investigated for the removal
of suspended solids, oil and fat in restaurant wastewater
(Chen et al., 2000), oils and fat in residuals from petroleum
reneries (Monte Alegre and Mart nez, 1993a, b), oil in
industrial wastewater (Oblinger et al., 1984), and in the
treatment of textile wastewater (Lin and Chen, 1997).
Because electrocoagulation is being satisfactorily used to
treat wastewater, the need for additional physical chemistry studies is indicated (Mollah et al., 2001). Many studies
have been designed to evaluate only the efciency of the
process as a function of uctuations in critical variables. In
this study, optimization of the chemical and electrochemical variables (of electrocoagulation) was carried out in
natural waters and simulated wastewater to improve
copper, lead and cadmium removal efciency. This work
includes the approach described by Levenspiel (1999) to
apply the methodology to industrial needs.
2. Experimental
2.1. Apparatus and analytical measurements
Analytical determination of the metals was carried out
using anodic stripping voltammetry. A voltammetric
analyzer BAS (Bioanalytical Systems Lafayette, IN,
USA), model CV-50 W, was used with a mercury lm
electrode on vitreous carbon as a work electrode, silver
electrode/silver chloride as reference and a platinum
electrode as auxiliary.
The experiments in batch were carried out on a BAS CV27 voltammograph as a potentiostat with continuous
current. For the experiments in continuous mode, a Phywe
power source (220 V and 50 Hz with variable current ow)
was used. An Ismatec MS-Reglo peristaltic pump, a
Goldstar ammeter in series, and a Goldstar voltmeter in
parallel to the circuit were also used.
2.2. Reagents and solutions
Solutions were prepared with distilleddemineralized
water from a NANO pure, ultra-pure Barnstead Water
System. In all experiments, a simulated solution control

385

Table 1
Cationic and anionic constituents of the simulated solution control


HCO

Cationic and anionic species K+ Ca2+ Mg2+ Na+ SO2

3 Cl
4

Concentration (mg dm
3)

102

48

94

192

250

182

Table 2
Cationic and anionic constituents of the synthetic wastewater
Cationic/anionic species

Concentration (mg dm
3)

Al3+
Astotal
Ba2+
Ca2+
Crtotal
Cl

Mg2+
Mn2+
Na+
SO2

4
CN



F
Fe2+
Ni2+
Pb2+
Cd2+
Cu2+

0.1
0.05
0.05
730
0.008
20
5.5
0.01
79
1000
0.01
0.2
0.02
0.01
0.3
0.8
2.7

was used. The constituents of this solution are shown in

Table 1.
Titrisol Mercks Standard Solutions of 1000 mg dm
3 of
copper, lead and cadmium were used, and solutions of
different concentrations were obtained by adequate dilutions. For pH adjustment, Mercks Solutions of
18.3 g dm
3 of HCl and 20.0 g dm
3 of NaOH were used.
For the study of the inuence of humic acid, a sodium salt
derived from humic acid with a4300 1C melting point
(Aldrichs) was used.
A synthetic wastewater was prepared to further evaluate
the efcacy of the electrocoagulation process. The synthetic
wastewater was CaSO4-dominated with an ionic composition similar to what might be encountered in real-world
efuent (Table 2).
2.3. Procedure in batch mode
A 600 cm3 beaker was used as a reactor, or electrocoagulation cell. Two sheets of rectangular laminate steel
(degree SAE 1020499% iron) with an electrode geometric
area of 54 cm2 and 0.8 mm thickness were used as
electrodes, and placed vertically in the bottom of the
reactor.
A current density of 36 A m
2 was applied for 10 min to
400 cm3 of control solution in the presence of 12 mg dm
3
of copper, 4 mg dm
3 of cadmium and 4 mg dm
3 of lead.
The mixture was then heated at 35 1C, gently agitated for

ARTICLE IN PRESS
C. Escobar et al. / Journal of Environmental Management 81 (2006) 384391

386

2.5 min, left to sit undisturbed for 8 min and then vacuum
ltered. A 1 cm3 aliquot of ltrate sample was taken and
diluted with 15 cm3 of base electrolyte. All experiments
were performed at room temperature (20 1C).

and 17 cm3 min
1, and current densities ranged between 11

and 108 A m
2. All the experiments were carried out at
room temperature (20 1C).
2.6. Procedure for the sludge-generation study

2.4. Procedure for copper electrodeposition

The electrolysis and analytical measurements were
completed using a batch mode. The retained fraction was
obtained by dissolving the coagulated product with HCl
18.25 g dm
3 to produce 50 cm3; from this volume, an
aliquot was withdrawn and analyzed. The fraction in
solution was determined in the ltrate and the electrodeposition fraction was determined by mass balance of the
copper retained in the coagulated product and the copper
in solution.
2.5. Procedure in continuous mode
The electrocoagulation cell and one-channel manifold
used in the experiments in continuous mode are shown in
Fig. 1. Two sheets of rectangular laminate steel (degree
SAE 1020499% iron) with an electrode geometric area of
14 cm2 and 0.8 mm thickness were used as electrodes. The
samples containing 36 cm3 of control solution, with
12 mg dm
3 of copper and 4 mg dm
3 of cadmium and
lead, were electrolyzed. The samples were collected in the
cell exit, centrifuged for 10 min and then analyzed. In the
study to evaluate the inuence of pH, the pH was
maintained between 4 and 9, ow rate was between 6.3

The general continuous mode procedure (described

earlier) was used, but without previous centrifugation.
The samples were collected in the electrocoagulation cell
exit in 25  2.5 cm tubes. Coagulated product was allowed
to form for 1 h, then the formed sludge was vacuum ltered
through a 0.45 mm lter (mixed cellulose esther) and
weighed. The mass of the sludge was determined by
weighing after the sludge was dried at 105 1C for 24 h.
2.7. Procedure for the electrode lifetime study
The general (continuous mode) procedure (described
earlier) was used. A ow rate of 6.3 cm3 min
1 and a
current density of 54 A m
2 were utilized. The initial pH
was neutral (approximately 7.0). After electrolysis, the
mass lost by the anode was determined by comparing the
initial and nal weights.
2.8. Copper, lead and cadmium analysis
Copper, lead and cadmium concentrations were determined by anodic stripping voltammetry. A base electrolyte
solution of 7.45 g dm
3 of KCl in the presence of
80.2 mg dm
3 of Hg2+ was used.

Flow out

6.1 cm

5.2 cm

Flow in
1.5 cm
2.7 cm

(a)

DC
Power

Sample

Peristaltic
Bomb

Electrocoagulation
Cell

Exit

(b)
Fig. 1. Procedure in continuous mode: (a) electrocoagulation cell and (b) one-channel manifold.

ARTICLE IN PRESS
C. Escobar et al. / Journal of Environmental Management 81 (2006) 384391

The calibration curves and the samples were recorded at

1100 mV, during an active period of 180 s, followed by a
20 s resting period. Scanning was carried out between

1100 and 300 mV, with a scan rate of 35 mV s
1,
sensitivity of 1 mA V
1, and instrumental recording interval of 1 mV. At lower concentrations, the calibration
curves and the samples were recorded at
1100 mV, during
an active period of 720 s with a 30 s resting period.
Scanning at lower concentrations was completed between

1100 and 300 mV, with a scan rate of 50 mV s
1,
sensitivity of 1 mA V
1, and instrumental recording interval of 1 mV.
2.9. Iron analysis
Iron was measured using the thiocyanate spectrophotometric method. After electrolysis, the samples were
centrifuged and ltered through a 0.45 mm lter (mixed
cellulose esther). A 1 cm3 aliquot of the ltrate was diluted
to 10 cm3, with 4 cm3 of 1 mol dm
3 NaSCN and 5 cm3 of
6 mol dm
3 H2SO4 solutions. The analytical wavelength
was 450 nm, using 10 mm optical path cells.
3. Results and discussion
Standard solutions were used to develop the calibration
graphs for copper, lead and cadmium. The anodic stripping
voltammetry method was validated using certied river
sediment of high-purity standard. The recovery (n 11)
was between 98% and 102% with a relative standard
deviation of 1.9%. These data indicate the method was
both accurate and repeatable.
3.1. Electrocoagulation results in batch mode
A logistical relationship between electrode geometric
area (AG) and copper removal efciency (r 0:9909;
w2 3:71) was found (Fig. 2). As expected, the increase
in copper removal was related to an increase in AG,

387

reaching an optimal value of 35 cm2, with an asymptotic

value near 80%.
The concentration of iron also increased since the
number of loci suitable for electrogeneration also increased. While substantial copper removal was expected, a
point was reached where the amount of coagulated iron
was sufciently high to counterbalance the transport
process, and maximum coagulation and removal were
therefore achieved.
In this context, the electrochemical system can behave as
a capacitor, and the capacitive current could become more
important than the faradic current. On the other hand,
under the pH conditions observed in these studies, the
copper partially precipitates as a hydroxylated form, and
the remaining copper fraction is removed by electrolysis.
Increasing the spatial separation of electrodes reduces
metal removal due to a decrease in current ow and
coagulant generation (Fig. 3). An optimal distance of
2.0 cm for removal of lead and 2.5 cm for removal of
cadmium and copper was identied. For later experiments,
the electrode separation value of 2.5 cm was used.
This procedure promotes competition for the metallic
cations between the generated coagulant agent and the
cathode. Varying the intensity of the electric eld causes
opposite effects. If electric eld intensity is increased,
electrostatic attraction also increases and metal removal
diminishes. Conversely, when eld intensity is reduced,
cathode attraction decays, thus increasing metal removal.
The study of the effect of electrolysis time on the copper
removal shows a gradual increase along time, with a
maximum copper removal of 80% occurring in 6 min.
Therefore, all the experiments in batch mode used an
electrolysis time of 10 min, ensuring maximum removal. A
similar trend was observed during the electrode geometric
area study. The pH of the test solution must be considered,
since at pH between 0 and 5, the hydroxylated species do
not signicantly affect metal removal. Other cations were
found to behave in a similar manner.

90

100
90
80
70
60
50
40
30
20
10
0

Metals removal (%)

Copper removal (%)

100
80
70 (A)
60
50 (B)
40 (C)
30
20
10
0
1.0
10

15

20

25

30

35

40

45

50

55

60

65

1.5
2.0
2.5
3.0
3.5
Distance between the electrodes (cm)

4.0

Electrode geometric area (cm2)

Fig. 2. Effect of geometric area of electrodes on copper removal:
copper 12 mg dm
3. pH 7.4, electrolysis time 10 min, distance
between electrodes 1 cm, conductivity 900 mS cm
1.

Fig. 3. Effect of distance between the electrodes on lead, copper and

cadmium removal efciency: (A) copper, 12 mg dm
3, (B) lead, 4 mg dm
3
and (C) cadmium, 4 mg dm
3. Current density 36 A m
2, electrolysis
time 10 min, conductivity 900 mS cm
1.

ARTICLE IN PRESS
C. Escobar et al. / Journal of Environmental Management 81 (2006) 384391

100
90
80
70
60
50
40
30
20
10
0

100
(A)

90
Copper retention (%)

Metals removal (%)

388

(B)
(C)

80
70
(A)

60
50
40
30
20
10

(B)

pH

10

The removal efciency of copper and cadmium peaked at

pH of 5 and 7, respectively (Fig. 4). The removal efciency
of lead did not appear to change substantially with pH. At a
neutral pH of 7, all the metals demonstrated an optimal and
consistent removal efciency. When solution pH becomes
acidic, the oxidation of ferrous iron (Fe II) to ferric iron (Fe
III) diminishes, and therefore metal removal decreases.
Alkaline pH, however, tend to favor Fe (II) to Fe (III)
oxidation as well as complex polymerization. Finally,
hydroxylated colloidal polymers and an insoluble precipitate of hydrated ferric oxide (Hiemenz and Rajagopalan,
1997) were formed and the removal efciency was
increased. At an alkaline pH, metal removal efciency
increased considerably, reaching nearly 100% removal, due
to the precipitation of the target analytes.
Humic acid was found to have an initial positive impact
on metal removal efciency. In all cases, removal efciency
was higher in the rst 5 min of agitation, probably due to
the formation of insoluble compounds with the cationic
metals in the presence of humic acid (Sauve et al., 1997,
1998). Over a longer period, however, the removal
efciency for all three metals was constant because the
concentration of metals and humic acid did not vary.
Higher copper concentrations were measured in the
coagulated product during the study to evaluate the impacts
of electrode geometric area (Fig. 5). Electrodeposited
copper increased along with the electrode geometric area,
reaching a maximum at 35 cm2, and decreasing for bigger
surfaces. On smaller surfaces, a signicant migration allows
copper to reach the cathode and be reduced on small
surfaces. On larger surfaces, the migration becomes less
signicant and copper cannot reach the cathode. For this
reason the copper percentage retained in the coagulated
product increases starting from 35 cm2 (Fig. 5A).
3.2. Electrocoagulation results in continuous mode
In the study to evaluate the effect of pH on the removal
efciency of copper, lead and cadmium, removal increased

15

20

25 30 35 40 45 50 55
Electrode geometric area (cm2)

60

65

Fig. 5. Effect of geometric area of electrodes on: copper retention in

coagulated product (A), copper electrodeposition (B). Copper,
12 mg dm
3, pH 7.5, electrolysis time 10 min, distance between
electrodes 2.5 cm, conductivity 900 mS cm
1.

100
90

(A)

80
Metals removal (%)

Fig. 4. Effect of pH on lead, copper and cadmium removal: (A) lead,

4 mg dm
3, (B) copper, 4 mg dm
3 and (C) cadmium, 12 mg dm
3. Current
density 36 A m
2, electrolysis time 10 min, distance between electrodes 2.5 cm, conductivity 1100 mS cm
1.

70
60
(B)

50
40
30
20
10

(C)

0
6

10

12

14

16

18

Flow rate (mL min-1)

Fig. 6. Effect of ow rate on copper, lead and cadmium removal
efciency: (A) lead, 4 mg dm
3, (B) copper, 4 mg dm
3 and (C) cadmium
4 mg dm
3. pH 6, current density 40 A m
2, distance between electrodes 1.5 cm, conductivity 1100 mS cm
1.

gradually when pH increased. Consequently, results from

the batch and continuous mode studies are similar. When
the pH was greater than 7, ow rate was 6.3 cm3 min
1, and
electrode distance was between 31 and 54 A m
2, a
continuous removal rate of close to 100% was observed.
Copper, lead and cadmium removal efciency decreased
when the ow rate increased (Fig. 6). This reduction is
likely due to a reduced residence time in the electrocoagulation cell. Removal of lead and copper remained
consistently higher than cadmium, regardless of the ow
rate. Lead removal was the least affected by increases in
ow, never dropping below approximately 95%, even at
the highest ow rates measured. Cadmium removal, on the
other hand, decreased to near 0 at the highest ow rate.
This substantial difference for cadmium is not unexpected

ARTICLE IN PRESS
since, under the pH conditions in the study, only a small
fraction of cadmium hydroxide and cadmium hydroxylated
species are present.
Changes in metal removal under different ow rates
(Fig. 6) occurred at a pH of 6. When the pH of the solution
was increased to 7, cadmium removal continued to
decrease when ow rate increased, again because of
reduced contact time with the coagulant. Lead and copper
removal at pH 7, however, proved to be more independent
of the ow rate, possibly due to an increase in the overall
process productivity at higher pH.
Removal efciency of all three metals increased when
current density increased, due to the generation of more
coagulant as a higher current ow passed through the
electrodes. Under these conditions, lead was completely
removed from solution, and it was not possible to make
quantitative observations regarding lead removal and
current density. Removal efciency was independent of
current density when tests were run at a pH of 7, possibly
because the process is generally favored at higher pH.
Similarly, iron precipitation was found to increase as the
pH rose, while at more acidic pH, electrogenerated iron is
more readily dissolved.
Chemical reactions in the treated water result in the
formation of gases, which alter metal speciation and affect
water quality parameters. Water undergoes anodic oxidation to form O2 (g), or cathodic reduction to form H2(g)
(Levine, 1995). In this electrochemical system, the main
anodic reaction is the oxidation of the Fe0 to form Fe+2,
and, therefore, the reduction of the water is more signicant
than oxidation. The evolved gas in the experiments was H2


ions.
(g), and the reduction of water also produced OH
While some hydroxyl ions are consumed in the formation of
iron and metal hydroxides, the OH
ions remaining solution
explain the increase in solution pH during the reaction.
To identify an approach for application of the electrocoagulation process at an industrial level, it was necessary
to establish a predictable relationship between current
density and specic energy consumption. A linear relationship (when pH 7) was found (r 0:9964, F 272,
p 0:004) (Fig. 7). The resulting equation (pH 7; ow
rate 6.3 cm3 min
1) was
Specific energy consumption kW h m
3
0:049  j
1:05,

where j is the current density, A m
2.

Specic energy consumption depends on cell voltage,
and in this case, energy consumption depends on the
equilibrium potential, the over-potentials at the cathode
and the anode and the ohmic voltage losses in the cell
(Scott, 1995). An increase in the current density causes a
proportional increase of the ohmic voltage losses in the cell
and of the specic energy consumption. This explains the
behavior observed in Fig. 7.
In the electrode lifetime study, a lost anode mass rate of
2.2 g d
1 was found. Considering this result and the

Specific consumption of energy (kW h m-3)

C. Escobar et al. / Journal of Environmental Management 81 (2006) 384391

389

5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0

10

20

30

40

50

60

70

80

90 100 110 120

Current Density (A m-2)

Fig. 7. Effect of current density on the specic consumption of energy.

Flow rate 6.3 cm3 min
1, pH 7, distance between electrodes 1.5 cm,
conductivity 1000 mS cm
1.

Table 3
Copper, lead and cadmium removal
Analyte

Initial conc.
(mg dm
3)

Final conc.
(mg dm
3)

Removal (%)

Copper

3.0
1.0
1
0.5
1
0.5

0.27
0.27
0.01
0.015
0.03
0.04

91
73
99
97
97
92

Lead
Cadmium

Current density 31 A m
2, ow rate 6.3 cm3 min
1, pH 7, distance

between electrodes 1.5 cm, conductivity 1100 mS cm
1.

dimensions and purity of the anode, an electrode lifetime

of 4 d operating continuously was estimated. However,
further studies that consider the passivity and scale-up of
the electrodes are necessary for determination of a more
accurate estimate of electrode lifetime.
There was a positive linear relationship between current
density and the mass of dry sludge generated at a pH of 7
(r 0:998, F 360, p 3:19  10
4 ). At a current density
of 31 A m
2, copper and cadmium removal rates decrease
when the initial concentration of these metals decreases in
the electrocoagulation cell (Table 3). For example, while
91% of the copper was removed when the initial
concentration was 3.0 mg dm
3, removal dropped to 73%
when the initial concentration was 1.0 mg dm
3. The nal
concentration in both cases was 0.27 mg dm
3. This drop in
percent removal occurs because the interaction probability
with the coagulant decreases when cationic ions are present
at lower concentrations. Because of its high mobility, the
removal of lead is not as greatly affected when initial
concentration is decreased. When the current density was
54 A m
2, percent removal of lead and cadmium was not

ARTICLE IN PRESS
C. Escobar et al. / Journal of Environmental Management 81 (2006) 384391

390
Table 4
Copper, lead and cadmium removal
Analyte

Initial conc.
(mg dm
3)

Final conc.
(mg dm
3)

Removal (%)

Copper

3.0
1.0
1
0.5
1
0.5

0.21
0.23
0.02
0.005
0.01
0.005

93
77
98
99
99
99

Lead
Cadmium

Current density 54 A m
2, ow rate 6.3 cm3 min
1, pH 7, distance

between electrodes 1.5 cm, conductivity 1100 mS cm
1.

were also indicated at 11 A m
2, although the removal

efciency was better at 31 A m
2.
Using the previously determined rate constant and a
cadmium removal efciency of 99.8%, and the piston ow
equation (Levenspiel, 1999), the residence time (t) was
5.9 min.
With a ow rate of 100 m3 h
1, the volume of the reactor
corresponds to 9.83 m3. The current density used was
31 A m
2, resulting in a specic consumption of
0.47 kW h m
3 of energy according to the Eq. (1). The
obtained results are a rst step toward an industrial
application of the process.
4. Conclusions

Table 5
Copper, lead and cadmium removal in a synthetic wastewater
Analyte

Initial conc.
(mg dm
3)

Final conc.
(mg dm
3)

Removal (%)

Copper
Lead
Cadmium

2.73
0.288
0.818

0.235
0.00288
0.00818

91
99
99

Flow rate 6.3 cm3 min
1, pH 7, current density 54 A m
2, distance

between electrodes 1.5 cm, conductivity 1100 mS cm
1.

affected by the decrease in initial metal concentrations

(Table 4). The reduction in copper removal at 54 A m
2
was very similar to the reduction observed at the lower
current density.
3.3. Application of electrocoagulation
Application of electrocoagulation to a synthetic wastewater at a pH of 7 was investigated. The copper
concentration was reduced by approximately one order
of magnitude, while both lead and cadmium were reduced
by two orders of magnitude (Table 5). These data
demonstrate that the electrocoagulation process is an
efcient means of reducing cationic metals in wastewater.
3.4. Theoretical industrial application of the
electrocoagulation process
In this application, previously identied optimized
variables were used. At a pH of 7, copper and lead
removal is nearly 100%, while the removal of cadmium
depends on current density and ow rate.
The study was conducted to evaluate the impacts of ow
rate on metal removal efciency, taking into account the
kinetics for cadmium. A linear relationship of the logtransformed cadmium concentration through time
(r 0:9936; F 155; p 0:0064) was identied. The
results indicated a rst-order kinetic reaction at a rate
constant of 1.053 min
1, for 31 A m
2. First-order kinetics

This study generated important information on the

optimal conditions of several variables that inuence
electrocoagulation. It was found that copper removal was
achieved primarily by adsorption in the coagulated
product. Electrodeposition of the metal did not play a
major role in metal removal, except at a short electrode
distance. At a critical electrode geometric area of 35 cm2
and electrolysis time of 6 min, a maximum copper removal
rate of 80% was observed. Optimum electrode distances of
2 cm for lead and 2.5 cm for cadmium and copper were
found. For both systems, the analyte removal efciency
increased considerably with the pH, reaching 100%
removal when the pH exceeded 7.
In continuous mode, optimal performance was achieved
when the pH was 7 (which resulted in a slightly alkaline
output), ow rate was 6.3 cm3 min
1 and current density
ranged between 31 and 54 A m
2. Also, an increase in the
copper and cadmium removal efciency at higher concentrations was observed. Removal appeared to follow rst
order kinetics, with a rate constant of 1.053 min
1 for
cadmium removal at a pH of 7. Using these results, it was
possible to determine the residence time and volume of an
industrial-scale reactor, in a rst attempt to upwardly scale
the electrocoagulation process. Additional studies are
necessary to verify these results and further rene parameters for industrial application.
References
Chen, G., Chen, P.X., Yue, L., 2000. Electrocoagulation and electrootation of restaurant wastewater. Journal of Environmental Engineering
126, 858863.
Hiemenz, P., Rajagopalan, R., 1997. Principles of Colloid and Surface
Chemistry. Marcel Dekker, New York.
Ibanez, J.G., Takimoto, M.M., Vasquez, R.C., Basak, S., 1995.
Laboratory experiments on electrochemical remediation of the
environment: electrocoagulation of oil wastewater. Journal of Chemical Education 72, 10501053.
Ibanez, J.G., Singh, M.M., Pike, R.M., Szafran, Z., 1997. Laboratory
experiments on electrochemical remediation of the environment, Part
2: microscale indirect electrolytic of organic wastes. Journal of
Chemical Education 74, 14491450.
Ibanez, J.G., Singh, M.M., Szafran, Z., 1998. Laboratory experiments on
electrochemical remediation of the environment, Part 4: color removal

ARTICLE IN PRESS
C. Escobar et al. / Journal of Environmental Management 81 (2006) 384391
of simulated wastewater by electrocoagulationelectrootation. Journal of Chemical Education 75, 10401041.
Levenspiel, O., 1999. Chemical Reaction Engineering. Wiley, New York.
Levine, I., 1995. Physical Chemistry. McGraw-Hill, New York.
Lin, S.H., Chen, M.L., 1997. Treatment of textile wastewater by
electrochemical methods for reuse. Water Research 31, 868876.
Mollah, Y., Schennach, R., Parga, J., Cocke, D., 2001. Electrocoagulation
(EC)science and applications. Journal of Hazardous Materials 84,
2941.
Monte Alegre, A., Mart nez, S.A., 1993a. Tratamento eletrol tico de euentes
de rener a de petroleo (parte I). Revista DAESABESP 171, 1115.
Monte Alegre, A., Mart nez, S.A., 1993b. Uso de eletrolise na depurac- ao
de correntes l quidas contendo oleo e graxas emulsicados (parte II).
Revista DAESABESP 173, 713.

391

Oblinger, F.G., Weintraub, M.H., Gealer, R.L., Blais, E.J., 1984. In-plant
operation of electrolytic cell for oil wastewater treatment. Environmental Progress 3, 15.
Sauve, S., McBride, M., Norvell, W., Hendershot, W., 1997. Copper
solubility and speciation of in situ contaminated soils: effects of copper
level, pH and organic matter. Water, Air, and Soil Pollution 100,
133149.
Sauve, S., McBride, M., Hendershot, W., 1998. Soil solution speciation of
lead (II): effects of organic matter and pH. Soil Science Society of
America Journal 62, 618621.
Scott, K., 1995. Electrochemical Processes for Clean Technology. The
Royal Society of Chemistry, Cambridge.
Vik, E.A., Carlson, D.A., Eikum, A.S., Gjessing, E.T., 1984. Electrocoagulation of potable water. Water Research 18, 13551356.