Separation and Purication Technology 107 (2013) 109117

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Separation and Purication Technology

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

Removal of copper, zinc and nickel present in natural water containing Ca2+
and HCO
3 ions by electrocoagulation
A. de Mello Ferreira a, M. Marchesiello b,, P.-X. Thivel b,c
a

Departamento de Qumica, Centro Federal de Educao Tecnologica de Minas Gerais (CEFET MG), Av. Amazonas 5253, Nova Suia, Belo Horizonte, CEP: 30.421-169 MG, Brazil
IUT 1 de Grenoble, Dpartement de Chimie, Universit Joseph Fourier, 39-41 Boulevard Gambetta, 38000 Grenoble, France
c
LEPMI, UMR 5279, CNRS, Grenoble INP-UdS-UJF, 1130 Rue de la Piscine, 38402 Saint Martin dHres Cedex, France
b

a r t i c l e

i n f o

Article history:
Received 9 November 2012
Received in revised form 14 January 2013
Accepted 15 January 2013
Available online 24 January 2013
Keywords:
Electrocoagulation
Wastewater treatment
Heavy metal removal
Carbonate calcium precipitation

a b s t r a c t
Electrocoagulation (EC) is an efcient technique for cleaning wastewater containing heavy metals before
discharge in the environment. Studies on EC are usually conducted by adding supporting electrolyte to
the medium investigated so as to increase the electrolyte conductivity and improve the sacricial anodic
dissolution of the electrodes. The present study was conducted with low-conductivity natural water
(Grenoble tap water) articially polluted with copper, zinc and nickel. It shows that addition of supporting salts is not necessary to obtain high removal efciencies. For these metals, elimination rates above
95% were obtained after only 60 min of treatment, especially in the case of aluminum electrodes. These
high removal efciencies can be explained by the partial precipitation of copper and zinc before treatment owing to the highest pH value of natural water (compared with distilled water), by pH increase during EC caused by the reduction of water on the cathode, and by possible co-precipitation of calcium
carbonate (formed from calcium and bicarbonate ions present in tap water) and metallic hydroxide species produced by the anodic dissolution of the electrodes.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Industrial wastewaters can contain various kinds of organic and
mineral toxic compounds. Among mineral pollutants, heavy metals
are widely present, for example, in surface treatments industry and
mining industry wastewater. One of the authors, from the Minas
Gerais state of Brazil, which is well-known for its important mining
activity, is particularly concerned by heavy metal removal from
wastewater before their discharge in the environment. Among
the different methods available to eliminate heavy metals from
solutions, the coagulation technique has proved to be very efcient. The coagulation usually follows a precipitation step occurring after an increase of pH obtained by addition of NaOH or
lime. Coagulation is performed by adding coagulants like iron chloride FeCl3 or aluminum sulfate Al2(SO4)3 to the medium [1]. An
alternative to coagulation is Electrocoagulation (EC) where the ions
responsible for the coagulation, mainly Fe3+ or Al3+, are in situ generated by the anodic dissolution of iron or aluminum electrodes. At
the same time, the reduction of water, which occurs on the cathode, participates to the elimination process owing to the production of hydroxide ions, and therefore to the increase of water pH
at the vicinity of the electrode, leading to metal hydroxides precipitation [2].
Corresponding author. Tel.: +33 456520207.
E-mail address: Marc.Marchesiello@ujf-grenoble.fr (M. Marchesiello).
1383-5866/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2013.01.016

Several advantages make EC a very attractive treatment: the

process is simple since no coagulant addition is required, easy to
conduct using a conventional electric power supply, cost-effective,
and characterized by short operating times (30 min or 1 h of treatment is often widely sufcient to obtain very good metal removal
efciencies). Another important advantage of EC is its suitability to
various kinds of wastewater containing organic or mineral pollutants [3]: Bakers yeast efuents (color removal, chemical oxygen
demand (COD) and total organic carbon (TOC) removal) [4]; tissue
paper wastewater (turbidity removal) [5]; paint manufacturing
wastewater (COD and TOC removal) [6]; textile wastewater [7];
leachate (COD and NH4N removal) [8].
Some recent papers deal with EC applied to the elimination of
inorganic compounds like heavy metals [918], boron [19], phosphate [20], and nitrate [21].
Table 1 indicates the values of EC parameters chosen by some
authors [911,15] for the removal of heavy metal using aluminum
or iron electrodes. These parameters, whose values will be compared with our own (also presented in Table 1), are: conductivity
and electrolyte composition; initial pH; number of metals present
in the medium and initial metal concentrations; volume of the
solution investigated; number of electrodes used; total electrode
surface area and distance between electrodes; current density;
operating time. As indicated in Table 1, EC is usually conducted
using high electrolyte conductivity [911,15] (from 1.5 to 20 mS/
cm). High conductivity can be obtained by addition of salts like

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A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

Table 1
Comparison between our experimental parameters and those found in the literature.
Reference
Kind of water and Salts added
besides metallic salts

[9]
Synth. Water
Na2SO4 1 g/L

[10]
Synth.
Water
NaNO3
17 g/L

[11]
Metal plating waste water

[15]
Synth. Water

Our conditions
Grenoble ground water

No other salt addition

No other salt addition

No other salt addition

1.47 (after addition of

the metallic
salts 150 mg/L for
each metal)
3; 5.68; 8.95

0.35 (20 C)

Conductivity (mS/cm)

NaCl 0,1 g/L

1.72.9

20

Initial pH

4.9

4.57.5

Metal concentration (ppm)

Cu

2+

59

3
2+

0.9
2
Al
40

0.65
6
Al or Fe
10

0.5
6
Fe
3

15
4
Al or Fe
15

54

300

200

100

720

0.074
0.271.08
50200
722
080
45 (Calculated from
the data at I = 1 A and
t = 60 min)

0.002
0.53
1698

0140

0.005
0.52
25100

060
2 (at I = 1 A and t = 15 min
with Fe electrodes)

0.003
0.22.5
20250
11.75 (at I = 2.5 A)
050
49 (at I = 2.5 A and
t = 50 min)

0.002
0.51
714
410.5
0180
0.6 and 0.59 (at I = 1 A and
t = 60 min with Fe
respectively Al electrodes)

67

Cr(VI)
Ni2+

at the cathode :

Al ! Al

44.5
394

3e

2H2 O 2e ! 2OH H2

The electrolytic dissolution of the aluminum anode produces

Al3+ ions which are immediately transformed into solid particles
of Al(OH)3 at the operated pH values. Depending on the pH of
the medium, other ionic species can be formed like Al(OH)2+,
AlOH
AlOH
and also polymeric ionic species like
2,
4,
4
4
5
Al2 OH2 , Al6 OH3
,
15 Al7 OH17 , Al13 OH34 [22,23,25].
These species are excellent coagulating agents.
Two mechanisms can then explain the removal of heavy metals
like Cu2+, Ni2+ and Zn2+ [22]:
(1) Adsorption of the metallic ions on the surface of the Al(OH)3
particles produced.
(2) Precipitation of the metallic ions as the corresponding
hydroxides Cu(OH)2, Ni(OH)2 and Zn(OH)2, particularly at
the vicinity of the cathode where pH is higher owing to
the hydroxide ions formation; the aluminum ionic species
can then adsorb on the surface of these hydroxide particles
and neutralize their surface charge, leading to their coagulation and their incorporation in the aluminum hydroxide precipitate to form large ocs whose decantation is quickly
obtained. These ocs are then composed of Al(OH)3,
Cu(OH)2, Ni(OH)2 and Zn(OH)2 particles.

50250

Zn2+ 50250

Zn2+

Ni2+ 50250

Ni2+ 20

Mn2+

Na2SO4 [9], NaCl [9], NaNO3 [10]. The role of salt addition is to lower the electrolysis potential [9,10] and, in the case of chloride ions,
to enhance anodic dissolution of the electrodes [9].
When aluminum is used both as anodic and cathodic electrode,
the following reactions occur [22]:

at the anode :

Cu

7.7 (7.1 after the addition

of the metallic salts)
Cu2+ 12

Cu

Ni2+

45

2+

Cu
50
250
Zn2+ 50
5000
Ni2+ 50
250
Cr(VI) 10
50
Ag+ 550
1.2
4
Al
5

Zn2+ 67

Treated volume V (L)

Number of electrodes used
Electrode metal
Distance between electrodes d
(mm)
Total anodic or cathodic surface
area S (cm2)
Ratio d/S (cm1)
Current I (A)
Current density (A/m2)
Voltage U (V)
Treatment time t (min)
Energy consumption UIt/V
(kW h m3)

2+

20

50250

When iron is used instead of aluminum, similar reactions are

responsible for the removal of heavy metals: electrolytic dissolution of iron leading to Fe3+, precipitation of Fe(OH)3 and formation
of ferric monomeric and polymeric species [22,24,25].
Total soluble Fe(III) concentration (or total soluble Al(III) concentration) in pure water can be obtained from solubility-pH diagrams found in [25]. In these diagrams the concentration of each
Fe(III) species (respectively soluble Al(III) species), when in equilibrium with freshly precipitated Fe(OH)3 (respectively freshly precipitated Al(OH)3), is plotted as a function of pH. The pH of
minimum solubility of solid Fe(OH)3 is about 8, and total soluble
Fe(III) concentration is 1010 to 109 M (or 6  105 to
6  106 mg/L) between pH 6 and 9 [25]. The pH of minimum solubility of solid Al(OH)3 is about 6.5, and total soluble Al(III) concentration is 3  106 to 3  104 M (or 0.0252.5 mg/L) between pH
6 and 9 [25]. Thus, in the pH range 69, the residual Fe(III) concentration in water, after EC operated with iron electrodes, is very low,
and much lower than the residual Al(III) concentration, after EC
conducted with aluminum electrodes: in the case of Al electrodes,
the EC treatment is more suitable for waters with neutral pH (between 6.5 and 7.5).
The mass m (g) of aluminum or iron dissolved can be determined using Faradays law:

ItM
zF

where M is the specic molecular weight (g mol1) of the metal dissolved, I the current (A), t the electrolysis time (s), z the number of
electrons involved in the reaction, and F Faradays constant
(96,485 C mol1).

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A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

The energy consumption per unit volume of treated water

(kW h m3) is given by:

E 103

UIt
V

Electrocoagulation
reactor

where U is the cell voltage (V), I the current (A), t the electrolysis
time (h) and V the volume of treated solution (m3).
The aim of the present study is to investigate the elimination of
heavy metals contained in low conductivity natural water (Grenoble ground water here) using EC without addition of salts in the
medium, and to highlight the role of calcium and bicarbonate ions
in this elimination. As indicated in Table 1, the solutions usually
investigated are synthetic wastewaters prepared at a laboratory
scale with distilled water or deionised water [9,10,15]. It seemed
interesting to investigate the case of natural water containing
Ca2+ and HCO
3 ions, and presenting higher pH than distilled or
deionised water. For this study, a pilot plant with a total water volume of 15 L was used, which corresponds to a volume 1530 times
higher than those usually investigated (see Table 1).

+
V

Power supply
Container

Pump

Fig. 1. Experimental set-up.

2. Materials and methods

The electrolytic solution was prepared by dissolving the following sulfate salts either in distilled water or in natural water (Grenoble tap water): CuSO45H2O; ZnSO47H2O; NiSO47H2O. In each
case, the concentration of copper, zinc and nickel in the medium
were respectively 12 mg/L, 20 mg/L and 20 mg/L. Other various
salts (Na2SO4, NaCl, CaCl2) were added in our experiments for reasons described below. All solutions used were prepared from analytical grade chemical reagents (Aldrich products) without any
further purication.
The physicochemical characteristics of Grenoble tap water are
presented in Table 2. Our sample is from alluvial ground water
fed by the Drac river and supplied without treatment; it presents
a total hardness of about 4 meq/L, a total alkalinity of about
3 meq/L and is slightly oversaturated with respect to CaCO3 (slight
tendency to precipitate CaCO3).
The EC reactor is constituted of a 5-L reactor connected to a 20-L
container. A pump (max head 4 m; max volume ow rate 0.7 m3/h)
is used to continuously circulate the electrolyte in the experimental setup during the treatment at a volume ow of 0.3 m3/h,
through 10 mm polypropylene pipes, as shown in Fig. 1. The total
volume of solution prepared in each experiment was 15 L.
The hydrodynamic inside the reactor and container was determined using a pulse of conductivity after injection of 10 mL of NaCl
100 g/L at the inlet of the pump [26]. The solution circulating in the
container and the reactor was initially distilled water. Two conductivity cells were placed, one in the EC reactor and the other in the
container. Fig. 2 shows the evolution of the conductivity for the
two positions of the conductivity cell. After 2 min, the conductivity,
both in the EC reactor and in the container, stabilizes at the same
value due to the circulation of the solution. The experimental data

Table 2
Physicochemical parameters of Grenoble tap water.
Conductivity (20 C)
pH (25 C)
Dissolved oxygen O2 (21 C)
Ca2+
Mg2+
Na+
K+
HCO
3
SO2
4
ClNO
3

0.350 mS/cm
7.75
8 mg/L
64 mg/L
7.5 mg/L
5 mg/L
0.8 mg/L
173 mg/L
43 mg/L
7.3 mg/L
3.3 mg/L

Fig. 2. Evolution of the conductivity in the reactor and container after injection of a
NaCl tracer solution. The points represent the experimental data and the solid and
broken lines correspond to the model of a mixed ow reactor.

were tted considering the EC reactor and the container as mixed

ow reactors (MFRs). Thus, the model curves were obtained by
resolving the transient mass balance equations in both reactors
associated in series. The model is in perfect adequacy for the EC
reactor, which shows that the uid ow in this reactor allows a
good homogenization of the solution to be treated. For the container, the model does not t exactly the rst experimental points
certainly because of the overow which was not included in the t.
However, the time constant s was estimated using this t and its
value is about 30 s (Fig. 2). Since this value is low in comparison
with the sampling time (15 or 20 min), at any given time, the samples from the container can be considered as representative of the
overall treated solution.
For the EC experiments Aluminum (Al) or iron (Fe) plates with a
1-mm thickness were used, the surface area in contact with the
electrolyte was in each case 180 cm2 per side. In each experiment,
four plates were used in the electrochemical reactor and the distance d between plates was xed at 15 mm. The electrodes are
placed using a monopolar conguration with a total anodic or
cathodic surface area S of 720 cm2.
The choice concerning the distance d between the electrodes
and the total electrode surface area S (depending on the number
of electrodes used) was made to minimize IR-drop when the current I passes through the solution. The IR-drop VIR is related to
the distance d, total surface area S, conductivity r and current I
by the following equation [27]:

V IR

dI

rS

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A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

As shown in Table 1, the ratio d/S of our experimental set up is

lower or equal to those found in other studies [911,15].
The current values were chosen from 0.5 to 3 A corresponding
to a current density from 7 to 42 A/m2 using a precision DC power
supply characterized by the ranges 06 A for current and 030 V
for voltage. Before each experiment, the electrodes were polished
with abrasive paper to remove any oxide lm and then thoroughly
washed.
The pH was continuously measured in the 20-L container and
was not adjusted during the treatment. All the experiments were
performed at room temperature.
To follow the progress during treatment, 20 mL samples were
periodically taken from the container and were ltered using
Whatman lter paper (grade 40) to separate the sludge from the
solution to be analyzed. The residual concentrations of metal ions
were determined using an atomic absorption spectrophotometer
(Perkin Elmer Analyst 300). Each analytical value corresponds to
the mean value of three measures.
To see the effect of NaCl concentration on the anodic dissolution
of iron, polarization curves were performed using a classical 3electrode cell and a PGP 201 Radiometer potentiostat driven by
the VoltaMaster 4 electrochemical software for data acquisition.
The iron-working electrode had a diameter of 2 mm. The reference
electrode was a saturated calomel electrode and a platinum electrode served as counter electrode.
The determination of the total hardness of the water, namely
the sum of Ca2+ and Mg2+ concentrations, is performed from samples of 100 mL previously ltered (Whatman lter paper, grade 40)
which are titrated with an EDTA 102 mol/L solution up to the color change of the complexing agent Eriochrome Black T [25].
The determination of the total alkalinity (TA) of the water is
made from samples of 100 mL previously ltered (Whatman lter
paper, grade 40) which are titrated with a solution of Hydrochloric
acid 102 mol/L to a pH value around 4.5 corresponding to the color change of the methylorange indicator [25]. For natural water
with pH value under 8.3 the total alkalinity is attributable to
HCO
3 ions.
3. Results and discussion
3.1. EC experiments in the presence of Na2SO4 and NaCl
In a rst stage, two kinds of electrolytes were prepared: one
with distilled water (initial pH around 6) and the other one with
tap water (initial pH 7.75). In each case, Na2SO4 and NaCl salts
were added at a concentration of 0.1 mol/L and 2  103 mol/L
respectively, leading to an ionic strength of about 0.3 for the two
electrolytes.
Table 3 indicates the solubility products of Cu(OH)2, Zn(OH)2,
Ni(OH)2, CuCO3, ZnCO3 and NiCO3 and minimum pH values
required for their precipitation (calculated for the two ionic

Table 3
Apparent pKs constants (298 K, 1 atom) and pH values corresponding to the start of
precipitation of metallic hydroxides and carbonates.
Species

Cu(OH)2
Zn(OH)2
Ni(OH)2
CuCO3
ZnCO3
NiCO3
CaSO4

Ionic strength: l = 0.009

Ionic strength: l = 0.3

pKs = log(Ks)

Precipitation
pH

pKs = log(Ks)

Precipitation
pH

18.2
15.4
14.4
9.3
10.5
8.7
4.3

6.7
8
8.5
7.3
5.9
7.7

17.7
14.9
13.9
8.5
9.7
7.9
3.5

6.9
8.2
8.7
7.7
6.3
8.1

strength values investigated in the present paper: l = 0.009 and

l = 0.3). The solubility products presented in Table 3 are apparent,
i.e., based on the concentration of the species involved; they were
calculated from the equilibrium constants found in Ref. [28] and
using the Davies Equation [29] which allows the determination
of activity coefcients for ions up to an ionic strength of about
0.5. The minimum pH values required for precipitation were calculated from the apparent solubility products previously determined
and from the metal concentrations chosen for the investigation
(Cu2+ 12 mg/L, Zn2+ 20 mg/L and Ni2+ 20 mg/L). In the case of carbonate salts, these minimum pH values were obtained only considering solutions prepared with tap water (HCO
3  = 0.0028 mol/L)
2
and using the acidity constant of the acidbase pair HCO
3 /CO3
[28]. In Table 3, the precipitation constant of CaSO4 is also given.
According to Table 3, no precipitation occurs when preparing
the solution (before starting the EC treatment) in distilled water
because of the low pH value (pH  6). When tap water is used
for the preparation of the solution, a decrease of the pH value from
7.75 (initial pH) to 7.15 is observed (the addition of CuSO4 is
mainly responsible for the decrease in pH). Once all salts are added,
the solution is clear with a slight blue/green color (no precipitation
appears). According to Table 3, the precipitation of Cu(OH)2 and
ZnCO3 is expected, based on thermodynamic considerations, but
is not observed before the start of EC treatment certainly because
of the slowness of these reactions under our experimental conditions (high ionic strength value: l = 0.3). No precipitation of CaSO4
is possible when tap water is used (for l = 0.3, the value of the
product [Ca2+]  [SO2
4 ] is lower than the corresponding solubility
constant).
Analysis results obtained after EC using iron electrodes and performed at a current of 1 A (14 A m2) are presented in Fig. 3. The
curves show that for both distilled and tap water the removal rate
is higher for copper than for zinc, and higher for zinc than for nickel
(i.e., of the same order as the corresponding metal hydroxides pKs
values). In both cases, the treatment leads to large amounts of iron
hydroxide sludge which quickly sedimentate. Nevertheless, the
best removal rates are obtained with tap water.
Fig. 4 shows the evolution of the removal efciency, calculated
for an operating time of 180 min, as a function of the current density used (14, 28 and 42 A m2) and depending on the water used.
The removal efciency or conversion rate, in percent, is given by:

X %

metal0  metalt
metal0

where [metal]0 is the initial metal concentration and [metal]t the

metal concentration after treatment at a given time.
The results are remarkable with regards to the use of tap water
since all the removal rates are above 95% after 180 min of treatment (the residual concentrations of Cu, Zn and Ni are respectively
below 0.01 mg/L, 0.02 mg/L and 1 mg/L) showing that in these conditions the cleaning up operation performs well. The difference between tap water and distilled water is noteworthy in the case of
nickel whose removal rate hardly reaches 20% in distilled water.
Among the different causes that explain the metal removal
improvement when tap water is used, the pH increase during electrolysis has certainly an important effect: the pH evolves from 7.15
before electrolysis to a mean value of 7.9 after 180 min of treatment. This pH variation, which is related to water reduction on
the cathode surface with production of hydroxide ions [2,22],
enhances metal hydroxides and metal carbonates precipitation.
At the vicinity of the cathode, high local pH values can be reached
making precipitation certain with a positive effect on the removal.
Moreover, because of this pH increase, another phenomenon
appears when tap water is used: the precipitation of calcium
carbonate CaCO3. This precipitation occurs during EC as shown

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A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

pH 6, hydroxide ions, produced at the cathode, react with Fe3+, generated at the anode, to form both FeOH
2 and solid Fe(OH)3 (from
FeOH
2 ) [25]. The pH stability during EC when distilled water is
used can be explained by fast formation reactions of FeOH
2 and
Fe(OH)3 that allow the neutralization of all hydroxide ions produced at the cathode.
For the current densities used (14, 28 and 42 A m2), we notice
an overall improvement of EC when the current density is increased (Fig. 4). However, in the case of tap water, there is no
use of applying a current density above 14 A m2 since metal removal is already very good for this value. At a current density of
14 A m2, cell potential is around 1 V for the two kinds of water
and energy consumption is then 0.067 kW h m3 after 1 h of EC.

25
[Cu] distilled water
[Zn] distilled water

[metal] mg/L

20

[Ni] distilled water

15

10

0
0

50

100

150

Time (min)

3.2. Inuence of NaCl during EC

(a)
25
[Cu] tap water
[Zn] tap water
[Ni] tap water

15

10

0
0

50

100

150

Time (min)

(b)

Conversion rate (%)

Fig. 3. Evolution of the metallic concentrations during the electrocoagulation

experiments conducted (a) in distilled water or (b) in Grenoble tap water. In both
cases, the conditions are: iron electrodes, I = 1 A (14 A/m2), Na2SO4 0.1 M and NaCl
2  103 M.

100
90

Cu

Zn

1A
2A
3A

Ni

80
70
60

3.3. EC experiments without Na2SO4 nor NaCl

One of the aims of the present work was to check the possibility
of operating without addition of NaCl and Na2SO4. For this reason,
an experiment was carried out only using tap water (without addition of NaCl, Na2SO4 and metal salts), at a current density of
7 A m2 (0.5 A in current), and using iron electrodes. This experiment showed that the iron anodic dissolution was possible with
production of a large amount of iron hydroxide sludge, in spite of

50
40

3000

30
20
10
0
DW

TW

DW

TW

DW

TW

Fig. 4. Metal removal efciency after 180 min of EC treatment in distilled water
(DW) or Grenoble tap water (TW). In both cases, the conditions are: iron electrodes,
I = 1 A, 2 A or 3 A (14, 28 or 42 A/m2), Na2SO4 0.1 M and NaCl 2  103 M.

by total alkalinity and total hardness measures made before and

after 180 min of treatment (see further down). In these conditions,
co-precipitation of metal hydroxides and metal carbonates, calcium carbonate and iron hydroxide is possible during EC experiments and could explain the improvement of the treatment
efciency.
In the case of distilled water (pH 6) the pH increase is not signicant after an operating time of 180 min. Between pH 5 and 7,
FeOH
2 is the predominant soluble ferric iron species [25]. At

Current density (A/m)

[metal] mg/L

20

The role played by NaCl in the electrochemical dissolution of

iron electrodes was investigated using voltammetry. Fig. 5 shows
the evolution of the anodic polarization curves obtained with a
2-mm diameter iron disk electrode as working electrode. These
curves, corresponding to the anodic dissolution of iron, were performed in tap water after addition of 0.1 mol/L Na2SO4 and for different concentrations of NaCl (from 0 to 5  103 M).
Fig. 5 shows a pronounced inuence of NaCl concentration on
the iron anodic dissolution beyond 1 V. In the range of concentration investigated beyond this potential, the higher the NaCl concentration, the higher the current density: NaCl causes the
breakdown of the passive lm and markedly enhances the electrode dissolution. However, in the experimental conditions investigated (the range of current densities is indicated in the gure), all
the curves are very close to one another, showing that in this current density range the NaCl concentration has no marked inuence
on the anodic dissolution of iron.
EC experiments can then be performed without NaCl addition.

2500

0.005 mol/L

2000

0.004 mol/L
0.003mol/L

1500

0.002 mol/L

0.001 mol/L

Current density range

investigated for EC
experiments

1000

0 mol/L

500
0
-1

-0.5

0.5

1.5

2.5

Voltage (V/SCE)
Fig. 5. Polarization curves at different NaCl concentrations (from 0 to 5  103 M)
obtained with a 2-mm diameter iron disk electrode as working electrode. The
experiments were conducted in tap water with Na2SO4 0.1 M. Reference electrode:
saturated calomel electrode. Counter electrode: platinum electrode.

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A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

25

Iron; 0.5 A (7 A/m)

Average voltage : 4.5 V
pH variation : + 0,8
TA variation : -1.92 meq/L

20
15

Aluminum; 0.5 A (7 A/m)

Average voltage : 6.1 V
pH variation : + 0.55
TA variation : -1.86 meq/L

[Cu] tap w ater

20

[Zn] tap w ater

[metal] mg/L

[mg/L]

25

[Ni] tap w ater

10
5

15

[Cu] tap w ater

[Zn] tap w ater
[Ni] tap w ater

10
5

50

100

150

200

50

100

150

Time (min)
25

25

Iron; 1 A (14 A/m)

Average voltage : 9.0 V
pH variation : + 0,9
TA variation : -2.16 meq/L

20
15

[Cu] tap w ater

Aluminum; 1 A (14 A/m)

Average voltage : 8.8 V
pH variation : + 1.15
TA variation : -2.00 meq/L

20

[Zn] tap w ater

[metal] mg/L

[mg/L]

200

Time (min)

[Ni] tap w ater

10
5

15

[Cu] tap w ater

[Zn] tap w ater
[Ni] tap w ater

10
5

50

100

150

200

50

100

Time (min)

(a)

150

200

Time (min)

(b)

Fig. 6. Evolution of the metallic concentrations during the EC experiments using (a) iron electrodes, (b) aluminum electrodes at two different current values: 0.5 and 1 A (7
and 14 A/m2). Electrolyte: Grenoble tap water without any addition of salts.

the low conductivity of the water (about 0.35 mS/cm at 20 C) and

its very low natural chloride concentration. However, as a consequence of low conductivity, the EC operated at a higher potential
value of about 5.8 V.
After 180 min of treatment the total alkalinity and total hardness decreased with a variation corresponding to 1 meq/L, which
indicates the transformation of bicarbonate and calcium ions to
CaCO3 precipitate. The CaCO3 precipitation can be explained by
the pH increase at the vicinity of the cathode due to the reduction
of water [2,22]. As a result, the following reactions occur [30]:

HCO3 OH ! CO2

3 H2 O
2
CO2
! CaCO3
3 Ca

Calcium carbonate precipitate can then be incorporated in the

ferric hydroxide sludge. As said previously, it is possible that the
CaCO3 precipitation and its probable co-precipitation with the
other precipitates are involved in the mechanisms leading to the
improvement of metal removal efciency when tap water is used.
When EC is performed in the presence of metallic salts, as already described, a change of pH is observed following salts addition. The metallic salts were added in tap water (initial
pH = 7.75) in the following order: NiSO4, ZnSO4 and CuSO4. The
resulting ionic strength is about 9  103. No pH variation is observed after the addition of NiSO4. The pH reaches the value of
7.45 after the addition of ZnSO4 and the value of 7.05 after the
addition of CuSO4. When all salts are added, the solution becomes
cloudy certainly because of the appearance of precipitates like
Cu(OH)2, CuCO3 and ZnCO3 (see Table 3). As indicated in Table 3,
the minimum pH values required for precipitation are lower for
l = 9  103 than for l = 0.3, explaining the precipitation occur-

rence for these compounds in the present experimental conditions.

Thus, copper and zinc precipitate before the start of EC treatment
as small suspended particles that are hardly sedimentable. Besides,
the analysis of samples taken just before the start of electrolytic
treatment and ltered shows that about 75% of copper ions and
10% of zinc ions precipitate. For nickel, no precipitation occurs.
The results for EC experiments performed in Grenoble tap water
containing copper, zinc and nickel ions without NaCl and Na2SO4
addition are presented in Fig. 6. Those experiments were conducted with iron and aluminum plates as electrodes, applying
two current values, 0.5 and 1 A (7 A m2 and 14 A m2). For each
metal, the initial value (operating time t = 0) corresponds to the
initial total amount (Cu2+ 12 mg/L, Zn2+ 20 mg/L and Ni2+ 20 mg/
L) without considering precipitation occurrence for copper and
zinc before the start of treatment.
As expected, the EC treatment is efcient in tap water without
any other addition of salts and for the two kinds of electrodes.
However, better efciency is observed when aluminum is used
particularly for zinc and nickel whose removal rates reached almost 100% after 60 min of electrolysis. For each experiment, the
mean electrolysis potential, pH and total alkalinity variations are
indicated in the corresponding gure. The pH variation is always
positive and is related to the cathodic reaction. An important decrease of total alkalinity is observed during the treatment. As discussed previously, this variation in alkalinity is caused by CaCO3
precipitation. Total hardness was not estimated here because of
the well-known interference of heavy metal ions during the titration with the EDTA solution. But hardness is assumed to follow
the same variation as alkalinity.
Three causes could explain high removal efciency when using
tap water without addition of Na2SO4 and NaCl:

115

Cu Conversion rate (%)

Cu Conversion rate (%)

A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

100
80
60
40
Without CaCl2
20

With CaCl2

0
60

2
120

100
80
60
40
20

Without CaCl2
With CaCl2

1803

60160

100
80
60
40
20

Without CaCl2
With CaCl2

3 180

100
80
60
40
20

Without CaCl2
With CaCl2

120

60
1
60

180

1202120

180 3180

Time (min)
Ni Conversion rate (%)

Time (min)
Ni Conversion rate (%)

180

0
60

100
80
60
40
20

1202 120

Time (min)
Zn Conversion rate (%)

Zn Conversion rate (%)

Time (min)

Without CaCl2
With CaCl2

100

80
60
40
20

Without CaCl2
With CaCl2

0
1
60

60

2
120

120

180

3180

60601

120 2120

Time (min)

Time (min)

(a)

(b)

180

3180

Fig. 7. Metal removal rates at different operating times (60, 120 or 180 min) for EC experiments conducted with iron electrodes in Grenoble tap water, with or without CaCl2
103 M, at (a) 0.5 A (7 A/m2) and (b) 1 A (14 A/m2).

(1) Precipitation of copper and zinc before EC, which anticipates

precipitation occurring for the same compounds at the vicinity of the cathode during the electrolytic treatment. However, precipitation before treatment cannot entirely explain
its efciency, particularly for zinc (only 10% of the metal is
concerned) and even more for nickel (no precipitation at
all is observed before treatment).
(2) pH increase during electrolysis: the pH evolves from the
value of 7.05 before electrolysis to a mean value of 7.9 after
180 min of treatment.
(3) Precipitation of calcium carbonate CaCO3.
At the current density of 14 A m2 the mean electrolytic potential between 0 and 60 min is 9 V when iron is used and 8.8 V with
Al. Therefore, the corresponding energy consumption is
0.60 kW h m3 and 0.59 kW h m3 respectively for Fe and Al after
1 h of EC. These values of energy consumption are very low compared with those found in the literature (see Table 1) and show
that EC treatment is more cost effective than expected.
3.4. Inuence of total hardness
In order to evaluate the inuence of total hardness on CaCO3
precipitation and on treatment efciency, some experiments were
conducted with addition of CaCl2 in tap water at a concentration of

103 mol/L, which corresponds to an increase in total hardness of

2 meq/L, and therefore to an increase of the saturation rate t of
the water given by [30]:

Ca2 CO2
3 
K 0s

where [Ca2+] and [CO2

3 ] are the calcium and carbonate concentration and K 0s is the apparent solubility product of CaCO3, namely
the solubility product expressed with the concentration of the species involved, not with their activity.
The saturation rate t indicates the distance existing between the
real water state and the equilibrium state between Ca2+, CO2
3 and
CaCO3, called calcium-carbonate equilibrium [30]. When t = 1,
the water is in equilibrium with respect to calcium carbonate. If
t < 1, the water is considered to be aggressive. This means that,
thermodynamically, it is liable to dissolve calcium carbonate. In
contrast, if t > 1, the water is said to be calcifying, indicating that,
thermodynamically, it is capable of precipitating calcium carbonate. The tendency to precipitation is all the more pronounced that
t is high [30].
Grenoble tap water is slightly calcifying with a saturation rate
of 1.2 at 20 C for the initial pH of the water (7.75). When CaCl2 is
added to Grenoble tap water with a concentration of 103 mol/L
the saturation rate reaches a value of 2 at 20 C for the same pH
(the saturation rates were calculated according to [30]). In these

A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

80
60
40
20

Without CaCl2
With CaCl2

0
160
60

Zn Conversion rate (%)

Cu Conversion rate (%)

100

1202120
Time (min)

100
80
60
40
20

100
80
60
40

Without CaCl2
20

Without CaCl2
With CaCl2

With CaCl2

180 3 180

601

2
120

60

100
80
60
40
20

Without CaCl2

3
180

With CaCl2

120

180

601

60

Time (min)

2
120
120
Time (min)

3
180180

100
Ni Conversion rate (%)

100
Ni Conversion rate (%)

3
180180

0
1
60

80
60
40
20

2
120
120
Time (min)

60

Zn Conversion rate (%)

Cu Conversion rate (%)

116

Without CaCl2
With CaCl2

60
40
20

Without CaCl2
With CaCl2

0
60

80

120
Time (min)

180

60

(a)

120
Time (min)

180

(b)

Fig. 8. Metal removal rates at different operating times (60, 120 or 180 min) for EC experiments conducted with aluminum electrodes in Grenoble tap water, with or without
CaCl2 103 M, at (a) 0.5 A (7 A/m2) and (b) 1 A (14 A/m2).

Table 4
Total alkalinity variations (meq/L) after 180 min of EC treatment in Grenoble tap
water with and without CaCl2 103 M.
Current (A)

0.5
1

Iron

Aluminum

No CaCl2

CaCl2 103 mol/L

No CaCl2

CaCl2 103 mol/L

1.92
2.16

2.20
2.34

1.86
2.00

1.96
2.20

does not lead to an improvement of the treatment. We can then

conclude that the role of CaCO3 in the mechanisms leading to removal of metals by EC is complex. Further studies will soon be con2+
ducted to study thoroughly the inuence of HCO
3 and Ca
concentrations on the precipitation of CaCO3 during the EC process
and to understand the role of this precipitation in metal
elimination.
4. Conclusion

conditions we can expect to increase the amount of CaCO3 precipitation and possibly to improve the treatment even more.
Figs. 7 and 8 present the results, obtained respectively with and
without addition of CaCl2 to Grenoble tap water, for EC experiments using iron or aluminum electrodes and for two different current densities, 7 and 14 A m2. No improvement on removal
efciency of the metals is observed following the addition of CaCl2.
On the contrary, an unexplained marked decrease is noticed in the
case of nickel with iron electrodes. The total alkalinity variations
are indicated in Table 4. In spite of an important Ca2+ addition,
whatever the current value, the increase in alkalinity elimination
rate is low in the presence of CaCl2 (about 0.2 meq/L). With regards
to the precipitation of CaCO3, it seems that a limit linked to the
initial concentration of HCO
3 is reached. Moreover and contrary
to our expectations, the additional amount of precipitated CaCO3

This study aimed at investigating the efciency of an EC process

on the removal of metallic ions present in natural water (Grenoble
tap water) containing bicarbonate and calcium ions.
The possibility of applying electrocoagulation without addition
of supporting salts was shown for natural water of low conductivity polluted by heavy metals. Metal removal was very efcient. We
particularly observed the occurrence of iron or aluminum dissolution in our conditions with no passivation of the electrodes.
The high removal efciency can be explained by the following
probable causes:
(1) Partial precipitation of copper and zinc before EC, which
anticipates precipitation occurrence for the same compounds at the vicinity of the cathode during the electrolytic
treatment. However, this precipitation, which concerns 75%

A. de Mello Ferreira et al. / Separation and Purication Technology 107 (2013) 109117

of copper ions and only 10% of zinc ions, consists of hardly

sedimentable particles. Therefore, EC treatment remains
essential for Cu, Zn and Ni removal by forming large ocs
whose decantation is quickly obtained.
(2) pH increase during electrolysis: this variation of pH, related
to water reduction on the cathode surface with production
of hydroxide ions, enhances metal hydroxide precipitation
and has then a positive effect on the removal.
(3) Precipitation of calcium carbonate CaCO3 from the bicarbonate and calcium ions present in the water.
This study was conducted with Grenoble tap water, which has a
slight tendency to precipitation (saturation rate hardly higher than
1). Further studies will be conducted with natural waters presenting different total hardness and total alkalinity values to understand the precise role of calcium carbonate precipitation in metal
elimination by EC.
Acknowledgments
This study was conducted in the framework of a co-operation
between the CEFET institute of Belo Horizonte (Brazil) and the
IUT1 institute of Grenoble (France). We want to thank the following students involved in this exchange program: Hortncia Nunez
Da Silva, Audrey Brunet-Manquat, Simon Ponton and Vianney Patrat-Delon.

References
[1] Memento technique de leau, nineth ed., Degrmont, Lavoisier Tech & Doc,
Paris, 1989.
[2] X.M. Chen, G.H. Chen, P.L. Yue, Investigation on the electrolysis voltage of
electrocoagulation, Chem. Eng. Sci. 57 (2002) 24492455.
[3] E. Butler, Y.T. Hung, R.Y.L. Yeh, M.S. Al Ahmad, Electrocoagulation in
wastewater treatment, Water 3 (2011) 495525.
[4] E. Gengec, M. Kobya, E. Demirbas, A. Akyol, K. Oktor, Optimization of bakers
yeast wastewater using response surface methodology by electrocoagulation,
Desalination 286 (2012) 200209.
[5] A. Vazquez, I. Rodriguez, I. Lazaro, Primary potential and current density
distribution analysis: a rst approach for designing electrocoagulation
reactors, Chem. Eng. J. 179 (2012) 253261.
[6] A. Akyol, Treatment of paint manufacturing wastewater by electrocoagulation,
Desalination 285 (2012) 9199.
[7] M. Kobya, O. Taner Can, M. Bayramoglu, Treatment of textile wastewaters by
electrocoagulation using iron and aluminum electrodes, J. Hazard. Mater. B100
(2003) 163178.

117

[8] F. Ilhan, U. Kurt, O. Apaydin, M. Talha Gonullu, Treatment of leachate by

electrocoagulation using aluminium and iron electrodes, J. Hazard. Mater. 154
(2008) 381389.
[9] G. Mouedhen, M. Feki, M. De Petris Wery, H.F. Ayedi, Behavior of aluminium
electrodes in electrocoagulation process, J. Hazard. Mater. 150 (2008) 124135.
[10] I. Heidmann, W. Calmano, Removal of Zn(II), Cu(II), Ni(II), Ag(I) and Cr(VI)
present in aqueous solutions by aluminium electrocoagulation, J. Hazard.
Mater. 152 (2008) 934941.
[11] F. Akbal, S. Camci, Copper, chromium and nickel removal from metal plating
wastewater by electrocoagulation, Desalination 269 (2011) 214222.
[12] F. Akbal, S. Camci, Comparison of electrocoagulation and chemical coagulation
for heavy metal removal, Chem. Eng. Technol. 33 (2010) 16551664.
[13] Hanay, H. Hasar, Effect of anions on removing Cu2+, Mn2+ and Zn2+ in
electrocoagulation process using aluminium electrodes, J. Hazard. Mater. 189
(2011) 572576.
[14] E. Bazrafshan, A.H. Mahvi, S. Nasseri, A.R. Mesdaghinia, F. Vaezi, Sh. Nazmara,
Removal of cadmium from industrial efuents by electrocoagulation process
using iron electrodes, Iran. J. Environ. Health. Sci. Eng. 3 (2006) 261266.
[15] B.A. Aji, Y. Yavuz, A.S. Koparal, Electrocoagulation of heavy metals containing
model wastewater using monopolar iron electrodes, Sep. Purif. Technol. 86
(2012) 248254.
[16] N. Adhoum, L. Monser, N. Bellakhal, J.E. Belgaied, Treatment of electroplating
wastewater containing Cu2+, Zn2+ and Cr(VI) by electrocoagulation, J. Hazard.
Mater. B112 (2004) 207213.
[17] I. Kabdash, T. Arslan, T. lmez-hanci, I. Arslan-Alaton, O. Tnay, Complexing
agent and heavy metal removals from metal plating efuent by
eletcrocoagulation with stainless steel electrodes, J. Hazard. Mater. B165
(2009) 838845.
[18] A.K. Golder, A.N. Samanta, S. Ray, Removal of trivalent chromium by
electrocoagulation, Sep. Purif. Technol. 53 (2007) 3341.
[19] G. Sayiner, F. Kandemirli, A. Dimoglo, Evaluation of boron removal by
electrocoagulation using iron and aluminium electrodes, Desalination 230
(2008) 205212.
[20] N. Bektas, H. Akbulut, H. Inan, A. Dimoglo, Removal of phosphate from aqueous
solutions by EC, J. Hazard. Mater. B106 (2004) 101105.
[21] A.S. Koparal, U.B. Ogutveren, Removal of nitrate from water by
electroreduction and electrocoagulation, J. Hazard. Mater. B89 (2002) 8394.
[22] M.Y.A. Mollah, P. Morkovsky, J.A.G. Gomes, M. Kesmez, J. Parga, D.L. Cocke,
Fundamentals, present and future perspectives of electrocoagulation, J.
Hazard. Mater. B114 (2004) 199210.
[23] M. Rebhun, M. Lurie, Control of organic-matter by coagulation and oc
separation, Water Sci. Technol. 27 (1993) 120.
[24] P.N. Johnson, A. Amirtharajah, Ferric-chloride and alum as single and dual
coagulants, J. AWWA 75 (1983) 232239.
[25] V.L. Snoeyink, D. Jenkins, Water Chemistry, John Wiley & Sons, New York,
1980.
[26] W. Djoudi, F. Aissani-Benissad, P. Ozil, Flow modeling in electrochemical
tubular reactor containing volumetric electrode: application to copper
cementation reaction, Chem. Eng. Res. Des. 90 (2012) 15821589.
[27] A. Vik, D.A. Carlson, A.S. Eikum, E.T. Gjessing, Electrocoagulation of potable
water, Water Res. 18 (1984) 13551360.
[28] M. Bernard, F. Busnot, Usuel de Chimie Gnrale et Minrale, Bordas, Paris,
1984.
[29] C.W. Davies, Ion Association, Butterworths, London, 1962.
[30] L. Legrand, G. Poirier, P. Leroy, Les quilibres carboniques et lquilibre calcocarbonique dans les eaux naturelles. Collection AGHTM, Eyrolles, Paris, 1981.