Technical Note

Removal of organic pollutants in industrial wastewater with an

integrated system of copper electrocoagulation and electrogenerated
H
2
O
2
Carlos Barrera-Daz
a,
, Bernado Frontana-Uribe
a
, Bryan Bilyeu
b
a
Centro Conjunto de Investigacin en Qumica Sustentable, UAEM-UNAM, Carretera Toluca-Atlacomulco, Km 14.5, Unidad El Rosedal, C.P. 50200 Toluca, Estado de Mxico, Mexico
b
Dept. Chemistry, Xavier University of Louisiana, New Orleans, LA 70125, United States
h i g h l i g h t s
A Cu electrocoagulation is effective in
pollutants removal of industrial
wastewater.
The electrocoagulation is enhanced
when H
2
O
2
electrochemically
produced is added.
Optimal conditions are initial
pH = 2.8, j = 14.2 mA cm
2
and 40 mL
of H
2
O
2
.
The system conguration is quite
simple and easy to operate.
The coupled system is effective for
disinfection and nal [Cu] is less than
4 ppm.
g r a p h i c a l a b s t r a c t
Cu electrocoagulation
H
2
O
2
electrogeneration
Removal of COD by 78%, BOD
5
by 81%,
color by 97% and fecal coliforms by 99.9%.
a r t i c l e i n f o
Article history:
Received 23 October 2013
Received in revised form 7 January 2014
Accepted 8 January 2014
Available online 18 February 2014
Keywords:
COD
Hydrogen peroxide
Industrial wastewater
Copper
Electrocoagulation
a b s t r a c t
The effectiveness of organics removal of an integrated electrochemical process, namely, electrocoagula-
tion with copper ions followed by the use of electrogenerated hydrogen peroxide was evaluated with an
industrial wastewater. The copper (II) ions addition into the wastewater using electro-dissolution of
copper electrodes, reduces the chemical oxygen demand (COD) by 56% after 30 min of treatment, under
optimal conditions of pH 2,8 and 14.2 mA cm
2
of current density. The integrated electrochemical
process reduces the COD by 78%, BOD
5
by 81%, color by 97% and fecal coliforms by 99.9%. The wastewater
quality was monitored using UVVis spectrometry and Z-potential in order to characterize raw and
treated wastewater.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Industrial efuents are very difcult to treat effectively due to
the large variations in both composition and load and the nature
of the organic molecules themselves (Riera-Torres et al., 2010;
Tsolaki et al., 2010; Secula et al., 2011). This variation is even more
extreme in mixed-industry wastewater froman industrial park and
tends to include stable, refractory organics. Electrochemical
advanced oxidation processes (EAOP) involve the generation of
highly reactive intermediate species like

OH radicals that initiate
the oxidation of organic compounds (Ibanez and Rajeshwar,
1997). These techniques are effective for the treatment of indus-
trial wastewater because they have high efciency, easy operation
http://dx.doi.org/10.1016/j.chemosphere.2014.01.026
0045-6535/ 2014 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +52 (722) 2173890; fax: +52 (722) 2175109.
E-mail address: cbd0044@yahoo.com (C. Barrera-Daz).
Chemosphere 105 (2014) 160164
Contents lists available at ScienceDirect
Chemosphere
j our nal homepage: www. el sevi er . com/ l ocat e/ chemospher e
and environmental compatibility (Caizares et al., 2009; del Rio
et al., 2011). Electrocoagulation which involves the electro-dissolu-
tion of sacricial metal electrodes (usually aluminum or iron) into
coagulating metal ions has been used to remove color and cloudi-
ness from turbid industrial wastewater (Barrera-Daz et al., 2003;
Bernal-Martnez et al., 2010; Bayar et al., 2011; Siles et al., 2011).
Until now, little attention has being paid to other metals such as
copper (Montero-Ocampo et al., 2007). Indeed, a very recent study
found that the use of copper electrodes increased arsenite removal
to 99.6% without any secondary contamination (Ali et al., 2013).
However, copper electrode electrocoagulation has not been applied
to industrial efuent electrocoagulation process. The main concern
in this copper based process is secondary contamination by copper
ions, which is regulated in nal wastewater disposition; the
maximum allowable concentration of copper in Mexico for
example is 4 mg L
1
(NOM-001-ECOL, 1996).
H
2
O
2
Cu(II) ions system has been reported as a source of

OH
radicals. In general, there are two mechanisms proposed for this
reaction: the free radical pathway in which Cu(II) oxidizes H
2
O
2
to form

OH, and the complex mechanism where Cu(II) forms a
complex with peroxide with no radical species (Moffett and Zika,
1987; Robbins and Drago, 1997). Also, the reaction of Cu(I) with
H
2
O
2
has been reported to follow a Fenton-like mechanism in
which the formation of

OH is the main path for pollutant oxidation
(Sharma and Millero, 1989; Gunther et al., 1995).
The goal of this work is to reduce the color, turbidity, COD, and
fecal coliforms in a real complex industry efuent. For this, not
only copper electrocoagulation was carried out but also the study
of the effect of adding hydrogen peroxide into the process. It is
proposed that H
2
O
2
can react with the remaining copper in solu-
tion via a Fenton like reaction and to increase the organics removal.
The optimization of the operational parameters of the proposed
process like pH, and peroxide concentration were studied.
2. Materials and methods
2.1. Wastewater samples
Wastewater samples were collected from the treatment plant of
an industrial park which receives the discharge of 144 different
facilities. Therefore, the chemical composition of this efuent is
rather complex. Samples were collected in plastic containers and
cooled to 4 C, then transported to laboratory for analysis and
treatment. The principal physicochemical parameters of the
wastewater are listed in Table 1.
2.2. Electrocoagulation reactor
A batch electrochemical reactor was constructed for this pri-
mary treatment step. The reactor cell contained 2 parallel monopo-
lar copper electrodes. Each electrode was 7.0 cm by 5.0 cm with a
surface area of 35 cm
2
. The total anodic surface (A
a
) was 70 cm
2
(including both sides). A direct-current power source supplied
the system with 1 A, corresponding to current density of
14.3 mA cm
2
, according with a previous work (Holt et al., 2002,
2004). While the capacity of the reactor vessel was 1.0 L, 0.6 L
was used at all experiments. A 10 mL sample was taken every
5 min during the 30 min of treatment. The pH of the aqueous
solution was adjusted using sulfuric acid. All experiments were
carried out by duplicate.
2.3. Galvanostatic production of H
2
O
2
A divided H-type cell was used with a pre-activated cationic
exchange membrane (Naon 424) supported on a ange. The
peroxide was produced in an acidic solution (pH = 2.0, conductivity
18.1 mS m
1
) prepared using 0.04 M Na
2
SO
4
and 0.05 M NaHSO
4
(both Fluka analytical grade). The catholyte was saturated with
O
2(g)
(99.96%, Infra) by bubbling it for 20 min through a ne
dispersing sintered glass tube before each experiment. The O
2(g)
supply was maintained during the entire electrolysis procedure
with the dispersing tube located as close as possible to the cathode
ensuring that the O
2(g)
bubbles reached the electrode surface.
Magnetic stirring was used during the entire electrolysis process
in both electrolyte chambers containing the acidic sulfate solution.
The cathode and anode consisted of 40 cm
2
boron doped diamond
(BDD) plates. The required current density (1.52 mA cm
2
) was
applied to the cathode with a power source maintaining the catho-
dic half-cell potential (E
cath
) at 1.1 to 1.25 V vs. SCE. Aliquots
(500 mL) of the oxygenated pH 2.0 solution were used as anolyte
and catholyte in all experiments. These solutions were recirculated
using peristaltic pumps (Master Flex L/S, model 77200-62) with a
ow rate of 4001000 mL min
1
. The H
2
O
2
concentration was
determined at 450 nm with a Cary-2000 spectrophotometer, after
reaction with ammonium metavanadate. The electrolysis was
stopped when the H
2
O
2
concentration exceeded 100 ppm (ca. 3 h
of electrolysis) (Espinoza-Montero et al., 2013).
2.4. Methods of analysis
The initial evaluations of the treatments were determined by
analysis of the COD. However, once the optimal conditions were
found the raw and treated wastewater samples were analyzed
for color, turbidity, pH, total solids, BOD
5
, and fecal coliforms using
the Standard Methods (APHA-AWWA-WPCF, 1998).
2.5. Zeta potential measurements
The Z-potential determination of wastewater was obtained
using a Zetasizer Nano-Z series (Malvern Instrument GmbH, UK).
Wastewater samples are injected into a folded capillary cell and
introduced into the equipment. The f-potentials reported here
were calculated from the average of three separate injections per
sample (Narong and James, 2006).
2.6. Copper quantication
The concentration of copper ions in solution, was determined
using a PerkinElmer 2380 atomic absorption spectrophotometer.
All calibrations and procedures were carried out in accordance
with standard methods (APHA-AWWA-WPCF, 1998).
Table 1
Physicochemical and microbiological parameters of wastewater under study prior
treatment and after combined electrochemical treatment.
Parameters Wastewater
from
industrial
treatment
plant
Combined treatment
(Electrocoagulation + H
2
O
2
electrogenerated)
Removal
%
COD (mg L
1
) 860 190 78
BOD
5
(mg L
1
) 481 90 81
Color (Pt-Co) 2500 70 97
Turbidity (NTU) 110 15 84
pH 7.8 (0.2) Initial 2.8, nal 7 (0.2)
[Cu] (mg L
1
) >1 4 (0.1)
Total solids
(mg L
1
)
3336 43 99
Fecal coliforms,
(MPN/100 mL)
160000 >3 99
C. Barrera-Daz et al. / Chemosphere 105 (2014) 160164 161
3. Results and discussion
3.1. Copper electrocoagulation, primary treatment
The electrocoagulation process is controlled by operational
parameters, such as current density (j), time, and initial pH. The
COD as a function of electrochemical treatment time with
j = 14.3 mA cm
2
at different initial pH values is shown in Fig. 1.
The results indicate that the COD drops quickly for the rst
20 min of the process then slows to a stable continuous process.
Under acidic conditions the COD removal reaches an efciency of
around 58%, whereas at natural wastewater pH (7.8) it only
reaches 30%, after 30 min of treatment.
The pH in the solution was not controlled and it changes
towards more basic with the electrolysis time. As indicates reac-
tion (2), the cathodic reaction is water reduction that generates
OH

ions to the solution resulting in pH increase during the

electrolysis (Fig. 1).
According to the Pourbaix diagram (E-pH) for copper, Cu
2+
gen-
erated by the electrodissolution is soluble only at pH values lower
than 7 and as copper concentration increases, the pH region where
this cation is soluble decreases. Also, as pH increases, Cu
2+
is not
soluble and generates CuO
(s)
via the dehydration of Cu(OH)
2(s)
(Beverskog and Puigdomenech, 1997). This behavior can explain
the better COD removal observed in the electrocoagulation exper-
iment for pH = 2.8; when the electrocoagulation starts at this pH,
the copper ions generated by the anodic reaction (1) in solution
give the hexahydrated copper complex reaction (3). They are trans-
ported to the cathode, where at the basic interface due to the high
OH

ions concentration the hexa-aqua copper complex reacts to

generate Cu(OH)
2(s)
species. This reaction generates the dark blue
occules characteristic of this compound, which are observed to
deposit in the bottom of the electrocoagulation reactor. These
copper hydroxide species may behave in a similar way to the Fe
or Al hydroxides occules, typically used in electrocoagulation
processes that adsorb organic pollutants and are responsible for
the COD removal observed. When the initial wastewater solution
has a pH = 2.8, the generation of the occules is very slow because
the only basic region is the cathodic interface, and the OH

concen-
tration increases with the electrolysis time (Fig. 1). This makes the
occules at the beginning small then little by little they grow,
aggregating better and trapping more organic matter. Thus the
slowpHincrease frompH = 2.8 to a neutral value of the electrolysis
solution is benecial for the wastewater treatment. Both reactions
of the electrolysis cell are useful for the process; the anode
provides the copper ions and the cathode generates the basic med-
ia to generate the Cu(OH)
2(s)
occules. On the other hand, when the
wastewater initial solution has a pH = 5 or 7, the Cu(OH)
2(s)
occules are rapidly generated on the anode interface. This limits
the interaction time with the pollutants and due to a smaller
contact surface the efciency of the process in these experimental
conditions is lower than in acidic media.
The electrocoagulation of wastewater using copper electrodes
takes place according to the following (Eqs. (1)(4)) (Baes and
Mesmer, 1986; Puigdomenech, 1997).
Anodic reaction:
Cu
s
! Cu
2
aq
2e

1
Cathodic reactions:
2H
2
O
l
2e

! 2OH

aq
H
2g
2
Solution reactions
Cu
2
aq
6H
3
O

aq
! CuH
2
O
6

2
aq
6H

aq
3
CuH
2
O
6

2
aq
2OH

aq
! CuOH
2s
6H
2
O
aq
4
Overall reaction:
Cu
s
2H
2
O
l
! CuOH
2s
H
2g
5
As previously described in Section 2.6 a copper quantication
was performed after the experiments. The results indicate that
the amount of Cu ions presents in the supernatant solution is
below 4 mg L
1
. This agrees with the solubility characteristic of
the Cu(OH)
2(s)
and the Pourboix diagrams since the nal pH is
above 7.0 as shown in Fig. 1 (Beverskog and Puigdomenech, 1997).
3.2. Effect of the addition of only H
2
O
2
into wastewater
Hydrogen peroxide was generated in an acidic media
(pH = 2.83.0) by oxygen electroreduction on BDD electrodes as
indicated in Section 2.3. When 10, 20, 30 and 40 mL of H
2
O
2
0
1
2
3
4
5
6
7
8
0
100
200
300
400
500
600
700
800
900
1000
0 5 10 15 20 25 30
C
O
D
/

m
g

L
-
1
Treatment time / min
A
q
u
e
o
u
s
S
o
l
u
t
i
o
n

p
H
Fig. 1. COD removal as a function of treatment time at pH values of 7.8 (raw) (e), 7.0 (j), 5.0 (D) and 2.8 (d). Increment of the pH as a function of treatment time (o).
162 C. Barrera-Daz et al. / Chemosphere 105 (2014) 160164
solution were added into 0.6 L of wastewater, COD decreases of
only 6%, 7%, 9% and 11% respectively were observed. This conrms
that H
2
O
2
alone has a low capacity for eliminating the organics
contained in the sample.
3.3. Integrated process: Electrocoagulation plus addition of
electrogenerated H
2
O
2
As previously show in Fig. 1, the best COD removal was
achieved in acidic conditions, thus experiments adding H
2
O
2
were
performed at acidic pH. In Fig. 2 the results of the COD removal
after the addition of different quantities of H
2
O
2
are shown. These
results indicate that a higher dose of H
2
O
2
increases the COD
removal. The maximum COD removal is around 80%, which repre-
sents an extra 20% COD removal as compared to the copper
electrocoagulation alone. This additional organics elimination can
be rationalized by a Fenton like reaction between Cu(II) ions that
remain in solution and the peroxide to generate

OH radicals,
which oxidize the organics that could not be adsorbed by the elec-
trocoagulation treatment. The color behavior followed the same
0
100
200
300
400
500
600
700
800
900
1000
0 5 10 15 20 25 30 35
C
O
D

/

m
g

L
-
1
Treatment time / min
0
500
1000
1500
2000
2500
3000
0 5 10 15 20 25 30 35
C
o
l
o
r

/

P
t
-
C
o

Treatment time / min
Fig. 2. COD removal as a function of treatment time when different doses of H
2
O
2
were added into solution (e) 0.010, (j) 0.020, (D) 0.030 and (d) 0.040 L. Inset: color
decrease as a function of treatment time when different doses of H
2
O
2
were added into solution (e) 0.010, (j) 0.020, (D) 0.030 and (d) 0.040 L. Initial pH = 2.8.
-30
-25
-20
-15
-10
-5
0
0 5 10 15 20 25 30 35
Treatment time / min
Z


p
o
t
e
n
t
i
a
l

/

m
V
0
0.5
1
1.5
2
2.5
0 200 400 600 800 1000
A
Wavelength / nm
Fig. 3. Z-potential of treated industrial wastewater as a function of treatment time. Inset UVVis spectra changes of the raw (e) and (d) treated wastewater in the range of
200900 nm.
C. Barrera-Daz et al. / Chemosphere 105 (2014) 160164 163
trend independently of the quantity of H
2
O
2
added, which indi-
cates that there are few colored species in solution and they are
degraded with low concentrations of H
2
O
2
.
Fig. 3 shows the zeta potential of wastewater as a function of
the integrated process treatment time for a pH of 2.8. The colloidal
system is stable, with the particles being negatively charged. When
the Cu
2+
is electrochemically added, the zeta potential decreases
monotonically to an isoelectric point. The isoelectric point
indicates that the positive ions can destabilize negatively charged
colloids by charge neutralization, the availability of positively
charged copper complexes is an important consideration for coag-
ulation of negatively charged colloids (Sharma and Millero, 1989).
The UVVis spectra of the raw and treated wastewater are shown
in inset of Fig. 3. The raw wastewater shows considerable absor-
bance in the visible range of 200400 nm which conrms that it
is highly colored as presented in Table 1. However, this color is
effectively reduced by the electrochemical treatment.
Table 1 shows the characterization of the raw wastewater and
that treated with the integrated process, using the best conditions
found in this study. It can be observed that the BOD
5
and COD
removal are 81% and 78%, respectively; the color of the wastewater
decreased by 97% while the turbidity reduction was 84%. A very
interesting effect is the disinfection by the electrochemical process,
resulting in a 99.9% fecal coliforms reduction. This is in accordance
with previous studies using electro-Fenton (Durn Moreno et al.,
2004). Indeed, electrocoagulation occurs when metal cations
combined with the negative particles carried toward the anode
by electrophoretic motion. In EC the destabilization mechanism
of contaminants, particle suspension and breaking emulsions are
by (1) Compression of the diffuse double layer around the charged
species by the interactions of ions generated by oxidation of the
sacricial anode. (2) Charge neutralization of the ionic species
present in wastewater. A zero net charge results in the process.
(3) Floc formation: the oc formed as a result of coagulation
creates a sludge blanket that entraps and bridges particles in the
aqueous medium (Comninellis and Chen, 2010).
4. Conclusions
The integrated electrochemical method presented in this study
reduces satisfactorily the concentration of organic pollutants in
wastewater. The use of electrogenerated copper ions into waste-
water reduces the amount of COD via rst an electrocoagulation
process, where the cathodic reaction is used to produce the
Cu(OH)
2
occules and, second using a Fenton like reaction with
electrogenerated H
2
O
2
produced by an ex-cell process. All the
colloidal matter is removed from wastewater as described in the
Z potential plots and in the COD, total solids and BOD
5
measure-
ments. The process practically eliminates the amount of fecal
coliforms present in the industrial wastewater.
Acknowledgments
The authors wish to acknowledge the support given by the
UAEM through the Project 3409/2013M and nancial support from
CONACYT in Project 153828 and 179356 as well as PAPIIT UNAM
202011 are greatly appreciated.
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