Separation and Purification Technology 120 (2013) 386–391

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Separation and Purification Technology

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

Electrocoagulation of yogurt industry wastewater and the production of

ceramic pigments from the sludge
Umran Tezcan Un a,⇑, Emel Ozel b
a
Anadolu University, Department of Environmental Engineering, Eskisehir, Turkey
b
Anadolu University, Department of Materials Science and Engineering, Eskisehir, Turkey

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

Article history: In this study, the treatment of strained (condensed) yogurt wastewater using a uniquely designed iron
Received 31 October 2012 reactor with electrocoagulation and the sludge produced during the electrocoagulation as a raw material
Received in revised form 28 August 2013 in the production of ceramic pigment were investigated. A rectangular iron cathode compartment and
Accepted 29 September 2013
parallel plate anodes were used, and various operating parameters, such as the current density, the elec-
Available online 10 October 2013
trolysis time, the supporting electrolyte concentration, the initial pH and the polyelectrolytes addition,
were examined in order to determine the best conditions for intensifying the performance of the process.
Keywords:
It was seen from the experiments that the COD removal efficiency was increased with the increasing cur-
Iron electrode
COD
rent density from 20 to 30 mA/cm2 and time while it was decreased with the increasing Na2SO4 concen-
Dairy industry tration from 0.05 to 0.2 M. The best treatment efficiency was observed at the original pH of the
Condensed yogurt wastewater (pH 4.53) and the cationic polyelectrolyte showed better performance than the anionic poly-
Ceramic pigment electrolyte. The strained yogurt wastewater, with a COD concentration of 6500 mg/L, was treated with a
removal efficiency of 84% after 90 min of electrocoagulation with the addition of 0.75 g/L cationic poly-
electrolyte. The sludge produced during the electrocoagulation was characterised and used as an iron
source to produce brown and black inorganic ceramic pigments because of their high iron oxide content.
The results show that this specially designed electrochemical reactor is an effective alternative for the
treatment of strained yogurt wastewater. It also shows that the sludge produced during electrocoagula-
tion can be used as a raw material in the ceramic industry and that it can be converted from waste to a
value-added product.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction
Dairy industries are involved in the manufacturing of various
types of milk products, such as fluid milk, butter, cheese, yogurt,
condensed milk, flavoured milk, milk powder, and ice cream. Yo-
gurt is a fermented milk product with a custard-like consistency
that differentiates it from other fermented milk products. The mar-
ket now offers a vast array of yogurts, and yogurt is made with a
variety of ingredients, including milk, sugar, stabilisers, fruits and
flavourings, as well as bacterial culture. Strained (condensed) yo-
gurt is a thick consistency yogurt that is obtained by filtering its
liquid.
The production of yogurt generates large amounts of wastewa-
ter characterised by high biological oxygen demand (BOD) and
chemical oxygen demand (COD) concentrations, reflecting their
high organic content and high levels of dissolved or suspended sol-
⇑ Corresponding author. Address: Anadolu University, Department of Environ-
mental Engineering, 26555 Eskisehir, Turkey. Tel.: +90 222 321 35 50x6418; fax:
+90 222 323 95 01.
E-mail address: utezcan@anadolu.edu.tr (U. Tezcan Un).
ids, including fats, oilsgrease and nutrients. Therefore, this waste-
water requires proper attention before disposal.
Treatment of dairy wastewaters are studied by several
researchers. The biological methods such as anaerobic sludge blan-
ket (UASB) reactor [1], two-stage anaerobic sequencing batch reac-
tor [2], aerated reactor [3] were intensively used. Additionally the
physical/chemical methods such as coagulation/flocculation [4],
constructed wetlands and intermittent sand [5], adsorption [6]
were also used. Among physical/chemical methods, electrocoagu-
lation (EC) is one of the efficient processes which utilised for the
removal of variety of contaminants from wastewater such as heavy
metal [7,8] and organics.
The electrocoagulation of dairy effluent has already been car-
ried out. Bensadok and co-workers [9] used two parallel plate elec-
trodes made of aluminium and platinised titanium (Ti/Pt) for the
treatment of synthetically prepared dairy effluent using commer-
cial milk powder. Kushwaha and co-workers also prepared syn-
thetic dairy effluent using commercial milk using two pairs of
aluminium plates [10] and four iron electrodes [11] connected in
parallel. Tchamango and co-workers [12] also treated artificial
dairy effluent using a pair of aluminium electrodes. Real milk

1383-5866/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2013.09.031
 U. Tezcan Un, E. Ozel / Separation and Purification Technology 120 (2013) 386–391
industry wastewater was treated by Yavuz and co-workers [13]
using three pairs of parallel iron and aluminium electrodes and
by Sengil and Ozacar [14] using four iron electrodes in parallel con-
nection. Although the electrocoagulation of dairy wastewater has
been utilised by various researchers, no report of the treatment
of yogurt industry wastewater by electrocoagulation has been
encountered in the current literature. Furthermore, the studies in
the field of electrocoagulation have mainly focused on two param-
eters: the electrode materials and the configuration of the parallel
plate electrodes. The electrocoagulation studies failed to examine
the usage of monotype reactors.
Although electrocoagulation has some advantages, such as no
added chemicals, this method presents a high removal of BOD
and COD. The inherent disadvantage of this method is the genera-
tion of chemical sludge (solid waste) and its classification as haz-
ardous waste requires the need for a secure land-filling of
hazardous solid wastes. Because of the unavailability of any suit-
able open area, the disposal of sludge creates a problem. In recent
years, certain studies [15–19] have focused on the characterisation
of the sludge produced during electrocoagulation. However, the
evaluation of the electrocoagulation sludge as a raw material in
any industry remains incomplete and is very important from an
environmental point of view. The recycling of industrial waste
and its natural sub-products has created a growing interest in
using them as an alternative and less-expensive raw material.
Therefore, the solid waste from industrial practices, such as elec-
troplating [20], coal mining [21], and Ni/Cr galvanising [22,23],
have been used as raw materials in the synthesis of ceramic pig-
ments. Because of the valuable metal content, the production of
ceramic pigments using electrocoagulation sludge as a raw mate-
rial has environmental and economic benefits because it converts
the waste into value-added products.
In this study, the treatment of yogurt industry wastewater by
electrocoagulation using a reactor designed differently from those
in previous studies was performed. The performance of the reactor
was evaluated based on various operational parameters, such as
the current density, the electrolysis time, the supporting electro-
lyte dosage, the initial pH and the addition of polyelectrolyte.
Afterwards, the sludge produced during the electrocoagulation of
the yogurt industry wastewater was used in the production of
black and brown inorganic ceramic pigments to reduce the envi-
ronmental effects of the sludge and the pigment price.
2. Experimental procedure
2.1. Electrocoagulation of strained yogurt wastewater
2.1.1. Materials
The effluent used throughout this study was obtained from a
strained yogurt factory in Antalya, Turkey. It was collected from
a line at the last stage of the yogurt filtration process before the
equalisation tank. It was typically turbid and had a pH of 4.53
and a COD of 6500 mg/L. The pH values were adjusted using
0.1 M H2SO4 and/or 0.1 M NaOH whenever the experiments re-
quired this pH modification. All of the reagents used in this work
were of analytical grade and were used without any further
purification.
2.1.2. Electrochemical treatment
Electrochemical treatments were carried out in a batch electro-
lytic cell. The cathode compartment was a rectangular iron elec-
trode with a dimension of 15 cm (length)  6 cm (width)  5 cm
(depth). The anode pack consisted of six pieces of iron plates
(5.5  4 cm) situated 2 cm apart. The anodes with a total immersed
surface area of 216 cm2 were incorporated into the cathode com-
387
partment 1 cm above the bottom. The experimental set-up used
in this study is shown in Fig. 1.
In each run, 400 ml of wastewater was placed into the cathode
compartment without any pre-treatment or dilution. Na2SO4 was
added as a supporting electrolyte to increase the conductivity,
and the pH was adjusted as required. The anode pack consisted
of six iron plates submerged into the cathode compartment con-
taining the wastewater. An initial sample was taken, and current
was applied to the circuit for 90 min. The anode and cathode sets
were connected to the positive and negative outlets, respectively,
of a DC power source (Statron, Type 2257). Slow agitation was im-
posed with a magnetic stirrer at 100 rpm during electrocoagulation
to provide contact between the colloids and the destabilising spe-
cies. All the runs were performed at room temperature. The pH and
the conductivity were monitored during electrocoagulation using a
pH-meter (Hanna Ins. 301) and a conductivity meter (Radiometer
Pioneer 30). Samples taken periodically and at end of the experi-
ment were centrifuged before analysis. The COD was measured
after the digestion of the resulting supernatant using a Hach COD
Digester, and the solution was analysed for COD using the titrimet-
ric method. All the analyses were repeated twice. The electrodes
were polished, washed with dilute H2SO4 and rinsed with distilled
water before each run.
2.2. Sludge characterisation and pigment production
After the electrocoagulation the bulk contains sludge and trea-
ted wastewater was poured into the glass column for settling the
sludge, settled for 24 h. Sludge was separated from the treated
wastewater by pouring the wastewater to the beaker. Then sludge
was dried in an drying oven (Nuve Model No:FN 120) at 100 °C for
24 h to eliminate its moisture until no moisture remains. Careful
sampling and homogenising were employed to assure reasonable
consistency in the sludge. The chemical composition of the sludge
was determined using an X-ray fluorescence spectrometer (XRF)
(RIGAKU, Rix 2000). The phases present in the sludge were deter-
mined using an X-ray diffractometer (XRD) (RIGAKU, D/Max-IIIC)
with Ni-filtered, Cu Ka radiation with a goniometer speed of 1°/s.
To produce pigments, the sludge was mixed with Cr2O3 (Merck),
Al2O3 (industrial grade), and ZnO (Merck) for a brown colour and
Co3O4 (Merck) for a black colour. The composition of the brown
pigment consisted of 17 wt% Fe2O3, 17 wt% Cr2O3, 16 wt% Al2O3
and 50 wt% ZnO, whereas the black pigment contained 75 wt%
Fe2O3 and 25 wt% Co3O4. The mixtures were ground for one hour
in a planetary ball mill containing water to obtain very homoge-
neous slurries. The slurries were then dried at 100 °C. Calcinations
Fig. 1. The experimental set up.
388 U. Tezcan Un, E. Ozel / Separation and Purification Technology 120 (2013) 386–391

were carried out in an electric furnace for three hours at 1250 °C 90

and 1000 °C for the brown and black pigments, respectively, in 80

COD Removal Efficiency, %

accordance with the literature [24,25]. The calcined pigment prod-
ucts were then ground in water in a ball mill for an hour and
washed with water to remove any undesirable soluble salts that
might have negative effects during glazing. Pigments with a
5 wt% were added to a wall tile transparent glaze applied onto
the ceramic tiles. The glazed tiles were fired at 1100 °C for
45 min. The ceramic tiles, glazes and porcelainised tile granules
were supplied from a ceramic factory in Eskisehir, Turkey.
A preliminary characterisation of the pigments involved the
identification (by XRD) of the main crystalline phases formed upon
firing and the measurements of the CIE Lab colour parameters
using a spectrophotometer (MINOLTA-3600 d). These parameters
were measured for an illuminant D65 following the CIE-Lab col-
orimetric method recommended by the CIE (Commission Interna-
tionale del’Eclairage). In this system, L is the degree of lightness
or darkness of the colour in relation to the scale ranging from white
(L = 100) to black (L = 0). a is the scale ranging from the green
(a) to the red (+a) axis and b is the scale extending from the
blue (b) to the yellow (+b) axis.
3. Results and discussion
3.1. Electrocoagulation of strained yogurt wastewater
3.1.1. Effect of current density and electrolysis time
The most significant operational parameter is the current den-
sity that is determinant on the quantity of iron generated. To inves-
tigate the effect of current density, a series of experiments were
carried out with the current density varying from 20 to 30 mA/
cm2 at the original pH and 0.1 M Na2SO4. When the current density
was increased from 20 to 30 mA/cm2, the COD removal efficiency
was increased from 56.4% to 76.4%, as shown in Fig. 2. As the cur-
rent density increased, comparable enhancements in the removal
efficiency of the COD were observed as expected from Faraday’s
Law (Eq. (1)), which can be written as a relation between the cur-
rent density and the amount of substance dissolved.
itM
m¼
nF
where m is the mass of iron dissolved (g Fe/cm2); i the current den-
sity (A/cm2); t the time (s); M the molecular weight of Fe (M = 56); n
the number of electrons involved in the oxidation reaction (n = 2);
and F Faraday’s constant, 96,500 C/mol.
With an increase in the current density, the amount of metal
oxidised also increased, resulting in a greater amount of hydroxide
90
80
COD Removal Efficiency, %
70
60
50
40
30
0.05M
20 0.1M
10 0.2M
0
0 20 40 60 80 100
Time, min
Fig. 3. The effect of the Na2SO4 concentration on the COD removal efficiency. pH:
4.53; i: 30 mA/cm2.
flocs for the removal of pollutants. The amount of the coagulant
also increased over time according to Faraday’s Law. Consequently,
as seen from Fig. 2, a high removal efficiency of the COD was ob-
served over a longer period.
3.1.2. Effect of the supporting electrolyte concentration
The conductivity of the wastewater should be sufficiently high
in order to reduce the cell voltage and, consequently, the energy
consumption. It was found by some researchers [26,27] that the re-
moval rate is higher for NaCl than for Na2SO4 because of the forma-
tion of hypochlorite. The most favourable supporting electrolyte is
Na2SO4 because of environmental considerations. To study the ef-
fect of the Na2SO4 concentration on the removal efficiency of the
COD, three concentrations were used: 0.05, 0.1 and 0.2 M. Fig. 3
illustrates the removal efficiency depending on the supporting
electrolyte dose. As seen from Fig. 3, after 90 min of electrocoagu-
lation, an increase in the electrolyte concentration from 0.05 to
0.2 M resulted in a decrease in the removal efficiency from 78.6%
to 55.6% at a current density of 30 mA/cm2 and a pH of 4.53. This
adverse effect can be attributed to the passivation of the electrodes
and an interaction of the excess SO2 4 ions with the hydroxyl ions
ð1Þ under high salt concentrations, which reduce the effect of the hy-
droxyl ions. This passivation is more significant at 0.2 M Na2SO4
than at 0.1 M Na2SO4. Therefore, further experiments were per-
formed at 0.1 M Na2SO4 because of the electrical energy
consumption.
3.1.3. Effect of the initial pH
The effect of the initial pH on the COD removal efficiency was
investigated at 30 mA/cm2 and 0.1 M Na2SO4 concentration. The
variation of the COD removal efficiency versus time for different

90
COD Removal Efficiency, %

70
80
60
70
50 60
40 50
40
30 20mA/cm2 pH:3
30
20 pH:4.53(orj)
25mA/cm2 20
pH:7
10 30mA/cm2 10
pH:9
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Time, min Time, min

Fig. 2. The effect of the current density on the COD removal efficiency. pH: 4.53; Fig. 4. The effect of the initial pH on the COD removal efficiency. i: 30 mA/cm2;
0.1 M Na2SO4. 0.1 M Na2SO4.
 U. Tezcan Un, E. Ozel / Separation and Purification Technology 120 (2013) 386–391
Fig. 5. The effect of polyelectrolytes on the COD removal efficiency. pH: 4.53; i:
30 mA/cm2; 0.1 M Na2SO4.
initial pH is shown in Fig. 4. The effects of the initial pH on an elec-
trocoagulation system are twofold. Firstly, as found by certain
researchers [28], the total iron dissolution is highly dependent on
the pH value of the solution, and they observed a higher iron dis-
solution than the theoretical value calculated by Faraday’s law.
Secondly, the solubility of the dominant dissolved iron species of
Fe(OH)3 can be affected by the pH of the solution. As seen from
Fig. 4, the removal rate was high in the first minutes and it de-
creased by increasing the pH over time, which was attributed to
the formation of H2 in the cathode and an aggregation of hydroxide
ions in the solution. As seen in Fig. 4, the best treatment efficiency
was observed at a pH of 4.53, which was the original pH of the
wastewater. When the pH < 4.53 or pH > 4.53, the reduction of
the removal efficiency is considerable.
3.1.4. Effect of the polyelectrolyte addition
The application of synthetic polyelectrolytes in water and
wastewater treatment has been known for many years. A large
number of synthetic polyelectrolytes are available commercially
under different trade names. In this study, the use of polyelec-
trolytes as a coagulant aid was intended to increase the perfor-
mance of the reactor and to obtain high removal efficiencies. For
this purpose, anionic and cationic polyelectrolytes were added to
the wastewater to achieve particle instability and increase the
particle size, consequently achieving the effective removal of or-
ganic substances present as the COD. The results obtained from
processing at 30 mA/cm2 with a pH of 4.53 and 0.1 M Na2SO4
are shown in Fig. 5. The addition of the polyelectrolyte increased
the removal efficiency from 76.4% to 77% and 78% at the pres-
ence of 0.25 g/L of anionic and cationic polyelectrolyte, respec-
tively. The cationic polyelectrolyte showed better performance
than the anionic polyelectrolyte. Increasing the amount of cat-
ionic polyelectrolyte from 0.25 g/L to 0.75 g/L further increased
the removal efficiency from 78% to 84%. The effluent COD con-
centration of 1040 mg/L was obtained with the addition of
0.75 g/L of cationic polyelectrolyte.
Fig. 6. The XRD pattern of sludge (: magnetite (FeFe2O4, card no. 019-0629)).
389
Fig. 7. The XRD patterns of brown pigment calcined at 1200 °C.
In literature COD removal efficiencies of 61%, %80 and 70.91%
for the treatment of dairy wastewater were obtained using parallel
plate aluminium electrodes by Tchamango and co-workers [12],
Bensadok and co-workers [9] and Kushwaha and co-workers [10]
respectively. Additionally the COD removal efficiency of the
79.2% using 3000 mg/L H2O2 was obtained at the iron and alumin-
ium parallel plate electrodes by Yavuz and co-workers [13]. Conse-
quently it can be say that our special designed reactor consisted of
rectangular iron cathode and six iron plates anode has better per-
formance with the removal efficiency of 84% than the parallel plate
electrode configuration given in the literature.
3.2. Production of brown and black pigments from the sludge produced
during the electrocoagulation of the strained yogurt wastewater
Although some recent studies have looked at the sludge pro-
duced during electrocoagulation, they have generally focused on
the sludge to clarify the electrocoagulation mechanisms. However,
there has been no study regarding the evaluation of the sludge.
Moreover, these waste products must be treated and stored. In fact,
sludge has economic value in certain industries, such as pigment
production. The use of sludge as a raw material in industry is very
important from an economic and environmental point of view be-
cause of the conversion of the waste into value-added products.
Therefore, using the sludge produced during the electrocoagulation
as a raw material for inorganic pigment production was investi-
gated to find solutions to reduce its negative environmental effects.
3.2.1. Sludge characterisation
The sludge was dried completely in a drying oven at 100 °C, and
an XRF analysis was performed. The chemical composition of the
sludge determined by the XRF analysis shows that this sludge is
mainly composed of iron oxide. The average chemical composition
in wt% is 76.95 Fe2O3, 10.82 Na2O, 9.80 SO3, 0.47 CaO, 0.51 K2O,
0.27 MnO and 1.18 other components. The XRD pattern of the
sludge reveals the magnetite (FeFe2O4) phase. Apart from magne-
tite, no other crystalline phase was observed. Magnetite is formed
after the formation of the ferric and ferrous hydroxides in the solu-
tion (Eq. (2)), as shown in the following [29]:
Fig. 8. The XRD patterns of black pigment calcined at 1000 °C.
390 U. Tezcan Un, E. Ozel / Separation and Purification Technology 120 (2013) 386–391
Fig. 9. (a) The electrocoagulation sludge, (b) the brown pigment powder and its colour in transparent glaze at 1100 °C, and (c) the black pigment powder and its colour in
transparent glaze at 1100 °C. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
2FeðOHÞ3 þ FeðOHÞ2 ! Fe3 O4 þ 4H2 O ðmagnetiteÞ
3.2.2. Pigment characterisation
The sludge formed during the electrocoagulation of the yogurt
industry wastewater was used as an iron source to produce brown
and black pigments because of its high iron oxide content (77%)
as seen from the XRD patterns in Fig. 6. The XRD patterns of the
brown pigment produced from the sludge and calcined at
1200 °C are shown in Fig. 7. The brown pigment contains spinel
(Zn(Al,Cr, Fe)2O4, card no. 021-0540) and excess zincite (ZnO, card
no. 036-1451) phases. The metal ions Fe3+, Cr3+, and Al3+ have sim-
ilar ionic radii, and therefore, the lattice constants of their oxides
are also similar. This fact favours the formation of a solid solution
between them to form mixed oxides [30,31]. In addition, ZnO is of
similar ionic size and valances with transition metal ions. Thus,
they react with each other and form complex spinels [32].
In the black pigment, with the addition of CoO into the sludge,
the spinel cobalt iron oxide (CoFe2O4, card no. 022-1086) was
determined (Fig. 8). Apart from the spinel phase, excess CoO or
Fe2O3 was not observed, indicating that the reaction between the
components was not complete. Therefore, sludge impurities seem
to exert a mineralising/fluxing action, increasing the reactivity of
the mixture.
The Lab values of the brown pigment powder and the col-
oured transparent glaze containing 5 wt% pigment were 40.32/
17.80/21.70 and 45.90/20.64/23.80, respectively. Fig. 9 shows the
electrocoagulation sludge and the produced pigment powders with
coloured transparent glazes. An intense and brilliant reddish-
brown colour can be seen on the glaze surfaces from Fig. 9b. CoO
containing pigment powder prepared with the sludge gives a
blue–black colour and has Lab values of 27.60/0.51/0.39.
Although the pigment has an intense black colour as a powder,
the blue–black colour was developed on the glaze surfaces with L-
ab values of 29.21/1.40/3.40 in the transparent glazes (Fig. 9c).
This blue tint could have arisen from the Co containing phases,
such as olivine (Co2SiO4), formed during the firing of the glaze, as
discussed in a previous study [24].
4. Conclusion
In this study, the electrocoagulation of strained yogurt waste-
water was performed. After electrocoagulation of the strained yo-
ð2Þ gurt wastewater, the obtained solid waste sludge was used in the
production of black and brown inorganic ceramic pigments in or-
der to reduce the negative environmental effects of the sludge.
Based on the results achieved from the experiments, the following
conclusions may be outlined:
1. In this study the COD removal efficiency of 84% for the treat-
ment of yogurt industry wastewater was obtained with the
addition of 0.75 g/L cationic polyelectrolyte at 30 mA/cm2 and
pH of 4.53 using special designed reactor consisted of rectangu-
lar iron cathode and six iron plates anode.
2. The operating conditions, such as the current density, the elec-
trolysis time, and the polyelectrolytes addition, affect the treat-
ment efficiency positively. Increasing current density from 20 to
30 mA/cm2, the COD removal efficiency was increased from
56.4% to 76.4% while increasing the Na2SO4 concentration from
0.05 to 0.2 M was resulted in a decrease in the removal effi-
ciency from 78.6% to 55.6%. The best treatment efficiency was
obtained at the initial pH of 4.53, which was the original pH
of the wastewater.
3. Although a complete evaluation of the composition and tem-
perature limits is still required, it seems that this sludge can
be used as an iron source to produce brown and black pigments
to be used in the ceramic industry and convert the waste into a
value-added product. Pigments containing this sludge and other
oxides gave a reddish-brown and blue–black colour in the
transparent glaze. In addition, waste and other oxide mixtures
transform the spinel structure, which has a high chemical and
thermal resistance in molten glazes at 1100 °C.
Acknowledgement
We would like to thank Miss Atihan Celik for the help during
this work.
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