Desalination 285 (2012) 91–99

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Desalination
journal homepage: www.elsevier.com/locate/desal

Treatment of paint manufacturing wastewater by electrocoagulation

Abdurrahman Akyol ⁎
Gebze Institute of Technology, Department of Environmental Engineering, Cayırova, 41400 Gebze, Turkey

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

Article history: Treatability of paint manufacturing wastewater (PMW) by electrocoagulation (EC) process was investigated. Ef-
Received 20 July 2011 fects of operating parameters for the EC process such as electrode type (Al or Fe), initial pH (2–10), current den-
Received in revised form 13 September 2011 sity (5–80 A/m2) and operating time (0–50 min) were evaluated for optimum operating conditions. The highest
Accepted 16 September 2011
removal efficiencies for COD and TOC in PMW were obtained with 93% and 88% for Fe and 94% and 89% for Al
Available online 22 October 2011
electrodes at the optimum conditions (35 A/m2, 15 min and pH 6.95). Operating costs for removal of PMW at
Keywords:
the optimum conditions were calculated for Fe and Al electrodes as 0.187 €/m3 and 0.129 €/m3. Toxicity test
Electrocoagulation was carried out to obtain information about toxic effect of the raw and treated wastewaters at optimum operat-
Paint manufacturing wastewater ing conditions. The samples measured by respirometric method contained hardly toxicities. Performance of Al
Operating cost electrode was better than that of Fe electrode in terms of removal efficiency and operating cost.
Toxicity © 2011 Elsevier B.V. All rights reserved.

1. Introduction
Effluents of paint manufacturing company (PMW) contain highly
toxic compounds and organic biorefractory compounds such as COD,
BOD and TOC. It harms fish, wildlife, and contaminates the food chain if
poured down a storm drain. Paint wastewaters have also adverse effects
on human health occupants. If used in closed areas, its chemical compo-
nents can irritate eyes, skin and lungs and causes headaches and nausea.
It can also contribute to respiratory problems; muscle weakness, liver and
kidney damage [1]. The PMW must be needed to discharge after treat-
ment due to legal restrictions in organized industrial zone and environ-
ment conservation.
There are many different techniques to remove COD, TOC and color
from industrial wastewater such as biodegradation, adsorption, mem-
brane filtration, coagulation–flocculation, advanced oxidation processes
such as ozone, photochemical, Fenton's, electrochemical etc. [2–8].
These technologies take considerable time; require an extensive set-
up and they are not economically applicable for plants of produced
small volume wastewater. Moreover, each step takes place in a separate
tank and the entire treatment requires several pH adjustments as well
as the addition of acid, coagulants such as alum, ferric sulfate and chlo-
ride, lime, caustic or polymeric flocculants. These conventional process-
es generate a considerable quantity of secondary pollutants (chloride,
sulfate in the coagulation–precipitation) and large volumes of sludge
or waste which pose serious environmental problems. The biological
processes are also insufficient to treatment this kind wastewater due
to leads to the partial inhibition of biodegradation [9].
In recent years, new and novel processes for efficient and adequate
treatment of various industrial wastewaters with relatively low operating
⁎ Tel.: + 90 262 6053290; fax: + 90 262 6053200.
E-mail address: abdakyol@gyte.edu.tr.
costs have been explored due to strict environmental regulations. Electro-
coagulation (EC) process has been attracted a great attention for treat-
ments of industrial wastewaters such as olive mill [10], chemical
mechanical polishing [11], poultry slaughterhouse [12], pulp and paper
mill [13], metal cutting [14] and textile wastewaters [15] because of the
versatility and the environmental compatibility. The EC unit is environ-
mentally friendly so that it does not create corrosion or any pollutants.
This technique has some advantages when compared to conventional
methods such as simple equipment, easy to operate, less retention time,
reduction or absence of adding chemicals, rapid sedimentation of the
electrogenerated flocs and less sludge production [16,17].
In this study, effects of the operating parameters such as initial pH,
operating time and current density using iron and aluminum elec-
trodes were investigated for treatment of PMW. Operating costs
were also calculated for the EC process.
2. EC mechanism removed pollutants
The EC process consists of in situ generating M n+ ions (Fe 2+, Al 3+)
in wastewater electrochemically dissolution of the iron (Fe) or alumi-
num (Al) electrode materials (M) at the anode and simultaneous hy-
drogen gas evolution occurs at the cathode according to Faraday's Law.
At the anode:
nþ −
MðsÞ →MðaqÞ þ ne ð1Þ
þ
2H2 O→4HðaqÞ þ O2ðgÞ þ 4e ð2Þ
At the cathode:
− −
nH2 Oþne →ðn=2ÞH2ðgÞ þnOHðaqÞ ð3Þ

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.09.039
92 A. Akyol / Desalination 285 (2012) 91–99

nþ −
MðaqÞ þ ne →MðsÞ ð4Þ

If iron or aluminum electrodes are used, the generated Fe 2+, Fe 3+

or Al 3+ ions will immediately undergo further spontaneous reactions
to produce corresponding many monomeric and polymeric Al or Fe
species such as Al(OH) 2+, Al(OH)2+, Al2(OH)24+, Al(OH)4−, Al6(OH)15 3+
,
4+ 4+ 7+ 5+
Al7(OH)17 , Al8(OH)20 , Al13O4(OH)24 , Al13(OH)34 , Al(OH)3 and
Fe(OH)2+, Fe(OH)2+, Fe(OH)24+, Fe(OH)4−, Fe(H2O)2+, Fe(H2O)5OH2+,
Fe(H2O)4(OH)2+, Fe(H2O)8(OH)24+, Fe2(H2O)6(OH)42+, Fe(OH)3 depend-
ing on the pH of the aqueous medium. Mn+ and OH− ions generated by
electrode reactions (1) and (3) react to form various monomeric and
polymeric species which transform finally into M(OH)3 according to com-
plex precipitation kinetics. Freshly formed amorphous M(OH)3 (sweep Fig. 1. A schematic diagram of experimental set-up.
flocs) have large surface areas which are beneficial for a rapid adsorption
of soluble organic compounds and trapping of colloidal particles [18,19].
In this study, removal of PMW was achieved by coagulation, adsorption filtrate was centrifuged at 2000 rpm and the electrodes were washed
and co-precipitation in the EC process. thoroughly with water to remove any solid residues on the surfaces,
dried and reweighted. The collected samples were filtered through
0.45-μm cut-off Millipore membranes and analyzed for COD and
3. Materials and methods
TOC. The amount of the sludge produced for each parameter affecting
of the EC process was determined after drying in an oven (Binder ED
3.1. Wastewater source and characteristics
115) at 105 °C for 24 h (Tables 2–4).
Experiments were conducted in triplicate under identical condi-
Wastewater was obtained from a paint manufacturing company in
tions to confirm the results and the mean values are presented. Max-
Turkey (Gebze) producing approximately 60 m 3 of wastewater per
imum error was found to be 2%.
day. The process wastewater contained a mixture of interior and ex-
terior emulsions, and polyvinyl acetate. The wastewater was filtered
3.4. Analytical procedures
using a screen filter to remove large suspended solids before being
used for the subsequent studies. Characterization of the wastewater
COD, TOC and pH determinations were carried out as proposed by
was shown in Table 1.
Standard Methods [21]. COD was measured by closed reflux titrimet-
ric method, TOC levels were determined through combustion of the
3.2. Experimental apparatus samples at 680 °C using a non-dispersive IR source (Tekmar
Dohrmann Apollo 9000). The pH was adjusted to a desirable value
The experimental setup was depicted in Fig. 1. Electrocoagulation re- using NaOH or H2SO4 and measured by a Mettler Toledo pH meter.
actor was made of plexiglas with dimensions of 120 mm×110 mm×
110 mm. Electrodes were connected to the EC reactor with monopolar 3.5. Toxicity testing
parallel connection mode. Two anodes and two cathodes electrodes
were used in the EC process. Both Al (purity of 99.53%) and Fe (purity The activated sludge inhibition test is rarely being used as a tool for
of 99.50%) electrodes in shape of rectangular plates had dimensions of evaluation of the toxicity in the industrial wastewaters which is an im-
45 mm×53 mm×3 mm. The total effective electrode area was 143 cm2 portant criterion to evaluate ecotoxicology risk of the wastewater. Acti-
and the spacing between electrodes was 10 mm. vated sludge consumes oxygen rapidly in the presence of easily
biodegradable substrate (reference material) such as glucose, peptone.
3.3. Experimental procedure Oxygen consumption by activated sludge functions as live cell concentra-
tion and specific respiration activity. The respiration rate of activated
The EC runs were conducted at 25 °C. The impurities on the sur- sludge decreases when the wastewater contains toxicants or inhibitors.
faces of electrodes were removed by dipping in a solution for 1– In this study, the respirometric measurements were applied with
2 min which was freshly prepared by mixing 0.1 L of HCl solution Applitek-RaCombo, BOI and Toxicity Meter at 20±2 °C. The respiromet-
(35%) and 0.2 L of hexamethylenetetramine aqueous solution ric tests were started with the reach of endogenous respiration level of
(2.80%) [20]. In each run, 0.80 L of PMW was placed into the EC reac- activated sludge by constant aerating. The reference material was
tor. The current density was adjusted to a desired value and the run added after the endogenous level (Re) was determined. Response of the
was started. At the end of the run, the solution was filtered, the system was monitored and maximum respiration rate (R0) was found.
After the reference material was consumed completely by activated
Table 1 sludge the respiration rate returned level of the endogenous respiration.
Characterizations of paint manufacturing wastewater. Test sample (wastewater) which can be toxic probably, was then added
Parameters Value (mg/L) in a vessel. After the respiration rate returns level of the endogenous res-
piration again, the same amount of reference material was added for the
BOD5 2800
COD 19,700
second time and maximum respiration rate (Rt) was found. Reduction of
SS 1100 respiration rate shows that microorganisms are affected by the test sam-
Cr+ 6 b 0.01 ple. The toxicity was calculated from the following Eq. (5);
Total Cr 0.021
Cd b 0.02
Pb 1.44 Toxicity % ¼ ½ðR0 –Rt Þ=ðR0 −Re Þx100 ð5Þ
Total Fe 4.82
Zn b 0.2
Total cyanide 0.05 where Ro is maximum respiration rate at first adding of the reference ma-
Conductivity (mS/cm) 1.53 terial (mg O2/L.h), Rt is maximum respiration rate at second time adding
pH 6.95
of the reference material (mg O2/L.h) and Re is endogenous respiration
 A. Akyol / Desalination 285 (2012) 91–99 93

Table 2
Experimental results of PMW for Fe and Al electrodes at different pH in the EC process.

pH Fe electrode Al electrode

Removal pHf ELC Ws OC Removal pHf ELC Ws OC

efficiency (%) (kg/m3) (kg/m3) (€/m3) efficiency (%) (kg/m3) (kg/m3) (€/m3)

COD TOC COD TOC

2 35 35 4.8 0.759 4.79 0.690 53 70.5 2.5 0.091 5.02 0.152

3 66 64.5 6.7 0.521 10.15 0.498 94 82.0 4.5 0.094 9.03 0.156
4 91 89 5.9 0.503 11.43 0.498 94.5 91.5 4.8 0.061 14.02 0.102
5 91 88.5 6.5 0.518 11.70 0.505 95 91 5.5 0.088 15.00 0.145
6 93 89 6.3 0.403 12.53 0.422 94 90.5 7,1 0.058 16.23 0.096
7 93.5 88.5 8.9 0.239 9.89 0.363 94.5 91 7.6 0.090 8.16 0.150
8 89 89.0 9.2 0.183 15.14 0.285 93.5 90.5 7.9 0.055 9.14 0.092
10 71 75.0 11.7 0.358 14.47 0.405 82 80 8.7 0.074 9.51 0.123

Table 3
Experimental results of PMW for Fe and Al electrodes at different current densities in the EC process.

Current density Fe electrode Al electrode

(A/m2)
Removal pHf ELC Ws OC Removal pHf ELC Ws OC
efficiency (%) (kg/m3) (kg/m3) (€/m3) efficiency (%) (kg/m3) (kg/m3) (€/m3)

COD TOC COD TOC

5 21 9 7.18 0.034 1.66 0.032 34 25.5 6.87 0.011 4.57 0.020

10 39.5 27.5 7.21 0.129 2.18 0.117 66 42 7.41 0.024 5.33 0.038
20 90 83.5 7.63 0.141 8.84 0.144 91 85.5 7.49 0.048 6.27 0.079
30 91 85 7.46 0.165 9.32 0.184 92.5 86 7.57 0.074 8.54 0.123
35 93 87.5 7.54 0.145 9.63 0.187 94 89 6.77 0.078 7.73 0.129
50 93.5 88.5 8.88 0.239 9.89 0.363 94.5 91 7.6 0.090 8.16 0.150
65 94 90 7.8 0.621 9.91 0.737 95.5 91.5 7.1 0.153 16.15 0.253
80 94 90 8.72 0.666 10.22 0.878 96 91.5 7.24 0.169 16.45 0.280

rate (mg O2/L.h), respectively. The toxicity tests were repeated three
times and average values are considered.
3.6. Operating cost
Operating cost (OC) is very important economical parameters in
the EC process. The OC includes material cost (mainly electrodes),
utility cost (mainly electrical energy), as well as labor, maintenance
and other fixed costs. In this study, energy, electrode material and
chemicals costs were taken into account as major cost items in the
calculation of the OC as €/m 3 for treatment of the PMW [22,23]:
Operating Cost ðOC Þ ¼ aENC þ bELC þ cCC
where ELC, ENC and CC are consumption quantities of electrode
(kg/m 3), energy (kWh/m 3) and chemicals (kg/m 3) of wastewater
treated. Costs for ELC (kg/m 3) in Eq. (9) and ENC (kWh/m 3) in
Eq. (10) were calculated. a, b and c given for Turkish market in May
2011 were electrical energy price (0.072 €/kWh), electrode material
price (1.65 €/kg Al) and chemical costs (CC, 0.73 €/kg for NaOH,
0.29 €/kg for H2SO4 and 0.15 €/kg for NaCl), respectively.
4. Results and discussion
4.1. Effect of initial pH
Initial pH is an important operating factor influencing performance of
the EC process. The influence of initial pH on COD and TOC removal effi-
ciency was studied between initial pHi 2–10 at current density of
50 A/m 2 and operating time of 15 min for Fe and Al electrodes (Figs. 2
and 3). As seen clearly in Figs. 2 and 3, COD and TOC removal efficiencies
were increased from 35% to 91% and from 35% to 89% at pHi 2–4 for Fe
electrode, and from 53% to 94% at pHi 2–3 and from 71% to 92% at pHi
2–4 for Al electrode. Moreover, there wasn't much changes observed in
removal efficiencies for COD at pHi 4–7 and TOC at pHi 4–8 for Fe elec-
ð6Þ
trode and at pHi 3–8 for COD and at pHi 3–8 for TOC for Al electrode, re-
spectively. There was also a decrease in removal efficiencies for COD
and TOC at pHi 10 which was 71% for Fe and 82% for Al electrodes. The op-
timum COD and TOC removal efficiencies for both electrodes at pHi 2–10
were obtained as 94% and 89% for Fe and 95% and 92% for Al electrodes.
The rest of EC experiments were carried out at pH 6.95 which was the
pH of PMW. Therefore, pH of PMW didn't need to adjust since this pH
fell into optimum pH range for both electrodes which makes the EC pro-
cess economically. Final effluent pHf for Fe and Al electrodes was observed

Table 4
Experimental results of PMW for Fe and Al electrodes at different operating times in the EC process.

Operating time Fe electrode Al electrode

(min)
Removal pHf ELC Ws OC Removal pHf ELC Ws OC
efficiency (%) (kg/m3) (kg/m3) (€/m3) efficiency (%) (kg/m3) (kg/m3) (€/m3)

COD TOC COD TOC

5 76.5 70 7.93 0.156 6.56 0.146 13 16 6.86 0.035 5.17 0.059

10 91.5 86.5 8.35 0.173 8.05 0.167 82 85.5 7.09 0.046 5.88 0.077
15 93 87.5 7.54 0.145 9.63 0.187 94 89 6.77 0.078 7.73 0.129
30 94 90 9.15 0.483 14.67 0.719 94.5 91.5 7.75 0.154 8.38 0.255
45 94 90 9.77 0.808 15.92 1.164 95 91 8.09 0.251 8.78 0.416
94 A. Akyol / Desalination 285 (2012) 91–99

100 100

90
80
COD Removal Efficiency (%)

COD Removal Efficiency (%)

80

60 Fe Electrode
70
Al Electrode
Fe electrode
60 Al electrode
40

50

20
40

30 0
2 4 6 8 10 0 10 20 30 40 50 60 70 80 90
Initial pH Current Density (A/m2)

Fig. 2. Effect of initial pH on the COD removal efficiencies of the EC process. Fig. 4. Effect of current density on the COD removal efficiencies of the EC process.

as 8.9 and 7.6 at 15 min, respectively. On the other hand, final effluent pHf
for Fe and Al electrodes fell into limits set by discharge standards of water
100
pollution control regulations (pHf 6–9). Therefore, there was no second-
ary treatment required for treated PMW by the EC process. COD and
TOC removal efficiencies decreased in lower acidic and higher basic pH
80
TOC Removal Efficiency (%)

values since hydroxide ions were oxidized at the anode as pH was greater
than 8. In addition, Fe(OH)6 3−
and Fe(OH)4− ions may be present at high
pH, which lacks a removing capacity [24]. At lower pH the protons in
the solution were reduced to H2 at the cathode and the same proportion 60
of hydroxide ions couldn't be produced [24]. However, COD and TOC re-
Fe Electrode
moval efficiencies decreased with aluminum electrode that could be
Al Electrode
explained by present of some chemical species according to the solution 40
pH [25]. It was known that if solution pH was below 3.5, the aluminum
ions and Al(OH)2+ were predominant, and Al(OH)3(s) was formed in
pH range 4–9 which was responsible to the formation of electrocoagulant 20
flocs. Finally, when pH was higher than 9, the monomeric anion, Al(OH)4−
was formed (Eqs. (7) and (8)) and didn't exhibit any positive effect on the
EC process performance [26]. 0
0 10 20 30 40 50 60 70 80 90
− −
2Al þ 6H2 O þ 2OH →2AlðOHÞ4 þ 3H2 ð7Þ Current Density (A/m2)
− −
AlðOHÞ3 þ OH →AlðOHÞ4 ð8Þ Fig. 5. Effect of current density on the TOC removal efficiencies of the EC process.

100 100

90
80
COD Removal Efficiency (%)
TOC Removal Efficiency (%)

80

60
70 Fe Electrode
Al Electrode

60 Fe electrode
40
Al electrode

50
20
40

30 0
1 2 3 4 5 6 7 8 9 10 11 0 5 10 15 20 25 30 35 40 45 50
Initial pH Operating Time (min)

Fig. 3. Effect of initial pH on the TOC removal efficiencies of the EC process. Fig. 6. Effect of operating time on the COD removal efficiencies of the EC process.
 A. Akyol / Desalination 285 (2012) 91–99 95

100 4.2. Effect of the current density

Current density is also an important parameter for controlling the

reaction rate in most electrochemical processes. It is well known that
TOC Removal Efficiency (%)

80
the amount of current density determines the coagulant dosage, and
size of the bubble production, and hence affects the growth of flocs
60
Fe Electrode
[27–29]. COD and TOC removal efficiencies at 5–20 A/m 2 for 15 min
Al Electrode
were changed from 21–90% and 9–84% for Fe electrode and from
34–91% and 26–86% for Al electrode (Figs. 4 and 5). There were no
40 drastic changes observed for COD and TOC removal efficiencies at
20–80 A/m 2. Removal efficiencies of COD and TOC at 80 A/m 2 were
94% and 90% for Fe electrode and 96% and 92% for Al electrode, re-
spectively. This can be attributed at high current densities; the extent
20
of anodic dissolution (Faraday's law, Eq. (9)) increased positively
charged polymeric metal species resulting in increased COD and
TOC removal efficiencies.
0
0 5 10 15 20 25 30 35 40 45 50 i:tEC :M w
Operating Time (min) ELC ¼ ð9Þ
z:F:v

Fig. 7. Effect of operating time on the TOC removal efficiencies of the EC process.
The electrode consumptions were calculated for pH 2–10 as 0.183–
0.759 kg Fe/m 3 for Fe and 0.055–0.094 kg Al/m 3 for Al electrodes re-
spectively. Values of electrode consumptions for Fe electrode were
2.67 times higher than that of Al electrode at pH 6.95 (Table 2). In addi-
tion, difference between consumptions of electrodes was 8.34 times
higher at pH 2.0. In especially acidic pH, while removal performance
for Fe electrode were lower than that of Al electrode, electrode con-
sumptions for Fe electrode were higher that of Al electrode. OCs was cal-
culated for Fe and Al electrodes were shown in Table 2. OC for
Fe electrode was 2.4 times more expensive than that of Al electrode at
optimum operating conditions. Difference in these costs was related
to high amount of electrode consumptions when Fe electrode was used.
where tEC(s) is operating time, z is the number of electrons involved
in oxidation/reduction reaction for Al, zAl = 3 and zFe = 2. Mw is
the atomic weight of anode material (Mw,Al = 26.98 g/mol; Mw,Fe =
56 g/mol), F is the Faraday's constant (96,485 C/mol) and v is the vol-
ume (m 3) of the wastewater in the EC reactor. It was also clear that a
technically efficient process must also be feasible economically. Major
operating cost of the EC was associated with electrical energy
consumption during process [30]. The electrical energy (kWh/m 3)
COD and TOC removal efficiencies for Al and Fe electrodes were calcu-
lated from Eq (10).
U:i:t EC
Cenergy ¼ ð10Þ
v
where U is cell potential (V) in the EC reactor. The cell voltage in-
creased from 2.10 to 16.36 V for Fe and from 2.22 to 14.47 V for Al

Table 5
Comparison of the conventional processes with EC process for PMW.

Treatment method Process conditions and variable Results Reference

Fenton process Column d, 11 × 1,5–5 × 5 cm; packing In optimum condition, [31]

material size (mix, 0.3–1.2); H2O2 dose,
1100–3320 mg/l; Fe, 15–105 mg/l;
time (125 h); pH (1.4–3.0)
Coagulation and microfiltration pH (7.0–7.5)
Alum (opt. dose; 700 mg/l.)
Polyelectrolyte (opt. dose; 6 mg/l.)
Electrochemical oxidation Residence time; temperature (°C);
Current density (5–80 A/m2);
time (0–50 min)
Coagulation–flocculation Coagulant type (Alum-FeSO4)
Coagulant dosage
Fenton oxidation H2O2 amount
Membrane process Membrane filtration
Coagulation Coagulant type (Alum and FeCl3)
Latex-based production (High COD)
PVA-based paint wastewater
Coagulation Coagulation agents: ferrous and aluminum
sulfate and polyaluminum chloride (PACl)
Coagulant dosage
Effective pH
Electrochemical coagulation Operating parameters,
Electrode type (Al or Fe),
Initial pH (2–10),
Current density (5–80 A/m2),
Operating time (0–50 min)
pH 1.4, H2O2 3320, Fe N15 mg/l, N10 g rust, mix reac.,
COD-RE, 80% (70 h.)
COD RE,74%; turbidity RE, 99.6%, [7]
Permeate was free from microorganisms.
Reduction in water consumption resulted in 55%
Opt. residence time 6 h, [32]
COD RE, 44,3%; Color RE, 86.2%; Turbidity
RE, 87.1%; OC, 42 kWh/kg CODa
Coagulation–flocculation [33]
COD RE, 67% (alum 1000 mg/l), 45% (FeSO4 750 mg/l)
Fenton oxidation [33]
COD RE. 81% (2 M H2O2 [H2O2]/[Fe+ 2]:10,)
Waste sludge, Coagulation N Fenton oxidation
Ultrafiltration, Total flux decline of membrane, 73%, membrane fouling, 9%. [33]
COD RE, 20–26%(Pre-aeration) [34]
COD RE, 80% PVA-based–90% latex-based Alum and FeCl3 (2000 mg/L)
Lime was also effective at high pH as it was combined with FeCl3.
COD RE, 30–80%; Turbidity RE, 70–99% (2 g/L FeSO4 opt. pH, 9.7). [35]
COD RE, 70–95%; Turbidity RE, 90–99% (2.5 g/L Al2(SO4)3 orj. pH)
COD RE, 98%; Turbidity RE, 98%(4 g/L PACl, opt. pH 7)
Fe electrode, (35 A/m2, 15 min, pH 6.95)
COD RE, 93%; TOC RE, 87.5% This study
Al electrodes, (35 A/m2, 15 min, pH 6.95)
COD RE, 94%; TOC RE, 89%.
OC, Fe electrode, 0.187 €/m3 OC, Al electrodes 0.129 €/m3.

Removal efficiency: RE, Operating cost: OC.

a
Energy cost only.

Table 6
Comparisons of treatment performances of different wastewaters with process conditions and variables in the EC process.
Wastewater type
Baker's yeast production wastewater
Poultry slaughterhouse wastewater
Textile wastewater
Potato chips manufacturing wastewater
Synthetic humic acids (HA)
Metal cutting wastewater
Textile dye (orange II)
Paper mill wastewater
Paint manufacturing company (PMW)
Suspended Solid: Ss, Operating Cost: OC, Humic acid: HA, Removal Efficiency: RE.
96
Type of EC reactor Process conditions and Variable Results Reference
Batch reactor Electrode type Al or Al electrode [36]
Monopolar parallel Fe electrodes; pH, 3–9 COD RE, 71%; TOC RE, 53%; Turbidity RE, 90%
Al or Fe electrodes rectangular plate Current density, 30–100 A/m2, Fe electrode
Operating time, 10–60 min. COD RE, 69%;TOC RE, 52%; Turbidity RE, 56%
OC Al, 1.54 $/m3 -0.82 $/kg; Fe, 0.51 $/m3- 0.27 $/kg.
Batch reactor Initial pH, 2–10 COD RE, 93 %,(25 min. pH 3, 150 A/m2, Al electrode) [12]
Al or Fe electrodes rectangular plate Current density, 30–200 A/m2, Oil-grease RE, 98% for Fe electrode
Operating time, 5–40 min. OC, 0.015 $/kg COD , 0.3-0.4 $/m3 Fe electrode
OC, 0.027 $/kg COD - 0.6-0.7 $/m3 Al electrode.
Batch reactor Initial pH (pH 6.9), Current density COD RE 78 %, Turbidity RE, 92%; [23]
(65 × 65 mm × 110 mm) (10 mA/cm2), Conductivity (3,990 mS/cm) Energy consumptions; 0.7 kWh/kgCOD, 1.7 kWh/m3,
Iron electrode (99.5%) Electrolysis time (10 min) Electrode consumptions, 0.2 kgFe/kgCOD, 0.5 kgFe/m3,
Batch mode Electrode type, Al or Fe electrodes Al electrodes N Fe electrode (COD, SS removal rate) [17]
Plexiglas thermostated electrocoagulator, pH, 2–8 COD RE, 60%; Turbidity, 98%; Retention time b 40 min.
(65 × 65 × 110 mm) Current density, 25-300 A/m2, Dried sludge 0.05–1.75 kg/removed kg COD
monopolar electrode Retention time. 5-40 min. OC, 0.48 - 5.42 $/m3 for 20–300 A/m2,
A. Akyol / Desalination 285 (2012) 91–99
OC, 0.62 - 6.32 $/m3 for 5–40 min,
Energy consumption, 4 kWh/m3 (b8 min).
Continuous and pH (3-7-11) HA RE, pH 7 (96%)-pH 3 (90%)-pH 11 (51%). (30 min) [37]
batch mode Time (0–25 min) EM treatment is in continuous mode and taken alone, it does
Al electrodes Continuous mode not have a significant effect on HA removal.
(20 × 2 cm × 2 mm) Electromagnetic treatment (EM) EM treatment is followed by EC in batch, it has an important
Active surface, 34 cm2 contribution to increase UV absorbance removal by EC near
100% at pH 7.
Batch mode Initial pH,(4–9) Fe electrode, [14]
Monopolar parallel Current density (30-100 Am-2) COD RE, 93.0%;TOC RE, 83.0%;Turbidity RE, 99.8 %
(25 × 19 × 8 cm) Operating time (10–40 min) Al electrode,
Volume 4.5 L COD RE, 93.5%; TOC RE, 85.2%;Turbidity RE, 99.9 %
Al or Fe electrodes OC, 0.371 €/m3 for Fe electrode
OC, 0.337 €/m3 for Al electrode.
Batch mode Conc. of dye (50–200 ppm), Electrodes distance Color RE, 98% (Conc. of orange II 200 ppm) [38]
Beaker reactor (1–5 cm), Current density (0-50Am-2), COD reduced, 84% (Conc. of orange II 200 ppm)
(250 ml) pH (1–10), Time (0–350 min), Temp. (0–75 °C), Optimum current density, 34.62 A/m2, pH of 7.5-8.5, stirring
Fe plates electrodes Flow (2–12 l/h) rate 100 rpm, electrodes distance (2 cm), water temperature
(Total area 0.0106 m2) (30 °C), volume flow (2 l/h)
Batch mode Electrode combinations Optimum pH of 5–7, current density, 70 mA/cm2 [39]
(240 × 110 × 110 mm) Initial pH (2–10) High temperature, negative effect.
Different combination Al or Fe electrodes Current density (10-70Am-2) Al-Al, high efficiency in the color removal
rectangular plate Water temperature (20–60 °C) Fe-Fe, effective COD and phenol removal
Monopolar parallel Time (10–70 min) Al-Fe or Fe-Al combination, not effective color, COD and
phenol removal.
Batch mode Electrode type (Al or Fe), Fe electrode, (35 A/m2, 15 min, pH 6.95) This study
(120 × 110 × 110 mm) Initial pH (2–10), COD RE, 93 %; TOC RE, 87.5 %
Al or Fe electrodes rectangular plate Current density (5–80 A/m2), Al electrodes, (35 A/m2, 15 min, pH 6.95)
Monopolar parallel Operating time (0–50 min) COD RE, 94 %; TOC RE, 89 %.
OC, Fe electrode, 0.187 €/m3
OC, Al electrodes 0.129 €/m3.
 A. Akyol / Desalination 285 (2012) 91–99 97

electrodes with increasing of the current density from 5 to 80 A/m 2.
According to Faraday's law, it was clear that Al 3+ or Fe 2+ dose re-
leased from anode depended on the electrolysis time and current
density. So in the EC process, current density and operating time
were important parameters affecting the COD and TOC removal effi-
ciencies and controlling the reaction rate in the EC reactor.
More sludge was also produced from Fe and Al electrodes at
higher current density due to elevated dissolution rate of anode
(Table 3). At a high current density, the extent of anodic dissolution
of Fe or Al increased, resulting in a greater amount of precipitate
and removal of COD and TOC. Moreover, the rate of bubble-
generation increased and the bubble size decreased with increasing
current density; both of these trends were beneficial in terms of
high pollutant-removal efficiency by H2 flotation. Therefore, when
high current densities were applied, the removal time of COD and
TOC removal efficiencies improved. However, these parameters
should be kept at low level to achieve a low-cost treatment. For that
reason, a compromise of the current density and electrolysis time
were necessary to optimize the treatment efficiency with the lowest
cost. Considering this operating cost factor, all further experiments
were carried out at 35 A/m 2 for both electrodes.
Total OC increased with increasing current density and operating
time in the EC process because energy and electrode consumptions
were related to these parameters. OCs at 5–80 A/m 2 were changed
from 0.032 to 0.878 €/m 3for Fe electrode and from 0.020 to
0.280 €/m 3 for Al electrode (Table 3). The OCs for removal efficiencies
of COD and TOC at the optimum conditions (pHi 6.95, 35 A/m2 and
15 min) were 0.187 €/m 3 for Fe electrode and 0.129 €/m3 for Al elec-
trode, respectively. OC for Fe electrode used in removal of COD and
TOC from PMW was 1.5 times more expensive than that of Al elec-
trode. This result indicated that Al electrode was more efficient than
Fe electrode in the EC process.
pH 6.95 for Al electrode was obtained as 94%. The EC process was su-
perior to the other techniques since conventional techniques had
some limitations such as use of chemical, large volume of sludge,
need of secondary treatment in some cases, longer operating time,
difficulty in monitoring, high installation, operating cost and lower ef-
ficiency in many cases.
Comparisons of different wastewaters with operating conditions in
the EC process were illustrated in Table 6. While the lowest COD removal
efficiency in the EC process with current density of 200 A/m2 and operat-
ing time of 30 min was obtained for potato chips manufacturing waste-
water as 65%, the highest COD removal efficiency in the EC process with
pHi 7.0, 33.3 A/m2 and 30 min was obtained as high as 96% in humic
acid synthetic solution. It was difficult to compare the operating costs of
the EC process since some of cost items were not given with details in
most of the published reports such as energy, electrode, chemicals, etc.
In this study, COD and TOC removal efficiencies of 93% and 88% for Fe elec-
trode and 94% and 89% for Al electrode were obtained (Table 6).
4.4. Toxicity studies
The activated sludge inhibition test was applied to assess the changes
in toxicity of raw and treated wastewaters under optimum experimental
a
6,0
5,5
Raw Wastewater
5 min EC
10 min EC
5,0
15 min EC
4,5 30 min EC
45 min EC
4,0
Absorbance

3,5
Amounts of sludge (Ws) generated during the EC process varied
from 4.79 to 15.14 kg/m 3 for Fe electrode and from 5.02 to 3,0
16.23 kg/m 3 for Al electrode at pH 2–10 due to increasing of current 2,5
density which is proportional to amount of sludge (Table 3). On the
2,0
other hand, when current density changed from 5 to 80 A/m 2, sludge
mass varied from 1.66 to 10.22 kg/m 3 for Fe electrode and from 4.57 1,5
to 16.45 kg/m 3 for Al electrode [12]. 1,0
0,5
4.3. Effect of operating time
0,0
200 300 400 500 600 700 800
Operating time is an important parameter for economic applica-
bility of the EC process. Based on the Faraday's law, the quantity of Wavelength (nm)
iron or aluminum released to the EC system using Fe or Al electrodes
may affect the residence time which lead to an increase in Fe or Al b 6,0
ions released to the system. Effect of operating time at 35 A/m 2 and Raw wastewater
pH 6.95 was shown Figs. 6 and 7. The removal efficiencies of COD 5,5 5 min EC
10 min EC
and TOC increased at 5–15 min from 77% to 94% and from 70% to 5,0 15 min EC
89% for Fe electrode and from 13% to 95% and from 16% to 91% for 4,5 30 min EC
Al electrode. The removal efficiencies for COD and TOC were not 45 min EC

changed much after operating time of 15 min for both electrodes. 4,0
Absorbance

This could be related to decreasing extent of cathodic reduction and 3,5

formation of new electrocoagulant flocs. The electrode consumptions 3,0
were calculated for operating time 5–45 min as 0.156–0.808 kg Fe/m 3
2,5
for Fe and 0.035–0.251 kg Al/m 3for Al electrodes respectively. The
electrode consumptions for Fe electrode were 1.86 times higher 2,0
than that of Al electrode at 15 min (Table 4). OCs were varied in the 1,5
range of 0.186–1.164 €/m 3 for Fe electrode and 0.059–0.416 €/m 3 for
1,0
Al electrode when the operating time was 5–45 min. The optimum
operating time for both electrodes in the EC process was selected as 0,5
15 min. 0,0
Table 5 was produced to show comparison of other techniques 200 300 400 500 600 700 800
with the EC process of PMW removals. While COD removal efficien- Wavelength (nm)
cies by conventional techniques were found in the range of 44%–
80%, COD removal efficiencies in the EC process 35 A/m 2, 15 min, Fig. 8. Absorbance spectra of PMW for (a) Fe and (b) Al electrodes during the EC process.
98 A. Akyol / Desalination 285 (2012) 91–99

100 process. Interestingly, slightly positive effect of treated wastewater on

microorganisms was observed.

98
4.5. Assessment of absorbance analysis
Transmitance [%]

96 The progress in the absorbance spectra of the wastewater during

the EC was also monitored with respect to operating time at optimum
conditions (pH 6.95, 15 min, 35 A/m 2). UV–vis spectra of the raw and
94 electrochemically treated wastewater were shown in Fig. 8a–b. There
were continuous signal curves in the region around 200–800 nm in
the spectra indicating for treatment of the wastewater. The intensity
92 of the curves decreased after the EC process. These results indicated
Residue sludge of Al electrode
Residue sludge of Fe electrode that there was a significant color reduction of the raw wastewater
with the EC process [25].
90
1000 1500 2000 2500 3000 3500 4000
Wavenumber (cm-1) 4.6. Characterization of the sludge from the EC

Fig. 9. FTIR spectrum of the sludge.
conditions. The biomass used in the activated sludge inhibition test was
fed with glucose and aerated well after being washed with tap water.
In the first step of toxicity analyses, two liters of the activated sludge
were placed in respirometer for each test sample. Toxicity in 0.1 L of
raw or treated wastewater was determined with an on-line respirome-
ter. For raw wastewaters, values of Re, Ro and Rt were 15.1 mg/L.h,
59.8 mg/L.h and 59.5 mg/L.h. Values of Re, Ro and Rt for treated waste-
waters were 16.2 mg/L.h, 58.7 mg/L.h and 63.3.2 mg/L.h. According to
Eq. (3), while toxicity of raw wastewater was 0.67%, no toxicity of trea-
ted wastewater was observed. These results proved that microorgan-
isms were hardly affected by raw and treated wastewaters in the EC
Characterizations of the sludge obtained from the EC were carried
out by Fourier transform infrared spectroscopy (FTIR) and X-ray fluo-
rescence (XRF). The sludge was collected by vacuum filtration after
the EC and dried at 105 °C in the oven. As seen in Fig. 9, FTIR spectrum
of the sludge (iron and aluminum hydroxide flocs) showed hardly any
significant spectroscopic changes in PMW which consisted of mixture
of phenol, formaldehyde and polyvinyl acetate. FTIR spectrum of sludge
showed a broad and intense band at 3340 cm−1 attributed to stretching
vibrations of \OH. The bands at 2958 and 1451 cm−1, and 1728 cm−1
indicated the presence of C\H and C_O. The strong bands at 1160 and
1065 cm−1 were referred to C\O stretching vibrations. The observed
variations in the sludge using were most likely due to the adsorption
of some functional groups in PMW.

Fig. 10. XRF spectra of sludge produced for (a) Fe and (b) Al electrodes during the EC process.
 A. Akyol / Desalination 285 (2012) 91–99
Table 7
XRF analysis of produced sludge in EC at optimum conditions.
Element and Sludge with Fe Sludge with
compounds electrode (%w/w) Al electrode
(%w/w)
S 0.0347 0.0338
Cr 0.0574 0.0259
SiO2 17.8670 18.0344
TiO2 8.7068 8.9374
Al2O3 0.0000 34.3124
Fe2O3 32.4577 1.2806
CaO 7.0454 5.8249
MgO 0.0000 0.4779
P2O5 0.2124 0.2159
Mn 0.1423 0.1166
XRF was used to determine the chemical components of the pro-
duced sludge. Fig. 10a–b and Table 7 presented for existence and per-
centage quantity of these components in the sludge. XRF analysis
provided direct evidence that raw material used in the paint produc-
tion (Table 7). Other components detected in the sludge came from
adsorption of the conducting electrolyte [40].
5. Conclusions
The EC process was successfully applied to PMW. The optimum oper-
ating conditions were determined as pH 6.95, current density of 35 A/m2
and operating time of 15 min. Removal efficiencies of COD and TOC in
PMW were 93% and 88% for Fe and 94% and 89% for Al electrodes at
15 min. Above 35 A/m2, no significant increases for the removal efficien-
cies of COD and TOC were observed. The COD and TOC removal efficien-
cies were hardly changed at higher current densities and operating
times. Operating costs for removal of PMW at the optimum conditions
were calculated for Fe and Al electrodes as 0.187€/m3 and 0.129€/m3.
As electrode material, aluminum electrode performs better than Fe elec-
trode in terms of removal efficiency and operating cost. Amounts of
sludge generated during the EC process were 9.63 kg/m3 for Fe electrode
and 7.73 kg/m3 for Al electrode at optimum conditions. Characterizations
of the sludge obtained from the EC were carried out by Fourier transform
infrared spectroscopy (FTIR) and X-ray fluorescence (XRF). FTIR spectrum
of the sludge (iron and aluminum hydroxide flocs) showed hardly any
significant spectroscopic changes in PMW. XRF analysis shows that
maghemite (Fe2O3), alumina (Al2O3) and raw material used in the paint
production were the major components in the sludge. The toxicity test
was carried out to obtain information about the toxic effect of the raw
and treated wastewaters at optimum operating conditions. The samples
measured by respirometric method contained hardly any toxicities. Ab-
sorbance spectra of raw and treated wastewaters were studied to observe
for decolorization which increased sharply with increasing of operating
time. These results indicated that the EC process would be very useful
for treatment of similar kinds of wastewaters.
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