Desalination 258 (2010) 201205

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / d e s a l

Treatment of petroleum renery wastewater by electrochemical methods

Yusuf Yavuz, A. Sava Koparal , lker Bakr tveren
Anadolu niversitesi, evre Sor.Uyg. ve Ara. Merkezi, Eskiehir, Turkey

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

Article history: Direct and indirect electrochemical oxidation by using boron doped diamond anode (BDD), direct
Received 18 November 2009 electrochemical oxidation by using ruthenium mixed metal oxide (Ru-MMO) electrode, and electrofenton
Received in revised form 3 March 2010 and electrocoagulation by using iron electrode were investigated for the treatment of petroleum renery
Accepted 5 March 2010
wastewater (PRW). The results have been given at the best operational conditions which were obtained for
Available online 10 April 2010
each electrochemical method. The results obtained from electrochemical methods were compared to each
Keywords:
other. Complete phenol and COD removal can be achieved in almost all electrochemical methods, except
Petroleum renery wastewater electrocoagulation, provided that electrolysis time is prolonged. The most efcient method was the
Phenol electrofenton process followed by the electrochemical oxidation using BDD anode. Phenol removal of 98.74%
Electrochemical oxidation was achieved in 6 min of electrolysis and COD removal of 75.71% was reached after 9 min of electrolysis in
Electrofenton electrofenton. Additionally, 99.53% phenol and 96.04% COD removal were obtained in direct electrochemical
Electrocoagulation oxidation at the current density of 5 mA/cm2. Initial phenol concentration was reduced to nal phenol
concentration of 0.91 mg/L after 40 min of electrolysis, and initial COD decreased to 36.7 mg/L and 23.3 mg/L
after 60 min and 75 min of electrolysis, respectively. Electrocoagulation was found to be ineffective for the
treatment of PRW.
2010 Elsevier B.V. All rights reserved.

1. Introduction
The petroleum renery industry converts crude oil into more than
2500 rened products, including liqueed petroleum gas, gasoline,
kerosene, aviation fuel, diesel fuel, fuel oils, and lubricating oils [1].
Large volume of water is used in renery processes, especially for
distillation, hydro-treating, desalting and cooling systems [1]. The
quantity and characteristics of wastewater generated depend on the
process conguration. Reneries generate polluted wastewater,
containing COD levels of approximately 300600 mg/L; phenol levels
of 20200 mg/L; benzene levels of 1100 mg/L; levels of heavy metals
of 0.1100 mg/L for chrome and 0.210 mg/L for lead; and other
pollutants [2].
Phenol and phenolic compounds, which are constituents of PRW, are
of widespread use in many industries, such as dyes, plastics, polymeric
resin production, pharmaceutical, and oil renery [3,4]. Therefore, these
compounds are commonly encountered in industrial efuents and
surface water. As a result of the formation potential of carcinogenic
chlorophenols during wastewater treatment, phenol containing efu-
ents have to be treated before disposal [5,6].
The traditional treatment of the wastewater originated from the
reneries is based on the mechanical and physicochemical methods
such as oilwater separation and coagulation followed by biological
Corresponding author. Tel.:+90 222 3213550; fax: +90 222 323 95 01.
E-mail address: askopara@anadolu.edu.tr (A.S. Koparal).
treatment. The wastewater arriving at the treatment plant has been
contaminated with a light fraction of aliphatic and aromatic
petroleum hydrocarbons and chlorinated organic substances origi-
nating from the cooling liquids used in the industrial processes [7].
Treatment technologies studied by the researchers for the treatment
of PRW include enhanced photo-degradation [7], fenton and photo-
fenton processes [8], biodegradation [9], membrane bioreactor [10],
occulation and ceramic membrane ltration [11], and electrochemical
methods [12,13].
Electrochemical treatment methods for water/wastewater con-
taining phenol and derivatives have been attracting great attention for
the last decade [35,1420], and offer many distinctive advantages
such as environmental compatibility, versatility, energy efciency,
safety, selectivity, amenability to automation, and cost effectiveness
[21]. Nevertheless most of these studies have been conducted by
using model wastewaters.
Electrode material which can signicantly inuence the mecha-
nism and consequently the products of the anodic reaction is one of
the most important parameters in the electrochemical studies and
applications. The results from the studies in which BDD, Ru-MMO, and
iron electrodes had been used were given in this report.
Ruthenium oxide (RuO2) is an important catalyst for the industry
because it is widely used for the Cl2 and O2 production [22,23]. RuO2
has good conductivity, good barrier properties against oxygen
diffusion and high thermal stability at the temperatures as high as
800 C. Ruthenium and ruthenium oxide have also excellent chemical
stability [24].

0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.03.013
202 Y. Yavuz et al. / Desalination 258 (2010) 201205

When oxide anodes (MOx) such as Ru-MMO are used, it is possible The reaction between H2O2 and Fe2+ produces also hydroxyl
to produce hydroxyl radicals (OH) unselective strong oxidizing radical according to the reaction (10).
agents. The mechanisms of the oxidation of organic matter and the
+ OH + OH
2+ 3+
formation of hydroxyl radicals on an oxide anode are represented H2 O2 + Fe Fe 10
below (Eq. (1)) [25];
Efciency of EF process depends heavily on factors such as the


OH + H + e
kOH
MOx + H2 O MOx

1 quantities of H2O2 and Fe2+ cation, pH of the solution, current density
and supporting electrolyte concentration [33,34].
The hydroxyl radicals are adsorbed at the electrode surface and In this study, feasibility of the PRW treatment by using different
degradation of organic matter occurs according to Eq. (2); electrochemical methods has been studied using an actual wastewater.
Performances of these electrochemical methods were also evaluated

and compared with each other.
R + MOx OH z z = 2O2 + zH + ze + MOx
kc
2
2. Experimental methods

BDD, as a novel catalyst, has a great potential for electrochemical
applications, especially in the treatment of wastewater and drinking
water due to the extraordinary chemical inertness and the opportu-
nity of using such electrodes (anodes as well as cathodes) in very
aggressive media. The electrochemical properties of diamond provide
a wide variety of applications due to the extreme electrochemical
window (N3 V) before the formations of hydrogen at the cathode and
oxygen at the anode [2628].
Once BDD anodes are used, they allow direct production of the
hydroxyl radicals (OH) from the electrolysis of water with very high
current efciencies [29] according to Eq. (3).
H2 OOH + e
+H 3 Magneto special anodes B.V. (Schiedam, The Netherlands) were con-
Electrocoagulation is based on in situ formation of the coagulant as the
sacricial anode corrodes due to an applied current. This technique
combines three main interdependent processes operating synergistically
to remove pollutants: electrochemistry, coagulation and hydrodynamics
[30]. The mechanism of EC is highly dependent on the chemistry of the
aqueous medium, especially on conductivity. Other characteristics such as
pH, particle size, and chemical constituent concentrations will also
inuence the EC process. According to Mollah et al. [31], oxidation of iron
in an electrolytic system produces iron hydroxide, Fe (OH)n, where n=2
or 3. Two mechanisms have been proposed for the production of Fe
(OH)n; one of them has been given below in reactions between (4) and
(7) and more details have been given elsewhere by Mollah et al. [31]:
Anode:
2+
4Fe4Fe + 8e 4
PRW, provided from a national oil renery plant located in Kocaeli
province of Turkey, was treated by different electrochemical methods.
All experimental studies were accomplished at ambient temperature
(2025 C) with a wastewater volume of 300 mL. PRW used had a
phenol concentration of 192.9 mg/L and a COD of 590 mg/L. Electrical
conductivity of PRW was 15.63 mS/cm. Wastewater preserved with
concentrated H2SO4 was stored in refrigerator for the use in the
experiments.
Electrochemical oxidation of PRW by using Ru-MMO electrode
was carried out in a parallel plate reactor consisted of mainly 4 com-
partments of total volume of 270 mL. 4 anodes and 4 cathodes made
of Ru-MMO in the dimensions of 3 4 cm which were supplied from
tained in each compartment. Studies were carried out in the batch
mode, and wastewater was recirculated by means of a peristaltic pump.
This experimental setup can be found elsewhere in more detail [3].
Direct and indirect electrochemical oxidation studies by using BDD
anode, and electrocoagulation and electrofenton studies by using iron
electrodes were accomplished in a bipolar trickle tower (BTT) reactor.
Both diamond and iron anodes were shaped as Raschig ring. The
thermo-jacketed BTT reactor of 125 mL was 2.5 cm in an inner diameter.
The feeder electrodes were 22.5 cm apart from each other. There were
26 layers in the reactor, and four electrodes in each layer. All electrode
layers were isolated from each other by using a dielectric material. The
detailed explanation including experimental setup can be found else-
where [4]. BDD anodes on niobium substrate were purchased from
Metakem GmbH (Usingen, Germany), and iron electrodes were pro-
vided from local suppliers.
During the experiments, samples were withdrawn from the
reactor at predetermined time intervals.

2+
2.1. Analysis
4Fe + 10H2 O + O2 4FeOH3 + 8H 5
NaCl (MERCK) was used in indirect electrochemical oxidation
Cathode: studies, and H2O2 (MERCK) was used in electrofenton studies. Phenol
was determined according to the standard methods (direct photo-
8H + 8e 4H2 6
metric method; ASTM 5530 D) [35], and COD was measured using a
COD reactor (HACH) and a spectrophotometer. All COD and phenol
Overall:
analysis were accomplished in duplicate and average values have
4Fe + 10H2 O + O2 4FeOH3 + 4H2 7 been reported. All chemicals used were in analytical grade.
Statron 3234.4 and 3234.9 model power supplies, OGSM 3900 digital
In EF process, Fe2+ and H2O2 can be generated on-site electrochem- multimeter, Multix MC 1000 PEC model peristaltic pump, Orion 420 A
ically, either separately or concurrently. H2O2 can be electrogenerated by model pH meter, Shimadzu UV-1700 model spectrophotometer were
the reduction of dissolved oxygen (Eq. (8)), and Fe2+ by the reduction of used as auxiliary equipments in the experimental studies.
Fe3+ (Eq. (9)) or the oxidation of a sacricial iron anode (Eq. (4)) [32,33]:
3. Results and discussion

O2 + 2H + 2e H2 O2 8 3.1. Electrochemical oxidation by using Ru-MMO electrode

Ru-MMO electrode was employed in a parallel plate reactor for the

3+ 2+
Fe + e Fe 9 electrochemical oxidation of PRW. Best experimental conditions were
 Y. Yavuz et al. / Desalination 258 (2010) 201205 203

reached at the current density of 20 mA/cm2, and the ow rate of
24.83 mL/min. This study was carried out without any need of sup-
porting electrolyte.
After 210 min of electrolysis, 94.5% phenol removal was reached.
However, COD removal is more difcult since the wastewater gener-
ally has a variety of organic and inorganic contaminants and longer
electrolysis time is necessary for COD removal compared to phenol
removal [3]. COD removal of nearly 70% was obtained with Ru-MMO
anode after 300 min of electrolysis as shown in Fig. 1a. Since efuent
complied with the discharge standards after 300 min of electrolysis,
complete removal of COD was not aimed.
added in electrofenton studies carried out at the same experimental
conditions as electrocoagulation (Fig. 1c).
It is clear from these results that just electrocoagulation is
inefcient for the treatment of PRW.
High removal efciency was attained in a short time period by
applying electrofenton method. However, removal rate decreased
when H2O2 in media consumed after a given time period. If the
discharge limits are not met in this situation, continuous feeding of
H2O2 to the electrochemical reactor can be suggested to solve this
problem according to Yavuz [33]. Yavuz [33] has demonstrated that
feeding type of H2O2 has an important factor affecting the perfor-
mance of an electrochemical system.

3.2. Electrocoagulation and electrofenton by using iron electrode 3.3. Direct and indirect electrochemical oxidation by using BDD electrode

Electrocoagulation and electrofenton studies were carried out
using a BTT reactor. Raschig ring shaped iron electrodes were used in
both studies. In electrocoagulation, without addition of any support-
ing electrolyte, 6.27% phenol and 2.26% COD removal values could be
obtained at a current density of 1 mA/cm2 after 120 min of elec-
trolysis. Variation of remaining phenol concentration and COD with
respect to time can be seen in Fig. 1b. Phenol removal of 98.74%
was achieved in 6 min of electrolysis and COD removal of 75.71% was
reached in 9 min of electrolysis provided that 1000 mg/L of H2O2 was
Direct and indirect electrochemical oxidation studies were also
performed in BTT reactor utilizing Raschig ring shaped BDD electrodes
in these studies.
Typical results obtained from direct electrochemical oxidation by
using BDD electrode have been given in Table 1. Phenol removal of
99.53% and COD removal of 96.04% were achieved in direct
electrochemical oxidation at the current density of 5 mA/cm2. Initial
phenol concentration of 192.9 mg/L was reduced to nal phenol
concentration of 0.91 mg/L at the end of 40 min of electrolysis. On the

Fig. 1. Variation of phenol and COD with time in (a) electrochemical oxidation by using Ru-MMO electrode (I = 7200 mA, i = 20 mA/cm2, Q = 24.83 10 3 L/min, t = 20 C),
(b) electrocoagulation (I = 176 mA, i = 1 mA/cm2, Q = 36.3 10 3 L/min, t = 20 C), (c) electrofenton (1000 mg/L H2O2, I = 176 mA, i = 1 mA/cm2, Q = 36.3 10 3 L/min,
t = 20 C), (d) direct electrochemical oxidation by using BDD electrode (I = 882 mA, i = 5 mA/cm2, Q = 36.3 10 3 L/min, t = 20 C), (e) indirect electrochemical oxidation by using
BDD electrode (0.05 M NaCl, I = 530 mA, i = 3 mA/cm2, Q = 24.83 10 3 L/min, t = 20 C).
204 Y. Yavuz et al. / Desalination 258 (2010) 201205

other hand, initial COD of 590 mg/L decreased to nal COD values of
36.7 mg/L and 23.3 mg/L after 60 min and 75 min of electrolysis,
respectively.
In indirect electrolysis, in the presence of 0.05 M NaCl, 98.9%
phenol removal at 60th min, and 95.48% COD removal at 90th min
were reached at the current density of 3 mA/cm2.
Time coarse variations of phenol and COD in direct and indirect
electrochemical oxidation by using BDD electrode have shown in
Fig. 1d and e. The graphics of these two studies have similar trends.
However, higher current density was utilized to obtain same
efciency in direct electrochemical oxidation than that in indirect
electrochemical oxidation although the results were similar. There-
fore, it can be concluded that lower current density is required to
reach same removal efciency in the presence of NaCl. Additionally,
there is no signicant difference in total energy consumption values
between these two methods.
3.4. Comparison of electrochemical methods
Prevailing mechanism in direct and indirect electrooxidation, and
electrofenton studies is degradation by OH radicals generated
electrochemically, except electrocoagulation. While degradation also
takes place at the electrode surfaces in Ru-MMO and BDD electrodes,
coagulation occurs in electrofenton additionally. In electrocoagula-
tion, after coagulant is generated electrochemically, complexation or
electrostatic attraction followed by coagulation will occur. Perfor-
mance of the electrocoagulation was considered to be limited due to
the high amount of soluble organic pollutants and low amount of
suspended solids contained in PRW. Thus, OH radical formation
potential becomes more important for the successful treatment of
PRW. OH radical formation potential of Ru-MMO and BDD electrodes
and electrofenton mechanism is well known today and was given in
the Introduction section. In this situation, results obtained from the
studies are compatible with that in the literature.
Time coarse variations of remaining phenol concentration, COD,
and energy consumption in the electrochemical methods studied
have been summarized in Figs. 24, respectively.
According to the results given in Fig. 2, electrochemical methods can
be put in order for phenol removal from best to worst as follows:
electrofenton, direct and indirect electrochemical oxidation by using
BDD (almost same), direct electrochemical oxidation by using Ru-MMO,
and electrocoagulation. Phenol concentration in wastewater decreased
gradually with time in all methods studied. However, phenol degrada-
tion reaction occurred very fast in electrofenton compared to the other
methods with a rst-order rate constant of 0.7825 1/min. Initial phenol
concentration of 192.9 mg/L was decreased to 2.43 mg/L in a very short
time period (only 6 min) by using electrofenton method (Fe2+ H2O2).
On the other hand, time necessary to reach phenol removal of over 95%
Table 1
Typical results obtained in direct electrochemical oxidation studies by using BDD electrode
(I = 882 mA, i = 5 mA/cm2, Q = 36.3 10 3 L/min, t = 20 C).
Fig. 2. Time coarse variation of phenol concentration with electrode materials employed.
varied 4060 min for direct and indirect oxidation at BDD anode. It
should be noted that the extension of electrolysis time leads to increase
in energy consumption. Thus, the removal of pollutants in a very short
time period makes the electrochemical method favorable for the
industrial wastewater treatment applications. Therefore electrofenton
can be suggested and utilized easily as a process step in a real waste-
water treatment plant. In addition, it took 210 min to achieve nearly 95%
phenol removal by using Ru-MMO anode. According to the results,
longer time is necessary for Ru-MMO electrode to reach an acceptable
removal value for pollutants compared to the other methods. All these
performance differences between the electrode materials used can be
attributed their specic OH radical formation potential. Furthermore,
additional reactions occurred at the electrode and/or in bulk solution
also contribute the treatment efciency.
Variation of COD with time depending on the electrode materials
has been plotted in Fig. 3. As it can also be seen from Fig. 3 that
variation of COD had a similar trend with the variation of remaining
phenol concentration (Fig. 2). These two gures reveal that the
electrochemical methods studied have exhibited similar performance
for both phenol and COD removal. In a matter of fact, phenol
concentration is included in COD value. Therefore it can be concluded
that if an electrochemical method is successful for phenol removal,
will also be successful for COD removal, and vice versa. It should be
noted that COD removal is more difcult than phenol removal because
of complex nature of COD. Results obtained from Figs. 2 and 3 have
proved this situation. As seen from these gures the removal
efciency of COD is lower than the removal efciency of phenol for
a given time period. For instance, in direct electrochemical oxidation
studies by using BDD anode removal efciencies of phenol and COD
after 10 min of electrolysis were 79.87% and 54.80%, respectively.
Same situation was also valid for other electrochemical methods
studied. It can be said that longer electrolysis time is required for COD
removal than that of phenol removal for all electrochemical method.
One of the most important parameters in the electrochemical
studies as well as in other wastewater treatment methods is energy

Time Applied potential Cout COD Removal Energy consumption

(min) (V) (mg/L) (mg/L) efciency (kWh/g)a
(%)

Phenol COD

0 285 192.90 590

5 285 70.10 296 63.67 49.72 0.94
10 284 38.80 266 79.87 54.80 1.68
15 283 11.50 176 94.02 70.06 2.32
20 280 4.55 126 97.64 78.53 2.92
30 270 2.73 103 98.58 82.48 3.49
40 265 0.91 60 99.53 89.83 4.05
50 260 50 91.52
60 250 36.7 93.78
75 247 23.3 96.04
a
Energy consumption values were calculated in the base of phenol removal. Fig. 3. Variation of COD values with time depending on the electrode materials.
 Y. Yavuz et al. / Desalination 258 (2010) 201205 205

Table 2
First-order rate constants for electrochemical methods studied.

Method Electrode Removal First-order R2

material efciency, % rate constant,
k, 1/min

Phenol COD Phenol COD Phenol COD

Electrooxidation Ruthenium 94.49 70.06 0.0162 0.0041 0.7921 0.9415

MMO
Electrocoagulation Iron (Fe) 8.23 6.27 0.0007 0.0002 0.5868 0.7320
Electrofenton Fe2+ +H2O2 98.74 75.71 0.7825 0.1806 0.9485 0.8645
Electrooxidation BDD 99.53 96.04 0.1478 0.0492 0.9353 0.8685
Electrooxidation BDD+NaCl 98.90 95.48 0.0876 0.0393 0.7974 0.6347

Optimum experimental conditions were obtained for all electro-

Fig. 4. Variation of energy consumption values with electrode materials in the experimental
studies.
consumption. Besides high removal efciency, low energy require-
ment is also a necessity for a treatment system. In electrochemical
studies, energy consumption is directly proportional with current
density applied and inversely proportional with electrical conductiv-
ity of the solution.
Cumulative energy consumption values have shown in Fig. 4. Aver-
age energy consumption values were 0.143 kWh/g in electrofenton
method and 4.05 kWh/g in direct electrochemical oxidation by using
BDD electrode. However, it was determined as high as 31.949 kWh/g for
electrocoagulation. This is approximately ten times higher than the
energy consumption values obtained in other methods. According to the
results, electrocoagulation was not a suitable method from the energy
consumption angle.
In the processes studied, COD or phenol removal rate is proportional
to the concentration of the organic pollutant and phenol concentration,
respectively. Therefore, the kinetics for COD or phenol removal can be
written as:
d [4] Y. Yavuz, A.S. Koparal, .B. tveren, J. Environ. Eng-ASCE 134 (2008) 24.
C  = k C 
dt
Rearranging and integrating Eq. (11) gives
Ct 
ln = kt
Co 
where, Co is the initial COD or phenol concentration of the wastewater
in mg/L, and Ct is the COD or phenol concentration in mg/L at time t.
Plotting Ct / Co on the y axis versus t on the x axis on semilog scale will
result in straight line with the slope of k. Removal efciency values,
rst-order rate constants, and correlation coefcients for phenol and
COD for electrochemical methods studied were listed in Table 2. The
lowest rate constant was obtained in electrocoagulation with a
numerical value of 0.0007 1/min, and the highest rate constant value
of 0.7825 1/min was achieved in electrofenton for phenol removal.
There is 1100 fold difference between these two values. Further-
more, rate constants were 0.0002 1/min in electrocoagulation and
0.1806 1/min in electrofenton for COD removal, respectively. Accord-
ing to Table 2, the fastest reaction took place in electrofenton among
the electrochemical methods studied.
4. Conclusions
Treatment of PRW by several electrochemical methods was
investigated in this study. For this aim, direct and indirect electrochem-
ical oxidation by using boron doped diamond (BDD) and ruthenium
mixed metal oxide (Ru-MMO) electrodes, and electrofenton and
electrocoagulation by using iron electrodes were employed.
chemical methods employed, and the results were evaluated for these
conditions. Then, performances of ve electrochemical systems were
determined and compared each other for the treatment of PRW.
In general, all electrochemical methods studied except electro-
coagulation were found to be successful for the treatment of PRW
according to the results obtained. The most efcient method was the
electrofenton process followed by either direct or indirect electro-
chemical oxidation using BDD anode. Electrocoagulation was found to
be ineffective for the treatment of PRW.
Acknowledgements
This study was supported by Anadolu University Research Fund
with Grant no: 01.02.52.
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