Journal of Hazardous Materials 165 (2009) 838845

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Journal of Hazardous Materials

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Complexing agent and heavy metal removals from metal plating efuent by
electrocoagulation with stainless steel electrodes
Isk Kabdasl , Tlin Arslan, Tugba lmez-Hanc, Idil Arslan-Alaton, Olcay Tnay
Istanbul Technical University, Civil Engineering Faculty, Environmental Engineering Department, 34469 Maslak, Istanbul, Turkey

a r t i c l e

i n f o

Article history:
Received 8 August 2008
Received in revised form 15 October 2008
Accepted 16 October 2008
Available online 1 November 2008
Keywords:
Metal plating efuent
Complexed metal treatment
Electrocoagulation with stainless steel
electrodes
Organic complex former removal
Nickel and zinc removal

a b s t r a c t
In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was
experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well
as sludge production and specic energy consumption. The results indicated that increasing the applied
current density from 2.25 to 9.0 mA/cm2 appreciably enhanced TOC removal efciency from 20% to 66%,
but a further increase in the applied current density to 56.25 mA/cm2 did not accelerate TOC removal
rates. Electrolyte concentration did not affect the process performance signicantly and the highest TOC
reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride
content (1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected
by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating efuent were established as follows: an applied current density of 9 mA/cm2 , the
efuents original electrolyte concentration and pH of the composite sample. TOC removal rates obtained
for all electrocoagulation runs tted pseudo-rst-order kinetics very well (R2 > 9299).
2008 Elsevier B.V. All rights reserved.

1. Introduction
The increasing demand for the control of toxic metals being
released from industrial activities has led to the search of more
effective treatment methods for heavy metal abatement. Conventional treatment methods have proven to be satisfactory in meeting
the discharge consents. Among them, metal hydroxide precipitation is the most common treatment method employed for the metal
nishing efuents [1]. On the other hand, complexed metals cannot
be efciently removed by this method under conventional treatment conditions. Complexed metals are the form of metals which
are bound to strong complexing agents (complex former) keeping
them in solution. In the metal nishing industry, electroless plating and immersion plating are two major sources of wastewater
bearing complexed metals [1]. Modied hydroxide precipitation or
pretreatment (such as oxidation and reduction) preceding hydroxide precipitation are applicable treatment methods to complexed
metal efuents. Modied hydroxide precipitation is based on the
addition of calcium to which complexing agents preferentially bind,
allowing freed metal ions to precipitate effectively [14]. The main

Corresponding author. Tel.: +90 212 285 65 86; fax: +90 212 285 65 75.
E-mail address: ikabdasli@ins.itu.edu.tr (I. Kabdasl).
0304-3894/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.10.065

obstacle of this process is that complexing agents which may be

harmful in many ways are simultaneously released into the environment. Via application of pretreatment the complexing agent
can be completely destroyed or converted into a form that does
not interfere with conventional precipitation. Reduction and oxidation processes employed as pretreatment methods have several
disadvantages such as the high cost and toxicity of the chemicals employed [15]. Hence, the development of new treatment
methods for efuents bearing complexed metals is an urgent issue.
Among the methods that have recently been studied, electrocoagulation (EC) is deemed a promising one as it proved to be very
efcient in removing pollutants such as organic and inorganic matters from the industrial wastewaters [617]. In addition, a number
of scientic works have indicated that heavy metals in the free form
can be successfully removed by EC using aluminum, iron and cast
iron electrodes [1824].
Adhoum et al. [18] experimentally investigated the treatability
of synthetic samples for the electroplating wastewater containing copper, zinc and hexavalent chromium by EC with aluminum
electrodes. Their study demonstrated that the increase of current
density that ranged between 8 and 48 mA/cm2 enhanced the treatment rate and highest removal efciencies could be achieved when
the pH was kept between 4 and 8. Lai and Lin [19] experimentally explored the EC application to chemical mechanical polishing

I. Kabdasl et al. / Journal of Hazardous Materials 165 (2009) 838845

(CMP) wastewater from semiconductor fabrication using cast iron,

aluminum and titanium plates in different combinations as the
anode/cathode pairs. Their results revealed that aluminum/cast
iron (anode/cathode) was a good electrode pair and was able to
achieve 99% copper removal, 96.5% turbidity reduction and 75%
COD removal in less than 100 min. In other studies published by
Lai and Lin [20,21], sludge characteristics of CMP treated by EC
were investigated and it was emphasized that the EC process generates a signicant amount of sludge that needs to be properly
disposed of. Golder et al. [22] searched the removal of chromium
(III) using a synthetic sample by EC with mild steel electrodes.
Almost complete chromium removal (99.9%) was obtained after
50 min of EC in the case of bipolar electrode arrangement at approximately 33.52 mA/cm2 against 81.5% removal for the monopolar
electrode conguration. In other study conducted by Golder et
al. [23] removal of trivalent chromium from synthetic solution
was investigated using EC with mild steel electrodes in order
to determine the effect of critical operating parameters such as
current density (1626 mA/cm2 ); initial pH (35) and NaCl concentration (1000 and 2000 mg/L) on process performance. In their
study, high chromium removal was observed at higher current
densities and solution pH. They found that increasing the chloride concentration from 1000 to 2000 mg/L reduced chromium
removal efciency. Golder et al. [24] studied electrotreatment of
nickel and boron containing plating rinse efuent by using mild
steel and aluminum electrodes. Their results showed that nickel
could be removed with 86% efciency at a current density of
48.78 mA/cm2 .
The above-mentioned studies have been carried out in order
to remove free metal ions that can easily be treated by hydroxide
precipitation. Although the electrochemical processes have been
applied to some organic complex formers such as EDTA, NTA and
citric acid that are also widely employed in the metal nishing
industry, these studies were also conducted on synthetic solutions
and involved membrane separation to recover metals and/or complex formers [2528]. On the other hand, the EC process has the
potential of simultaneously removing both organic complex former
and heavy metals. Therefore, taking into account the high performance of EC in removing a variety of pollutants, the performance of
the process for complexed metal treatment and the effect of operating parameters on the process efciency need to be experimentally
explored.
The target of the present study was to examine the treatability of a metal plating wastewater containing complexed metals
originating from the nickel and zinc plating process, by EC using
stainless steel electrodes and to explore the effect of varying
operating parameters such as the applied current density, initial pH of solution, electrolyte concentration and electrical energy
consumption on heavy metal removal as well as organic matter
removal.
2. Materials and methods
2.1. Metal plating efuent
The source-based composite samples were taken from a metal
nishing factory located in Yalova, Turkey. These samples comprised of the exhausted nickel and zinc plating bath and its
subsequent rinses. The metal plating bath consisted of an organic
complexing agent, carrier, brightener, zinc chloride, nickel chloride
and potassium chloride. The contribution of the complexing agent
to the TOC content of the total efuent was approximately 90% [29].
The environmental characterization of the composite samples used
in our experimental study is delineated in Table 1 in terms of main
pollution parameters.

839

Table 1
The environmental characterization of the composite samples.
Parameter

Unit

Composite
Sample I

Composite
Sample II

Composite
Sample III

TOC
Zinc
Nickel
Chloride

mg/L
mg/L
mg/L
mg/L

173
232
248
1480

170
217
270
1515

170
236
282
1725a

After acidication to pH 3 with HCl.

2.2. The electrocoagulation unit

The electrocoagulation unit is a 1800-mL-effective capacity rectangular reactor (with a height of 28.3 cm, a length of 34.3 cm and
a width of 12.5 cm) which is made of polyethylene (PE 1000). It
is equipped with six monopolar, parallel connected stainless steel
(SS 304) electrodes used as both anodes and cathodes with effective
surface areas of 38.5 cm2 (L: 11.9 cm and d: 1.02 cm). The distance
between the electrodes was xed at 3 mm. The applied current density (Jc ) was kept constant by means of a high precision DC power
supply (Maksimel Proffesional Systems UPS 023 model; Emax : 20 V;
Jc : 2.2588.00 mA/cm2 ). After each experimental run, the EC reactor and electrodes were carefully rinsed twice with 50% (v/v) nitric
acid solution for 24 min and several times with distilled water
to remove impurities and metal hydroxide precipitates from the
electrocoagulation unit. The electrodes were renewed each time
whenever more than 10% of electrode material was consumed. The
electrode consumption was followed by precise measuring of the
diameter.
2.3. Experimental procedure
The electrocoagulation experiments were run at room temperature. The initial pH values of the composite samples were adjusted
with 6N KOH or 6N HCl in order to keep the original composition
of the efuent and to avoid the addition of foreign ions into the
solution for Runs 1520. Samples were withdrawn from the reactor at proper time intervals during the course of EC. Thereafter, the
samples were allowed to settle for 30 min prior to vacuum ltration
through Millipore membrane lters with a pore size of 0.45 m.
2.4. Analytical procedure
In the composite (raw) and EC-treated samples, TOC, nickel, zinc
and pH were analyzed in order to follow the process performance.
All analyses were performed as dened in Standard Methods [30]
except the COD measurements that was determined by the Open
Reux Titrimetric Method according to ISO 6060 (1986). TOC was
monitored on a Tekmahr-Dorhmann Apollo 9000 model carbon
analyzer. Unicam 929 model atomic absorption spectrophotometer
was used for nickel and zinc determination, while pH measurements were made with Orion 920 model pH meter. The amount
of produced sludge consisting of Fe(OH)3 together with removed
nickel, as Ni(OH)2 , zinc, as Zn(OH)2 , and adsorbable organic matter was determined as the total suspended solids (TSS) parameter
according to Standard Methods after EC process [30].
3. Results
3.1. Effect of applied current density
Applied current density is one of the main operating parameters directly affecting process performance and operating cost.
Therefore, as a beginning, a series of EC experiments was car-

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I. Kabdasl et al. / Journal of Hazardous Materials 165 (2009) 838845

Fig. 1. The effect of applied current density on EC process performance (initial conditions: TOC0 : 173 mg/L; Ni0 : 248 mg/L; Zn0 : 232 mg/L; pH0 : 6; Cl0 : 1480 mg/L)
(:2.25 mA/cm2 ; :4.5 mA/cm2 ; :6.75 mA/cm2 ; :9 mA/cm2 ; *:11 mA/cm2 ; :22.5 mA/cm2 ; +:33.75 mA/cm2 ; :45 mA/cm2 ; :56.25 mA/cm2 ).

ried out on the Composite Sample I at a wide range of applied

current densities varying between 2.25 and 56.25 mA/cm2 at
an initial pH 6.0 and a chloride concentration of 1480 mg/L
(the original composition of Composite Sample I) to assess the
effect of applied current density on process performance and
to determine the optimum current density in terms of removal
efciencies as well as electrical energy requirements and sludge
production.
3.1.1. Effect on the organic complex former removal
Fig. 1 displays changes in TOC (a), nickel (b), zinc (c) and pH (d)
during the EC process run under different applied current densities.
As can be seen from Fig. 1(a), increasing the applied current density
from 2.25 to 9.0 mA/cm2 appreciably improved the TOC removal
efciency from 20% to 66%. On the other hand, in the range of
22.556.25 mA/cm2 practically the same TOC removal efciencies
(60%) were obtained, however, within relatively shorter reaction
times. For instance, 60% TOC was removed after 150 min at the
applied current density of 9.0 mA/cm2 and the same removal efciency was obtained in only 45 min at 45 mA/cm2 [29]. Hence, it can
be easily deduced that an increase in the applied current density
accelerated TOC removal kinetics. This observation can also be sup-

ported by regression analyses applied to t the TOC concentrations

as a function of EC operation time obtained for different applied current densities to the pseudo-rst-order kinetic expression as given
below:
ln

(TOC)t
= kTOC t
(TOC)0

(1)

where t is EC treatment time (in min) and kTOC is the pseudorst-order reaction rate constant (in min1 ). The calculated
pseudo-rst-order TOC rate constants are tabulated in Table 2. As
can be seen from the table and Fig. 2, the tness to the data was
very satisfactory (R2 > 0.92) and increasing the applied current density signicantly enhanced TOC removal rates. This interpretation is
consistent with the results given in the related literature [9,10,16].
In addition, a linear increase has also been obtained for the pseudorst-order TOC rate constants versus the applied current densities

Table 2
TOC removal rate coefcients for EC applied under different applied current density
(pH0 : 6.0 and chloride: 1450 mg Cl/L).
Run

Jc (mA/cm2 )

kTOC (min1 )

Time interval (min)

R2

1
2
3
4
5
6
7
8
9

2.25
4.50
6.75
9.00
11.00
22.50
33.75
45.00
56.25

0.0014
0.0021
0.0037
0.0042
0.0046
0.0083
0.0121
0.0173
0.0247

0180
0180
0180
0105
090
0120
090
060
030

0.92
0.96
0.97
0.99
0.99
0.98
0.97
0.92
0.99

Fig. 2. Application of the pseudo-rst-order reaction kinetic for EC run at different applied current densities (:2.25 mA/cm2 ; :4.5 mA/cm2 ; :6.75 mA/cm2 ;
:9 mA/cm2 ; * 11 mA/cm2 ; :22.5 mA/cm2 ; +:33.75 mA/cm2 ; :45 mA/cm2 ;
:56.25 mA/cm2 ).

I. Kabdasl et al. / Journal of Hazardous Materials 165 (2009) 838845

(kTOC = 0.0004 Jc , R2 = 0.98) which may facilitate decision making for the operation of the EC process.
3.1.2. Effect on nickel and zinc removals
Three mechanisms being involved in the abatement of pollutants via EC process are of importance for heavy metal removal. One
of these mechanisms is the removal of organic matter, which consists of the organic complex former for the present case, by indirect
oxidation apparently through chlorine species formed from chloride ions (according to Eqs. (4)(7)) [6]. TOC abatements obtained
through the EC process implied the degree of mineralization e.g.
complete oxidation of the organic matter. However, complete oxidation of the organic matter is not required to free the heavy metal
bound by organic complex former. Organic matter (organic complex
former) undergoes the structural changes by which it loses its complexing ability. This may take place at a certain extent of oxidation
and the complexed metals convert into free metal forms which are
removed by the hydroxide precipitation. In our experimental study,
for the case of nickel this conversion was realized after achieving
4050% TOC removal. However, zinc removal was observed to be
independent of TOC abatement indicating that the organic complex
former used in the investigated metal plating bath does not form
complex species with zinc and it is only able to bind the nickel as
a complexed metal. This observation was justied with hydroxide
precipitation run at the pH range of 712 as control experiments
(data not shown). The results showed that only zinc can completely
be removed by hydroxide precipitation at its optimum pH [29].
The second reaction mechanism having an integral role in the
heavy metal removal with EC is hydroxide precipitation of heavy
metals by increasing the solution pH. The increase in pH is a consequence of the following cathodic reaction taking place during the
EC process [17,23]:
2H2 O(aq) + 2e H2 (g) + 2OH

(2)

In hydroxide precipitation, the optimum pH of metal hydroxide

solubility is the key parameter of the heavy metal removal performance. The optimum pH values for zinc and nickel removal are 9.2
and 10.2, respectively [1].
The third mechanism is the removal of colloidal material
through the formation of Fe(OH)3 ocs. This mechanism enhances
the removal of metal hydroxide solids which have a colloidal form.
Since the amount of coagulation material namely Fe(OH)3 was
always higher than the amount required for sweep oc destabilization of colloids, the effect of this mechanism could be considered
equivalent in all experimental studies carried out in the present
work.

841

As mentioned above, nickel removal was closely related not

only to the degree of TOC abatement but also pH increases being
occurred during the EC process. As is evident from Fig. 1(d), pH
gradually increased through the EC processes and very limited pH
changes were obtained at the end of reaction at lower applied current densities than 9 mA/cm2 . Hence nickel removal efciencies
were limited to 80%. Signicant nickel removal began after TOC
concentrations fell below 100 mg/L in our EC applications. Together
with these TOC abatements and when the solution pH was attained
to or exceeded the optimum pH of nickel, complete removals were
achieved (cf. Fig. 1(b) and (d)). These two prerequisites were provided for the applied current densities of 9 and 22.5 mA/cm2 in 180
and 90 min, respectively. On the other hand, as zinc removal was
only related to the nal solution pH, complete zinc removals were
obtained in all EC applications (Runs 19).
3.1.3. Effect on specic energy consumption and sludge
production
The major operating cost of the process is considered to be
directly related to the specic energy consumption during EC [16].
The specic energy consumption (SEC) is dened as the amount
of electrical energy consumed per unit mass of pollutant (TOC and
nickel in the present case) removed [31]. Table 3 summarizes the
specic electrical energy consumptions obtained for EC processes
run with a wide range of the applied current densities. The specic
energy consumptions were calculated using the equation given as
follows;
SEC =

UIt
g removed pollutant

(3)

where U is the voltage measured during the reaction (in V), I the
applied electrical current (in A) and t the reaction time (in hour).
As clearly seen from Table 3, the calculated specic energy consumptions for TOC and nickel increased with increasing applied
current densities as expected. When the applied current density
was elevated from 2.3 to 9.0 mA/cm2 , the SEC values increased in
parallel from 0.08 to 0.16 kWh/g TOC removed for 3 h operation
time. As also delineated in Table 3, the calculated SEC value for
22.5 mA/cm2 (corresponding to 0.44 kWh/g TOC removed) was signicantly higher than for the calculated value for 9.0 mA/cm2 . The
same trend was also observed for nickel removal. The calculated SEC
values for TOC removal were relatively higher than the calculated
values for nickel removal. However, the main target of the process
is to remove nickel almost completely to comply with the national
discharge standards (2 mg/L according to [32]) and only the SEC values satisfying this prerequisite are meaningful from this standpoint.

Table 3
Specic electrical consumptions and sludge characteristics.
Run

TOCrem (%)

SECTOC (kWh/g TOCrem )

Nirem (%)

SECNi (kWh/g Nirem )

Sludge (mg TSS/L)

SVI (mL/g TSS)

1
2
3
4
5
6
10
11
12
13
14
15
16
17
18
19
20

15
36
50
66
48
63
66
62
63
62
56
45
40
44
50
46
40

0.08
0.10
0.14
0.16
0.20
0.44
0.16
0.15
0.15
0.14
0.14
0.14
0.15
0.14
0.14
0.15
0.14

80
80
80
100
96
100
100
100
100
100
100
78
79
78
77
83
96

0.01
0.03
0.06
0.07
0.07
0.20
0.05
0.06
0.06
0.05
0.05
0.049
0.046
0.048
0.054
0.049
0.037

2,290
4,075
5,900
8,085
11,100
13,900
7,490
7,615
7,250
7,500
7,270
3,000
3,200
4,130
4,000
4,200
3,800

185
108
68
60
45
36
75
74
59
47
53
90
82
74
69
55
60

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I. Kabdasl et al. / Journal of Hazardous Materials 165 (2009) 838845

Fig. 3. Effect of electrolyte (chloride) concentration on EC process performance (at 9.0 mA/cm2 ; initial conditions: TOC0 : 170 mg/L; Ni0 : 270 mg/L; Zn0 : 217 mg/L; pH0 : 6; Cl0 :
1515 mg/L) (:1510 mg Cl/L; :1875 mg Cl/L; :2250 mgCl/L; :2635 mg Cl/L; *:3000 mg Cl/L).

Consequently, among the applied current densities employed in the

present study, 9.0 mA/cm2 gave the optimum result on the basis of
both organic matter (66% TOC) and nickel (100%) removals as well
as the calculated SEC values.
The amount of sludge produced at the end of the EC processes
run at varying applied current densities are also given in Table 3.
It is not surprising that the sludge production during EC process
increased upon increasing the applied current density. The results
indicated that an increase in the applied current density from 2.25
to 9.0 mA/cm2 brought about a threefold increase in the sludge
formation rate. On the other hand, the sludge volume index (SVI)
values revealed that the sludge settling characteristics signicantly
improved with increasing the applied current density. Nevertheless, SVI values measured for all EC runs represented a good settling
character except the value obtained for lower applied current density employed e.g. Runs 1 and 2.
Within the context of the above evaluations and from the standpoints of both removal efciencies and process operation, it was
decided that 9 mA/cm2 is the optimum applied current density for
the particular efuent under study. This optimum current density
is markedly lower than that found by Golder et al. as 32.82 mA/cm2
[22,23] for chromium removal. Hence, the forthcoming experiments were all run at an applied current density of 9.0 mA/cm2 .

2H2 O + 2e H2 (g) + 2OH

(5)

Cl2 (g) + H2 O HOCl(aq) + H+ + Cl

(6)

HOCl H+ + OCl

(7)

The chlorine/hypochlorite couple oxidizes the pollutants

thereby getting reduced to chloride ions [6]. Therefore, in order
to determine the effect of electrolyte concentration on the process performance, another set of EC experiments was carried out
at varying chloride concentrations at the optimum applied current density of 9 mA/cm2 and original pH (=6) of the efuent. As
Composite Sample II already bore 1515 mg/L chloride which was an
advantage of the wastewater sample thus providing a suitable electrolyte concentration that is essential for EC, the experiments were
initiated with the original sample composition and the chloride
concentration was then increased up to 3000 mg/L.

3.2. Effect of electrolyte concentration

As mentioned in the literature, increasing the electrolyte
(NaCl) concentration accelerates inorganic and organic pollutant
removals, decreases the power consumption and shortens the
reaction time [33,34]. In addition, chloride may generate chlorine/hypochlorite serving as an oxidizing agent during EC process
at a proper pH range (pH < 11) and for an appropriate electrode
material e.g. stainless steel [6,33].

2Cl (aq) Cl2 (g) + 2e

(4)

Fig. 4. Application of the pseudo-rst-order reaction kinetic for EC run at

various electrolyte (chloride) concentration (:1510 mg Cl/L; :1875 mg Cl/L;
:2250 mgCl/L; :2635 mg Cl/L; *:3000 mg Cl/L).

I. Kabdasl et al. / Journal of Hazardous Materials 165 (2009) 838845

Table 4
TOC removal rate coefcients for EC applied at varying chloride concentrations (Jc :
9 mA/cm2 and pH0 : 6).
Run

Chloride (mg/L)

kTOC (min1 )

Time interval (min)

R2

10
11
12
13
14

1512
1875
2250
2635
3000

0.0054
0.0053
0.0052
0.0050
0.0050

090
090
090
090
090

0.99
0.99
0.99
0.99
0.99

3.2.1. Effect on the organic complex former

Fig. 3(a) illustrates time-dependent changes in TOC values as a
function of chloride concentration during the EC process. From the
gure it is clear that the originally present chloride concentration of
1515 mg/L in the composite sample was sufcient for the removal
of organic complex former and provided a high degree of mineralization yielding the lowest remaining TOC of 57 mg/L. On the other
hand, further increase in chloride concentration did not enhance
TOC removal efciencies even resulting in a slight decrease in the
process performance. The highest TOC removal efciency (66%) was
achieved at the lowest chloride concentration (1515 mg/L). However, as can be seen from Fig. 4 the pseudo-rst-order kinetics
(Eq. (1)) was obeyed for all tested chloride concentrations and
the TOC removal rate coefcients were all close to each another
(Table 4). Nevertheless, a slight decrease in TOC removal rates with
increasing chloride concentration was evident. These ndings were
all in accordance with the literature data [9] where no signicant effect of chloride concentrations was observed over 1500 mg/L
while increasing chloride concentrations up to 1500 mg/L improved
organic matter removal.
3.2.2. Effect on nickel and zinc removals
Although gradually increasing within the rst 120 min of reaction, the pH shifted to highly alkaline pH values at the end of
EC. The nal efuent pH values were around 11 for all experimental runs except the EC run with a chloride concentration of

843

3000 mg/L (Fig. 3(d)) yielding a nal pH of 12. From Fig. 3(c) it is
evident that more or less the same zinc removal efciencies were
attained at any time of EC application for all experimental runs.
Though the solution pH values were in the range of 6.57.5 being
much lower than optimum pH of zinc after 60 min EC, almost complete zinc removals were obtained. This zinc removal other than
hydroxide precipitation may be attributable to binding onto freshly
produced Fe(OH)3 ocs described in Section 3.1.2 as the third
mechanism.
As aforementioned, in order to ensure complete nickel removal,
two prerequisites have to be fullled: (i) conversion into the free
metal state through the structural change of the organic complex
former and (ii) reaching its optimum pH condition. In the present
study, 4050% TOC abatement spoke for the loss of the agents
complexing ability. It can be inferred that these prerequisites were
practically satised at the end of 105 min EC (Fig. 3(a)). Although
the remaining TOC content was in the range of 90100 mg/L, unsatisfactory nickel removal efciencies (80%) were obtained at the end
of this time interval due to low pH and resulting efuent nickel concentrations varying between 25 and 50 mg/L and thus exceeding
the national discharge standards (Fig. 3(b)). Under all EC conditions, as the solution pH values reached the optimum pH, nickel
was completely precipitated after 150 min EC. It is interesting that
similar to the zinc removal pattern, more or less the same remaining nickel concentrations were measured at any time for all chloride
concentrations tested.
3.2.3. Effect on the specic energy consumption and sludge
production
The calculated SEC values for both TOC and nickel removals
obtained during EC at varying chloride concentrations were practically identical as obvious from Table 3. The amount of sludge
produced during EC remained unchanged with increasing chloride concentration as well. Thus it can be concluded that increasing
the electrolyte (chloride) concentration had no positive inuence
on treatment performance. Therefore, as long as the targeted TOC

Fig. 5. Effect of initial pH on EC process performance (at 9.0 mA/cm2 ; initial conditions: TOC0 : 170 mg/L; Ni0 : 282 mg/L; Zn0 : 236 mg/L; pH0 : 6; Cl0 : 1725 mg/L) (:pH 3; :pH
4; :pH 5; :pH 6; * pH 7; :pH 8).

844

I. Kabdasl et al. / Journal of Hazardous Materials 165 (2009) 838845

Fig. 6. Application of the pseudo-rst-order reaction kinetic for EC initiated at different initial pH values (:pH 3; :pH 4; :pH 5; :pH 6; *:pH 7; :pH 8).

reductions and complete heavy metal removals are achieved, there

is no need to increase the conductivity by chloride addition.
3.3. Effect of initial pH
It has already been established that the initial as well as nal
pH achieved after through EC are important operation parameters
dramatically affecting the EC process performance [68,16,17]. In
order to examine the effect of initial pH on TOC and heavy metal
abatements, another set of EC process was performed using acidied Composite Sample III (see Table 1) at the optimum applied
current density (9 mA/cm2 ). The reason of primary acidication
was to work with the same initial chloride concentration; hence,
rst the initial pH of the composite sample was adjusted to 3 with
1N HCl and then it was increased to the desired pH with 1N KOH.
A wide range of initial pH varying between 3 and 8 was tested.
3.3.1. Effect on the organic complex former removal
The results illustrated in Fig. 5(a) indicated that TOC reduced
with increasing treatment time and TOC abatements were not very
different from each other for all initial pH values for 120 min of EC
operation. At the end of EC operation, the highest TOC removal efciency (50%) together with the highest reaction rate were observed
for EC started at an initial pH of 6 and resulting in a remaining
TOC of 85 mg/L. Regression analyses were applied to t the data
obtained for EC initiated at different pH values to the pseudo-rstorder kinetic (Fig. 6). The tness to the data was very satisfactory
and all the TOC removal rate coefcients found to be close to one
another (see Table 5). TOC removal rates were also very close to
those run with varying chloride concentrations.
3.3.2. Effect on nickel and zinc removal
Fig. 5(d) depicts time-dependent pH evolution as a function of
EC treatment time. pH slowly shifted from slightly acidic to around
neutral pH values (7.27.9) except the EC initiated at pH 8. After
90 min of operation time, reaction solution pH values remained
Table 5
TOC removal rate coefcients for EC started at varying initial pH (Jc : 9 mA/cm2 and
chloride: 1725 mg Cl/L).
Run

pH0

kTOC (min1 )

Time interval (min)

R2

15
16
17
18
19
20

3.0
4.0
5.0
6.0
7.0
8.0

0.0049
0.0035
0.0048
0.0056
0.0049
0.0042

0120
0105
0120
0120
0120
0120

0.99
0.99
0.99
0.99
0.99
0.99

practically at the same level with increasing time. In spite of the

lower pH values than the optimum of zinc, complete zinc removals
were achieved at the end of 60 min for these runs (Fig. 5(c)). During
EC starting at an initial pH of 8, the pH gradually increased upon
increasing EC time and the nal pH was obtained as 10.34. In this
case, the discharge standard (3 mg/L [32]) for zinc was met even
after 10 min of operation time.
The experiments clearly indicated that as long as a TOC reduction of 4050% was reached, nickel could be totally removed when
the solution pH reached a proper value of around 10 corresponding to its optimum pH. Upon closer inspection of Fig. 5(a) and (d)
it can be seen that these two prerequisites were satised during
only one run, e.g. the EC initiated at pH of 8 resulted in almost
complete nickel removal. In case of the other EC runs, while the
TOC removal condition was ensured, the nal pH values were
far from the optimum pH condition. Therefore, nickel concentrations were reduced to around 50 mg/L accompanied with 80%
removal efciency exceeding the discharge standards for these EC
runs (Fig. 5(b)). Considering these EC runs for which 4050% TOC
removals were obtained, to cope with this pH constraint further pH
adjustment can be made using a proper alkali agent such as lime, or
NaOH. In this case, a signicant cost reduction would be possible in
terms of sludge handling, treatment duration and electrical energy
consumption. Further pH adjustment of the efuents obtained at
the end of 120 min EC in the present study justied the applicability
of this alternative. An experiment that was conducted to check this
issue yielded complete nickel removal. Another alternative would
be the prolongation of EC operation just for the purpose of increasing the pH at the expense of increasing the amount of operating
(electrical energy and sludge handling) costs (cf. Runs 10 and 18).
3.3.3. Effect on the specic energy consumption and sludge
production
Although the calculated SEC values for TOC removals were found
to be similar, the lowest value for nickel was obtained for the EC run
initiated at a pH of 8 (Run 20) as can be seen from Table 3.
From Table 3 it is evident that shorter treatment time brought
about appreciably lower sludge production. For instance, in the case
of EC run at a current density of 9 mA/cm2 and an initial pH of 6,
the decrease in treatment time from 180 to 120 min resulted in
a signicant decrease in sludge formation from 7490 to 4000 mg
TSS/L, as would be expected.
4. Conclusions
In the present study, electrocoagulation using stainless steel
electrodes proved to be a promising treatment method for complexed metal removal as well as organic matter reduction from
complexed metal wastewater originating from metal plating industry. The following conclusions could be drawn from the present
study:
The experimental results revealed that the organic complex former used in the metal plating bath formulation could be oxidized
through the EC process to free nickel ion corresponding to 4050%
TOC removal. Therefore, the effective mechanism of the process
can be postulated as breaking of the complexing agent structure
via oxidation, followed by hydroxide precipitation and adsorption/entrapment on freshly produced ferric hydroxide ocs.
The experimental results indicated that the highest TOC abatement (66%) as well as nickel and zinc removals (100%) were
achieved with an applied current density of 9 mA/cm2 at the original electrolyte (chloride) concentration and original pH of the
composite sample used. Therefore, it can be concluded that the

I. Kabdasl et al. / Journal of Hazardous Materials 165 (2009) 838845

national discharge standards could be complied with by applying 9 mA/cm2 current density without any electrolyte addition
and/or pH correction.
The results obtained at varying operation conditions in order to
elucidate their effects on process performance implied that TOC
and heavy metal removals as well as sludge production and specic energy consumption rates were signicantly affected by the
applied current density. On the other hand, the process performance was not signicantly affected by increasing the chloride
concentration. Reduction of the initial pH of the composite sample did not enhance the process performance in terms of TOC
and zinc removals, but reduced nickel removal due to low efuent pH values achieved unless the reaction time was extended to
180 min.
Results of regression analyses applied to the obtained experimental data revealed that in all cases TOC removal perfectly obeyed
the pseudo-rst-order reaction kinetics. While TOC removal rates
were signicantly accelerated with increasing the applied current density, increasing the chloride concentration and varying
the initial reaction pH did not signicantly affect the TOC removal
efciency.
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