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Key Words: Electrochemical advanced oxidation processes (EAOPs), malachite green, orange II,
hydroquinone-like intermediates, wastewater treatment
ABSTRACT
Electro-Fenton process is a potentially useful oxidation process for destroying toxic organic
compounds in aqueous medium. In this study, the electro-Fenton degradation of a solution mixture
of Malachite Green (MG) and Orange II catalyzed by ferric ions was examined. Results showed that
this system could degrade and mineralize the dye mixture. It was shown that absorbance decrease in
MG was accelerated in the presence of Orange II, whereas absorbance decrease of Orange II at the
same conditions was depressed. This behavior was attributed to generation of hydroquinone-like
intermediates from degradation of Orange II that can accelerate Fenton reaction by reduction of Fe3+
to Fe2+ ions. GC-MS detection of the products formed in the Orange II electro-Fenton degradation
showed the generation of dihydroxynaphthalene compounds that are probably responsible for
acceleration of MG degradation.
INTRODUCTION 15% of dyes of the total world production are lost dur-
ing synthesis and processing with wastewater [4].
Rapid industrialization and urbanization result in Thus, there is an urgent need for textile industries to
the discharge of large amount of waste to the envi- develop effective methods of water processing.
ronment, which in turn creates more pollution. The Many studies have reported decoloration of solu-
majority of colored effluents are caused by the release tions containing only one dye by different methods.
of dyes to the environment from textile, dyestuff, and However, industrial effluents usually contain mixture
dyeing industries. Color is usually the first contami- of dyes. As a result, investigation of treatment of real
nant to be recognized in wastewater. A very small wastewater or mixture of dyes is important.
amount of dye in water (10-20 mg L-1) is highly visi- Development of the appropriate techniques for
ble and affects water transparency and gas solubility treatment of mixture of dyes wastewater is important
of waterbodies [1]. for the protection of natural waters. To eliminate dyes
Many industrial and agricultural activities use from aqueous colored effluents and reduce their eco-
water in an excessive way. However, it is now well logical consequences, several biological, chemical and
known that the fresh water resources are limited, so electrochemical techniques have been proposed: an-
they must be protected. The availability of clean water aerobic/aerobic degradation [5,6], Fenton’s reagent [7],
for various human needs in the next decades seems to TiO2 photocatalyst [8], electro-coagulation/electro-
become a challenge to take up. There are many classes flocculation [9] and anodic oxidation [10]. Other
of dyes such as acidic, basic, neutral, azo, disperse, di- physical/chemical techniques including adsorption [11]
rect, reactive, etc. Out of these dyes, azo dyes are and flotation [12] have also been employed. Physi-
most frequently used. These dyes contain one or more cal/chemical methods do not degrade the pollutants
azo bonds (–N=N–) in their structure [2]. Triphenyl- but they only transfer them from the liquid phase to
methane dyes are the next in the list. Some of these the solid phase, thus causing secondary pollution.
dyes are toxic and potentially carcinogenic [3]. About Conventional wastewater treatment based on biologi-
*Corresponding author
Email: vahidvatanpoor@yahoo.com
278 J. Environ. Eng. Manage., 19(5), 277-282 (2009)
tro-Fenton process, a catalytic amount of 10-4 M Fe3+ Results show that degradation of MG is faster than
was added to the solution. Orange II.
The oxidizing power of the electro-Fenton sys-
4. Analysis Procedure tem to mineralize dye solutions was evaluated from
their TOC decay. Figure 1b shows selected TOC-time
Samples were withdrawn from the reactor at plot for the degradation of the mixture of MG and Or-
regular time intervals and the removal of color was ange II solution using 9.5 cm2 graphite felt cathode. A
evaluated by simultaneous spectrophotometeric de- continuous TOC abatement was observed attaining
termination using mean centering of ratio spectra [28]. 79% of mineralization after 180 min of electrolysis.
This method has been inspired from successive ratio TOC decay shows that this electro-Fenton system can
derivatives of ratio spectra in two steps. The mean degrade and mineralize organic pollutants.
centering method uses mean centering of ratio spectra
instead of derivatives of them. By eliminating deriva- 2. Electro-Fenton Degradation of MG and Orange
tive steps, signal-to-noise ratio is enhanced dramati- II in Separate and Mixed Solution
cally.
Figures 2a and 2b show the absorbance decrease
RESULTS AND DISCUSSION at 619 nm (MG) and 484 nm (Orange II) alone or in
mixed solution. The removal efficiency of both MG
1. Decoloration and Mineralization of a Mixture and Orange II was altered in the mixed solution com-
Containing MG and Orange II pared with the separate case. In the presence of Or-
ange II, decoloration of MG was accelerated whereas
A mixture of MG and Orange II at initial con- decoloration of Orange II was reduced to some extent
centration of 10-5 M for each one was treated by elec- when MG was present. The depression of the absorb-
tro-Fenton process at -0.5 V. Electrochemically gen- ance decrease at 484 nm can be attributed to competi-
erated hydroxyl radicals react with dye molecules tive trap of hydroxyl radicals by MG [29] and the ef-
leading to their oxidation. Figure 1a shows a rapid de- fect of high concentration of pollutant. However, the
cay of each dye present in the synthetic dye mixture as absorbance decrease at 619 nm was surprisingly ac-
a function of time during the electro-Fenton process. celerated in the presence of Orange II. It was men-
tioned that some degradation intermediates obtained
1
from degradation of aromatic compounds such as
(a) MG
Orange II
quinone-like compounds could expedite the reduction
0.8 of ferric ions to ferrous ions (Eqs. 10 and 11) [29-32].
As a result, rate of Fenton reaction was accelerated.
0.6
C/C0
0.4
k = 1×109 M-1 s-1 (8)
0.2
0
1.2
(b)
1 k = 1×109 M-1 s-1 (9)
0.8
TOC/TOC0
0.6
0
0 50 100 150 200
Time (min) k = 4.4×104 M-1 s-1 (11)
Fig. 1. Removal of an aqueous mixture of dyes MG and
Orange II (C0 = 10-5 M of each dye) during electro-
Fenton treatment in the presence of Fe3+ ions as
catalyst. [Fe3+] = 10-4 M, [NaClO4] = 0.05 M, pH =
k = 1×109 M-1 s-1 (12)
3 and E = -0.5 V vs. SCE. (a) decoloration; (b)
mineralization.
280 J. Environ. Eng. Manage., 19(5), 277-282 (2009)
30 only MG 30
◊ : 2 × 10-5 M
Fig. 2. Destruction of dyes by electro-Fenton Fig. 3. Effect of one dye on the other: [NaClO4] = 0.05
degradation of: (a) MG, alone or mixed, (b) M, pH = 3.0, [Fe3+] = 10-4 M and E = -0.5 V. (a)
Orange II, alone or mixed. [MG] = 10-5 M, Influence of Orange II concentration on MG (619
[Orange II] = 10-5 M, [NaClO4] = 0.05 M, pH = nm) at [MG] = 10-5 M; (b) Influence of MG
3.0, [Fe3+] = 10-4 M and E = -0.5 V. concentration on Orange II (484 nm) at [Orange
II] = 2 × 10- 5 M.
It can be hypothesized, based on what observed
for Fenton systems, that Orange II or some intermedi- Fe3+ + H2O2 → Fe2+ + HO •2 + H+ (14)
ates generated in the degradation of Orange II could
accelerate the removal of MG by accelerating of hy-
droxyl radical production. 3. Influence of Initial Orange II Concentration on
In order to show whether hydroquinone-like in- MG Degradation
termediates generated in degradation of Orange II or
not, electro-Fenton degradation intermediates of Or- With regard to these findings, that Orange II is
ange II alone was determined after 60 min electrolysis source of hydroquinone-like intermediates, investiga-
by GC-MS analysis. Results were reported in previous tion of the effect of the Orange II initial concentration
work [27]. It is observed that one of the identified in- on MG degradation is examined. Figure 3a shows that
termediates is 1,2-dihydroxynaphthalene. It was re- removal efficiency of MG increased by increasing Or-
ported that ortho-dihydroxy aromatic compounds such ange II concentration up to 2 × 10-5 M. This effect can
as catechol and 2,3-dihydroxybenzoic acid can reduce be attributed to more conversion of Fe3+ to Fe2+ by in-
ferric ions to ferrous ions [32,33]. Probably generated creasing of produced intermediates from degradation
1,2-dihydroxynaphthalene from degradation of Or- of Orange II. However, at higher Orange II concentra-
ange II can reduce Fe3+ to Fe2+ and therefore, lead to tion, scavenging of hydroxyl radicals overcome in ac-
increasing of absorbance decrease rate at 619 nm in celerating effect and therefore, removal efficiency of
electro-Fenton process. MG is reduced.
Generally speaking, in electro-Fenton system
Fe2+ is regenerated through the reduction of Fe3+ in 4. Influence of MG Concentration on Orange II
cathode surface (Eq. 13) and then reduced to Fe2+ by Degradation
H2O2 (Eq. 14). However, at the same time in the pres-
ence of hydroquinone-like intermediates, regeneration In previous sections, it was observed that ab-
of Fe2+ is prompted and causing a rapid degradation of sorbance decrease at 484 nm (Orange II) in the pres-
contaminant. ence of MG was depressed. Figure 3b shows that by
increasing MG concentration, removal efficiency of
Fe3+ + e− → Fe2+ (13) Orange II is lower. It can be attributed to high scav-
Vatanpour et al.: MG and Orange II Mixture Treatment by EF 281
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Fenton’s reagent at carbon-felt cathode, Manuscript Received: March 28, 2008
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