Journal of Hazardous Materials 168 (2009) 129–136

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Journal of Hazardous Materials

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Oxidative degradations of reactive blue 4 dye by different advanced

oxidation methods
Belgin Gözmen a,∗ , Berkant Kayan a , A. Murat Gizir a , Arif Hesenov b
a
Department of Chemistry, Arts and Sciences Faculty, Mersin University, 33343 Mersin, Turkey
b
Department of Chemistry, Arts and Sciences Faculty, Cukurova University, 01330 Adana, Turkey

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

Article history: The degradations of an anthraquinone dye, the reactive blue 4 (RB4), were studied by wet air oxida-
Received 24 June 2008 tion (WAO), wet peroxide oxidation (WPO), photocatalytic oxidation, and electro-Fenton (EF) advanced
Received in revised form oxidation. The RB4 oxidation was evaluated by the decrease in total organic carbon (TOC) content and
23 December 2008
concentration. The most efficient method for mineralization of RB4 was WPO, but in all methods TOC
Accepted 4 February 2009
removal efficiency was above 75% after 60 min of treatment.
Available online 12 February 2009
© 2009 Elsevier B.V. All rights reserved.
Keywords:
Wet air oxidation
Wet peroxide oxidation
Electro-Fenton
Photocatalytic oxidation
Degradation
Reactive blue 4

1. Introduction The interaction between this semiconductor and UV radiation pro-

duces electron-hole pairs in the surface of semiconductors. The
Textile manufacturing is one of the largest industrial producers highly oxidative hVB + can react with surface bound H2 O to produce
of wastewater, which is characterized by strong color, highly fluctu- hydroxyl radicals or can directly react with the organic molecules
ating pH, high chemical oxygen demand (COD), and biotoxicity [1]. [5,12,13]. Photoactivated periodate (UV/TiO2 /IO4 − system) was pro-
Although various traditional methods such as adsorption, coagula- posed as a novel advanced oxidation method. The periodate ions
tion, and biological treatments have been used to treat textile dye (IO4 − ) capture released electrons from TiO2 , thus elongating the
wastewater, none of these treatments was satisfactory because of life of hVB + [14–16]. Fenton’s reagent is an acidic mixture of hydro-
the effluent’s high degree of polarity and complex molecular struc- gen peroxide and Fe(II). Recently, a new electrochemical advanced
ture [2,3]. Promising results have been achieved using advanced process called electro-Fenton (EF) was used successfully to degrade
oxidation processes (AOPs) for effluent from the dyeing industry various organic pollutants. Electro-Fenton methods broadly involve
in recent years [4–7]. These processes are based on the production the continuous production of hydrogen peroxide by reduction of
of highly reactive radicals, especially hydroxyl radicals, which pro- dioxygen at the cathode in aqueous medium [17–21]. Wet air
mote destruction of the target pollutant until mineralization [8]. oxidation can be defined as the oxidation of organic and inor-
The remarkable advantage of AOPs over all chemical and biological ganic compounds in aqueous solution or suspension by air or
processes is that they neither transfer pollutants from one phase to oxygen. Under oxygen pressure (5–200 bar) at elevated temper-
the other nor produce massive amounts of hazardous sludge [9–11]. ature (125–320 ◦ C), this process can completely remove organic
Advanced oxidation processes include ozonation, photocatalytic pollutants [22,23]. However, the application of WAO under rigor-
degradation, Fenton’s reagents (H2 O2 /Fe2+ ), photo-Fenton, and wet ous conditions (high temperature and oxygen pressure) is limited
air oxidation (WAO). The photocatalytic system involves illumi- due to the high apparatus requirements, which result in high run-
nation of large-bandgap semiconductor particles such as TiO2 ning costs. Therefore, it is necessary to study this process under
dispersed as slurry in contaminated solution or immobilized film. mild conditions. If a relatively good performance for the treatment
of dye wastewater can be achieved, this WAO process could find
widespread use in industry [24]. In order to improve the conditions
∗ Corresponding author. Tel.: +90 324 3610001; fax: +90 324 3610046. of such a process, homogeneous or heterogeneous catalysts, and
E-mail address: [email protected] (B. Gözmen). strong oxidant such as hydrogen peroxide were added [22,23,25].

0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.02.011
130 B. Gözmen et al. / Journal of Hazardous Materials 168 (2009) 129–136

Nomenclature

AOPs advanced oxidation processes

COD chemical oxygen demand (mg/L)
C0 initial dye concentration (mg/L)
Ct dye concentration at any time (mg/L)
DE degradation efficiency
DOC dissolved organic carbon (mg/L)
RB4 reactive blue 4 Fig. 1. Molecular structure of reactive blue 4 dye.
TOC total organic carbon
WAO wet air oxidation
WPO wet peroxide oxidation treatments. TiO2 (Anatase form 99.9%) was purchased from Aldrich
(USA) with average particle size of approximately 1 ␮m, specific
surface area 8.9 m2 g−1 , and pHzpc approximately 3.8 [35]. A car-
bon felt electrode (RVG 2000) was obtained from Carbone Loraine
Reactive dyes are frequently used for the dyeing of cotton, (France). All other chemicals, including anhydrous Na2 SO4 , HClO4 ,
woolen, and polyamide fibers [26]. Under typical reactive dyeing H2 O2 , KIO4 , and Fe(NO3 )3 ·9H2 O, were analytical grade. Oxygen was
conditions, not all dyes bind to the fabric; depending on the class supplied by Tek Oksijen (Mersin, Turkey), in 99.9% purity.
of dye, up to 50% of the initial dye (up to or exceeding 800 mg/L)
remains in the spent dyebath in its hydrolyzed form, which has no
2.2. Oxidation experiments
affinity for the fabric and results in colored effluent [26,27]. Reac-
tive dyes are known to be non-degradable under the typical aerobic
2.2.1. Wet air oxidation experiments
conditions found in conventional biological treatment systems, and
Wet air oxidation experiments were carried out at various tem-
adsorb very poorly to biological solids, resulting in residual color
peratures between 100 and 250 ◦ C with oxygen pressure fixed at
in discharged effluents [28–30]. In this study, the oxidative degra-
5.05 MPa in a 150 mL stainless steel reactor as shown in Fig. 2. The
dation and mineralization of reactive anthraquinone dye, reactive
quantity of dissolved oxygen in water was calculated using an oxy-
blue 4 (RB4), in aqueous solutions using wet air/peroxide oxidation,
gen solubility model for the needed degradation of 100 mg/L RB4
UV/TiO2 /periodate, and electro-Fenton systems were investigated.
in distilled water [36].
Anthraquinone dyes constitute the second largest class of textile
dyes after azo dyes, and are used extensively in the textile industry.
Reactive blue 4 was selected for this research based on commercial 2.2.2. Wet peroxide oxidation
used and previous frequently research conducted. Recently, many Wet peroxide oxidation (WPO) experiments were carried out at
advanced oxidation processes using Fenton’s reagent (H2 O2 and various temperatures between 100 and 200 ◦ C and 35% hydrogen
Fe2+ ) with or without ultraviolet irradiation, heterogenous catalysts peroxide solution was added to the 150 mL stainless steel reactor,
such as TiO2 combined with artificial UV or solar light sources or with 1% as void volume.
solar photocatalytic–Fenton system (UV/Fenton/TiO2 ), have been
evaluated for the decolorization and degradation of BR4 dye. Nep- 2.2.3. Photocatalytic oxidation (UV/TiO2 /IO4 − )
polian et al. reported that direct solar light induced and TiO2 process The photocatalytic experiments were run with 150 mL, 100 mg/L
achieved complete degradation of 4 × 10−4 M RB4 solution within aqueous dye solution in a 180 mL cylindrical water jacket Pyrex
8 h in the presence of 300 mg/L of H2 O2 [31]. Photo-Fenton process reactor placed on a magnetic stirrer. The pH of the dye solution
under artificial and solar irradiation of BR4 was investigated and the was adjusted to 3.00 by the addition of small quantities of 0.5 mM
best results were obtained using 1.0 mM ferrioxalate and 10 mM of HClO4 solution. Then TiO2 and KIO4 were added to the solution. The
H2 O2 . Under these experimental conditions, 80% TOC and 100% of reaction mixture was sonicated in an ultrasonic bath for 10 min to
color removal were obtained for 0.1 mM RB4 dye in 35 min of solar disperse TiO2 uniformly in the solution. A mercury vapor UV lamp
irradiation [32]. Durán and et al. also reported that photo-Fenton (UVP-CPQ-7871) that emits its maximum radiation at 365 nm was
process achieved 75% TOC removal of 20 mg/L RB4 solution after placed inside the reactor. The intensity of the incident light inside
nearly 120 min at pH 2 in the presence of 300 mg/L of H2 O2 and the photoreactor was measured as 0.38 × 10−6 Einstein s−1 using
4 mg/L of Fe2+ [33]. The heterogeneous photocatalytic degradation a uranyl actinometer [37]. At regular time intervals 26 mL sample
of RB4 solution under Fenton reagent and TiO2 assisted by concen- aliquots were taken and centrifuged for spectrophotometric analy-
trated solar light irradiation using a Fresnel lens was studied [34]. ses. Another experiment under the same conditions was performed
But result showed that mineralization was a slower process, so that for TOC measurements and 3 × 10 mL sample aliquots were with-
a longer time was needed for the complete TOC elimination. drawn from homogeneous 150 mL of solution during treatments.

2. Materials and methods 2.2.4. Electro-Fenton experiments

Electrochemical experiments were performed at constant cur-
2.1. Materials rent with a DC power supply (TT-T-ECHNI-C) in a 250 mL undivided
cylindrical glass cell. 0.05 M Na2 SO4 was used to enhance the con-
Commercial C.I. Reactive Blue 4 (Procion Blue MX-R; Color Index ductivity and 0.5 M HClO4 solution was added to bring the pH to 3.0.
61205; CAS no. 13324-20-4) was obtained from DyStar (Germany) Electrolyses of 200 mL RB4 solutions were performed on a carbon
and used without any further purification. The molecular structure felt working electrode (50 cm2 = 12.5 × 4 cm) by applying a constant
of RB4 (C23 H14 Cl2 N6 O8 S2 ) was shown in Fig. 1. It has been esti- current of 60, 100, and 200 mA. The counter electrode was Pt gauze
mated that approximately 50% of applied reactive dyes is wasted (6 cm2 ) placed on the center of the cell. The solution was stirred
because of dye hydrolysis in the alkaline dyebath. As a result, typ- with a magnetic bar. A catalytic quantity of Fe3+ (0.2 mM) was added
ical spent dyebaths contain dyes at a concentration in the range of to solutions before starting the electrolysis. Prior to the electrolysis,
10–200 mg/L [4,29]. Therefore, the solution of RB4 was prepared oxygen gas was bubbled for 15 min to saturate the aqueous solution,
in 100 mg/L initial concentration with distilled water for all the which was fed with pure O2 at 20 mL/min during the experiments.
 B. Gözmen et al. / Journal of Hazardous Materials 168 (2009) 129–136 131

Fig. 2. Schematic illustration of the wet air peroxide system.

Twenty and thirty milliliter samples of aliquots were taken from to 280 ◦ C at 4 ◦ C min−1 and hold 1 min, and the temperatures of
the dye solution for UV and TOC analyses, respectively, in different the inlet, transfer line and detector were 250, 250 and 280 ◦ C,
experiments. All the samples were filtered through 0.45 ␮m Titan2 respectively. Samples were prepared by the extraction of dye
filter before their TOC analysis. All experiments were repeated twice decomposition products with 45 mL of hexane or dichloromethane
and averages are reported. solvents in three times. Each collected organic solution was then
dried with anhydrous natrium sulfate, filtered and its volume
2.3. Analytical method reduced to 2 mL to concentrate the remaining products for analysis
by GC–MS.
In this study, dye concentration was analyzed spectrophotomet-
rically on a UV–vis spectrometer (Shimadzu UV-160A) at 595 nm by 3. Results and discussion
measuring the absorbance of the untreated and treated samples at
the maximum wavelength, and the percentage of RB4 degradation 3.1. Degradation experiments
efficiency (DE) % was calculated using the following formula:
Co − Ct 3.1.1. Wet air oxidation
DE% = 100 (1)
Co It has been suggested that wet air oxidation occurs through
the formation of alkyl, alkyl peroxide radicals, and hydroperox-
where Co and Ct are the initial and remaining RB4 concentration at
ides, with the third of these being responsible for the autocatalytic
given time t, respectively.
decomposition of organic compounds (RH), as shown in Eqs. (2–8)
The total organic carbon (TOC) of the initial dye solution and
[38].
samples was determined on a Tekmar-Dohrmann Apollo 9000 ana-
lyzer. A calibration curve was prepared using standard solutions RH + O2 → R • + HO2 • (initiation) (2)
of potassium hydrogen phthalate (KHP). An Shimadzu LC-10ADVP
model ion chromatograph equipped with a CDD-6A conductiv- R • + O2 → RO2 • (propagation) (3)
ity detector, a Shodex I-524A anion and Shimpack IC-CI cation •
RO2 + RH → ROOH + R• (propagation) (4)
exchange columns were used to measure nitrate, nitrite, sulfate,
chlorine and ammonium ions using 2.5 mM phthalic acid eluent at ROOH → RO• + OH• (autocatalyticdecomposition) (5)
pH 4 which adjusted with TNs and a total flow rate of 1.2 mL/min
for anions; 5 mM nitric acid a total flow rate of 1.5 mL/min for RO• + RH → ROH + R • (propagation) (6)
ammonium ion. Generated carboxylic acids were identified by HPLC
fitted with a Bio-Rad Aminex HPX 87H column and a 4 mM sulfu- OH• + RH → R • + H2 O (propagation) (7)
ric acid solution as mobile phase at 210 nm. Intermediates were 2ROO• → ROOR + O2 (termination) (8)
identified by gas chromatography–mass spectrometry (GC–MS)
with a Thermo Finnigan Trace-Mass system composed of a Thermo These reactions generated organic radicals and other free rad-
Finnigan GC fitted with a RESTEK Rtx-5MS (crossbond 5% diphenyl- icals, which, in turn, initiated chain reactions of dye degradation
95% dimethyl polsiloxane) 0.25 ␮m, 30 m × 0.25 mm, column and with the help of dissolved oxygen. Many operating parameters
coupled with a Thermo Finnigan Trace-Mass mass spectrome- influence the aforementioned formation of free radicals and thus
ter operating in EI mode at 70 eV. The temperature ramp was the pollutants degradation rate, among which temperature plays
40 ◦ C min−1 , 5 ◦ C min−1 up to 80 ◦ C and hold time 1 min, then the most important role in the case of sufficient oxygen supply [39].
132 B. Gözmen et al. / Journal of Hazardous Materials 168 (2009) 129–136

Fig. 5. Degradation % of RB4 solution by: IO4 − only, TiO2 only, UV/IO4 − and
UV/TiO2 /IO4 − systems. TiO2 = 1 g/L (+, , , ♦, ); 2 g/L (䊉); [IO4 − ]0 = 1 mM (); 3 mM
(x, , , ♦); 5 mM (, 䊉); [RB4]0 = 100 mg/L, V = 150 mL, pH 3.0.

Fig. 3. Effect of temperature on degradation of RB4 in wet air oxidation: 3.1.3. UV/TiO2 /IO4 − process
[RB4]0 = 100 mg/L, V = 150 mL.
In the photocatalytic system, the interaction between a semicon-
ductor and UV radiation produces electron-hole pairs in the surface
of semiconductors such as TiO2 (Anatase). The highly oxidative hVB +
The effect of temperature on degradation after 60 min for wet air can react with surface bound H2 O to produce hydroxyl radicals or
oxidation is shown in Fig. 3. In the case of 100 ◦ C, degradation was can directly react with the organic molecules [15,37,41].
not effective (15.0%) after 60 min treatment. When the temperature
was increased above 100 ◦ C, the degradation was enhanced up to TiO2 + h → eCB − + hVB + (9)
100%. The degradations were 48.0%, 94.0%, and 100% at 150, 200, and hVB + + H2 O(ads) → • OH + H+ (10)
250 ◦ C, respectively. It can be seen that the removal efficiency was
promoted by the increase in temperature due to the enhancement Dye + • OH → degradationproduct (11)
of the hydrothermal reaction and oxygen solubility. +
Dye + TiO2 (hVB ) → oxidationproduct (12)
−
Dye + TiO2 (eCB ) → reductionproduct (13)
3.1.2. Wet peroxide oxidation (WPO)
Fig. 5 shows the decomposition of a 100 mg/L RB4 solution at pH
WPO experiments were carried out at various temperatures
3 by the UV/TiO2 /IO4 − system. In the presence of periodate (IO4 − )
between 100 and 200 ◦ C, and 35% hydrogen peroxide solution was
alone in the dark, no detectable extent of degradation could be
added to the 150 mL stainless steel reactor, with 1% as void vol-
achieved after 60 min treatment. In the UV/IO4 − process without
ume (Fig. 2). At 100 ◦ C the degradation efficiency reached 92% after
TiO2 , the degradation efficiency was only 7% after 60 min of treat-
60 min of treatment. With the temperature further rose to 200 ◦ C,
ment. The effects of TiO2 on degradation of RB4 in the dark and in
the degradation efficiency increased to 100%, which is shown in
the UV system were 27% and 39%, respectively. The addition IO4 −
Fig. 4. Almost complete degradation was reached since first min-
to the UV/TiO2 system is known to enhance the reaction rate due to
utes of reaction at 150 and 250 ◦ C. The fast reaction rate of WPO
IO4 − capture of released electrons from TiO2 , thus elongating the
as opposed to WAO is due to the following reasons: (1) H2 O2 is
life of hVB + by Eq. (14) [14–16]. Degradation efficiency increased
a stronger oxidant; (2) WPO does not require the transfer of oxy-
with increasing concentration of periodate from 1 to 5 mM in the
gen from the gas phase to the liquid phase as required for WAO.
presence of 1 g/L TiO2 suspensions. Degradation of RB4 was 97%,
The WPO mechanism may be considered similar to that of Fenton’s
98%, and 99% after 60 min of treatment for 1, 3, and 5 mM IO4 − ,
reaction, with OH• HO2 • or ROO• radicals being the main oxidants
respectively.
depending on the pH of the solution [40].
IO4 − + 8e(CB) − + 8H+ → 4H2 O + I− (14)
The previous research of Gozmen [42] showed that the decom-
position slightly increased with increasing periodate concentration
from 2 to 5 mM, whereas TOC removal efficiency showed that con-
siderable increase for BR46 dye. However, TOC removal efficiency
was decreased at higher concentration periodate due to scavenging
the hydroxyl radicals with excess periodate ions by Eq. (15) [41]:
• OH + IO4 − → OH− + IO4 • (15)
When the amounts of TiO2 changed from 1 to 2 g/L in the pres-
ence of 5 mM IO4 − 100% degradation of RB4 was achieved after
50 min of treatment because production of hVB + increased with
TiO2 . We did not use higher catalyst amounts due to the decreasing
effect on degradation. The suitable amount of TiO2 for the photo-
catalytic reaction is about 1–3 g/L, although it strongly depends on
the type of reactor and TiO2 powder [43].

3.1.4. Electro-Fenton process

Fig. 4. Effect of temperature on degradation of RB4 by wet peroxide oxidation. In electro-Fenton methods, H2 O2 is continuously produced on
[RB4]0 = 100 mg/L, V = 150 mL. the cathode by two-electron reduction of dissolved oxygen by Eq.
 B. Gözmen et al. / Journal of Hazardous Materials 168 (2009) 129–136 133

Fig. 8. TOC % Removal of RB4 by the UV/TiO2 /IO4 − (5 mM) and electro-Fenton sys-
tems ([Fe3+ ]0 = 0.2 mM, 0.05 M Na2 SO4 ), [RB4]0 = 100 mg/L, pH 3.0.

Fig. 6. Degradation of [RB4] solution with the electro-Fenton system. [RB4]0 : temperatures. To make a comparison, RB4 at 100 ◦ C was also inves-
100 mg/L, [Fe3+ ]0 : 0.2 mM, V = 200 mL, pH 3.0. tigated, and almost no effective degradation was observed. At the
lowest temperature for WAO, the TOC removal efficiency was only
(16) [12,13,18,20]: 12.6%. A further increase in temperature enhanced the mineraliza-
tion, which increased significantly to 81.3% when the temperature
O2 + 2H+ + 2e− → H2 O2 (16)
rose to 250 ◦ C. When using H2 O2 instead of O2 , there was a very
Ferrous ion is usually added to solution in a catalytic concentra- fast increase in the reaction rate. For example, at 100 ◦ C, the TOC
tion because ferrous ion may also be produced by reduction of ferric removal reached 33%. When the temperature rose to 200 ◦ C at
ions at the cathode. According to the classical Fenton’s reaction 60 min, the TOC removal efficiency increased significantly to 87%.
hydroxyl radical is produced in the solution [44]. An anaerobic experiment was also performed to degradation
100 mg/L RB4 solution for comparison. For that purpose, RB4
Fe2+ + H2 O2 → Fe3+ + OH− + • OH (17)
solution was purged with nitrogen for removing oxygen. In the
3+ − 2+
Fe + e → Fe (18) anaerobic condition, TOC removal of degradation of RB4 was
obtained 45% after 60 min at 250 ◦ C. By helping water dye was
Fig. 6 shows the degradation of RB4 solution at pH 3 produced in
degradated in this temperature.
an undivided cell by electro-Fenton in the presence of 0.2 mM Fe3+ .
Fig. 8 shows the TOC decay of a 100 mg/L RB4 solution at
Under electro-Fenton conditions, a progressive increase in degrada-
pH 3 by UV/TiO2 /periodate and electro-Fenton processes. In the
tion was observed by increasing the applied constant current from
UV/TiO2 /IO4 − system, by adding 5 mM IO4 − a slight increase in TOC
60 to 100 mA. This trend could be associated with increasing of
% removal was observed by increasing the concentration of pho-
in situ electrogenerated H2 O2 concentration. After 20 min of elec-
tocatalyst (TiO2 ) from 1 to 2 mg/L. After 60 min illumination with
trolysis at 200, 100, and 60 mA, degradation efficiencies were 100%,
1 g/L TiO2 and 2 g/L TiO2 , 75% and 79% TOC removal was achieved,
90%, and 68%, respectively. RB4 was slowly degraded at 60 mA and it
respectively. With the increase in the treatment time to 300 min,
was completely degraded after the 45 min treatment in this reaction
the mineralization efficiency gradually increased to 78% and 81%
medium.
for initial TiO2 concentrations of 1 and 2 g/L, respectively.
In the electro-Fenton system after 30 min of electrolysis, TOC
3.2. TOC removal experiments
removal efficiencies with 60, 100, and 200 mA constant current
were 35%, 68%, and 72%, respectively. The worst mineralization was
The oxidizing power of the four oxidation processes to miner-
50%, obtained with 60 mA for RB4 after 300 min. In the case of
alize RB4 solution was evaluated based on their TOC decay. Fig. 7
100 and 200 mA, TOC removal efficiency levels were similar (85%)
shows the TOC decay of a 100 mg/L RB4 solution by wet air oxi-
after 300 min of treatment. In the first hour of treatment in both
dation (block A) and wet peroxide oxidation (block B) at different
methods, TOC removal was greater than 65%, except with 60 mA in

Fig. 7. TOC % Removal of RB4 by wet air peroxide oxidation (A) 5 MPa O2 (B) H2 O2 Fig. 9. GC–MS analysis of the organic intermediates of RB4 after 5 min WAO treat-
at 60 min. [RB4]0 = 100 mg/L, V = 150 mL. ment. Reaction condition: T = 200 ◦ C; [RB4]0 = 100 mg/L.
134 B. Gözmen et al. / Journal of Hazardous Materials 168 (2009) 129–136

higher, but the processing costs are lower. The capital costs for a
wet air oxidation system based on the flow rate, wastewater com-
position, extent of oxidation and the needed processing conditions
[45].

3.3. Identification of degradation intermediates

In this part of the study, organic and inorganic intermediates

generated during the degradation of RB4 dye detected by GC-
MS, HPLC and IC. The main intermediates identified during WAO
and EF treatments of RB4 by GC-MS were shown on GC chro-
matogram in Figs. 9 and 10. The partial charge showed that the
• OH attacks to N-positions on the RB4 structure to form three

intermediates groups (A, B and C) in Fig. 11. In part A, because

of • OH-addition to N-position, 1-amino-9,10-anthracenedione was
found to be initial oxidative product. The benzene rings of this prod-
uct were further cleaved to yield, alllyl phthalate, diethyl phthalate,
Fig. 10. GC–MS analysis of the organic intermediates of RB4 after 5 h EF treatment. 1,4-napthalenedione, phthalic anhydride, 1,2-benzene dicarboxylic
Reaction condition: I = 200 mA; ([Fe3+ ]0 = 0.2 mM; 0.05 M Na2 SO4 ; [RB4]0 = 100 mg/L.
acid and benzoic acid by the cooperation of • OH and water. In
part B, 4-nitrophenol, hydroquinone and p-benzoquinone were
electro-Fenton, but it slowed down after 1 h due to the recalcitrant formed after • OH attacks to N-positions. Then the compounds in
structural compounds that formed during the degradation. these parts have broken down into the smaller compounds such
The above results indicate that WPO, electro-Fenton, and as oxalic acid, acetic acid and carbon dioxide that these organic
UV/TiO2 /periodate methods were very effective for degrading RB4, acids were identified by HPLC analysis. In the last part C, two
an anthraquinone dye. In general, when compared with the other triazine groups, including 2-amino-4,6-dichloro-1,3,5-triazine and
oxidation techniques the capital costs for wet air oxidation are 2-amino-4,6-dihydroxy-1,3,5-triazine were identified. The pres-

Fig. 11. Proposal of degradation reaction pathway for RB4.

 B. Gözmen et al. / Journal of Hazardous Materials 168 (2009) 129–136 135

Table 1
Organic intermediates identified by GC–MS.

EF (1 h) (200 mA) EF (5 h) (200 mA) WAO 5 min + 1 h WPO (5 min) UV/TiO2 /IO4 − (5 h)
√
Napthalene
√
Benzoic acid
√
Styrene
√
2-Methyl napthalane
√ √ √
Hydroquinone
√
Phthalic anhydride
√
Salicylic acid
√ √
1-Phenyl-1-propanone
√ √
1,4-Naphthalenedione
√
1(2H)-3,4-dihydro naphthalenone
√
3,4-Dimethyl benzoic acid
√ √ √ √ √
Diethyl phthalate
√ √ √ √ √
Dibutyl phthalate
√ √ √ √ √
Diallyl phthalate
√
2-Amino-9,10-anthracendione
√
Benzophenone
√
1,2-Benzenedicarboxylic acid
√
Phenol 2,4-bis(1,1-dimethylethyl)
√
Butyl benzene
√ √ √ √ √
6-Amino, 2,4-dihydroxy-1,3,5-triazine
√ √ √
6-Amino, 2,4-dichloro-1,3,5-triazine
√ √
4-Nitrophenol
√ √ √
Butylparaben

Table 2 most effective method for the mineralization of RB4. By this pro-
Inorganic intermediates identified by IC.
cess, which used 5 mM IO4 − and 2 g/L TiO2 , TOC removal was 79%
Sample Cl− SO4 2− NH4 + (mg/L) and 81% after 60 and 300 min of treatment, respectively. These
EF 3 h (200 mA)* 4.64 12.1 <1
four processes are acceptable, fast, and efficient ways of enhancing
EF 5 h (200 mA)* 5.12 12.4 <1 the process of destroying textile manufacturing effluent or other
WAO 1 h (200 ◦ C) 7.73 7.5 <1 organic compounds.
UV/TiO2 /(5 mM IO4 − ) 3 h 3.78 12.1 <1
UV/TiO2 /(5 mM IO4 − ) 5 h 4.22 14.4 <1
*
LiClO4 was used to enhance the conductivity. Acknowledgements

This work was supported by the Mersin University Scientific

ence of these triazine groups after 5 h treatment indicated that they
Research Foundation. We wish to thank Prof Ayla Özer and master
are not completely degradable with photocatalytic and electro-
student Muhammet Demirel for their supports.
Fenton systems. In Table 1 we summarized identified organic
intermediates regarding to applied methods.
The mineralization of RB4 involves the formation of NO2 − ,NO3 − , References
SO4 2− ,Cl− and NH4 + can also be expected. In this study nitrate and
nitrite could not be detected, whereas less than 1 mg/L NH4 + was [1] G.M. Walker, L.R. Weatherley, COD removal from textile industry effluent: pilot
plant studies, Chem. Eng. J. 84 (2001) 125–131.
detected for all oxidative methods by using ion chromatography, [2] Y.M. Slokar, M. Marechal, Methods of discoloration of textile wastewaters, Dyes
these results are agree with those previously reported [4] with Fen- Pigments 37 (1997) 335–356.
ton of RB4. RB4 mineralization involves the formation of sulfate [3] O.J. Hao, H. Kim, P.C. Chiang, Decolorization of wastewater., Crit. Rev., Environ.
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