Int. J. Chem. React. Eng.

2021; 19(5): 527–532

Ibtissem Bousnoubra, Soumia Fassi* and Kamel E. Djebbar

Decolorization and mineralization of diazo dye

under artificial and solar light assisted Fenton and
photo-Fenton conditions
https://doi.org/10.1515/ijcre-2021-0002 natural environment, mainly in aqueous medium, is un-
Received January 2, 2021; accepted April 10, 2021; desirable because of the potential transformation of these
published online April 22, 2021
compounds to toxic and carcinogenic of species (Bowers
et al. 1988). Organic dyes represent one of the large groups
Abstract: The aim of this study is to verify the ability of
of these effluents. However, several treatment processes
some photochemical processes in the absence of light
are available for the removal of this type of pollutants,
(Fenton) and in its presence (photolysis/UV, photo-Fenton/
such as precipitation and biological treatment (Kurbus,
UV and photo-Fenton/Solar) to obtain total decolorization
March Stokar, and Marechal 2002), flocculation (Papro-
and mineralization of an diazo dye in aqueous solution: the
wiez and Slodezyk 1988), coagulation (García-Montaño
Evans Blue (abbreviated as EB). Batch experiments were
et al. 2008), adsorption on various supports (Ahmed and
carried out to evaluate, on the first stage, the influence of
Ram 1992)… Unfortunately, most of these conventional
different processes on EB decolorization and mineralization.
methods were ineffective, very expensive and may often
During the second stage the optimal operational conditions
produce secondary pollution by a transfer of the pollut-
like: H2O2 dosage, EB concentration and source of light were
ants from one phase to another like adsorption. In the case
investigated. The reaction efficiencies have been compared
of non-biodegradable or toxic wastewater sources, alter-
for the same system in the dark or under the assistance of an
native treatments have to be used in these later decades,
artificial or solar light source. The obtained results showed
photochemical systems, mainly, the advanced oxidation
that color removal followed the increasing order: photol-
processes (AOPs), have been described as effective
ysis/UV (18.2%) < Fe(II)/H2O2 (64.12%) < Fe(II)/H2O2/
methods for decontamination of wastewaters. The AOPs
UV365 nm (83.4%) < Fe(II)/H2O2/solar light (86.3%) < Fe(II)/
are characterized by production of hydroxyl radicals
H2O2/UV254 nm (99.9%) with a reaction time of 60 min This
(OH•), a powerful oxidizing agent with oxidation potential
improvement could be related to a better production of
of 2.8 V, reacting with rate constants usually in the order
radicals OH•. In another hand, The efficiency of substrate
of 106–109 M−1s−1 OH• (Buxton et al. 1988a) and non-
mineralization in each process has been comparatively
selectively with a broad range of organic pollutants
discussed by total organic carbon (TOC) and total chemical
(Buxton et al. 1988b). Thus, a process of oxidation takes
oxygen demand content of EB solutions.
place until the final stage of mineralization which is
Keywords: decolorization; Evans Blue; Fenton and photo- characterized by the production of CO2 and H2O2. AOPs are
Fenton reaction; mineralization; solar light. existing in homogeneous medium: Fe2+/H2O2, Fe3+/H2O2,
Fe2+/H2O2/UV, Fe3+/H2O2/UV, H2O2/UV, S2O82/UV … and
in heterogeneous medium: UV/Semi-conductors (Ale-
boyh and Aleboyeh 2006; Al-Qaradawi and Salman 2002;
1 Introduction Djellabi and Ghorab 2013; Gau and Chang 1996; Lucas and
Peres 2006; Salari et al. 2009; Sauer et al. 2002).
The release of colored wastewaters from the textile in-
Among these processes, Fenton appears to be very
dustry is a current problem encountered by developed and
interesting because of their simple implementation which
under developed countries over the world. This release in
consists of simple equipment and availability of chemical
reagents used as H2O2 and ferrous ions. However, the only
*Corresponding author: Soumia Fassi, Laboratory of Science and disadvantage for this system is their use in an acid medium
Technology Environment, Department of Chemistry, Faculty of (pH = 3) to prevent the formation and precipitation of hy-
Sciences, University of Constantine, Constantine, 25000, Algeria,
droxide. Thus, the oxidation mechanism of the pollutant is
E-mail: fassisoumia@umc.edu.dz
Ibtissem Bousnoubra and Kamel E. Djebbar, Laboratory of Science
as follows Eqs. (1)–(5) (R is an organic binder) (De Laat and
and Technology Environment, Department of Chemistry, Faculty of Gallard 1999; Hsuch et al. 2005; Neamtu et al. 2003;
Sciences, University of Constantine, Constantine, 25000, Algeria Swaminathan et al. 2003):
528 I. Bousnoubra et al.: Decolorization and mineralization of diazo dye
H2 O2 + Fe2+ + H+ → Fe3+ + H2 O + HO• (1)
Fe3+ + H2 O → Fe(OH)2+ + H+ (2)
Fe3+ + HOO· → Fe2+ + O2 + H+ (3)
R − H + HO· → R· + H2 O (4)
R· + Fe3+ → R+ + Fe2+ (5)
Moreover, The combination of UV radiation with the
Fenton process could be an interesting ally in dye decol-
orozation due to its ability to influence the direct forma-
tion of HO• radicals (Feng et al. 2003; Muruganandham
and Swaminathan 2004). Recently, other processes have
been studied trying to use solar light instead of artificial
UV radiation (Marco-Lucas and Peres 2007). However,
photo-Fenton reaction can be driven with low energy
photons in the visible part of the spectrum. Thus, photo-
Fenton processes are a potential low cost AOPs that can be
run under solar irradiation (Safarzadeh-Amiri, Bolton,
and Cater 1996).
The goal of this study is to evaluate and compare the
efficiency of photochemical processes (direct photo-
degradation and AOPs such: Fenton and photo-Fenton)
under artificial and solar light on the elimination of
Evans Blue. The efficiency of substrate decolorization
and mineralization in each process has been compara-
tively discussed. The effect of light, H2O2 concentration
and concentration of EB were investigated in this work.
2 Materials and methods
2.1 Materials
The diazo dye, Evans Blue, (abbreviation EB), was obtained from
Sigma–Aldrich and used without further purification (molecular
weight: 960.81 g mol−1) which is a highly water soluble, was used
as a model solute. The structure EB is shown in Figure 1. Iron and
hydrogen peroxide were commercial products of the purest grade
available. All solutions were prepared with ultra-pure water from a
Milli pure water. The pH of the solutions was adjusted with NaOH
or HCl (supplied both by Labosi) to attain desired values. The
concentration of solution the substrate is 20 mg L −1 and its natural
pH is 6.3.
2.2 Photoreactor and source light
A light source is placed 7 cm above the reactor of irradiation. Two types
of lamps were used as an artificial light source:
2.2.1 The first type: Different aqueous solutions are irradiated at
254 nm in cylindrical reactor in quartz (100 cm of length and 2 cm in
diameter), located on one of the principal axis of the assembly, and
equipped with three symmetrical external low-pressure Mercury
lamps (germicide lamp, Philips TUV 15 W) emitting mainly at 254 nm.
The reactor is surrounded symmetrically by these lamps. The tem-
perature of the reactor is maintained between 18 and 20 °C by the use of
an air flow provided by a ventilator. The entire system is placed in a
cylindrical enclosure (Djebbar et al. 2009).
2.2.2 The second type: A fluorescent tube of type “Philips TLAD 15 W/
05” with an emission spectrum having a maximum at around 365 nm
with a half-band width of 50 nm.
2.2.3 The third type: In solar light, aqueous solution of the dye were
degraded in presence of H2O2 and salt of Fe (II) using a pilot plant
containing a reservoir delivery, a pump, and an assembly of tubes on
Pyrex. They are located closely to each other and in a vertical position
towards natural light. Samples were withdrawn at regular time in-
tervals and analyzed immediately (Fassi et al. 2013) (Figure 2).
Solar light experiments were performed during sunny days of
July at University of Constantine – Algeria. The temperature of the
reactor during those experiments rose from approximately 38 to 40 °C.
The intensity of the incident light inside the photoreactor, measured
was 0.98 W cm−2, using solar light radiometer PMA2100. The order of
magnitude of the number of photons emitted per second calculated
from Plank’s equation is 1018.
2.3 Analysis method
The UV–vis spectra of both dyes are recorded from 200 to 800 nm
using a spectrophotometer “Unicam Helios α” with a cell made in
quartz and having a path length of 1 cm. The residual concentrations of
substrate at different irradiation times are obtained at λmax = 604 nm
for EB, Total Organic Carbon (TOC) and total chemical oxygen demand
measurements were carried out with a Skalar Formacs TOC/TN
analyzer and COD/WTW.CR320 respectively.
Figure 1: Molecule structures of Evans Blue
(EB).
In our experimental conditions (pH 6.3).
 I. Bousnoubra et al.: Decolorization and mineralization of diazo dye
Figure 2: Set up of pilot plant solar light.
(a) The solar reactor (b) scheme of the device (1: tube in pyrex, 2: dye solution, 3: pump).
3 Results and discussion
3.1 UV–vis spectrum of EB
The UV–vis spectrum of EB is presented in Figure 3. It is
clear that EB (pH = 6.3) absorbs light in the range of
wavelength: 200–700 nm and shows an intense band
located around 608 nm. It can be seen that pH affects
spectrum of dye. Thus, in basic solution (pH = 12.1), for EB,
a shift and a decrease in wavelength occurs for the band
positioned at 608 nm. This shift is equal to 558 nm and
involves a hypsochromic effect, with a color change
(turning into violet). In acidic solution (pH = 3.5), no shift
and no color change are observed for substrate.
pH=3.5
pH=6.3
pH=12.1
Absorbance
Wavelength (nm)
Figure 3: UV–vis spectrum of EB, [dye]o = 20 mg L−1.
Influence of pH.
529
3.2 Direct photodegradation of EB
Figure 4 presents typical data obtained from the photolysis
of EB ([EB]o = 20 mg L−1) in aerated medium, in a tubular
reactor and under UV irradiation at 254 nm. The experi-
mental results show that the decolorization process
decreases as the initial concentration increases. Indeed, the
results obtained for this process are: 31.8% (10 mg L−1),
29.6% (20 mg L−1) and 16.6% (30 mg L−1) for a reaction time of
120 min. This could be attributed on one part to the size of the
molecules presented in the solution, preventing the expo-
sure of certain of them to light and on the other part on
absence of radicals OH• which are generated by H2O2.
Therefore,the efficiency was not significant (Fassi et al. 2012).
Figure 4: Direct photodegradation of EB at 254 nm with different
initial concentrations.
530 I. Bousnoubra et al.: Decolorization and mineralization of diazo dye
3.3 Fenton process
3.3.1 Effect of hydrogen peroxide
Fenton process appears to be very interesting because of
their simple implementation, which consists of simple
equipment and availability of the used chemical reagents
like H2O2, ferrous ions. In an acidic medium if hydrogen
peroxide is added to an aqueous system containing an
organic substrate and ferrous ions, a complex redox re-
action will occur (Marco-Lucas and Peres 2007).
The hydrogen peroxide is used as a bleaching agent
for treatment. Various concentrations of H2O2, with
constant Fe2+ concentration (10−4 mol/L), were studied to
obtain maximum removal efficiency of decolorization
and COD. The experiment was carried out at a pH of 3 by
varying hydrogen peroxide concentration,
The results obtained from the solutions of the EB
(20 mg/l) and hydrogen peroxide (0.05, 0.1, 0.2, 0.5 and
1 mM) in ultra-pure water (Figure 5) show that: the effi-
ciency of this oxidation process (Fenton) increases with
increasing dose in hydrogen peroxide.
We observed also that the maximum decolorization
and COD removal was 64.12 and 50.3% respectively at the
maximum concentration of 1 m mol/l. It is concluded that
the COD removal efficiency increases as increasing in
H2O2 concentration. The maximum COD removal is ob-
tained at a reaction time of 60 min which is represented
graphically in inserted Figure 5.
Decolorization
COD
Figure 5: Effect of hydrogen peroxide on decolorization process of
EB in aqueous medium by Fenton process, in insertion: Comparison
between decolorization and COD removal of EB after Fenton process.
Experimental conditions: [EB] = 20 mg/l; [Fe2+] = 10−4 mol/L, pH = 3
and reaction time = 60 min.
3.4 Photo-Fenton process
3.4.1 Effect of hydrogen peroxide
Initially, the photochemical degradability of dye EB was
carried out with Fenton/UV process. A better result was
observed when combining Fenton with radiation light at
254 nm. From the results below, it is observed that the EB
decolorozation efficiency reaches 99% at a H2O2 concen-
tration of 1 m mol/l and reaction time of 60 min. It is
concluded that the color removal efficiency is increased as
increase in H2O2 concentration with an increase in the re-
action time. This is graphically represented in Figure 6. As
seen before, it appeared that the Fenton/UV process is
more rapid than that obtained by Fenton. Indeed, the
combination of Fenton process with radiation light at
254 nm facilitates the formation of the radicals •OH from
different sources like: (Fassi et al. 2013).
– The reaction between Fe2+ with H2O2.
– The photolysis of H2O2 at 254 nm.
– The photoreduction of species resulting from the
hydrolysis of Fe3+ (Fe(OH)2+) and Fe2+ (Fe(OH)+).
3.4.2 Effect of light
The oxidation of the dye was greatly enhanced by light.
Therefore, to evaluate the effect of light in the photo-
Fenton process. The experiment was performed at a pH of 3
by varying the light source. At this point it is important to
Figure 6: Effect of hydrogen peroxide dosage on the decolorization
of EB by Fenton/UV process.
Experimental conditions: [EB] = 20 mg/L; iron
concentration = 10−4 mol/L; pH = 3; reaction time = 60 min.
 I. Bousnoubra et al.: Decolorization and mineralization of diazo dye
differentiate between the results obtained with the artifi-
cial light source and the solar light. Figure 7 shows that the
color removal efficiency resulting from Fenton/UV365 nm (in
artificial light) was about 83.4% in 60 min, whereas in
natural light it was about 86.3%. However, from these re-
sults it is possible to conclude that, in the presence of solar
light, the efficiency was still higher as compared with that
obtained in the artificial light. This fact may be explained
by better absorption of sunlight from the substrate.
4 Comparative study between COD,
TOC and color removal efficiency
It is known that reaction intermediates can be formed
during the oxidation of diazo dye and some of them could
be long-lived and even more toxic than the parent com-
pounds. Therefore, it is necessary understand the miner-
alization degree of the diazo dye EB to evaluate the
degradation level applied by Fenton, Fenton/UV254 nm;
Fenton/UV365 nm and Fenton/solar light processes.
Figure 7: Comparison between Fenton/Solar light and Fenton/
UV365 nm processes.
Experimental conditions: [EB] = 20 mg/l; [Fe2+] = 10−4 mol/L,
[H2O2] = 1 m mol/L; pH = 3; solar light intensity = 0.98 W cm−2.
531
In Figure 8, we present a comparison between the re-
sults obtained on COD, TOC and color removal efficiency.
Based in the obtained results we observed that:
– A better efficiency was obtained when artificial or solar
light was coupled to the Fenton system compared to
that in dark solution. The color removal was total in
60 min for Fe2+/H2O2/UV254 nm process.
– Under the same experimental conditions, 80.6, 66.8,
62.6 and 50.3% COD removal were achieved for Fen-
ton/UV254 nm, Fenton/sunlight, Fenton/UV365 nm and
Fenton respectively.
– It is observed also an increase in TOC removal effi-
ciency as we coupled light (artificial or solar) to Fenton
system: 46.2% for Fe2+/H2O2, 74.8% for UV254 nm/Fe2+/
H2O2, 59.8% for UV365 nm/Fe2+/H2O2 and finally 61.8%
for solar/Fe2+/H2O2. These efficiencies have all been
measured in 60 min.
5 Conclusion
This work illustrates the performance and the comparison
of different systems to eliminate EB from aqueous and
homogenous medium. Experiments conducted in one side
by direct photodegradation and in other side by Fenton,
Fenton/UV at various wavelengths and Fenton/Solar are
achieved. The results conclude that the optimal experi-
mental conditions for these processes, with an EB con-
centration of 20 mg/L, can be summarized as: pH = 3,
hydrogen peroxide dosage = 1 m mol/L and iron
dosage = 10 m mol/L. Under these experimental condi-
tions, 18.2, 64.12, 99.9, 83.4 and 86.3% decolorization were
achieved for direct photodegradation, Fenton, Fenton/
UV254 nm,Fenton/UV365 nm and Fenton/solar light respec-
tively. Indeed, we observed that, dye decolorization is
much higher than COD and TOC removal in the presence of
the systems listed above, where the percentages of the
elimination are in the order of (50.3, 80.6, 62.6, 66.8%) and
(46.2, 74.8, 59.8% 61.8%) respectively. These efficiencies
have all been measured in 60 min.
Figure 8: Comparison between COD, TOC
and color removal of EB after Fenton/
UV254 nm; Fenton/UV365 nm and Fenton/solar
light processes.
Experimental conditions: [EB] = 20 mg/l;
[H2O2] = 1 m mol/L; [Fe2+] = 10−4 mol/L;
T = 38 °C, solar light intensity = 0.98 W cm−2
pH = 3 and reaction time = 60 min.
532 I. Bousnoubra et al.: Decolorization and mineralization of diazo dye
Author contributions: All the authors have accepted
responsibility for the entire content of this submitted
manuscript and approved submission.
Research funding: The authors thank the Algeria
Government (Ministry of Higher Education and Scientific
Research) for the financial support.
Conflict of interest statement: The authors declare no
conflicts of interest regarding this article.
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