RESEARCH ARTICLE
Degradation of azo dye Acid Red 14 (AR14) from
aqueous solution using H2O2/nZVI and S2O82–/nZVI
processes in the presence of UV irradiation
Mohammad Reza Samarghandi ,1 Abdollah Dargahi ,2,3,*
Esmail Ghahramani ,5,6 Sohrab Salehi 4
1
Research Center for Health Sciences
and Department of Environmental
Health Engineering School of Public
Health, Hamadan University of Medical
Sciences, Hamadan, Iran
2
Department of Environmental Health
Engineering, School of Health, Ardabil
University of Medical Sciences, Ardabil, Iran
3
Social Determinants of Health Research
Center, School of Health, Ardabil University
of Medical Sciences, Ardabil, Iran
4
Department of Environmental
Health Engineering, School of Public
Health, Hamadan University of Medical
Sciences, Hamadan, Iran
5
Environmental Health Research
Center, Research Institute for Health
Department, Kurdistan University of Medical
Sciences, Sanandaj, Iran
6
Student Research committee, Hamadan
University of Medical Sciences, Hamadan,
Iran
Received 3 October 2019; Revised 12
February 2020; Accepted 14 February 2020
Hamadan University of Medical Sciences,
Grant/Award Number: 9804182912
Correspondence to: Abdollah Dargahi,
Department of Environmental Health
Engineering, School of Health, Ardabil
University of Medical Sciences, Ardabil,
Iran.
Email: a.dargahi29@yahoo.com
DOI: 10.1002/wer.1312
© 2020 Water Environment Federation
Water Environment Research • 1–11, 2020
Hasan Zolghadr Nasab ,4
• Abstract
Azo dyes are mostly toxic and carcinogenic and cause harm to humans and the envi-
ronment. This study was conducted to investigate the degradation of azo dye acid red
14 (AR14) from aqueous solution using hydrogen peroxide (H2O2)/nano zerovalent
iron (nZVI) and persulfate (S2O82–)/nZVI processes in the presence of ultraviolet
(UV) irradiation. This experimental study was carried out in a laboratory-scale batch
photoreactor with a useful volume of 1 L. The nZVI was synthesized by the sodium
borohydride (NaBH4) reduction method. In these processes, the effects of parameters
including initial pH, H2O2 concentration, S2O82– concentration, nZVI dose, concen-
tration of AR14 dye, and reaction time were studied. The results showed that decol-
orization increased by increasing the nZVI dosage, H2O2 and S2O42- concentrations,
and reaction time, or decreasing dye concentration and pH. However, a too high
oxidant concentration (H2O2 and S2O42-) could inhibit the degradation. The experi-
mental conditions for degradation of AR14 by UV/S2O82-/nZVI and UV/H2O2/nZVI
processes were as follows: [H2O2] = 10 mM, [S2O82–] = 8 mM, AB14 dye = 100 mg/L,
pH = 3, and nZVI dose = 0.05 g. Under these conditions, the highest removal effi-
ciencies of AR14, chemical oxygen demand (COD), and total organic carbon (TOC)
for the UV/S2O82–/nZVI process were 93.94%, 86.5%, and 81.6%, respectively, while
these values were 89.3%, 79.57%, and 72.9% for the UV/H2O2/nZVI, respectively.
Also, the average oxidation state (AOS) was decreased from 2.93 to 2.14 in the effluent
of the UV/S2O82–/nZVI process and from 2.93 to 2.2 for the UV/H2O2/nZVI process.
The results showed that the ratio of biochemical oxygen demand (BOD5) to COD in
the effluents of the UV/S2O82/nZVI and UV/H2O2/nZVI processes after 90 min was
0.63 and 0.74, respectively. These findings suggest biodegradability improvement. ©
2020 Water Environment Federation
• Practitioner points
• Photocatalytic degradation of azo dye Acid Red 14 (AR14) was achieved using H2O2/
nZVI and S2O82–/nZVI processes in the presence of UV irradiation.
• Effects of operating parameters on photocatalytic degradation AR14 dye were evalu-
ated in the UV/H2O2/nZVI and UV/S2O82–/nZVI processes.
• Biodegradability and mineralization studies of AR14 dye photocatalytic degradation
were performed for the UV/H2O2/nZVI and UV/S2O82–/nZVI processes.
• Key words
acid red 14 dye degradation; hydrogen peroxide; nano zerovalent iron (nZVI);
persulfate
Introduction
Contamination of water resources occurs via different pollutants such as dyes, toxic
metal ions, and oil, which are released to the environment from different industries
RESEARCH ARTICLE
(e.g., textile, food, cosmetics, plastics, paper, and printing)
(Akerdi, Bahrami, Arami, & Pajootan, 2016; Dargahi et al.,
2019; Shokoohi, Jafari, Dargahi, & Torkshavand, 2017; Thiam,
Sirés, Centellas, Cabot, & Brillas, 2015). Among these indus-
tries, it has been recognized that water is highly consumed
through different processes applied in textile industries (dye-
ing, finishing, scouring, etc.) which consequently lead to
generation of a large amount of dye-containing wastewater,
pollution of the water resources, and creation of numerous
noxious outcomes on the environment and human health
(Nguyen & Juang, 2013). One of the extensively used dyes in
the textile industries is azo dyes, which are among the most
important pollutants in the water (Lam, Sin, Abdullah, &
Mohamed, 2012). The azo dyes are hardly degraded due to
their properties, for example, high chromaticity, complex
molecular structure, high chemical stability, and low biode-
gradability (Xia, Zhou, Shi, Pan, & Ni, 2014). Hence, these
groups of dyes can be frequently detected in effluents dis-
charged from various industries and cause different prob-
lems, for example, aesthetic and health issues such as cancers
and reproductive and neurological disorders in humans and
aquatic organisms (Khodam, Rezvani, & Amani-Ghadim,
2015). To minimize the pollution, many countries have estab-
lished different regulations to restrict the release of the col-
orful wastewaters into the environment (Akerdi et al., 2016).
Therefore, these types of wastewaters and effluents should be
properly treated, because the discharge of them into receiv-
ing waters not only limits the favorable uses of water, but also
causes acute or chronic toxic effects on aquatic organisms
(Al-Amrani, Lim, Seng, & Ngah, 2014; Dargahi, Mohammadi,
Amirian, Karami, & Almasi, 2017). Removal of acid red 14
(AR14) dye from aquatic solution can be achieved by sev-
eral technologies, for example, adsorption (Khodam et al.,
2015; Roth, Gendel, Buzatu, David, & Wessling, 2016; Wang,
Zhong, Yu, Aprea, & Hao, 2019), biosorption (Ahmed, El-Dib,
El-Gendy, Sayed, & El-Khodary, 2016; Al-Amrani et al., 2014;
Gao, Wang, Yang, Wang, & Peng, 2011), and advanced oxi-
dation processes (AOPs) (Akerdi, Es’haghzade, Bahrami, &
Arami, 2017; Xia et al., 2014). Among them, AOPs have repre-
sented a potential solution to eliminating the dyes due to the
production of strong oxidizing radicals including hydroxyl
radicals (OH●), sulfate radicals (SO4⋅−), and superoxide radi-
cal (O⋅−
2 ), which play an essential role in degradation of var-
ious chemicals such as dyes (Akerdi et al., 2017; Zarei et al.,
2018). The OH●, which can be in-situ produced by chemical
or photochemical reactions, are highly unstable and reactive
(Seid-Mohammadi, Asgarai, Ghorbanian, & Dargahi, 2019).
It can degrade organics through different mechanisms, such
as hydrogen (H) atom abstraction (Dargahi et al., 2015). The
performance and ability of these processes in degradation of
pollutants can be also mounted by the combination of oxi-
dizing agents (e.g., O3 and H2O2) and/or catalysts (e.g., Fe,
Mn, and TiO2) in the presence of ultrasound (US), ultraviolet
(UV) radiation, and/or electricity. Among the different AOPs,
the UV/H2O2 (an eco-friendly oxidant) process has been pre-
ferred due to its excellent properties, for example, no sludge
production, simple operation, and low cost (Oancea & Meltzer,
2 Samarghandi et al.
2014). On the other hand, persulfate ion (S2 O2− 8 ) is another
strong oxidizing agent with an oxidation–reduction potential
(ORP) of 2.01 V and has been successfully employed for the
degradation of persistent compounds. However, this soluble
oxidant is stable at the environmental condition and very
selective for compound oxidation (Seid-Mohammadi, Asgari,
Poormohammadi, Ahmadian, & Rezaeivahidian, 2016). To
achieve an aggressive oxidative process, various methods such
as UV radiation and electron transfer by transition metals are
used to activate S2 O2−
8 for production of more reactive
SO⋅−
4
2+
. Among the transitional metals, divalent iron (Fe ) is the
most widely used, but its use brings about such problems as
production of a large quantity of sludge and a consumption of
4 at high concentrations (Oh, Kang, & Chiu, 2010). Due to
SO⋅−
the issues associated with the use of this activator, nano zerov-
alent iron (nZVI) or (Fe0) was used in this study. The nZVI
can act as a continuous source of Fe2+ for the persulfate acti-
vation reaction. The nZVI not only overcomes the drawback
of Fe2+ but also avoids the addition of anions in ferrous salts.
The reactions of Fe0 with S2 O2−8 are shown in reactions 1-3
(Rodriguez, Vasquez, Costa, Romero, & Santos, 2014). Also,
the reactions of Fe0 with H2O2 are shown in reactions 4 and 5.
S2 O2−
8
+ Fe0 → Fe2+ + 2SO2−
4 (1)
S2 O2−
8
+ Fe2+ → SO4⋅− + Fe3+ + SO2−
4
(2)
Fe0 + 2Fe3+ → 3Fe2+ (3)
Fe0 + H2 O2 → Fe2+ + 2OH− (4)
Fe2+ + H2 O2 → Fe3+ + OH− + OH⋅ (5)
Because of the advantages of UV-based AOPs in the deg-
radation of organic compounds, especially dyes, and the lack
of sufficient information about the roles of different oxidants
(e.g., H2O2 and S2 O2−8 ) activated by nZVI, the present study
was conducted to evaluate the effectiveness of the two differ-
ent processes (i.e., UV/H2O2/nZVI and UV/S2 O2− 8 /nZVI) on
the degradation of AR14 dye. The effects of system variables
such as initial solution pH, nZVI dose, H2O2 concentration,
8 concentration, and initial AR14 concentration were also
S2 O2−
investigated, and the biodegradability of the aqueous solutions
contaminated by AR14 dye was finally determined.
Materials and methods
Chemicals and instruments
All the chemicals used in this study were of analytical grade
type and used without further purification. In this study,
AR14 (dye index: 14720), a commercial dye with a chemi-
cal formula of C20H12N2Na2O7S2 and the molecular weight
of 502.42 g/mol, was purchased from Merck Co. (Germany).
The chemical structure of AR14 is presented in Figure 1. All
the materials required such as H2O2 (purity 30%), sodium
hydroxide (NaOH), hydrochloric acid (HCl), ferrous sulfate

(FeSO4.7H2O), sodium borohydride (NaBH4), ethanol, starch,
and S2 O2−
8 were provided from Merck (Germany). Double dis-
tilled water was utilized for the preparation of the solutions.
Synthesis of nZVI
The synthesis of nZVI was carried out by the NaBH4 reduction
method. About 10.0 g of FeSO4.7H2O was dissolved in a 2.3/1
(V/V) ethanol/water mixture (30% ethanol + 70% deionized
water) and was thoroughly stirred using a mechanical stirrer.
Solution pH was adjusted to 6.8 using 1 N HCl and NaOH.
About 1.8 g NaBH4 was gradually added to the mixing solu-
tion. The mixing was 20 min at 150 rpm. Lastly, the separation
of nZVI was performed through centrifugation at 2,800 g for
5 min. After the centrifugation, the precipitates were filtered by
a vacuum membrane filter under a protective nitrogen (N2) gas,
washed several times with 98% ethanol and deionized water,
and finally dried at an ambient temperature (Mikhailov et al.,
2017). In addition to centrifugation, a strong magnet (1.6 T)
was applied to separate the nanoparticles. Because nZVI can be
strongly oxidized to Fe3+ in the presence of oxygen, it should be
daily synthesized prior to use (Vilardi, 2019; Vilardi, Palma, &
Verdone, 2017; Vilardi, Parisi, & Verdone, 2019).
Experimental procedure
This experimental study was performed in a laboratory-scale
batch photoreactor (useful volume of 1 L). A quartz-coated
UV-C mercury lamp (55 W) was used inside a highly reflective
stainless steel (SS) chamber. About 90% of the output beams
of these lamps (Philips, Netherlands) were at λmax = 253.7 nm.
The space between the UV-C lamp and the stainless steel
chamber was for the reactions. Stirring in the reactor using a
magnetic stirrer ensured a complete mixing state. The sche-
matic of the reactor is presented in Figure 2. In this work, a
synthetic dye wastewater was prepared in the laboratory using
different concentrations of AR14. The studied parameters
affecting the performance of the studied system were initial pH
(3–11), H2O2 concentration (2–20 mM), S2 O2− 8 concentration
(2–10 mM), nZVI dose (0.01–0.1 g), concentration of AR14
dye (50–300 mg/L), and reaction time (5–90 min). The power
supplier was a transformer (210–240 V). All the experiments
were performed in triplicates.
To investigate the effects of pH (3–11), AR14 dye solutions
(100 mg/L) containing 10 mM H2O2, 8 mM S2 O2− 8 , and 0.05 g
nZVI were used. The samples were taken at designated time
intervals in the range of 5–90 min. In order to study the effect of
Figure 1. Chemical structure of AR14 dye.
Water Environment Research • 1–11, 2020
RESEARCH ARTICLE
nZVI dose on the AR14 dye removal efficiency, treatment was
run under the following conditions: nZVI dose of 0.01–0.1 g,
pH of 3, H2O2 of 10 mM, S2 O2−8 of 8 mM, AR14 dye of 100 mg/L,
and the reaction time between 5 and 90 min. Experiments to
evaluate the effects of H2O2 and S2 O2−
8 concentrations were car-
ried out under the following conditions: [H2O2] = 2–20 mM,
[S2 O2−
8 ] concentration = 2–10 mM, nZVI dose = 0.05 g, pH = 3,
and AR14 dye = 100 mg/L. In order to determine the effect of
initial AR14 concentration on the dye degradation efficiency,
experiments were performed under the conditions as follows:
AR14 dye = 50–300 mg/L, [H2O2] = 10 mM, [S2 O2− 8 ] = 8 mM,
nZVI dose = 0.05 g, pH = 3, and reaction time = 5–90 min.
In order to study the sole and combined effects of different
treatment components in the two above joint AOPs, the opti-
mal values of different parameters ([H2O2] = 10 mM, [S2 O2− 8
] = 8 mM, nZVI dose = 0.05 g, pH = 3, and AR14 dye concen-
tration = 100 mg/L) were used, and the samples were collected
at designated times between 5 and 90 min. All experiments
were performed at the temperature of 22 ± 3°C in a batch mode.
Analytical methods
After the samples were collected at predetermined time inter-
vals, a UV–Vis Spectrophotometer (DR 6000, HACH, USA)
was used at a wavelength of 510 nm to determine the residual
concentrations of AR14 in the solutions. High-performance
liquid chromatography ((HPLC), Agilent 1260 infinity,
Agilent Technologies Co. Ltd., USA) was used to ensure
that the UV spectrometry method could accurately quan-
tify AR14. Conditions for the operation of the HPLC were
as follows: the mobile phase = a mixture of water and ace-
tonitrile (50:50 v/v, HPLC grade, Merck), flow rate = 1 ml/
min, and temperature = 25°C. A 20 μl of AR14 dye solution
was injected into the column. The retention time was 3.5–
3.8 min at a wavelength of 510 nm. The analytical method
was evaluated by sensitivity/the limit of detection (LOD) and
the limit of quantification (LOQ). The value of the LOD was
three times as the standard deviation of the blank solution
divided by the slope of the analytical curve. The LOQ was
estimated as tenfold of the standard deviation of the blank
solution divided by the slope of the analytical curve for each
colorant analyzed. AR14 dye exhibited a linear relationship
Figure 2. Schematic diagram of the experimental setup
employed in this study. 1) Transformer, 2) Low pressure Hg UV
lamp, 3) Quartz Jacket, 4) Stainless stell Jacket, 5) Photocell, 6)
Pump, 7) Sample vessel, 8) Shaker, and 9) Sampling tube.
3
RESEARCH ARTICLE

(R2 > 0.99) in the range of 0.01–300 mg/L. The LOD and
LOQ were 2.4 × 10–3 and 8 × 10–3 mg/L, respectively. Dye
degradation efficiency was estimated using Equation 6.
AR140 − AR14t
AR14 degradation (% ) = × 100 (6)
AR140

Where AR140 and AR14t represent the initial concentra-

tion of AR14 at the time 0 and the concentration of AR14 at
time t, respectively. Moreover, the chemical oxygen demand
(COD) ampoules (HACH Chemical) using a UV–Vis spec-
trophotometer (DR 6000, HACH, USA) were utilized for
the determination of COD. Total organic carbon (TOC) of
the AR14 dye was measured by a TOC analyzer (Elementar,
Germany). The TOC values were calculated by subtracting
inorganic carbon (IC) from total carbon (TC). In order to
determine the effects of S2 O2−
8 /nZVI and H2O2/nZVI photo-
catalytic processes in biodegradability, average oxidation state
(AOS), COD/TOC, and 5-day biochemical oxygen demand
(BOD5)/COD ratio were utilized. Measurement of BOD5 was
performed in a BOD thermostat system at 20 ± 1°C in the
dark condition and with 500 ml BOD bottles (HACH, USA)
with the Standard Method 5,210. The calculation of AOS was
carried out through the Equation 7:

COD
AOS = 4 − 1.5 (7)
TOC

Where TOC and COD are expressed in moles of C per

liter and moles of O2 per liter, respectively. The maximum
value of + 4 corresponds to the most oxidized state of carbon
and CO2. Transmission electron microscopy (TEM) analysis Figure 3. TEM image of the nZVI.
(H-800 Hitachi Japan) was used to confirm the synthesized
nZVI structure. The surface morphology properties of the
synthesized nZVI were determined using the scanning elec-
tron microscope (SEM) technique (model KYKY EM3200,
Japan).

Results and discussion

Characterization of nZVI particles
To better understand morphology of the nZVI particles, TEM
analysis was performed (Figure 3). The TEM images of the syn-
thesized nZVI show a dense spherical structure with a chain-
like connection. This is in agreement with the results of Vilardi,
Rodriguez-Rodriguez, Ochando-Pulido, Palma, and Verdone
(2019). In addition, the diameter of the synthesized particles
was found to be between 12.5 and 50 nm. Figure 4. SEM image of the nZVI.
SEM is another tool to investigate the morphological
features of the synthesized nZVI. As shown in Figure 4, the nanoparticles, so that the nZVI had an excellent porosity
iron nanoparticles had a small cluster in the range of 100 (55–60 m2/g).
to 150 nm. The surface of nZVI nanoparticles was rough,
while the nanoparticles were generally spherical and existed Effect of pH
in the form of chain-like agglomerates, which is consistent According to previous studies, pH can dramatically influence
with the results of TEM analysis. These agglomerates formed the performance of AOPs. In this section, UV/S2 O2− 8 /nZVI
due to aggregation of the small iron particles. In addition, and UV/H2O2/nZVI processes were evaluated in the pH
the images show a uniform distribution of cavities on the range of 3–11. This study exhibited an inverse relationship

4 Samarghandi et al.

Figure 5. Effect of pH on the degradation efficiency of AB114 dye by a) UV/S2 O2−
tions: [H2O2] = 10 mM, [S2 O2−
8
] = 8 mM, nZVI dose = 0.05 g, and AB14 dye concentration = 100 mg/L)
between pH and dye removal efficiency. That is, the removal
efficiency was enhanced by decreasing pH (Figure 5a and b).
In Figure 5, it is evident that the highest AR14 removal effi-
ciency in both studied processes was obtained at pH 3. Under
the studied conditions, the best AR14 removal efficiency for
UV/S2 O2− 8 /nZVI was 94.3% and 86.4% for UV/H2O2/nZVI
process, separately.
It is known that pH directly affects the stability of H2O2,
generation of OH●, and fractions of different iron species in
an AOP system. Dong et al. (2019) and Seid-Mohammadi,
Shabanloo, Fazlzadeh, and Poureshgh (2017) reported that the
highest removal efficiencies of pollutants occurred at an acidic
pH in similar treatment systems. At pH > 3, H2O2 becomes
unstable and then broken up into O2 and H2O, leading to a
lower oxidation efficiency. Meanwhile, the oxidation potential
of OH● may decline with the increase in pH. At pH > 5 in the
UV/H2O2/nZVI process, Fe2+ is precipitated as iron hydrox-
ides, which reduces the catalytic activity for H2O2 and decreases
generation of OH●. Further increase in the pH values can lead
to the precipitation of Fe3+ into Fe(OH)3 and thus increase in
the amounts of sludge produced. The participation of iron for
activation of hydrogen peroxide only occurs when it exists in
the dissolved phase, which is in agreement with the results
Water Environment Research • 1–11, 2020
RESEARCH ARTICLE
8
/nZVI and b) UV/H2O2/nZVI processes (experimental condi-
of the studies conducted by Akerdi et al. (2017) and Vilardi,
Rodriguez-Rodriguez, et al. (2019).
In the UV/S2 O2−8 /nZVI process, similar to the UV/H2O2/
nZVI process, pH has a direct effect on the iron phase for acti-
vation of S2 O2−8 and affects roles of predominant radical species
produced. At pH > 3, Fe2+ ions are converted to Fe3+, which has
little ability to activate S2 O2−
8 and produce
SO4⋅−. Subsequently,
3+
Fe ions are converted to ferric hydroxide, increasing sludge
production. This is in agreement with the results of Khan, He,
Khan, Shah, and Dionysiou (2013).
Effect of oxidant concentration (S2O82- and H2O2)
The type and concentration of oxidizing agents can influ-
ence the performance of AOPs (Pi, Feng, Sun, & Sun, 2013).
Therefore, in this study, the effect of S2 O2−
8 (2–10 mM) and
H2O2 (2–20 mM) concentrations in the degradation of AR14
dye by UV/S2 O2− 8 /nZVI and UV/H2O2/nZVI processes was
evaluated under the optimal conditions including pH = 3,
nZVI dose = 0.05 g, and AB14 dye concentration = 100 mg/L
(Figures 6 and 7). The results showed that as the S2 O2−
8 con-
centration increased from 2 to 8 mM, the AR14 degradation
efficiency in the UV/S2 O2−
8 /nZVI process was increased from
59.4% to 94.1% (Figure 6), which is consistent with the results
5
RESEARCH ARTICLE

Figure 6. Effect of persulfate concentration on the degradation efficiency of AB114 dye by UV/S2 O2−
8
/nZVI process (experimental conditions:
pH = 3, nZVI dose = 0.05 g, and AB14 dye concentration = 100 mg/L).

Figure 7. Effect of H2O2 concentration on the degradation efficiency of AB114 dye by UV/H2O2/nZVI process (experimental conditions:
pH = 3, nZVI dose = 0.05 g, and AB14 dye concentration = 100 mg/L).

of studies of Khan et al. (2013), Seid-Mohammadi et al. (2017), Furthermore, the effect of H2O2 concentration on the
and Vilardi, Rodríguez-Rodríguez, et al. (2018), but the removal degradation of AR14 dye in the UV/H2O2/nZVI process
efficiency was decreased by further increasing the concentra- was evaluated at 2–20 mM (Figure 7). As seen, at 0–10 mM
tion of S2 O2−
8 to 10 mM. The reduced removal efficiency at a
H2O2, the increasing H2O2 dose improved the degradation
high S2 O2−
8 concentration can be explained by the dual behav-
of AR14.
ior of S2 O2−
8 at different concentrations. S2 O8 can produce
2−
However, higher concentrations of H2O2 inhibited the
SO4 radicals for degradation of pollutants and OH● through
−
degradation, at which H2O2 scavenged OH● and decreased the
direct reaction with H2O. Thus, increasing the concentration yield of OH●, leading to a decreasing degradation efficiency
of S2 O2−
8 (up to a certain value) can result in the production of
(Rahmani, Kermani, Gholami, Jafari, & Mahmoodi, 2012).
a high amount of free radicals, which subsequently result in the In fact, at a very high concentration of H2O2, other reactions
degradation of AR14 dye. However, a too high concentration (Equations 10-13) may become increasingly dominant (Seid-
of S2 O2−
8 (10 mM in this study) can produce too many sulfate
Mohammadi et al., 2019).
radicals that enhance recombination of these radicals, so that
HO⋅ + H2 O2 → HO⋅2 + H2 O (10)
less sulfate radicals are available for degradation of target pol-
lutants, as follows:
SO4⋅− + SO4⋅− → S2 O2− (8) HO⋅2 + H2 O → HO⋅ + H2 O + O2 (11)
8

2HO⋅2 → H2 O2 + O2 (12)
SO4⋅− + S2 O2− → SO2− + S2 O8⋅− (9)
8 4 HO⋅2 + HO⋅ → H2 O + O2 (13)

6 Samarghandi et al.

Figure 8. Effect of AR14 dye concentration on the degradation efficiency of dye by a) UV/S2 O2−
imental conditions: [H2O2] = 10 mM, [S2 O2−
8
] = 8 mM, nZVI dose = 0.05 g, and pH = 3).
As shown in Equation 10, H2O2 can react with hydroxyl
radicals to generate less reactive HO●2, so that the degra-
dation of AR14 dye was inhibited. For an AOP system, the
optimal concentration of H2O2 exists. Babuponnusami and
Muthukumar (2012) affirmed that the phenol removal effi-
ciency was markedly improved by increasing H2O2 concen-
tration in a hydrogen peroxide based AOP, but the removal
efficiency decreased as peroxide concentration exceeded a
certain level.
Effect of AR14 dye concentration
Effect of AR14 dye concentration was investigated at differ-
ent AR14 concentrations (50–300 mg/L) in the UV/S2 O2− 8 /
nZVI and UV/H2O2/nZVI processes. Figure 8 shows that the
removal efficiency decreased with an increase in the dye con-
centration. By increasing the concentration of AR14 from 50
to 300 mg/L, the AR14 dye removal efficiency was decreased
from 98.9% to 63.3% in the UV/S2 O2−
8 /nZVI process and from
94.0% to 58.3% in the UV/H2O2/nZVI process. As observed
in Figure 8a and b, under the experimental condition (reac-
tion time = 90 min, [H2O2] = 10 mM, [S2 O2−8 ] = 8 mM, nZVI
Water Environment Research • 1–11, 2020
RESEARCH ARTICLE
8
/nZVI and b) UV/H2O2/nZVI processes (exper-
dose = 0.05 g, and pH = 3), the highest dye removal efficiencies
(for initial dye concentration of 50 mg/L) using the UV/S2 O2−8
/nZVI and UV/H2O2/nZVI processes were found to be 98.9%
and 94.0%, respectively. The difference in removal efficiency
of AR14 dye at initial concentrations of 100 and 50 mg/L was
insignificant (<5%).
It should be noted that the removal efficiency of dyes in
the both processes was higher than 90% at 60 min. Saleh and
Djaja (2014) and Yari et al. (2016) employed the photocatalytic
process and the H2O2/nZVI process to remove dyes in water,
respectively. And they reported that the removal efficiency
declined by increasing dye concentration (Saleh & Djaja, 2014)
(Yari et al., 2016), which is in agreement with the results of
the present study. Decreasing the removal efficiency of AR14
by increasing its concentration can be explained as follows:
(a) The fraction of AR14 decomposed by the same amount of
OH● or SO⋅− 4 was lower at a higher initial AR14 concentration;
and (b) production of more intermediates at higher concentra-
tions of AR14 dye may result in stronger competition for OH●
or SO4⋅−, thereby reducing the dye removal efficiency (Akerdi
et al., 2017) (Vilardi, Rodríguez-Rodríguez, et al., 2018).
7
RESEARCH ARTICLE

Figure 9. Effect of nZVI dose on the degradation efficiency of AR14 dye by a) UV/S2 O2−
8
/nZVI and b) UV/H2O2/nZVI processes (experimental
conditions: [H2O2] = 10 mM, [S2 O2−
8
] = 8 mM, AB14 dye concentration = 100 mg/L, and pH = 3).

Figure 10. AR14 removal under different operational conditions (experimental conditions: [H2O2] = 10 mM, [S2 O2−
8
] = 8 mM, AB14 dye con-
centration = 100 mg/L, pH = 3, and nZVI dose = 0.05 g).

8 Samarghandi et al.
 RESEARCH ARTICLE

Figure 11. Effect of nZVI on the degradation efficiency of AR14 dye by UV/S2 O2−
8
/nZVI and UV/H2O2/nZVI processes, a) COD removal and b)
TOC removal (experimental conditions: [H2O2] = 10 mM, [S2 O2−8
] = 8 mM, AB14 dye concentration = 100 mg/L, pH = 3, nZVI dose = 0.05 g,
COD0 = 82 mg/L, and TOC0 = 28 mg/L).

Figure 12. AOS and COD/TOC of AR14 dye in the UV/S2 O2− 8
/nZVI and UV/H2O2/nZVI processes at the optimum conditions ([H2O2] = 10 mM,
[S2 O2−
8
] = 8 mM, AB14 dye concentration = 100 mg/L, pH = 3, nZVI dose = 0.05 g, COD0 = 82 mg/L, and TOC0 = 28 mg/L).

Effect of nZVI dose between 0.01 g and 0.1 g. The experimental conditions are
The influence of the nZVI dosage on the degradation of as follows: [H2O2] = 10 mM, [S2 O2− 8 ] = 8 mM, AB14 dye
AR14 dye using the UV/S2 O2−8 /nZVI and UV/H2O2/nZVI concentration = 100 mg/L, reaction time = 5–90 min, and
processes was investigated by varying the nZVI dosage pH = 3). Based on the results shown in Figure 9a and b, when

Water Environment Research • 1–11, 2020 9

RESEARCH ARTICLE
the nZVI dosage was increased from 0.01 g to 0.05 g/L, the
AR14 degradation efficiency was increased from 60.4% to
94.2% in the UV/S2 O2− 8 /nZVI process and from 57.4% to
90.7% in the UV/H2O2/nZVI process. Conversely, a further
increase in the nZVI dosage led to a decrease in the degrada-
tion efficiency of AR14. It is supposed that an increase in the
nZVI dosage provides a greater surface area or the number of
active sites on the surface, thereby increasing the number of
yielded OH●. However, when the dose of nZVI was > 0.05 g in
this study, the degradation efficiency was reduced due to the
increased opacity of the suspension because the light inter-
ception increased the scattering of the light. Consequently,
the effective illumination diminished and the portion of the
nZVI surface was not available for absorption of light (Saleh
& Djaja, 2014).
Effect of UV irradiation
The individual and joint roles of all the studied parameters on
the AR14 dye removal efficiency were investigated (Figure 10).
The highest AR14 removal efficiency for the UV irradiation
only, nZVI only, H2O2 only, and S2 O2− 8 only processes were
39%, 21%, 25%, and 29%, respectively. In contrast, S2 O2− 8 /nZVI
and H2O2/nZVI could remove the dye by 56 and 63%, respec-
tively. This finding means that the efficiencies of the two com-
bined processes were more effective than the treatment using
one single component in the joint treatments. Moreover, the
use of UV in the UV/H2O2/nZVI and UV/S2 O2− 8 /nZVI pro-
cesses led to an increase in the dye removal efficiency by 86%
and 91%, respectively. According to the results, the synergistic
effects of UV radiation in the UV/H2O2/nZVI and UV/S2 O2− 8
/nZVI processes were 40 and 41%, respectively, which is con-
sistent with the results of other studies (Seid-Mohammadi et
al., 2017; Zhu et al., 2000).
The UV radiation activates the oxidants through homo-
lytic cleavage of the peroxide bond, leading to activation of
●
H2O2 and S2 O2− 8 for the generation of OH and 4 , respec-
SO⋅−
tively (Lin, Liang, & Chen, 2011).
Mineralization and biodegradability
To identify the efficiencies of degradation and mineralization
of AR14 dye through the studied processes, that is, UV/S2 O2−8
/nZVI and UV/H2O2/nZVI, the removal efficiencies of TOC
and COD were assessed (AB14 dye concentration = 100 mg/L,
pH = 3, [H2O2] = 10 mM, [S2 O2− 8 ] = 8 mM, nZVI dose = 0.05 g,
COD0 = 82 mg/L, and TOC0 = 28 mg/L) (Figure 11). The
results showed that the increase in reaction time from 5 to
90 min improved the TOC removal from 38.47% to 81.6% for
the UV/S2 O2−
8 /nZVI and from 32.4% to 72.9% in the UV/H2O2/
nZVI process (Figure 11a). Meanwhile, the COD removal was
increased from 41.6% to 86.5% for UV/S2 O2− 8 /nZVI and from
35.5% to 79.57% for UV/H2O2/nZVI process (Figure 11b).
The biodegradability of AR14 dye in the effluents of
UV/S2 O2−8 /nZVI and UV/H2O2/nZVI processes was investi-
gated using COD/TOC, BOD5/COD, and AOS. As seen, as the
reaction time was increased from 5 to 90 min, AOS increased
from −0.39 to 0.78 in the effluent of UV/S2 O2−
8 /nZVI and from
−0.39 to 0.69 in the effluent of the UV/H2O2/nZVI process
10
(Figure 12). At the same time, COD/TOC decreased from 2.93
to 2.14 after the UV/S2 O2−8 /nZVI treatment, while this ratio
went down from 2.93 to 2.20 in the effluents of UV/H2O2/
nZVI process. This finding is indicative of the improved biode-
gradability of AR14 dye in the studied treatment processes, in
agreement with the observations of Ferrag-Siagh et al. (2014).
Moreover, biodegradability was assessed based on BOD5/COD
(biodegradable (>0.6), partially biodegradable (0.4–0.6), and
nonbiodegradable (<0.4)) (Rahmania, Rahimzadeha, Samadia,
Farmanib, & Asgaria, 2019). The biodegradability of samples
was studied at AR14 = 100 mg/L. The initial BOD5/COD
was < 0.1, suggesting that the origanic compound was bio-
logically refractory. As the reaction time increaased from 30
to 60 min, the BOD5/COD in the effluent of the UV/S2 O2− 8 /
nZVI was increased from 0.19 to 0.63, while it was improved
from 0.28 to 0.74 in the effluent of UV/H2O2/nZVI. This find-
ing clearly demontrated that either of the AOPs was capable of
improving the biodegradability of AR14 dye.
Conclusion
This study demonstrates that the UV/H2O2/nZVI or UV/S2 O2− 8
/nZVI process was very effective for removing AR14 from dye-
containing wastewater. The treatment performance heavily
relies upon solution pH, nZVI dose, the oxidant concentra-
tion (H2O2 or S2 O2−
8 ), initial dye concentration, and reaction
time. During the treatment, the biodegradability of AR14
dye solutions was improved. Therefore, low-cost aerobic bio-
logical wastewater treatment may be an appropriate option as
post-treatment.
Acknowledgments
The study was funded by Vice-chancellor for Research and
Technology, Hamadan University of Medical Sciences (No.
9804182912). So, we acknowledge research and technology
deputy of the University for Financial Aids providing the
financial support.
References
Ahmed, S. M., El-Dib, F. I., El-Gendy, N. S., Sayed, W. M., & El-Khodary, M. (2016).
A kinetic study for the removal of anionic sulphonated dye from aqueous solu-
tion using nano-polyaniline and Baker’s yeast. Arabian Journal of Chemistry, 9,
S1721–S1728.
Akerdi, A. G., Bahrami, S. H., Arami, M., & Pajootan, E. (2016). Photocatalytic discolor-
ation of Acid Red 14 aqueous solution using titania nanoparticles immobilized on
graphene oxide fabricated plate. Chemosphere, 159, 293–299.
Akerdi, A. G., Es’haghzade, Z., Bahrami, S. H., & Arami, M. (2017). Comparative study of
GO and reduced GO coated graphite electrodes for decolorization of acidic and basic
dyes from aqueous solutions through heterogeneous electro-Fenton process. Journal
of Environmental Chemical Engineering, 5, 2313–2324.
Al-Amrani, W. A., Lim, P.-E., Seng, C.-E., & Ngah, W. S. W. (2014). Bioregeneration of azo
dyes-loaded mono-amine modified silica in batch system: Effects of particle size and
biomass acclimation condition. Chemical Engineering Journal, 251, 175–182.
Babuponnusami, A., & Muthukumar, K. (2012). Advanced oxidation of phenol: A compar-
ison between Fenton, electro-Fenton, sono-electro-Fenton and photo-electro-Fenton
processes. Chemical Engineering Journal, 183, 1–9.
Dargahi, A., Ansari, A., Nematollahi, D., Asgari, G., Shokoohi, R., & Samarghandi, M.
R. (2019). Parameter optimization and degradation mechanism for electrocatalytic
degradation of 2, 4-diclorophenoxyacetic acid (2, 4-D) herbicide by lead dioxide elec-
trodes. RSC Advances, 9, 5064–5075.
Dargahi, A., Mohammadi, M., Amirian, F., Karami, A., & Almasi, A. (2017). Phenol re-
moval from oil refinery wastewater using anaerobic stabilization pond modeling and
Samarghandi et al.

process optimization using response surface methodology (RSM). Desalination and
Water Treatment, 87, 199–208.
Dargahi, A., Pirsaheb, M., Hazrati, S., Fazlzadehdavil, M., Khamutian, R., & Amirian, T.
(2015). Evaluating efficiency of H2O2 on removal of organic matter from drinking
water. Desalination and Water Treatment, 54, 1589–1593.
Dong, H., Hou, K., Qiao, W., Cheng, Y., Zhang, L., Wang, B., … Zeng, G. (2019). Insights
into enhanced removal of TCE utilizing sulfide-modified nanoscale zero-valent iron
activated persulfate. Chemical Engineering Journal, 359, 1046–1055.
Ferrag-Siagh, F., Fourcade, F., Soutrel, I., Aït-Amar, H., Djelal, H., & Amrane, A. (2014).
Electro-Fenton pretreatment for the improvement of tylosin biodegradability.
Environmental Science and Pollution Research, 21(14), 8534–8542.
Gao, J.-F., Wang, J.-H., Yang, C., Wang, S.-Y., & Peng, Y.-Z. (2011). Binary biosorption of
Acid Red 14 and Reactive Red 15 onto acid treated okara: Simultaneous spectropho-
tometric determination of two dyes using partial least squares regression. Chemical
Engineering Journal, 171, 967–975.
Khan, J. A., He, X., Khan, H. M., Shah, N. S., & Dionysiou, D. D. (2013). Oxidative deg-
radation of atrazine in aqueous solution by UV/H2O2/Fe2+, UV/S2O82-/Fe2+ and UV/
HSO5-/Fe2+ processes: A comparative study. Chemical Engineering Journal, 218,
376–383.
Khodam, F., Rezvani, Z., & Amani-Ghadim, A. R. (2015). Enhanced adsorption of Acid
Red 14 by co-assembled LDH/MWCNTs nanohybrid: Optimization, kinetic and iso-
therm. Journal of Industrial and Engineering Chemistry, 21, 1286–1294.
Lam, S.-M., Sin, J.-C., Abdullah, A. Z., & Mohamed, A. R. (2012). Degradation of waste-
waters containing organic dyes photocatalysed by zinc oxide: A review. Desalination
and Water Treatment, 41, 131–169.
Lin, Y.-T., Liang, C., & Chen, J.-H. (2011). Feasibility study of ultraviolet activated persul-
fate oxidation of phenol. Chemosphere, 82, 1168–1172.
Mikhailov, I., Komarov, S., Levina, V., Gusev, A., Issi, J.-P., & Kuznetsov, D. (2017).
Nanosized zero-valent iron as Fenton-like reagent for ultrasonic-assisted leaching of
zinc from blast furnace sludge. Journal of Hazardous Materials, 321, 557–565.
Nguyen, T. A., & Juang, R.-S. (2013). Treatment of waters and wastewaters containing sul-
fur dyes: A review. Chemical Engineering Journal, 219, 109–117.
Oancea, P., & Meltzer, V. (2014). Kinetics of tartrazine photodegradation by UV/H2O2 in
aqueous solution. Chemical Papers, 68, 105–111.
Oh, S.-Y., Kang, S.-G., & Chiu, P. C. (2010). Degradation of 2, 4-dinitrotoluene by persul-
fate activated with zero-valent iron. Science of the Total Environment, 408, 3464–3468.
Pi, Y., Feng, J., Sun, J., & Sun, J. (2013). Facile, effective, and environment-friendly deg-
radation of sulfamonomethoxine in aqueous solution with the aid of a UV/Oxone
oxidative process. Environmental Science and Pollution Research, 20, 8621–8628.
Rahmani, Z., Kermani, M., Gholami, M., Jafari, A. J., & Mahmoodi, N. M. (2012).
Effectiveness of photochemical and sonochemical processes in degradation of Basic
Violet 16 (BV16) dye from aqueous solutions. Iranian Journal of Environmental
Health Science & Engineering, 9, 14.
Rahmania, A., Rahimzadeha, H., Samadia, M.-T., Farmanib, A., & Asgaria, G. (2019).
Bisphenol S degradation using Fe-SBA-15/UV/US/peroxymonosulfate: Performance
optimization, biodegradability, mineralization and toxicity studies. Desalination and
Water Treatment, 163, 297–309.
Rodriguez, S., Vasquez, L., Costa, D., Romero, A., & Santos, A. (2014). Oxidation of orange
G by persulfate activated by Fe (II), Fe (III) and zero valent iron (ZVI). Chemosphere,
101, 86–92.
Roth, H., Gendel, Y., Buzatu, P., David, O., & Wessling, M. (2016). Tubular carbon nano-
tube-based gas diffusion electrode removes persistent organic pollutants by a cyclic
adsorption–electro-Fenton process. Journal of Hazardous Materials, 307, 1–6.
Water Environment Research • 1–11, 2020
RESEARCH ARTICLE
Saleh, R., & Djaja, N. F. (2014). UV light photocatalytic degradation of organic dyes with
Fe-doped ZnO nanoparticles. Superlattices and Microstructures, 74, 217–233.
Seid-Mohammadi, A., Asgarai, G., Ghorbanian, Z., & Dargahi, A. (2019). The removal of
cephalexin antibiotic in aqueous solutions by ultrasonic waves/hydrogen peroxide/
nickel oxide nanoparticles (US/H2O2/NiO) hybrid process. Separation Science and
Technology, 1–11.
Seid-Mohammadi, A., Asgari, G., Poormohammadi, A., Ahmadian, M., & Rezaeivahidian,
H. (2016). Removal of phenol at high concentrations using UV/Persulfate from saline
wastewater. Desalination and Water Treatment, 57, 19988–19995.
Seid-Mohammadi, A., Shabanloo, A., Fazlzadeh, M., & Poureshgh, Y. (2017). Degradation
of acid blue 113 by US/H2O2/Fe2+ and US/S2O82–/Fe2+ processes from aqueous solu-
tions. Desalination and Water Treatment, 78, 273–280.
Shokoohi, R., Jafari, A. J., Dargahi, A., & Torkshavand, Z. (2017). Study of the efficiency
of bio-filter and activated sludge (BF/AS) combined process in phenol removal from
aqueous solution: Determination of removing model according to response surface
methodology (RSM). Desalination and Water Treatment, 77, 256–263.
Thiam, A., Sirés, I., Centellas, F., Cabot, P. L., & Brillas, E. (2015). Decolorization and
mineralization of Allura Red AC azo dye by solar photoelectro-Fenton: Identification
of intermediates. Chemosphere, 136, 1–8.
Vilardi, G. (2019). Mathematical modelling of simultaneous nitrate and dissolved ox-
ygen reduction by Cu-nZVI using a bi-component shrinking core model. Powder
Technology, 343, 613–618.
Vilardi, G., Di Palma, L., & Verdone, N. (2017). Competitive reaction modelling in aque-
ous systems: The case of contemporary reduction of dichromates and nitrates by
nZVI. Chemical Engineering Transactions, 60, 175–180.
Vilardi, G., Parisi, M., & Verdone, N. (2019). Simultaneous aggregation and oxidation
of nZVI in Rushton equipped agitated vessel: Experimental and modelling. Powder
Technology, 353, 238–246.
Vilardi, G., Rodriguez-Rodriguez, J., Ochando-Pulido, J. M., Di Palma, L., & Verdone, N.
(2019). Fixed-bed reactor scale-up and modelling for Cr (VI) removal using nano
iron-based coated biomass as packing material. Chemical Engineering Journal, 361,
990–998.
Vilardi, G., Rodríguez-Rodríguez, J., Ochando-Pulido, J. M., Verdone, N., Martinez-Ferez,
A., & Di Palma, L. (2018). Large laboratory-plant application for the treatment of
a Tannery wastewater by Fenton oxidation: Fe (II) and nZVI catalysts comparison
and kinetic modelling. Process Safety and Environmental Protection, 117, 629–638.
Wang, H., Zhong, Y., Yu, H., Aprea, P., & Hao, S. (2019). High-efficiency adsorption for
acid dyes over CeO2· xH2O synthesized by a facile method. Journal of Alloys and
Compounds, 776, 96–104.
Xia, S.-J., Zhou, X.-B., Shi, W., Pan, G.-X., & Ni, Z.-M. (2014). Photocatalytic property and
mechanism studies on acid red 14 by MxOy/ZnTi–layered double hydroxides (M=
Fe, Sn, Ce). Journal of Molecular Catalysis A: Chemical, 392, 270–277.
Yari, A., Nazari, S., Majidi, G., Alizadeh Motobave, S., Asgari, E., Rastegar, A., & Dehghan,
S. (2016). Nanoparticles zero valent iron (NZVI) Synthesis and application of H2O2/
Fe0 and H2O2 in the treatment of dye solution containing acid red 18 from aqueous
environments. Journal of Sabzevar University of Medical Sciences, 22, 982–991.
Zarei, A., Biglari, H., Mobini, M., Dargahi, A., Ebrahimzadeh, G., Narooie, M., …
Poursadeghiyan, M. (2018). Disinfecting poultry slaughterhouse wastewater using
copper electrodes in the electrocoagulation process. Polish Journal of Environmental
Studies, 27, 1907–1912.
Zhu, C., Wang, L., Kong, L., Yang, X., Wang, L., Zheng, S., … Zong, H. (2000).
Photocatalytic degradation of AZO dyes by supported TiO2+ UV in aqueous solution.
Chemosphere, 41, 303–309.
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