Journal of Environmental Management 271 (2020) 110964

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Journal of Environmental Management

journal homepage: http://www.elsevier.com/locate/jenvman

Research article

Photocatalytic degradation of model pharmaceutical pollutant by novel

magnetic TiO2@ZnFe2O4/Pd nanocomposite with enhanced photocatalytic
activity and stability under solar light irradiation
Najmeh Ahmadpour a, Mohammad Hossein Sayadi a, *, Sara Sobhani b, Mahmood Hajiani a
a
Department of Environmental Engineering, Faculty of Natural Resources and Environment, University of Birjand, Birjand, Iran
b
Department of Chemistry, College of Sciences, University of Birjand, Birjand, Iran

A R T I C L E I N F O A B S T R A C T

Keywords:
Composite TiO2@ZnFe2O4/Pd photocatalyst
Batch and continuous systems- visible light
photocatalysis
Photocatalytic degradation- diclofenac
photocatalytic degradation
Magnetic characteristics of the photocatalyst
In the last decades, the use of magnetic nanocomposites as a catalyst was considered for removal of organic
pollutants due to its easy separation. Therefore, initially, TiO2@ZnFe2O4/Pd nanocomposite was prepared and
then used in the photodegradation of diclofenac under direct solar irradiation in the batch and continuous
systems. The structure, morphology and other specifications of produced nanocatalyst were determined via XRD,
VSM, FESEM/EDX, FTIR, GTA, UV–Vis, Zeta potential, XPS and ICP-OES. The effective factors on diclofenac
removal via nanophotocatalyst viz. pH, catalyst concentration, initial concentration of diclofenac, and flow rate
and column length on diclofenac photodegradation were studied. Based on the results, the optimal rate for pH,
catalyst concentration, and initial concentration of diclofenac was 4, 0.03 g/l and 10 mg/l respectively. Pd-
coated TiO2@ZnFe2O4 magnetic photocatalyst had higher photocatalytic activity in diclofenac photo­
degradation in relation to ZnFe2O4 and TiO2@ZnFe2O4 under solar light irradiation. The findings showed that
after five recycles, the photocatalytic efficiency did not show much reduction i.e. the removal efficiency from
86.1% in the first cycle reduced only to 71.38% in the last cycle. Likewise, in this study, with flow rate reduction
and column length increase diclofenac degradation rate increased.

1. Introduction
In the past few years, the growing of industrialization and excessive
utilization of available resources by humans has emerged water pollu­
tion as one of the global environmental issues (Hasija et al., 2019). Entry
of pharmaceutical pollutants to the environmental resources viz. surface
waters, ground waters, sediments, soil and even drinking water, has
created a serious danger for the humans and freshwater besides marine
water ecosystem. The pharmaceutical industries, hospitals and improper
disposal of pharmaceuticals are the main resources of pharmaceutical
pollutants. Among the pharmaceutical pollutants diclofenac 2-[2-[(2,
6-dichlorophenyl)amino]phenyl]acetic acid is a non-steroidal anti-in­
flammatory drug that is used as antipain, anticancer, and anti-rheumatic
combinations and is one of the most commonly used drugs that have
potential toxic effects (Zhao et al., 2017). Considering the nonpolar
putative nature, the distribution and release of diclofenac in the envi­
ronment takes place naturally via aquatic migration and its accumula­
tion in the food chain (Acu~ na et al., 2015) and in the recent years,
diclofenac (DCF) has been determined at its highest concentration i.e.
28.4 μg/l in the surface waters. Moreover, in the ground waters it has
been reported at highest concentrations of 0.59 μg/l (De Oliveira et al.,
2018). Therefore, numerous techniques were used to remove pharma­
ceutical pollutants from wastewater (Guo et al., 2018). Among them, the
Advanced Oxidation Process (AOP) is an effective technique in which a
semiconductor catalyst can with use of natural energy i.e. solar irradi­
ation eliminate the pharmaceutical pollutants (Zuorro et al., 2013).
Advanced oxidation processes such as photocatalysis (Calza et al.,
2006), UV (Kim and Tanaka, 2009), UV/H2O2 (Vogna et al., 2006),
Photo-Fenton (Ravina et al., 2002; Perez-Estrada et al., 2005), ozonation
(Vieno et al., 2007) and sonolysis (Naddeo et al., 2010) for DCF removal
from polluted water has been reported wherein among these processes,
photocatalysis is an effective technique due to low cost, good stability,
eco-friendly nature, and energy efficiency wherein a semiconductor
catalyst can via use of natural energy of solar irradiation eliminate the
organic pollutants (Sharma et al., 2019). Basically, photocatalysis
mechanism is transfer of photon energy to chemical energy. Here, a

* Corresponding author.
E-mail address: mh_sayadi@birjand.ac.ir (M.H. Sayadi).

https://doi.org/10.1016/j.jenvman.2020.110964
Received 5 January 2020; Received in revised form 5 June 2020; Accepted 12 June 2020
Available online 29 June 2020
0301-4797/© 2020 Elsevier Ltd. All rights reserved.
N. Ahmadpour et al.
photocatalyst plays an important role that using solar light absorption
(hv), leading to creation of electron-hole recombination pair, separation
of electrons in conduction band and oxidizing holes in valence band in
energy level platform (Hasija et al., 2020). Among the different cata­
lysts, semiconductor photocatalysts have exhibited a significant per­
formance against the degradation of organic and inorganic pollutants.
TiO2 is one of the commercial and efficient photocatalysts that is used
for the degradation of most of the pollutants, due to its flexibility, ease of
synthesis, ability to control and good stability (Czili and Horv�ath, 2009).
However, the two inherent weaknesses of TiO2 viz. large bandgap (EV
3.2) and high recombination rate, limits its photoresponse in the UV
region (4–5% of solar spectrum) and quantum efficiency reduces the
photocatalytic reactions, besides its separation after the process is an
issue (Lim et al., 2017; Chen and Burda, 2008). Several attempts to in­
crease TiO2 photocatalyst efficiency has been carried out. The use of a
magnetic core is due to its biocompatibility, low cost, and abundance for
easy catalyst recovery has been carried out that simply exits using a
magnetic field (Singh et al., 2019). To reduce TiO2 bandgap and its use
in the visible light, noble metals such as Ag, Pt, Pd and Au doped onto
TiO2 can be used that simply is via coating of these metal ions on the
surface of a semiconductor (Bokare et al., 2013). This operation causes
TiO2 photoresponse improvement and photodegradation under solar
light irradiation occurs with an ease. In addition, it prevents the
recombination of electrons and holes that are caused as the result of
photodegradation (Huang et al., 2015). Also, Due to its high reactivity,
this nanoparticles have good adsorption ability due to their specific
surface area. The nanoparticles are also used to correct and absorb
environmental pollution (Arsiya et al., 2017). Thus, the aim of this study
was magnetic nanocomposite synthesis of palladium supported
TiO2@ZnFe2O4 with photodegradation ability of DCF under direct solar
irradiation in the batch and continuous systems.
2. Experimental
2.1. Material
All the reagents were purchased from Aldrich and Merck and used
without further purification. The chemicals ZnCl2 (<98%), FeCl3.6H2O
(<97%), CH3COONa.3H2O (NaOAc <99%), NaOH (96%), HCl (97%),
ethylene glycol (EG), tetra butyl orthotitanate (TBOT) besides ethanol
and methanol were procured from Merck, Germany and Pd(NO3)22H2O
from Aldrich Company. Moreover, DCF was purchased from Sigma-
Aldrich Co. In all the stages, deionized water was used to prepare the
solutions.
2.2. Preparation of ZnFe2O4, TiO2@ZnFe2O4 and Pd supported
TiO2@ZnFe2O4 magnetic nanoparticles
ZnFe2O4 magnetic nanoparticles were synthesized via Solvothermal
method based on the previous reports (Guo et al., 2016;Gu et al., 2016)
and the accurate details is mentioned as follows: 1.08 g FeCl3.6H2O (2
mmol) and 0.82 g NaOAc (4 mmol) was dissolved in the ethylene glycol
(EG) mixture and stirred at RT for 30 min. The resultant brownish dark
yellow color mixture was autoclaved for 4 h at 180 � C. After autoclaving
the solution at cold room temperature, the resultant black color sedi­
ment was separated from the mixture with a strong magnet and after
washing with deionized water (DW) and ethanol, was dried in an oven at
70 � C for 24 h.
For preparation of TiO2@ZnFe2O4, 60 g of ZnFe2O4 nanoparticles
were mixed with (0.24 ml) DW and (60 ml) ethanol and was sonicated
for 20 min. In the next step, 200 ml of Tetrabutyl Orthotitanate (TBOT)
and 10 ml ethanol under vigorous stirring (3 h at 40 � C) was added
dropwise to the ferrite solution. At the reaction end, the resultant
nanoparticle was separated with a magnet and washed with DW and
ethanol and dried at 70 � C (Chi et al., 2013).
In the next stage, TiO2@ZnFe2O4//Pd nanoparticles were
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Journal of Environmental Management 271 (2020) 110964
synthesized using the photodeposition technique. Initially 0.0052 g Pd
(NO3)2 2H2O was dissolved in 40 ml DW and later 0.1 g TiO2@ZnFe2O4
was added to it. To obtain a homogenous solution of magnetic nano­
structures in the solvent, it was sonicated for 20 min. Later, the mixture
was transferred to a Quartz tube; 0.4 ml methanol was added and sub­
jected for 10 h under ultraviolet light. In this stage, it can be stated that
palladium ions are reduced to metallic palladium and is positioned at
TiO2 level, later Pd are trapped at electron sites and are stored as an
oxide.
2.3. The characterization of TiO2@ZnFe2O4/Pd nanoparticles
The crystalline structure of the samples was determined via X-ray
Diffraction (XRD) (Rigaku MiniFlex 600) using the Cu Ka radiation (1
nm ¼ 0.15418). The magnetic properties of nanocomposites were
measured using a Vibrating Sample Magnetometer (VSM) (Lake Shore
7403) at an ambient temperature. The morphology and structure of
resultant composite nanoparticles was obtained from Field Emission
Scanning Electron Microscopy (FESEM) (TE-SCAN, MIRA3 FESEM
Model). The elemental analysis was determined using an alternating
Electron Dispersion X-Ray Spectroscopy (EDS along with FESEM). Zeta
potential of TiO2@ZnFe2O4/Pd composite combination was measured
via Zetasizer 3000HS. The palladium distinctive features of Pd sup­
ported TiO2@ZnFe2O4 sample was determined via Inductively Coupled
Plasma Optical Emission Spectrometry (ICP-OES, Leeman Direct
Reading Echelle). The Fourier-Transform Infrared Spectroscopy (Shi­
madzo, FT_IR1650 Spectrophotometer, Japan) with KBr pellets was used
for chemical nature display of the prepared composites at the range of
400–4000 cm 1. The reflexive spectrum of UV radiation i.e. the UV–Vis
(DRS) spectra of the samples were recorded on the UV–Vis Spectro­
photometer (Shimadzu, UV-2550, Japan). The Thermographic analysis
(TGA) was determined using the PerkinElmer System (USA) at 50� to
800 � C in N atom.
2.4. Batch system
Optimum pH levels, concentration of DCF and magnetic catalyst was
determined using the batch system. In this study, the photocatalytic
system was subjected to direct solar light irradiation with an intensity of
72–76 Klux. A magnetic stirrer with 70 rotations/min was used for
mixture of the samples. To adjust pH of the samples 0.1 M HCl and NaOH
were used. Before turning on the lamps and or exposure of the sample to
solar light irradiation, initially the solution was stirred for 30 min in
dark, to assure the sorption – desorption equilibrium between the pho­
tocatalyst and Diclofenac. In a specified timescale, an amount of re­
action’s solution was withdrawn and after centrifugation and for
removal of residual particles a filter paper was used and finally
measured via spectrophotometer at the range of 276 nm. DCF photo­
degradation efficiency was calculated as under (Ahmadpour et al.,
2019):
� �
C t C0
Removal DCFð%Þ ¼ �100 (1)
Ct
where C0 and Ct were the initial and final concentrations respectively
after different time intervals of solar light irradiation.
2.5. Continuous system
To assess the effect of column length and flow rate in breakthrough
curves, the system length (5, 10, 15 and 25 cm) and three flow rates (5,
10 and 15 mm/min) was used in the continuous system. In this study, 10
mg/l of DCF and 0.03 g/l of Pd supported TiO2@aZnFe2O4 composite
catalyst was added to the system and subjected to direct solar light
irradiation. It is imperative to mention that in this system the entire
optimized parameters in the batch system were used. To adjust the flow
N. Ahmadpour et al.
rate a peristaltic pump was used. Furthermore, a magnetic stirrer (with
70 rotations/min) to mix the sample and an aeration pump (1.5 l/min)
to provide the required solution oxygen was used. In these experiments,
the temperature was kept constant at 25 � C. The output liquid volume
(Veff) was achieved from the equation (Sayadi et al., 2019)
Veff ¼ Qt (2)
where Q was flow (ml/min) and t was total flow time (min).
2.6. Kinetic degradation of DCF
In general, the first order kinetic is used for the micropollutants
(Bahnemann et al., 2007). The k constant rate was calculated from the
first order equation:
dC
¼ kC (3)
dt
where C is DCF concentration and k is reaction constant rate. The pho­
tocatalytic kinetic reactions can be described using the first order re­
action for 10 mg/l concentration of DCF solutions. The constant rate (k)
and correlation coefficient (R2) was assessed via the linear regression
curve Ln (C0/C) and UV light irradiation time. The first order equations
are as follows (Sharma et al., 2012):
C0
Ln ¼ Kt (4)
C
here “k” is equation constant rate (min 1); C and C0 are the final and
initial concentrations of DCF (mg/l) respectively.
3. Results and discussion
3.1. Characterization of TiO2@ZnFe2O4 nanoparticles
3.1.1. Morphology
The FESEM images showed that ZnFe2O4 and TiO2@ZnFe2O4 nano­
particles were almost uniform in size and shape (see supplementary
material SM 1). When TiO2@ZnFe2O4 surface is coated with Pd, the
coarseness and size of particles increases. As observed, TiO2@ZnFe2O4/
Pd particles were 33.44–37.16 nm in size that are in concurrence with
XRD results. One of the reasons for compactness of agglomeration in
TiO2@ZnFe2O4/Pd nanoparticles is related to the magnetic properties of
ferrite nanoparticles (Nguyen et al., 2019). The absence of sonication
prior to imaging could also be the cause of nanoparticles compactness
(Moreno-Valencia et al., 2017; Wang et al., 2017). The elemental anal­
ysis for chemical purity of TiO2@ZnFe2O4/Pd sample was carried out
with X-ray Spectroscopy analysis (EDS). EDS spectrum showed that the
elements Zn, Fe, O, Ti and Pd are present in the sample. Therefore, EDS
spectrum validates that Pd particles are present on the titanium mag­
netic nanoparticles (see supplementary material SM 1). The reason for
high TiO2 rate is that TiO2 nanoparticles lack magnetic interaction thus
in nanoparticles washing phase, it is unable to separate them via the
magnet.
3.2. Crystalline structure, X-ray diffraction (XRD) analysis
The structure of magnetic nanoparticles was determined using the X-
ray diffraction (XRD). The XRD pattern of ZnFe2O4 is completely allo­
cated to the cubic phase of ZnFe2O4 (see supplementary material SM 1).
The diffraction peaks at ¼ 2θ showed 30.45� ,32.15� , 35.8� , 43.45� ,
53.8� , 57.35� ,62.95� , 73.5� pertain to ZnFe2O4 and pertain to the crys­
tals surface (220), (222), (311), (400), (331), (422), (511) and (533)
respectively (JCPDS 22-1012) (Chen et al., 2015; Yang et al., 2015; Guo
et al., 2013). In case of TiO2@ZnFe2O4 composite, the cubic structure
peaks in the axis showed the composites; therefore it was clear that
ZnFe2O4 nanocrystals do not alter their phases. Besides XRD pattern of
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Journal of Environmental Management 271 (2020) 110964
TiO2@ZnFe2O4 core/shell, the peaks at 2θ showed 25.75⁰, 27.2⁰, 35.8⁰,
47.4⁰, 57.35⁰ and 62.95⁰ that pertain to surfaces (101), (110), (311),
(102), (422) and (511) of TiO2 respectively (JCPDS No. 1272-21)
(Hasanpour et al., 2012). TiO2 peaks with tetrahedron shell anatas
structure in some of the peaks had ZnFe2O4 nuclei. The dispersion ra­
diation intensity reduction of ZnFe2O4 was resultant of TiO2 coating due
to absorption of X-ray via TiO2 shell. The peaks at 2θ, 46.5⁰ and 68.1⁰
pertained to the cubic surfaces of palladium (200) and (220) respec­
tively (JCPDS No. 89-4897) and showed that metallic palladium exists in
the composition of composite material.
3.3. Fourier transform infrared (FTIR) analysis
FTIR spectra of ZnFe2O4, TiO2@ZnFe2O4 and TiO2@ZnFe2O4/Pd
nanoparticles are indicated at the range of 400–4000 cm 1 (see sup­
plementary material SM 1). From FTIR spectra, it was clear that ZnFe2O4
was strong absorption group at 540 cm 1 level that is in accordance with
Fe–O vibrations (Rahimi et al., 2015). Moreover, Zn–O stretching vi­
brations was depicted at 552 cm 1 and the band with 1384 cm 1 range
could be observed with Ti–O–Ti vibrations in TiO2 (Dhiman et al.,
2012). The other two peaks at 3250 cm 1 and 1644 cm 1 respectively
were created at the surface that pertained to O–H vibrations in the hy­
droxyl group absorbed from the water (Ullattil and Periyat, 2016). After
modification of TiO2@ZnFe2O4 with Pd the peaks appeared at 1627
cm 1 and 2929 cm 1 respectively that show the presence of palladium
in the composition.
3.4. X-ray photoelectron spectroscopy analysis
X-ray photoelectron spectroscopy (XPS) is a powerful instrument to
study the elemental composition of the surface, the oxidation state, and
the binding energy of the core electron of the metal. The peaks related to
O 1s, Fe 2p, Zn 2p, Ti 2p and palladium are clearly found in this spec­
trum. It contains two dominant band peaks corresponding to Fe2p3/2
and Fe2p1/2 at 711.6 and 724.2 eV, respectively. The Zn 2p XPS spectra,
confirmed by the binding energies of Zn 2p3/2 and Zn 2p1/2 at 1020.3
and 1043.2 eV, respectively. The Ti 2p, the two peaks 2p1/2 and 2p3/2 of
the Ti4þ were found in 464 eV and 458.3 eV, respectively. The two peaks
at 530.7 and 529 eV are attributed to oxygen in ZnFe2O4 and Ti–O
bonding to O, respectively (Wang et al., 2013). There is an XPS spectrum
of Pd binding energy with two peaks of 337.8 and 343.1 eV, which is
attributed to Pd 3d3/2 and Pd d35/2 (see supplementary material SM 2
for further details).
3.5. UV-VIS spectrum (DRS) analysis
For photoproperties perception of ZnFe2O4, TiO2@ZnFe2O4 and
TiO2@ZnFe2O4/Pd composite nanoparticles, UV–Vis spectrum (DRS) of
the samples was carried out (Fig. 1a). As indicated, ZnFe2O4,
TiO2@ZnFe2O4 and TiO2@ZnFe2O4/Pd composite nanoparticles were
able to absorb the visible light. ZnFe2O4 nanoparticles can totally absorb
UV and visible light due to narrow bandgap. Therefore, it enhances the
electron-hole recombination (Yu, 2004). After TiO2 deposition, the ab­
sorbency of TiO2@ZnFe2O4 increases in visible light which is due to
synergy effects of TiO2 transfer and ZnFe2O4 absorption (Yu et al.,
2011). Later with palladium coating the absorbency in visible light
significantly increases that is due to the surface plasmon resonance ef­
fects of Pd arising from the visible light (Guo et al., 2013; Hasanpour
et al., 2012; Rahimi et al., 2015; Dhiman et al., 2012; Ullattil and Per­
iyat, 2016; Wang et al., 2013; Yu, 2004; Yu et al., 2011; Lin et al., 2012).
3.5.1. Measurement of magnetic properties (VSM)
The magnetic properties of nanoparticles were determined via a
magnetometer (VSM). As shown in Fig. 1b all of them indicated high
saturation magnet. Magnetic saturation level (Ms) of ZnFe2O4 nano­
particles was 42.57 emu/g. After modification with TiO2 and doped Pd,
N. Ahmadpour et al.
Fig. 1. UV–Vis spectrum (DRS) (a), and (b) VSM of ZnFe2O4, TiO2@ZnFe2O4 and TiO2@ZnFe2O4/Pd magnetic nanocomposite.
the magnetism saturation reached 37.32 and 27.28 emu/g respectively.
In fact, it can be stated that saturation magnetism of magnetic nano­
particles gradually reduced due to reduction of ZnFe2O4 content in the
composite nanoparticles. Although, TiO2@ZnFe2O4/Pd in relation to
ZnFe2O4 encounters a lower magnetism, but still is located in the
paramagnetic domain wherein the resultant nanocomposite nano­
particles can be immediately separated from the solution under an
external magnetic field.
3.5.2. N2 adsorption-desorption isotherms
To examine the specific surface area and the pore size distribution,
N2 adsorption-desorption isotherms are performed. As Figure (2 a,b)
shows, the N2 adsorption-adsorption isotherms correspond to the IUPAC
type III, which indicated little pore on the ZnFe2O4 surface morphology.
The total pore volume and the surface area were 0.457 cm3 g 1 and
46.03 m2 g 1 respectively. The isotherm of the composite nanoparticles
TiO2 @ ZnFe2O4 and TiO2 @ ZnFe2O4/Pd corresponds to the IUPAC IV
and with H2 hysteresis loops, which indicates the mesoporous charac­
teristic (Chen et al., 2015). The average pore diameter of these nano­
particles were 3.7 and 5/7 nm. The total pore volume and surface area of
these nanoparticles were 0.442 cm3g 1 and 349.25 m3/g 1, respec­
tively. After coating with Pd metal nanoparticles, the surface area
increased to 131.18 m2 g 1 and the average pore diameter decreased to
6.821 nm and the total pore volume 0.399cm3g-1. It should be noted
that, the mesoporous structure is suitable for enhancing specific surface
area and improving catalytic performance (Zhao et al., 2019).
Fig. 2. (a) N2 adsorption-desorption isotherms; (b) pore size distribution curve.
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Journal of Environmental Management 271 (2020) 110964
3.6. Thermodynamic stability
The thermal stability of TiO2@ZnFe2O4/Pd nanocatalysts and as well
the percent performance of the functional groups on the magnetic sur­
face of nanoparticles was assessed using TGA analysis. The weight of all
the samples at the temperature over 500 � C was stable. 8.93% weight
loss in the samples occurred at 50⁰ to 500 � C wherein it guarantees the
thermal stability of ZnFe2O4 nanoparticles at high temperature (see
supplementary material SM 3 for further details). After the ferrite
coating with titanium dioxide in the initial stages weight loss was
observed. This was due to physical evaporation of alcohol and absorbed
water and loss of some of the residual organic solvents. After nano­
particles coating with palladium the thermal stability showed 31.7%
reduction in the sample weight in TiO2@ZnFe2O4/Pd which is created in
the nanoparticles heating at 500 � C and it was due to degradation of
some of the organic molecules of solvent groups or hydroxyl present in
the sample surface (Ba-Abbad et al., 2012) and as well dehydration of
the water and phase structure of the conversion (Tekmen et al., 2008).
At 800 � C and higher the sample became stable.
3.7. Zeta potential
Zeta potential has a role in the behavior of nanoparticles and its ef­
fect on the stability and durability rate of very tiny particles dispersed in
the aqueous solutions. Zeta potential determines the repulsive rate of
similar and adjacent loaded particles dispersed in a solution. The par­
ticles which are adequately small, for higher stability need a higher Zeta
potential. The particles with low Zeta potential show an inclination to
N. Ahmadpour et al.
turn into mass and accumulate (Doostmohammadia et al., 2001). The
particles with zeta potential higher than �30 mV are stable due to
electrostatic divergence between the particles that prevent accumula­
tion and finally are deposited (Chalasani and Vasudevan, 2013; Pierce
and Zhao, 2011). pHpzc is an important and effective factor on the ab­
sorbent’s load, and for better understanding, pH on the absorbent was
assessed, pH wherein the positive and negative loads of absorbent are
equivalent and or in other words the absorbent has a neutral load is
called an isoelectric point. In a manner that in pH < pHpzc, the absor­
bent load due to presence of hydrogen (Hþ) ions gets a positive load and
in pH > pHpzc, the absorbent load due to presence of hydroxide ions
(OH ) becomes negative (Kakavandi et al., 2016). The isoelectric point
of synthesized ZnFe2O4 nanoparticles was approximately equivalent to
6.3 which showed a positive load surface in ferrite. As observed, at
acidic pH, most of the DCF species have positive and negative load,
wherein the catalyst surface has a positive load; considering the low
surfaces in zinc ferrite it encounters a lower stability during the time
period, whereas with TiO2 coating considering the repulsive energy
among the particles that signifies a negative energy between the parti­
cles there is a higher stability and homogeneity. Therefore, with stability
increase in the suspension, the absorption and removal of different
pollutant molecules on TiO2 surfaces increases (Wang and Ku, 2007; Xu
et al., 2007). Besides, with increase of electrostatic gravity between the
DCF molecules and positive surface of catalytic nanoparticles, the ab­
sorption efficiency of drug increases (see supplementary material SM 3
for further details).
3.8. UV-light induced photodecomposition of DCF
3.8.1. pH effect
Initial pH is one of the most effective parameters on the photo­
catalytic process affecting sorption/desorption capacity of target
organic compositions that in turn affects the peculiarities of photo­
catalyst’s superficial charge and determines ionization state of catalyst’s
surface (Safari et al., 2014). In fact, solution pH is in correlation with the
photocatalytic performance and shows that organic wastewater com­
positions differ in hydrophobity, dissolubility and varied behaviors. The
magnetic TiO2@ZnFe2O4/Pd nanocomposite was assessed for DCF
degradation at different pH’s (4, 5, 7 and 9). In this experiment, 10 mg/l
of initial drug concentration was mixed in 100 ml of aqueous solutions
wherein for pH adjustment 0.1 M NaOH and HCl were used. Later,
0.005 g/l TiO2@ZnFe2O4/Pd composite catalyst was added to the
considered solution. It mandates to mention that prior to sample’s
exposure to solar light irradiation, initially the solution was stirred for
30 min in dark, to assure the sorption/desorption equilibrium between
the photocatalyst and DCF. The photocatalytic degradation experiment
after DCF absorption equilibrium was carried out on TiO2@ZnFe2O4/Pd
composite surface with solar light irradiation. Fig. 3a depicts DCF
removal at different time periods with varied pH’s (see supplementary
Fig. 3. The C/Co curve for the photodegradation of DCF on (a) pH; (b)catalyst dose; (c) DCF concentration.
5
Journal of Environmental Management 271 (2020) 110964
material SM 4 for further details). As shown in Fig. 3a, the removal ef­
ficiency after 120 min irradiation was 81.11, 73.48, 65.98 and 46.21%
at pH’s 4, 5, 7 and 9 respectively. As observed, pH variations were
effective in DCF removal efficiency wherein with pH reduction the
removal efficiency increases and eventually at pH 4 the highest removal
efficiency was observed. In other words, pH is one of the effective factors
in degradation rate of organic materials in a photocatalytic process and
pH variations can affect DCF molecules adsorption on TiO2@Zn­
Fe2O4/Pd catalyst surface. pH value affects the absorption capacity and
compounds dissociation, charge distribution on the catalyst’s surface
and oxidation potential of catalyst’s valence band. Therefore, pH vari­
ations can affect DCF molecules absorption on TiO2@ZnFe2O4/Pd
catalyst surfaces. pH ZPC is pH value wherein the load flow on absorption
surface is zero. The zero potential point for TiO2@ZnFe2O4/Pd catalyst
is equivalent to 8.2 indicating that catalyst surface is activated in acidic
conditions and pH below 8.2 (Zarei et al., 2010). On the other hand, OH
radicals can be formed in the reaction between hydroxyl ions and pos­
itive holes wherein these positive holes are formed at low pHs. DCF
degradation rate due to pH reduction and absorption load reduction
reduces at pH < PH ZPC. Therefore, the maximum DCF reduction
occurred at pH ¼ 4. The probable description of this finding is ampho­
teric behavior of semiconductor materials and TiO2@ZnFe2O4/Pd
nanocomposite’s variation in surface charge properties that is propor­
tional with pH variations. This theory could be related to the presence of
sole electron pair on DCF molecules that causes electrostatic absorption
between negative DCF molecule and positive TiO2@ZnFe2O4/Pd com­
posite in the acidic conditions and vice-versa. The other reason for DCF
degradation efficiency increase at acidic pHs is that in acidic solutions
the high concentration of Hþ ion causes (OH ) hydroxyl radical for­
mation whereby via oxygen’s present in the solution, form superoxide
radical and eventually converts to hydroxyl radical. The high efficiency
of this process at acidic pHs can be related to the following reactions in
the acidic conditions.
2HO2 ​ → O2∘ ​ þ ​ H2O2 (5)
H2O2 ​ þ ​ O2∘→OH∘ þ OH ​ þ ​ O2 (6)
e ​ þ ​ O2→O2∘ (7)
O2 ∘ ​ þ ​ H þ →2HO∘2 (8)
Furthermore, based on the previous reports DCF exists more in ionic
rather than molecular form in an alkaline condition. In a photocatalytic
process, Diclofenac’s molecular form is more considered since molecular
absorption of DCF on the catalyst surface is higher than its ionic ab­
sorption (Arsiya et al., 2017). Therefore, formation of hydroxyl radicals
in acidic conditions is more which in turn causes degradation increase
(Bagal and Gogate, 2014). Mugunthan et al., 2018, in their study on
photocatalytic degradation of DCF under visible light using WO3/TiO2
N. Ahmadpour et al.
nanoparticles, reported that the highest degradation occurred at acidic
condition due to Diclofenac’s molecular form (Meng et al., 2018).
On the other hand, it was determined that pH directly affects radical
generation (Norzaee et al., 2017). One of the influential parameters in
pH included the greater presence of Hþ ions in the acidic media, fol­
lowed by the formation of OH� radicals, as well as electrostatic reactions
between pollutants and catalyst surface (Busca et al., 2008). The reason
for the increase in removal efficiency in acidic pH is that the catalyst
surface has a positive charge and causes more DCF degradation, as well
as more radical hydroxyl production and decomposition in the acidic
media, thus increasing the removal efficiency. While in an alkaline
condition, the surface of nanoparticles has a negative surface charge and
reduced the production of radical hydroxyl and reduced the efficiency in
the alkaline media (Kansal et al., 2010; Hosseinzadeh et al., 2012). Also,
reducing the efficacy of removal in alkaline conditions can be attributed
to the formation of insoluble compounds that reduced light intensity and
reduced radical hydroxyl production (Dehghani et al., 2014). In addi­
tion, it has been reported that changing the pH around the pHZPC causes
catalyst particles to adhere and thus settle the particles. This settling will
reduce the efficiency of the degradation (Malato et al., 2009).
3.8.2. Catalyst dose effect
Different catalyst concentrations are one of the important parame­
ters than can affect the degradation rate of DCF. As shown in Fig. 3b,
DCF degradation percent and as well (C/C0) degradation ratio and time
intervals, the effect of photocatalyst concentration on DCF removal ef­
ficiency using TiO2@ZnFe2O4/Pd composite nanoparticles was evalu­
ated at the range of 0.005–0.1 g/l at the initial concentration of 10 mg/l
DCF and optimal pH ¼ 4 (see supplementary material SM 4 for further
details). It mandates to mention that prior to solar light irradiation
exposure, initially the solution was stirred in dark for 30 min, to assure
sorption/desorption equilibrium between the photocatalyst and Diclo­
fenac. Initially the photolysis experiments showed that in case of lack of
photocatalyst use the degradation rate reduces to an extent. This sig­
nifies that light has an insignificant effect on DCF degradation. As
observed, with addition of a photocatalyst to the initial degradation
process, considering the catalyst concentration, it increases up to a
specific level and after that, removal occurred at a lower rate which
signified the saturated photon absorption (Mugunthan et al., 2018). At
low catalyst concentration, light transfers at a higher rate to the solu­
tion. The absorption dose increase from 0.005 to 0.1 g/l causes DCF
degradation increase since with absorbent’s dose increase the access and
active absorption sites between the absorbent and absorptive in a re­
action increases. Even the other studies proved that catalyst dose in­
crease at specified levels; causes increase in the photocatalytic function
and surface access increase (Parra et al., 2002; Elmolla and Chaudhuri,
2010). In addition, more active radicals are formed. In some researches,
the accumulative effect of photocatalysts and light penetration lack in
the solution has been stressed. In this study, catalyst rate increase caused
solution turbidity and lack of light penetration to the solution and
degradation efficiency reduction at the higher doses.
3.8.3. The initial DCF concentration effect
Photocatalytic degradation rate is intensely affected by the initial
concentration of target pollutant. To assess the initial pollutant con­
centration effect on the photocatalytic efficiency, a wide range of DCF
concentration from 10 to 30 mg/l was prepared and the other experi­
mental conditions at initial pH 4 and catalyst concentration 0.03 g/l was
constant and results are depicted in Fig. 3c, and see supplementary
material SM 4 for further details. As observed, with DCF concentration
increase the removal efficiency reduces in a manner that the maximum
degradation rate occurred at 10 mg/l concentration. This finding can be
due to reason that at low concentration of pollutants, the probability of a
reaction between reactive species and pollutant increases and at higher
DCF concentration, the excessive amount of target molecules are accu­
mulated on the catalyst surface that causes reduction of an effective
6
Journal of Environmental Management 271 (2020) 110964
surface in the degradation process (Kermani et al., 2013). In addition,
the removal efficiency can increase with concentration increase, but
after a time period it reaches an equilibrium state because initially the
active sites on catalyst surface are easily accessible and after the passage
of time and or with concentration increase, these active sites are occu­
pied and efficiency reduces (Chen et al., 2015). Therefore, the reduction
of hydroxyl radicals’ formation can occur to an extent that affects the
photocatalytic activity of the catalyst (Muruganandham et al., 2006; Das
et al., 2015).
3.8.4. Disentangle of significant parameters using analysis of variance
The analysis of variance for removal efficiency of DCF using Pd-
coated TiO2@ZnFe2O4 magnetic photocatalyst was performed and the
significant factors can extricate according to Pvalue. Hence, the pa­
rameters like pH, catalyst dose, DCF concentration, and aeration and
magnetic stirrer have an effect on the photodegradiation of DCF,
whereas low Pvalue (Pvalue ¼ 0.00) obtained for all of the parameters
and assigned as significant factors (Ekrami-Kakhki et al., 2018).
Therefore, F value can demonstrate the importance of the parameters
(Abbasi et al., 2019). Consequently, the sequence importance of the
parameters is equal to catalyst dose (30.717) > DCF concentration
(21.506)> pH (19.770) > aeration and magnetic stirrer (7.905).
3.9. Kinetic photocatalytic degradation of DCF
To assess kinetic photocatalytic degradation of DCF in the photo­
catalytic process at varied concentrations of the pollutant, the experi­
ments were conducted at optimal conditions (nanocatalyst dose: 0.03 g/
l, contact time: 120 min and pH 4 at different DCF concentrations) to
evaluate kinetic degradation of DCF. For conduction of this experiment,
initially the solution was kept in dark for 30 min and its photo­
degradation and kinetic mechanism was determined (see supplementary
material SM 4 for further details). As results reveal DCF photocatalytic
degradation follows the kinetic pseudo order one and can be well
described via Langmuir-Hinshelwood model (Daghrir and Drogui, 2013;
Subramonian and Wu, 2014). As observed with pollutant concentration
increase the constant rate (k) reduces in a manner that it changes from
0.0172 min 1 at 10 mg/l DCF concentration to 0.0128 min 1 at 30 mg/l
DCF concentration. The constant speed for different reaction concen­
trations is tabulated in Table 1.
3.10. Comparison of PCP degradation rates by the synthesized catalysts
The photocatalytic activities of ZnFe2O4, TiO2@ZnFe2O4 and
TiO2@ZnFe2O4/Pd was evaluated with optimal DCF concentration (10
mg/l) and pH ¼ 4 for DCF photodegradation in the aqueous solution
exposed to solar light irradiation for 120 min (see supplementary ma­
terial SM 4 for further details). Prior to solar light irradiation exposure,
initially the solution was kept in dark for 30 min. DCF absorption on
catalyst’s surface in dark was very insignificant. When it was exposed to
light considering the catalyst type, DCF degradation increased. As
observed, TiO2@ZnFe2O4/Pd magnetic composite encounters a higher
removal in relation to TiO2@ZnFe2O4 and ZnFe2O4 in the similar
experimental conditions. This is due to bandgap energy related to ab­
sorption in the visible region which can lead to efficiency improvement
Table 1
Reaction rate constant of diclofenac photocatalytic degradation with different
concentrations.
Diclofenac concentration (mg/L) Equation K0(min 1
) R2
10 Y ¼ 0.0172x þ 1.5067 0.0172 0.9952
15 Y ¼ 0.0137x þ 1.2228 0.0137 0.9916
20 Y ¼ 0.0131x þ 1.0573 0.0131 0.9808
25 Y ¼ 0.013x þ 0.7941 0.013 0.9812
30 Y ¼ 0.0128x þ 0.5457 0.0128 0.9958
N. Ahmadpour et al.
in the catalytic degradation. Therefore, after subjection to solar light
irradiation for 120 min, DCF degradation efficiency via TiO2@ZnFe2O4/
Pd nanocomposite was 84.87% which was much higher than
TiO2@ZnFe2O4 (73.33%) and ZnFe2O4 (49.9%). Therefore, TiO2@Zn­
Fe2O4 composite catalyst had the highest photocatalytic activity among
the different catalysts in this study exposed to solar light irradiation that
was due to synergy effect between Pd, TiO2 and ZnFe2O4 nanoparticles.
Likewise, palladium causes load and Plasmon Resonance Energy transfer
between TiO2. On this basis, considering the interactions, it eases the
transfer and separation of photogenerated electrons and holes that leads
to higher improvement in the photocatalytic function.
3.11. Aeration effect in DCF photodegradation process
One of the persisting issues in photocatalytic process is solution
immobilization, since the catalyst is positioned on an immobilized solid
carrier (Minsker et al., 2001). This limitation is resolved by complete
mixing and turbulence formation in the reactor. Likewise, the presence
of solution oxygen has an important role in the photocatalytic degra­
dation of organic materials. The oxygen molecule can as an electron
acceptor get trapped and separate the electron from positive holes to
assist the reduction of probable electron-hole recombination. Never­
theless, in this study, the simultaneous effect of aeration and magnetic
stirrer on DCF photocatalytic degradation via TiO2@ZnFe2O4/Pd
nanocomposite at 120 min in three aeration conditions; use of magnetic
stirrer and simultaneous use of aeration/magnetic stirrer was assessed
and the results are depicted in supplementary material SM 5. As
observed, the highest degradation rate (86.5%) was achieved in the
aeration/magnetic stirrer system, whereas in the sole system of aeration
and magnetic stirrer the degradation rates were 81.73% and 78.02%
respectively. The aeration caused oxygen production in the solution that
acts as an electron acceptor (Chong et al., 2010). The presence of elec­
tron acceptor causes increased separation of photogenerated electrons
and holes in the photocatalytic process and eventually its improvement.
In fact, this system provides the oxygen required for photoelectrons
evacuation and forms superoxide anionic radicals. The role of oxygen as
an electron acceptor is summarized as the following equations (Wang
et al., 2002). The molecular oxygen as an electron acceptor for trap and
removal of electrons uses TiO2@ZnFe2O4/Pd catalyst particles surface to
reduce the free electron, the reaction of absorbed oxygen with photo­
generated electrons at TiO2@ZnFe2O4/Pd catalyst surface is relatively
slow and could control the speed in photocatalytic oxidation reaction
(Wang et al., 2002).
Fig. 4. Schematic illustration of proposed photocatalytic mechanisms of ZnFe2O4@TiO2/Pd nanocomposite.
7
Journal of Environmental Management 271 (2020) 110964
e ​ þ ​ O2 →O2 (9)
H þ ​ þ ​ O2� →HO2� (10)
2HO2� → H2O2 ​ þ ​ O2 (11)
H2 O2 →2OH� (12)
H2 O2 ​ þ ​ O2� →� OH ​ þ ​ OH ​ þ ​ O2 (13)
H2 O2 ​ þ ​ e →� OH ​ þ ​ OH (14)
In fact, airflow causes production of higher oxygen besides reaction
with excited electrons via photon and forms O2 anions. Formation of O 2
causes degradation rate increase in the aeration flow increase (Lee et al.,
2004). However, the flow over 1.5 l/m causes light penetration due to
formation of large amount of bubbles during photocatalysis radiation.
3.12. Mechanism of DCF photodegradation process
Fig. 4 shows the possible reaction mechanisms for DCF photo­
degradation by Pd supported TiO2@ZnFe2O4 nanocomposites in the
presence of solar light. When palladium nanoparticles come in contact
with TiO2 nanoparticles without solar light radiation, due to the energy
level of palladium is higher than TiO2, The electrons are transferred
from palladium to TiO2 to balance the two systems. Whenever the
TiO2@ZnFe2O4/Pd TiO2 photocatalysts are irradiated under solar light
with photon energy that is higher than the TiO2 band gap, optical
excited electrons and holes are formed in the conduction band (CB) and
the valence band (VB) of TiO2 (Nguyen and Doong, 2017; Ahmadpour
et al., 2020). Since palladium nanoparticles have a high ability to
accumulate large amounts of electrons, the transfer of photoexcited
electrons from TiO2 to palladium nanoparticles causes the energy level
of the composites to shift to negative potential. Therefore the electrons
in the CB can be transferred from TiO2 to Pd. Therefore, Pd nanoparticles
act as electron acceptors, and results in reduced electron-hole recom­
bination and prolongs the lifetime of the electron-hole pairs. Afterward,
the electrons can be trapped by O2 and the holes can be captured trapped
by the surface hydroxyl group, eventually leading to the formation of
superoxide anion radical (O2) and hydroxyl radical species (OH) (Kumar
and Devi, 2011). This radical groups (�O2 and �OH) are highly reactive
to DCF degradation.
N. Ahmadpour et al.
3.13. Photocatalytic degradation of DCF in higher volume
In this study, DCF removal was also evaluated at higher volume. The
experimental conditions were as follows: in a 1000 ml vessel containing
DCF pollutant solution along with other optimized parameters (pH ¼ 4,
catalyst concentration 0.03 gm/l, drug dose 10 mg/l) was used (see
supplementary material SM 4 for further details). The present results
showed that with the passage of time the degradation efficiency in­
creases wherein this degradation rate under solar light irradiation after
120 min was 78.52%.
3.14. DCF removal in the photocatalytic process in the continuous system
3.14.1. Flow rate effect
Flow rate is an important parameter in the photocatalytic processes,
since it determines the pollutant’s contact time with an absorbent in the
column length. The breakthrough curves at three different flows (5, 10,
15 ml/min) are revealed in supplementary material SM 5. As observed,
the progressive as well as saturation period reduces with flow rate in­
crease since with higher flow the retention time in the column is not
sufficiently high to create absorption equilibrium in the column.
Therefore, considering the mass transfer limitations and sufficient
retention time, the degradation performance of DCF reduces (Bulgariu
and Bulgariu, 2016). In real time where the flow increases from 5 to 15
ml/min, the retention time in the column reduces. Whereby, with flow
rate reduction due to higher retention time in the column and contact
increase, DCF degradation efficiency increases.
3.14.2. Column length effect
Column length is an essential factor that affects the removal capacity
and estimation time of absorption bed. Therefore, a suitable column
length and or moisture volume increases adsorbent’s access and assists
Fig. 5. (a) Efficiency of reuse on activity of TiO2@ZnFe2O4/Pd nanoparticles; (b) the XRD spectra, and (c) FTIR spectra of TiO2@ZnFe2O4/Pd before and after
recycling test.
8
Journal of Environmental Management 271 (2020) 110964
the maximal removal rate of the target pollutants (Zhang et al., 2018).
The column length breakthrough curves for DCF removal are demon­
strated at different length of 5–25 cm. In this study, the initial concen­
tration of DCF was 10 mg/l and flow rate was 5 ml/min. As observed
with column length increase from 5 to 25 cm, the breakthrough curve
slope reduces. This could be due to an access to pollutant connector sites
in the higher column lengths for absorption and resultantly the mass
transfer zone is higher (Jain et al., 2013; Mishra et al., 2013). The
reaching time to the column break point at the length of 5, 10, 15 and 25
cm was 80, 65, 50 and 45 min respectively, and DCF degradation rate
reduced from 83.49% to 90.48% from 5 to 25 cm length. Besides, the
higher column length provides a longer residential phase of pollutant in
the column. Therefore, a higher volume of DCF pharmaceutical
pollutant can be filtered (see supplementary material SM 5 for further
details).
3.15. Reusability of the photocatalytic nanoparticles
An important point for the application of photocatalytic nano­
particles in the water filtration process was separation and reuse of
nanoparticles. For this reason, reuse of synthetized nanocomposite was
assessed as a photocatalyst for DCF degradation during 5 recycles at
optimum conditions in a batch system. After each cycle, the nanocatalyst
was separated via an external magnet from the solution and washed
several times with deionized water and ethanol and later dried in an
oven and used in the next stage of DCF removal (Shekari et al., 2017). As
demonstrated in Fig. 5a, TiO2@ZnFe2O4/Pd catalysts have relatively
stable photocatalytic activity and are recyclable and can be reused in a
manner that after 5 photocatalyst recycles, DCF degradation reduced
from 86.1% in the first stage to 71.38% in the fifth stage. As denoted the
photocatalytic activity loss was insignificant which signifies the photo­
catalytic stability of these nanoparticles during the photocatalytic
N. Ahmadpour et al.
reactions. Therefore, its application from the commercial viewpoint due
to its reuse potentiality is very useful. The Inductively Coupled Plasma
Atomic Emission Spectrometry (ICP-AES) showed that only a very little
amount (less than 1%) of Pd metal was eliminated after five recycles of
magnetic catalyst.
However, XRD and FTIR results of TiO2@ZnFe2O4/Pd photocatalyst
were used after five recycles. XRD results before and after degradation
showed nil apparent change in the crystalline structure of nanoparticles
after five recycles (Fig. 5b). Besides, FTIR analysis of TiO2@ZnFe2O4/Pd
nanocomposite was carried out before and after DCF degradation
(Fig. 5c). Based on Fig. 5c, much variation was not depicted between the
two FTIR patterns. Considering Fig. 5c, the additional peaks of peak
1707 cm 1 pertained to C– – O vibrations, whereas peaks 3347 cm 1 and
1
1178 cm pertained to O–H and C–O stretching vibrations respectively
in the fifth reuse. As observed much variation did not occur in the FTIR
chart peaks before and after the degradation process. This result showed
that TiO2@ZnFe2O4/Pd nanocomposite had a very good chemical sta­
bility and can safely be used as a reusable photocatalyst in most of the
applications.
3.16. TOC analysis
TOC analysis was used to accurately assess the degradation rate of
DCF molecules during photodegradation. TOC measure exhibits the
carbon rate present in the organic combinations wherein it more accu­
rately reflects the total amount of organic combinations available in the
solution. For TOC removal rate at optimal conditions in the continuous
system; the photocatalytic reaction was evaluated after 30 min darkness.
TOC analysis results demonstrated (see supplementary material SM 6 for
further details) that TOC degradation rate at 120 min was 39.20%. TOC
increase in the initial hours of light irradiation was due to light ab­
sorption from DCF or formation of intermediates. Therefore, these pro­
duced intermediates are not so sensitive in relation to photolysis. This
means that due to intermediates sensitivity to photolysis the degrada­
tion was lower wherein DCF was degraded via photolysis process
(Abellan et al., 2007).
4. Conclusion
TiO2@ZnFe2O4/Pd nanocomposites were prepared using the pho­
todeposition method and identified using XRD, VSM, FESEM/EDX, FTIR,
GTA, UV–Vis, Zeta Potential and ICP-OES techniques. The resultant
composite material had catalytic function and an excellent degradation
efficiency using the optimal parameters in the reduction of DCF
pollutant and showed a super magnetic behavior that caused magnetic
separation and easy recovery of nanocatalysts from the reaction
mixture. In addition, this composite catalyst has a thermal stability, high
photocatalytic activity, competent magnetic separation, good chemical
stability and relatively low cost which causes it to act as a green reliable
photocatalyst with superior photocatalytic activity to remove the pol­
lutants under the solar light irradiation. Therefore, it can as a promising
user have an application in the high scale photocatalytic reactions in the
industries.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Najmeh Ahmadpour: Writing - original draft, Data curation,
Methodology. Mohammad Hossein Sayadi: Supervision, Validation,
Writing - review & editing. Sara Sobhani: Visualization, Conceptuali­
zation, Investigation, Writing - review & editing. Mahmood Hajiani:
9
Journal of Environmental Management 271 (2020) 110964
Software, Methodology.
Acknowledgements
This paper was adapted from a Ph.D. student thesis (ID Num­
ber:1156/1397) in the Department of Environmental Engineering, the
Faculty of Natural Resources and Environment, the University of Bir­
jand, which has been conducted with the financial support the Iran
National Science Foundation (INSF) (Grant No. 97024168/1398). The
authors of this research highly appreciate the support of Faculty of
Natural Resources and Environment, University of Birjand.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jenvman.2020.110964.
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