Chemical Engineering Journal 371 (2019) 404–413

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Chemical Engineering Journal

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The enhanced catalytic potential of sulfur-doped MgO (S-MgO) T

nanoparticles in activation of peroxysulfates for advanced oxidation of
acetaminophen
⁎
Farzaneh Fanaeia, Gholamreza Moussavia, , Varsha Srivastavab, Mika Sillanpääb
a
Department of Environmental Health Engineering, Faculty of Medical Sciences, Tarbiat Modares University, Tehran, Iran
b
Department of Green Chemistry, School of Engineering Science, Lappeenranta University of Technology, Sammonkatu 12, FI-50130 Mikkeli, Finland

H I GH L IG H T S

• PMS was efficiently activated with S-MgO nanoparticles.

• S-MgO/PMS process generated a high amount of hydroxyl and sulfate radicals.
• AS-MgO/PMS
very high ACT oxidation rate was obtained in S-MgO/PMS process.
• S-MgO/PMS process transformed ACT molecules to harmless compounds.
• process is an efficient AOP for removing emerging contaminants.

A R T I C LE I N FO A B S T R A C T

Keywords: The peroxymonosulfate (PMS) and peroxydisulfate (PDS) were activated using plain and S-doped MgO (S-MgO)
AOP for oxidation of acetaminophen (ACT) in the contaminated water. The findings indicated that S-MgO was more
Catalytic activation efficient than plain MgO in activating the oxidants and that PMS was much better activated than PDS using S-
Peroxymonosulfate MgO. The complete degradation and significant mineralization (up to 62.4%) of 50 mg/L ACT could be achieved
Peroxydisulfate
in the S-MgO/PMS process using 1.4 mM PMS within a reaction time of 30 min and 60 min, respectively. Both
Emerging contaminants
SO·4− and HO· species were simultaneously generated in the S-MgO/PMS process with the contributions of 73.8%
Pharmaceuticals
and 26.2%, respectively, in the ACT removal attained in the process. ACT removal in the S-MgO/PMS process
was not considerably affected by the solution pH between 4 and 10 and the maximum ACT removal of 93.4%
was achieved at the neutral condition and optimum PMS to catalyst ratio of 0.07 mM L/g. The performance of S-
MgO/PMS process for removal of ACT was not affected by the presence of conventional anions in natural waters.
The pathway of ACT degradation in the S-MgO/PMS process was proposed based on the Liquid chromato-
graphy–mass spectrometry (LC/MS) analysis of the effluent. Accordingly, the S-MgO is a very active catalyst to
activate the PMS for simultaneous generation ofSO·4− and HO· reactive species hence S-MgO/PMS process is an
emerging AOP for high rate degrading the pharmaceutical compounds present in contaminated waters.

1. Introduction
Pharmaceuticals are one of the main groups of recalcitrant com-
pounds released to the environment through the municipal wastewater
and the pharmaceutical manufacturing plants. Advanced oxidation
processes (AOPs) are an emerged class of advanced technologies widely
used for the elimination of recalcitrant and synthetic organic com-
pounds from the contaminated water, the wastewater and the industrial
effluents [1]. Considerable attention has been paid recently on the
sulfate radical (SO·4− , E0 = 2.6 V ) based AOPs, mainly due to the high
oxidation potential of SO·4−, the higher lifetime of SO·4− compared to
hydroxyl radicals (%OH) [2], simultaneously generation of both SO·4−
and •OH as well as high efficiency in the degradation of diverse water
contaminants [3–5]. SO·4− is generated mainly through activation of
peroxysulfates (peroxymonosulfate (PMS) or peroxydisulfate (PDS)) by
heat [6,7], UV radiation [8,9], metals [10–14], metal oxides [15–18].
Based on the published studies, minerals and metal oxides are het-
erogeneous catalysts capable of efficiently activating PMS and PDS to

⁎
Corresponding author.
E-mail address: moussavi@modares.ac.ir (G. Moussavi).

https://doi.org/10.1016/j.cej.2019.04.007
Received 8 January 2019; Received in revised form 31 March 2019; Accepted 2 April 2019
Available online 02 April 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
F. Fanaei, et al.
generate the reactive oxidizing species of SO·4− and •OH. The previous
studies have examined PDS activation with different metals and metal
oxides including Fe2O3-Cu2O [10], Fe0 [11,12], Fe2+ [14], iron-based
bimetals and trimetals [13], reduced graphene oxide–elemental silver/
magnetite nanohybrids [18], etc. for the degradation of pharmaceutical
compounds. In addition, PMS was activated with perovskite [15], Fe3O4
[16] and MnFe2O4 and CoFe2O4 [17] for the degradation of pharma-
ceutical compounds. These studies indicate that the activation of PMS
and PDS with metal oxides for the generation of SO·4− is a promising
AOP efficient for decomposition of water toxic contaminants.
In order to improve the SO·4−-based AOPs in terms for mineralization
extent of such recalcitrant compounds as pharmaceuticals, sustain-
ability, and reaction stoichiometric efficiency (% RSE), finding a more
active catalyst is required and thereby the activation potential of other
agents needs to be investigated. Due to its unique features, recently a
considerable focus has been paid on using magnesium oxide (MgO) as a
catalyst in the water and wastewater treatment field. For instance, re-
cently a new sulfur-doped MgO (S-MgO) was prepared which showed
high catalytic activity in the ozonation of acetaminophen (ACT) in
aqueous solution [19]. Due to the formation of surface defects in the
MgO structure upon doping with S [19], the S-MgO may be an attrac-
tive metal oxide catalyst for the activation of PMS and PDS and thus for
the generation of an increased amount of reactive oxidative species
mainly SO·4− and %OH.
Accordingly, the present study aimed at comparing the efficacy of
plain MgO and S-MgO in activating PMS and PDS for the degradation
and the mineralization of ACT as a model of emerging water con-
taminants. ACT (C8H9NO2) is an antipyretic pharmaceutical, which is
easily accessible around the world. Over 50% of ingested ACT is ex-
creted unchanged from the body upon ingestion and find its way to the
wastewater resulted in the contamination of the receiving water bodies.
The PS activation was examined by using plain MgO and S-MgO na-
noparticles under different experimental conditions of the solution pH,
the catalyst to PS ratio, ACT concentration, and the reaction time for
the degradation and mineralization of ACT. The generation of radicals
was indicated using the related scavengers and confirmed by the EPR
analysis. The kinetics of degradation and mineralization of ACT was
evaluated in the S-MgO/PMS process under their optimum experi-
mental conditions.
2. Materials and methods
2.1. Materials and experimental procedures
The pure ACT powder was obtained from a local company. The
stock solution of ACT was prepared by dissolving 0.5 g ACT powder in
per liter of bidistilled water and stored at 4 °C. The reaction solution
was prepared by dissolving the aliquots of stock solution by distilled
water. All chemicals used in the present study were of the analytical
grade. PMS (2KHSO5·KHSO4·K2SO4) was purchased from Aldrich Co.
and used as received. The amount of PMS used in the tests was calcu-
lated based on(H3 O18 S4 )5 −. The plain MgO and S-MgO catalysts used in
this work were prepared as detailed in our previous study [19]. Sodium
dodecyl sulfate (SDS) used as a capping agent and the sulfur source for
S-MgO. Various amount of SDS was used to prepare MgO doped with
different percentages of S between 0 and 3%. The S-MgO with S content
of 2% as an optimum catalyst was a semi-spherical and flaky-shaped
mesoporous nanoparticle, had a BET surface area of 257.3 m2/g, an
average crystallite size of 23.6 nm and an average particle size of
13.6 nm, a pHpzc of 10.9, with a high density of active surface func-
tional groups [19]. It has been shown that the S-MgO is a stable and
durable material that its catalytic potential is relatively preserved
during the several reuse times.
The ACT oxidation tests by S-MgO/PMS and S-MgO/PDS were
conducted in batch mode in a 100 mL glass column as reactor at room
temperature. For each test, 50 mL of ACT reaction solution with specific
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Chemical Engineering Journal 371 (2019) 404–413
composition (pH and ACT concentration) was transferred to the reactor
into which the predetermined amount of PMS or PDS and of catalyst
was added. Then the suspension was magnetically stirred at 150 rpm for
the specific time period. At the end of the reaction period, the sus-
pension was sampled and 1 mL of sodium thiosulfate solution (1 M) was
immediately added to the sample to quench the oxidation reaction.
Finally, the quenched sample was filtered through a 0.22 µm filter and
the filtrate was analyzed for the target parameters. The effect of initial
solution pH, type of oxidant (PDS and PMS), PMS to S-MgO, reaction
time, and inorganic (chloride, bicarbonate, phosphate, nitrate) and
organic (tert-butanol and ethanol acid) radical scavengers was in-
vestigated on ACT degradation. The concentration molar ratio of sca-
venger to ACT in the radical scavenging tests was kept 1:1. The control
experiments were conducted with the catalyst and the oxidants (PMS
and PDS) alone under the same reaction conditions. Initial solution pH
was adjusted at the desired value using 0.1 M NaOH or HCl. In order to
avoid scavenging the reactive radicals by buffer species such as bi-
carbonate and phosphate, no buffer was used in the preparation of re-
action solutions. All experiments were conducted in duplicate and the
results were reported as mean value ± SD (standard deviation).
2.2. Analysis
The X-ray photoelectron spectroscopy (XPS) analysis of MgO and S-
MgO was examined by (ESCALAB 250) with an Al-K x-ray source of
1486.6 eV for the investigation of binding energies of elements and
surface composition of catalysts. The photoluminescence (PL) mea-
surements of the MgO and S-MgO nanoparticles were conducted via
FL3-TCSPC. The aqueous samples taken from the reactor were filtered
through 0.2 μm cellulose acetate syringe filter and the filtrate was
analyzed for the target parameters. The concentration of ACT in the
reaction solutions before and after the reaction was determined by
HPLC (Agilent Co.) equipped with a UV detector at 242 nm. A reversed-
phase C18 column (Eclipse plus C18 column; 3.5 µm, 4.6 × 100 mm)
was used in the HPLC. The mobile phase was a mixture of phosphate
buffer (pH = 4.8) and acetonitrile at a volumetric ratio of 85:15 in-
jected at the flow rate of 1 mL/min. The concentration of total organic
carbon (TOC) residual was measured with a TOC analyzer (Shimadzu,
TOC analyzer –VCSH model) under optimum experimental conditions.
The sample volume required for each TOC analysis was 25 mL, and two
measurements were performed for each sample and the average was
reported. The PDS and PMS residual concentrations were measured by
the iodometric titration with sodium thiosulfate as titrant with a de-
tection limit below 0.1 mg/L. The concentration of sulfate ions was
determined using the turbidimetric method as described in standard
methods [20]. The pH was determined by a Jenway Co. selective
electrode. The concentration of PMS was measured using the iodo-
metric titration with standardized sodium thiosulphate. The main in-
termediates of ACT degradation in the S-MgO/PMS process were
identified using liquid chromatography–mass spectrometry (LC/MS,
2010 A, Shimadzu) equipped with an Eclipse Atlantis T3, C18 column
(2.1 × 100 mm, 3 µ particle size) in the ambient temperature using the
Quadrupole mass analyzer. The mobile phase consisted of 60% acet-
onitrile (with 0.1% Formic Acid) and 40% water (with 0.1% formic
acid) injected at a flow rate of 0.3 mL/min. The quadrupole mass
spectrometer was operated under the following conditions: Gas nebu-
lizer: N2, Probe Volt: 4 kV, Detection gain: 1.8 kV, CDL Volt: 25 V, CDL
and Block temperature: 250 °C and Flow gas: 1.2 L/min. The spectro-
meter scanning was conducted for m/z ranging between 50 and 500.
The injection sample volume for the chromatographic separation was
20 µL.
The reactive oxidative species (ROSs) generated by the MgO and S-
MgO catalysts were determined by electron paramagnetic resonance
(EPR) technique (EPR- CMS 8400). Two different spin trapping agents
5,5-Dimethyl-1-Pyrroline N-Oxide (DMPO) and 2, 2, 6, 6-tetra-
methylpiperidinyloxyl (TEMP) spin trapping agents were used for ROS
F. Fanaei, et al.
detection [15]. The EPR analysis was carried out by adjusting Power
attenuation: 20 dB, Sweep time: 80 s, Sweep width: 150,00 G, Mod.
amplitude: 1000 mG and Microwave frequency: 9438,80 MHz using
TEMP (100 mM) and DMPO (100 mM).
2.3. Performance indices
The oxidation of ACT in the S-MgO/PS process was evaluated based
on ACT degradation (Eq. (1)) and mineralization (Eq. (2)) percentages.
ACT0 − ACTt
ACT degradation (%) = × 100
ACT0
where ACT0 and ACTt demonstrate the concentrations of ACT before
and after the reaction, respectively.
The degree of ACT mineralization in the S-MgO/PMS process was
determined from Eq. (2) by measuring the concentration of TOC in the
solution before (TOC0) and after (TOCt) the reaction. The degree of ACT
mineralization was then calculated from Eq. (2).
TOC0 − TOCt
ACT mineralization (%) = × 100
TOC0
The kinetics of ACT degradation and mineralization were evaluated
by fitting the pseudo-first order (PFO) reaction model (Eqs. (3) and (4))
with the related experimental results.
C centers as oxygen vacancies in the S-MgO. The formation of surface
ln ⎛ t ⎞ = −k obst
⎜ ⎟
⎝ C0 ⎠
dC
robs = − = k obsC
dt
where C0 and Ct are the ACT or TOC concentrations at the beginning
and the time t of the reaction, respectively, kobs is the PFO reaction rate
constant and robs is the PFO reaction rate. The RSE defined as the
number of ACT moles degraded over the number of PMS moles con-
sumed during a specific reaction time [21] was calculated for the S-
MgO/PMS process conducted under the optimum experimental condi-
tion.
3. Results and discussion
3.1. Catalytic potential of MgO and S-MgO in PDS and PMS activation
Fig. 1 shows the ACT removal in the different processes under the
selected experimental conditions. The ACT removal in the presence of
MgO and S-MgO was around 1% and 2.9%, respectively. When PDS and
PMS were added into the reaction medium containing MgO, the ACT
removal efficiency increased to 8.2% and 21.5%, respectively. In
Fig. 1. Removal of ACT in different processes (ACT = 50 mg/L; catalyst = 1 g/
L; PDS = 0.5 g/L; PMS = 0.5 g/L; solution pH = 7; reaction time = 30 min).
Chemical Engineering Journal 371 (2019) 404–413
(1)
Fig. 2. PL of MgO and S-MgO.
comparison, 43.8% and 95.6% of ACT could be removed in the S-MgO/
PDS and S-MgO/PMS processes, respectively. It was found that both
PMS and PDS were better activated by S-MgO than plain MgO.
Fig. 2 depicts the PL spectra of MgO and S-MgO nanoparticles. A
(2)
broad PL peak observed for MgO and S-MgO nanoparticles at the wa-
velength around 550 nm is related to the defects as oxygen vacancy
[22]. It is seen in Fig. 2 that the peak intensity of MgO increased con-
siderably upon doping with S indicating the development of defect
defects favor the valence band and charge separation and enhanced the
(3)
transfer rates of photogenerated electron and hole resulting in the more
degradation of ACT [23]. Therefore, the greater PDS/PMS activation
(4) potential of S-MgO than that of plain MgO is related to the increased
surface defects as oxygen vacancies in the S-MgO upon S-doping due to
the substitution of O by S atoms in MgO lattice upon doping with sulfur
[19,22]. The effect of different S content between 0 and 3% in the MgO
was evaluated on the catalytic activity of the prepared material in ac-
tivating PMS and the results showed that the ACT degradation was
21.5, 68.3, 100 and 80.5% for 0, 1, 2 and 3% of S-doped content (Fig.
S1). Therefore the S-MgO contained 2% S was used as a catalyst in the
rest of the experiments and characterization.
Figs. 3a,b shows the XPS analysis results of MgO and S-MgO cata-
lysts. In MgO (Fig. 3a), binding energies at 1306.6 eV and 531.7 eV are
attributable to Mg1s and O1s respectively. XPS clearly showed the
presence of S in modified catalyst S-MgO (Fig. 3b). No sulfur specific
XPS signal was observed in MgO catalyst. For both catalysts, the range
of binding energy for O1s spectra was 531.7–532.3 eV, which is the
characteristic of metal oxides. C1s (289.8 eV) is taken as the reference.
The presence of another band of C1s in S-MgO sample indicates carbon
contamination due to CO32− species [24]. The binding energies
1303.0 eV for Mg ls is in good agreement with the reported studies
[25,26]. Presence of sulfur was evidenced by S2p peak at 169.4 eV,
which can be attributed to the positive oxidation state of sulfur as a
sulfate (SO42–) groups [27]. It is reported that the broad peak of O1s at
∼528 eV represent the lattice oxygen, ∼530.2 eV for surface oxygen,
∼531.1 eV for defect oxygen and ∼532.3 eV for the adsorbed oxygen
[15]. In S-MgO it was observed that O1s peak position is 532.3 eV is due
to oxygen defect on the surface. Oxygen vacancy acted as active centers
giving S-MgO a high catalytic activity [19,22,28] for activation of PDS/
PMS.
Higher ACT removal in the S-MgO/PMS than that in the S-MgO/PDS
indicates that PMS could be faster oxidized than PDS by S-MgO, which
is attributed to the asymmetric molecular structure of PMS [29]. In-
deed, PDS is a symmetric compound and SO·4− is generated (Eq. (5))
when activated with S-MgO, whereas PMS is asymmetrical around the
peroxide bond which is broken down by S-MgO yielding both SO·4− and
HO· oxidative radicals (Eq. (6)) [30] work together for efficient de-
gradation of ACT molecules.
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F. Fanaei, et al. Chemical Engineering Journal 371 (2019) 404–413

Fig. 3a. XPS analysis of MgO catalyst.

Fig. 3b. XPS analysis of S-MgO catalyst.

407
F. Fanaei, et al.
S−MgO
S2 O82 − → 2SO·4− (5)
HSO−
S−MgO
→ SO·4− + HO· (6)
5
In addition, (H3 O18 S4 )5 −
used a source of PMS is dissociated in water
to two molecules of HSO− −
5 and a molecule of HSO4 (Eq. (7)). When S-
MgO was added to the reaction medium, these molecules were de-
composed to SO·4−. Therefore, a greater amount of oxidative radicals was
generated per molecule of (H3 O18 S4)−5 (Eqs. (6) and (8))) than that of
S2 O−8 2 resulted in achieving higher ACT degradation percentages [4].
(H3 O18 S4 )5 − → 2HSO5− + HSO−4 + SO24− (7)
HSO−4 + HO· → SO·4− + H2 O (8)
The ACT molecules were then reacted with the generated radicals
(SO·4− and/or HO·) and were degraded into the products as simply shown
in Eqs. ((9) and (10)).
SO·4− + ACT → products (9)
HO· + ACT → products (10)
Normally, SO·4−
reacts with organic compounds through the electron
transfer process while HO∙ do so via the hydrogen-atom abstraction and
electron transfer mechanisms [31]. Therefore, the degradation of ACT
in the S-MgO/PMS is more efficient than that in the S-MgO/PDS process
due to the greater number of reaction mechanisms involved in the de-
gradation process. Accordingly, the high oxidation potential of SO·4− and
HO· along with the high stability of PMS made the S-MgO/PMS process
very efficient for the degradation of recalcitrant organic compounds
[31] such as ACT.
In order to confirm the formation SO·4− and HO· and to indicate their
relative contribution in the degradation of ACT in the S-MgO/PMS
process, the ACT removal was evaluated in the absence and presence of
ethanol and tert-Butanol as radical scavengers with a considerably
different rate constant with SO·4− and HO·. The complete degradation of
50 mg/L ACT was obtained in the S-MgO/PMS process within 30 min
reaction time in the absence of scavengers (Figs. 3a,b).
However, when tert-butanol was added to the reaction medium, the
degradation rate decreased and it took 40 min to complete removal of
50 mg/L ACT. Moreover, the ACT degradation reached to 86.3% within
60 min in the S-MgO/PMS process in the presence of ethanol. The inset
Fig. 4 depicts the PFO plots of ACT removal in the S-MgO/PMS process
in the absence and in the presence of the selected radical scavengers. As
shown in inset Fig. 4, the PFO rate constant of ACT degradation reac-
tion was 0.289 min−1 in the absence of radical scavengers, whereas it
decreased to 0.232 and 0.037 min−1 in the presence of tert-butanol and
Fig. 4. Effect of radical scavengers on ACT degradation in the S-MgO/PMS
process (ACT = 50 mg/L, S-MgO = 1 g/L, PMS = 1 g/L, solution pH = 7, re-
action time = 0–60 min).
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Chemical Engineering Journal 371 (2019) 404–413
ethanol, respectively. The reduction in PFO reaction rate constant of
ACT removal in the presence of both tert-butanol and ethanol clearly
indicates that both SO·4− and HO· were generated in the S-MgO/PMS
process but with the different contribution in the removal attained. The
reaction rate constant of tert-butanol and ethanol with HO· are
(3.8–7.6) × 108 M−1s−1 and (1.2–2.8) × 109 M−1s−1, respectively,
while those react with SO·4− at the rate constants of
(4.0–9.4) × 105 M−1s−1 and (1.6–7.7) × 107 M−1s−1, respectively [2].
These reaction rate constants indicate that tert-butanol selectively re-
acts with HO· around 1000 times faster than with SO·4−, whereas ethanol
reacts with both SO·4− and HO· at the relatively close rate. Accordingly,
much greater reduction of ACT removal in the presence of ethanol than
that at the presence of tert-butanol clearly reveals that although both
SO·4− and HO· were generated and involved in the ACT degradation re-
actions, SO·4− played a dominant role in ACT degradation under the
selected conditions. The contributions of SO·4− (Eq. (11)) [10] and HO·
(Eq. (12)) in the ACT removal process were calculated to be 80.3% and
19.7%, respectively. Zhang et al. [10] reported a contribution of 79.9%
for SO·4− in the degradation of ACT in the Fe2O3@Cu2O/PDS process.
k obs with HO· scavenger
Contribution of SO·4− (%) = × 100
k obs without scavenger (11)
Contribution of HO· (%) = 100 − contribution of SO·4− (12)
Based on Fig. 5, the EPR spectrum taken with DMPO did not show
any peaks which revealed that catalysts themselves or in the presence of
PMS do not give HO· as no peaks for DMPO-OH adduct was observed
[32,33]. When TEMP spin trapping agent was used, a triplet pattern of
equal intensity was recorded for both MgO and S-MgO catalysts, which
is characteristic for TEMP-1O2 adducts and confirm the singlet oxygen
in both catalysts [32]. The ACT degradation in the S-MgO/PMS process
was compared in the presence of aeration and N2 blowing. It was found
that the ACT degradation in the process with aeration was 17% higher
than that with N2 blowing; confirming that dissolved oxygen played a
role in producing ROSs in solution. It can be seen that intensity of tri-
plet peaks is higher for MgO in comparison of S-MgO, which also
confirmed the surface composition modification due to the presence of
S. EPR of MgO and S-MgO samples was also collected in presence of
PMS by using DMPO [33]. EPR spectrum clearly indicates the presence
of sulfate radicals in S-MgO/PMS, which is in good agreement with a
seven-line pattern for sulfate radicals as reported by Lin et al. [34].
However, no peak for sulfate radicals was observed in MgO/PMS pro-
cess. This study clearly confirms that SO·4− was the main reactive specie
involved in degradation of ACT in the S-MgO/PMS process and in-
dicates that the S doping enhanced the generation of sulfate radicals
and hence higher degradation of ACT molecules was obtained once S-
MgO was used as a catalyst.
3.2. Effect of solution pH
The effect of initial solution pH between 4 and 10 was evaluated on
the degradation of 50 mg/L ACT in the S-MgO/PMS process. The results
are shown in Fig. 6 indicating that ACT degradation in the S-MgO/PMS
process had the same trend as that in the S-MgO/PDS process, although
with a higher level of efficiency. As observed in Fig. 6, ACT degradation
was not affected considerably by the solution pH between 4 and 10.
Since the pH of natural waters is around neutral condition and that the
ACT removal in the selected processes was highest at the neutral con-
dition, the remained tests were conducted at solution pH of 7. It should
be noted that the adsorption of ACT (absence of PMS) onto the catalyst
(MgO or S-MgO) was below 2% over the selected range of the initial pH
(4–10), suggesting that adsorption had not any significant contribution
in removing ACT and thus is negligible.
Since the natural waters are almost neutral in pH, obtaining the
maximum ACT degradation in the S-MgO/PMS process at the neutral
solution pH reveals that the process can be appropriately applied for
F. Fanaei, et al.
Fig. 5. Detection of reactive species by EPR spectra collected with (a) TEMP for
MgO and S-MgO samples, (b) DMPO for MgO and S-MgO samples and (c) DMPO
for MgO/PMS and S-MgO/PMS.
efficient treatment of the contaminated water without needing pH ad-
justment [16,35]. The observed trend of ACT degradation as a function
of solution pH in the selected processes can be explained considering
the effect of solution pH on the PMS dissociation in the solution and on
409
Chemical Engineering Journal 371 (2019) 404–413
Fig. 6. Effect of initial solution pH on ACT degradation in the S-MgO/PMS
process (ACT concentration = 50 mg/L, S-MgO = 1 g/L, PMS = 1 g/L, reaction
time = 10 min).
the surface charge of the catalyst. S-MgO has a zero point charge pH
(pHzpc) of 10.9 [19], causing the increase of the final solution pH to the
alkaline range around 9, the surface of the catalyst was positively
charged at all the selected solution pHs. Moreover, considering its
pKa1 = 0 and pKa2 = 9.2, HSO5− was the dominant species of PMS
under the acidic and neutral solution pHs below 9.2 whereas SO52−
would be dominated at the solution pHs over 9.2 [16,35]. Therefore, at
solution pH < 9.2 the negative HSO5− anions were attracted toward
the positively charged surface of S-MgO resulted in its becoming cata-
lyzed into SO·4− and HO· (Eq. (8)). The lower ACT removal efficiency at
the acidic pHs can be related to the significant inhibition effect of so-
lution pH on the formation of H-bond between H+ and the O − O group
of HSO5− which caused the attachment of positive charge to HSO5−
and thus impeding the reaction rate between HSO5− and positively
charged surface of S-MgO [16,35]. The effect of solution pH on the ACT
removal efficiency in the S-MgO/PMS is in accordance with the related
literature on catalytic activation of PMS with metal oxides. For in-
stance, the maximum ACT degradation efficiency was obtained in the
Fe3O4/PMS [16] and CuFe2O4/PMS [35] sulfate-based AOPs at the
neutral condition.
3.3. Effect of PMS to catalyst ratio
The effect of PMS concentrations between 0.2 and 1 g/L (0.025 and
0.12 mM) with a constant S-MgO concentration of 1 g/L as activator
catalyst corresponding to PMS to S-MgO ratio between 0.025 and
0.12 mM.L/g was investigated on the degradation of 50 mg/L ACT in
the S-MgO/PMS process. Fig. 7 shows the ACT degradation at different
PMS to S-MgO ratio as a function of reaction time, generation of radical
species as well as for providing greater time for the reaction between
ACT molecules and radical species.
It can be seen in Fig. 7 that at a given concentration of PMS (PMS to
S-MgO ratio), the ACT degradation improved with the increase in re-
action time, which can be related to the increased interaction time
between the PMS and the catalyst resulted in forming the greater
amount of reactive species and thereby in increasing the degradation of
ACT molecules. In addition, at a given reaction time, the ACT de-
gradation increased with the increase in the PMS concentration (PMS to
S-MgO ratio). For instant, the ACT degradation in the process was
around 45.7, 65.2, 75.3, 88.2, 90.2 and 91.7% at ratio of 0.025, 0.04,
0.05, 0.07, 0.1 and 0.12 mM.L/g, respectively, within a reaction time of
10 min. It is worth noting that the ACT removal both in the absence of
PMS and S-MgO was below 3% at a reaction time of 60 min. It indicates
that the adsorption onto S-MgO as well as oxidation by single PMS was
ineffective in ACT removal and thus that ACT was removed in the
process through degradation by reaction with the generated radicals
F. Fanaei, et al. Chemical Engineering Journal 371 (2019) 404–413

cause the reduction of the ACT degradation percentages. The ACT re-
moval rate decreased to 14.95 and 13.40 mg/L.min with further in-
crease in PMS concentration to 0.8 and 1 g/L (PMS to catalyst ratio of
0.1 and 0.12 mM.L/g) likely due to the recombination of SO·4− (Eq. (13))
or HO· (Eq. (14)) reactive species of the reaction between the radical
species and the extra PMS (Eqs. (15)–(17)) [16,36,37].
SO·4− + SO·4− → S2 O−8 2 (13)

HO· + HO· → H2 O2 (14)

SO·4− + HO· → HSO−4 + 0.5O (15)

SO·4− + HSO5− → SO24− + HSO·5− (16)

Fig. 7. Effect of PMS to S-MgO ratio on ACT degradation in the S-MgO/PMS
process (ACT = 50 mg/L, solution pH = 7, reaction time = 2.5–30 min).
rather than by adsorption onto S-MgO. The ACT degradation was faster
in the first 10 min-time mainly due to the greater amount of PMS mo-
lecules available for participating in the reaction with S-MgO and thus
the generation of the greater amount of radicals, as well as to the
greater amount of ACT molecules available for interaction with the
generated radicals. Tan et al. [16] also reported the same trend for ACT
removal in the Fe3O4/PMS process. The ACT removal efficiency in
MnFe2O4/PMS and CoFe2O4/PMS processes increased with the increase
in PMS to catalyst ratio from 0.25 to 1.0 [17]. It clearly indicates that
the optimum ratio of the PMS oxidant to catalyst greatly depends on the
type of the catalyst. The highest value of RSE was calculated during the
first 10 min of the reaction of the S-MgO/PMS process conducted under
the optimum conditions (PMS = 0.6 g/L, S-MgO = 1 g/L) in which
95.6% of ACT was degraded to be 43.6% (Fig. S2). The value of RSE for
the ACT removal in the activated PMS process has not been reported to
compare with the S-MgO.
In order to better illustrate the effect of PMS concentration on the
performance of S-MgO/PMS process in degradation of ACT, the PFO
reaction kinetic model was fitted with the experimental data shown in
Fig. 7. The kinetic information of ACT degradation in the S-MgO/PMS
process at different PMS concentrations is given in Table S1. As ob-
served in Table S1, the rate of ACT degradation in the S-MgO/PMS
process increased from 3.1 to 15.7 mg/L.min due to an increased in the
generated SO·4− and HO· (Eq. (8)) when the PMS concentration was in-
creased from 0.2 to 0.6 g/L corresponding to the increase of PMS to
catalyst ratio of 0.025 to 0.07 mM L/g. With considering the constant
amount of S-MgO used in the tests, the increase of ACT removal rate
with the increase in PMS to S-MgO ratio up to 0.07 mM L/g is attributed
to the generation of greater amount of radical species due to the in-
crease in availability of the precursor which limited the radical gen-
eration in the process [16,17]. Indeed, it shows that when the PMS was
further increased, the recombination of the generated radicals might
HO· + HSO− ·−
5 → SO5 + H2 O (17)
The optimum mass ratio of PMS to catalyst was therefore found to
be 0.07 mM.L/g for S-MgO, which is much lower than that reported for
Fe3O4 [16] and for CoFe2O4 and MnFe2O4 [17]. It is clearly deduced
that the S-MgO is a more efficient catalyst than the other tested ones for
activation of PMS. Table 1 compares the performance of the S-MgO/
PMS process as the most efficient process developed in this study with
different SO·4−-based AOPs for the degradation of ACT. As given in
Table 1, the S-MgO/PMS process had much greater performance than
the other SO·4−-based AOPs for the degradation of ACT. It shows that the
S-MgO has a high activity for activation of the PMS for the increased
generation of oxidative radicals.
3.4. Effect of water anions
Contaminated waters contain different anions, which may affect the
performance of AOPs used for the decontamination. Fig. 8 shows the
results of the effect of main water anions (concentration of each anion
was 100 mg/L) including chloride, carbonate, nitrate, sulfate, and
phosphate the performance of S-MgO/PMS process for the degradation
of ACT. The degradation of ACT in the contaminated tap water was also
tested to find out the effect of a mixture of anions. Fig. 8 indicates that
the presence of anions at the selected concentrations either individually
or as a mixture did not affect considerably the ACT degradation in the
process under the examined conditions.
Although the selected anions may act as the radical scavengers, the
finding revealed that they could not compete with the generated SO·4−
and HO· at the selected concentrations. Generally, the degradation rate
of organic pollutant is retarded in the presence of Cl- ions because it can
consume HO· radicals. But, in the presence of PMS, the direct reaction
between PMS and Cl- could lead to the formation of active chlorine
species (Cl2/HClO), which are capable of degrading pollutants [40]. In
this case, there may be mainly SO·4−, HO·, Cl·2−, and HClO in the aqueous
system [41]. All of these strong oxidizers might participate in the de-
gradation of organic contamination. Further, the active chlorine species
(HClO/Cl2) are dominant oxidants under neutral/alkaline conditions.
PMS is more stable at pH < 4.0 in comparison to alkaline conditions
(pH > 7.0) hence faster degradation rates of ACT were expected under

Table 1
Summary of ACT removal in the sulfate radical-based AOPs with metal/metal oxides as the activator.
Oxidant Catalyst pH ACT (mg/L) Oxidant to catalyst (mM L/g) Removal efficiency kobs (min−1) robs (mg/L.min) Ref.

PDS Fe2O3-Cu2O 6.5 100 10.4 ∼90% @ 40 min 0.045 4.50 [10]
PDS Fe0 3 10 1 > 90% @ 180 min 0.023 0.23 [11]
PDS Fe2+ 3 7.5 14.3 ∼70% @ 30 min – – [14]
PMS Fe3O4 7 10 0.25 – 0.012 0.12 [16]
PMS MnFe2O4 7 10 1 100% @ 60 in 0.121 1.21 [17]
PMS CoFe2O4 9 10 1 100% @ 120 min 0.053 0.53 [18]
PDS rGO-Ag0 /Fe3O4 7 1.5 10 > 90% @ 60 min 0.008 0.01 [19]
PDS Bicarbonate 8.3 1.5 6.6 ∼70% @ 420 min 0.003 0.0045 [38]
PDS TiO2-x/rGO-Vis 10 28.6 ∼100% @ 40 min 0.452 4.52 [39]
PMS S-MgO 7 50 0.07 100% @ 30 min 0.314 15.70 Present work

410
F. Fanaei, et al.
Fig. 8. Effect of water anions on ACT degradation in the S-MgO/PMS process
(ACT = 50 mg/L, S-MgO = 1 g/L, PMS = 0.6 g/L, initial solution pH = 7, re-
action time = 30 min).
neutral or alkaline conditions due to the availability of more reactive
species. S-MgO has a zero point charge pH (pHzpc) of 10.9, which re-
sults in an increase of the final solution pH to the alkaline range. Tan
et al. [16] found slightly increased ACT degradation rate in the
MnFe2O4/PMS and CoFe2O4/PMS processes in the presence of bi-
carbonate concentration of 2 mM and related the enhancement to in-
crease in solution pH rather than inhibition caused by scavenging effect
of bicarbonate. They [16] also report the reduction in ACT degradation
rate at the presence of 2 mM chloride. It is deduced that due to the
generation of a high amount of radicals in the S-MgO/PMS process, the
scavenging effect of anions was insignificant. Accordingly, it implies
that the S-MgO/PMS process can be efficiently applied for treating the
contaminated real streams.
3.5. Mineralization of ACT in the S-MgO/PMS process
Fig. 9 depicts the mineralization of 50 mg/L ACT (32 mg/L TOC) in
the S-MgO/PMS process under optimum experimental conditions. As
can be seen in Fig. 9, the ACT mineralization increased from 8% at the
reaction time of 10 min to 62.4% when the reaction time was increased
to 60 min. The PFO reaction rate constant of ACT mineralization in the
S-MgO/PMS process obtained from fitting the PFO reaction kinetic
model with the mineralization experimental results (Fig. 7) was
0.025 min−1 under the selected conditions. The information on the
mineralization of ACT in sulfate radical-based AOPs is limited. Deng
et al. [11] reported an ACT (10 mg/L) mineralization of 38.9% in the
Fe0/PDS process within 180 min. The degree of ACT mineralization in
CoFe2O4/PMS and MnFe2O4/PMS processes within 120 min reaction
Fig. 9. Degradation and mineralization of ACT in the S-MgO/PMS process as a
function of the reaction time (ACT = 50 mg/L, S-MgO = 1 g/L, PMS = 0.6 g/L,
solution pH = 7, reaction time = 0–60 min).
411
Chemical Engineering Journal 371 (2019) 404–413
time was 16.2% and 3.5%, respectively, at PMS and catalyst con-
centrations of 0.2 mM and 0.2 g/L, respectively [17]. Yang et al. [39]
reported a 53% mineralization efficiency for 0.07 mM ACT in the TiO2-
x/rGO-PDS-Vis process using 1 g/L catalyst and 2 mM PDS. The higher
degree of ACT mineralization in the S-MgO/PMS process as compared
to other processes is attributed again to the greater activity of the S-
MgO, due to the creation of oxygen vacancies in its structure [15,42],
than the other tested materials for activation of peroxysulfates and thus
greater generation of oxidative radicals.
3.6. ACT degradation intermediates and pathway
The intermediates of ACT degradation (reaction time = 60 min,
catalyst concentration = 1 g/L, ACT concentration = 50 mg/L, solution
pH = 7, PMS concentration = 0.6 g/L) in the S-MgO/PMS process was
identified using LC/MS analysis. The LC/MS analysis data compared
with the NIST mass spectrometry data center revealed the formation of
some intermediates during ACT degradation (Table S2). Table S2
summarizes the reaction intermediates along with their molecular
structure identified in the LC/MS analysis. Fig. S3 shows the signals and
abundances of a scan LC/MS analysis of ACT degradation intermediates
in [M + H+] mode at different m/z values. Based on intermediates
products found in the LC/MS analysis (Fig. S3), Fig. 10 proposes the
reaction pathways of ACT degradation in the S-MgO/PMS process,
showing that two groups of reactions through mainly SO·4− and HO·
species were possibly involved in ACT degradation. The SO·4− interacted
with ACT molecules and its degradation intermediates through trans-
ferring the single electron to ACT/intermediates and through producing
of HO· species resulted in cleaving the bonds and finally in mineralizing.
N-(2,4-dihydroxyphenyl)acetamide (TP3), N-(3,4-dihydroxyphenyl)
acetamide (TP3), 4-aminophenol (TP4), N-(1-hydroperoxy-4-ox-
ocyclohexa-2,5-dienyl)acetamide (TP10), N-(3,4,5-trihydroxyphenyl)
acetamide (TP5), N-(1,4-dihydroxycyclohexa-2,4-dienyl)acetamide
(TP6) and ACTdimer (TP1) were the intermediates produced through
paths I, II, III, IV, V and VI respectively, during the degradation of ACT
in the S-MgO/PMS process under the selected conditions. Single elec-
tron transfer and oxidation could attack the weak bonds such as hy-
droxyl, oxygen or amide groups. Because of unpaired electrons, the
amide and hydroxyl groups resonated to the respective conjugated sites
at the benzene ring. It leads to different suitable sites for connecting
toHO·, the formation of multiple radical-radical complexes and finally
several isomers.
Further, the oxidation of these intermediates and hydroxylation
products by SO·4− and HO· led to breaking down the amide bonds and
aromatic structures and thereby being converted to some linear pro-
ducts like 3-hydroxypropanoic acid (TP20), malonic acid (TP19) and
Other compounds, finally mineralized to CO2 and H2O. It should be
mentioned that the m/z value for TP15 and TP17, TP9 and TP19, and
TP14 and TP20 (Fig. 10) were the same indicating that these pairs of
products could be probably formed during the degradation pathway of
ACT. The measurement of nitrate as an inorganic intermediate in the
effluent (TP15) clearly reveals the mineralization of nitrogen-con-
taining bonds in ACT and the degradation intermediates.
3.7. Toxicity bioassay
The acute 48-h toxicity of the ACT solution before and after treat-
ment in the S-MgO/PMS process was bio-assessed using Daphnia magna.
The LC50 of 50 mg/L ACT solution before treatment was determined to
be 30.7% or 18.1 mg/L, which is within the previously reported range
[43,44]. In comparison, the solution treated in the S-MgO/PMS process
under the optimum condition had the LC50 of 265.5% meaning the
toxicity of CAT solution decreased by 8.6 times upon treating in the S-
MgO/PMS process. TU values of ACT solution before and after treat-
ment in the S-MgO/PMS process was calculated to be 3.26 and 0.38,
respectively. Considering the classification made by Persoone et al.
F. Fanaei, et al.
Fig. 10. Pathway of ACT degradation in the S-MgO/PMS process (ACT = 50 mg/L, S-MgO = 1 g/L, PMS = 0.6 g/L, solution pH = 7, reaction time = 60 min).
[45], the bioassay findings indicate that the toxicity of ACT solution
decreased from ‘acute toxicity’ class for the raw solution to ‘no acute
toxicity’ class for the S-MgO/PMS process-treated solution. It implies
that the effluent from the S-MgO/PMS process has no hazard to be
discharged to the water environment.
4. Conclusion
An emerging water contaminant, ACT, was selected to evaluate the
catalytic activity of S-MgO nanoparticles as compared to plain MgO in
activating the PMS and PDS compounds. It was found that the S-doped
MgO was more active than the plain MgO in activating the selected
oxidants and that higher amount of radical species were generated
when using PMS rather than PDS. High degradation efficiency was
achieved in the case of using S-MgO as catalyst and PMS as oxidant;
ACT removal efficiencies in MgO/PMS, MgO/PDS, S-MgO/PDS, and S-
MgO/PMS were 8.0, 21.5, 43.8 and 95.6%, respectively. ACT de-
gradation was evaluated in the S-MgO/PMS process under various ex-
perimental conditions. A high rate of ACT degradation and miner-
alization could be achieved in the S-MgO/PMS process under neutral
pH. It was found that although both SO·4− and HO· species were gener-
ated in the S-MgO process, SO·4−played the main role in the achieved
ACT degradation in the process. A few simple intermediates were
identified by LC/MS analysis in the effluent of the S-MgO/PMS process,
412
Chemical Engineering Journal 371 (2019) 404–413
which along with the mineralization findings are evidence of complete
transformation of ACT molecules to harmless compounds. Treatment in
the S-MgO/PMS process considerably decreased the toxicity of the ACT
solution from acute toxicity to no acute toxicity. In conclusion, the
present work is of great importance for developing the novel advanced
oxidation technologies for efficient degradation of emerging con-
taminants in the contaminated waters.
Acknowledgments
This study was funded by Iran National Institute for Medical
Research Development (NIMAD) under grant No. 963379. The authors
are also grateful to Tarbiat Modares University, Tehran, Iran for pro-
viding technical support. Meghdad Karimi is acknowledged for his help
in interpreting LC-MS data and in preparing the degradation pathway.
Santtu Heinilehto, (University of Oulu-Finland) is also acknowledged
for providing XPS analysis of catalyst samples.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.04.007.
F. Fanaei, et al.
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