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Degradation of ibuprofen using ozone combined

with peroxymonosulfate†
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Cite this: DOI: 10.1039/c7ew00174f

Zhen Yuan, Minghao Sui,* Bojie Yuan, Pan Li,* Jingyu Wang,
Jie Qin and Guangyi Xu

Received 4th June 2017,
Accepted 13th July 2017
DOI: 10.1039/c7ew00174f
rsc.li/es-water
Ozone combined with peroxymonosulfate (O3/PMS) for degradation of ibuprofen (IBP) was studied in this
work. The oxidation capacity of O3/PMS and four other related oxidation processes for IBP degradation
was compared. O3/PMS demonstrated a compelling degradation ability towards IBP compared with O3,
PMS, O3/PDS, and O3/H2O2 processes. The generation of ˙OH and SO4˙− in O3/PMS was proved by electron
spin resonance detection, and the dominant highly oxidative species was determined based on the differ-
ent scavenging performances of tert-butanol and ethanol towards ˙OH and SO4˙−. The affecting factors in-
cluding O3 and PMS dosage, initial pH, and organic and inorganic constituents in water were investigated.
An optimum dosage of O3 and PMS was observed for degradation of IBP in O3/PMS. Though a notably
synergistic effect was observed in O3/PMS for IBP degradation under pH 3.0, 5.0, 7.6 and 9.0, alkaline con-
ditions were found to be more beneficial for IBP degradation. Humic acid, which was used to simulate the
natural organic water matrix, posed different effects on O3 and O3/PMS for IBP degradation. The presence
of Cl−, which is a typical reductive inorganic ion and ubiquitous in natural water, inhibited O3/PMS oxidation
on the degradation of IBP. The degradation kinetics of IBP in O3/PMS was also studied in this work.

Water impact
Ibuprofen, a non-steroidal anti-inflammatory drug, is widely used and inevitably discharged into the aquatic environment, which increases the risk of
drinking water pollution and further threatens the health of human beings. Conventional water treatment processes are inefficient in degradation of
emerging pollutants. In this study, the use of ozone combined with peroxymonosulfate was employed as an effective method to treat ibuprofen. Due to the
involvement of SO4˙− and ˙OH, the novel treatment process showed compelling efficiency compared to O3, PMS, O3/H2O2 and O3/PDS. Therefore, the adverse
effects of ibuprofen in the water treatment process can be decreased.

1 Introduction treatment processes, including coagulation/flocculation, sedi-

In recent decades, pharmaceuticals and personal care prod-
ucts (PPCPs) have been continuously detected in water bodies
including groundwater,1 surface water, and wastewater.2
PPCPs have been recognized as contaminants of emerging
concern because of their persistent presence in aquatic
environments.3–5 The occurrence of PPCPs in water sources
may lead to serious water quality risks and public concern
and has become a challenging multidisciplinary problem. De-
spite the low concentration of PPCPs ranging from ng L−1 to
μg L−1, their residues may have serious adverse health im-
pacts and unknown long-term effects.6 Conventional water
State Key Laboratory of Pollution Control and Resource Reuse, College of
Environmental Science and Engineering, Tongji University, #1239 Siping Road,
Shanghai 200092, China. E-mail: minghaosui@tongji.edu.cn, lipan@tongji.edu.cn;
Tel: +86 21 65982691
† Electronic supplementary information (ESI) available: Competitive kinetics re-
sults and speciation of PMS. See DOI: 10.1039/c7ew00174f
mentation, and sand filtration, are ineffective in removing
PPCPs from water with less than 30% removal efficiency.7–10
Therefore, advanced treatment techniques such as chemical
oxidation which can offer significant treatment efficiency are
highly required to degrade or even remove PPCPs from water.
Ozone is widely applied in water and wastewater treatment
all over the world.11,12 The effectiveness of ozonation in dis-
infection, decoloration, and elimination of micropollutants
has been practically proved.13 A unique property of ozone in
water is its decomposition into OH radicals (˙OH), which are
one of the strongest oxidants in water.14 Ozone is a very se-
lective oxidant. It is prone to attack the double bonds, acti-
vated aromatic groups and non-protonated amines of organic
compounds.14 ˙OH radicals react much faster with pollutants
than ozone molecules in water in a non-selective way. For the
ozonation process, the assessment of ozonation effectiveness
always involves the contribution of ozone molecules and/or
OH radicals. With respect to refractory micro-organic

This journal is © The Royal Society of Chemistry 2017 Environ. Sci.: Water Res. Technol.

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pollutants in water, OH radicals commonly play key roles in
their degradation and removal.15,16 Therefore, researchers
have devoted their efforts to exploring ways to enhance the
generation of OH radicals in the ozonation process.17–19
In recent years, a more reactive oxidizing species, sulfate
radicals (SO4˙−), has been given more attention due to their
relatively higher oxidation ability than OH radicals.20,21 The
redox potential of SO4˙− is 2.5–3.1 V, and it has a longer half-
life than ˙OH due to its preference for an electron transfer re-
action.22 Recent studies have shown that sulfate radical-
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based advanced oxidation processes are effective in oxidizing
various pollutants in water such as endocrine disruptors,
perfluorinated compounds and pharmaceuticals and their
metabolites.23–27 Peroxymonosulfate (PMS) or persulfate
(PDS) is the source of SO4˙−. Many activation methods to
generate SO4˙− have been proposed including thermolysis,
use of ultrasound, UV irradiation, base activation, laser flash,
and catalysis by transition metals or metal oxides.28–32 Tradi-
tional oxidants were also reported to be able to activate PMS
or PDS to generate SO4˙− in the last few years.33,34 SO4˙− and
˙OH have been detected in a H2O2/S2O82−/Fe2+ system and it
has been proved that ˙OH was the predominant species com-
pared to SO4˙−.34 Recently, it was reported by Ma et al. that
ozone can also activate PMS to produce SO4˙− and ˙OH.35,36
Ozone itself is a strong oxidant, and the combination of oz-
one with PMS is expected to exhibit a much stronger oxidiz-
ing ability than the case when they are applied individually.
However, it is a pity that only a few studies are concerned
with this novel process for PPCP degradation in water.
In this work, O3/PMS oxidation of ibuprofen (IBP) was
studied. IBP is known as a non-steroidal anti-inflammatory
drug, and is widely used and detected in aquatic environ-
ments for the sake of ineffective treatment of industrial, hos-
pital and wastewater treatment plant effluents.37,38 The oxida-
tion capacity of O3/PMS and four other related oxidation
processes for IBP degradation was compared. The affecting
factors such as O3 and PMS dosage, initial pH, and organic
and inorganic constituents in water were investigated. The
degradation kinetics of IBP in O3/PMS was also studied.
2 Materials and methods
2.1 Reagents and materials
IBP, peroxymonosulfate, potassium indigo trisulfonate,
benzoic acid (BA), 5,5-dimethyl-1-pyrroline-N-oxide (DMPO,
97%), sodium thiosulfate pentahydrate, potassium iodide
and humic acid (HA) were purchased from Sigma-Aldrich. HA
was first dissolved in 0.1 M NaOH. Then, the solutions were
filtered through 0.45 μm pore size filter paper. The filtrate
was used in the experiments after its pH was adjusted to neu-
tral using 1.0 M HCl. The nonsoluble residues were dried
and weighed. The concentration of HA was expressed as the
mass difference of original HA and the residues per liter.
tert-Butanol (TBA), ethanol (EtOH), perchloric acid and so-
dium hydroxide were purchased from Sinopharm Chemical
Reagent Co. Ltd. These reagents were used as-received except
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for DMPO which was purified with powdered activated car-
bon under a N2 atmosphere. All stock solutions were pre-
pared using Milli-Q water (Millipore, Billerica, MA).
2.2 Experimental procedures
O3/PMS oxidation experiments were carried out in batch
mode. An ozone stock solution was first prepared by input-
ting O3 gas into Milli-Q water cooled at 4 °C in an ice bath.
The degradation experiment was conducted in a 250 mL glass
reactor under continuous mixing. The reaction was initiated
by injecting the O3 solution into IBP and PMS solution. The
samples were withdrawn at predetermined time intervals and
0.1 M Na2S2O3 was used to quench the reaction further. The
pH was adjusted using 0.1 M HClO4 and 0.1 M NaOH.
2.3 Analytical methods
IBP was analyzed using a Waters UPLC system (Acquity UPLC
H-Class) and a 50 mm × 2.1 mm C18 1.7 μm reversed-phase
column (Acquity UPLC BEH) at 220 nm. A 0.1% acetic acid and
acetonitrile eluent with a ratio of 35 : 65 (v/v) was used at a flow
rate of 0.5 mL min−1 and the injection volume was 50 μL. BA
was analyzed using the Waters UPLC at 227 nm using an acetic
acid (0.1%) and methanol eluent with a ratio of 50 : 50 (v/v).
The ozone concentration in the stock solution was measured
based on UV258 absorbance, under which the ε258nm is 2900
M−1 cm−1. The dissolved ozone concentration in the reaction
system was measured using a modified indigo method.39 Two
milliliters of solution were withdrawn from the reaction system
and added into a 10 mL glass tube with 0.5 mL of 0.2 mM po-
tassium indigo trisulfonate, and then the absorbance of the
mixture was measured at 600 nm. PMS was determined by the
KSCN method.40 The PDS concentration was standardized by
the KI method.41 H2O2 was measured using the titanium sul-
fate method.42 Electron spin resonance (ESR) spectra were
recorded at 293 K on a Bruker EMX-8/2.7 spectrometer (ER
4119HS cavity). Instrument parameters were controlled as fol-
lows: central field: 3500 G; microwave frequency: 9.81 GHz;
microwave power: 20 mW; modulation frequency: 0.1 GHz;
modulation amplitude: 1.0 Gs; sweep width: 100 G.
2.4 Reaction kinetics of IBP by O3/PMS
Competitive kinetics were adopted to obtain the second-order
rate constants of IBP with SO4˙−. Herein, BA was used as a ref-
erence compound (kSO4˙−,BA = 1.2 × 109 M−1 s−1) and UV/PDS
was adopted to generate SO4˙−. Direct photolysis and com-
bined photolysis were used to degrade IBP and BA as de-
scribed in eqn (1) and (2):
(1)
(2)
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Environmental Science: Water Research & Technology
where kd,IBP and kd,BA refer to the direct photolysis rate con-
stants (s−1) and kSO4˙−,IBP and kSO4˙−,BA are the second-order rate
constants of IBP and BA, respectively (M−1 s−1).
Combining eqn (1) and (2) led to eqn (3):
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By plotting vs.
second-order rate constants of IBP and SO4˙− could be calcu-
lated based on the slope of the straight line.
The reaction of O3/PMS between compounds can be
expressed using second-order kinetics as follows:
where kO3,IBP, k˙OH,IBP and kSO4˙−,IBP are the second-order rate
constants for the reaction of IBP with O3, ˙OH and SO4˙−, re-
spectively. Eqn (4) can be converted as follows:
where , and refer to O3 exposure,
−
˙OH exposure and SO4˙ exposure, respectively. Von Gunten43
proposed the Rct,˙OH value to define the ratio of ˙OH exposure
to O3 exposure. Thus, the ratio of SO4˙− exposure to O3 expo-
sure can be termed Rct,SO4˙−.
Substituting eqn (6) and (7) into eqn (5) yielded eqn (8):
By plotting the logarithm of contaminant degradation vs.
O3 exposure according to eqn (8), the value of the apparent
reaction rate kapp,IBP can be calculated, which is defined as
follows:
kapp,IBP = kO3,IBP + k˙OH,IBPRct,˙OH + kSO4˙−,IBPRct,SO4˙−
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3 Results and discussion
3.1 The oxidation capacity of O3/PMS towards IBP
3.1.1 Comparison of O3/PMS with other related oxidation
systems for IBP degradation. The degradation effectiveness of
IBP in five oxidation systems, namely O3/PMS, O3, PMS, O3/
(3) PDS and O3/H2O2, is displayed in Fig. 1. O3/PMS demon-
strated a compelling degradation ability towards IBP com-
pared with the other four processes. The degradation effi-
ciency towards IBP of O3/PMS was 72.0% in 20 min, which
, the was 22.9% higher than that of O3/H2O2. It should be the syn-
ergistic effect of PMS and O3 that led to the high degradation
effectiveness of O3/PMS towards IBP. PMS alone cannot oxi-
dize IBP under the current experimental conditions (less than
1.0%), and no IBP was found to be degraded as shown in
Fig. 1. Ozonation alone can lead to 32.1% degradation effi-
(4)
ciency towards IBP, while the oxidation efficiency towards
IBP increased by about 39.9% with the combination of PMS
and O3. From Fig. 1, the O3/PDS system did not show higher
degradation efficiency (31.6%) compared with O3, which
suggested that PDS cannot be activated by O3.
3.1.2 Active species in O3/PMS and related oxidation sys-
tems. The strong oxidizing ability of O3 or PMS-based oxida-
(5)
tion systems is commonly ascribed to the promotion of the
generation of hydroxyl radicals (˙OH) and/or sulfate radicals
(SO4˙−). In this work, ESR was adopted to detect the genera-
tion of ˙OH and SO4˙− in O3/PMS and O3/H2O2 systems with
O3/PDS as a contrast. It is clearly shown in Fig. 2 that both
˙OH and SO4˙− were detected in O3/PMS, and only OH radicals
were found in O3/H2O2. For O3/PDS, no radical signal was
detected. PDS exists in the form of S2O82−. The sulfonate
groups are connected by a peroxy group (O–O), which are sta-
(6)
ble and do not react with O3.44 Cong et al. also reported that
O3 decomposition was only slightly enhanced in the presence
of PDS.35,36 For PMS, it exists in monoanionic (HSO5−) and
dianionic (SO52−) forms. Yang et al. proposed that O3 initially
reacted with SO52− (eqn (10)), forming SO82−, which decayed
(7)
in two different ways as shown in eqn (11) and (12).36,45 O3˙−
further transformed into ˙OH (eqn (13) and (14)) while SO5˙−
could be converted into SO4˙− either by reacting with O3 or
decaying bimolecularly (eqn (15) and (16)).45 Meanwhile,
SO4˙− could react with H2O or OH− to produce ˙OH as shown
in eqn (18) and (19).20,46 Therefore, two kinds of radicals
(8)
were responsible for the degradation of IBP.
SO52− + O3 → SO82− (10)
SO82− → SO5˙− + O3˙− (11)
SO82− → SO42− + 2O2 (12)
(9) O3˙− ⇌ O2 + O˙− (13)
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HO2− + O3 ⇌ HO5− (21)

HO5− → HO2˙ + O3˙− (22)

HO5− + 23O2 + OH− (23)

In order to determine the prevalence of ˙OH and SO4˙− in

O3/PMS, TBA and EtOH were used as radical scavengers to
verify the radicals' contribution to IBP degradation. TBA, a
strong hydroxyl radical scavenger, is able to quench ˙OH at a
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Fig. 1 The degradation of IBP by different oxidation systems
(experimental conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 μM
or 1.5 mg L−1, [PMS]0 = 6.5 μM or 2.0 mg L−1, [H2O2]0 = 10 μM or 0.34
mg L−1, [PDS]0 = 20 μM or 5.4 mg L−1, initial pH 7.0, T = 20 °C).
Fig. 2 ESR spectra of O3/PMS, O3/H2O2 and O3/PDS (experimental
conditions: [O3]0 = 31.3 μM or 1.5 mg L−1, [PMS]0 = 50 μM or 15.37 mg
L−1, [H2O2]0 = 50 μM or 1.70 mg L−1, pH 7.0, [DMPO]0 = 100 mM or
11.32 g L−1, T = 20 °C, recording time: 4 min; ■: SO4˙− adduct, ●: ˙OH
adduct).
O˙− + H2O ⇌ ˙OH + OH− (14)
high rate (k˙OH,TBA = 3.8–7.6 × 108 M−1 s−1) but less reactive to
SO4˙− (kSO4˙−,TBA = 4.0–9.1 × 105 M−1 s−1), while EtOH can
quickly react with both ˙OH and SO4˙− (k˙OH,EtOH = 1.2–2.8 ×
108 M−1 s−1; kSO4˙−,EtOH = 1.6–7.7 × 107 M−1 s−1).22,46 Fig. 3 and
4 illustrate that the degradation efficiency towards IBP
dropped as much as 30% when 0.5 mM TBA/EtOH was
added, and the inhibiting effects enhanced with the increase
of the respective dosing amount of TBA/EtOH, which con-
firmed that both ˙OH and SO4˙− radicals were responsible for
IBP degradation. At the same time, it was seen that EtOH in-
duced more adverse effects than TBA on IBP degradation,
which suggested that SO4˙− dominated the reaction in O3/
PMS compared with ˙OH at pH 7.0.
3.1.3 Reaction rate constant of IBP with sulfate radicals.
The second-order rate constant of IBP and ˙OH was reported
to be k˙OH,IBP = 5.23 × 109 M−1 s−1,48 while no information
about the kinetics data of IBP with SO4˙− could be obtained.
In this work, the competitive kinetics method was used to
measure the reaction rate constant of IBP with SO4˙−. The re-
action rate constant of IBP and SO4˙− was determined to be
1.08 × 109 M−1 s−1 in this study (see Fig. S1, ESI†), which is
lower than that with ˙OH. The sulfate radical is electrophilic49
and tends to react with electron-donating moieties like hy-
droxyl (–OH), alkoxy (–RO) and amino (–NH2) groups but is
not favorable to react with electron-withdrawing groups like
nitro (–NO2) or carbonyl (CO) in aromatic compounds.50
On the other hand, OH radicals are nonselective toward or-
ganic pollutants in the oxidation reaction.

SO5˙− + O3 → SO4˙− + 2O2 (15)

2SO5˙− → 2SO4˙− + O2 (16)

2SO5˙− → S2O82− + O2 (17)

SO4˙− + H2O → H+ + SO42− + ˙OH (18)

SO4˙− + OH− → SO42− + ˙OH (19)

In the O3/H2O2 reaction, hydroxyl radicals were formed

and served as the core active species (eqn (13), (14) and (20)–
(23)47). Hence, 17.0% more IBP was removed by O3/H2O2
compared to the O3-alone system due to the generation of
˙OH. Fig. 3 The effect of TBA on the degradation of IBP (experimental
conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 μM or 1.5 mg L−1,
H2O2 ⇌ H+ + HO2− (20) [PMS]0 = 6.5 μM or 2.0 mg L−1, initial pH 7.0, T = 20 °C).

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Fig. 4 The effect of EtOH on the degradation of IBP (experimental
conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 μM or 1.5 mg L−1,
[PMS]0 = 6.5 μM or 2.0 mg L−1, initial pH 7.0, T = 20 °C).
3.2 Affecting factors for IBP degradation in O3/PMS
3.2.1 Effect of dosage of oxidants. As shown in Fig. 5, the
degradation efficiency towards IBP rose with increasing O3
concentration. When the initial concentration of O3 reached
1.5 mg L−1, the degradation ratio rose dramatically. This
should be due to the stronger promoting effects on the gener-
ation of radicals under higher ozone dosage. With respect to
PMS, the increase of its dosage did not result in obviously
higher degradation efficiency towards IBP under three ozone
dosages. Also, it seems that with higher dosage of PMS, the
degradation efficiency towards IBP slightly decreased under
the same dosage of ozone. On one hand, it was proposed
that HSO5− in excess could react with ˙OH and SO4˙− and may
form less oxidative species (eqn (24) and (25)).51 On the other
hand, with the excess amount of ˙OH and SO4˙−, it was possi-
ble that radicals could be self-consumed (eqn (26)–
(28)).46,52,53 As a result, less IBP was oxidized.
Fig. 5 The degradation of IBP by O3 and PMS of different amounts
(experimental conditions: [IBP]0 = 5 μM or 1.0 mg L−1, initial pH 7.0,
reaction time: 20 min, T = 20 °C).
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HSO5− + SO4˙− → SO5˙− + HSO4− (24)
HSO5− + ˙OH → SO5˙− + H2O (25)
SO4˙− + SO4˙− → S2O82− (26)
˙OH + ˙OH → H2O2 (27)
SO4˙− + ˙OH → HSO5− (28)
O3 consumption at the initial concentration of 1.5 mg L−1
with different PMS dosages was also detected. Though the
larger amount of PMS did not enhance the degradation of IBP
based on the results from Fig. 5, it was found that O3 was
decomposed faster with the increase of PMS dosage (Fig. 6).
This result further implied that excess PMS could react with
radicals, quenched the active species and thus deteriorated the
reaction of IBP with radicals. Overall, the dosage of O3 and
PMS is of importance to O3 consumption and the degradation
efficiency towards IBP. It is not always favorable to increase the
dosage of oxidants because redundant oxidants might not im-
prove the degradation of target pollutants and are just a waste.
3.2.2 Effect of initial pH. The degradation of IBP in PMS,
O3 and O3/PMS at pH 3.0, 5.0, 7.6 and 9.0 was investigated.
The experimental results are shown in Fig. 7. pH is a critical
factor affecting the decomposition of O3 and the dissociation
of PMS. Aqueous solution pH is very important for the ozona-
tion process because hydroxide ions can initiate ozone de-
composition into OH radicals under alkaline conditions.54,55
Under acidic conditions, ozone reacts with the target com-
pound mainly in its molecular form, while with the increase
of pH, ozone molecules and OH radicals both contribute to
the oxidation reaction. As expected, the degradation effi-
ciency towards IBP increased with increasing pH. At pH 3.0,
only 15.0% degradation efficiency towards IBP was observed,
however, 67.4% of IBP was degraded at pH 9.0. The much
higher degradation efficiency towards IBP was ascribed to the
involvement of OH radicals under alkaline conditions.
Fig. 6 The effect of PMS dosage on O3 consumption (experimental
conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 μM or 1.5 mg L−1,
initial pH 7.0, T = 20 °C).
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netics of IBP in O3/PMS under different pH conditions was

also studied. The result is shown in Fig. 8(c). Under alkaline
conditions, IBP degradation occurred more rapidly accompa-
nying the rapid decomposition of ozone than that under
acidic conditions. The degradation of IBP fitted the second-
order kinetics well as described in eqn (4). Also, it was obvi-
ous that at pH 7.6 and 9.0, IBP degradation occurred at a
faster speed than that at pH 3.0 and 5.0.
3.2.3 Effect of humic acid. HA was used to simulate the
natural organic water matrix to determine the effect of natu-
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ral organic matter on PMS/O3 for the degradation of IBP. As

shown in Fig. 9, HA exhibited different trends of effect on
Fig. 7 Oxidation of IBP in O3, PMS and O3/PMS at different pH values
O3-alone and PMS/O3 processes. The degradation efficiency
(experimental conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 μM towards IBP of ozonation alone depended on the concentra-
or 1.5 mg L−1, [PMS]0 = 6.5 μM or 2.0 mg L−1, T = 20 °C). tion of HA (Fig. 9(a)). The presence of lower concentrations
of HA, i.e., 0.6 mg L−1 and 1.2 mg L−1, improved the degrada-
tion of IBP by ozonation. However, with the further increase
PMS existed in different forms of species under different of HA concentration, the degradation of IBP by ozonation
pH conditions. The speciation of PMS was calculated based was inhibited. In the presence of 6.0 mg L−1 HA, the degrada-
on its second pKa 9.4 because its parent acid of PMS, H2SO5, tion efficiency towards IBP was 7.6% lower than that in the
was reported to be an acid as strong as sulfuric acid.56,57 At absence of HA within 20 min. Natural organic matter (NOM)
pH 3.0 and 5.0, PMS existed in the form of HSO5−, at pH 7.6, in water can directly react with ozone and OH radicals and af-
PMS was present in the form of 1.6% HSO5− and 98.4% fect ozone-related reactions acting as a promoter and inhibi-
SO52−, and at pH 9.0, PMS existed in the form of 28.5% tor for the generation of OH radicals.14 It was found in many
HSO5− and 71.5% SO52−. As illustrated in Fig. 7, insignificant tests that the effect of NOM on ozonation seemed to be
degradation of IBP was observed under the pH conditions
studied in this work, and the degradation efficiency towards
IBP was less than 1.0%. The result suggested that IBP was re-
fractory to both HSO5− and SO52−.
For the O3/PMS system, a notably synergistic effect was ob-
served under the four pH conditions, and alkaline conditions
were found to be beneficial for IBP degradation compared to
acidic conditions. At pH 3.0 and 5.0, the degradation effi-
ciency towards IBP was 25.3% and 32.0% in O3/PMS, which
was 10.7% and 8.0% higher than that in O3 alone. When the
pH increased to 7.6 and 9.0, the degradation efficiency to-
wards IBP reached 78.0% and 82.1%, which were much
higher than those under lower pH conditions. It was also
noted that the strongest synergistic effect of O3/PMS occurred
at pH 7.6, in which the degradation efficiency towards IBP
was 38.8% higher than that in O3 alone. Considering the dis-
sociation of PMS under different pH conditions (see Fig. S2,
ESI†), it seemed that SO52− was easier to be activated by O3. It
was also reported that OH radicals can induce the accelera-
tion of PMS decomposition.51 At pH 7.6, some ozone should
decompose into OH radicals, which should also contribute to
the higher activation capacity of PMS.
Ozone decomposition in O3 and O3/PMS at different pH
values was tested. As shown in Fig. 8(a) and (b), at pH 3.0
and 5.0, the introduction of PMS posed an insignificant effect
on ozone decomposition. However, under neutral pH condi-
tions, ozone decay was faster in O3/PMS than ozonation and,
under higher pH conditions, ozone decomposition was much
Fig. 8 Ozone decomposition in O3 (a) and O3/PMS (b) at different
faster in O3/PMS than ozonation. Within 1.0 min, more than initial pH values and IBP degradation kinetics (c) (experimental
95% of ozone decayed at pH 9.0, while at 20 min, there was conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 μM or 1.5 mg L−1,
still 2.6% of ozone left in ozonation alone. The reaction ki- [PMS]0 = 6.5 μM or 2.0 mg L−1, T = 20 °C).

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51.8% and 36.5% in the presence of 1.0 mM and 10.0 mM Cl−,

respectively. Different trends of effect were observed in differ-
ent SO4˙−-based oxidation systems. Using
p-nitrosodimethylaniline (RNO) as a model compound,
Bennedsen et al. found that iron/PMS at neutral pH was not af-
fected by Cl−, and alkaline activation and heat activation of
PMS for degradation of RNO were both enhanced in the pres-
ence of Cl−.59 Gu observed that the presence of Cl− greatly
inhibited the oxidation ability of a vacuum UV/PMS process for
degradation of 1,1,1-trichloroethane in aqueous solution.60
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Two major reasons should account for the inhibiting ef-

fects of chloride ions. Chloride ions could consume PMS and
could form less reactive species when reacting with SO4˙− and
Fig. 9 Effect of HA on O3 (a) and O3/PMS (b) for the degradation of
IBP (experimental conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 ˙OH.61,62 Cl− can react with SO4˙− to form ˙Cl. The subsequent
μM or 1.5 mg L−1, [PMS]0 = 6.5 μM or 2.0 mg L−1, pH 7.0, T = 20 °C). reaction of ˙Cl and Cl− could form Cl2˙− with an oxidation po-
tential of 2.0 V.63 The self-consumption of ˙Cl and Cl2˙− leads
to the formation of Cl− and Cl2 (eqn (29)–(34)).62 The Cl radi-
related to the concentration of NOM. NOM with low concen- cals formed are selective reactive chlorine species and can re-
trations served more likely as the promoter for the generation act with electron-rich moieties through one-electron oxida-
of OH radicals, which commonly resulted in the promotion of tion, H-abstraction, and addition to unsaturated C–C
the degradation of target organic pollutants. However, at rela- bonds.62,64 Bennedsen et al. suggested that the enhanced ef-
tively high concentrations of NOM, the degradation of organic fect on RNO degradation when Cl− was present in alkaline ac-
compounds deteriorated due to the inhibiting effect of NOM tivation and heat activation processes could be caused by di-
on the chain reaction of OH radicals.58 It is a pity that till now rect attack of reactive Cl2 produced by oxidation with sulfate
it has been impossible to estimate the fraction of NOM which radicals.59 From the negative effect of Cl− on IBP degradation,
promotes or inhibits ozone decay due to its complex structure.
Different from the ozonation system, the degradation effi-
ciency towards IBP decreased in PMS/O3 under the four
tested concentrations of HA (Fig. 9). Lutze has reported that
NOM could consume SO4˙− and OH˙ with second-order reac-
tion rate constants of 6.8 × 103 L mg C−1 s−1 and 1.4 × 104 L
mg C−1 s−1, respectively.23 At pH 7.0, both ozone molecules
and ˙OH contributed to the degradation of IBP in the
ozonation-alone system. In O3/PMS, the high degradation ef-
ficiency was ascribed to SO4˙− and ˙OH. The competing con-
sumption of NOM with IBP towards SO4˙− and ˙OH should be
an important reason for the deterioration of IBP degradation.
Whether HA also served as the inhibitor is another consider-
ation for the negative effect on IBP degradation, however,
this cannot be proven and needs further investigation.
Ozone decay and IBP degradation versus ozone decay in
the presence of HA were studied. IBP degraded faster at the
beginning of the reaction in O3/PMS (Fig. 9(b)), which should
be due to the rapid consumption of ozone by HA, so the
fitting of IBP degradation was carried out within 120 s. The
presence of HA accelerated ozone decay in the PMS/O3 sys-
tem (Fig. 10(a)). In the presence of HA, IBP degradation still
followed the second-order kinetics well but with a slower deg-
radation rate than that in the absence of HA (Fig. 10(b)).
3.2.4 Effect of chloride ions. Cl− is a typical reductive inor-
ganic ion and ubiquitous in natural water. In this work, the im-
pact of Cl− was investigated to explore the effect of this inor-
ganic ion on PMS/O3 for degradation of IBP. Fig. 11 shows that
Fig. 10 Effect of HA on O3 decomposition (a) and IBP degradation
Cl− induced adverse effects on the degradation of IBP and the kinetics (b) (experimental conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0
negative impacts increased with the increase of Cl− concentra- = 31.3 μM or 1.5 mg L−1, [PMS]0 = 6.5 μM or 2.0 mg L−1, pH 7.0, T =
tion. The degradation efficiency towards IBP decreased to 20 °C).

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Paper
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Fig. 11 Effect of Cl− on O3/PMS for the degradation of IBP
(experimental conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0 = 31.3 μM
or 1.5 mg L−1, [PMS]0 = 6.5 μM or 2.0 mg L−1, pH 7.0, T = 20 °C).
Fig. 12 Effect of Cl− on O3 decomposition (a) and IBP degradation
kinetics (b) (experimental conditions: [IBP]0 = 5 μM or 1.0 mg L−1, [O3]0
= 31.3 μM or 1.5 mg L−1, [PMS]0 = 6.5 μM or 2.0 mg L−1, pH 7.0, T = 20
°C).
it seemed that the chlorine species formed were not so reac-
tive to IBP compared to SO4˙− and ˙OH in O3/PMS. Besides, it
was reported that Cl− could also compete with IBP for ˙OH, as
described in eqn (35)–(37),65,66 which should also be the rea-
son for the decrease of IBP degradation efficiency in O3/PMS.
2Cl− + HSO5− + H+ → SO42− + Cl2 + H2O (29)
Cl− + HSO5− → SO42− + HOCl (30)
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Cl− + SO4˙− → SO42− + ˙Cl (31)
Cl− + ˙Cl → Cl2˙− (32)
Cl2˙− + Cl2˙− → 2Cl− + Cl2 (33)
˙Cl + ˙Cl → Cl2 (34)
Cl− + ˙OH → ClOH˙− (35)
ClOH˙− + H+ → ˙Cl + H2O (36)
ClOH˙− + Cl− → Cl2˙− + OH− (37)
Though the presence of Cl− slightly affected O3 decay as
shown in Fig. 12(a), IBP degraded at a slower speed than that
in the absence of Cl− (Fig. 12(b)). In addition, the degrada-
tion rate constant of IBP decreased with increasing concen-
tration of Cl−.
3.3 Degradation of IBP by O3/PMS in a real water background
To further investigate the oxidation effectiveness of O3/PMS in
practical applications, the degradation efficiency towards IBP
of O3/PMS in an authentic water background was measured.
Filtered effluent from Lake Chao Water Treatment Plant (LC
water, using conventional water treatment processes, Anhui
Province, China) was collected. LC water was characterized by
a CODMn of 1.8 mg L−1, a DOC of 3.7 mg L−1, a pH of 7.6, and a
UV254 of 0.065. As shown in Fig. S3 (see the ESI†), the degrada-
tion efficiency towards IBP in the real water background
lowered by 14% compared with that in pure water within 20
min. However, the degradation of IBP was still very effective
with 64.8% degradation efficiency, which suggested that the
use of O3/PMS was a promising method for degradation of or-
ganic pollutants in practical applications.
4 Conclusions
The oxidation capacity of O3/PMS for IBP degradation was stud-
ied in this work. The combination of O3 with PMS greatly im-
proved the degradation efficiency towards IBP. The degradation
efficiency towards IBP of O3/PMS was 70.0%, 39.9%, 40.3% and
22.9% higher than those of PMS, O3, O3/PDS and O3/H2O2 un-
der the experimental conditions used in this work. The high ox-
idation capacity of O3/PMS should be attributed to the genera-
tion of ˙OH and SO4˙−. It was proved that SO4˙− dominated the
reaction in O3/PMS compared with ˙OH at pH 7.0. The effects
of O3 and PMS dosage, pH, and coexistent organic and inor-
ganic matter (HA and Cl−) in water on O3/PMS for IBP degrada-
tion were investigated. There existed an optimum O3 and PMS
dosage for IBP degradation. Alkaline pH conditions were favor-
able for IBP degradation in both O3 and O3/PMS systems. The
presence of HA posed different effects on O3 and O3/PMS. The
effect of HA on O3 oxidation was found to be concentration-re-
lated. Lower concentrations of HA promoted the degradation
of IBP, while in the presence of higher concentrations of HA,
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Environmental Science: Water Research & Technology
the degradation efficiency towards IBP decreased. For O3/PMS,
the degradation efficiency decreased under all the concentra-
tions of HA used in the current work. The inhibiting effect of
chloride ions on IBP degradation was observed in O3/PMS. The
reaction rate constant of IBP with SO4˙− of 1.08 × 109 M−1 s−1
was obtained by the competitive kinetics method. The degrada-
tion of IBP in O3/PMS under different water quality conditions
(different pH values, in the presence of HA and Cl−) fitted the
second-order kinetics well.
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Acknowledgements
Funding for this work was provided by the National Natural
Science Foundation of China (Grant 51478322 and 51278351)
and the Major National Water Pollution Control and Manage-
ment Project (Grant 2014ZX07405-003). We appreciate the
critical comments of the anonymous reviewers.
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