Water Air Soil Pollut (2016) 227:53

DOI 10.1007/s11270-016-2746-x

Degradation of Bisphenol A Using Ozone/Persulfate Process:

Kinetics and Mechanism
Ying Yang & Hongguang Guo & Yongli Zhang &
Qinzu Deng & Jing Zhang

Received: 4 July 2015 / Accepted: 5 January 2016

# Springer International Publishing Switzerland 2016

Abstract Advanced oxidation of bisphenol A (BPA) in
aqueous system by O3/Na2S2O8 was investigated, the
degradation of BPA was affected by ozone concentra-
tion, persulfate dosages, initial pH, and BPA concentra-
tion. Experimental results indicated that the degradation
of BPA was proved to follow the pseudo-first order
kinetics model and was enhanced with the increase of
O3 concentration and the decrease of initial BPA con-
centration. pH played a significant role in the BPA
removal especially under the alkaline condition. Free
radical species in the O3/Na2S2O8 system were identi-
fied by using tertiary butyl alcohol (TBA) and ethanol
(ETOH) as two probes, the results found that the major
free radical was SO4− · at acidic condition (pH = 3), and
the concentration of ·OH increased with the pH
Y. Yang : H. Guo (*) : Y. Zhang : J. Zhang
College of Architecture and Environment, Sichuan University,
Chengdu, China CN 610065
e-mail: hgguo@scu.edu.cn
Y. Yang
e-mail: yystardust@163.com
Y. Zhang
e-mail: zxm581212@163.com
J. Zhang
e-mail: zjing428@163.com
Q. Deng
Southwest municipal engineering design & research institute,
Chengdu, China CN 610065
e-mail: dengqinzu_scu@163.com
increased. Eight products were detected during the re-
action according to liquid chromatograph-mass spec-
trometry analysis. Most of the intermediates contained
quinonoid derivatives, carboxylic acid, and the relevant
mechanism for BPA degradation by O3/Na2S2O8 system
were proposed.
Keywords Ozone . Sulfate radical . Bisphenol A .
Kinetic . Mechanism
1 Introduction
A kind of typical endocrine disrupting chemicals
(EDCs), bisphenol A (BPA) has special estrogen
feature and affinity with estrogen receptors causing
adverse health effects such as thyroid hormone
disruption, obesity-promoting effects, liver damage
estrogenic potency, and increasing the prevalence
of cardiovascular disease (Olmez-Hanci et al.
2013). Meanwhile, BPA may get into the environ-
mental system in the process of synthesis, trans-
port, and use (Katsumata et al. 2004; Chang et al.
2009). As a matter of fact, BPA has been detected
in the aquatic environment at the concentration
level from nanograms to micrograms per liter of
water in many countries and regions (Yamamoto
and Yasuhara 1999).
Due to the inefficiency of BPA removal for the
common methods (physicochemical, biological,
and electrochemical methods), advanced oxidation
process was applied (Poerschmann et al. 2010).
53 Page 2 of 12 Water Air Soil Pollut (2016) 227:53

Ozonation, one of the advanced oxidation process- Ο3 − ⋅ þ Η2 Ο→⋅ΟΗ þ Ο2 þ ΟΗ− ; k 3

es (AOPs) based on highly active free radicals
(like ·OH), has been adopted for BPA removal ¼ 3  101 L mol−1 s−1 ðvon Gunten 2003Þ ð3Þ
and showed a great of efficiency (Rosenfeldt and
Linden 2004; Poerschmann et al. 2010). Sulfate − − 1
8 þ ⋅ΟΗ→ΗSΟ4 ⋅ þ SΟ4 ⋅ þ Ο2
S2 Ο2− ðAbu Amr et al: 2013Þ
radical (SO4− ·, E0 = 2.06 V) has raised extensive 2
attention in emerging compounds removal, as a ð4Þ
newest advanced oxidant (Poerschmann et al.
1
2010; Amr et al. 2014). Moreover, sodium persul- SΟ−4 ⋅ þ ⋅ΟΗ→ΗSΟ−4 þ Ο2 ðAbu Amr et al: 2013Þ ð5Þ
2
fate (Torres et al. 2007), peroxymonosulfate
(Kondrakov et al. 2014), and ammonium persulfate
ð6Þ
−
SΟ4 ⋅ þ ΟΗ− →SΟ2− þ ⋅ΟΗ; k 4 ¼ 6:5  107 M−1 s−1
(Guo et al. 2010) can be activated to produce 4

sulfate radical using several methods like
thermolysis (Kondrakov et al. 2014), transition
metal ions and iron catalysis (McCallum et al.
2000; Liang et al. 2004), ultrasound (Katsumata
et al. 2004), base activation (Janzen et al. 1992),
laser flash (Gao et al. 2012), H2O2, UV (De Laat
and Le 2005; Lau et al. 2007), and activated
carbon (Lau et al. 2007). Olmez-Hanci et al.
(2013) have studied the oxidation products and
toxicity of BPA degraded by persulfate, several
aromatic and a few aliphatic compounds could be
detected by gas chromatography/mass spectrometry
(GC/MS), like succinic acid. O3/H2O2 process is
demonstrated to be an effective AOP on the deg-
radation of organic contaminants and considering
the similar characteristic between H2O2 and per-
sulfate. It is practical to combine O3 and persulfate
constituting the O3/Na2S2O8 process for the oxida-
tive characteristics. With the composition of O3 in
S2O82− solution, it was possible to raise the con-
tent of ·OH, then lead to the generation of SO4−·
by activated S 2 O 8 2− (Abu Amr et al. 2013).
Compared to SO4− ·, · OH would non-selectively
react with most of the intermediates and therefore
weaken the BPA degradation, as shown in
Eqs. (1)–(8). As a product owing to the self-
decomposition of O3 in water, · OH could lead
to the generation of SO4−· improving the oxidizing
ability of this compound system.
Ο3 þ ΟΗ− →ΗΟ−2 þ Ο2 ; k 1 ¼ 7  101 L mol−1 s−1 ðvon Gunten 2003Þ
ð1Þ
Ο3 þ ΗΟ−2 →ΗΟ2 ⋅ þ Ο−3 ; k2
¼ 2:2  106 L mol−1 s−1 ðvon Gunten 2003Þ ð2Þ
ðAbu Amr et al: 2013Þ
S2 Ο2− þ
8 þ Η2 Ο2 →2Η þ 2SΟ4 þ Ο2 ðLau et al: 2007Þ
2−
ð7Þ
SO−4 ⋅ þ H2 O2 →Hþ þ SO2−
4 þ HO2 ⋅ ; k 5
¼ 1:2  107 M−1 s−1 ðDe Laat and Le 2005Þ ð8Þ
To our best known, there was virtually limited study
on the mechanism of O3/Na2S2O8 system or the degra-
dation pathways of targets like BPA. In this article, the
degradation of BPA in O3/Na2S2O8 system under vari-
ous conditions was comprehensively studied, including
initial concentrations of ozone and BPA and pH values.
Nine intermediate products were detected and the pos-
sible mechanism of BPA degradation was proposed.
2 Materials and Methods
2.1 Materials
Bisphenol A (C15H16O2, 99.0 %) was purchased from
TCI Development Co., Ltd (Shanghai, China) and meth-
anol for HPLC and HPLC-DPD-MS was obtained from
Sigma-Aldrich (Shanghai, China). All other chemicals
were analytical grade without further purification and
obtained from Chengdu Kelong chemical reagents Co.,
Ltd (Chengdu, China). The water used for the prepara-
tion of reagents and reaction solutions was purified by
Milli pore reverse osmosis (RO).
2.2 Experimental Procedure
A batch experiments were taken at 293 K, and O3/
Na2S2O8 oxidation experiments were performed in
Water Air Soil Pollut (2016) 227:53
500 mL-capacity glass containers as shown in Fig. 1. A
magnetic stirrer was used to ensure complete mixing at
the rate of 200 rpm during all experiment. The pH value
of the system was adjusted with phosphoric acid and
phosphate buffer solutions (0.1 M in all experiments),
and the species of free radicals were identified by adding
the probe materials of tertiary butyl alcohol (TBA) and
ethanol (ETOH). Samples (10 mL every time) were
withdrawn at regular time intervals and immediately
placed in a glass tube with 0.1 mL Na2SO3 (83.0 mM
in this study) to terminate the reaction. Replicate exper-
iments were conducted and the mean value was adopted
in the results.
2.3 Analytical Procedures
2.3.1 HPLC Measurements
BPA was determined using a high-performance liquid
chromatography (HPLC) (Shimadzu LC-10 ATVP)
equipped with a Diode-Array Detector (SPD-10A
single wavelength of ultraviolet detector) set at 278 nm
and Diamonsil chromatograph column (C18-
4.6 × 150 mm, 5.0 μm). The mobile phase containing
methanol and phosphate buffer solution with a volume
ratio of 60: 40 at the flow rate of 1.0 mL/min under
column temperature of 303 K.
2.3.2 HPLC/MS Measurements
The degradation intermediates and final products of
BPA were identified by liquid chromatography-mass
spectrometry (LC/MS) using Agilent Technologies sys-
tem (6120). Helium was used as the carrier gas at a
Fig. 1 The reactor device of O3/
Na2S2O8 oxidation experiments
Page 3 of 12 53
temperature of 623 K. Full scan mode was adopted to
analyze intermediate products. The mass spectrometer
was operated with negative mode electrospray ioniza-
tion for m/z (mass charge ratio) 80–300, and the disso-
ciation voltage was −30 eV.
3 Results and Discussion
3.1 Kinetic Model
As a critical part of the organic pollutant degradation in
water, the kinetic model of BPA degraded by O3/
Na2S2O8 process was established. Previously published
papers have been reported to determine second-kinetic
reaction constants between ozone with compounds (Yao
and Haag 1991; von Gunten 2003; Garoma and
Matsumoto 2009; Wen et al. 2011), and the rate of
BPA degradation can be written as follow:
d ½BPA
− ¼ k app ½BPA½O3  ð9Þ
dt
In our reaction process, BPA could be oxidized
through two pathways of direct ozonation and indirect
radical oxidation (Keykavoos et al. 2013), and the ap-
parent rate constant kapp can be applied to describe the
comprehensive influence on degradation as Eq. (10):


k app ¼ k ′′O ½O3  þ k ′′⋅ OH ½⋅OH þ k ′′SO− ⋅ SO−4 ⋅
3 4
′′
þ k others ½others ð10Þ
Where k^ is the second-kinetic reaction constant of
relevant oxidant, and k^others is the kinetics reaction
53 Page 4 of 12 Water Air Soil Pollut (2016) 227:53

constant of other oxidant like HO2· and HSO5−. It could

be inferred that the proportion of other oxidants was
small, thus the effect on the degradation could be ig-
nored. In addition, the change of ·OH and SO4−· was
along with O3 as shown in Eqs. (1)–(4). Hence, Eqs. (9)
and (10) could be simplified to Eqs. (11) and (12):
 
k app ¼ k ′′O þ k ′′⋅ OH ⋅k ′′O ⋅OH þ k ′′SO ⋅ ⋅k ′′O SO ⋅ ½O3 
3 3; 4 3; 4

′
¼ k app ½O3  ð11Þ

d ½BPA
− ¼ k app ½BPA½O3  ¼ k ′app ½BPA½O3 2 ð12Þ
dt
After integrated, Eq. (12) can be converted to
Eq. (13):
Z
½BPAt 0
−ln ¼ k app ½O3 2 dt ð13Þ
½BPA0

At the beginning of reaction, the O3 concentration

was excessive compared with BPA, and the concentra-
tion of O3 could be seen as constant during the first 40 s,
so Eq. (13) could be converted to Eq. (14), which
indicates that the degradation of E3 by O3/Na2S2O8
process follows the pseudo-first-order kinetic model.

½BPAt
−ln ¼ k ″app t ð14Þ
½BPA0

3.2 Effects of O3 and Na2S2O8 Concentrations

A series of experiments were conducted at an initial pH

of 7.0 with 5.0 mg/L BPA. The adding concentrations of
O3 were 0.5, 1.0, and 2.0 mg/L. The mole ratio of BPA/
Na2S2O8 was 1:10, 1:25, and 1:50.
As illustrated in Fig. 2, the removal of BPA ascended
with the increased of O3 concentration and Na2S2O8
exhibited different impacts for varies of O3 concentra-
tions. At the experimental reaction conditions, the incre-
ment on initial BPA degradation (2 min) removal was
approximately 1.5-fold as the initial ozone concentra-
tion increased from 0.5 to 1.0 mg/L. Then, with the
concentration of O3 further increased to 2.0 mg/L,
Na2S2O8 made an inhibition on the degradation of
BPA. This might be attributed to the excessively high
concentration of O3, it decomposed to a large number of Fig. 2 Different mole ratios of BPA/Na2S2O8 on BPA degradation
·OH existed in the solution. As shown in Eq. (5), the under initial concentration of O3 at a 0.5, b 1.0, and c 2.0 mg/L
Water Air Soil Pollut (2016) 227:53
excessive ·OH would annihilate with SO4−· leading to
the inhibition of BPA degradation, which became stron-
ger with the increase of Na2S2O8 dosage. Depending on
the report of Salem et al. (Abu Amr et al. 2013), Eqs. (4)
and (5) could be promoted by the existing of excessive
S2O82−, leading to the consumption of ·OH and the
inhibition of BPA degradation, so the removal of BPA
decreased with the dosage of Na2S2O8 increased.
Theoretically, increasing S2O82− concentration should
generate more SO4−· and lead to the removal of BPA
increase. However, the experiment suggested the oppo-
site results as shown in Fig. 2. It was consistent with
other researchers, Tizaoui et al. (2007) found that land-
fill leachate COD removal and BOD5/COD did not
increase with the increase of H2O2 concentration in the
system of O3/H2O2, uniformly, increasing S2O82− would
change its role from being initiator for the produc-
tion of SO4−· and ·OH to the inhibitor of O 3
decomposition through Eqs. (1)–(8). As shown in
Eqs. (15)–(18), the excess sulfate radicals would
recombine and react with other intermediates lead-
ing to the generation of some radicals with
lower redox potential like . SO 5 − , . S 2 O 8 − and
HSO4−, which would reduce the oxidation capacity
of O3/Na2S2O8 system.
SΟ−4 ⋅ þ SΟ−4 ⋅→S2 Ο2−
8 ; k6
¼ 4:0  108 M−1 s−1 ðLau et al: 2007Þ ð15Þ
⋅SΟ−4 þ ΗSΟ−5 →⋅SΟ−5 þ ΗSΟ−4 ; k 7
< 105 M−1 s−1 ðDe Laat and Le 2005Þ ð16Þ
SΟ−4 ⋅ þ S2 Ο2− −
8 →SΟ4 þ S2 O8 ⋅; k 8
2−
¼ 6:1  105 M−1 s−1 ðLau et al: 2007Þ ð17Þ
SO−4 ⋅ þ HO2 ⋅→SO2− þ
4 þ H þ O2 ; k 9
¼ 3:5  109 M−1 s−1 ðLau et al: 2007Þ ð18Þ
3.3 Effect of pH and BPA Dosages
Previous studies have shown that the types of radicals
and the corresponding concentrations are much
Page 5 of 12 53
dependent on the reaction pH for AOPs (Gao et al.
2012). Several pH values (3.0, 7.0, and 9.0) were ap-
plied in order to examine the influence of pH on the
BPA degradation in O3/Na2S2O8 system. Based on the
results in Section 3.2, 1.0 mg/L O3 and 260 mg/L
Na2S2O8 were selected for the oxidation.
As shown in Fig. 3, at pH = 3, the lower concentra-
tion of BPA made the higher removal rate. After reacting
20 min, the removal rate of BPA reached 58.58, 41.28,
and 38.59 % with the initial concentration was 2.0, 5.0,
and 10.0 mg/L, respectively. Under acidic condition,
few ·OH is generated by O3 system, however, under this
condition SO4−· can be produced through the asymmet-
ric break of –O–O– bond by acid activated S2O82−
(Eq. (19)) (De Laat and Le 2005). According to the
literature (Kolthoff and Miller 1951), the activation
energy of S2O82− is 33.5 kcal in the non-catalytic reac-
tion, while it is 26.0 kcal in acid catalyzed reaction,
which confirmed the high removal of BPA in lower
pH conditions.
þ − −
S2 Ο2−
8 þ Η →ΗSΟ4 þ SΟ4 ⋅ ð19Þ
At pH = 7, the removal of BPA was lower than that of
pH = 3. Under neutral condition, the faster declination of
O3 leading to the decrease of direct oxidation of the
target compound, while the generation of ·OH and
SO4−· ascend through chain reactions. Salem’s research
in leachate treatment by O3/Na2S2O8 obtained the same
result, COD removal was 65 % at pH 3 higher than 56 %
at pH 6.5 (Abu Amr et al. 2013).
At pH = 9, the removal of BPA was higher than that in
neutral and acidic conditions. After reacting 20 min, the
removal of BPA rose to 63.59, 39.82, and 39.26 % for
the concentration at 2.0, 5.0, and 10.0 mg/L, this was
attributed to the more ·OH resulting from O3 decompo-
sition and transformation from Eq. (6). Besides, the
alkaline condition can activate persulfate to H2O2 and
·SO4− demonstrated by Furman et al. (2010) leading to
the slow decomposition at the later stages of the batch
reactor.
The pH effect was in agree with Lau’s conclusion
(Lau et al. 2007), in which persulfate activated by ultra-
violet (UV) was used to degrade butylated
hydroxyanisole (BHA), and the results showed that the
removal efficiency in alkaline condition was higher than
that of the acidic and neutral conditions. SO4−· generat-
ed from the oxidation pyrolysis of peroxide bonds in
persulfate leaded to the production of ·OH in basic
53 Page 6 of 12 Water Air Soil Pollut (2016) 227:53

solutions and improved the oxidability of this complex

system. However, in acidic condition, S2O82− reacted
with H2O to generate ·OH, and ·OH combined with each
other to produce H2O2, which consumes a large number
of active free radicals. Besides, in acid system SO4−·
could react with S2O82− to generate various of interme-
diates with lower oxidizing capacity like HS2O8− and
H2S2O5, as shown in Eqs. (20)–(24) (McElroy and
Waygood 1990; McCallum et al. 2000; Liang et al.
2004).
SO−4 ⋅ þ H2 SO4 →HSO4 ⋅ þ HSO−4 ð20Þ

Hþ þ S2 O2− −
8 →HS2 O8 ð21Þ

HS2 O−8 →HSO−4 þ SO4 ð22Þ

ΗS2 Ο−8 þ Η2 Ο→ΗSΟ−4 þ Η2 SΟ5 ð23Þ

H2 SO5 þ H2 O→H2 SO4 þ H2 O2 ð24Þ

The initial degradation of BPA could be depicted
using pseudo-first order kinetics as shown in the inner
graphs of Figs. 2 and 3 at first 40 s, and the kinetic
parameters of BPA at different conditions in O3/
Na2S2O8 system were shown in Table 1.

3.4 Free Radicals Identification in O3/ Na2S2O8 Process

According to previous studies, a large number of free

Fig. 3 Effects of BPA dosages on BPA degradation when pH
were a 3, b 7, and c 9
radicals existed in the solutions based on the SO4−· chain
reactions, and the main radicals were SO4−· and ·OH.
Under acidic condition (pH = 2–7), the main free radical
species of system is SO4− ·; under neutral and weak
alkali conditions (pH = 9), they are ·OH and SO4− ·;
under basic conditions (pH 12 or higher), · OH played
a main role in solutions (Lau et al. 2007). In order to
study the mechanism of BPA degradation under differ-
ent pH, ETOH and TBA were used as two probes to
identify the existed free radicals in solutions. The reac-
tion rate constant of ETOH reacting with SO4−· is (1.6–
7.7) × 108 M−1 s−1, which is comparative to (1.2–
2.8) × 109 M−1 s−1 for ·OH, while the reaction rate
constant of TBA reacting with SO 4 − · is (4–
9.1) × 105 M−1 s−1, it’s far less than that with ·OH, which
is (9.8–7.6) × 108 M−1 s−1 (Braga et al. 2005). It meant
Water Air Soil Pollut (2016) 227:53 Page 7 of 12 53

Table 1 Kinetic parameters of BPA at different conditions in O3/Na2S2O8 system

Number Initial pH O3 concentration Mole ratios of BPA dosage kapp Half-life period r2
(mg/L) BPA/Na2S2O8 (mg/L) (min−1) (t1/2)

1 7.0 0.5 1:10 5.0 0.0084 82.518 0.9558

2 7.0 0.5 1:25 5.0 0.0098 70.729 0.9487
3 7.0 0.5 1:50 5.0 0.0112 61.888 0.9560
4 7.0 1.0 1:10 5.0 0.0080 86.643 0.9490
5 7.0 1.0 1:25 5.0 0.0127 54.579 0.9528
6 7.0 1.0 1:50 5.0 0.0141 49.159 0.9678
7 7.0 2.0 1:10 5.0 0.0149 46.520 0.9903
8 7.0 2.0 1:25 5.0 0.0138 50.228 0.9896
9 7.0 2.0 1:50 5.0 0.0146 47.476 0.9804
10 3.0 1.0 1:50 2.0 0.0099 70.015 0.9582
11 3.0 1.0 1:50 5.0 0.0100 69.315 0.9844
12 3.0 1.0 1:50 10.0 0.0079 87.740 0.9553
13 7.0 1.0 1:50 2.0 0.0138 50.228 0.9447
14 7.0 1.0 1:50 10.0 0.0090 77.016 0.9475
15 9.0 1.0 1:50 2.0 0.0093 74.532 0.9531
16 9.0 1.0 1:50 5.0 0.0055 126.027 0.9602
17 9.0 1.0 1:50 10.0 0.0060 115.525 0.9535

that by comparing TBA with ETOH, the main oxidants
in the composite system can be identified.
These experiments were conducted at several pH
values (3.0, 7.0, and 9.0) with an initial O3 concentration
of 1.0 mg/L, 2.0 mg/L BPA, and mole ratio 1:50 for
BPA/Na2S2O8, and the effects of ETOH on BPA degra-
dation differed from TBA at different pH values were
shown in Table 2 and Figs. 4, 5, and 6. In general,
adding ETOH could inhibit the reaction, while adding
TBA made a complex impact. On the other hand, with
the increase of pH, the effects of ETOH and TBA on
BPA degradation gradually descended.
At pH = 3, when 0.5 mM ETOH was added, the
removal of BPA went down compared to the control
experiment and with the increase of ETOH, the inhibi-
tion strengthened, after reacting for 20 min. The initial
reaction rate of BPA degradation in 2.0 mM ETOH
system was 0.551 × 10−7 M s−1, which was 61.20 %
smaller than that for the control experiment. The main
reason was that ETOH had a high reactivity with both
·OH and SO4−· which could make competition, effect
with BPA.
At pH = 3, TBA had a significant promotion on BPA
degradation in the system of O3/Na2S2O8. After reacting
20 min, when adding 0.5 mM TBA in the solutions, the
initial reaction rate of BPA degradation, it was 48.94 %
larger than that for the control experiment. When the
dosages of TBA were 1.0 and 2.0 mM, the initial

Table 2 Effect of ETOH and TBA on initial reaction rate of BPA degradation under different pH values (×10−7 M s−1)

pH Control ETOH TBA

0.5 mM 1.0 mM 2.0 mM 0.5 mM 1.0 mM 2.0 mM

3 1.420 1.258 1.313 0.551 2.115 2.363 2.357

7 1.384 1.023 0.950 0.451 1.868 1.864 1.852
9 0.732 0.693 0.839 0.320 0.801 1.117 1.046
53 Page 8 of 12
Fig. 4 Effects of ETOH and TBA on BPA degradation (pH = 3)
reaction rates of BPA degradation increased to
2.363 × 10−7 M s−1 and 2.357 × 10−7 M s−1, it indicating
that lower concentration TBA will greatly promote the
reaction, while high dose TBA resulted to the declina-
tion of promotion effect. The reason might attribute to
the great difference of the reaction capacity for TBA
with ·OH and TBA. When the dosage of TBA was
small, the capture of ·OH would inhibit the Eq. (4) and
avoid the annihilation among radicals. While the dosage
of TBA exceeded a certain amount, a large proportion of
·OH can be captured resulting in the declination of
oxidants amount. However, TBA still played a promo-
tional role in the system of O3/Na2S2O8 indicating the
main free radical of solution was SO4−· in this case.
Fig. 5 Effects of ETOH and TBA on BPA degradation (pH = 7)
Water Air Soil Pollut (2016) 227:53
At pH = 7, ETOH and TBA showed a similar impact
on the degradation of BPA. After reacting 20 min, com-
pared to the control test, the initial reaction rates of BPA
degradation were 34.97, 34.68, and 46.80 % larger for
the dosages of TBA was 0.5, 1.0 and 2.0 mM.
Nevertheless, at pH = 9, the inhibition of adding
ETOH to reaction reduced significantly, after reacting
20 min, and adding 0.5, 1.0, and 2.0 mM ETOH, rela-
tively to blank experiment, the removal of BPA reduced
0.56, 0.001, and 3.15 %. When dosages of TBA were
1.0 and 2.0 mM, the maximum removal of BPA had
increased 29.77 and 28.02 % indicating that lower con-
centration TBA will greatly promote the reaction, while
high dose TBA resulted to the declination of promotion
Water Air Soil Pollut (2016) 227:53 Page 9 of 12 53

Fig. 6 Effects of ETOH and TBA on BPA degradation (pH = 9)

Table 3 Intermediates of BPA degradation by the system of O3/Na2S2O8

Molecular weight
Compound Icon peak Molecular structure Reference
(g/mol)

(Peller, Mezyk et al.

BPA Catechol 244 243 2009), (Guo, Ge et al.
2010)

(Torres, Nieto et al.

BPA Dicatechol 260 259
2008)

(Kondrakov, Ignatev et
Quinone derivative 242 241
al. 2014)

4-(1-hydroxypropan-2-yl) (Katsumata, Kawabe et

152 152
catechol al. 2004)

(Poerschmann, Trommler
P-isopropenyl phenol 134 134 et al. 2010), (Torres,
Abdelmalek et al. 2007)

(Poerschmann, Trommler
4-Hydroxybenzyl Alcohol 124 124
et al. 2010)

(Janzen, Kotake et al.

p-hydroxy benzaldehyde 122 121
1992)

(Poerschmann, Trommler
Succinic acid 118 118
et al. 2010)
53 Page 10 of 12
Fig. 7 Degradation pathway of BPA in the system of O3/Na2S2O8
effect. It indicated that in this case, except SO4− ·, the
proportion of other free radicals started to increase, and
in general, the proportion of total free radicals of reac-
tion system had declined.
3.5 Exploration of Degradation Mechanism
According to previous studies (Kondrakov et al. 2014)
and the intermediates identified by HPLC-DPD-MS
shown in Table 3, a series of products (like succinic
acid, carboxylic acid, and quinonoid derivants) were
generated on the degradation of BPA using O 3 /
Na2S2O8 process.
As shown in Fig. 7, the suggested degradation
in pathway of BPA by the system of O3/Na2S2O8
was inferred. BPA could be attacked by ·OH or
SO 4 − · to generate product B1, B2, and B3.
Product B1 was the primary product of BPA, and
then further oxidized to form product B6 and B7,
the groups on the para-position to the phenolic
hydroxyl group in the benzene ring were easily
oxidized by ·OH to form product B8. And it was
the same for product B2 to form product B8, it
was coincided with the mechanisms of Hideyuki
Katsumata (Katsumata et al. 2004). As for product
B3 to generate product B4 and product B5, ·OH
played an important role in this process from the
report of Kondrakov et al. (2014). After a series of
Water Air Soil Pollut (2016) 227:53
oxidation, all of these intermediate products could
be degraded to small molecules like succinic acid.
4 Conclusions
In this study, the BPA degradation by the system
of O3/Na2S2O8 was extensively studied. It was
demonstrated that the degradation rate of BPA
fitted to the pseudo-first order kinetics model
and strongly affected by several factors including
the initial concentrations of O3 and Na2S2O8, dos-
age of BPA and the pH value. The obtained
optimum conditions included a reaction pH 9,
1.0 mg/L O3, 1:50 BPA: Na2S2O8 and 2.0 mg/L
BPA. The removal of BPA went up to 62.43 %
after reacting 20 min. The results showed that the
main radical of system was SO4−· at acidic con-
dition (pH = 3), while the quantity of ·OH increase
with the pH value ascend. Eight intermediates
were identified using HPLC-DPD-MS, most of
which are quinonoid derivants and some cleavage
products indicating the incomplete mineralization.
However, the toxicity of these intermediates in the
system needs further investigation to optimize
BPA degradation and other EDCs in the water
using O3/Na2S2O8 system.
Water Air Soil Pollut (2016) 227:53
Acknowledgments This work was financially supported by Na-
tional Natural Science Foundation of China (NO. 51508354),
Sichuan Provincial Environmental Protection Office (NO.
2013HB08), and Science Foundation for The Excellent Youth
Scholars of Sichuan University (NO. 2082604174048). The au-
thors are thankful to all the anonymous reviewers for their insight-
ful comments and suggestions.
Compliance with Ethical standards
Conflict of Interest The authors declare that they have no
competing interests.
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