Chemical Engineering Journal 276 (2015) 193–204

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Oxidative removal of Bisphenol A by UV-C/peroxymonosulfate (PMS):

Kinetics, influence of co-existing chemicals and degradation pathway
Jyoti Sharma a, I.M. Mishra a,⇑, Dionysios D. Dionysiou b,⇑, Vineet Kumar a,c
a
Department of Chemical Engineering, Indian Institute of Technology, Roorkee, Roorkee 247667, India
b
Environmental Engineering and Science Program, Department of Biomedical, Chemical and Environmental Engineering (DBCEE), 705 Engineering Research Center,
University of Cincinnati, Cincinnati, OH 45221-0012, United States
c
Present Address: Department of Chemical Engineering, Indian School of Mines, Dhanbad, Jharkhand, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 UV activated PMS oxidation is

effective for BPA oxidation and
mineralization.
 BPA degradation rate is not affected
by Cl (5 mM), but it is adversely
affected by HCO3 and HA.
 The possible radical adduct formation
and degradation pathway are also
proposed.
 The proposed pathway supports
sulfate radical attack as the main
route.

a r t i c l e i n f o a b s t r a c t

Article history: In the present study, a sulfate radical-based advanced oxidation process was applied for the degradation of
Received 25 December 2014 an industrial chemical and suspected endocrine disruptor, Bisphenol A (BPA). UV-C (k = 254 nm; 40 W
Received in revised form 1 April 2015 power; Io = 1.26 lE s1) activated peroxymonosulfate (PMS) was used as an oxidant. The effect of operating
Accepted 2 April 2015
parameters (initial concentration of BPA, dose of PMS, initial solution pH (pHo), and water matrix compo-
Available online 9 April 2015
nents such as chloride (Cl), bicarbonate (HCO 3 ) ions and humic acid (HA) was evaluated. At the initial pH
of reaction mixture (5.15) and room temperature (29 ± 3 °C), the optimum dosage of PMS was found to be
Keywords:
0.66 mM, giving a BPA removal of 96.7 ± 0.05% and a total organic carbon (TOC) removal of 72.5 ± 0.05%
Advanced oxidation process (AOP)
Humic acid
after 360 min of irradiation. With an increase in initial BPA concentration and PMS dosage greater than
Pathway 0.66 mM, the BPA and TOC removal decreased. The extent of BPA removal increased with an increase in
Peroxides pHo (3 6 pHo 6 12) of the reaction mixture. The degradation of BPA followed pseudo-first-order kinetics
Peroxymonosulfate (PMS) and the apparent first order rate constant for BPA was found to be 0.025 min1 at the optimum oxidation
Persulfate conditions (CBPA = 0.22 mM, CPMS = 0.66 mM, pH = 5.15, temperature = 29 ± 3 °C). The Cl ions have negli-
gible inhibition effect on the BPA removal. However, the HCO 3 and HA inhibited the BPA oxidation under
UV-C irradiation. The identification of intermediates and final products was carried out with HPLC, GC/MS
and FTIR, and a degradation pathway was proposed. The present study reveals that the UV-C/PMS oxidation
process is effective for BPA removal under real water/wastewater conditions.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction

⇑ Corresponding authors. A growing number of contaminants are entering water bodies

E-mail addresses: immishra49@gmail.com, imishfch@iitr.ac.in (I.M. Mishra),
ranging from traditional heavy metals to emerging micropollutants
dionysios.d.dionysiou@uc.edu (D.D. Dionysiou). such as natural hormones, pesticides, pharmaceuticals and

http://dx.doi.org/10.1016/j.cej.2015.04.021
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
194 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204
industrial chemicals. Bisphenol A (BPA) is an industrial chemical
which is largely used in the production of various items such as
epoxy resins, polycarbonate, etc. It is identified as an endocrine
disrupting chemical (EDC), and it finds its way in the water bodies
either directly or indirectly via degradation of various BPA contain-
ing materials such as plastic bottles, containers, toys, food/soft
drink cans, packaged food, etc. [1–3]. The presence of EDCs in the
water bodies affects the aquatic lives and other life-forms through
consumption of contaminated water [4]. The concentration of BPA
in water/wastewaters can be as low as 0.01 lg/L to as high as
17 mg/L in some industrial effluents and landfill leachates
[2,3,5,6]. It has affinity to estrogen acceptor and thereby induces
feminization in a number of aquatic organisms [7,8]. The United
States Environmental Protection Agency (USEPA) and the
European Food Safety Authority (EFSA) set a reference dosage of
50 lg/kg body weight/day of BPA for human consumption [9].
Conventional physical–chemical water treatment processes
such as adsorption, filtration, chlorination, and coagulation/floccu-
lation as well as biological processes are not able to remove BPA
from water satisfactorily, they rather transfer it from one phase
to another (adsorption, filtration, coagulation/flocculation) [10].
The limitations of conventional processes to remove BPA have
led to efforts to explore alternative methods such as advanced oxi-
dation processes (AOPs). A number of AOP studies described
Fenton/photo-Fenton degradation [11,12], sonochemical degrada-
tion [13], photochemical/photocatalytic oxidation [14–16], ozona-
tion [17], and hybrid processes [18,19] for BPA removal from
water.
The AOPs are based on highly reactive species such as hydroxyl
(HO) and/or sulfate (SO 4 ) radicals. These radicals are capable of
degrading the organic molecules and yielding intermediates and
CO2. Radical species can be produced mainly from the thermal,
UV and transition metal activation of oxidants such as hydrogen
peroxide, persulfate (PS) and peroxymonosulfate (PMS).
PS and PMS are comparatively newer oxidants in surface water
treatment applications, but they have long been used as in-situ
chemical oxidation agents in ground water applications. PS and
PMS were used by researchers for the removal of pharmaceuticals
[20], herbicides [21], phenols [22], perfluorinated compounds [23],
disinfection of Escherichia coli [24] and chlorinated compounds
[25,26] in water treatment and groundwater remediation.
PS and PMS are favored for use in environmental remediation
applications because of their easier activation and higher stability
than that of hydrogen peroxide under typical water/ground water
treatment conditions [27]. The high standard reduction potential
(2.5–3.1 V) of SO4 radicals and wider operating pH range [28,29]
makes SO 4 radicals comparatively more effective and selective
for oxidation of target compound in water/wastewater treatment
[30–33].
PMS is a triple salt of potassium monopersulfate
(2KHSO5KHSO4K2SO4), a product manufactured by DuPont, and
available commercially as OXONEÒ. PMS is considered to be a
green oxidant because it is benign, as are most of the byproducts
of its reactions [34]. The decomposition rate of organic compounds
with PMS at room temperature is low, but it can be enhanced
through activation by photolysis or thermolysis (Eq. 1) or by using
transition metals such as cobalt (Eq. 2), thereby producing highly
reactive SO 
4 and HO radicals
hv=D
HSO5 ƒƒƒƒƒ! SO
4 þ HO

ð1Þ
HSO5 þ Metal ion ðMn Þ ! Mnþ1 þ SO
4 þ OH

ð2Þ
Cobalt/PMS is reported to have higher rate of degradation than
Cobalt/H2O2 system. Cobalt can effectively activate PMS and gener-
ate SO
4 radicals at enhanced rate, which in turn gives higher rate
of degradation than the Cobalt/H2O2 system [35]. Some dissolved
metal ions used for activation of oxidants in water/wastewater
treatment may lead to several health problems such as asthma,
pneumonia, and other lung ailments [32,36–38]. However, the
use of UV irradiation is considered to be environment-friendly.
PMS is slightly more powerful than hydrogen peroxide as an oxi-
dant (Eo(HSO 
5 /HSO4 ) = +1.82 V; Eo(H2O2/H2O) = 1.76 V) [39].
When irradiated by a low pressure mercury lamp (k = 254 nm),
PMS generates SO 
4 and HO radicals through the cleavage of
peroxide bond [40,41], as explained by Eq. (1), and subsequently
produces SO2 + 
4 , H and HO species through reaction with water
(Eq. 3):
þ 2
SO
4 þ H2 O ! H þ SO4 þ HO

ð3Þ
Several studies reported on the effect of water matrix compo-
nents such as natural organic matter (NOM) and alkalinity (carbon-
ate/bicarbonate) on the degradation of target compounds by AOPs.
NOM represents a complex mixture of naturally occurring
organic compounds in the surface and ground water. Humic acid
(HA) is generally used as a representative NOM [13,16,42]. The
effect of water matrix components on the oxidation process is
poorly understood. It is assumed traditionally that they have neg-
ative impact on the reaction system [30]. However, a few studies
showed that the presence of water matrix components enhances
the efficiency of the sulfate radical-based AOPs and reduces the
efficiency of HO radical-based AOPs under real water treatment
conditions [43,44]. The composition of HA is source-dependent
and varies greatly. Therefore, its impact on the oxidation of the tar-
get compound may sometimes be confounding, depending on its
source, the method of oxidation used for the target compound,
and the presence and composition of various other water matrix
components [45,46].
The reaction intermediates and degradation products play a
crucial role in the toxicity of treated water. Some studies have
reported on the byproducts of AOPs during/at the end of the pro-
cess [11,12,47,48]. The mechanism of degradation and the forma-
tion of intermediates and byproducts have been studied mostly
for HO radical-based processes. Not much has been reported on
these aspects for the UV-C activated PMS-based AOP for the treat-
ment of BPA contaminated water.
The present study, reports on the degradation of 0.22 mM
(50 mg/L) BPA solution by UV-C/PMS AOP under natural reaction
mixture pH and room temperature conditions. The optimum
dosage of PMS was used for the mineralization and degradation
of BPA. The effects of pHo and water matrix components
(Cl, HCO3 and HA) on the removal of BPA were also studied.
The intermediates and the end-products were analyzed and identi-
fied by GC–MS and FTIR spectroscopy, and a reasonable degrada-
tion pathway is also proposed.
2. Experimental
2.1. Reagents and chemicals
Bisphenol-A (BPA, CAS 80-05-7), molecular weight = 228 with a
purity >99% was purchased from Sigma Aldrich and used as
received. PMS, anhydrous sodium sulfate, HA (sodium salt),
dichloromethane and NaHCO3 were obtained from Hi Media,
Mumbai; acetonitrile (>99% purity) from Merck India and NaCl
and NaOH were obtained from RFCL, New Delhi. Sulfuric acid
(H2SO4) was purchased from Fine Chemicals, New Delhi. Ethanol
and tert-butyl alcohol (TBA) were obtained from Merck (India)
and Loba Chemie (Mumbai), respectively. A quenching agent,
sodium thiosulfate (Na2S2O35H2O, 99.5%) (New India Chemical
Enterprises, Kochi) was used to stop the reaction in the sample.
Millipore water was used from laboratory (Milli-Q Biocel) system.
 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204
2.2. Batch experiments
The present study was conducted using a borosilicate glass
photo-reactor (1 L). 450 mL of BPA (0.22 mM or 50 mg/L) aqueous
solution was irradiated by using 5  8 W low pressure mercury
UV-C light (k = 254 nm). The radiation intensity as measured by
ferrioxalate actinometry was 1.26 lE s1. A magnetic stirrer and
a cooling fan system were used for proper mixing and cooling dur-
ing the degradation experiments. Initial pH of the BPA solution and
the room temperature at the time of experimentation were 6.2 and
29 ± 3 °C, respectively. The degradation experiments were con-
ducted for 360 min under these conditions. Based on preliminary
tests, 1 mL sodium thiosulfate solution (1 M) per mL of sample
was used to quench the reaction. During the reaction, a solid pro-
duct was also detected. The quenched sample was filtered through
a 0.20 lm syringe filter (Axiva, India). The filtrate was used for
HPLC analysis and the filtered solid matter was subjected to FTIR
analysis. The experiments were carried out at the natural pH of
the reaction mixture except during the studies on the effect of ini-
tial pH on degradation. In such experiments, the initial pH of the
solution was adjusted using 0.1 N NaOH or 0.1 N H2SO4, as
required. Control experiments were carried out in the dark as well
as in the absence of PMS. A loss of 9.78% of BPA was detected under
UV-C irradiation in the absence of PMS, while up to 42% BPA was
removed by PMS alone at the room temperature (29 ± 3 °C) and
natural reaction mixture pH of the system without UV-C, as the
PMS gets activated by temperature also [49].
2.3. HPLC measurements
The BPA concentration in the filtrate was determined by HPLC
(Waters India), equipped with a C18 column (3.9 mm  150 mm)
and a UV detector set at 276 nm. The mobile phase was the mixed
solvent of acetonitrile (HPLC grade) and water (50/50; v/v) at a
flow rate of 1 mL/min.
2.4. Other measurements
A TOC analyzer (TOC-VCPH, Shimadzu) and a pH meter
(Cyberscan 510 pH) were used to determine the total organic car-
bon (TOC) and pH of the treated samples (filtrate), respectively.
The samples were quenched by using 1 M sodium thiosulfate aque-
ous solution before TOC analysis. FTIR spectral measurements of
the solid product were carried out using a Thermo Nicolet (model
Magna 760) instrument (the details of the method are reported in
the Supporting Information Material) for the identification of func-
tional groups [50]. All the experiments were carried out in tripli-
cate and the average values are reported with the error bars
representing 95% confidence of interval.
2.5. GC/MS analysis
The analysis of the products was carried out by a GC/MS (Clarus
-680 model GC with Elite 5-MS, 30 m  0.25 mm capillary column
coupled with Clarus SQ8C model MS; Perkin Elmer, USA). Helium
was used as the carrier gas at a flow rate of 1.5 mL/ min. One
microliter aliquot samples were injected at 220 °C in splitless
mode. The temperature program for GC followed the sequence:
start at 40 °C, hold for 5 min; 40–200 °C (10 °C/min), hold for
5 min; 200–230 °C (5 °C/min), hold for 5 min. The transfer line
and ion source temperature were maintained at 200 °C and
170 °C, respectively. Qualitative analysis was performed in the
electron impact (EI) mode at 70 eV using the full scan mode in
the m/z range of 40–500 amu. The unknown peaks were identified
using the library of Wiley and NIST. Dichloromethane (DCM) was
used as the solvent to extract the BPA and the organic products
195
of the oxidation process (the details of the extraction method are
reported in Supporting Information Material) [51,52].
2.6. Identification of dominant radicals
In order to understand the principal oxidation radicals, HO or
SO
4 or both effecting the degradation of BPA, ethanol and TBA
were used as scavenging agents for HO and SO 4 radicals
[31,15,53]. The scavenger, oxidant and BPA were used in the molar
ratio of 200:1:1. The radical identification studies were conducted
at optimum conditions (CBPA = 0.22 mM, CPMS = 0.66 mM,
t = 360 min), but with excess of the scavenging agent [15].
3. Results and discussion
3.1. Effect of PMS dosage
From Fig. 1, it is seen that 96.7% BPA was removed in 360 min
reaction time when no scavenger was used. However, in the pres-
ence of ethanol, the BPA removal decreased to 35% only. In the
presence of TBA, the BPA removal was 85%. The scavenging rate
constants for ethanol vary from 1.2 to 2.8  109 M1 s1 for HO
and from 1.6 to 7.7  107 M1 s1 for SO 4 [31,53]. For TBA, the
rate constant is approximately 1000 fold greater for HO (3.8–
7.6  108 M1 s1) than that for SO (4–9.1  105 M1 s1)
4
[31,53].
The ratio of scavenging rates of oxidant radicals by ethanol and
TBA varies between 1.3 and 3.5 for HO radicals and between 18
and 200 for SO4 radicals. The scavenging by ethanol is about one
order of magnitude faster for HO radicals and about two orders
of magnitude faster for SO4 radicals than the scavenging rates of
the respective radicals by TBA. Therefore, the BPA degradation is
much lower in the presence of ethanol than that for TBA. In the
case of TBA, SO4 radicals are scavenged at much lower rate than
HO radicals, and thus, the SO 4 radicals present in the reaction
mixture are responsible for BPA degradation.
This behavior can also be explained by calculating the utiliza-
tion efficiency of PMS after 360 min of reaction. The inset of
Fig. 1 shows an insignificant utilization efficiency of PMS (9%)
due to poor degradation of BPA (35%), and a high consumption
of PMS because of high reaction rates of ethanol with SO 4 and
Fig. 1. Effect of scavengers on the degradation of BPA at 29 ± 3 °C: —d— [PMS/BPA],
—s— [TBA/PMS/BPA], —.— [ethanol/PMS/BPA], (Inset: PMS utilization efficiency
for different systems at 360 min of reaction time).
196 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204
HO radicals. In the presence of TBA, the PMS utilization efficiency
increases to 55%, while the PMS utilization efficiency increases to
92% in the absence of alcohol (scavenging agent).
The higher removal of BPA in the presence of TBA in comparison
to ethanol explains the selectivity of SO
4 radicals for BPA degrada-
tion. The maximum efficiency in alcohol-free system explains the
dominance and selectivity of SO 4 radicals [54]. Wang et al. [55]
also reported >90% utilization efficiency of PMS for As(III) removal
from groundwater at As(III)/PMS molar ratio of 1:2.
Fig. 2 shows the effect of PMS concentration (0.16 < CPMS
< 1.62 mM) on the degradation of BPA. The experiments at room
temperature (29 ± 3 °C) showed 42% removal of BPA without
UV-C irradiation. This means that the PMS was thermally
activated [49], and therefore, it also partly contributed to the
removal of BPA. The removal of BPA increased from 64.2% to
96.7% when the CPMS was increased from 0.16 mM to 0.66 mM.
At CPMS > 0.66 mM, the incremental removal of BPA was not
significant. This is because of the scavenging of SO 4 and HO

radicals by HSO 
5 , and the formation of less reactive SO5 radicals
[56]:
HSO5 þ HO ! SO
5 þ OH

ð4Þ
HSO5 þ SO
4 ! SO2
4
þ
þH ð5Þ
Thus, the optimum CPMS was found to be 0.66 mM. Wang and
Chu [41] also observed a similar trend during the degradation of
2,4,5-trichlorophenoxy acetic acid (0.1 mM) by UV activated PMS
in the presence of iron. Ji et al. [57] also found that the CuO acti-
vated PMS is effective at 1.5 mM PMS with 100% phenol (50 mg/
L) removal and 86% TOC removal in 60 min. The phenol removal
efficiency decreased when PMS dosage was 1.25 mM.
The degradation of BPA by UV-C/PMS system can be explained
by pseudo-first order reaction kinetics (ln(C/C0) = kt) [19,44].
The nonlinear regression analysis shows a good fit to the experi-
mental data during the initial 60 min of reaction time (inset of
Fig. 2). The apparent first order rate constant for the removal of
BPA at its initial concentration of 0.22 mM, varied from
0.003 min1 to 0.025 min1 with an increase in the PMS dosage
from an initial 0.16 mM to an optimum dosage of 0.66 mM, but
decreased to 0.011 min1 at 1.62 mM PMS dosage. Based on the
above results, 0.66 mM PMS concentration was used in further
experimental study.
Fig. 2. Effect of PMS concentration on the degradation efficiency of BPA.
[BPA]o = 0.22 mM. [PMS]o = —d— 0.16 mM, —s— 0.32 mM, —.— 0.66 mM, —D—
0.98 mM, —j— 1.30 mM, —h— 1.62 mM (Inset: Pseudo-first–order kinetics).
3.2. Effect of BPA concentration
Fig. 3 shows the variation of residual fractional BPA concentra-
tion with the time of oxidation for four initial BPA concentration
values of 0.04 mM (10 mg/L), 0.13 mM (30 mg/L), 0.22 mM
(50 mg/L) and 0.31 mM (70 mg/L). As the initial concentration
increased, the residual BPA concentration also increased: 0.1, 0.6,
1.65 and 21 mg/L for an initial BPA concentration of 10, 30, 50
and 70 mg/L, respectively. The retardation in BPA removal may
be attributed to the requirement of a larger number of SO 4 radicals
by the BPA molecules and the intermediates present in the solution
and the competition between BPA molecules and the intermedi-
ates for free radicals. These results are consistent with those
reported in literature [15]. The initial degradation rates of the pho-
tooxidation process were estimated from the slope of the plot of
BPA concentration versus time at t = 0 for the initial 60 min of reac-
tion time (Inset of Fig. 3). It can be seen that the initial degradation
rate of BPA increased from 2.2  104 mmol L1 min1 to
10.0  104 mmol L1 min1 with an increase in the initial BPA
concentration from 0.04 mM to 0.31 mM. This is because of the
availability of the larger number of BPA molecules to oxidizing free
radicals and thereby enhancing the rate of reaction [58]. In accor-
dance with these observations, the degradation time for >90% BPA
removal is also found to have decreased for the initial BPA concen-
tration <0.13 mM.
3.3. Effect of initial solution pH on BPA degradation
The pH of the reaction mixture has profound effect on the total
radical concentration and their formation in SO 4 based AOPs [40].
In order to investigate the effect of initial pH of reaction mixture on
BPA degradation by PMS under UV-C irradiation, experiments were
performed at five initial pH values of BPA reaction mixture (pHo:
3.0, 5.0, 7.0, 10.0 and 12.0).
It is seen that the BPA removal increased with an increase in the
initial pH of the reaction mixture (Fig. 4): 74.3% (pHo = 3), 88.3%
(pHo = 5), 97.1% (pHo = 7), 97.9% (pHo = 10), and 98.8% (pHo = 12)
as against 96.7% BPA removal at the natural reaction mixture pH.
The time course of BPA removal at different pH values follows
the order: pHo3 < pHo5 < pHN  pHo7 < pHo10 < pHo12.
The variation in removal with pHo can be explained on the basis
of three factors (a) absorption coefficient, (b) conversion of SO 4
radicals to HO radicals with pH, and (c) the rate of reaction of
radicals with deprotonated BPA.
Fig. 3. Time course of BPA degradation under UV/PMS system [PMS]o = 0.66 mM;
[BPA]o = —d— 0.04 mM; —s— 0.13 mM; —.— 0.22 mM; —D— 0.31 mM. (Inset:
Initial rate vs BPA concentration).
 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204 197

Fig. S2(a)). It is thermodynamically feasible for PMS (1.85 V) to oxi-

dize chloride ions (Cl) into less reactive chlorine species viz. Cl2/
2Cl (1.36 V) and Cl/HOCl (1.48 V) [24,62]. Therefore, the observed
higher degree of inhibition to BPA degradation at 10–20 mM Cl
concentration than that at 5 mM is due to the consumption of sul-
fate radicals by Cl ions [29], and the formation of less reactive
chlorine species Cl2, HOCl, Cl and Cl2 [24,62,63]. The chemical
reactions involved in (but not limited to) UV-C/PMS/BPA system
in the presence of Cl ions can be given as follows [24,64]:

HSO5 þ Cl ! SO2
4 þ HOCl ð6Þ

HSO5 þ 2Cl þ Hþ ! SO2
4 þ Cl2 þ H2 O ð7Þ
 2 
SO4 þ Cl ! SO4 þ Cl ð8Þ
  
Cl þ Cl $ Cl2 ð9Þ
  
Cl2 þ Cl2 ! Cl2 þ 2Cl ð10Þ

Cl2 þ H2 O ! HOCl þ Hþ þ Cl ð11Þ

Fig. 4. Effect of pH on the degradation efficiency of BPA. [BPA]o = 0.22 mM, HOCl ! Hþ þ OCl ðpKa ¼ 7:5Þ ð12Þ
[PMS]o = 0.66 mM, —D— pHN = 5.15, —s— pH = 3, —.— pH = 5, —j— pH = 7,
—h— pH = 10, —d— pH = 12. Similar trends have also been observed by Yuan et al. [64] for
sulfate radical-based (Co/PMS) AOP of Acid Orange 7.
As the pH of the reaction system increases, the absorption coef-
HA is shown to act as a photosensitizer, light filter and quencher
ficient of PMS ( PMS) increases ( PMS = 13.8–149.5 M1 cm1; pH
” ”
of free radicals. The overall effect of HA on the photodegradation of
6–12), with the enhanced photolysis of PMS, which, in turn,
BPA will, therefore, depend on the competition between the BPA
resulted in the increased concentration of SO 
4 and HO radicals
and the HA molecules [45]. It has also been reported that the dif-
[40]. The BPA molecule has two dissociation constants: pKa1 = 9.6
ferences in the quality and the type of the HA (or NOM) would give
and pKa2 = 10.2 [2]. BPA can dissociate as Bis(OH)(O) or Bis(O)2
different results on the degradation of organics [65,66]. In the pre-
in the reaction mixture. As indicated by the BPA speciation dia-
sent study, the HA is found to adversely affect the oxidation of BPA
gram (Supporting Information Material Fig. S1), the first deproto-
(Supporting Information Material Fig. S2(b)). The degradation of
nation of BPA starts at about pH 7 and the second one at about
BPA in the presence of 10 mg/L HA was 54.0% as compared to
pH 9. At pH < pKa1, undissociated BPA (i.e., Bis(OH)2) is predomi-
96.7% without HA. An increase in the HA concentration further
nantly present in the solution. In the pH range, pKa1 < pH < pKa2,
increases the degree of inhibition. Similar trends were also
the predominant species is Bis(OH)(O), and at pH > pKa2, the
observed by Zhang et al. [13]. At high concentration, the HA may
majority species is the Bis(O)2. The phenolate ions are reported
be in competition with BPA for SO 
4 and HO radicals, thereby
to have higher reaction rate constant in comparison to neutral
reducing the availability of oxidizing radicals for BPA degradation.
molecules of BPA [59]. It may, therefore, be suggested that all the
This slows down the BPA degradation rate. The increased concen-
above three factors act in a synergistic manner to effect the
tration of HA also lowers the solution transparency, thereby
removal of BPA from the solution.
inhibiting the UV-C irradiation to pass through the reaction
It has also been reported, that the degradation of butylated
mixture.
hydroxyl anisole increases as the pH increases from 3 to 11 in a
The bicarbonate ion (HCO 3 ) is an efficient hydroxyl and sulfate
PS/UV system [60], and the degradation of nitrobenzene improves
radical scavenger [53,67]. Therefore, the presence of bicarbonate
as the pH increases from 7 to 12 in a thermally activated PS system
ions would have an adverse effect on BPA degradation. The results
[61] due to conversion of SO 
4 to HO at alkaline pH [40]. During the
of the present study also support the above inference (Supporting
course of oxidation, the pH of the reaction mixture decreases from
Information Material Fig. S2(c)). The redox potential of bicarbonate
its initial value with its value dropping down to 3 for 5 < pHo < 10
ion is 1.78 V and its capability for scavenging SO 
4 and HO radicals,
and to 9 for pH 12. This is because of the acidic byproducts
are given by Eqs. (13) and (14) [53]:
obtained at the end of the oxidation (as explained in Section 4).
It can be seen that the BPA removal increases as pHo increases SO  2  þ
ðk13 ¼ 1:6  106 M1 s1 Þ
4 þ HCO3 ! SO4 þ CO3 þ H ð13Þ
from the acidic region to the alkaline region, although the differ- 
HO þ HCO3 ! CO
3 þ H2 O ðk14 ¼ 8:5  106 M1 s1 Þ ð14Þ
ence is not appreciable. On the basis of above results, further study
was carried out at the natural solution pH (pHN), because of the So the scavenging or reactive radical species (SO 
4 or HO ) is
marginal increment in BPA removal with an increase in pHo from responsible for the BPA removal inhibition. A comparative chart
the natural pH of the solution to the alkaline region. for the effect of water matrix components on the BPA removal by
UV-C/PMS system after 360 min of irradiation is illustrated in
3.4. Effect of co-existing water matrix chemicals Fig. 5. In comparison to 96.7% removal of BPA by UV-C/PMS alone,
the removal of BPA increases to 99.0% in the presence of 5 mM Cl
The components of the water matrix in ionized form also affect ion, but decreases to 54% and 70% in the presence of 5 mM HCO 3

the fate of the target compound. The effect of water matrix compo- ion and 5 mg/L HA (inset of Fig. 5), respectively. This means that
nents such as Cl and HCO the BPA degradation is not affected much in the chloride bearing
3 ions and HA on BPA removal by UV-C/
PMS oxidation was studied. The experiments were conducted in water, whereas the presence of HCO 3 and HA have measurable

the concentration range of 5–20 mM for Cl and HCO adverse effect on BPA degradation by PMS under UV-C irradiation.
3 ions, and
in the concentration range of 5-20 mg/L for HA. The results indi-
cated that the BPA degradation was not significantly influenced 3.5. Degree of mineralization and PMS consumption
at 5 mM Cl ion concentration. However, as the concentration of
Cl ions was increased to 10 and 20 mM, an inhibition in degrada- TOC is used as a measure of mineralization of target organic
tion of BPA was observed (Supporting Information Material compounds. The requirement of Oxone for the oxidation of
198 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204
Fig. 5. Effect of degradation of BPA using Cl, HA and HCO
3 under UV/PMS system.
[BPA]o = 0.22 mM, [PMS]o = 0.66 mM; UV/PMS; Cl or HCO3:
  
HCO3 : 10 mM; Cl or HCO3 : 20 mM. (Inset: UV/PMS; HA:
10 mg/L; 20 mg/L).
50 mg/L of BPA was calculated to be 4.85 g/L from the following
equation (Eq. 15) as [68]
C15 H16 O2 þ 72 HSO5 ! 72 SO4 þ 44 H2 O þ 15 CO2
The effect of PMS dosage on the degree of mineralization of BPA
(50 mg/L) was studied at the PMS dosage of 0.16, 0.66 and 1.62 mM
(Inset of Fig. 6). It is seen that at 0.16 mM dosage of PMS, 64%
removal of BPA and 58% TOC removal were obtained with a con-
sumption of 83% of PMS in the oxidation process.
With an increase in the PMS dosage from 0.66 mM to 1.62 mM,
the BPA degradation decreased from 96.7% to 90% and the TOC
removal was also observed to decrease from 72.5% to 67%, respec-
tively, with the PMS consumption being 35% and 37%, respectively.
Yang et al. [69] also reported 40% PMS consumption for the
degradation of the azo dye (AO7) under 254 nm UV irradiation,
when applied in the PMS: AO7 molar ratio of 10:1. Fig. 6 shows
the TOC removal corresponding to BPA degradation during the
course of oxidation over a period of 360 min. During the oxidation
Fig. 6. Time course of fractional removal of BPA and TOC. [BPA]o = 0.22 mM;
[PMS]o = 0.66 mM. BPA removal; TOC removal. [Inset: BPA removal, h TOC
removal, PMS consumption at specific PMS dosage].
process, the solution pH dropped rapidly within the initial 30 min
of reaction, and thereafter, followed a gradual decrease
(Supporting Information Material Fig. S3).The decrease in pH is
because of the formation of H+, HSO 5 species and the oxidation
intermediates which are acidic in nature. The intermediates which
are formed during the BPA oxidation also contributed to the resid-
ual TOC in the reaction mixture [70,53].
After 60 min of reaction time, 81.9% BPA was removed as
against 24.4% TOC removal. After 180 min, the BPA degradation
was found to be 93.0% with 51.6% TOC removal. After 360 min of
irradiation, the BPA removal was 96.7% with a TOC removal of
72.5%. This showed BPA decrement of only 14.8% with a TOC decre-
ment of 48% in the later 300 min of oxidation. The ratio of TOC
removal to that of BPA improves from about 0.29 after 60 min to
about 0.75 after 360 min of reaction. This means that the interme-
diates get mineralized, albeit slowly.
5 mM; Cl or
5 mg/L; 4. Transformation products
To the best of the author’s knowledge, the mechanism of BPA
degradation by UV-C activated PMS has not yet been reported.
The extract obtained from the reaction mixture using DCM as a sol-
vent was subjected to GC/MS analysis. Methanol [70], acetonitrile
[71], ethyl acetate [11,72], diethyl ether and DCM [12,73,74] have
ð15Þ been used as solvents to extract the oxidation products from AOP
reaction mixture. Each solvent has its limitation in extracting some
chemicals and intermediates and leaving out some others.
Therefore, it is possible that some chemicals and intermediates
may not have been extracted by DCM. The reaction products at
very low concentration may also have escaped detection by the
GC/MS. The GC/MS mass spectra of these intermediates were eval-
uated on the basis of literature information using the NIST and
Wiley libraries. The FTIR analysis confirmed the formation of inter-
mediates through identification of bonds and functional groups.
GC chromatogram at 180 min reaction time revealed seven
stable intermediates (Supporting Information Material Fig. S4).
The number of peaks representing intermediates decreased to five
as also their magnitudes at 360 min reaction time. Relative abun-
dance of the degradation intermediates was calculated by normal-
izing the peak areas at the defined reaction time to the highest
peak area (Supporting Information Material Fig. S5). The stable
intermediates along with some unstable compounds which were
identified from the rigorous analysis of the data are reported in
Table 1.
Among the identified products, one product having a molecular
weight of 206 is detected for the first time. Some of the identified
compounds have lower molecular weights (acids, 3,5-dimethy-
lethyl phenol, phenol) than BPA, while some have higher molecular
weights (1-isopropyl-1-phenoxy-2-isopropyl-4-phenol, and qui-
none of dihydroxylated BPA) than BPA.
The formation of compounds having similar molecular weight
characteristics are also reported in the literature [11,71].
The UV-spectra of the freshly prepared reaction mixture com-
prising 0.22 mM BPA and 0.66 mM PMS initially were obtained at
different reaction times over a time period of 0–360 min. For the
freshly prepared solution, the absorbance spectrum shows a band
with a maximum wave length (kmax) around 276 nm. This spectral
band is the manifestation of BPA. There is intense absorption
because of PMS. The spectra of the reaction mixture after different
reaction times show the absence of BPA and an increase in the
absorbance over the entire range of the wavelength span from
190 nm to 500 nm. This is the characteristic of absorbance and dis-
persion of light due to presence of almost invisible tiny particles
(Supporting Information Material Fig. S6) [75]. This illustrates that
 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204 199

Table 1
Possible by-products formed during oxidation of BPA under optimum conditions.

Compound/formula Tentative structure MW/ Detected Remaining

(m/z) intermediates
reported by/in other
AOPs
p
Bisphenol-A 228

p
Formic acid (16.75 min) 116

p
p-Phenol-2-hydroxy carboxylic acid (19.2 min) 168

p
Biphenyldiol (24.5 min) 186

p
Quinone of MHBPA (21.11 min) 242

Benzaldehyde 106 [70]

p-Hydroxyacetophenone 136 [16,17]

Benzophenone 182 [33]

p
Monohydroxylated BPA (MHBPA) 24.1 min 244

p
Phenol,2,4-bis(1,1-dimethyl ethyl) (18.2 min) 206

p
Phenol,3,5-bis(1,1-dimethyl(ethyl) 206

p
2-Hydroxy-4-(2-(3-hydroxy-4-oxocyclohexa-2,5-dienyl)propan-2- 257
yl)cyclohexa-2,5-dienone [or quinone of dihydroxylated BPA]
(26.11 min)

(continued on next page)

200 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204
Table 1 (continued)
Compound/formula
Quinone of dihydroxylated BPA
4-isopropyl-1-phenoxy-2-isopropyl-4-phenol (29.12 min)
Hydroxylated (4-isopropyl-1-phenoxy-2-isopropyl-4-phenol)
Coupling product
the depletion of BPA with reaction time is accompanied by the
increasing amount of a brownish solid product.
The FTIR analysis of the filtrate confirmed the formation of
various products as the spectra show the presence of benzene
and aromatic ring stretch (<1000 cm1), along with acidic (2800–
3200 cm1), carbonyl (1660–1651 cm1), and hydroxyl functional
groups (3300–3400 cm1). The FTIR spectrum of the filtered
brownish solid product (Supporting Information Material inset of
Fig. S6) shows peaks at 3408 cm1 (–OH stretching, vibrations),
2969 cm1 (–OH stretching of acidic groups as the 2400–
3000 cm1 medium intensity band is described for acidic com-
pounds [76], 1612 cm1 (benzene ring, aromatic groups),
1505 cm1 (phenyl ring), 1221 cm1 (C–O–C stretching), 832 (band
of para substituted aromatic compounds), and 567 cm1 attributed
to C–H stretching out of the benzene plane. These characteristics
indicate the formation of solid polyphenols. Similar characteristics
were also observed during the degradation of phenol by thermally
activated PMS [75], and for polyphenol polymers containing phe-
nylene and oxyphenylene units [77].
A number of studies reported on the toxicity of the degradation
byproducts [78–80]. It has been concluded that the phenolic moi-
ety is responsible for the estrogenic activity in comparison to qui-
none like and aromatic ring opened products [16,81]. Fang et al.
[81] showed that the substituted group (–OH) on the aromatic
structure imparted binding affinity to receptors through H-bond
interaction. In the present study, only one hydroxylated BPA inter-
mediate (stable) was identified while the others were the quinones
and the ring opened structures. These compounds are stated to be
less estrogenic as compared to BPA [16,81,82].
5. Degradation mechanism and pathway
The radical identification study performed in this work demon-
strates that the UV-C activation of PMS produces SO
4 radicals pre-
dominantly. The sulfate radicals react with the substrate via direct
electron transfer and/or by addition/elimination reaction, and
form HO adducts via hydrolysis [42,82]. But the possibility of
Tentative structure MW/ Detected Remaining
(m/z) intermediates
reported by/in other
AOPs
p
257
p
270
286 [12]
320 [12]
H-abstraction cannot be ruled out, and the nature, ring position,
and H-bond formation capacity of the substituted phenols will
dictate the H-abstraction efficiency by different radicals [75,83].
The sulfate radicals react with aromatic ring and olefinic double
bonds, thereby forming sulfate radical adducts having very short
life (<200 ns) [82,49]. The sulfate adducts can also be formed due
to electron transfer from aromatic ring to SO 4 by releasing a sul-
fate group (SO24 ) [84,85]. The sulfate radical adducts, thus formed,
produce hydroxycyclohexadienyl (HCHD) radicals by nucleophilic
attack of water [22,86,87]. The elimination of water molecule from
HCHD radical (under acidic conditions) is responsible for the pro-
duction of highly oxidizing phenoxyl BPA (PhxBPA) radical
(Fig. 7) [22,88]. Alternative path of PhxBPA radical formation can
be via H-abstraction from BPA molecule as stated earlier.
Addition of oxygen (from air and/or decomposition of PMS) to
HCHD radical will form dioxygen radical adducts which are further
responsible for the formation of hydroxylated BPA byproducts such
as 1,2-benzenediol (catechol) and hydroquinone [22,87] by elimi-
nation of HO2.
Also, because of the b-scission (C–C) in the PhxBPA radical, the
phenoxy (PhO) and isopropenylphenol (IPP) radicals are formed
(Fig. 7) which is responsible for further degradation of BPA to phe-
nol, hydroquinone, benzoquinone, and simpler organic acids
[16,89]. The addition/coupling of these radicals to each other or
with themselves or with neutral BPA molecules generate oligo-
meric/high molecular weight compounds [12] (as is also evidenced
by the formation of polyphenols observed through FTIR spec-
troscopy). The detected species with m/z = 320 is due to the
bimolecular combination of PhxBPA followed by the elimination
of IPP radicals. The combination of IPP radicals followed by the
removal of water molecules results in the formation of a byproduct
identified at m/z = 270 in this study [12].
The monohydroxylated BPA (m/z = 244) is formed by the reac-
tion of isopropenylphenol with hydroquinone or as a result of
HO addition on the aromatic ring of BPA [71]. Monohydroxylated
BPA serves as a precursor for the formation of its quinone
(m/z = 242) and the quinone of dihydroxylated BPA (m/z = 257).
This may be due to the SO 4 radicals which are predominantly
 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204
Fig. 7. Possible formation of radical adducts during BPA oxidation by UV/PMS system.
present in the reaction media and have high reactivity toward
hydroxylated intermediates. The byproduct identified at m/z = 206
is observed for the first time in the reaction mixture after AOP.
This might be formed due to resonance stabilization of PhO radical
and the alkyl chain of the IPP radical.
The detection of low molecular weight (m/z = 168, m/z = 116)
acidic compounds, such as oxalic, acetic and formic acids, may be
the result of further oxidation and ring opening of the aromatic
compounds.
Similar pathways were also reported for the phenol degradation
by UV/H2O2, UV/PS and UV/PMS AOP [22] for TCA degradation
under UV activated persulfate [42] and Fenton like treatment of
BPA [12].
It can, therefore, be concluded that when SO
4 radical oxidizes
the BPA molecule, one electron is transferred from the BPA mole-
cule to produce C-centered BPA radical cation (BPA+). This carbon
centered radical is also known as HCHD radical. Hydrolysis of the
radical cation forms OH adducts, (OH) (BPA+). H abstraction gener-
ates a hydroxyl BPA radical, ((OH)BPA) which gets degraded to
smaller molecules. The reaction process can proceed as follows:
þ 2
SO
4 þ BPA ! BPA þ SO4
BPAþ þ H2 O ! ðOHÞBPA þ Hþ
HO þ BPA ! ðOHÞBPA
þ
ðOHÞBPA ! intermediates ! CO2 þ H2 O
201
The degradation pathway and mechanism are illustrated in
Fig. 8. Several researchers [22,87,90] have reported the hydroxycy-
clohexadienyl and phenoxy radical pathways in SO 4 based AOPs
for phenol. The formation of quinone of dihydroxylated BPA, iso-
propyl phenol, and phenol proves the involvement of hydroxycy-
clohexadienyl and phenoxy radicals. Further attack of sulfate and
hydroxyl radicals may be responsible for the formation of lower
molecular weight phenols and acids.
6. Conclusions
The results obtained in this study indicate that the AOP using
PMS under UV-C irradiation is a feasible treatment method for
the elimination of BPA from aqueous phase. It is found that the per-
cent of BPA removal decreases with an increase in the initial BPA
concentration and at the higher PMS concentration than its opti-
mum value. The optimum dosage of PMS was observed to be
0.66 mM for 0.22 mM BPA concentration. At the optimum treat-
ment conditions, the removal of BPA and TOC was found to be
96.7% and 72.5%, respectively. The degradation of BPA under UV-
C/PMS system followed the pseudo-first order reaction kinetics,
ð16Þ under optimum conditions, with the rate constant being
ð17Þ 0.025 min1 in 60 min of UV-C irradiation.
ð18Þ The BPA degradation increases with an increase in the initial pH
of the solution which is ascribed to the absorption coefficient, con-
ð19Þ version of SO 
4 radicals to HO and the speciation of BPA with
202 J. Sharma et al. / Chemical Engineering Journal 276 (2015) 193–204

CH3
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