Chemosphere xxx (2014) xxxxxx

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

S2O2
8 /UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment
of toxicity, estrogenic activity, degradation products and results in real
water
Tugba Olmez-Hanci a,, Duygu Dursun a, Egemen Aydin a, Idil Arslan-Alaton a, Binhan Girit a, Luigi Mita b,
Nadia Diano b,c, Damiano G. Mita b, Marco Guida b,d
a

Istanbul Technical University, Civil Engineering Faculty, Environmental Engineering Department, 34469 Maslak, Istanbul, Turkey
I.N.B.B. National Laboratory on Endocrine Disruptors, Via Pietro Castellino 111, 80131 Napoli, Italy
c
Seconda Universit di Napoli, Department of Experimental Medicine, Via de Crecchio 7, 80138 Napoli, Italy
d
Universit di Napoli Federico II, Department of Biology, Via Cinthia ed. 7, 80126 Napoli, Italy
b

a r t i c l e

i n f o

Article history:
Received 30 December 2013
Received in revised form 15 May 2014
Accepted 11 June 2014
Available online xxxx
Handling Editor: J. de Boer
Keywords:
Bisphenol A
Acute toxicity
Yeast Estrogen Screen (YES) assay
S2O82/UV-C and H2O2/UV-C treatments
Degradation products
Real freshwater matrix

a b s t r a c t
The performance of S2O2
8 /UV-C and H2O2/UV-C treatments was investigated for the degradation and
detoxication of Bisphenol A (BPA). The acute toxicity of BPA and its degradation products was examined
with the Vibrio scheri bioassay, whereas changes in estrogenic activity were followed with the Yeast
Estrogen Screen (YES) assay. LC and LCMS/MS analyses were conducted to determine degradation products evolving during photochemical treatment. In addition, BPA-spiked real freshwater samples were also
subjected to S2O2
8 /UV-C and H2O2/UV-C treatment to study the effect of a real water matrix on BPA
removal and detoxication rates. BPA removal in pure water was very fast (67 min) and complete via
both H2O2/UV-C and S2O2
8 /UV-C treatment, accompanied with rapid and signicant mineralization rates
ranging between 70% and 85%. V. scheri bioassay results indicated that degradation products being more
toxic than BPA were formed at the initial stages of H2O2/UV-C whereas a rapid and steady reduction in
toxicity was observed during S2O2
8 /UV-C treatment in pure water. UV-C treatment products exhibited
a higher estrogenic activity than the original BPA solution while the estrogenicity of BPA was completely
removed during H2O2/UV-C and S2O2
8 /UV-C treatments parallel to its degradation. 3-methylbenzoic and
4-sulfobenzoic acids, as well as the ring opening products fumaric, succinic and oxalic acids could be
identied as degradation products. BPA degradation required extended treatment periods (>20 min)
and TOC removals were considerably retarded (by 40%) in the raw freshwater matrix most probably
due to its natural organic matter content (TOC = 5.1 mg L1). H2O2/UV-C and S2O2
8 /UV-C treatment in
raw freshwater did not result in toxic degradation products.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Bisphenol A (2,2-bis(4-hydroxyphenyl)propane; abbreviated as
BPA herein), a potential endocrine disrupting compound (EDC), has
been widely used in the production of epoxy resins and polycarbonate plastics, employed in food and drink packaging applications, baby bottles and dental sealants (Staples et al., 1998). It
has been reported that BPA is ubiquitous in the environment,
including surface water, groundwater and treated drinking water
(Umar et al., 2013). In natural waters, BPA is usually present at
lower concentrations (<0.011.9 lg L1), however, landll leachate

Corresponding author. Tel.: +90 212 285 6579.

E-mail address: tolmez@itu.edu.tr (T. Olmez-Hanci).

concentrations as high as 17 mg L1 have been detected (Staples

et al., 1998; Yamamoto et al., 2001). Several studies indicate that
BPA might result in adverse health effects, such as human prostate
cancer, cardiovascular diseases, diabetes mellitus type 2, hormonal
imbalance and liver enzyme abnormalities, in addition to reproduction and developmental effects, neurochemical and behavioral
effects (Wetherill et al., 2002; vom Saal and Hughes, 2005;
Signorile et al., 2010). The widespread existence of BPA in the
aquatic environment, at low but environmentally relevant levels,
implies that conventional water and wastewater treatment technologies are not sufciently effective for BPA removal (Chen
et al., 2006). Consequently, advanced remediation techniques have
to be applied for efcient BPA removal from the contaminated
environment including water, wastewater, sewage sludge, sediments and soils (Mohapatra et al., 2010; Avila et al., 2014).

http://dx.doi.org/10.1016/j.chemosphere.2014.06.020
0045-6535/ 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020

T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

Advanced oxidation processes (AOPs) have received great attention and academic interest in recent years as complementary
methods to conventional water treatment or as alternative treatment strategies for industrial wastewater prior to discharge into
sewage or into receiving water bodies (Parsons, 2004). There is a
growing interest in investigating the use of ultraviolet (UV) irradiation and UV based AOPs for treatment of EDCs (Chen et al., 2006;
Gultekin and Ince, 2007; Huang and Huang, 2009). The effectiveness of direct UV-C photolysis is governed by the absorption spectra of the contaminant and the quantum yield, the addition of
hydrogen peroxide (H2O2) or persulfate (S2O2
8 ) to generate highly
active free radicals such as hydroxyl (HO) and sulfate (SO
4 ) often
signicantly lowers the UV dose required for oxidation as compared to direct photolysis (Antoniou et al., 2010; Gao et al., 2012;
Olmez-Hanci and Arslan-Alaton, 2013).
Activation of symmetrical peroxides such as H2O2 and S2O2
8
under UV-C radiation results in the formation of two HO and SO
4 ,
respectively (Eqs. (1) and (2)) through the homolytic cleavage of the
peroxide (OO) bond (Baxendale and Wilson, 1957; Mark et al.,
1990; Anipsitakis and Dionysiou, 2004):

H2 O2 hm ! 2HO

U 1:0


S2 O2
8 hm ! 2SO4 U 1:4 de-oxygenated; 1:8 oxygen saturated

liquid chromatography (HPLC) to enable comparison of reaction

pathways of the selected treatment processes. In the nal part of
the study, a series of S2O2
8 /UV-C and H2O2/UV-C experiments were
conducted in raw freshwater spiked with BPA to elucidate the
treatability and detoxication behavior of BPA in real water
matrices.
2. Materials and methods
2.1. Materials

BPA (228 g mol1; C15H16O2; CAS No: 80-05-7, purity: 99.9%)

and potassium persulfate (K2S2O8; purity P99.5%) were purchased
from SigmaAldrich (USA) and used as received. Hydrogen peroxide (H2O2; 35% w/w) of analytical grade and acetonitrile of chromatographic grade were obtained from Merck (Germany).
Aqueous BPA solutions were prepared with distilled water. Ultrapure water for the chromatographic measurements was prepared
with an Arium 611UV water purication system (Sartorius AG,
Germany). All other chemicals required for analytical and experimental procedures were at least of analytical grade.

2.2. The raw freshwater sample

Both of these radicals are extremely active and short-lived

(103 ls for HO and 3040 ls for SO
4 ) due to their high reduction
potentials (Eo = 1.892.72 eV for HO and Eo = 2.53.1 eV for SO
4 ;
Pikaev and Zolotarevskii, 1967; Buxton et al., 1988; Neta et al.,
1988).
During the application of AOPs, the main concern relates to the
formation of various degradation products that can potentially be
more toxic, estrogenic and persistent than the original compound
(Ioan et al., 2007; Li et al., 2007). Thus, the identication of degradation products accompanied with a comprehensive toxicity
assessment becomes important when deciding for the feasibility
and ecotoxicological risk of an oxidative treatment application
(Huang and Huang, 2009; Rizzo, 2011; Catapane et al., 2013). In
order to increase the reliability of toxicity assessment, especially
if EDCs and their degradation products are questioning, bioassays
covering different modes of toxic action (e.g. estrogenicity or
non-specic toxicity) must be used. In recent works examining
oxidation and the corresponding removal of estrogenic activity
associated with EDCs via AOPs, a consistency between removal of
estrogenic activity, toxicity and parent compound abatements
was discovered (Chen et al., 2006; Neamtu and Frimmel, 2006;
Frontistis et al., 2011).
2
The presence of carbonate species (HCO
3 , CO3 ), natural organic
matter (NOM) and other organic and inorganic compounds in natural water matrices might signicantly affect the efciency of AOPs
(Trov et al., 2009; Snchez-Polo et al., 2013). Moreover, the degradation products formed during the application of AOPs in pure and
natural water might be different and consequently their ecotoxicological behavior might differ as well (Trov et al., 2009; Aydin,
2014). It is not exactly known how EDCs will behave in real water
matrices during photochemical treatment; probably different than
in pure water. From the practical point of view it would be of interest to investigate treatability of EDCs in real water samples (FattaKassinos et al., 2011).
In the present study the treatability of BPA via H2O2/UV-C and
S2O2
8 /UV-C was comparatively evaluated. Changes in acute toxicity and estrogenic activity patterns were studied by employing two
different bioassays; namely the Vibrio scheri (V. scheri) test protocol and the Yeast Estrogen Screen (YES) assay. Liquid chromatography-tandem mass spectrometry-mass spectrometry (LCMS/MS)
analysis was carried out to identify the BPA degradation products.
Moreover, carboxylic acids were quantied via high performance

Raw (untreated) freshwater sample was obtained from a local

water treatment plant of the Istanbul Metropolitan Municipality.
Raw freshwater sample was shipped in 25 L plastic bottles and
stored in a cool room at 4 C until the experiments were performed. The environmental characterization of the raw freshwater
sample is shown in Table 1. TOC and absorbance at 254 nm (UV254)
constitute a signicant indication of the NOM present in raw freshwater. The experimental conditions for raw freshwater sample
spiked with 20 mg L1 BPA were similar to those carried out in
pure water however the initial pH was the natural pH of raw freshwater (8.6).
2.3. The UV-C photoreactor and experimental procedure
UV-C, H2O2/UV-C and S2O2
8 /UV-C treatment experiments were
conducted at room temperature (25 2 C) in an octagonal photochemical reaction chamber (diameter: 30 cm) equipped with a digitally controlled thermometer, a chronometer and a magnetic
stirrer. The chamber consisted of a maximum of six UV-C lamps
(8 W each), with three of them being placed on two (left and right)
reactor walls. The maximum emission band of the UV-C lamps was
253.7 nm. The UV-C light uency was determined as 2.27 W L1
via H2O2 actinometry (Nicole et al., 1990). All experiments were
run in a 2500 mL-capacity cylindrical quartz reactor that was continuously stirred at a constant rate of 100 rpm with a magnetic stir
bar from the reactor bottom to keep the reaction mixture mixed.
No temperature control was provided since the low pressure UVC lamp used in the present work did not heat up during the experiments. 20 mg L1 (88 lM) of BPA aqueous solutions were treated
at pH 6.5 in all experiments based on preliminary baseline experiments, where oxidant concentration, pH and photochemical treatment time were optimized (Olmez-Hanci et al., 2013). Samples
were taken at regular time intervals for up to 120 min and analyzed for BPA, total organic carbon (TOC), S2O2
8 or H2O2 and pH.
Although the initial BPA concentration investigated was extremely
high as compared to the concentrations typically detected in water
and wastewater, it was decided to select a high BPA concentration
to enable accurate kinetic, toxicological and analytical assessment
of BPA and its degradation products. All experiments were done at
least in duplicate and average values were used in presenting the
results.

Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020

T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

Table 1
Environmental characterization of the raw freshwater sample.
Parameter
TOC
Alkalinity
Hardness
Color
Turbidity
SS
pH
UV254
UV280
UV400
UV436
Cl
F
NO
2
NO
3
2
SO4
3
PO4
BPA
a

Unit

Value
1

mg L
mg CaCO3 L1
mg CaCO3 L1
PtCo
NTU
mg L1

mg L1
mg L1
mg L1
mg L1
mg L1
mg L1
mg L1

5.1
124
116
10
1.5
bdla
8.6
0.0795
0.0640
0.0085
0.0063
25.5
0.11
bdla
1.6
13
bdla
bdla

Below the detection limit.

2.4. Analytical procedures

night at 26 C by shaking in minimal medium (Yeast Nitrogen

Base) and enriched with a solution of amino acids and glucose.
After 24 h, cells were counted in a Brker chamber and a specic
aliquot of the culture was diluted in fresh minimal medium. The
obtained suspension was incubated, for 1618 h, in the presence
of the samples to be tested (50% v/v). Each sample and different
17b-estradiol concentrations, as positive control, were assayed in
triplicate and error bars representing standard deviation are
depicted in gures. Control samples for the used catalase and thiosulfate concentrations were also assayed. As the negative control,
the pure water used for all experiments was employed. Then, yeast
cells were collected by serial centrifugations at 4000 rpm for 5 min
in Z-buffer (30 mM Na2HPO412H2O, 20 mM NaH2PO4H2O, 5 mM
KCl, 0.5 mM MgSO47H2O) plus a 0.025% b-mercaptoethanol,
CH2Cl2 and SDS 0.1%. The b-galactosidase activity was determined
by the addition of 700 lL of ONPG (4 mg mL1 in Z-buffer). The
chromogenic reaction was stopped by the addition of 500 lL of
1 M Na2CO3. Thereafter, cell debris was removed by centrifugation
at 14 000 rpm for 2 min, and the absorbance of the sample at
420 nm was measured, normalized for the cell growth of samples
(OD600), and expressed in Miller units (MU) using the following
formula (Miller, 1972);

MU OD420  1000=t  V  OD600

2.4.1. BPA analysis
BPA was quantied with an Agilent 1100 Series HPLC equipped
with a Diode-Array Detector (DAD; G1315A, Agilent Series) set at
214 nm. A C18 Symmetry column (3.9 mm  150 mm; 5 lm particle size; Waters, USA) was employed as a stationary phase, while
the mobile phase was a mixture of acetonitrile/water used at a
ratio of 50/50 (v/v). The ow rate and temperature of the column
were set as 1.0 mL min1 and 25 C, respectively. The instrument
detection and quantication limit of BPA for an injection volume
of 50 lL was calculated as 70 lg L1 and 210 lg L1, respectively.
2.4.2. Vibrio scheri bioassay
The acute toxicity toward the luminescent bacteria V. scheri
was measured during UV-C, H2O2/UV-C and S2O2
8 /UV-C treatments in pure and raw freshwater spiked with BPA using a commercial assay kit marketed as BioTox (Aboatox Oy, Finland)
according to the test protocol ISO 11348-3 (2007). Prior to the
assay the pH and salinity of all samples was adjusted to 7.0 0.2
and 2% (w/v), respectively. After mixing 500 lL of untreated or
photochemically treated BPA solutions with 500 lL luminescent
bacterial suspensions, the light emission after 15 min contact time
was measured at a temperature of 15 C. Percent relative inhibition
rates were calculated on the basis of a toxicant-free control. A positive control sample with potassium dichromate was also included
for each test and all bioassays were run in triplicate. In order to
eliminate their positive effect on toxicity measurements, residual/unreacted H2O2 or S2O2
8 in the reaction solution was removed
with sodium thiosulfate (Merck; Germany) and enzyme catalase
(made from Micrococcus lysodeikticus; Fluka; Sweden), respectively. Control samples were prepared for catalase and thiosulfate
exactly at the concentration used to remove the above mentioned
oxidants. Their presence in the test solution did not cause any signicant bioluminescence inhibition (<5%).
2.4.3. YES bioassay
The estrogenic activity of BPA samples in pure water before and
after UV-C, H2O2/UV-C and S2O2
8 /UV-C treatments was determined by YES bioassay. The yeast strain used in the YES test was
Saccharomyces cerevisiae RMY326. This strain contains the human
estrogen receptor a (gEPa) amd an estrogen-responsive element
(ERE) bound to the reporter gene lacZ encoding for the enzyme
b-galactosidase (Liu et al., 1999). The yeast cells were grown over-

where t is the time of chromogenic reaction before stopping (min);

V the volume of culture used in the assay (mL); OD420 and OD600 =
optical density at 420 and 600 nm, respectively.
2.4.4. Degradation products analyses
LCMS/MS analysis was carried out using Thermo Electron Corporation Accela ultra performance liquid chromatography (UPLC)
coupled with a TSQ Quantum Access triple quadrupole tandem
mass spectrometer (MS) and a electrospray ionizer. Firstly, all samples were introduced to the MS by means of the MS syringe pump
at negative ionization full can mode (spray voltage = 3000 V,
sheath gas pressure = 15 arb., ion sweep gas pressure = 2 arb., auxiliary gas pressure = 5 arb., capillary temperature = 270 C, tube
lens offset = 75). Ions between 30 m/z and 400 m/z were scanned
through direct infusion of the samples. Possible transformation
products were picked from full-scan spectra of the samples. In
the second phase, the samples were injected to a Waters Symmetry
C18 column (3.9 mm  150 mm; 5 lm particulate size) with a gradient elution. Acetonitrile and 10 mM ammonium acetate were
used as mobile phase at a ow rate of 400 lL min1. The injection
volume was 25 lL. At the beginning of the gradient elution, acetonitrile was 50% and kept at this ratio for 2 min, followed by an
increase to 90% in 8 min and kept at this ratio for 3.5 min. Finally,
the acetonitrile concentration was decreased to 50% in 0.1 min and
kept at this ratio for 6.5 min. Potential degradation products were
scanned throughout each run using single ion monitoring (SIM)
mode with 0.002 s scan time, 0.01 m/z scan width and 0.4 halfvalue width (FWHM) resolution. In the last phase, MS/MS transitions of the possible transformation products were determined
using the same chromatographic conditions. MS/MS transitions
could be recorded successfully for each selected possible transformation product since they were separated chromatographically.
Different collision energy values were applied to obtain different
MS/MS transition spectra of the possible transition products and
these transitions. Comparison of the obtained MS/MS spectra and
Massbank LCMS library was used to propose transformation of
BPA during studied oxidation processes (Horai et al., 2010).
The concentrations of carboxylic acid products were monitored
via HPLC. An Acclaim OA (4  250 mm, 5 lm; Dionex Corporation,
USA) analytical column was used for the identication of C1C7
aliphatic and aromatic carboxylic acids with the mobile phase consisting of sodium sulfate (100 mM) aqueous solution at pH 2.65

Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020

T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

3. Results and discussion

3.1. H2O2/UV-C and S2O2
8 /UV-C treatment of BPA

TOCDP

16

(a)

90

14
12

70
60

10

50

40

30

TOCDP (mg L-1)

80

4
20
2

10

0
0

10

20

30

40

50

60

70

80

90

100 110 120

Treatment Time (min)

TOC

BPA

TOCDP

100

16

90

14

(b)

70

12

60

10

50

40

30

TOCDP (mg L-1)

80

4
20
2

10

0
0

10

20

30

40

50

60

70

80

90

100 110 120

Treatment Time (min)

TOC

BPA, TOC Removal Efficiency (%)

In order to assess the capacities of H2O2/UV-C and S2O2

8 /UV-C
treatment processes to degrade BPA and its organic carbon content,
experiments were conducted with 20 mg L1 (88 lM) aqueous BPA
solutions at an initial oxidant concentration and pH of 2.5 mM and
6.5, respectively. Selection of these experimental reaction conditions was based on preliminary baseline experiments that were
conducted to establish most suitable oxidant concentration and
reaction pH to enhance BPA treatment by H2O2/UV-C and S2O2
8 /
UV-C processes (Olmez-Hanci et al., 2013).
Fig. 1 displays the time dependent changes in BPA and TOC
removal efciencies for direct UV-C photolysis (a), H2O2/UV-C (b)
and S2O2
8 /UV-C (c) treatment experiments which were conducted
in order to evaluate the degradation pattern of BPA. The evolution
of the TOC content of degradation products (TOCDP; in mg L1)
being calculated by subtracting the organic carbon content coming
from the remaining BPA (OCBPA; organic carbon equivalent of residual BPA; in mg L1) from the measured TOC (in mg L1) were also
shown in Fig. 1. As it is evident in Fig. 1(a), direct UV-C photolysis
of BPA was slow and hence incomplete, resulting in an overall BPA
removal of 52% after 120 min.
In principle, complete mineralization of organic pollutants may
be achieved by means of UV-C photolysis. However, this would
require extended irradiation times and large energy quantities. It
is generally expected that degradation (photolysis) products might
be more problematic from a toxicological point of view, like in the
case of hydroxylamines (Huber et al., 2003), phenols, quinones carboxylic acids and aldehydes (Toor and Mohseni, 2007). Thus, the
oxidation efciency measured in terms of the TOC parameter might
be more important than the removal of the parent compound due to
ecotoxicological safety concerns. As expected, for a degradation
process carried out in the absence of any enhancing oxidant and/
or (photo)catalyst, no signicant TOC removal was observed during
treatment (Molkenthin et al., 2013). Furthermore, TOCDP gradually
increased during the course of UV-C treatment supporting evidence
of the formation and subsequent accumulation of degradation
products. Different from UV-C photolysis, BPA removal was very
fast and complete in a few min during H2O2/UV-C treatment. TOC
removal also proceeded rapidly; a gradual decrease was observed
resulting in 85% TOC removal. After complete degradation of BPA,

BPA

100

BPA

TOCDP

100
90

16

(c)

80

14
12

70
60

10

50

40

30

TOCDP (mg L-1)

2.4.5. Other measurements

TOC was measured on a Shimadzu VPCN analyzer (Japan)
equipped with an autosampler by catalytic oxidative combustion
at 680 C, using an infrared detector. An Orion (USA) 720 + model
pH-meter was used for pH measurements. Residual H2O2 and
S2O2
concentrations were traced by employing the iodometric
8
method according to Wahba et al. (1959) and Ofcial Methods of
Analysis (1980), respectively. The UV absorbance of the pure and
raw freshwater samples was measured on a Perkin Elmer Lambda
25 spectrophotometer in 1 cm quartz cuvettes. Anion analysis
was conducted using a Dionex ICS-1500 ion chromatography unit
equipped with a conductivity detector, a Dionex IonPac AG14A
(4  50 mm) guard column and a Dionex IonPac AS14A
(4  250 mm) analytical column. The ion chromatography unit
was operated in auto-suppression mode with 1 mM sodium bicarbonate/8 mM sodium carbonate eluent at a ow rate of 1 mL min1.

TOC

BPA, TOC Removal Efficiency (%)

(adjusted with methanesulphonic acid). The ow rate and injection

volume were 0.6 mL min1 and 50 lL, respectively. The organic
acids were qualied via DAD at 210 nm and the column temperature was set as 30 C.

BPA, TOC Removal Efficiency (%)

4
20
2

10

0
0

10

20

30

40

50

60

70

80

90

100 110 120

Treatment Time (min)

Fig. 1. UV-C (a) H2O2/UV-C (b) and S2O2
8 /UV-C (c) treatment of aqueous BPA.
Experimental conditions: BPA = 20 mg L1 (88 lM); TOC = 16 mg L1; Oxidant
dose = 2.5 mM; initial reaction pH = 6.5; Applied UV-C dose = 21 W h L1.

the TOC content of the degradation products (TOCDP) reached their

highest value of 13.8 mg L1 and the removal of TOCDP coincided
with the measured TOC. As it can be also followed from Fig. 1(c),
BPA removal was complete after 5 min treatment for the S2O2
8 /
UV-C process. As in the case of H2O2/UV-C oxidation, TOC gradually
decreased and the overall, nal TOC removal efciency of 70% was
reached at the end of 120 min treatment. Residual S2O2
8 concentrations followed a similar trend to TOC removal patterns; after
120 min treatment time, S2O2
was completely consumed (data
8
not shown). After 5 min, where BPA was entirely converted to its
degradation products, TOCDP concentration peaked at a level of
13.5 mg L1 and decreased steadily to 4.4 mg L1 after 120 min.
During photochemical treatment, oxidant abatement was also followed (not shown data). H2O2 and S2O2
8 were totally consumed
in 6090 and 120 min, respectively, indicating that sufcient
amounts of oxidants to produce HO and SO
4 were available in
the reaction solution during treatment.
Under the studied reaction conditions, BPA and TOC removals
as well as S2O2
and H2O2 consumption rates followed pseudo
8

Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020

T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

3.2. Acute toxicity results

The toxicity analysis of the BPA solutions during different stages
of UV-C, H2O2/UV-C and S2O2
8 /UV-C treatments in pure water was
monitored with V. scheri (Fig. 2). Toxicity results indicated that
the untreated BPA sample caused an inhibitory effect of 75%. Nevertheless, as UV-C photolysis progressed, a general reduction in the
inhibitory effect of BPA was evident speaking for the fact that UV-C
photolysis products of BPA were not more toxic than the original
BPA solution. However photo-intermediates generated during
UV-C photolysis were not further transformed and thus, they,
and their associated toxicity (64%), remained in solution at the
end of the 120 min treatment (corresponding to a UV dose of
21 W h L1). V. scheri appeared to be very sensitive; reacting rapidly to the decrease in BPA concentration as well as formation of
degradation products during H2O2/UV-C treatment. As can be seen
from Fig. 2, a prompt decrease down to 14% (5 min) was observed,
followed by a re-increase to 94% after 30 min treatment. Beyond
this treatment period the inhibitory effect decreased to practically
non-toxic levels (13% relative inhibition) after 120 min oxidation due to the ultimate oxidation of BPA degradation products
that resulted in over 80% TOC abatement. From the ndings it is
apparent that rapid BPA degradation accompanied with efcient
TOC elimination during H2O2/UV-C treatment also decreased the
acute toxicity of BPA and its degradation products. In case of
S2O2
8 /UV-C treatment, the toxic effect of BPA solution rapidly
decreased to practically non-toxic levels (<4%) after 10 min treatment and did not change or increase thereafter which was in
agreement with the observed, progressive mineralization. From
the toxicity proles it may be inferred that relatively less biotoxic
degradation products were formed during S2O2
8 /UV-C treatment
of BPA under the investigated experimental conditions as compared with H2O2/UV-C. Similar results were also reported by
Snchez-Polo et al. (2013) who investigated the effectiveness of
oxidation processes based on UV radiation (UV, UV/H2O2, UV/
K2S2O8, and UV/Na2CO3) to remove BPA from different water
matrices. In their study the highest inhibition toward V. scheri
was obtained with the UV/H2O2 system, indicating the formation
of degradation byproducts that are more toxic than BPA.
3.3. YES bioassay results
No estrogenic or toxic activity was detected in the water
employed for solutions, and in catalase and thiosulfate concentrations used for experiments (data not shown). The estrogenic activity decreased rapidly to non-detectable levels parallel to BPA
removal when AOPs were employed to treat BPA in pure water
(Fig. 3). No substantial differences between the two AOPs were evident in terms of effectiveness in removing estrogenic activity,
Table 2
Apparent rst-order abatement rate constants for BPA, TOC and oxidants in pure
water (PW) and raw freshwater (RW).
Process

kBPA (min1)

kTOC (min1)

kOx (min1)

PW

RW

PW

RW

PW

RW

H2O2/UV-C
S2O2
8 /UV-C

0.5065
0.5202

0.1875
0.2685

0.0155
0.0099

0.0048
0.0024

0.0415
0.0298

0.0111
0.0050

UV-C

2-

H2O2/UV-C

100

S2O8 /UV-C

90
80
70

Inhibition (%)

rst-order kinetics with high correlation coefcients (R2 P 0.96).

Table 2 presents the apparent rst-order BPA and TOC removals
1
as well as S2O2
)
8 and H2O2 consumption rate constants k (in min
calculated for photochemical treatment in pure water (PW) and
raw freshwater (RW). From Table 2 it can be seen that BPA removal
rates were similar for both processes whereas TOC and oxidant
abatements rates were slightly higher for H2O2/UV-C process.

60
50
40
30
20
10
0
0

10

20

30

40

50

60

70

80

90

100

110

120

Treatment Time (min)

Fig. 2. Evolution of V. scheri toxicity during UV-C, H2O2/UV-C and S2O2
8 /UV-C
treatment of BPA. Experimental conditions as in Fig. 1.

which was expected considering the similarities in the removal

efciencies and kinetics being observed in terms of BPA and TOC
abatements. A similar pattern in estrogenic activity decreasing parallel to BPA removal was evidenced in previous related work (Chen
et al., 2006; Neamtu and Frimmel, 2006; Frontistis et al., 2011). On
the other hand, in agreement with the results obtained for direct
UV-C treatment resulting in only moderate (52%) BPA and insignificant TOC (<5%) removals, UV-C photolysis was not effective in
decreasing the estrogenic activity. Moreover, UV-C photolysis led
to formation of some degradation products exhibiting an estrogenic activity being higher than that of the untreated BPA sample.
Experimental results highlight the importance of using the AOPs
both S2O2
8 /UV-C and H2O2/UV-C and not UV-C treatment in
removing the estrogenic activity of biorefractory of emerging pollutants including BPA.
3.4. Degradation products
29 Ions were selected as possible transformation products for
each oxidation process after detailed review of full-scan chromatograms of the UV-C, S2O2
8 /UV-C and H2O2/UV-C treated BPA in pure
water. However, most of the selected ions either could not be
observed or observed even in control samples during the SIM mode
injections.
Possible degradation products for UV-C photolysis were 133 m/z,
149 m/z, 213 m/z, 218.9 m/z, and 308.9 m/z with 2.3 min, 5.52 min,
3.60 min, 4.47 min, and 3.60 min retention times, respectively.
133 m/z was observed starting from the 1st minute of the UV-C photolysis and reached its maximum peak area after 30 min treatment.
149 m/z was observed with very small peaks reaching its maximum
at 30 min. 213 m/z appearance started after 60 min treatment and
reached its maximum peak area in 120 min. 218.9 m/z was observed
after 10 min treatment and reached its maximum peak area in
30 min. The maximum peak area for 308.9 m/z was present in the
90 min sample and rst appeared after 7 min (Supporting Information Fig. S1). Spectra of MS/MS transitions for possible transformation products of BPA during UV-C treatment were provided in
Supporting Information Figs. S2S5. No matches were found for
these spectra in Massbank Library. 135 m/z, 194.6 m/z, 201 m/z,
and 276 m/z with 2.60 min, 4.35 min, 2.32 min, and 2.16 min retention times, respectively were the possible transformation products
for H2O2/UV-C process. 135 m/z was formed 1st minute of the process and was observed in all samples. It was reached its maximum
peak area in 30 min. 194.6 m/z was observed between 1 and
5 min. 201 m/z was observed between 3 and 60 min with a maximum peak area in 10 min sample. 276 m/z was observed between
3 and 30 min (Supporting Information Fig. S6). It might be proposed

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T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

1200

E2

(a)

1000

MU

800
600
400
200
0
-11

-10

-9

-8

Estrogenic activity reduction (%)

Log [M]
UV-C

160

H 2 O2 / UV - C

2-

S 2 O8 /UV- C

(b)

140
120
100
80
60
40
20
0

10

30

60

90

120

Time (min)
Fig. 3. Estrogenic activity of estradiol expressed in MU (a) and changes in
estrogenic activity of the reaction solutions during photochemical treatments (b).
Estrogenic activity reductions were expressed as percent MU with respect to t = 0.
Experimental conditions as in Fig. 1.

that 135 m/z is 3-methylbenzoic acid thanks to very good match

(score = 0.94) with Massbank library (Fig. 4). 201 m/z was proposed
as 4-sulfobenzoic acid with a match with Massbank library having
0.88 score (Fig. 5). No Massbank library match could be found with
the MS/MS spectra of other ions (Supporting Information Figs. S7
S9). Since no MS/MS transitions can be found for the S2O2
8 /UV-C
process samples, any transformation product cannot be proposed
for this process.
In previous studies it was reported that oxidative cleavage of
aromatic compounds led to ring opening products consisting of
short chain aliphatic acids such as maleic and fumaric acids as well
as simpler organic acids including acetic, formic, glyoxylic and oxalic acids (Skoumal et al., 2008; Karci et al., 2012). Oxalic and formic
acids are regarded as the ultimate carboxylic acids because they
are directly oxidized to carbon dioxide (Garcia-Segura et al.,
2012). In the present study HPLC analysis of H2O2/UV-C and
S2O2
8 /UV-C treatment of BPA in pure water revealed the generation of oxalic, succinic and fumaric acids. As aforementioned, UVC photolysis was found to be inefcient in BPA degradation into
ring opening products, as veried by the absence of carboxylic
acids. Oxalic acid, being the common short-chain carboxylic acid
for the studied treatment processes was formed at 3040 min of
treatment (Fig. 6). In case of H2O2/UV-C treatment, oxalic acid
remained in the efuent at the end of 60 min treatment. In contrast, succinic and fumaric acids were only generated during the
initial stages of H2O2/UV-C treatment only at relatively low levels.
Conclusively, the presence of some common carboxylic acids
evolving as later-stage photochemical degradation at varying concentrations products speak for similarities in the reaction pathways of S2O2
8 /UV-C and H2O2/UV-C processes.
3.5. S2O2
8 /UV-C and H2O2/UV-C treatment of BPA in raw freshwater
Normalized BPA and TOC abatements being obtained during
application of S2O2
8 /UV-C and H2O2/UV-C processes in pure water

(PW) and raw freshwater (RW) are shown in Fig. 7(a) and (b),
respectively. In addition, previously shown in Table 2 compares
apparent rst-order rate constants in terms of BPA, TOC and oxidant
abatements for raw freshwater with rate constants obtained in pure
water. From Fig. 7 it is obvious that, as expected, BPA degradation
was appreciably faster in pure water than in raw freshwater; when
subjected to S2O2
8 /UV-C treatment, BPA removal in pure water was
very rapid and complete in less than 4 min, whereas 99% removal
took 10 min in the raw freshwater matrix. In the case of H2O2/
UV-C oxidation, BPA degradation carried out in pure water and
raw freshwater was complete within 7 min and 20 min, respectively, implying that the raw water components cause a signicant
inhibition in BPA oxidation rates. Controversial to BPA abatements,
appreciably faster TOC removal rates were observed for H2O2/UV-C
treatment as compared to S2O2
8 /UV-C process. Similar results were
reported for surfactant treatment, where S2O2
8 /UV-C appeared to
be more selective for the removal of the parent compound rather
than for mineralization of oxidation intermediates (Arslan-Alaton
et al., 2013; Olmez-Hanci et al., 2014). This retardation is also evident from the TOC results of the same treatment experiments. In
fact, inhibition rates were more pronounced for the TOC parameter.
TOC removal efciency decreased from 70% to 28% after 120 min
S2O2
8 /UV-C treatment, whereas TOC removals dropped from 85%
to 45% for H2O2/UV-C treatment for the same reaction period
(Fig. 7(b)). The decrease in treatment efciencies is thought to be
a consequence of decreased UV-C photolysis of oxidants (S2O2
8 ,
H2O2) being hindered by the NOM content of the raw freshwater
matrix (TOC = 5.1 mg L1; UV254 = 0.0794 cm1) that competed for
UV irradiation. In addition it should be mentioned that inhibition
of oxidation rates is also attributable to HO and SO
4 scavenging
effect of the raw freshwater components. Considering the low alkalinity, chloride, phosphate and sulfate content of the raw freshwater sample (Table 1), the major parameter causing reduced
treatment performance is thought to be its NOM (TOC) content.
According to Table 2, BPA removal rates decreased by a factor of
approximately 2 and 3 in raw freshwater for S2O2
8 /UV-C and H2O2/
UV-C processes, respectively. Results in terms of the TOC parameter was also negatively affected; 4 and 3-fold reduction in TOC
removal rates were found for S2O2
8 /UV-C and H2O2/UV-C treat2
ments, respectively. In the S2O2
8 /UV-C process S2O8 consumption
1
rate constant decreased from 0.0298 min
to 0.0050 min1
whereas the same constant decreased from 0.0415 min1 to
0.0111 min1 for the H2O2/UV-C process. These results implied
that S2O2
8 /UV-C process was more selective in terms of BPA
removal and vulnerable in terms of ultimate oxidation than
H2O2/UV-C process.
Different degradation patterns resulting in different ecotoxicological responses depending on the water matrix have been shown
by several researchers (Zwiener and Frimmel, 2000; Trov et al.,
2009; Richard et al., 2014). Thus the effect of S2O2
8 /UV-C and
H2O2/UV-C treatments on the acute toxicity of BPA in raw freshwater samples was also elucidated in the present study. Fig. 8 displays
changes in acute toxicity of raw freshwater samples spiked with
BPA (20 mg L1) for the S2O2
8 /UV-C and H2O2/UV-C treatments.
Initial inhibition percentage of raw freshwater samples spiked with
BPA was found as 71%, thus being very close to values obtained in
toxicity tests with pure water samples. As can be seen from Fig. 8
the acute toxicity evolutions showed similar trends for S2O2
8 /UV-C
and H2O2/UV-C treated raw freshwater BPA samples; a general
reduction in the relative inhibitions was observed being faster for
S2O2
8 /UV-C process. Complete detoxication was achieved with
the S2O2
8 /UV-C and H2O2/UV-C treatments in raw freshwater,
where relatively poor treatment efciencies were obtained compared to pure water. Despite the H2O2/UV-C oxidation of BPA in
pure water, where uctuations were realized in inhibition values,
no increase in toxicities was observed in raw freshwater. The

Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020

T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

Fig. 4. Massbank match of 135 m/z and 3-methylbenzoic acid.

Fig. 5. Massbank match of 201 m/z and 4-sulfobenzoic acid.

inhibitory effect occurred only in pure water and not in raw freshwater with BPA might be associated to the matrix effect (Zwiener
and Frimmel, 2000; Trov et al., 2009; Richard et al., 2014). As a

consequence of competing reactions and different degradation

mechanism, the H2O2/UV-C treatment of BPA in raw freshwater
did not lead the formation of toxic degradation products.

Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020

T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

1.6

Oxalic Acid -H2O2/UV-C

Oxalic Acid -S2O82-/UV-C
Succinic Acid -H2O2/UV-C
Fumaric Acid -H2O2/UV-C

1.2

90
80

1.0

70

0.8
0.6
0.4
0.2

50
40
30

10

10

20

30

40

50

60

Treatment time (min)

Fig. 6. Evolution of carboxylic acids during H2O2/UV-C and
of BPA. Experimental conditions as in Fig. 1.

S2O2
8 /UV-C

0.8

0.6

0.5
0.4
0.3
0.2
0.1
0.0

10
Treatment Time (min)

15

20

1.0
0.9
0.8
0.7

0.6
0.5
0.4

2/UV-C - RW
S22O882-/UV-C
2S22O882-/UV-C
/UV-C - PW
DW
O22/UV-C
/UV-C - RW
H22O
H22O
O22/UV-C
/UV-C - PW
DW

0.3
0.2
0.1

0.0
0

10

20

30

40

50

60

70

80

30

40

50

60

70

80

90

100

110

120

Fig. 8. Evolution of V. scheri toxicity during H2O2/UV-C and S2O2

8 /UV-C treatment
of BPA in raw freshwater samples. Experimental conditions as in Fig. 7.

H22O22/UV-C - RW
H22O22/UV-C - PW
DW

0.7

20

treatment

S22O882-/UV-C - RW
2PW
S22O882-/UV-C - DW

0.9

10

Treatment Time (min)

1.0

BPA/BPA o

60

20

0.0

TOC/TOC o

S2O82-/UV-C

H2O2/UV-C

100

Inhibition (%)

Concentration (mg L-1)

1.4

90

100

110

120

Treatment Time (min)

Fig. 7. Changes in normalized BPA (a) and TOC (b) concentrations during H2O2/UVC and S2O2
8 /UV-C treatments of BPA in raw freshwater. Experimental conditions:
BPA = 20 mg L1 (88 lM); TOC = 21 mg L1; oxidant dose = 2.5 mM; initial reaction
pH = 8.6; applied UV-C dose = 21 W h L1.

4. Conclusions
The present work aimed at comparatively investigating the
treatability of BPA with the H2O2/UV-C and S2O2
8 /UV-C processes
in pure and raw freshwater samples. The study mainly focused
on examination of toxicity and estrogenic activity changes being
observed during photochemical treatment. Besides, identication
and quantication of photochemical degradation products via
LCMS/MS and HPLC analyses was targeted. The following conclusions could be drawn from the obtained experimental results:

oxidation processes have to be applied for the efcient treatment and complete detoxication of aqueous BPA.
H2O2/UV-C treatment in pure water resulted in a rapid and complete BPA degradation accompanied with high TOC removals
exceeding 80%. Acute toxicity tests revealed that V. scheri were
very sensitive to photochemically induced changes in the reaction solution. The YES test results indicated an abrupt reduction
of the estrogenic activity within the rst 5 min of photochemical
treatment. As long as the organic carbon content of BPA was
transformed to various degradation products, V. scheri toxicity
kept on uctuating, but decreased as TOC removal progressed.
S2O2
8 /UV-C treatment in pure water also brought about rapid
and complete BPA as well as TOC removals. Different from
H2O2/UV-C oxidation, the inhibitory effect of BPA on V. scheri
decreased gradually, almost parallel to BPA abatement and
remained stagnant thereafter. Concerning estrogenic activity,
there were no signicant differences, in terms of effectiveness,
between the two AOPs.
3-Methylbenzoic and 4-sulfobenzoic acid were proposed as the
H2O2/UV-C degradation products. Although at different concentrations, oxalic acid was generated as the common ring opening
product of H2O2/UV-C and S2O2
8 /UV-C treatments whereas succinic and fumaric acids were additionally detected during H2O2/
UV-C treatment.
The raw freshwater matrix (TOC: 5.1 mg L1; pH: 8.6; alkalinity: 124 mg L1 CaCO3) exhibited a negative effect on BPA and
TOC abatements. The reduced degradation and mineralization
of BPA might be attributable to the high natural organic matter
content that signicantly hindered UV-C absorption by S2O2
8

and H2O2 but also acted as a SO
4 /HO scavenger. Nevertheless,
the raw freshwater samples were found to be non-toxic after
BPA treatment. The water matrix seemed to be playing a significant role in the toxicity changes in the presence of BPA and its
degradation products.

The presence of BPA in the environment is likely to disturb the

ecosystems and negatively affect human health. Thus, the need for
developing advanced processes for water and wastewater
treatment remains of major environmental concern. Comparison
of different photochemical processes on the basis of their treatment and detoxication performance for emerging contaminants
found in real water and wastewater remains a challenging task.

Acknowledgements
 UV-C photolysis of BPA solution resulted in poor BPA degradation and TOC removals. This was also ecotoxicologically conrmed by the V. scheri and YES bioassays. Hence, advanced

The nancial support of the Scientic and Technological

Research Council of Turkey (TUBITAK) under Project No:

Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020

T. Olmez-Hanci et al. / Chemosphere xxx (2014) xxxxxx

111Y257 is gratefully acknowledged. The authors are thankful to

Prof. Dr. Isk Kabdasl for her support during Vibrio scheri analysis.
Idil Arslan-Alaton is a member of the Academy of Science, Turkey.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemosphere.
2014.06.020.
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Please cite this article in press as: Olmez-Hanci, T., et al. S2O82/UV-C and H2O2/UV-C treatment of Bisphenol A: Assessment of toxicity, estrogenic activity,
degradation products and results in real water. Chemosphere (2014), http://dx.doi.org/10.1016/j.chemosphere.2014.06.020