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Feasibility of a two-stage reduction/subsequent oxidation

for treating Tetrabromobisphenol A in aqueous solutions
Si Luo, Shao-gui Yang*, Cheng Sun*, Xiao-dong Wang
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093, PR China

article info

abstract

Article history:

A two-stage reduction/subsequent oxidation (T-SRO) process consists of FeeAg reduction

Received 3 July 2010

and Fenton-like oxidation under ultrasound (US) radiation. Due to the refractory oxidation

Received in revised form

of brominated flame retardant, T-SRO was employed to remove Tetrabromobisphenol

22 October 2010

A (TBBPA) by the combination of first debromination and succeeding oxidation. It indicated

Accepted 31 October 2010

that the T-SRO process resulted in a complete decrease in TBBPA concentration and

Available online 10 December 2010

a 99.2% decrease in BPA concentration. The T-SRO process for the removal of TBBPA is
much effective than Fenton-like oxidation of TBBPA alone. The result showed that US

Keywords:

radiation improved the Fenton-like oxidation rate of BPA solutions. The addition of dis-

Two-stage

solved iron into the Fenton-like oxidation system could accelerate the first 2 min reaction,

Debromination

but had little effect on the following process. The main intermediate products resulting

Fenton-like oxidation

from TBBPA reduction and BPA oxidation were identified by GCeMS and LC-MS/MS. On the

Tetrabromobisphenol A

basis of this analysis, reactions with
OH radical were identified as the major chemical

Bimetallic nanoparticles

pathways during BPA oxidation.

2010 Published by Elsevier Ltd.

Ultrasound radiation

1.

Introduction

Tetrabromobisphenol A (TBBPA) is one of the most widely

used brominated flame retardant around the world. It can be
covalently bound to the polymer in the manufacturing
process (de Wit, 2002). TBBPA and its dimethylated derivative
have been detected in various environmental matrices, and
they negatively affect various aspects of mammalian and
human physiology (Sellstrom and Jansson, 1995; Helleday
berg et al., 2002). Conseet al., 1999; Meerts et al., 2000; O
quently, removal of TBBPA in the contaminated environment
is necessary and significant. The reported treatment mainly
includes biotransformation, photochemical transformations
and thermal decomposition (Mackenzie and Kopinke, 1996;
Barontini et al., 2004; Eriksson et al., 2004). In addition, it
also indicated that removal of the halogen substituent is a key
step in the degradation of halogenated aromatic compounds.

This may occur as an initial step via reductive, hydrolytic, or

oxygenolytic mechanisms or may occur after ring cleavage at
a later stage of degradation (Monserrate and Haggblom, 1997).
Zero valent iron (ZVI) and bimetallic particles have been
used for degradation of halogen-containing organic substance
(Orth and Gillham, 1996; Cwiertny et al., 2006). In our previous
work (Luo et al., 2010), we reported that TBBPA was reductively
debrominated to bisphenol A (BPA) over FeeAg bimetallic
nanoparticles under US radiation. However, it is well known
that BPA exhibits estrogenic activity, which increases the
proliferation rate of breast cancer cells and induces the acute
toxicity to freshwater and marine species (Pulgar et al., 1998;
Kaiser, 2000). Therefore, the debromination of TBBPA in
FeeAg/US system is incomplete, BPA must be further
degraded. An effective method for BPA mineralizing is the
application of Fenton (Fenton-like) oxidation technologies
(Gozmen et al., 2003; Ioan et al., 2007). On the other hand,

* Corresponding authors. Tel./fax: 86 25 89680580.

E-mail addresses: yangdlut@126.com (S.-g. Yang), envidean@nju.edu.cn (C. Sun).
0043-1354/$ e see front matter 2010 Published by Elsevier Ltd.
doi:10.1016/j.watres.2010.10.039

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ZVI can be used to substitute ferrous salts in the Fenton-like

oxidation, and it seems to have similar degradation rates to
homogeneous ferrous catalyst. It has confirmed that phenol
(Bremner et al., 2006) and 4-chlorophenol (Zhou et al., 2008)
could be rapidly degraded in ZVI/H2O2 system.
Since iron can reductively transform the electron-withdrawing moieties and render recalcitrant compounds more
amenable to subsequent oxidation processes, several
researchers presented the ZVI reduction for the pretreatment
of wastewater (Mantha et al., 2001, 2002; Oh et al., 2005). Oh
et al. (2003) reported the enhanced Fenton oxidation of TNT
and RDX through pretreatment with ZVI. Thus, in consideration of the complete treatment of TBBPA, ZVI-based reductive debromination followed by Fenton-like oxidation is
proposed, where FeeAg bimetallic nanoparticles are used to
debrominate TBBPA because of its higher catalytic activity
relative to ZVI.
This paper evaluates the effectiveness and feasibility of
a T-SRO treatment of TBBPA. Experiments are conducted to
examine separately the performance of the FeeAg nanoparticles reductive and Fenton-like oxidative systems. The
effect of US radiation in Fenton-like oxidation process is discussed; the influence of dissolved iron (ferrous and ferric ions)
on the oxidation kinetics of ZVI/H2O2 system is also investigated. On the basis of identifying intermediate and final
products, the reaction pathways are proposed.

2.

Experimental section

2.1.

Materials

2.3.

The reduction of TBBPA (5 mg L1) was conducted by FeeAg

nanoparticles (0.8 g L1) under US radiation (40 kHz and
100 W). Debromination experiments were performed in
a chamber as shown in Fig. SM-1 (a) attached in Supplemental
Material (SM). The detailed procedure of reduction experiment
was reported in the literature (Luo et al., 2010).

2.4.

2.2.
Synthesis and characterization of FeeAg bimetallic
nanoparticles
FeeAg bimetallic nanoparticles with core-shell structure were
synthesized by reductive deposition of Ag on ZVI nanoparticles as described in the literature (Luo et al., 2010).
Various analytical techniques including XRD, XPS and
XRF were used to characterize the fresh and reacted (after
reduction process) FeeAg bimetallic samples. X-ray diffraction (XRD) analyses of the samples were performed using
).
Switzerland ARL XTRA X-ray diffractometer (l 1.5418 A
The metal oxidation states and surface atomic composition
of FeeAg samples was examined via X-ray photoelectron
spectroscopy (XPS, Thermo VG Scientific ESCALAB 250).
X-ray fluorescence (XRF, Switzerland ARL Corporation) was
used to measure the mass of Ag deposited on the surface of
nanoiron.

Fenton-like oxidation experiment

To keep a constant temperature (25  1  C), the Fenton-like

process was conducted in a chamber as presented in Fig. SM-1
(b). The reduction and oxidation experiments were carried out
in the same vessel. In each bottle, the solution contained BPA
and FeeAg nanoparticles after reduction. Its initial pH was
adjusted to 3.0  0.1 with 0.1 M H2SO4 and 0.1 M NaOH solutions. The oxidation experiments were started by dropping
H2O2 solutions into the mixture by a separatory funnel. The
flow rate was controlled at 2 mg L1 min1 and lasted 10 min in
the whole oxidation process. At the given reaction time
intervals, 1 mL sample was withdrawn. 10 mL 1 M tert-butanol
was immediately added into the sample as reaction inhibitor.
Then the samples were filtered by a syringe filled with a little
silanized glass wool. The concentrations of BPA and intermediates in the filtrate were measured by high-performance
liquid chromatography (HPLC). If no specific instructions are
given, initial pH of Fenton-like oxidation is 3.0  0.1, nanoparticles loading is 0.8 g L1 and Ag content in FeeAg
composite material is 1 wt.%.

2.5.
Tetrabromobisphenol A, bisphenol A and tert-butanol were
obtained from SigmaeAldrich Company. H2O2 (30%, v/v) was
purchased from Fisher Company. AgCl, FeSO4$7H2O, Fe2(SO4)3,
H2SO4, NaOH, Na2SO3, 1,10-phenanthroline and ferrous
ammonium sulfate were provided by Nanjing Chemical
Company. HPLC-grade methanol and dichloromethane were
purchased from Tedian Company and used without further
purification. Milli-Q water was used throughout this study.
The zero valent iron used was iron powder (Shenzhen Junye
Nano Material Co., Ltd, >99.9, <60 nm).

Reduction experiment of TBBPA

Analytical methods

The concentrations of TBBPA were analyzed via HPLC (Agilent

1200, USA), with a C18 reversed-phase column (150 mm 
4.6 mm, 5 mm particles, Agilent, USA). Identification of reductive debromination products was performed by LC-ESI-MS/MS
(Thermo LCQ Advantages, QuestLCQ Duo, USA) equipped with
electrospray ionization with Beta Basic-C18 HPLC column
(150 mm  2.1 mm id, 5 mm Thermo, USA). The specific operation conditions of HPLC and LC-ESI-MS/MS were provided in
the literature (Luo et al., 2010).
The HPLC operation conditions of BPA were as follows: the
mobile phase was 30% water in methanol. At the detection
wavelength of 226 nm and flow rate of 1.0 mL min1, the BPA
retention time was 3.4 min. Since the oxidation products were
so complex, a Thermo Finnigan Trace gas chromatography
interfaced with a Polaris Q ion trap mass spectrometer (GC/
MS, Thermo, Finnigen, USA) equipped with DB-5 fused-silica
capillary column (30 m  0.32 mm i.d, 0.25 mm film thickness)
was used for analyzing the samples. Prior to GCeMS analysis,
the samples were extracted with dichloromethane for three
times. The extracted solution was dehydrated using anhydrous sodium sulfate and concentrated to 1 mL by rotary
evaporation. After the solvent was blown away by the gentle
nitrogen, trimethylsilylation was carried out at 50  C for
30 min using 0.2 mL of bis(trimethylsilyl)trifluoroacetamide
(BSTFA). The initial temperature of the column oven was 40  C
and following 1 min hold at this temperature, and then
increased up to 300  C with a heating rate of 6  C min1.

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w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 1 5 1 9 e1 5 2 8

Helium was used as the carrier gas. Mass spectrometric

detection was operated with 70 eV electron impact (EI) mode.
The degradation products were also analyzed by LC-ESI-MS/
MS. The injection volume was 20 mL, and the mobile phase was
methanol to water (70:30). The MS analysis was conducted
with negative-ionization mode with electrospray interface
(ESI) source. Full scanning analyses were performed by scanning m/z range from 50 to 600 in profile mode.
The dissolved bromide ion was determined using a Dionex
ion chromatograph (IC, Dionex model ICS 1000) equipped with
a dual-piston (in series) pump, a Dionex IonPac AS11-HC
analytical column (4 mm  250 mm) and a Dionex DS6
conductivity detector. Suppression of the eluent was achieved
with a Dionex anion ASRS 300 electrolytic suppressor (4 mm)
in the auto suppression external water mode. The concentration of dissolved iron and ferrous ion was measured by the
o-phenanthroline colorimetric method (l 510 nm,
e 1.1  104 M1 cm1). Ferric concentration calculated by
subtracting dissolved iron with ferrous concentration.

3.

Results and discussion

3.1.

Characterization

Detailed morphology and structure characterization of the

FeeAg particles were presented in the literature (Luo et al.,
2010). Fig. 1 is the XRD spectra of the fresh and reduced
FeeAg particles. The XRD patterns of aged samples show
peaks associated with iron oxides, indicating that surface of
the used reductant is covered by a layer of oxide film which
may form during the reduction process. The XPS survey scans

Fig. 1 e XRD of Fe-Ag bimetallic nanoparticles. (a) Fresh

samples, (b) Reacted samples.

Table 1 e Composition of surface elements.

Element

Ag 3d
Fe 2p
O 1s
C 1s

XPS surface composition (atom %)

Before

Reacted

0.57
40.59
36.11
22.73

0.53
24.69
53.88
20.91

of Fe and Ag over the surface of the FeeAg nanoparticles are

described in Fig. SM-2. Table 1 shows elements (iron, silver
and oxygen) composition of the samples before and after
reaction. After reduction, iron oxide layer is adopted a larger
amount of oxygen which indicated the structure of the particles with iron oxide in the outer of the sphere and ZVI in the
inner.

3.2.
Fenton-like oxidation of TBBPA in a heterogeneous
FeeAg/H2O2 system
In order to investigate the Fenton-like oxidation effect of
TBBPA in a heterogeneous FeeAg/H2O2/US system, experiments were conducted in an 150 mL conical bottle with
5 mg L1 TBBPA and 0.8 g L1 FeeAg nanoparticles. The other
conditions were as the same as the Fenton-like oxidation of
BPA, which was mentioned in the Section 2.4.
A typical reaction profile of TBBPA in FeeAg/H2O2/US
system is given in Fig. 2. The result shows that more than 30%
of TBBPA was removed in 2 min and then the degradation rate
decreased. Up to 40% of TBBPA disappeared as the reaction
was prolonged to 30 min. To gain more chemical structure
information on the reaction products, reaction solution was
subsequently extracted and possible polar products were
silylated with BSFTA, and then subjected to GCeMS analysis.
The detailed data are provided in the Supplemental Material.
The results show that the main TBBPA oxidation products
are brominated phenol species. In fact, there is strong

Fig. 2 e Degradation of TBBPA in aqueous solution by

Fe-Ag/H2O2/US. [Fe-Ag bimetallic] [ 0.8 g LL1; flow rate of
H2O2 [ 2 mg LL1 minL1, lasted 10 min;
[TBBPA]0 [ 5 mg LL1; US conditions: 40 kHz, 100 W.

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w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 1 5 1 9 e1 5 2 8

Fig. 3 e (a) Temporal disappearance of TBBPA and appearance of by-products in aqueous solution during FeeAgeUS
reduction treatment. [Fe-Ag bimetallic] [ 0.8 g LL1, Ag content (wt %) [ 1%, and [TBBPA]0 [ 5 mg LL1. (b) Temporal change
of BPA and its hydroxylated products concentration in the solution during Fe-Ag/H2O2/US oxidation treatment. [Fe-Ag
bimetallic] [ 0.8 g LL1; flow rate of H2O2 [ 2 mg LL1 minL1, lasted 10 min; [BPA]0 [ 4.64 mg LL1; US conditions: 40 kHz,
100 W.

evidence that halogen, when placed in the organic moleculecarbon group, could increase the bio-toxicity of the organic
compound. Bromine, due to its weaker electronegativity,
could be considered better leaving groups and hence should
be more toxic (Lag et al., 1994; DeWeese and Schultz, 2001;
Huang et al., 2007). Several studies have presented the
results from ecotoxicologic investigations of the brominated
aromatic compounds, including brominated benzenes,
brominated phenols and indoles, 2-bromo- hydroquinone and
 ska, 1998; Bruchajzer et al., 2002; Reineke et al.,
so on (Szyman
2006). Therefore, the Fenton-like oxidation of TBBPA in
a heterogeneous FeeAg/H2O2 system is unsuitable and inadequate. Considering that the primary step in the degradation
of halogenated compounds is the removal of halides from the

aromatic ring, such a T-SRO process mentioned above is

proposed for the treatment of TBBPA.

Fig. 4 e Degradation of BPA in aqueous solution by Fe-Ag/

H2O2 with and without ultrasonic radiation. [Fe-Ag
bimetallic] [ 0.8 g LL1; flow rate of H2O2 [ 2 mg LL1 minL1,
lasted 10 min; [BPA]0 [ 5 mg LL1; US conditions: 40 kHz,
100 W.

Fig. 5 e Degradation of BPA in aqueous solution by Fe-Ag/

H2O2/US with and without addition of dissolved iron. [Fe-Ag
bimetallic] [ 0.8 g LL1; flow rate of H2O2 [ 2 mg LL1 minL1,
lasted 10 min; [BPA]0 [ 5 mg LL1; [Fe2D] [ 1.26 mg LL1,
[Fe3D] [ 0.37 mg LL1; US conditions: 40 kHz, 100 W.

3.3.
TBBPA debromination by FeeAg bimetallic
nanoparticles
Fig. 3 (a) shows the time course profiles for disappearance of
TBBPA and appearance of by-products in aqueous solution
over FeeAg bimetallic nanoparticles coupled with US radiation. The initial TBBPA concentrations and catalysts amount
were chosen based on results of previous reduction experiments (Luo et al., 2010). In neutral conditions (pH 6.94),
FeeAg bimetallic nanoparticles completely degraded TBBPA
(5 mg L1) in 20 min coupled with US radiation.

w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 1 5 1 9 e1 5 2 8

Along with the decrease of TBBPA concentration, almost

100% of TBBPA was gradually debrominated to lowly brominated compounds. The released bromine was in hydrogen
bromine form. TBBPA might be transformed into tri-BBPA and
di-BBPA, then tri-BBPA and di-BBPA were dehalogenated to

1523

mono-BBPA, at last, BPA was generated by the debromination

reaction of these three intermediates. The BPA concentration
increased stably and continuously in the all 70 min and
reached 4.64 mg L1 at the end of reduction process. The
carbon mass balance at the end of the experiment (calculated

Fig. 6 e (a) Total ions chromatogram of BPA in the solution during Fe-Ag/H2O2/US oxidation treatment. (b) LC-MS/MS
analysis of BPA degradation intermediates.

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as the sum of all organic species measured) was approximately 94% of the calculated initial TBBPA concentration. We
suspect that minor losses may have occurred during filtering
through the silanized glass wool.

3.4.
Fenton-like oxidation of BPA in a heterogeneous
FeeAg/H2O2/US system
Experiments of BPA control, FeeAg nanoparticles alone and
H2O2 alone were also carried out in 150 mL conical bottles
under US radiation, and the initial concentration of BPA was
5 mg L1. The results in Fig. 3 (b) indicate that no obvious
removal of BPA was observed in the control and FeeAg
nanoparticles alone experiments throughout 30 min. In the
H2O2 alone degradation experiment, 15% degradation of BPA
was observed after 30 min reaction. It means that the hydroxyl
radicals generated by ultrasounds radiation could destroy the
BPA with adding H2O2. The effect of US radiation will be discussed in detail in Section 3.4.1
As shown in Fig. 3 (b), after 2 mg L1 min1 of H2O2 (lasted
10 min) was added to the BPA solution debrominated from
TBBPA, BPA concentration rapidly declined from 4.64 to
0.11 mg L1 over 30 min with removal efficiency of 99.2%.
Concentration change profile of BPA derivatives is also given in
Fig. 3 (b) in terms of the HPLC peak areas of the corresponding

compounds versus the charge applied to the system. The

typical chromatogram of BPA during the oxidation in 30 min is
depicted in Fig. SM-4. It can be seen that peak I corresponded to
the parent compound BPA and two main intermediates peaks
appeared (II and III). Peak II had a retention time of 2.7 min,
which increased at first but decreased quickly after radiation
for 6 min. Peak III had a retention time of 2.5 min, which
appeared after reaction for 8 min and decreased afterward.
These two intermediates were the products for the Fenton-like
oxidation of BPA, whose decrease implied that further oxidation of BPA continued in solution.

3.4.1. Effect of ultrasonic radiation on BPA Fenton-like

oxidation
It is all well known that introduction of US can evidently
improve pollutant degradation in Fenton system (Ioan et al.,
2007; Namkung et al., 2008). When US were introduced into
Fenton-like reaction, the mechanism would be more complex.
The results of oxidation experiments in the presence and
absence of US radiation are compared and presented in Fig. 4.
Under US radiation, an obvious increase of BPA degradation
efficiency in the solution was observed. Thus, there was
a synergistic effect between US and Fenton-like reactant,
which could improve the degradation of BPA in the heterogeneous FeeAg/H2O2/US system.

Fig. 7 e GC/MS analysis of BPA degradation intermediates and final products.

1525

w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 1 5 1 9 e1 5 2 8

In general, introduction of US radiation into a heterogeneous system could produce both chemical and physical
effect. The possible reasons for synergistic effect between US
and Fenton-like reactant are as follows. Firstly, US could
increase the
OH radical concentration by US cavitation. Guo
and Feng (2009) described that the US elimination of BPA in
aqueous solution is mainly attributed to the
OH radical
oxidation. BPA was decomposed by
OH radicals principally at
the bubble-bulk solution interface in absence of FeeAg nanoparticles. In FeeAg/H2O2/US Fenton-like oxidation experiments, US cavitation increased the amount of
OH radical and
therefore accelerated the degradation reaction. Secondly, US
shock wave could enhance dissolution of ferrous ion from iron
surface. The main reason was ascribed to the removal or
destruction of passivation films on the metal surface by cavitation effects (Tomlinson, 1990; Namkung et al., 2008). Thus,
the increase of iron concentration in the solution might lead to
enhance the oxidation of BPA. In addition, US radiation can
transform BPA slightly with H2O2, as shown in Fig. 3 (b).

3.4.2. Effect of dissolved iron (Fe2 and Fe3)

on BPA Fenton-like oxidation
To demonstrate the role of dissolved iron, ferrous ion and
ferric ion were added to the FeeAg/US system with 5 mg L1
BPA. The concentrations of Fe2 and Fe3 in the solution after
debromination were 1.26 mg L1 and 0.37 mg L1, respectively.
These values were taken as the dissolved iron amount used
for addition in the oxidation experiments for comparison.
Fig. 5 shows that BPA decayed during the treatment by only
FeeAg and FeeAg with dissolved iron Fenton-like process. In
the two cases, BPA concentration was under the detection
limit after 20 min, indicating that the oxidation capacity of the
two systems (FeeAg and FeeAg dissolved iron) showed less
difference throughout the reaction. However, in the first
2 min, 56% decomposition of BPA was achieved in the presence of Fe2 and Fe3 ion while only 22% BPA removal was
observed in the absence of Fe2 and Fe3 ion.
Zhou et al. (2008) reported that the two-stage kinetic of 4chlorophenol degradation in a heterogeneous ZVI/H2O2 system

Table 2 e Identification of the intermediates of BPA during the Fenton-like oxidation by GC/MS.
Product

Rt (min)

m/z

Name

3.28

90

Oxalic acid

4.89

116

Maleic acid

5.67

108

p-Benzoquinone

6.97

94

phenol

7.45

90

2-hydroxypropanoic acid

Molecular structure
HO

OH

O O
HO

OH

OH

OH
OH

13.01

92

propane-1,2,3-triol

14.72

134

4-isopropenylphenol

15.75

110

p-hydroquinone

19.20

136

4-hydroxyacetophenone

30.52

228

BPA

35.53

244

BPA-o-catechol.

OH

OH

HO

OH

OH

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Scheme 1 e Main Fenton-like oxidation reaction pathway of BPA.

was composed of an initial slow degradation stage and a followed rapid degradation stage. In the first stage, the decomposition of H2O2 occurred on/near the ZVI surface, dissolving
iron to ferrous, and Fenton reaction occurred concomitantly
on/near surface in the presence of ferrous and H2O2. Based on
this, the addition of dissolved irons species could increase the
degradation rates of BPA, especially in the initial stage. As the
reaction progresses, ferrous ion and ferric ion leached from
iron surface and their concentrations increased gradually.
Accordingly, addition of dissolved iron would not affect the
removal efficiency in the entire Fenton-like process.

3.5.
Identification of Fenton-like oxidation
products of BPA
The analyses of main BPA products formed during the Fentonlike oxidation were carried out using LC-MS/MS and GCeMS.
The intermediates and products were identified by the analysis
of mass spectra obtained from LC-MS/MS and/or GCeMS
applications and by the comparison with the library data of
NIST.
Fig. 6 (a) is the total ion chromatogram of BPA solution
throughout oxidation reaction, which shows three peaks with
retention time at 12.69 min, 9.78 min and 8.23 min, respectively. Fig. 6 (b) is the mass spectra for them. It can be seen that
the compound at 12.69 min was BPA (I) with m/z 227. The peaks
labeled with II (9.78 min, m/z 243) and III (8.23 min, m/z 257)
corresponded to the monohydroxylated BPA product and the
dihydroxylated BPA product, respectively. The former gave
base ion at 243 m/z on ESI negative mode detection, was BPA-ocatechol. This compound also showed other ion at 241 m/z,
suggesting that BPA could be transformed via the following
reversible equilibration between BPA-o-catechol (MW 244)
and BPA-o-quinone (MW 242). These products obviously have
a greater hydrophilicity than BPA, so their retention times were
shorter under the HPLC condition in our experiment.

Other products in the Fenton-like oxidation, including 4isopropenylphenol and the open ring products, were detected
by GCeMS (Fig. 7). This result is similar to that reported by
Gozmen et al. (2003) in their studies on the electro-Fenton
oxidation of BPA. After all the peaks in the chromatograms
were carefully examined, up to 10 compounds were identified
as possible intermediates. Detailed data are listed in Table 2.
The intermediates with benzene ring could be further
oxidized into small organic molecules, with the retention
times at 3.28, 4.89, 7.47 and 13.01 min, most of which were
organic acids, such as oxalic acid, and so on. However, some
products such as HCOOH were not observed due to their low
levels and unavoidable loss during the sample preparation
course. Based on the intermediates and the results obtained
by other researchers (Katsumata et al., 2004; Guo and Feng,
2009), the possible pathways of BPA oxidation were represented in Scheme 1. The expatiation of these pathways is
presented in the Supplemental Material.
In addition, the brominated compounds were not present in
the Fenton-like degradation products. After reduction and
oxidation processes, the amount of dissolved Br measured by IC
was 2.5 mg L1 and 2.3 mg L1, respectively, which showed that
the variation of Br concentration in the solution was negligible
in Fenton-like experiments. Based on analysis described above,
we referred that the debromination of TBBPA was to release HBr
and the bromination of decomposition products by bromine that
was not formed even in the present of
OH radicals. In other
words, the bromine generated from TBBPA reduction did not lead
to the formation of secondary brominated products by interaction with the primary oxidation products of BPA.

4.

Conclusions

The degradation of TBBPA in aqueous solution was investigated by Fe-Ag reduction and Fenton-like oxidation under US

w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 1 5 1 9 e1 5 2 8

radiation. TBBPA was completely debrominated to BPA after

70 min over FeeAg bimetallic nanoparticles. For BPA, removal
efficiency of 99.2% was achieved after 30 min under the
optimum conditions. The US radiation enhanced the degradation rate of BPA as compared to Fenton-like only. In addition, dissolved iron was found to increase the rate of the first
2 min oxidation reactions, however, the existence of Fe2 and
Fe3 did not affect entire Fenton-like degradation of BPA. This
work shows that it is feasible for T-SRO treatment to
completely decompose TBBPA in aqueous solutions.
GCeMS and LC-MS/MS techniques were used to identify the
oxidation intermediates in order to gain a deeper insight of the
reaction mechanism. The main intermediates include monohydroxylated BPA, 4-isopropenylphenol, p-hydroquinone,
4-(1-hydroxy-1-methyl-ethyl)-phenol, 4-hydroxyacetophenone
and phenol. Besides,
OH radical-mediated oxidation was
found to be the major destruction pathway during BPA decomposition. Future work will need to be done to improve the
potential mineralization of BPA, as well as the fate of the
organic molecules to confirm mineralization.

Acknowledgements
The authors greatly acknowledge the National Natural
Science Foundation of China (20707009), National Major
Project of Science & Technology Ministry of China (NO.
20082X07421-002) for financial support, and National Natural
Science Foundation of China (50938004).

Appendix. Supplementary data

Supplementary data associated with the article can be found
in online version, at doi:10.1016/j.watres.2010.10.039.

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