Oxidation of Bisphenol A by UVS 2 O - Comparison With UVH 2 O
Oxidation of Bisphenol A by UVS 2 O - Comparison With UVH 2 O
Oxidation of Bisphenol A by UVS 2 O - Comparison With UVH 2 O
Environmental Technology
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http://www.tandfonline.com/loi/tent20
Water Environmental Centre, Korea Institute of Science and Technology (KIST) , 39-1
Hawolgok-dong, Seongbuk-gu, Seoul , 136-791 , Republic of Korea
Accepted author version posted online: 27 May 2011.Published online: 19 Dec 2011.
To cite this article: Sung-Hwan Yoon , Seongpil Jeong & Seockheon Lee (2012) Oxidation of bisphenol A by UV/S2O :
Comparison with UV/H2O2 , Environmental Technology, 33:1, 123-128, DOI: 10.1080/09593330.2011.579181
To link to this article: http://dx.doi.org/10.1080/09593330.2011.579181
Environmental Technology
Vol. 33, No. 1, January 2012, 123128
(pHi = 4) < basic pH (pHi = 10). The main oxidizing species in the UV/S2 O2
8 system was sulphate radical (SO4 ),
whereas the main oxidizing species in the UV/H2 O2 system was OH radical (OH ). Compared with UV/H2 O2 , the
UV/S2 O2
8 process showed higher performance for not only BPA degradation but also its mineralization, which means
that SO
4 is a more eective oxidant for BPA than the OH . The results shown in this study imply that the SO4 -based
UV/S2 O2
8 process can be an excellent alternative process for the widely used UV/H2 O2 process, with higher remediation
performance.
Keywords: endocrine-disrupting chemical; bisphenol A, UV/S2 O2
8 , UV/H2 O2 , sulphate radical, OH radical.
Introduction
Endocrine-disrupting compounds (EDCs) are natural and
synthetic chemicals that cause adverse eects on humans
and animals by inuencing the endocrine system. They
include natural estrogens, synthetic estrogens and anthropogenic chemicals, and they have been reported to be a
signicant cause of reproductive and sexual disturbance in
animals [1,2]. Various EDCs are released into the aquatic
environment, mainly via the euents of sewage treatment
plants (STPs). The detected concentrations of EDCs in
the aquatic environment are known to range from ng/L
to g/L level [3,4]. Even with those low concentrations,
EDCs can pose a serious threat to the endocrine system of humans and animals. The widespread existence of
EDCs in the aquatic environment implies that EDCs are
not suciently removed by conventional water treatment
processes (e.g. activated sludge, activated carbon, chlorination). Because of the highly hazardous eects on humans
and animals, it is necessary to remove EDCs more eectively from STPs and drinking water treatment plants. For
this purpose, advanced oxidation processes (AOPs) have
been recommended owing to the high potential for the
oxidation of persistent micropollutants such as EDCs, pharmaceutically active compounds and personal care products
Corresponding
Photochemical experiments
Disodium hydrogen phosphate (Na2 HPO4 ) was added for
maintaining a desired pH, and 0.1 M H2 SO4 and 0.2 M
NaOH were used for pH adjustment. Experiments were
carried out using a cylindrical borosilicate glass reactor (50 mm i.d. 230 mm height). An aqueous solution
(250 mL) containing BPA and an oxidant (S2 O2
8 or H2 O2 )
was poured into the reactor. The solution was irradiated with UV-C light ( = 254 nm) with magnetic stirring. Sample aliquots were intermittently withdrawn for
analysis. Sodium thiosulphate (Na2 S2 O3 ) was immediately added as a quenching reagent into every sample
before high-performance liquid chromatography (HPLC)
and total organic carbon (TOC) analyses, in order to
stop the potential reaction between BPA and persulphate
([Na2 S2 O3 ]/[persulphate] > 10).
0.6
0.4
0.2
0.0
0
10
15
20
Analysis
The concentration of BPA was measured using a Shimadzu
high-performance liquid chromatography (HPLC) system
with a uorescence detector. A C-18 reverse-phase column served as the stationary phase, with 1 mL/min of
the eluent consisting of 50% acetonitrile and 50% 10 mM
phosphoric acid. An excitation wavelength of 229 nm and
an emission wavelength of 309 nm were used to detect
the uorescence. Mineralization eciency was determined
using a Shimadzu TOC analyser. The S2 O2
8 concentrations were determined by the iodometric spectrophotometer
method [21], and H2 O2 concentrations were measured by
the 2,9-dimethyl-1,10-phenanthroline (DMP) method [22].
An Orion 250 pH meter was used for the pH measurements.
A HACH DR 5000 spectrophotometer was employed for
the absorption measurements.
1.0
0.8
1.0
0.8
[BPA]t / [BPA]0
Experimental
Materials
radicals
to
react
with BPA
causes a higher amount of SO
4
for a given amount of BPA, and thus the required reaction
time is shortened.
[BPA]t / [BPA]0
124
100 M S2O820.6
0.4
0.2
0.0
0
10
15
20
Environmental Technology
1.0
1.0
0.8
[BPA]t / [BPA]0
0.8
[BPA]t / [BPA]0
125
0.6
0.4
0.6
0.4
UV/S 2O8
0.2
0.2
HA-DOC = 0 mg/L
HA-DOC = 8.5 mg/L
HA-DOC = 17 mg/L
2-
w/o alcohols
w/ 10 mM t-butanol
w/ 10 mM ethanol
0.0
0.0
0
1.0
[BPA]t / [BPA]0
0.8
pH 4
pH 7
pH 10
0.8
[BPA]t / [BPA]0
1.0
0.6
0.6
0.4
UV/H 2O2
0.2
0.4
w/o alcohols
w/ 10 mM t-butanol
w/ 10 mM ethanol
0.0
0
0.0
0
rapid dissociation of S2 O2
8 to SO4 . The higher eciency
at the acidic pH than at the neutral pH also seems due
to the more rapid decomposition of S2 O2
8 and formation
.
The
acidand
base-catalysed
decomposition
of
of SO
4
persulphate is a well-known phenomenon [24,25]. However, it seems that this pH dependence (pHi 7 < pHi 4 <
pHi 10) is not always apparent in the UV/S2 O2
8 system.
In a previous study by Lau et al. [18], it was reported
that the degradation eciency of butylated hydroxyanisole
(BHA) by UV/S2 O2
8 increases with the increase in initial
pH (pHi = 312). It is inferred that the pH eect on the
UV/S2 O2
8 process is not constant but varies depending on
target pollutants.
1.0
BPA degradation
0.8
UV + 2 mM S2O82UV + 2 mM H2O2
UV + 0.5 mM S2O82-
0.6
UV + 0.5 mM H2O2
UV alone
0.4
0.2
0.0
0
1.0
UV + S2O82UV + H2O2
0.8
0.6
0.4
BPA mineralization
0.2
0
10
20
30
40
Ct
C0
= kt
(1)
1.0
S2O82H 2 O2
0.8
0.6
C / C0
[BPA]t / [BPA]0
of t-butanol with SO
4 is greatly dierent from that with
dierentiating SO
4 -induced reactions from OH -induced
reactions [17]. Alcohols containing no -hydrogen, such
5
is c.1000-fold greater than that with SO
4 (4.0 10 to
5
1 1
9.1 10 M s ) [26,27]. On the other hand, alcohols
containing -hydrogen, such as ethanol, react at comparable
9
OH (1.2 10 to 2.8 109 M1 s1 ) is approximately
7
7
50-fold greater than that with SO
4 (1.6 10 to 7.7 10
1 1
M s ) [26,27]. Hence, the change in the oxidation eciency caused by t-butanol makes it possible to dierentiate
between SO
4 -induced reactions and OH -induced reactions. As shown in Figure 4a, the eciency change due
to t-butanol was very small in the UV/S2 O2
8 process compared with the eciency decrease due to ethanol. On the
other hand, as shown in Figure 4b, in the UV/H2 O2 process,
t-butanol caused a great inhibition eect on the degradation
of BPA, similarly with ethanol. These results imply that the
2
SO
4 is the main oxidizing species in the UV/S2 O8 pro
cess, whereas the OH plays the main role in the oxidation
by the UV/H2 O2 process.
[DOC]t / [DOC]0
126
0.4
0.2
2-
0.0
0
10
20
30
40
produce two SO
4 radicals and two OH radicals (Equations (2) and (3)), the result shown in Figure 5c implies that
2
the number of SO
4 radicals produced by UV/S2 O8 was
fewer than that of OH radicals produced by UV/H2 O2 .
S2 O2
8 + hv 2SO4
H2 O2 + hv 2OH .
(2)
(3)
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that the SO
4 is more eective than the OH for the oxida2
tion of BPA. Therefore, the UV/S2 O8 process can be an
excellent alternative to the widely used UV/H2 O2 process,
with higher remediation performance. The redox potentials
of OH and SO
4 are 2.7 and 2.6 VNHE , respectively. In
our assumption, due to the lower redox potential (i.e. lower
reactivity), SO
4 is more stable and is able to transport to
greater distances (i.e. greater mass transfer rate) in aque
Conclusions
This study focused on the comparison of UV/S2 O2
8 and
UV/H2 O2 for the oxidation of BPA. The BPA oxidation
eciency by UV/S2 O2
8 could be increased by increasing the ratio of [S2 O2
8 ]/[BPA]. The increase in HA
concentration showed an inhibitory eect on the BPA oxidation by UV/S2 O2
8 . The BPA oxidation eciency by
UV/S2 O2
was
increased
in the following order: neutral pH
8
(pHi = 7) < acidic pH (pHi = 4) < basic pH (pHi = 10).
The main oxidizing species in the UV/S2 O2
8 system was
sulphate radical, whereas the main oxidizing species in
the UV/H2 O2 system was OH radical. The UV/S2 O2
8
process was more eective for not only BPA removal
but also BPA mineralization than the UV/H2 O2 process,
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
References
[1] T.B. Hayes, K. Haston, M. Tsui, A. Hoang, C. Haeele, and
A. Vonk, Feminization of male frogs in the wild: Waterborne herbicide threatens amphibian populations in parts of
the United States, Nature 419 (2002), pp. 895896.
[2] K.K. Samir, B. Xie, M.L. Thompson, S.W. Sung, S.K.
Ong, and J.V. Leeuvent, Fate, transport, and biodegradation of natural estrogens in the environment and engineered
systems, Environ. Sci. Technol. 40 (2006), pp. 65376546.
[3] D. Kolpin, E.D. Furlong, M.T. Meyer, E.M. Thurman, S.
Zaugg, L.B. Barber, and H.T. Buxton, Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S.
streams, 19992000: A national reconnaissance, Environ.
Sci. Technol. 36 (2002), pp. 12021211.
[4] P. Hohenblum, O. Gans, W. Moche, S. Scharf, and G.
Lorbeer, Monitoring of selected estrogenic hormones and
industrial chemicals in groundwaters and surface waters in
Australia, Sci. Total Environ. 333 (2004), pp. 185193.
[5] V.J. Pereira, K.G. Linden, and H.S. Weinberg, Evaluation of
UV irradiation for photolytic and oxidative degradation of
[18]
[19]
[20]
[21]
[22]
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